Jing - Yang - Thesis - PDF Semina Paper PDF

SYNTHESIS AND
CHARACTERISATION OF METAL
OXYHYDROXIDE AND OXIDE
NANOMATERIALS
by
JING (JEANNE) YANG

Bachelor of Science, Beijing Normal University, China
Chemistry Discipline
Faculty of Science and Technology
Queensland University of Technology
A thesis submitted to the Queensland University of Technology, in

fulfillment of the requirements of the degree of Doctor of Philosophy
November 2010
谨以此论文
献给我挚爱的父母：
杨百良先生和许再美女士
PREFACE
ABSTRACT
In this work, a range of nanomaterials have been synthesised based on metal

oxyhydroxides MO(OH), where M=Al, Co, Cr, etc. Through a self-assembly
hydrothermal route, metal oxyhydroxide nanomaterials with various morphologies
were successfully synthesised: one dimensional boehmite (AlO(OH)) nanofibres,
zero dimensional indium hydroxide (In(OH)3) nanocubes and chromium
oxyhydroxide (CrO(OH)) nanoparticles, as well as two dimensional cobalt hydroxide
and oxyhydroxide (Co(OH)2 & CoO(OH)) nanodiscs. In order to control the synthetic
nanomaterial morphology and growth, several factors were investigated including
cation concentration, temperature, hydrothermal treatment time, and pH.
Metal ion doping is a promising technique to modify and control the properties of
materials by intentionally introducing impurities or defects into the material.
Chromium was successfully applied as a dopant for fabricating doped boehmite
nanofibres. The thermal stability of the boehmite nanofibres was enhanced by
chromium doping, and the photoluminescence property was introduced to the
chromium doped alumina nanofibres. Doping proved to be an efficient method to
modify and functionalize nanomaterials.
The synthesised nanomaterials were fully characterised by X-ray diffraction (XRD),

transmission electron microscopy (TEM) combined with selected area electron
diffraction (SAED), scanning electron microscopy (SEM), BET specific surface area
analysis, X-ray photoelectron spectroscopy (XPS) and thermo gravimetric analysis
(TGA). Hot-stage Raman and infrared emission spectroscopy were applied to study
the chemical reactions during dehydration and dehydroxylation. The advantage of
these techniques is that the changes in molecular structure can be followed in situ
and at the elevated temperatures.
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PREFACE
KEYWORDS
Aluminium oxyhydroxide; Chromium oxyhydroxide; Cobalt oxyhydroxide; Cobalt
hydroxide; Indium hydroxide; Chromium doped; Dopant; Alumina; Aluminium
oxide; Indium oxide; Chromium oxide; Chromium oxide gel; Cobalt oxide;
Boehmite; Grimaldiite; Eskolaite; Heterogenite; Nanostructure; Nanofibres;
Nanorods; Nanoparticles; Nanodiscs; Nanocubes; Nanotubes; Nanosheets;
Nanomaterials; Self-assembly; Hydrothermal treatment; X-ray diffraction;
Transmission electron microscopy; Scanning electron microscopy; X-ray
photoelectron spectroscopy; N2 adsorption/desorption; Thermal decomposition;
Thermogravimetric analysis; Raman spectroscopy; Hot-stage Raman; Infrared
spectroscopy; Infrared emission spectroscopy.
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PREFACE
TABLE OF CONTENTS
Abstract ........................................................................................................................ i
Keywords .................................................................................................................... ii
Table of contents ....................................................................................................... iii
List of tables ............................................................................................................. viii
List of figures ............................................................................................................. ix
Publication and conference presentations ............................................................ xiv
List of publications as a result of this project ........................................................ xiv
List of other publications in which I was a co-author ............................................ xv
List of conferences attended in this course of study ............................................ xvii
Abbreviations ........................................................................................................ xviii
Statement of originality .......................................................................................... xix
Acknowledgements ................................................................................................... xx
CHAPTER 1
INTRODUCTION ...................................................................................................... 1
1. INTRODUCTION ........................................................................................... 2
2. DESCRIPTION OF SCIENTIFIC PROBLEMS INVESTIGATED ............... 2
3. RESEARCH OBJECTIVES OF THE STUDY ............................................... 3
4. ACCOUNT OF SCIENTIFIC PROGRESS LINKING THE SCIENTIFIC
PAPERS ................................................................................................................... 3
REFERENCES ......................................................................................................... 5
CHAPTER 2
LITERATURE REVIEW.......................................................................................... 7
1. INTRODUCTION ........................................................................................... 8
2. NANOTECHNOLOGY AND NANOMATERIALS ...................................... 8
3. METAL OXYHYDROXIDE AND OXIDE NANOMATERIALS .............. 10
4. DOPED NANOMATERIALS ....................................................................... 20
5. CONCLUSIONS ............................................................................................ 23
REFERENCES ....................................................................................................... 24
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PREFACE
CHAPTER 3
SYNTHESIS AND CHARACTERISATION OF BOEHMITE
NANOFIBRES .......................................................................................................... 31
SYNOPSIS ............................................................................................................. 32
STATEMENT OF CONTRIBUTION OF CO-AUTHORS .................................. 33
RESEARCH HIGHLIGHTS .................................................................................. 34
ABSTRACT ........................................................................................................... 35
KEYWORDS.......................................................................................................... 35
1. INTRODUCTION .......................................................................................... 35
2. EXPERIMENTAL ......................................................................................... 36
3. RESULTS AND DISCUSSION .................................................................... 37
4. CONCLUSIONS ............................................................................................ 42
ACKNOWLEDGMENTS ...................................................................................... 42
REFERENCES ....................................................................................................... 43
CHAPTER 4
SYNTHESIS AND CHARACTERISATION OF INDIUM HYDROXIDE
IN(OH)3 NANOCUBES ........................................................................................... 45
SYNOPSIS ............................................................................................................. 46
CHAPTER 4.1
THERMOGRAVIMETRIC ANALYSIS AND HOT-STAGE RAMAN
SPECTROSCOPY OF CUBIC INDIUM HYDROXIDE..................................... 47
ABSTRACT ........................................................................................................... 50
KEYWORDS.......................................................................................................... 50
1. INTRODUCTION .......................................................................................... 51
2. EXPERIMENTAL ......................................................................................... 52
4. CONCLUSIONS ............................................................................................ 63
ACKNOWLEDGMENTS ...................................................................................... 63
REFERENCES ....................................................................................................... 64
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PREFACE
CHAPTER 4.2
APPLICATION OF INFRARED EMISSION SPECTROSCOPY TO THE
THERMAL TRANSITION OF INDIUM HYDROXIDE TO INDIUM
OXIDE NANOCUBES ............................................................................................ 67
ABSTRACT ........................................................................................................... 70
KEYWORDS ......................................................................................................... 71
1. INTRODUCTION ......................................................................................... 71
2. EXPERIMENTAL ......................................................................................... 72
4. CONCLUSIONS ............................................................................................ 84
ACKNOWLEDGEMENTS ................................................................................... 84
REFERENCES ....................................................................................................... 85
CHAPTER 5
SYNTHESIS AND CHARACTERISATION OF CHROMIUM DOPED
BOEHMITE NANOFIBRES .................................................................................. 89
SYNOPSIS ............................................................................................................. 90
ABSTRACT ........................................................................................................... 93
KEYWORDS ......................................................................................................... 93
1. INTRODUCTION ......................................................................................... 94
2. EXPERIMENTAL ......................................................................................... 95
4. CONCLUSIONS .......................................................................................... 106
ACKNOWLEDGEMENTS ................................................................................. 106
REFERENCES ..................................................................................................... 107
CHAPTER 6
SYNTHESIS AND CHARACTERISATION OF CHROMIUM
OXYHYDROXIDE CRO(OH) NANOPARTICLES ......................................... 111
SYNOPSIS ........................................................................................................... 112
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PREFACE
CHAPTER 6.1
SIZE-CONTROLLABLE SYNTHESIS OF CHROMIUM
OXYHYDROXIDE NANOMATERIALS USING A SOFT CHEMICAL
HYDROTHERMAL ROUTE ............................................................................... 113
STATEMENT OF CONTRIBUTION OF CO-AUTHORS ................................ 114
RESEARCH HIGHLIGHTS ................................................................................ 115
ABSTRACT ......................................................................................................... 116
KEYWORDS........................................................................................................ 117
1. INTRODUCTION ........................................................................................ 117
2. EXPERIMENTAL ....................................................................................... 118
3. RESULTS AND DISCUSSION .................................................................. 121
4. CONCLUSIONS .......................................................................................... 139
ACKNOWLEDGEMENTS.................................................................................. 139
REFERENCES ..................................................................................................... 140
SUPPORTING INFORMATION......................................................................... 144
CHAPTER 6.2
TRANSITION OF SYNTHETIC CHROMIUM OXIDE GEL TO
CRYSTALLINE CHROMIUM OXIDE: A HOT-STAGE RAMAN
SPECTROSCOPIC STUDY ................................................................................. 145
ABSTRACT ......................................................................................................... 148
KEYWORDS........................................................................................................ 149
1. INTRODUCTION ........................................................................................ 149
2. EXPERIMENTAL ....................................................................................... 150
4. CONCLUSIONS .......................................................................................... 161
ACKNOWLEDGMENTS .................................................................................... 161
REFERENCES ..................................................................................................... 162
CHAPTER 6.3
TRANSITION OF CHROMIUM OXYHYDROXIDE NANOMATERIALS
TO CHROMIUM OXIDE: A HOT-STAGE RAMAN SPECTROSCOPIC
STUDY .................................................................................................................... 165
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PREFACE

ABSTRACT ......................................................................................................... 168
KEYWORDS ....................................................................................................... 169
1. INTRODUCTION ....................................................................................... 169
2. EXPERIMENTAL ....................................................................................... 170
4. CONCLUSIONS .......................................................................................... 179
ACKNOWLEDGMENTS .................................................................................... 179
REFERENCES ..................................................................................................... 180
CHAPTER 7
SYNTHESIS AND CHARACTERISATION OF COBALT HYDROXIDE,
COBALT OXYHYDROXIDE AND COBALT OXIDE NANODISCS ............ 183
SYNOPSIS ........................................................................................................... 184
ABSTRACT ......................................................................................................... 187
KEYWORDS ....................................................................................................... 188
1. INTRODUCTION ....................................................................................... 188
2. EXPERIMENTAL ....................................................................................... 190
4. CONCLUSIONS .......................................................................................... 208
ACKNOWLEDGEMENTS ................................................................................. 208
REFERENCES ..................................................................................................... 209
SUPPORTING INFORMATION ........................................................................ 213
CHAPTER 8
GENERAL DISCUSSION & FUTURE WORK................................................. 215
1. GENERAL DISCUSSION........................................................................... 216
2. FUTURE WORK ......................................................................................... 222
REFERENCES ..................................................................................................... 224
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PREFACE
LIST OF TABLES
CHAPTER 5
Table 1 Results of the thermogravimetric analyses of the undoped and various % Cr

doped boehmite nanofibres. ....................................................................................... 98
CHAPTER 6.1
Table 1 Samples ID used in this paper and their preparation conditions. ............... 119
Table 2 BET specific surface area (SBET), pore volume (Vp), and pore diameter for
synthesised CrO(OH) nanomaterials. ....................................................................... 128
Table 3 Results for curve-fitted binding energies and their atomic contents (at.%) of
highly resolved Cr 2p3/2 and O 1s XPS spectra shown in Fig. 7 for sample ppt-5.0,
CrO(OH)-5.0, CrO(OH)-7.5and CrO(OH)-10.0. ..................................................... 129
Table 4 Summary of peaks shown in dTG curves for synthesised chromium

materials. .................................................................................................................. 137
CHAPTER 6.2
Table 1 Summary of Raman shifts (cm-1) and their assignment for synthetic Cr-gel
and its thermal-decomposed product Cr2O3 in the hot-stage Raman spectroscopic
study. ........................................................................................................................ 157
CHAPTER 6.3
Table 1 Summary of Raman shifts (cm-1) and their assignment for -CrO(OH) and
Cr2O3 nanomaterials in the hot-stage Raman spectroscopic study. ......................... 178
CHAPTER 7
Table 1 Curve-fitted XPS binding energies of as-prepared cobalt hydroxide, cobalt

oxyhydroxide and cobalt oxide nanomaterials. ........................................................ 202
Table S1 Results of Raman spectra of Co(OH)2, CoO(OH) and Co3O4 in comparison

with published work. ................................................................................................ 213
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PREFACE
LIST OF FIGURES
CHAPTER 3
Fig. 1 XRD pattern of the synthetic boehmite nanofibres, after hydrothermal

treatment at 170 ºC for 2 days under pH 5. ................................................................ 38
Fig. 2 SEM image of the synthetic boehmite nanofibres, after hydrothermal treatment
at 170 ºC for 2 days under pH 5. ................................................................................ 38
Fig. 3 IES spectra of the synthetic boehmite nanofibres, collected at an interval of

50 ºC, over the range 100 ºC – 850 ºC. ...................................................................... 40
Fig. 4 Raman spectra of the synthetic boehmite nanofibres, after hydrothermal

treatment at 170 ºC for 2 days under pH 5. ................................................................ 41
CHAPTER 4.1
Fig. 1 Thermo gravimetric analyses of synthetic In(OH)3 nanocubes. ...................... 54
Fig. 2 XRD patterns of synthetic In(OH)3 (a) and its thermally treated products In2O3
(b). The peaks are labeled with their Miller indices................................................... 55
Fig. 3 (a) Image of In(OH)3 synthesised at 180 °C and (b) image of In2O3, product of
as-synthetic In(OH)3 calcined at 500 ºC for 4 h. ........................................................ 56
Fig. 4 Raman spectrum of In(OH)3 in the 100 – 700 cm-1 region. ............................ 57
Fig. 5 Raman spectrum of In(OH)3 in the 950 – 1200 cm-1 region. .......................... 58
Fig. 6 Raman spectrum of In(OH)3 in the 2600 – 3600 cm-1 region. ........................ 59
Fig. 7 Hot-stage Raman spectra of In(OH)3 in the 100 – 800 cm-1 region. ............... 60
Fig. 8 Hot-stage Raman spectra of In(OH)3 in the 2400 – 3900 cm-1 region. ........... 61
Fig. 9 Hot-stage Raman spectra of In(OH)3 in (a) 3900 – 2400 cm-1 region and (b)
800 – 1800 cm-1 region. ............................................................................................. 62
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PREFACE
CHAPTER 4.2
Fig.1 XRD pattern of the synthetic indium hydroxide nanomaterials with a reference
pattern: JCPDS card No. 01-076-1463 In(OH)3......................................................... 74
Fig. 2 Schematic of In(OH)3 in cubic structure (space group Im 3 ) ........................ 75
Fig.3 Infrared absorption spectrum (curve-fitted) of the synthetic In(OH)3 nanocubes

in the region of 3600 – 600 cm-1. ............................................................................... 76
Fig. 4 (a) Infrared emission spectra of the synthetic In(OH)3 nanocubes in the region
of 4000 – 650 cm-1 and (b)curve-fitted Infrared emission spectra from 100 – 300 °C.78
Fig. 5 Curve-fitted Infrared emission spectra in the region of 1200 – 650 cm-1. ....... 80
Fig. 6 Curve-fitted Infrared emission spectra in the region of 3700 – 2600 cm-1. ..... 81
Fig. 7 XRD patterns of thermal products at 300 and 500 °C from In(OH)3 nanocubes
with a reference pattern: JCPDS card No. 01-071-2195 In2O3. ................................. 82
CHAPTER 5
Fig. 1 (a) XRD patterns of undoped boehmite and 1% Cr-doped boehmite nanofibres
with different hydrothermal treatment time at 170 ºC. (b) XRD patterns of undoped
boehmite and various Cr % doped boehmite nanofibres, after hydrothermal treatment
at 170 ºC for 3 days. ................................................................................................... 97
Fig. 2 TEM images of the synthetic nanofibres with 3-day hydrothermal treatment: (a)
undoped boehmite, (b) 3% Cr-doped and (c)5% Cr-doped. ...................................... 97
Fig. 3 Thermogravimetric analyses patterns of (a) undoped boehmite nanofibres and

1% Cr doped boehmite with different hydrothermal treatment time: (b) 1 day, (c) 3
days, (d) 5 days, and (e) 10 days. ............................................................................. 101
Fig. 4 Dehydroxylation temperature of the dTG peak as a function of added Cr

content and with the hydrothermal treatment time................................................... 102
Fig. 5 Thermo gravimetric analyses patterns of various % Cr-doped boehmite

nanofibres with 3-day hydrothermal treatment:(a) 3% , (b) 5%, (c)10%, and (d) 20%.104
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PREFACE
Fig. 6 Temperature of the main dTG peak and the total mass loss percentage as a
function of added Cr content. ................................................................................... 105
function of the hydrothermal treatment time. .......................................................... 105
CHAPTER 6.1
Fig .1 XRD patterns of ppt-5.0, ppt-7.5, ppt-10.0, CrO(OH)-5.0, gel-7.5-a and

gel-10.0-a. XRD pattern from literature: JCPDS card No. 01-070-0621 Grimaldiite.122
Fig. 2 SEM images of (a) ppt-5.0 and (b) CrO(OH)-5.0. ........................................ 123
Fig. 3 XRD patterns of CrO(OH)-10.0 and CrO(OH)-7.5. XRD pattern from

literature: JCPDS card No. 01-070-0621 Grimaldiite. ............................................. 124
Fig. 4 (a) TEM image of CrO(OH)-5.0; (b) SAED result of the corresponding area
in Fig.4 (a); (c) TEM image of CrO(OH)-7.5 and its SAED result (inset); (d)
TEM image of CrO(OH)-10.0 and its SAED result (inset). .................................... 125
Fig. 5 N2 adsorption/desorption isotherms for CrO(OH)-5.0, CrO(OH)-7.5 and

CrO(OH)-10.0. ......................................................................................................... 126
Fig. 6 Pore size distribution study for CrO(OH)-5.0, CrO(OH)-7.5 and

CrO(OH)-10.0. ......................................................................................................... 127
Fig. 7 XPS high resolution spectra of Cr 2p3/2 and O 1s for ppt-5.0, CrO(OH)-5.0,
CrO(OH)-7.5 and CrO(OH)-10.0 ............................................................................. 131
Fig.8 Thermogravimetric analyses (TGA) of (a) ppt-5.0, (b) CrO(OH)-5.0, (c)

CrO(OH)-7.5 and (d) CrO(OH)- 10.0. ..................................................................... 134
Fig. 9 Mass spectrometric analysis associated with the thermal decomposition

process for sample CrO(OH)-10.0. .......................................................................... 136
Fig. 10 XRD patterns of products after TGA from ppt-5.0, CrO(OH)-5.0,

CrO(OH)-7.5 and CrO(OH)-10.0. XRD patterns from literature: JCPDS card No.
01-084-1616 Cr2O3. ................................................................................................. 138
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PREFACE
CHAPTER 6.2
Fig. 1 (a) XRD pattern of the precipitated Cr-gel material and a reference pattern:
JCPDS card No. 01-070-0621 CrO(OH) and (b) SEM image of the precipitated
Cr-gel material.......................................................................................................... 152
Fig. 2 Hot-stage Raman spectrum of the precipitated Cr-gel material in the region of
100 to 2000 cm-1 at 25 °C ........................................................................................ 153
Fig. 3 Hot-stage Raman spectra of the precipitated Cr-gel material in the region of
100 to 2000 cm-1 from 130 to 350 °C ...................................................................... 156
Fig. 4 XRD pattern of thermal product at 350 °C from the precipitated Cr-gel
material and a reference pattern: JCPDS card No. 01-084-0314 (Cr2O3). ............... 158
100 to 2000 cm-1 at 550 °C ...................................................................................... 159
material and a reference pattern: JCPDS card No. 01-084-0314 (Cr2O3). ............... 160
Fig. 7 Schematic of Cr2O3 in rhombohedral structure (space group R-3c).............. 160
CHAPTER 6.3
Fig. 1 XRD pattern for the synthetic -CrO(OH) and a reference pattern: JCPDS
card No. 01-085-1374 (Grimaldiite). ....................................................................... 172
Fig. 2 Schematic of the synthetic -CrO(OH) in rhombohedral structure (space

group R3m) observed from different directions. The hexagonal unit cells are shown.173
Fig. 3 TEM image of the synthetic -CrO(OH) nanomaterial ................................ 174
Fig. 4 Hot-stage Raman spectra of the synthetic -CrO(OH) nanomaterial in the 200
to 1800 cm-1 region at 25 and 100 °C....................................................................... 175
Fig. 5 Raman spectra of the synthetic -CrO(OH) nanomaterial in the 200 to 1800
cm-1 region at 350 and 550 °C.................................................................................. 177
xii
PREFACE
CHAPTER 7
Fig. 1 XRD patterns of (a) synthesised Co(OH)2, (b) synthesised CoO(OH), (c)
synthesised Co3O4, (d) JCPDS card No. 00-030-0443, (d‟) -Co(OH)2 pattern
synthesised according to literature, (e) JCPDS card No. 01-073-1213 and (f) JCPDS
card No. 01-071-0816. ............................................................................................. 193
Fig. 2 SEM images of (a, b) Co(OH)2, (c, d) CoO(OH) (e, f) Co3O4 at two
magnifications. ......................................................................................................... 195
Fig. 3 TEM images of (a) Co(OH)2, (c) CoO(OH) and (d) Co3O4; SAED patterns of
the corresponding particles showing in TEM images: (b) Co(OH)2 and (e) Co3O4 197
Fig. 4 XPS survey spectra of (a) Co(OH)2, (b) CoO(OH) and (c) Co3O4................ 199
Fig. 5 XPS high resolution Co 2p3/2 spectra of (a) Co(OH)2, (c) CoO(OH) and (e)
Co3O4; O 1s spectra of (b) Co(OH)2, (d) CoO(OH) and (f) Co3O4.......................... 201
Fig. 6 Raman spectra of (a) Co(OH)2, (b) CoO(OH), and (c) Co3O4 in the 100 – 1200
cm-1 region ............................................................................................................... 204
Fig. 7 Thermo-gravimetric analyses of (a) Co(OH)2, (b) CoO(OH) nanomaterials. 206
Fig. 8 XRD patterns of the thermal products after TG study: (a) from Co(OH)2, (b)
from CoO(OH). XRD patterns from literature: (c) JCPDS card No. 01-080-1533 (d)
JCPDS card No. 00-043-1004. ................................................................................. 207
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PREFACE
PUBLICATION AND CONFERENCE

PRESENTATIONS
LIST OF PUBLICATIONS AS A RESULT OF THIS PROJECT
1. Yang, J.; Frost, R. L., "Synthesis and characterization of boehmite nanofibres."

Research Letters in Inorganic Chemistry 2008. DOI:10.1155/2008/602198.
2. Yang, J.; Frost, R. L.; Yuan, Y., "Synthesis and characterization of chromium
doped boehmite nanofibres." Thermochimica Acta 2009, 483 (1-2), 29-35.
(SCI) Impact Factor: 1.742. Citation: 3.
3. Yang, J.; Zhao, Y.; Frost, R. L., "Surface analysis, TEM, dynamic and
controlled rate thermal analysis, and infrared emission spectroscopy of gallium
doped boehmite nanofibres and nanosheets." Applied Surface Science 2009, 255
(18), 7925-7936. (SCI) Impact Factor: 1.616
4. Yang, J.; Zhao, Y.; Frost, R. L., "Infrared and infrared emission spectroscopy of
gallium oxide α-GaO(OH) nanostructures." Spectrochimica Acta Part A:
Molecular and Biomolecular Spectroscopy 2009, 74A (2), 398-403. (SCI)
Impact Factor: 1.566
5. Yang, J.; Liu, H.; Martens, W. N.; Frost, R. L., "Synthesis and characterization
of cobalt hydroxide, cobalt oxyhydroxide, and cobalt oxide nanodiscs." The
Journal of Physical Chemistry C 2010, 114 (1), 111-119. (SCI) Impact Factor:
4.224. Citation: 6.
6. Yang, J.; Baker, A. G.; Liu, H.; Martens, W. N.; Frost, R. L., "Size-controllable
synthesis of chromium oxyhydroxide nanomaterials using a soft chemical
hydrothermal route." Journal of Materials Science 2010, 45 (24), 6574-6585.
(SCI) Impact Factor: 1.471
7. Yang, J.; Martens, W. N.; Frost, R. L., "Transition of chromium oxyhydroxide
nanomaterials to chromium oxide: a hot-stage Raman spectroscopic study."
Journal of Raman Spectroscopy 2010, in press. DOI: 10.1002/jrs.2773. (SCI)
8. Yang, J.; Martens, W. N.; Frost, R. L., "Transition of chromium oxide gel to
crystalline chromium oxide: a hot-stage Raman spectroscopic study." Journal of
Raman Spectroscopy 2010, in press. DOI:10.1002/jrs.2794. (SCI) Impact Factor:
3.147
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PREFACE
9. Yang, J.; Frost, R. L.; Martens, W. N., "Thermogravimetric analysis and

hot-stage Raman spectroscopy of cubic indium hydroxide." Journal of Thermal
Analysis and Calorimetry 2010, 100 (1), 109-116. (SCI) Impact Factor: 1. 587.
Citation: 1.
10. Yang, J.; Cheng, H.F.; Martens, W.N.; Frost, R.L. "Application of infrared
emission spectroscopy to the thermal transition of indium hydroxide to indium
oxide nanocubes." Applied Spectroscopy 2011, 65 (1). In press. (SCI) Impact
Factor: 1.564
11. Yang, J.; Martens, W. N.; Frost, R. L., "Synthesis and characterisation of cobalt
hydroxyl carbonate Co2CO3(OH)2-relationship to the rosasite mineral group."
Spectrochimica Acta, Part A: Molecular Spectroscopy 2010, in press. DOI:
10.1016/j.saa.2010.11.004. (SCI) Impact Factor: 1.566
12. Zhao, Y.; Yang, J.; Frost, R. L.; Martens, W. N., "Size and morphology control
of gallium oxide hydroxide GaO(OH), nano- to micro-sized particles by
soft-chemistry route without surfactant." The Journal of Physical Chemistry C
2008, 112 (10), 3568-3579. (SCI) Impact Factor: 4.224. Citation: 6.
13. Zhao, Y.; Yang, J.; Frost, R. L., "Raman spectroscopy of the transition of
α-gallium oxyhydroxide to β-gallium oxide nanorods." Journal of Raman
Spectroscopy 2008, 39 (10), 1327-1331. (SCI) Impact Factor: 3.147
14. Zhao, Y.; Yang, J.; Frost, R. L.; Kristof, J.; Horvath, E., "Synthesis,
Characterisation and thermal analysis of Fe-doped boehmite nanofibres and
nanosheets." Journal of Materials Science 2009, 44 (14), 3662-3673. (SCI)
LIST OF OTHER PUBLICATIONS IN WHICH I WAS A CO-AUTHOR
1. Cheng, H.F.; Yang, J.; Frost, R. L.; Liu, Q.F.; Zhang, J.S., "A spectroscopic
comparion of kaolinite, coal bearing kaolinite and halloysite: a mid-infrared and
near-infrared study." Spectrochimica Acta part A: Molecular and Biomolecular
Spectroscopy 2010, 77 (4), 856-861. (SCI) Impact Factor: 1.566
2. Cheng, H.F.; Yang, J.; Frost, R. L.; Liu, Q.F.; Zhang, Z.L., "Thermal analysis
and Infrared emission spectroscopic study of kaolinite-potassium acetate
intercalate complex." Journal of Thermal Analysis and Calorimetry 2010, in
press. DOI: 10.1007/s10973-010-0917-3. (SCI) Impact Factor: 1. 587
xv
PREFACE
3. Cheng, H.F.; Liu, Q.F.; Zhang, J.; Yang, J.; Frost, R. L.,"Delamination of
kaolinite–potassium acetate intercalates by ball-milling." Journal of Colloid and
Interface Science 2010, 348 (2),355-359. (SCI) Impact Factor: 3.019
4. Cheng, H.F.; Yang, J.; Liu, Q.F.; He, J.K.; Frost, R. L., "Thermogravimetric
analysis – mass spectrometry (TG – MS) of selected Chinese kaolinites."
Thermochimica Acta 2010, 507-508 (C), 106-114. (SCI) Impact Factor: 1.742
5. Cheng, H.F.; Liu, Q.F.; Yang, J.; Zhang, Q.; Frost, R. L., "Thermal behavior
and decomposition of kaolinite-potassium acetate intercalation composite."
Thermochimica Acta 2010, 503-504 (C), 16-20. (SCI) Impact Factor: 1.742
6. Cheng, H.F.; Liu, Q.F.; Yang, J.; Frost, R. L.,"Thermogravimetric analysis of
selected coal-bearing strata kaolinite." Thermochimica Acta 2010, 507-508 (C),
84-90. (SCI) Impact Factor: 1.742
7. Cheng, H.F.; Frost, R. L.; Yang, J.; Liu, Q.F.; He, J.K., "Infrared and infrared
emission spectroscopic study of typical Chinese kaolinite and halloysite."
Spectrochimica Acta part A: Molecular and Biomolecular Spectroscopy 2010,
77(5), 1013-1019. (SCI) Impact Factor: 1.566
8. Cheng, H.F.; Liu, Q.F.; Yang, J.; Frost, R. L., "Thermal analysis and infrared
emission spectroscopy study of halloysite-potassium acetate intercalation
complex." Thermochimica Acta 2010, in press. DOI:10.1016/j.tca.2010.08.003.
(SCI) Impact Factor: 1.742
9. Cheng, H.F.; Yang, J.; Frost, R. L., "Thermogravimetric analysis-mass
spectrometry (TG-MS) of selected Chinese palygorskites." Thermochimica Acta
2010, in press. DOI:10.1016/j.tca.2010.10.008. (SCI) Impact Factor: 1.742
10. Cheng, H.F.; Liu, Q.F.; Yang, J.; Du, X.M.; Frost, R. L., "Influencing factors
on kaolinite-potassium acetate intercalation complexes." Applied Clay Science
2010, in press. DOI: 10.1016/j.clay.2010.09.011. (SCI) Impact factor: 2.784
xvi
PREFACE
LIST OF CONFERENCES ATTENDED IN THIS COURSE OF STUDY
1. GeoRaman Conference
Sydney, Australia 28th June – 2nd July, 2010
Oral presentation: "Raman spectroscopy of the transition of chromium

oxyhydroxide to chromium oxide nanoplates", Jing Yang, Llew Rintoul, Wayde
N. Martens and Ray L. Frost.
2. 21st Australian Clay Minerals Society Conference

Brisbane, Australia 7th – 8th August, 2010
Oral presentation: "Facile self-assembly synthesis of high-quality disc-like

heterogenite (CoO(OH)) nanomaterials ", Jing Yang, Wayde N. Martens and
Ray L. Frost.
3. 5th International Conference on Advanced Vibrational Spectroscopy

Melbourne, Australia 12th – 17th July, 2009
Poster: "Hot-stage Raman spectroscopic study of cubic indium hydroxide", Jing

Yang and Ray L. Frost.
4. 21st International Conference of Raman Spectroscopy (ICORS)

London, United Kingdom 17th – 22nd August, 2008
Posters:
 "Thermo-Raman spectroscopy study of the transition of alpha GaO(OH) to

beta Ga2O3 nanorods", Jing Yang, Yanyan Zhao and Ray L. Frost.
 "Raman spectroscopy of the uranyl phosphate minerals yingjiangite and
phosphuranylite", Ray L. Frost and Jing Yang.
xvii
PREFACE
ABBREVIATIONS
1D One dimensional
nm Nanometer
XRD X-ray diffraction
TEM Transmission electron microscopy
SAED Selected area electron diffraction
EDX Energy dispersive X-ray spectroscopy
SEM Scanning electron microscopy
XPS X-ray photoelectron spectroscopy
BET Brunauer-Emmett-Teller
TGA Thermogravimetric analysis
MS Mass spectrometry
IR Infrared spectroscopy
IES Infrared emission spectroscopy
UV-vis Ultraviolet-visible spectroscopy
PL Photoluminescence spectroscopy
ICP Inductively coupled plasma
VOC Volatile organic compounds
xviii
PREFACE
STATEMENT OF ORIGINALITY
The work contained in this thesis has not been previously submitted to meet
requirements for an award at this or any other higher education institution. To the
best of my knowledge and belief, the thesis contains no material previously
published or written by another person except where due reference is made.
Signature:
Jing (Jeanne) Yang
Date:
xix
PREFACE
ACKNOWLEDGEMENTS
Thanks a lot to all the people and organisations who made this thesis a possibility.
They include:
 My supervisors: Prof. Ray L. Frost, Dr. Wayde N. Martens and Prof.

Huaiyong Zhu for their patience, guidance, and continuous encouragement
and help. I cannot thank you enough. It was my huge fortune having you with
me throughout this PhD journey. You are the best supervisors in the world.
 Dr. Xuebin Ke and Dr. Dongjiang Yang for their extensive support.
 Dr. Llew Rintoul for all his assistance and help with the vibrational
spectroscopy instruments.
 AsPro. Godwin Ayoko, AsPro. Peter Fredericks, Prof. Graeme Millar, Dr.
Eric Waclawik, Dr. Geoffrey Will and other QUT SPCS staff for your great
help and encouragement.
 Mr. Anthony (Tony) Raftery for advice and technical support with XRD,
crystallography and software.
 Dr. Thor E. Bostrom, Prof. Hongwei Liu, Mr. Lambert Bekessy, Dr. Loc
Doung, Dr. Deborah Stenzel, Mr. Ashley Locke, Dr. Christina
Theodoropoulos and Dr. Marek Zbik for their patience, advice and technical
support with the operation of the electron microscope. And my thanks also go
to the other QUT AEMF staffs for the training and allowing me access to
your instruments.
 Dr. Barry Wood from UQ for your help with XPS.
 My fellow postgraduate students who have helped and encouraged me, and
provided an interesting and supportive work environment and friendship.
 Lovely thanks to Milica Ivkovic from Croatia, the office cleaner for our H
block. I will miss your sunshine smile in the early morning and massage.
Last but not least, I would like to acknowledge my family and friends for their love,
supports and encouragement, especially my dearest parents (Bailiang Yang and
Zaimei Xu) and my boyfriend Jinming Zeng. Thank you so much for your company,
without which I could not complete this work.
xx
Chapter 1 Introduction
CHAPTER 1
INTRODUCTION
1
1. INTRODUCTION
This thesis, entitled “Synthesis and characterisation of metal oxyhydroxide and oxide
nanomaterials”, reports the effect of various synthesis conditions on the formation of
metal (Al, Co, Cr and In) hydroxide, oxyhydroxide and oxide nanomaterials which
synthesised by the hydrothermal method. This chapter details the scientific problems
investigated, the research objectives of the study and the links between the
manuscripts in this study, in order to build the framework for the thesis as a whole.
2. DESCRIPTION OF SCIENTIFIC PROBLEMS

INVESTIGATED
Because of their high surface area, chemical and thermally stability and their high
porosity, nanostructured metal oxides have been extensively used as catalysts or
catalytic supports for a variety of industrial reactions.1-3 There are many literature
reports on the formation of metal oxides through the thermal dehydration of their
corresponding hydroxides or oxyhydroxides, which preserve the morphology of their
precursors.4,5 To apply these nanostructured metal oxides in industry, their phases,
morphology, properties and formation mechanism must to be fully understood.
Moreover, it is known that metal ion doping is a promising technique to modify and
control the properties of materials by intentionally introducing impurities or defects
into a material.6 Without a comprehensive study of the synthesis of these metal
oxides and their doped counterparts, the application of these materials to industrial
problems, would not be fully achieved. This study investigated the effect of synthesis
conditions on the formation and properties of nanomaterials, with particularly focus
on the hydrothermally treatment procedure, and on the effect of metal ion dopants.
Vibrational spectroscopy, especially Raman and infrared, has proven useful

technique for the non-destructive identification of various minerals and
nanomaterials through its use as an easy finger printing technique.7,8 However,
limited studies have been reported on the detailed interpretation of the spectra of
metal oxyhydroxide and oxide nanomaterials. This study aims to address this issue
through the detailed investigation of the effect of doping on the spectra of these
materials.
2
3. RESEARCH OBJECTIVES OF THE STUDY
The research objectives of this study were:
To examine the synthesis conditions of selected metal hydroxide and oxyhydroxides

through hydrothermal treatment, and to determine the influencing factors during the
formation of the nanomaterials. It is intended to realise the control of the size, phase
and morphology of the nanomaterials during synthesis and to discover their
formation mechanism.
To investigate the effect of metal ion dopants on the morphology, size and properties
of hydroxide and oxyhydroxide nanomaterials. Trivalent metal elements such as
chromium and cobalt will be employed as dopants into boehmite structure.
To determine the properties of the synthesised nanomaterials using various

characterisation techniques. Phase identification, element analysis, pore,
morphological studies, surface area analysis, thermal stability and vibrational spectra
of these nanomaterials will be investigated in detail. Their potential application will
also be proposed.
4. ACCOUNT OF SCIENTIFIC PROGRESS LINKING

THE SCIENTIFIC PAPERS
The following flow chart, presents the structure of this thesis, indicating the linkage
between the objectives and the outcomes reported in the published papers which
were written in this course of study.
3
Chapter 2 Literature review
Group IIIA elements (Al & In)
Chapter 3 Chapter 4
AlO(OH) In(OH)3
nanofibres nanocubes
Chapter 5 (In progress)

Cr-AlO(OH) Co-AlO(OH)
nanofibres nanofibres
Modification Modification
of AlO(OH) of AlO(OH)
Chapter 6 Chapter 7
by Cr doping by Co doping
CrO(OH) CoO(OH)
nanoparticles nanodiscs
Chapter 8 General discussion & future work
4
REFERENCES
[1] J. C. W. Chien, J. Am. Chem. Soc. 2002, 93, 4675-4684.
[2] Y.-Y. Lyu, Seung Hwan Yi, Jeong Kuk Shon, Seok Chang, Lyong Sun Pu,
Sang-Yun Lee, Jae Eui Yie, Kookheon Char, Galen D. Stucky, J. M. Kim, J.
Am. Chem. Soc. 2004, 126, 2310-2311.
[3] P. Yang, D. Zhao, D. I. Margolese, B. F. Chmelka, G. D. Stucky, Nature
(London) 1998, 396, 152-155.
[4] X. B. Ke, Z. F. Zheng, H. W. Liu, H. Y. Zhu, X. P. Gao, L. X. Zhang, N. P.
Xu, H. Wang, H. J. Zhao, J. Shi, K. R. Ratinac, J. Phys. Chem. B 2008, 112,
5000-5006.
[5] S. C. Shen, Q. Chen, P. S. Chow, G. H. Tan, X. T. Zeng, Z. Wang, R. B. H.
Tan, J. Phys. Chem. C 2007, 111, 700-707.
[6] S. C. Erwin, L. Zu, M. I. Haftel, A. L. Efros, T. A. Kennedy, D. J. Norris,
Nature (London, United Kingdom) 2005, 436, 91-94.
[7] X. Yang, H. Zhu, J. Liu, X. Gao, W. N. Martens, R. L. Frost, Y. Shen, Z.
Yuan, Micropor. Mesopor. Mater. 2008, 112, 32-44.
[8] R. L. Frost, W. N. Martens, K. L. Erickson, J. Therm. Anal. Calorim. 2005,
82, 603-608.
5
6
CHAPTER 2
LITERATURE REVIEW
7
1. INTRODUCTION
Nanoscience involves a study of nanotechnology and nanomaterials, of which at least

one of the dimensions is in 1 – 100 nm range. Compared to the bulk materials, the
nanoscale size of materials brings the materials new quantum mechanical effects,
like “quantum size effect”.1-3 And the size dependent behaviour of nanomaterials
enables researchers to design and produce devices with advanced properties by
employing nanostructures as building blocks. Interest has increased significantly in
the inorganic nanomaterials with particular morphology for their novel chemical,
electrical, optical, magnetic, mechanical and other properties.4-8 There is no doubt
that the synthesis and characterisation of nanomaterials has great significance.
This chapter will introduce the concepts of nanotechnology and nanomaterials first.
Then focus on the discussion of the controllable synthesis of desired nanomaterials.
Techniques for characterising nanomaterials properties will be reviewed.
2. NANOTECHNOLOGY AND NANOMATERIALS
2.1 Nanotechnology
Nanotechnology refers to a highly multidisciplinary field of applied science whose

theme is the fabrication with dimensions of less than 100 nm (1 nm is a billionth of a
metre) on an atomic and molecular scale. The involved fields include nutritional
sciences, pharmaceutical science, applied physics, materials science, interface and
colloid science, device physics, chemical engineering, mechanical engineering,
biological engineering, and electrical engineering. Nanotechnology is making a
further significant contribution to the fields of computer storage, semiconductors,
biotechnology, manufacturing and energy.
The concept of nano-technology was first introduced by physicist Richard P.

Feynman, who gave a talk titled “There‟s Plenty of Room at the Bottom” at an
American Physical Society meeting at Caltech in 1959.9 The possibility was
proposed by Feynman that one can manipulate individual atoms and molecules, by
using one set of precise tools to build and operate another proportionally smaller set,
so on down to the needed scale. In the system, instead of gravity, surface tension and
Van der Waals attraction would become much more important.
8
Until 1974, the term “nanotechnology” was firstly defined by Professor Norio
Taniguchi10 from Tokyo Science University: “„Nano-technology mainly consists of
the processing of, separation, consolidation, and deformation of materials by one
atom or by one molecule.” Then Dr. K. Eric Drexler, in 1980s, developed and
promoted the technological significance of nano-scale phenomena and devices. So
the term of “nanotechnology” acquired its current sense.11,12
2.2 Nanomaterials
As a crucial aspect of nanotechnology research, synthesis of nanomaterials and their

characterisation and property studies are attracting more and more attention.
Nanomaterials present specific functionality, such as field emission, gas sensing,
medical diagnostics, transistor action, lasing behaviour, photovoltaic properties and
catalytic properties. It becomes a challenging issue to explore ways to control and
manipulate the desired physical and chemical properties of nanomaterials. Mainly,
the unique properties and potential application of nanomaterials are greatly
determined by two important nanoscale geometrical parameters: size and shape.13
2.2.1 Size effect
For nanoscale materials, it is found that most of their behaviour cannot be described
by classical mechanics, but can only be explained by quantum mechanics.14,15 As
materials are reduced to the nanoscale, they can suddenly show very different
properties compared to what they exhibit on a macroscale, enabling unique
applications.16,17 “Size effect” refers to the strong influence in physical properties
of nanocrystals caused by the size of the nanocrystals.18-25 In nanoscale, particles are
small enough to confine their electrons and often obtain unexpected visual
properties. For instance, when the gold particle size was reduced in nanoscale, the
material appears red, deep violet and blue, instead the colour of gold.20 A large
ratio of surface area to volume is found in nanomaterials, which enables the increase
of surface activities of the materials.26 Take gold as an example again, which is
chemically inert as a bulk metal; however gold nanoparticles are reported to be
excellent catalyst for the oxidation of secondary alcohols into ketones.27 Most
important application of nanomaterials has been in catalysis and gas sensing because
of their unique size dependent properties.
9
2.2.2 Morphology control
The term, morphology, is used to describe the study of form comprising shape, size
and structure.28 Unlike bulk materials, the functional characteristics of nanomaterials
or nanodevices are strongly correlated to their shapes.28,29 It is reported that the
most distinct shape effects are observed in the density of energy states, and the
band-gap energy of nanomaterials is also influenced by their shapes.13
Nanomaterials can be simply classified by their dimensionalities: zero – dimensional
(0 D) nanomaterials including particles, isotropic spheres, cubes, and polyhedrons;
one – dimensional (1 D) nano-rods, fibres, tubes, ribbons and wires; two –
dimensional (2 D) nanodiscs, prisms and plates; and other advanced three –
dimensional (3 D) hetero-structural shapes such as rod-based multi-pods and
nano-stars. Low dimensional nanocrystals and nanostructures have become important
building blocks for assembling and patterning future nanodevices. Therefore, the
control of nano-building blocks is crucial for the success of future nanodevices.
3. METAL OXYHYDROXIDE AND OXIDE

NANOMATERIALS
3.1 Metal hydroxide, oxyhydroxide and oxide nanomaterials
Metal oxide nanomaterials have been widely studied because of their high surface
area, porosity, and catalytic activities.13,30,31 Properties of materials can be controlled
not only by the morphology of individual nanocrystals, but also by the nature of the
chemicals. The nanomaterials involved in this project are mainly trivalent metal
hydroxides and their oxides. In nature, these metal hydroxide minerals are important
sources for the corresponding metal. Whereas, their synthetic materials with unique
nanostructures have great potential for application in industry as catalysts, gas
sensors, etc.
Metal hydroxides and their oxyhydroxides are crucial precursors for metal oxides.
This research focuses on the synthesis of metal oxyhydroxides nanomaterials.
Transformation into the corresponding metal oxides is usually found to be a
topological process. The oxides obtained by the dehydroxylation normally preserve
the morphology of metal oxyhydroxide nanomaterials.
10
3.1.1 Group IIIA metal oxides nanomaterials
The series of elements in Group IIIA (“boron group”, or “group 13” by IUPAC,
International Union of Pure and Applied Chemistry) are characterised by having
three electrons in their outer energy levels (valence layers), and form trivalent
compounds. Their oxides share the same formula as M2O3, where M = aluminium
(Al), gallium (Ga) and indium (In).
Aluminium oxides, known as alumina Al2O3, exist in many forms

etc, which arise during the heat treatment of aluminium
hydroxide or aluminium oxyhydroxide. Among these oxides, the most
thermodynamically stable form is Al2O3. Because of their high specific surface
areas and the large number of defects in their crystalline structure, most alumina
phases are important for ceramic catalysts,32 membranes,33 coatings,34,35 and
adsorbents.36,37 Especially, -Al2O3 is widely used in catalysis as active phase and is
characterised by having acidic sites which determines the activity and selectivity of
the catalyst for specific catalytic reactions.38 Furthermore, due to its excellent
thermal stability and chemically properties, 1D -Al2O3 nanomaterials have been
extensively used as carrier and supports for a variety of industrial catalysts in many
chemical processes including cracking, hydrocracking, and hydrodesulfurization of
petroleum feedstock.39-41
Similar to alumina, gallium oxide (Ga2O3) has several polymorphs and

among which, Ga2O3 is the only thermodynamically stable oxide. Ga2O3 is also
an important semiconductor having a wide direct bad gap (Eg = 4.9 eV), and known
for its conduction and luminescence properties.42-45 Ga2O3 nanobelts are46 reported
to be efficient gas sensor for NO2 detection, and it can also be used combined with
other oxides or metal as sensor nanodevices for hydrogen detection.47 It can be
applied to dye-sensitized solar cells, which are based on GaN/gallium oxide
core-shell structures.48
Indium hydroxides and oxides are a series of important semiconductor materials,

which have attracted much attention in the past decade. In(OH)3 is a wide-gap
semiconductor with Eg = 5.15 eV,49 which has potential applications in
photocatalystic, electronic, and solar energy fields.50-52
11
While In2O3 is known as n-type semiconductor with a direct band gap of 3.6 eV
(which is close to that of GaN53 ) and an indirect band gap of 2.6 eV.54 In2O3 has
been used widely as solar cells, transparent conductors and sensors.55-59 In2O3 is
mostly used in combination with tin dioxide, forming tin doped indium oxide (ITO).
ITO is well known for application of transparent conducting devices.60,61
3.1.2 Transition metal hydroxide, oxyhydroxides and oxide
Transition metal elements are those whose atoms have an incomplete d sub-shell, or
which can give rise to cations with an incomplete d sub-shell, according to IUPAC
definition. Because of this electron filling status, transition metal compounds exhibit
unique properties which are not found in other elements. Firstly, they can form
compounds in many oxidation states. Take chromium as an example, it has a very
wide range of oxidation states, from Cr (0) to Cr (VI). The oxidation state Cr (III) is
the most stable; and chromia (Cr2O3) is important in specific applied applications
such as in high-temperature resistant materials,62-64 solar energy collectors,65-67 liquid
crystal displays,68,69 and catalysts.70-73 Cr (VI) compounds are toxic and can be very
powerful oxidants, which are commonly found to be CrO42- and Cr2O72- anions.
Secondly, the transition metal compounds are normally colorful, which is due to the
electronic transitions. Cr (III) is normally a green color; and because of its stability,
chromia (Cr2O3) can be used as green pigment. However, Cr (VI) appears the color
of orange or yellow. Co(OH)2 shows a pink color, while CoO(OH) is brown and
Co3O4 is black. Thirdly, the transition metal compounds show magnetism when the
element in the compound have one or more unpaired d electrons. For instance, CrO2
is the magnetic substance once widely used in magnetic tape industry. Because of
these unique properties, transition metal oxides are received more and more attention
and become important materials in industry in heterogenous catalysis, which support
materials as well as active components.
3.2 Synthesis approaches
As discussed above, the size and shape of nanomaterials are key factors for the
determination of materials properties. If the precise control of size and shape of
nanocrystals is possible, their chemical and physical properties can be manipulated
as desired.8 Various procedures for controllable inorganic nanomaterials synthesis
12
have been reported, and can be classified into two methods, according to the present
of morphology directing reagents or not. Here in this section, the synthesis of
boehmite (AlO(OH)) nanofibres was discussed as an example to present various
synthesis routes for nanomaterials.
A common approach to direct the size and morphology of crystals formed under
hydrothermal conditions is the use of surfactant templates or directing agents that
control the nucleation process or growth in a specific crystallographic direction.74,75
The template-assisted approaches were already widely employed in the synthesis of
boehmite nanomaterials.
In the condition of adding no surfactants as template, sol-gel and the neutralisation of

acidic aluminium salts by direct addition of a base such as NaOH, ammonia
(NH4OH) or thermal decomposition of urea are the most common employed
synthesis methods of boehmite nanoparticles. Through a self-assembling process, the
size and morphology of metal oxyhydroxides formed depend on the conditions such
as pH, temperature, pressure, nature of salts and bases, and also the ageing of the
hydrolysates.76 The first report on synthesis of boehmite nanofibres was published by
Bugosh in 1961.77 In this study, the procedure includes the addition of Al powder to
an aqueous solution of AlCl3 with an Al/Cl ratio of 2:3. The obtained aluminium
chloride solution was diluted and heated at 160 ˚C for 40 hours. The resulting
boehmite consists of stable colloidal fibrils with a length of 100-200 nm and a width
of 5 nm, which are physically analogous to linear, high molecular weight organic
molecules. This route was further investigated by Brusasco et al.78
Soda was used as a precipitant reacted with aluminium nitrate to produce boehmite in
Hochepied‟s research.79,80 In the studies, experimental conditions such as pH,
temperature and mixing procedure on the morphology and porosity of boehmite
particles synthesized were investigated. Through a one-step synthesis at 60 ˚C and
pH=9, a crystallized boehmite phase with fibre shape was observed. In the other
two-step synthesis an isolable amorphous hydroxide was firstly found, and then the
irregular boehmite nanocrystals were aggregated and transformed into porous
boehmite.80 The mixing procedure was also crucial for the formation of products: a)
when soda was added into nitrate aluminium solution, micro-porous bayerite was
formed; b) adding nitrate aluminium solution into soda resulted micro-porous
13
boehmite; whereas c) boehmite nanofibres can be recovered from a double jet

procedure.79
Bunches of aligned boehmite nanowires were produced with widths of 700 to 800
nm and lengths of about 1 m by Zhang et al. with Na2B4O7 as the mineralizer.81
AlCl3 and Na2B4O7 were used as precursors. High quality boehmite nanowires with
an average diameter of ~20 nm were obtained through a hydrothermal treatment at
200 ˚C for 24 hours. The synthesised boehmite nanowires were arrayed in an ordered
fashion and are closely packed together. It was proposed that the addition of
Na2B4O7 in the reaction increased the chemical potential of the chemicals for 1D
nanostructure growth.82
Besides, NH4OH is a common precipitant in the formation of boehmite as well. For

example, a neutralisation of aluminium nitrate solution with NH4OH was taken place
by Morgado et al.,83 in the investigation of the relationship between the synthesis
conditions and the peptisation ability of the resulting boehmite gel.
In the assistant of NH4OH, Shen et al.84 synthesized boehmite nanorods with

clear-cut edge via a steam-assisted solid wet-gel conversion process. Al(NO3)3 and
NH4OH were the precursors and hydrothermally treated at 200 ˚C for up to 48 hours.
After five hours calcination at 600 ˚C, -Al2O3 nanorods were obtained and the 1D
nanostructures of boehmite was well preserved. The influence of pH values during
precipitation to the morphology control of resulting was investigated, and it was
found that under pH 5.0 or 7.0, boehmite nanorods with lengths in the range of
100-400 nm and uniform diameters (20-30 nm) were gained, whereas irregular
boehmite particles were obtained under alkaline condition (pH=10.0). This process
was unique in the simplicity of preparation and the high efficiency of crystal growth,
which can be operated at a large scale. In addition to the high yield and high purity of
uniform 1D boehmite nanomaterials, this method proved superior because of the
negligible formation of other phase by-products.
As mentioned above, numerous synthesis methods have been developed for boehmite
nanomaterials, especially for 1D nanomaterials with various structures. Different
method could be used depending on the different purposes. Since the main task of
my project is to achieve doped boehmite nanomaterials, especially with 1D
nanostructures, the first step to produce undoped boehmite nanomaterials, simplicity
14
of the experimental operation and high efficiency of the crystal growth are important
for the further study of doping. Moreover, in this synthesis process, no organic
surfactants or additives need to be used and the main by-product NH4NO3 from the
reaction of precipitant NH4OH and nitrate slats can be easily removed by annealing,
which provides high purity of the product. Considering this, it is worthwhile to apply
Shen‟s method84 into my research to investigate the synthesis of doped boehmite.
Furthermore, in Shen‟s study,84 hydrothermal treatment was used. It is considered

that hydrothermal synthesis is an important way to yield inorganic materials with
large good-quality crystals at high vapor pressures from high-temperature aqueous
solutions. The crystal growth is performed in an apparatus consisting of a steel
pressure vessel called an autoclave. Synthesis under hydrothermal conditions offers
some significant advantages over other chemical synthesis techniques.85 First, it is
easy to control particle size and morphology by varying the synthesis conditions.
Secondly, many materials can be synthesised directly in the desired crystalline phase
at low temperature. Finally, a substance with an elemental oxidation state can be
produced and since the particles are produced in a sol form, the resultant sol can be
used directly in the production of green bodies using pressure filtration or
extrusion.85 Most of the formation reported of boehmite nanofibres was carried out
using the hydrothermal method.
After reviewing most of the boehmite synthesis approaches, we prefer Shen‟s84

steam-assisted solid wet-gel idea as the basic method for my project to facilitate
large-scale manufacturing of 1D boehmite nanomaterials, even 1D doped boehmite
nanomaterials.
3.3 Characterisation of nanomaterials
To study the obtained products, conventional characterisation techniques will be

applied, such as: Raman spectroscopy, X-ray diffraction (XRD), selected area
electron diffraction (SAED), X-ray photoelectron spectroscopy (XPS), scanning
electron microscopy (SEM), transmission electron microscopy (TEM), N2
adsorption/desorption and BET, thermal gravimetric analysis (TGA/dTA) – mass
spectrometer (MS), IR spectroscopy, UV-Vis, and photoluminescence studies, etc.
15
3.3.1 Phase, structure and morphology studies
X-ray diffraction (XRD) and Raman spectroscopy are basically used as the common
methods to determine the purity of the products.
Powder X-ray diffraction (XRD) is a most useful technique used to characterise the
crystallographic structure, crystallite size (grain size), and preferred orientation in
polycrystalline or powdered solid samples. X-ray methods of characterisation
represent a powerful approach to study of nanophase materials. By characterizing the
sample as a whole, they are an essential complement to other high-resolution
methods, which provide rather detailed information on only a few particles.
Moreover, based on XRD data, much information on crystals, such as lattice
parameters and crystal size etc., can be provided. For example, crystal sizes can be
calculated using the Scherrer Equation: D = Kλ/βcosθ, where D is the crystalline size
(nm), K presents as Scherrer, which has a value of 0.89, λ is the wavelength (nm), β
is the observed peak width, and θ is the diffraction angle. With these crystal
parameters, one can analysis the influence of dopants to boehmite crystal lattice.
Scanning electron microscopy (SEM) with energy-dispersive spectroscopy (EDS)

and transmission electron microscopy (TEM) with selected area electron diffraction
(SAED), as well as high-resolution transmission electron microscopy (HRTEM) are
important and direct ways to study not only morphology of the samples, but also
their composition and crystalline properties.
Scanning electron microscope (SEM) is a type of electron microscope that images

the sample surface by scanning it with a high-energy beam of electrons in a raster
scan pattern. The electrons interact with the atoms that make up the sample
producing signals that contain information about the sample's surface topography,
composition and other properties such as electrical conductivity. SEM has a large
depth of field, which allows more of a specimen to be in focus at one time than
optical microscopic methods. SEM also has much higher resolution, so closely
spaced specimens can be magnified at much higher levels than with an optical
microscope. Because SEM uses electromagnets rather than lenses, the researcher
has easily much more control in the degree of magnification. During the SEM
study, the EDS spectrum can be obtained and roughly reveal the presence of
aluminium, oxygen and dopant metals.
16
Transmission electron microscopy (TEM) is a microscopy technique whereby a

beam of electrons is transmitted through an ultra thin specimen, interacting with the
specimen as it passes through it. It is also possible to produce an image from
electrons deflected by a particular crystal plane. By either moving the aperture to the
position of the deflected electrons, or tilting the electron beam so that the deflected
electrons pass through the centred aperture, an image can be formed of only
deflected electrons, known as a Dark Field image. In the most powerful diffraction
contrast TEM instruments, crystal structure can also be investigated by High
Resolution Transmission Electron Microscopy (HRTEM), also known as phase
contrast imaging as the images are formed due to differences in phase of electron
waves scattered through a thin specimen. Images taken form TEM or HRTEM are in
much higher magnification than that from SEM, telling much more details of sample
morphology in nano scale. Furthermore, the SAED patterns detected by TEM or
HRTEM can indicate the crystal structure of resulting doped boehmite
nanomaterials, which patterns are match with the XRD patterns and can be compared
with the JCPDS powder diffraction files to defied materials. The SAED patterns tell
the sample is polycrystalline by appearing in rings or monocrystalline by showing
separated dots.
XPS analyses the binding energy of elements within a compound and can be used to
study their chemical environment. Through the binding energies bonding of the
atoms can be determined (i.e. Al-O, O-H, etc). Al3+, O2- and the metal dopant ions
are in different environments due to different symmetries and bonding environments
in their unit cells and are therefore expected to have different binding energies. With
the characterisation and comparison of the binding energies of the undoped and
doped nanomaterials, XPS can be used to evaluate the doping efficiency.
As mentioned above, boehmite and alumina are important porous materials, whose
pore prosperities are important for further applications in industry, such as catalysis
applications. Brunauer-Emmett-Teller (BET) method is the most widely used
procedure for the determination of specific surface area of porous solids. The
gradual changes in the texture of the doped boehmite nanofibres can also be reflected
in the nitrogen adsorption isotherms. The N2 adsorption isotherm curve presents the
relationship, at constant temperature, between the amount of gas adsorbed and the
17
pressure, or relative pressure, respectively.86 The data of the isotherm are used to
detect BET surface area and porosity of solids.
3.3.2 Vibrational spectroscopy
Raman spectroscopy is the measurement of the wavelength and intensity of

inelastically scattered light from molecules. The Raman scattered light occurs at
wavelengths that are shifted from the incident light by the energies of molecular
vibrations. Indeed, Raman spectroscopy has proven most useful for the study of
diagenetically related minerals as often occurs with oxyhydroxide and carbonate
87-90
minerals. Some previous studies have been undertaken using Raman
spectroscopy to study complex secondary minerals formed by crystallisation from
concentrated solutions. Limited spectroscopic studies of nanomaterials have been
forthcoming. The mechanism of Raman scattering is different from that of infrared
absorption, and Raman and IR spectra provide complementary information.
Vibrational information is very specific for the chemical bonds in molecules, Raman
spectroscopy therefore provides a fingerprint by which the molecule can be
identified. The fingerprint region of organic molecules is in the range 500-2000 cm-1.
Another way that the technique is used is to study changes in chemical bonding of
the boehmite nanomaterials after doping.
3.3.3 Thermal analysis techniques
As mentioned above, for a further application of metal oxides, metal hydroxides and
oxyhydroxides are required to be calcined through the thermal decomposition
process. For a better understanding of these nanomaterials, it is important to monitor
the dehydration and dehydroxylation process during heating by thermal analysis
techniques. Three instruments for the study on decomposition procedure were
employed: thermogravimetric analysis coupled to a mass spectrometer for gas
products analysis, Raman spectroscopy combined with a hot-stage and the infrared
emission spectroscopy.
The thermogravimetric analysis (TGA/dTG) is a method to determine changes in

mass with change in temperature. TGA is commonly employed in research of the
dehydration and decomposition point and then to determine the thermal stability for
samples.
18
In this study, the thermal stability of the synthetic nanomaterials can be easily
investigated by comparing their main decomposition temperatures and the
corresponding mass loss. The mass spectrometer (MS) is set up for gas analysis, and
only water vapour, nitric oxide, carbon dioxide, and oxygen were analysed. TG-MS
proves to be very useful to monitor the reasons for every mass loss step.
The combination of Raman spectroscopy with a hot-stage lends itself as the

technique of choice for studying the chemical reactions during dehydration and
dehydroxylation. The advantage of this technique is that the changes in molecular
structure can be followed in situ and at the elevated temperatures. Spectroscopic
studies with a hot-stage to reveal the thermal transition from metal hydroxides and
oxyhydroxides nanomaterials to metal oxides are limited.91-93 Hot-stage Raman
spectroscopy allows us to monitor the changes occurring in the molecular structure
during the thermal transition procedure. Spectra at elevated temperatures were
obtained using a Linkam thermal stage (Scientific Instruments Ltd., Waterford
Surrey, England). Spectra were taken from room temperature (25 ºC) at certain
temperature intervals up to a desired high temperature (limit to 600 ºC).
Infrared emission spectroscopy (IES) has proven to be a very useful tool that can be
applied in situ. IES measures discrete vibrational frequencies emitted by thermally
excited molecules.94 Frost and Kloprogge have developed extensive work on
minerals at the molecular level using infrared emission spectroscopy. 95-99 They
applied infrared emission spectroscopy in the studies on the dehydration,
dehydroxylation, decarbonization behavior and other changes of minerals, especially
clay minerals.100-103 However, limited work has been published on inorganic
nanomaterial using this in-situ thermal analysis technique. Interpretation of the
changes in the obtained infrared emission spectra with temperature increase can yield
information concerning the thermal reaction and thermal stability of materials.
Changes in the molecular structure, particularly in the hydroxyl groups and water, as
a function of temperature of the synthetic nanomaterials can be determined using
infrared emission spectroscopy. This will enable the further studies on applications
of the synthetic nanomaterials in industry.
19
4. DOPED NANOMATERIALS
4.1 Doping
Doping refers to the intentional introduction of impurities into a material, and is

applied in many semiconductor industry fields. Introducing impurities is fundamental
to controlling the properties of bulk semiconductors,104 and this has stimulated
similar efforts to dope semiconductor nanocrystals.4,8,23,105 Doping is critical for
semiconductors, which would otherwise be electrically insulating. For this reason,
much work has been done to explore how dopants can influence semiconductor
nanocrystals, crystallites a few nanometres in scale with unusual and size-specific
optical and electronic behaviour.23 With the development of modern industry, it is
exciting to find out that the promise of nanocrystals as a technological material, for
applications including solar cells,106 bioimaging,107 and wavelength-tunable lasers,108
may ultimately depend on tailoring their behaviour through doping.
Impurities can strongly modify electronic, optical and magnetic properties of bulk
semiconductors.104,108,109 For instance, it is reported109 that a substitutional impurity
with one more valence electron than the host atom it replaces can be ionized by
thermal energy and donate its extra electron to the semiconductor (n-type doping).
These electrons or holes are then available as carriers of electrical current. For
nanocrystals, where applications often require thin conducting films, the ability to
introduce these carriers is essential. Besides, dopants can also strongly influence
optical behaviour of materials. Take CdSe nanocrystals are an example, the lasing
threshold in these quantum dots can be reduced threefold by adding extra
electrons.110 As for the bio-imaging applications, fluorescent dopants may mitigate
toxicity problems by producing visible or infrared emission in nanocrystals made
from less-harmful elements than those currently used.111 Moreover, carriers whose
spins are aligned one way are conducted preferentially, while others are blocked, an
effect that could be used in future spintronic devices.109
4.2 Metal ions doped AlO(OH) (boehmite)
To a large extent, the key for fabrication of functional catalysts, ceramics and
nanostructures is manipulation of the surface and interfacial energies. As for
alumina, the transformation from -alumina (defect spinel structures) into the
20
-alumina (corundum structure) leads to a dramatic decrease in surface area.

Therefore, the major challenge for alumina in applications as catalyst supports and
ceramic precursors is to retain large surface areas during high-temperature annealing.
In order to manipulate phase transformation temperature and surface area of alumina,
Castro et al.112 investigated the relationship between dopants and surface energy and
thermodynamic stability of -alumina by using Zr and Mg as additives. Results
showed that dopants changed the pattern of phase transformation and densification.
Zr doped -alumina showed a higher energy of the hydroxylated surface than that of
pure -alumina but showed a lower energy of the anhydrous surface. Mg addition did
not significantly change surface energies but decreases the energetic instability of the
-alumina phase. Djuričić et al.113 also studied the morphology and thermal stability
of Zr doped alumina prepared by homogeneous precipitation from an aqueous salt
solution followed by calcination in air. Boehmite nanofibres and nanosheets with
irregular shape were formed after hydrothermal treatment. Results showed that
zirconia was insoluble in -Al2O3 so that phase transformation to -Al2O3 was
accompanied by a phase separation to form an alumina-zirconia nanocomposite. The
thermal stability of the transition phases was increased both by the dopant and by
hydrothermal treatment.
Besides the application in high-temperature catalytic industry, doped boehmite

nanomaterials have potential to exhibit novel properties compared with undoped
boehmite nanomaterials. In recent years, a great deal of research on rare-earth (RE)
and transition metal (TM) ions doped nanostructure materials has been focused to
find their potential applications in photonic applications.114 For transition metal (TM)
ions, the electronic d-d transitions involve electrons which are localised in atomic
orbitals of the ions. In this case, no size-dependent quantization effect (due to
confinement of delocalised electrons) is found in these transitions.114,115 However,
confinement effects may be induced by inter-ionic electronic interaction and
particularly, through electron-phonon interaction,116 which has crucial manifestations
in influencing the optical properties. Take chromium as an example. As mentioned
before,117 -Al2O3 containing chromium is basically naturally occurring ruby, the
crystal of which is known as ruby laser. And since nanoparticles have recently been
recognised to hold tremendous potential in the area of photonic applications,115 it is
expected that ruby nanomaterials will offer interesting possibilities for novel laser
21
applications using powdered media.118 As we know, boehmite is a vital precursor for

-Al2O3, therefore, chromium doped -Al2O3 nanomaterials can be expected to be
obtained by annealing chromium doped boehmite with nanostructures. It is
predicted that the luminescence properties of ruby nanocrystals will strongly depend
on the phase of the nanocrystals, the concentration of Cr3+ ions and the sintering
temperature.
As for magnetic properties, Xue et al.119 successfully synthesized iron doped Al2O3
nanocomposite by reducing the mixture of FeO(OH) and AlO(OH) dry gel at
different temperatures in a hydrogen atmosphere and then studied the magnetic
properties of Fe doped Al2O3 nanocomposite. The results showed that the magnetic
properties of the nanocomposite can be controlled by the concentration and size of
the dopant Fe nanoparticles.
To our knowledge, there have been several reports on doped alumina with dopants
such as chromium114,120-122 and iron,119 however most of these studies are about bulk
materials, less work has been done on doped boehmite nanocrystals. One of the main
aims of my project is to produce doped boehmite nanomaterials.. As mentioned
above, undoped alumina is a promising material in that it is stable at high
temperatures, an electrical insulator and chemically inert, which makes it suitable for
several technical applications, for example, diffusion barrier,32,33 or hard coating.34,35
The introduction of dopants, such as chromium and iron, would bring additional
interesting properties of the aluminas.
22
5. CONCLUSIONS
Nanomaterials science is a significant area of research and more efforts are needed to
produce novel and functional materials and devices. For a better application in
industry, it is important to develop controllable synthesis methods for nanomaterials
(building blocks) with desired morphologies, to functionalise the materials such as
by introducing a dopant, and to study and characterise the synthetic materials
comprehensively. Therefore, this study was aimed to produce the nanostructures
with desired properties, to establish controllable synthesis methods, to generate new
classes of good performance nanomaterials with or without introducing dopants, and
to investigate the detailed properties of the synthetic materials, including thermal
stability, porous and surface properties, etc.
23
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29
30
Chapter 3 Boehmite AlO(OH) nanofibres
CHAPTER 3
SYNTHESIS AND
CHARACTERISATION OF
BOEHMITE NANOFIBRES
This paper was originally published:
Yang, J.; Frost, R. L., "Synthesis and characterization of boehmite nanofibers."

Research Letters in Inorganic Chemistry 2008. DOI:10.1155/2008/602198.
31
SYNOPSIS
The aluminium oxyhydroxide is well known as boehmite, AlO(OH), which is a

crucial precursor for alumina. Boehmite nanomaterials have attracted great attention
in catalyst science, especially their one dimensional structures, such as, nanofibres,
nanotubes, nanorods, etc. In Chapter 3, hydrothermal synthesis of uniform
high-quality boehmite nanofibres was present. This synthesis route without use of
any surfactants or structure directing agents showed its advantages in manufacturing
1D boehmite nanofibres in large quantities environmental friendly, facilely and
economically. 500 nm long and 4-6 nm wide boehmite nanofibres were fabricated.
The synthesised boehmite nanofibres were characterised by X-ray diffraction (XRD),
scanning electron microscopy (SEM), infrared emission spectroscopy (IES) and
Raman spectroscopy.
32
STATEMENT OF CONTRIBUTION OF CO-AUTHORS
The authors listed below have certified* that:

1. they meet the criteria for authorship in that they have participated in the conception,
execution, or interpretation, of at least that part of the publication in their field of
expertise;
2. they take public responsibility for their part of the publication, except for the
responsible author who accepts overall responsibility for the publication;
3. there are no other authors of the publication according to these criteria;
4. potential conflicts of interest have been disclosed to (a) granting bodies, (b) the editor
or publisher of journals or other publications, and (c) the head of the responsible
academic unit, and
5. they agree to the use of the publication in the student’s thesis and its publication on
the Australasian Digital Thesis database consistent with any limitations set by
publisher requirements.
In the case of this chapter:
Synthesis and Characterisation of Boehmite Nanofibres
Yang, J.; Frost, R. L., Research Letters in Inorganic Chemistry 2008.

DOI:10.1155/2008/602198.
Contributor Statement of contribution*
Jing Yang Developed experimental design, conducted experiments and

data analysis, and wrote the manuscript.
Ray L. Frost * Overall supervisor of the project, aided in experimental design,

data analysis, manuscript writing and editing.
Principal Supervisor Confirmation

I have sighted email or other correspondence from all Co-authors confirming their certifying
authorship.
____________________ ________________________ ______________________

Name Signature Date
33
RESEARCH HIGHLIGHTS
The article reports a facile hydrothermal synthesis of boehmite nanofibres. The

reaction was carried out at low temperature (170 ºC) without any assistance of
surfactants templated or directing agents. The synthesised boehmite nanofibres were
uniform in size and shape with an average length of 500 nm and width of 4 – 6 nm.
In their Raman spectra, bands for hydroxyl stretching vibrations were found at 3216,
3077 and 2989 cm-1; hydroxyl deformation modes at 448 and 340 cm-1 ; and doubly
degenerate mode of AlO6 octahedron at 495 and 675 cm-1. The thermal stability of
the resultant boehmite nanomaterials were studied by infrared emission
spectroscopy, which confirms that their dehydroxylation starts at 250 ºC and is
completed by 450 ºC.
34
SYNTHESIS AND CHARACTERISATION OF

BOEHMITE NANOFIBRES
Jing Yang and Ray L. Frost*
Inorganic Materials Research Program, School of Physical and Chemical Sciences,

Queensland University of Technology, GPO Box 2434, Brisbane Queensland 4001,
Australia. E-mail: r.frost@qut.edu.au
Received: June 18, 2008

Accepted: August 5, 2008
ABSTRACT
Boehmite nanofibres of high quality were synthesised through a wet-gel conversion

process without the use of a surfactant. The long nanofibres of boehmite with
clear-cut edges were obtained by steaming the wet-gel precipitate at 170 ºC for 2
days under a pH 5. Hydrothermal treatment of the boehmite gels enabled
self-assembly through directed crystal growth. Detailed Characterisation using
X-ray diffraction (XRD), scanning electron microscopy (SEM), infrared emission
spectroscopy (IES) and Raman spectroscopy is presented.
KEYWORDS
Boehmite; Nanofibres; Hydrothermal Treatment; Nanomaterials
1. INTRODUCTION
The - and -Al2O3 polymorphs have found numerous applications in technical

ceramics, thin solid films, catalysis, and many others. In many cases, boehmite
-AlO(OH) is the starting material in the applications of alumina phases. As a typical
oxyhydroxy compound, boehmite is also extensively used as absorbents,[1, 2]
catalysts,[3] and optical materials.[4] Nanosized materials are well known for their
35
quantum size effects [5] and are expected to gain novel physical and chemical
properties, with many more potential applications in a wide range of areas. In recent
years, boehmite with nanoscale dimensions and morphological specificity has
attracted enormous interest from both fundamental and practical viewpoints.
Boehmite nanofibres were reported to be assembled with the assistance of

poly(ethylene oxide) (PEO) surfactant [6] and tubular γ-Al2O3 was fabricated via soft
solution route using N-cetyl-N,N,N-trimethylammonium bromide surfactant.[7] It
has been reported a solution-based chemical synthesis of boehmite nanofibres and
alumina nanorods by a modified sol-gel process in the presence of organic
solvents.[8] Shen et al. reported that a steam-assisted solid-phase conversion of
amorphous aluminium hydroxides wet gel to well crystallized 1D nanostructure of
boehmite nanorods without using surfactants and solvents.[9] The process is unique
in the simplicity of preparation and the high efficiency of crystal growth, which can
be operated on a large scale. In this work, long, large boehmite nano/microfibres
with high crystallinity and purity were synthesised based on Shen‟s methodology,[9]
and the characterisation of these the nano/microfibres are reported.
2. EXPERIMENTAL
2.1 Preparation procedures
15 g of Al(NO3)3•9H2O was dissolved in 25 mL ultrapure water, and 28% ammonia

was diluted into 10% solution. At room temperature 10% ammonia solution was
added dropwise into Al(NO3)3 solution at a constant rate of 5 mL/min while stirring
vigorously. Ammonia was ceased to be added when the pH value of the reaction
mixture reached pH 5, which was measured at room temperature. (Please note that at
high temperature the pH value of the reaction was probably slightly different.) The
reaction mixture was stirred constantly in air at room temperature for 1 hour. The
obtained white gel was filtrated to obtain the gel-cake, which was then transferred
into a glass beaker (25 mL). Before adding the gel-cake to a Teflon vessel (200 mL),
2 mL of ultrapure water was added. The Teflon vessel was sealed and heated at 170
ºC for 2 days. The resulting white material was washed with ultrapure water,
centrifuged and dried at 35 ºC for 2 days.
36
2.2 Characterisation
X-ray diffraction analyses were performed on a PANalytical X‟Pert PRO X-ray

diffractometer, with a Cu X-ray tube ( = 1.54 Å), operating at 40 kV and 40 mA.
The scanning electron microscopy (SEM) images were taken with a FEI Quanta 200
operating at 25 kV. The specimens were mounted on SEM mounts with carbon tape
and sputter-coated with a thin layer of gold. The infrared emission spectroscopy
(IES) was carried out on a Nicolet Nexus 870 FTIR spectrometer. The emission
spectra were collected at an interval of 50 ºC, over the range 100 ºC – 850 ºC.
Further details have been published.[10-13] Raman spectra were obtained using a
Renishaw 1000 Raman microscope system, which also includes a monochromator, a
filter system and a Charge Coupled Device (CCD). 64 Raman spectra were
collected using 5 mW of power at the sample. Further details of the Raman
technique have been published [14-19].
3. RESULTS AND DISCUSSION
3.1 X-ray diffraction
X-ray diffraction is normally used to determine the phase and phase purity of the
synthesised boehmite. Fig. 1 displays well-defined XRD patterns observed and all
diffraction peaks were perfectly indexed to the XRD pattern of pure boehmite
(JCPDS card 01-083-2384). No XRD peaks representing other crystalline phases
were detected, indicating that the nanofibres of the synthetic boehmite exhibited
excellent crystallinity and a high purity.
3.2 Scanning electron microscope
Whilst TEM images are normally used to show the morphology of the boehmite
nanomaterials, if the nanofibres are large enough in length then scanning electron
microscopy (SEM) can be used to prove the nature of the nano/micro-material.
Fig. 2 presents the SEM images of the synthetic boehmite nanofibres. It is clearly
seen the long nanofibres in bundles. Zhu [20] et al. reported that through a
soft-templated process with PEO surfactant micelles at 100 ºC, the nanofibres could
be assembled, the maximum length of which was 100 nm.
37
In this study, the nanofibres were synthesised in the absence of surfactant, and in a
supersaturated hydrothermal condition, which was reported by Shen et al. [9]. This
steam-assisted self-assembly fabrication of boehmite yielded high-quality 1D
nanostructures with clear-cut edges and high purity. The structure was confirmed by
the XRD patterns.
Fig. 1 XRD pattern of the synthetic boehmite nanofibres, after hydrothermal

treatment at 170 ºC for 2 days under pH 5.
Fig. 2 SEM image of the synthetic boehmite nanofibres, after hydrothermal treatment
at 170 ºC for 2 days under pH 5.
38
3.3 Infrared emission spectroscopy

Infrared emission spectroscopy (IES) is known as a measurement of discrete
vibrational frequencies emitted by thermally excited molecules. The major
advantages of IES are that the samples are measured in situ at the elevated
temperature and IES requires no sample treatment other than making the sample of
submicron particle size.
Fig. 3 clearly shows such a suite of the dehydroxylation of the synthetic boehmite
nanofibres. The dehydroxylation is followed by the decrease of intensity of the
hydroxyl deformation modes and the loss of intensity of the hydroxyl stretching
frequencies. The hydroxyl deformation frequencies are observed at 840 cm-1 and 757
cm-1. The spectral changes in these low- frequency bands show that dehydroxylation
commenced at 250 ºC. The three bands displayed at 3671 cm-1, 3360 cm-1, 3140 cm-1
are recognized in the hydroxyl stretching region. Above 450 °C the hydroxyl
stretching bands are no longer observed. These spectral changes confirm that
dehydroxylation starts at 250 ºC and is completed by 450 ºC.
Each of the hydroxyl stretching bands shows an increase in bandwidth with
temperature increase, and this indicates that the molecular structure of the boehmite
nanofibres was becoming more disordered during the dehydroxylation process.
39
Fig. 3 IES spectra of the synthetic boehmite nanofibres, collected at an interval of

50 ºC, over the range 100 ºC – 850 ºC.
40
3.4 Raman spectroscopy
Many minerals both natural and synthetic lend themselves to analysis by Raman
spectroscopy. The great advantage of Raman spectroscopy is that just so long as the
materials are 1 micron in size or larger than individual nanofibres can be analysed as
is the case for the boehmite fibres shown above.
(a) (b)
Fig. 4 Raman spectra of the synthetic boehmite nanofibres, after hydrothermal

treatment at 170 ºC for 2 days under pH 5.
Fig. 4 depicts the Raman spectra of the synthetic boehmite nanofibres. The bands at
3216, 3077 and 2989 cm-1 are in the region of the hydroxyl stretching vibrations.
Frost et al. [21] characterised hydroxyl stretching bands in the Raman spectrum of
boehmite and reported bands at 3413, 3283, 3096 and 2997 cm-1. The
low-wavenumber region (1100-200 cm-1) of boehmite consists of hydroxyl
deformation modes (1050-900 cm-1) and hydroxyl translation modes (800-400 cm-1).
The doubly degenerate mode of the AlO6 octahedron caused the observation of the
bands at 495 and 675 cm-1. [22] The band at 362 cm-1 was attributed to the
vibration of fully symmetric Ag mode, in which all aluminium and oxygen atoms
move parallel to the b-axis. [23] The weak bands at 732, 448 and 340 cm-1 were
attributed to OH- deformation modes. [24]
41
4. CONCLUSIONS
In this research, long boehmite nanofibres with high crystallinity and purity were
formed under steam-assisted hydrothermal treatment at 170 ºC for 48 hours with pH
5. The structure and morphology of the nanofibres were detected by XRD and SEM,
while the IES spectra illustrated their thermal properties. Raman spectroscopy was
applied to characterize the 1D-nanostructured boehmite.
ACKNOWLEDGMENTS
The financial and infrastructure support of the Queensland University of Technology

Inorganic Materials Research Program of the School of Physical and Chemical
Sciences is gratefully acknowledged.
42
REFERENCES
[1] V.S. Burkat, V.S. Dudorova, V.S. Smola, T.S. Chagina, Light Metals (1985)
1443-1448.
[2] C. Nedez, J.-P. Boitiaux, C.J. Cameron, B. Didillon, Langmuir 12 (1996)

3927-3931.
[3] J.-L. Le Loarer, H. Nussbaum, D. Bortzmeyer, Alumina extrudates, methods

for preparing and use as catalysts or catalyst supports. (Rhodia Chimie,
Fr.). Application: WO, 1998, p. 44.
[4] D. Mishra, S. Anand, R.K. Panda, R.P. Das, Materials Letters 42 (2000)
38-45.
[5] G.D. Stucky, J.E. Mac Dougall, Science 247 (1990) 669-678.
[6] H.Y. Zhu, X.P. Gao, D.Y. Song, Y.Q. Bai, S.P. Ringer, Z. Gao, Y.X. Xi, W.
Martens, J.D. Riches, R.L. Frost, Journal of Physical Chemistry B 108
(2004) 4245-4247.
[7] D. Kuang, Y. Fang, H. Liu, C. Frommen, D. Fenske, Journal of Materials

Chemistry 13 (2003) 660-662.
[8] S.C. Kuiry, E. Megen, S.D. Patil, S.A. Deshpande, S. Seal, Journal of
Physical Chemistry B 109 (2005) 3868-3872.
[9] S.C. Shen, Q. Chen, P.S. Chow, G.H. Tan, X.T. Zeng, Z. Wang, R.B.H. Tan,
Journal of Physical Chemistry C 111 (2007) 700-707.
[10] R.L. Frost, G.A. Cash, J.T. Kloprogge, Vibrational Spectroscopy 16 (1998)
173-184.
[11] R.L. Frost, B.M. Collins, K. Finnie, A.J. Vassallo, Clays Controlling the
Environment, Proceedings of the International Clay Conference, 10th,
Adelaide, July 18-23, 1993 (1995) 219-224.
[12] R.L. Frost, J.T. Kloprogge, Spectrochimica Acta, Part A: Molecular and
Biomolecular Spectroscopy 55A (1999) 2195-2205.
[13] R.L. Frost, J.T. Kloprogge, Tijdschrift voor Klei, Glas en Keramiek 19
(1998) 11-15.
43
[14] R.L. Frost, J. Cejka, Journal of Raman Spectroscopy 38 (2007) 1488-1493.
[15] R.L. Frost, J. Cejka, G.A. Ayoko, M.L. Weier, Journal of Raman
Spectroscopy 38 (2007) 1311-1319.
[16] R.L. Frost, J.M. Bouzaid, Journal of Raman Spectroscopy 38 (2007)

873-879.
[17] R.L. Frost, M.L. Weier, P.A. Williams, P. Leverett, J.T. Kloprogge, Journal
of Raman Spectroscopy 38 (2007) 574-583.
[18] R.L. Frost, J.M. Bouzaid, W.N. Martens, B.J. Reddy, Journal of Raman
Spectroscopy 38 (2007) 135-141.
[19] R.L. Frost, S.J. Palmer, J.M. Bouzaid, B.J. Reddy, Journal of Raman
Spectroscopy 38 (2007) 68-77.
[20] H.Y. Zhu, J.D. Riches, J.C. Barry, Chemistry of Materials 14 (2002)
2086-2093.
[21] R.L. Frost, J.T. Kloprogge, S.C. Russell, J. Szetu, Applied Spectroscopy 53
(1999) 572-582.
[22] A.B. Kiss, G. Keresztury, L. Farkas, Spectrochimica Acta, Part A:

Molecular and Biomolecular Spectroscopy 36A (1980) 653-658.
[23] C.J. Doss, R. Zallen, Physical Review B: Condensed Matter and Materials
Physics 48 (1993) 15626-15637.
[24] T. Assih, A. Ayral, M. Abenoza, J. Phalippou, Journal of Materials Science

23 (1988) 3326-3331.
44
Chapter 4 Synthesis and characterisation of In(OH)3 nanocubes
CHAPTER 4
SYNTHESIS AND
CHARACTERISATION OF
INDIUM HYDROXIDE In(OH)3
NANOCUBES
45
SYNOPSIS
Since high-quality one dimensional AlO(OH) nanofibres can be successfully

achieved through hydrothermal treatment (see Chapter 3), it is of great interest to see
if this hydrothermal synthesis route works on indium, which is also an important
metal element in Group IIIA. However, in this chapter, it is found that instead of
indium oxyhydroxide InO(OH), In(OH)3 was achieved. The synthetic In(OH)3
nanocubes were 350 nm in size. A topotactical relationship was observed between
In(OH)3 and its thermal product In2O3.
Hot-stage Raman and infrared emission spectroscopy prove to be useful tools to

study the thermal decomposition behaviour of nanomaterials in situ. Two published
articles compose this chapter, one (Chapter 4.1) is on hot-stage Raman study and the
other (Chapter 4.2) is on the infrared emission spectroscopy of the synthetic indium
hydroxide nanocubes. It is investigated that changes happened in the molecular
structure as a function of temperature of the indium hydroxide to indium oxide
nanocubes. Interpretation of the changes in the obtained spectra with temperature
increase can yield important information concerning the thermal reaction and thermal
stability of materials.
46
CHAPTER 4.1
THERMOGRAVIMETRIC
ANALYSIS AND HOT-STAGE
RAMAN SPECTROSCOPY OF
CUBIC INDIUM HYDROXIDE
Yang, J.; Frost, R. L.; Martens, W. N., "Thermogravimetric analysis and hot-stage
Raman spectroscopy of cubic indium hydroxide." Journal of Thermal Analysis and
Calorimetry 2010, 100 (1), 109-116.
47

expertise;
academic unit, and
Thermogravimetric Analysis and hot-stage Raman Spectroscopy of Cubic Indium

Hydroxide
Yang, J.; Frost, R. L.and Martens, W. N., Journal of Thermal Analysis and Calorimetry 2010,
100 (1), 109-116.

*
Ray L. Frost Overall supervisor of the project, aided in experimental design,
Wayde N. Martens Aided in experimental design, data analysis, manuscript writing
and editing.

authorship.
____________________ _______________________ ______________________

Name Signature Date
48
RESEARCH HIGHLIGHTS
The article reports that 400 nm In(OH)3 nanocubes were obtained after a 2 days
hydrothermal treatment at 180 ºC. Thermo-gravimetric analysis revealed that the
dehydroxylation of the synthesised In(OH)3 nanocubes happed at 219 ºC, which was
also confirmed by the hot-stage Raman spectroscopic study. The cubic morphology
was retained even after a thermal treatment at 500 ºC for 4 h, which was known as a
topotactical relationship between and In(OH)3 its thermal product In2O3.
49
THERMOGRAVIMETRIC ANALYSIS AND

HOT-STAGE RAMAN SPECTROSCOPY OF
CUBIC INDIUM HYDROXIDE
Jing Yang, Ray L. Frost* and Wayde N. Martens

Received: March 24, 2009

Accepted: October 09, 2009
Published Online: November 01, 2009
ABSTRACT
The transition of cubic indium hydroxide to cubic indium oxide has been studied by
thermogravimetric analysis complimented with hot-stage Raman spectroscopy.
Thermo gravimetric analyses showed the transition of In(OH)3 to In2O3 occurred
mainly at 219 °C. The structure and morphology of In(OH)3 synthesised using a soft
chemical route at low temperatures was confirmed by X-ray diffraction and scanning
electron microscopy. A topotactical relationship existed between the nanocubes of
In(OH)3 and In2O3. The Raman spectrum of In(OH)3 was characterised by an intense
sharp band at 309 cm-1 attributed to ν1(In-O) symmetric stretching mode, bands at 1137
and 1155 cm-1 attributed to δ(In-OH) deformation modes, and bands at 3083, 3215, 3123
and 3262 cm-1 assigned to the OH stretching vibrations. Upon thermal treatment of
In(OH)3 new Raman bands were observed at 125, 295, 488 and 615 cm-1 attributed to
In2O3. Changes in the structure of In(OH)3 with thermal treatment were readily
followed by hot-stage Raman spectroscopy.
KEYWORDS
Thermo-gravimetric Analysis; Hot-Stage Raman Spectroscopy; Indium Hydroxide;
Indium Oxide
50
1. INTRODUCTION
Indium hydroxides and oxides are a series of important semiconductor materials,

which have attracted much attention in the past decade. In(OH)3 is a wide-gap
semiconductor with Eg = 5.15 eV, [1] which has potential applications in
photocatalytic, electronic, and solar energy fields. [2-4] While In2O3 is known as
n-type semiconductor with a direct band gap of 3.6 eV (which is close to that of GaN
[5] ) and an indirect band gap of 2.6 eV. [6] In2O3 has been used widely as solar
cells, transparent conductors and sensors. [7-11]
In recent years, In(OH)3 and In2O3 with various morphologies (e.g. nanowires, [12]
nanobelts, [13] nanorods, [14] nanotubes [15] and nanospheres, [16] etc.) have been
synthesised via different methods, such as chemical vapour deposition,
hot-injection techniques, organic solution synthetic routes, hydrothermal methods,
and solvothermal and others. It is known that cubic particles expose a specific
surface, which provides an ideal model for the study of surface related properties,
[17] and connecting these cubic particles into microscale devices may provide future
applications. In particular, the production of indium hydroxide and indium oxide
microcubes has been realized up to now. There are several reports on synthesis of
indium hydroxide microcubes via hydrothermal routes. [6, 17] However the
characterisation on indium hydroxide and oxide microcubes is not fully recorded yet,
or appreciated, especially the thermo gravimetric analyses and spectroscopic studies.
The underlying objective of this research is to synthesise an adequate indium oxide

semiconductor [18-20]. The properties of these semiconductors depend very
heavily on the synthesis method and preparation of the indium oxide [1, 21].
Therefore the aim of this research is to demonstrate the use of thermo gravimetric
analyses and hot-stage Raman spectroscopy to assess the thermal stability of indium
hydroxide, and to determine the changes in the molecular structure of the material as
the indium hydroxide is thermally treated. Such research compliments the thermo
gravimetric analyses and differential thermogravimetric analysis of materials
[22-36]. It is reported that many factors, such as disorder, size and shape
distribution, can all influence the thermal analytical properties and vibrational
properties. Moreover, the vibrational properties of semiconductors are also strongly
affected by temperature.
51
An increase in temperature introduces perturbations in the harmonic potential term,

which changes the vibrational properties. There are only limited thermal Raman
spectroscopic studies of synthetic nanomaterials or micromaterials have been
forthcoming, for example GaO(OH) nanorods. [37] In the present work, we report
the thermo gravimetric analyses and hot-stage Raman spectroscopy of cubic indium
hydroxide, and study the transition of cubic In(OH)3 to cubic In2O3, relating the
spectra to the structure and morphology of the synthesised materials.
2. EXPERIMENTAL
2.1 Synthesis of In(OH)3 cubic materials
Analytical grade In(NO3)3•5H2O and ammonia solution (wt 28%) were used as
precursor to prepare the indium hydrate precipitate. 3 g of In(NO3)3•5H2O was
dissolved in 15 mL ultrapure water, and 28% ammonia was diluted into 10%
solution. At room temperature, 10% ammonia solution was added dropwise into the
indium ions solution while stirring vigorously. Stop adding ammonia when the pH
value of the reaction mixture reached 8, and then kept the mixture stirring in the air
at room temperature for 0.5 hour.
The obtained mixture was filtrated, and then transferred into a Teflon vessel (125
mL) together with 2 mL ultrapure water. Sealed the Teflon vessels and heated it at
180 ºC for 2 days. The resulting material was washed with ultrapure water by
centrifuging, and dried at 35 ºC for 3 days. Finally, the obtained In(OH)3 sample was
calcined in a furnace at 500 ºC for 4 h to form In2O3 product.
X-ray diffraction (XRD) analyses were performed on a PANalytical X‟Pert PRO

X-ray diffractometer (radius: 240.0 mm). Incident X-ray radiation was produced
from a line focused PW3373/10 Cu X-ray tube, operating at 40 kV and 40 mA,
wavelength of 1.540596 Å.
52
2.3 Scanning electron microscopy
and sputter-coated with a thin layer of gold.
2.4 Raman microprobe spectroscopy
The crystals of In(OH)3 were placed and oriented on the stage of an Olympus BHSM
microscope, equipped with 10x and 50x objectives and part of a Renishaw 1000
Raman microscope system, which also includes a monochromator, a filter system
and a Charge Coupled Device (CCD). Raman spectra were excited by a 633 nm laser
at a resolution of 2 cm-1 in the range between 100 and 4000 cm-1. Repeated
acquisition using the highest magnification was accumulated to improve the
signal-to-noise ratio. Spectra were calibrated using the 520.5 cm-1 line of a silicon
wafer. Details of the technique have been published by the authors. Spectra at
elevated temperatures were obtained using a Linkam thermal stage (Scientific
Instruments Ltd., Waterford Surrey, England). Spectra were taken from room
temperature (25 ºC) at 50 ºC intervals up to a temperature of 550 ºC in order replicate
the acquisition of data in the TGA-MS plots. Spectral Manipulation such as
baseline adjustment, smoothing and normalisation was performed using GRAMS®
software package (Galactic Industries Corporation Salem, NH, USA).
Band component analysis was undertaken using the Jandel „Peakfit‟ software
package, which enabled the type of fitting function to be selected and allows specific
parameters to be fixed or varied accordingly. Band fitting was done using a
Lorentz-Gauss cross-product function with the minimum number of component
bands used for the fitting process. The Lorentz-Gauss ratio was maintained at values
greater than 0.7 and fitting was undertaken until reproducible results were obtained
with squared correlations of r2 greater than 0.996.
2.5 Thermal analysis
Thermal decomposition of the indium hydroxide sample was carried out in a TA®
Instruments incorporated high-resolution thermo gravimetric analyser (series Q500)
in a flowing nitrogen atmosphere (60 cm3 min–1).
53
Approximately 35 mg of sample underwent thermo gravimetric analyses, with a

heating rate of 5 °C/min, with resolution of 6 from 25 to 1000°C. With the
isothermal, isobaric heating program of the instrument the furnace temperature was
regulated precisely to provide a uniform rate of decomposition in the main
decomposition stage.
In order to confirm the results obtained from the hot-stage Raman spectroscopy,
thermo gravimetric analysis was undertaken. Fig. 1 shows typical the TG-dTG
curve of the synthesised indium hydroxide In(OH)3. A large mass loss is observed at
219 ºC. The total mass loss of 15.76% is in good agreement with the value of 16.28%
calculated by assuming the following thermal decomposition:
2In(OH)3→In2O3+3H2O. A small mass loss at 197 °C of 0.35% is observed. This
mass loss step is attributed to the thermal decomposition of InO(OH), some of which
is formed during the synthesis of the In(OH)3. The reaction is 2InO(OH)
→In2O3+H2O. The results of the gravimetric analyses are in harmony with the
results inferred from hot-stage Raman spectroscopic results (see below). Both
techniques show the transition occurs between 200 and 225 °C.
Fig. 1 Thermo gravimetric analyses of synthetic In(OH)3 nanocubes.
54
X-ray diffraction (XRD) was used to determine the phase structure of the
as-synthesised In(OH)3 and its thermally manufactured products (In2O3). Fig. 2
shows the typical XRD patterns of the synthetic In(OH)3 and In2O3 and all the
diffraction peaks of these XRD patterns could be perfectly indexed to those of
body-centred cubic In(OH)3 with a lattice constant a = 7.9743 Å (JCPDS Card No.
01-076-1463) and In2O3 (JCPDS Card No. 01-071-2195). The miller indices are used
to label the diffraction peaks. No XRD peaks representing other crystalline phases
were detected, indicating that the final product exhibited excellent crystallinity and
high purity. Fig. 2 also shows the calcined product of In(OH)3 is purely In2O3. No
other materials were found. Thermal treatment of In(OH)3 results in the formation of
In2O3.
Fig. 2 XRD patterns of synthetic In(OH)3 (a) and its thermally treated products
In2O3 (b). The peaks are labeled with their Miller indices.
55
Scanning electron microscopy (SEM) is a well-known microscopy technique heavily

used in material sciences for the study of the morphology of materials. Fig. 3a and 3b
compare the morphology of the In(OH)3 and its thermally treated product In2O3 after
treatment at 500 ºC for 4 h. Fig. 3a clearly shows the cubic nature of the In(OH)3.
The cubes are between 300 and 400 nm. Fig. 3b displays the morphology of the
thermally treated In(OH)3. It is noted that the cubic morphology is retained in the
In2O3. It is apparent there is a topotactical relationship between the In(OH)3 and the
In2O3 microcubes. Some shrinkage of the micro-nanocubes is observed upon thermal
treatment.
(a) (b)
Fig. 3 (a) Image of In(OH)3 synthesised at 180 °C and (b) image of In2O3, product of
as-synthetic In(OH)3 calcined at 500 ºC for 4 h.
3.4 Raman spectroscopy
Many minerals both natural and synthetic lend themselves to analysis by Raman
spectroscopy. The great advantage of Raman spectroscopy is that just so long as the
materials are 1 micron in size or larger than individual cubes can be analysed as is
the case for In(OH)3 as shown above. In order to study the changes in the spectra of
In(OH)3 as the nanomaterial is thermally treated it is necessary to describe the
spectra collected at room temperature.
56
Fig. 4 Raman spectrum of In(OH)3 in the 100 – 700 cm-1 region.
Fig. 4 depicts the Raman spectra of cubic In(OH)3 in the 100 to 700 cm-1 region. The
spectrum is dominated by an intense band at 309 cm-1. This band is attributed to the
ν1 In-O symmetric stretching vibration. Two additional bands are found at 356 and
391 cm-1. These bands are attributed to the ν3 In-O antisymmetric stretching
vibrations. Low intensity bands are observed at 142, 186, 208 and 227 cm-1. The
three bands at 186, 208 and 227 cm-1 are assigned to the O-In-O bending modes.
Two low intensity Raman bands are found at 660 and 670 cm-1.
57
Fig. 5 shows the Raman spectrum of cubic In(OH)3 in the 950 to 1200 cm-1 region.
The spectrum is composed of a broad band centred upon 1044 cm-1 together with two
overlapping bands at 1137 and 1155 cm-1. These bands are assigned to In-OH δ
deformation modes. The Raman spectrum in the hydroxyl stretching region is shown
in Fig. 6. A complex set of overlapping bands are observed which may be
decomposed into selected component bands at 3083, 3215, 3123 and 3262 cm-1.
These bands are attributed to the OH stretching vibrations.
58
The other bands fitted in Fig. 6 were understood to be the combinations or overtones
of bands at lower wavenumbers.
3.5 Hot-stage Raman spectroscopy
Hot-stage Raman spectra of the transition of In(OH)3 to In2O3 in the 100 to 800 cm-1
region over the temperature range ambient to 400 °C are displayed in Fig. 7. The
Raman spectrum at 25 °C shows the typical Raman bands of In(OH)3 at 137, 204,
307, 356, 390 and 659 cm-1. Raman can be used as a semi-quantitative technique and
the decrease of Raman peak intensity reveals the loss of the corresponding sample. As
the temperature increases, the intensity of these bands decreases obviously,
indicating that the amount of In(OH)3 reduces.
59
After 200 ºC, the Raman spectrum of In(OH)3 were replaced by a totally different
spectrum, indicating the completion of dehydroxylation of In(OH)3. No Raman bands
or bands of very low intensity are observed in the spectra collected at 300 to 350 °C.
It is proposed the thermally decomposed indium hydroxide goes through a
recrystallisation stage over this temperature range. At temperatures of 400 °C and
above new Raman peaks are observed at 125, 295, 488 and 615 cm-1. These bands
are attributed to the new phase formed by the thermally decomposed In(OH)3 that is
In2O3.
Fig. 7 Hot-stage Raman spectra of In(OH)3 in the 100 – 800 cm-1 region.
The base-lined and curve-resolved Raman spectra at 150 and 400 °C are reported in
Fig. 8, which displays the phase changes over temperature increase. In the spectrum
of 150 °C, typical Raman bands of In(OH)3 were found at 306, 318, 353, 387 and
652 cm-1.
60
A huge massif can be observed between 100 and 200 cm-1 and was fitted using 9
band components, which were assigned to be the metal-oxygen vibrations.
According to group theory the bands are assigned as follows 615 cm-1 (E2g), 488 cm-1
(A1g), 295 cm-1 (E1g).
According to Wang et al., Raman bands at 630, 497, 366 and 307 cm-1 belong to the
vibrational modes of the bcc-In2O3. The position of the bands differs from those
reported in this research. Liu et al. [38] studied the effect of pressure on the Raman
spectra of In2O3 in the 100 to 700 cm-1 region up to a pressure of 26 GPa.
Fig. 8 Hot-stage Raman spectra of In(OH)3 in the 2400 – 3900 cm-1 region.
The Raman spectra in the OH stretching region are shown in Fig. 9a. Clearly the
intensity of the bands in the OH stretching region at 2844, 3079 and 3240 cm-1
diminish in intensity. No intensity remains in these bands at 300 °C. At 400 °C, a
very weak band is observed at 3637 cm-1.
61
The band may be due to the OH stretching vibration of OH units from the
intermediate compound InO(OH). No intensity remains in this band at 550 °C.
Evidence for these changes is also observed in Fig. 9b, in which the Raman spectra
of the 800 to 1800 cm-1 region are displayed.
Raman bands are observed at 1037and 1135 cm-1 with other low intensity bands
observed at 1288, 1453 and 1593 cm-1. The intensity of these bands approaches
zero at 200 °C. Intensity is observed only in the band at 1120 cm-1. New Raman
-1
bands appear in the 300 and 350 °C spectrum at 1333 and 1569 cm . It is thought
that these bands are associated with InO(OH).
(a) (b)
Fig. 9 Hot-stage Raman spectra of In(OH)3 in (a) 3900 – 2400 cm-1 region and (b)
1800 – 800 cm-1 region.
62
4. CONCLUSIONS
Micro and nanocubes of In(OH)3 were synthesised by using soft chemical techniques
without surfactants at low temperatures. The conversion of In(OH)3 to In2O3 cubes
was achieved by thermal treatment. The phase composition was proven by X-ray
diffraction and SEM showed there was a topotactical relationship between the micro
and nanocubes of In(OH)3 and micro and nanocubes of In2O3. The transition of
In(OH)3 to In2O3 was studied by hot-stage Raman spectroscopy and thermo
gravimetric analysis.
The In(OH)3 nanocubes are characterised by Raman spectroscopy. An Intense

Raman band at 309 cm-1 is assigned to the ν1 symmetric stretching mode of In(OH)3.
The intensity of this band decreases as the temperature increases to 300 °C after
temperature which no intensity remains. A new band at 295 cm-1 is observed above
this temperature and is attributed to the ν1 symmetric stretching mode of In2O3. The
intensity of the two Raman bands at 3079 and 3240 cm-1 attributed to the OH
stretching bands of In(OH)3 decrease in intensity until at temperatures above 200 °C
no intensity remains. At the same time the intensity of the Raman band at 1135 cm-1
assigned to the δ(In-OH) deformation modes decrease in intensity such that at 250 °C
no intensity remains. Raman spectroscopy shows that the transition of In(OH)3 to
In2O3 occurs in the 200 to 225 °C temperature range. Such a transition temperature
was confirmed by thermo gravimetric analyses.
ACKNOWLEDGMENTS
The financial and infra-structure support of the Queensland University of

Technology Inorganic Materials Research Program is gratefully acknowledged. The
Australian Research Council (ARC) is thanked for funding the instrumentation.
One of the authors (JY) is grateful to the Queensland University of Technology
Inorganic Materials Research Program for the award of an international doctoral
scholarship.
63
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Hara, K. Domen, C. Li, J. Catal. 237 (2006) 322-329.
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(2003) 143-148.
[13] Z.W. Pan, Z.R. Dai, Z.L. Wang, Science 291 (2001) 1947-1949.
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4632-4634.
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[16] B.X. Li, Y. Xie, M. Jing, G.X. Rong, Y.C. Tang, G.Z. Zhang, Langmuir 22
(2006) 9380-9385.
[17] X.H. Liu, L.B. Zhou, R. Yi, N. Zhang, R.R. Shi, G.H. Gao, G.Z. Qiu, J.
Phys. Chem. C 112 (2008) 18426-18430.
[18] H.-X. Dong, H.-Q. Yang, W.-Y. Yin, W.-Y. Yang, L.-F. Wang, Huaxue
Xuebao 65 (2007) 2611-2617.
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66
CHAPTER 4.2
APPLICATION OF INFRARED
EMISSION SPECTROSCOPY TO
THE THERMAL TRANSITION OF
INDIUM HYDROXIDE TO
INDIUM OXIDE NANOCUBES
Yang, J.; Cheng, H.F.; Martens, W.N.; Frost, R.L. "Application of infrared emission
spectroscopy to the thermal transition of indium hydroxide to indium oxide
nanocubes" Applied Spectroscopy 2011, 65 (1). In press.
67

expertise;
academic unit, and
Application of infrared emission spectroscopy to the thermal transition of indium

hydroxide to indium oxide nanocubes
Yang, J.; Cheng, H.F.; Martens, W.N.; Frost, R.L. Applied Spectroscopy 2011, 65 (1). In
press.

Jing (Jeanne) Yang Developed experimental design, conducted experiments and
Hongfei Cheng Aided in data presentation and manuscript revising.

and editing.

authorship.
____________________ _______________________ ____________________

Name Signature Date
68
RESEARCH HIGHLIGHTS
The article reports the application of infrared emission spectroscopy (IES) in the
study on phase change of In(OH)3 nanocubes during a thermal treatment from room
temperature to 600 ºC. A typical infrared spectrum at room temperature of In(OH)3
nanocubes was characterised by an intense OH deformation band at 1150 cm-1 and
two OH stretching bands at 3107 and 3221 cm-1. These bands diminished
dramatically upon heating and no intensity remained after 200 ºC, which indicated
the completion of dehydroxylation. IES also detected that new InOH bonds formed
during calcination of nanomaterials because of the release and transfer of protons. In
this study, IES spectra were well related to the structure of the materials and this
technique has proven to be a very useful tool to investigate changes in the material
structure upon thermal treatment.
69
APPLICATION OF INFRARED EMISSION

SPECTROSCOPY TO THE THERMAL
TRANSITION OF INDIUM HYDROXIDE TO
INDIUM OXIDE NANOCUBES
Jing (Jeanne) Yang, Hongfei Cheng, Wayde N. Martens and Ray L.

Frost*
Chemistry Discipline, Faculty of Science and Technology, Queensland University of

Technology, GPO Box 2434, Brisbane Queensland 4001, Australia. E-mail:
r.frost@qut.edu.au
Received: July 29, 2010

Accepted: September 27, 2010
ABSTRACT
Cubic indium hydroxide nanomaterials were obtained by a low-temperature

soft-chemical method without any surfactants. The transition of nano-cubic indium
hydroxide to cubic indium oxide during dehydroxylation has been studied by infrared
emission spectroscopy. The spectra are related to the structure of the materials and
the changes in the structure upon thermal treatment. The infrared absorption
spectrum of In(OH)3 is characterised by an intense OH deformation band at 1150
cm-1 and two O–H stretching bands at 3107 and 3221 cm-1. In the infrared emission
spectra, the hydroxyl-stretching and hydroxyl-bending bands diminish dramatically
upon heating, and no intensity remains after 200 ºC. However, new low intensity
bands are found in the OH deformation region at 915 cm-1 and in the OH stretching
region at 3437 cm-1. These bands are attributed to the vibrations of newly formed
InOH bonds because of the release and transfer of protons during calcination of the
nanomaterial. The use of infrared emission spectroscopy enables the low-temperature
phase transition brought about through dehydration of In(OH)3 nanocubes to be
studied.
70
KEYWORDS
Infrared Absorption Spectroscopy; Infrared Emission Spectroscopy; Nanomaterials;

Indium Hydroxide; Indium Oxide
1. INTRODUCTION
Special attention has been focused on indium hydroxides and oxides as a series of
important semiconductor materials. As a wide-gap semiconductor (Eg = 5.15 eV),1
In(OH)3 has potential applications in the photocatalytic, electronic, and solar energy
fields.2-4 Also, In2O3 is known as an n-type semiconductor with a direct band gap of
3.6 eV (which is close to that of GaN5) and has been used widely as solar cells,
transparent conductors, and sensors.6-10 By controlling the synthesis techniques
and/or conditions, In(OH)3 and In2O3 can be produced with various morphologies
(e.g., nanowires,11 nanotubes,12 and nanospheres,13 etc.). We have successfully
prepared indium hydroxide nanocubes without any organic surfactants through a
low-temperature hydrothermal process.14 The average size of In(OH)3 nanocubes was
350 nm, and a topotactical relationship was observed between the synthesised
In(OH)3 and In2O3. Thermal decomposition of In(OH)3 is one of the synthetic routes
of In2O3. Studies are important on the thermal transformation of In(OH)3 to In2O3 for
further application of these nanomaterials to industry.
Infrared emission spectroscopy (IES) has proven to be a very useful tool that can be
applied in situ. IES determines vibrational wavenumbers emitted by thermally
excited molecules at elevated temperatures.15 Frost and Kloprogge have developed
extensive work on minerals at the molecular level using infrared emission
spectroscopy.16-20 They applied infrared emission spectroscopy in studies on the
dehydration, dehydroxylation, decarbonization behavior, and other changes of
minerals, especially clay minerals.21-24 However, limited work has been published on
inorganic nanomaterial using this in situ thermal analysis technique. Interpretation of
the changes in the obtained infrared emission spectra with temperature increase can
yield information concerning the thermal reaction and thermal stability of materials.
Our interest in nanomaterials for industrial applications led our motivation for this
research.
71
In this paper, we report changes in the molecular structure as a function of

temperature of the synthetic indium hydroxide nanocubes as determined using
infrared emission spectroscopy.
2. EXPERIMENTAL
2.1 Synthesis of cubic Indium hydroxide nanomaterial
Analytical grade In(NO3)3·

5H2O and ammonia solution (28 wt%) were used as
precursors to prepare the indium hydroxide precipitate. Three grams of
In(NO3)3·
5H2O was dissolved in 15 mL ultrapure water, and 28% ammonia was
diluted into 10% solution. At room temperature, the diluted ammonia solution (10%)
was added at a rate of 1 mL min-1 into the indium ion solution with vigorous stirring.
Ammonia solution addition ceased when the pH of the reaction mixture reached 8.
The reaction mixture was kept stirring constantly in the air at room temperature for
0.5 h. The obtained mixture was centrifuged and washed at 13,000 rpm for 10 mins,
3 times. The resultant precipitate was transferred into a vessel (125 mL) together
with 2 mL ultrapure water. The vessel was then sealed and placed in a 180 ºC oven.
After a 2-day hydrothermal treatment, the ultrapure resultant product was washed
and collected by centrifugation (at 13,000 rpm for 10 min, repeated 3 times). Sample
was dried at 65 ºC overnight.
2.2 X-ray diffraction analyses

from a line-focused PW3373/10 Cu X-ray tube, operating at 40 kV and 40 mA, with
Cu Kα radiation of 1.540596 Å. The incident beam passed through a 0.04 rad soller
slit, a 1/2ºdivergence slit, a 15 mm fixed mask, and a 1°fixed anti-scatter slit.
2.3 Infrared spectra
Infrared spectra were obtained using a Nicolet Nexus 870 FTIR spectrometer with a
smart endurance single-reflection diamond attenuated total reflection (ATR) cell
(Thermo Scientific). Spectra over the 4000-525 cm-1 range were obtained by the
co-addition of 64 scans with a resolution of 4 cm-1.
72
2.4 Infrared emission spectroscopy
Infrared emission spectroscopy (IES) was carried out on a Nicolet Nexus 870 FTIR
spectrometer equipped with a MCT detector, which was modified by replacing the IR
source with an emission cell. A description of the cell and the principles of the
emission experiment have been published elsewhere.25-28 Approximately 0.2 mg of
synthesised indium hydroxide was spread as a thin layer (approximately 0.2 μm) on a
6 mm diameter platinum surface and held in an inert atmosphere within a
nitrogen-purged cell during heating. The emission spectra were collected at intervals
of 50 ºC over the range 100-600 ºC. The spectra were acquired by co-addition of 64
scans for the whole temperature range, with a nominal resolution of 4 cm-1. Three
sets of spectra were obtained: (1) the blackbody radiation at selected temperatures,
(2) the platinum plate radiation at the same temperature, and (3) the spectra from the
platinum plate covered with the sample. Only one set of blackbody and platinum
radiation is required for each temperature. The emission spectrum at a particular
temperature was calculated by subtraction of the single-beam spectrum of the
platinum backplate from that of the platinum + sample, with the result ratioed to the
single beam spectrum of an approximate blackbody (C-graphite). This spectral
manipulation is carried out after all the spectral data have been collected.
2.5 Spectral manipulation
Spectral manipulation such as baseline adjustment, smoothing, and normalization

was performed using the GRAMS® software package (Galactic Industries
Corporation, Salem, NH). Band component analysis was undertaken using the Jandel
„Peakfit‟ (Erkrath, Germany) software package, which enabled the type of fitting
function to be selected and allows specific parameters to be fixed or varied
accordingly. Band fitting was done using a Lorentz–Gauss cross-product function
with the minimum number of component bands used for the fitting process. The
Lorentz–Gauss ratio was maintained at values greater than 0.7 and fitting was
undertaken until reproducible results were obtained with squared correlations (r2)
greater than 0.999. Band fitting of the spectra is quite reliable providing there is
some band separation or changes in the spectral profile.
73
3.1 Phase identification
X-ray diffraction (XRD) is normally used to determine the phase and structure of the
as-prepared samples. Fig. 1 displays a typical XRD pattern of the synthetic indium
hydroxide nanocubes, which is in excellent agreement with the pattern reported in
the literature (JCPDS Card No. 01-076-1463, cubic In(OH)3 with a lattice constant a
= 7.9743 Å). All the diffraction peaks were well indexed by Miller indices. It is also
reported that the (200) peak is particularly strong, which results from the regular
cubic shape and ordered assembly of as-prepared In(OH)3.10 No other crystalline
impurities, such as InO(OH) or In2O3, were detected in the sample, which indicates
high purity of the synthetic cubic In(OH)3 nanomaterial. The cubic morphology of
the synthetic material was confirmed by scanning electron microscopy (SEM)
published in our previous work.14
Fig.1 XRD pattern of the synthetic indium hydroxide nanomaterials with a reference
pattern: JCPDS card No. 01-076-1463 In(OH)3
74
Fig. 2 Schematic of In(OH)3 in cubic structure (space group Im 3 )
3.2 Infrared spectroscopy of the synthetic cubic In(OH)3
It is important to understand that the structure of cubic In(OH)3 adopts a polyhedral

framework consisting of two distorted pentagonal dodecahedra and twelve 7-hedra
per cell in a body-centered cubic arrangement.29 By X-ray and neutron diffraction
methods, Mullica et al. found that six oxygen atoms were octahedrally coordinated
about each indium atom, and each oxygen atom was coordinated by two indium
atoms, while the hydrogen atoms were disordered.29,30 Indium hydroxide nanocubes
crystallize in space group Im 3 ( Th5 ). The cubic unit cell of In(OH)3 is shown in Fig.
2. There are eight formula units in a unit cell. This means there are 81 degrees of
freedom. The irreducible representation is given by Γ = 3Au + 4Ag + 3Eu + 4Eg + 8Fg
+ 12Fu. All the Au and Fu modes are infrared active and all the Ag and Eg modes are
Raman active.
The infrared absorption spectrum of the synthetic indium hydroxide nanocubes in the
region of 3600-600 cm-1 is presented in Fig. 3. Two intense bands at 3221 and 3107
cm-1 are observed, which was attributed to OH stretching modes. Bands were
observed in similar positions in our previous work on Raman spectra of In(OH)3,14 in
which bands are found at 3215 cm-1 and 3083 cm-1.
75
These results are in good agreement with the infrared absorption at 3240 cm-1 and
3120 cm-1 for In(OH)3 reported by Cao et al,31 who synthesised In(OH)3 nanocubes
32
using a amino acid-assisted hydrothermal process. Likewise, Wang et al. found a
OH stretching band for lotus-root-like In(OH)3 at 3200 cm-1. Bands observed in
region of 2600-1300 cm-1 are attributed to overtones and combination bands.
Two OH deformation bands were reported by Chen et al.33 at 1154 and 1067 cm-1.
However, curve fitting of the IR spectrum shows 3 bands at 1150 (sharp), 1129
(shoulder) and 1066 cm-1. The Raman spectrum14 in the hydroxyl-bending region
showed bands at 1155, 1137 (sharp), 1132, 1072 and 1044 cm-1. Cao et al.31
published bands at 1160, 783 and 498 cm-1 to OH deformation modes. Instead, for
the lower wavenumber region, we assign the infrared absorption bands at 852 and
772 cm-1 found in this work to OInO vibrational modes.
Fig.3 Infrared absorption spectrum (curve-fitted) of the synthetic In(OH)3 nanocubes

in the region of 3600 – 600 cm-1.
3.3 Infrared emission spectroscopic study
One method of studying the thermal decomposition of indium hydroxide is through

the changes in the structure caused by dehydration of the material.
76
The use of infrared emission spectroscopy enables the molecular structural changes,
especially of the hydroxyl units, to be observed. The infrared emission spectra (IES)
of the synthetic In(OH)3 nanocubes as a function of temperature are shown in Fig.
4a. The infrared emission spectra below 250 °C are similar to the correlated
room-temperature infrared absorption spectrum (Fig. 3). This observation is in
accordance with Kirchoff‟s law of thermal radiation, which states that for a body (or
surface) in thermal equilibrium with its surroundings the absorbed and emitted
energies are equal.15
(a)
77
(b)
Fig. 4 (a) Infrared emission spectra of the synthetic In(OH)3 nanocubes in the region
of 4000 – 650 cm-1 and (b)curve-fitted Infrared emission spectra from 100 – 300 °C.
As shown in Fig. 4a, the intensity of bands in the hydroxyl-stretching and

hydroxyl-bending regions decreases dramatically after 200 °C, which indicates the
obvious loss of hydroxyl groups happened between 200 and 250 °C. This finding is
in harmony with the results of the thermo gravimetric analyses,14 which showed the
dehydration of In(OH)3 happened from 200 to 225 °C.
78
Bands in the hydroxyl-stretching region approach zero intensity by 450 °C upon

dehydroxylation of the indium hydroxide nanomaterial. For a further study on
structural change in the thermal decomposition process, the infrared emission spectra
below 300 °C were curve-fitted and displayed in Fig. 4b.
In the lower wavenumber region as shown in Fig. 5, bands at 1156, 1139 and 1063
cm-1 are attributed to the OH deformation modes. These bands display a shift to
lower wavenumbers with temperature increase. Such a shift indicates a lessening of
the bond strength of the hydroxyl units upon thermal treatment. Moreover, these
bands diminish rapidly in intensity upon heating, and disappeared above 250 °C.
This observation records the loss of hydroxyl units in the structure of indium
hydroxide according to the work of Martens et al.34 It is published that various
hydroxyl-deformation bands represent different energy levels of the
hydroxyl-deformation modes and the intensity of the bands is a population
measurement of the hydroxyl units at any of these energy levels. 34 Furthermore, a
weak band is observed at 915 cm-1with a shoulder at 972 cm-1 in the spectrum at 250
°C, which are assumed to be OH deformation modes without hydrogen-bonds.
Associated with the hydroxyl-bending vibrations are the hydroxyl-stretching bands,

as shown in Fig. 6. Before 250 °C, the infrared emission spectra show complex
hydroxyl-stretching vibrations, which present various energy levels for the OH
stretching modes in the molecular. It still can be observed that these
hydroxyl-stretching bands shift to higher wavenumbers with the temperature
increase. This shift is caused by the destruction of hydrogen bonds with the loss of
hydroxyl groups. A new weak band is found at 3437 cm-1 at 250 °C, which is
assigned to be OH stretching modes without hydrogen bonding.
79
Fig. 5 Curve-fitted Infrared emission spectra in the region of 1200 – 650 cm-1.
80
Fig. 6 Curve-fitted Infrared emission spectra in the region of 3700 – 2600 cm-1.
In this infrared emission spectroscopic study, small bands which may be assigned to
OH groups is observed both in the hydroxyl stretching and deformation regions from
250 to 400 °C. One possible explanation for this observation is the formation of new
transitional hydroxyl groups upon calcination of indium hydroxide nanomaterial.
This shows the correlation with the previous thermo gravimetric analyses, which
indicated that after the major mass loss between 200 and 225 °C, there was a very
slow mass loss observed with the temperature increase.
81
It is assumed that during the later stage of dehydroxylation, calcination of indium

hydroxide results in the release of protons which are able to diffuse through the
molecular structure which interact with InOIn groups forming a new In(OH) bond.
These protonated In(OH)In linkages can be characterised by infrared emission
spectroscopy which show a stretching band at 3437 cm-1 and a bending band at 915
cm-1. This phenomenon has been observed previously in the calcination of clay
minerals using infrared emission spectroscopy.21, 35 In this experiment the advantage
of infrared emission spectroscopy as a sensitive tool for detecting the OH
environments in minerals and nanomaterials is easily seen.
3.4 Indium oxide converted from indium hydroxide
For a better understanding to the phase transition, the resultant In(OH)3 sample was
calcined in furnace at 300 ºC and 500 ºC separately for 4 hours. The thermal products
were characterised by X-ray diffraction, and the results shown in Fig. 7. The Only
crystalline phase was found in these thermal products to be cubic In2O3 (JCPDS No.
01-071-2195, cubic In2O3 with a lattice constant a =10.1170 Å). This suggests that
the nucleation and growth of In2O3 crystals occurred before 300 ºC. The product
from 500 ºC calcination shows a better crystallinity than the 300 ºC heated product,
indicating that the increase of temperature improves the crystallinity of In2O3
nanocubes.
Fig. 7 XRD patterns of thermal products at 300 and 500 °C from In(OH)3 nanocubes
with a reference pattern: JCPDS card No. 01-071-2195 In2O3.
82
According to the crystallography data, the In2O3 material is body centred cubic and
its crystal structure belongs to the space group Ia 3 , with the point group Th. The
structure contains two types of cations: 8 In3+ cations with site symmetry S6.
Secondly there are 24 In3+ cations with point symmetry C2. The 48 oxygens in the
body centred cubic structure have site symmetry C1. Thus the irreducible
representation for the vibrational spectroscopy of In2O3 is given by: 4Ag + 4Eg + 14
Fg + 5Au + 5Eu + 16Fu. The modes with symmetry Ag, Eg and Fg are Raman
active/infrared inactive. The vibrational modes Fu are infrared active/Raman inactive.
The modes Au + Eu are both Raman and infrared inactive. However, due to the
detecting limit of our instrument, no infrared bands of significant intensity for In2O3
are reported in this study.
83
4. CONCLUSIONS
Infrared absorption spectroscopy and infrared emission spectroscopy were applied to

follow the changes in the structure during the dehydration and dehydroxylation of the
material. The infrared emission spectra of the synthetic indium hydroxide nanocubes
at low temperatures are similar to the correlated room-temperature infrared
absorption spectrum. In the infrared emission spectrum at 100 °C, OInO vibrational
modes are observed at 771 and 853 cm-1. Bands at 1063, 1139 and 1156 (sharp) cm-1
are assigned to be In(OH) bending modes, and the OH stretching modes are observed
at 3123 and 3247 cm-1.
The intensity of these bands nearly reaches zero above 200 °C, which indicates that
almost all the OH units are lost in the structure. However, new weak bands were
found at 915 and 3437 cm-1 in infrared emission spectra from 250 to 450 °C, which
are assumed to due to OH bending and stretching modes separately. This observation
shows the releasing and transfer of protons and formation of transition new OH
bonds upon calcination. The results presented in this paper clearly show the strength
of infrared emission spectroscopy to study in situ the transformation taking place
during the thermal treatment of indium hydroxide nanocubes. Cubic In2O3 has been
confirmed by XRD to be the thermal product from indium hydroxide nanocubes after
heated at 300 °C. The crystallinity of the thermal product is improved by increase the
calcination temperature to 500 °C.
ACKNOWLEDGEMENTS

Technology Chemistry Discipline is gratefully acknowledged. The Australian
Research Council (ARC) is thanked for funding the instrumentation. One of the
authors (JY) is grateful to the Queensland University of Technology Chemistry
Discipline for the award of an international doctoral scholarship.
84
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88
Chapter 5 Cr doped AlO(OH) nanofibres
CHAPTER 5
SYNTHESIS AND
CHARACTERISATION OF
CHROMIUM DOPED BOEHMITE
NANOFIBRES
Yang, J.; Frost, R. L.; Yuan, Y., "Synthesis and characterization of chromium doped
boehmite nanofibres." Thermochimica Acta 2009, 483 (1-2), 29-35.
89
SYNOPSIS
To achieve multi-functional boehmite nanomaterials, the technique doping was

applied. In this chapter, chromium doped boehmite nanofibres were fabricated
through hydrothermal treatment based on the synthesis method reported in Chapter 3.
The effect of the adding dopant amount and hydrothermal treatment period to the
material properties was investigated. Thermal stability of these doped and undoped
boehmite nanofibres was studied by thermogravimetric analysis and infrared
emission spectroscopy. It is found that doping of chromium resulted in an increase of
the main dehydroxylation temperature of boehmite nanofibres from 406.5 °C to
436.5 °C.
90

expertise;
academic unit, and
Synthesis and Characterization of Chromium Doped Boehmite Nanofibres
Yang, J.; Frost, R. L.; Yuan, Y., Thermochimica Acta 2009, 483 (1-2), 29-35.

Yong Yuan Conducted TEM and data analysis, manuscript editing.


authorship.
____________________ _____________________ ____________________

Name Signature Date
91
RESEARCH HIGHLIGHTS
The article is the first published paper on chromium doped boehmite nanofibres
using a hydrothermal method without any assistance of surfactants. The synthesised
Cr-doped boehmite nanofibres were uniform in shape and size, up to 500 nm long
and 6 nm wide. It is also found that doping with chromium resulted in an increase in
the dehydroxylation temperature of boehmite from 406.5 ºC to 436.5 ºC. Besides, as
the dehydroxylation temperature of the Cr-doped boehmite nanofibres increased, the
mass loss in the dehydroxylation step decreased.
92
SYNTHESIS AND CHARACTERIZATION OF

CHROMIUM DOPED BOEHMITE NANOFIBRES
Jing (Jeanne) Yang, Yong Yuan and Ray L. Frost*

Received: September 8, 2008

Revised Manuscript Received: October 27, 2008
Accepted: October 28, 2008
Published Online: November 6, 2008
ABSTRACT
Chromium doped boehmite nanofibres have been synthesised and characterised by

X-ray diffraction, transmission electron microscopy and thermal analytical
techniques. Hydrothermal treatment of doped boehmite with chromium resulted in
the formation of nanofibres over a wide dopant range. Nanofibres up to 500 nm
and between 4-6 nm wide were synthesised. Doping with chromium resulted in an
increase in the dehydroxylation temperature of boehmite from around 406.5 °C to
436.5 °C. The temperature of dehydroxylation increases with time of hydrothermal
treatment. As the dehydroxylation temperature increases the mass loss from the
dehydroxylation step decreases. The dehydroxylation temperature increases
significantly from 0% to 5% doping, after which the dehydroxylation temperature
shows a small steady increase up to the 20% doping level.
KEYWORDS
Boehmite; Chromium Doping; Nanofibres; Nanomaterial; Transmission Electron

Microscopy; Thermo-gravimetric Analysis
93
1. INTRODUCTION
Compared to their micro and macro counterparts, nanosized materials have been
received wider attention because of their intrinsic properties, which are determined
by their composition, size, shape, and structure. [1] Such as nanofibres, nanotubes,
nanoribbons and nanorods, one dimensional (1D) nanoscale inorganic materials have
attracted intensive interest due to their distinctive geometries, novel physical and
chemical properties, and the potential applications in many fields. [2] Boehmite (γ
-AlO(OH)) and its oxide derivatives such as α-Al2O3 and γ -Al2O3 have been studied
extensively because they can be used as catalysts, adsorbents, flame retardants and
optical materials. [3-6]
Synthesis forms an essential component of nanoscience and nanotechnology. While

nanomaterials have been generated by physical methods such as laser ablation,
arc-discharge and evaporation, chemical methods have proved to be more effective, as
they provide better control as well as enable different sizes, shapes and
functionalization. Among these methods, hydrolysis and precipitation are the most
common. John Bugosh first synthesised the boehmite nanofibres by a hydrothermal
method in 1961. [7] Since then, numerous studies on boehmite nanofibres have been
undertaken, for example, boehmite (AlO(OH)) nanofibres were reported to be
assembled with the assistance of poly(ethylene oxide) (PEO) surfactant [8] and
tubular γ -Al2O3 was fabricated via soft solution route using
N-cetyl-N,N,N-trimethylammonium bromide surfactant. [9] Shen et al. [10] reported
that a steam-assisted solid-phase conversion of amorphous aluminium hydroxides wet
gel to well crystallized 1D nanostructure of boehmite AlO(OH) nanorods without
using surfactants and solvents. The process is unique in the simplicity of preparation
and the high efficiency of crystal growth, which can be operated at a large scale.
As for doping clays, the addition of other metal ions into boehmite, especially into
nanostructured boehmite would have great potential to contribute the further
application of these inorganic nanomaterials due to the enhancement of its properties,
and there have been reports on boehmite doped by Fe, Ga, and Eu. [11-13] It is also
reported that materials doped with Chromium could obtain special electric, magnetic
or optical properties and gain more application. [14-17] This paper would present our
work on Cr-doped boehmite, which has not been seen before.
94
Thermal analysis has been proved as the most useful method for the analysis of
minerals and related materials. [18-27] In this work, boehmite nanofibres based on
Shen‟s methodology were synthesised by introducing Chromium as dopant and a
series of Chromium doped boehmite nanofibres with different iron content
percentage and varying hydrothermal treatment time have been systematically
studied with the thermo gravimetric techniques.
2. EXPERIMENTAL
2.1 Synthesis of chromium doped boehmite nanofibres
A total amount of 0.02 mol aluminium nitrate and chromium nitrate were mixed
before being dissolved in ultra-pure water. To make a comparison, mixtures with
chromium molar percentage of 0, 1, 3, 5, 10 and 20% were prepared separately and
then dissolved in ultra-pure water to form solutions with a metal ion to H2O molar
ratio of 1:35. At room temperature, 10% ammonia solution was added dropwise into
the metal ions solution while stirring vigorously. Stop adding ammonia when the pH
value of the reaction mixture reaches 5, and then keep stirring in the air at room
temperature for 1 hour. The obtained gel was filtrated to obtain the gel-cake, which
was then transferred into a glass beaker (25 mL). Before putting the beaker with
gel-cake into a Teflon vessel (200 mL), 2 mL ultrapure water was poured to the
bottom of each vessel separately. Sealed the Teflon vessels and heated them at 170
ºC for 1, 3, 5 and10 days. The resulting materials were washed with ultrapure water by
centrifuging, and dried at 35 ºC for 2 days.
XRD analyses were performed on a PANalytical X‟Pert PRO X-ray diffractometer

(radius: 240.0 mm). Incident X-ray radiation was produced from a line focused
PW3373/10 Cu X-ray tube, operating at 40 kV, 40 mA, wavelength of 1.540596 Å.
2.3 TEM analysis
A Philips CM 200 transmission electron microscopy (TEM) at 200 kV was used to

investigate the morphology of the boehmite nanofibres. All samples were dispersed
in absolute ethanol solution and then dropped on copper grids.
95
Thermal decomposition of the Cr-doped boehmite was carried out in a TA®

Instruments incorporated high-resolution thermo gravimetric analyser (series Q500)
in a flowing nitrogen atmosphere (60 cm3 min–1). Approximately 20 mg of each
sample underwent thermogravimetric analyses, with a heating rate of 5°C/min, with
resolution of 6 from 25 to 1000°C. With the isothermal, isobaric heating program of
the instrument the furnace temperature was regulated precisely to provide a uniform
rate of decomposition in the main decomposition stage.
X-ray diffraction is normally used to determine the phase and purity of the
synthesised boehmite. Fig. 1a and 1b display well-defined XRD patterns observed
and all diffraction peaks were perfectly indexed to the XRD pattern of pure boehmite
(JCPDS card 01-083-2384). No XRD peaks representing other crystalline phases
were detected, indicating that the chromium doped-nanofibres of the synthetic
boehmite exhibited excellent crystallinity and a high purity. Fig. 1a shows that the
peaks are higher and narrower with the increase of the hydrothermal treatment time
to 10 days, which means the crystals are growing better as synthesis time getting
longer.
3.2 Transmission electron microscopy
The transmission electron microscopy images of the synthesised Cr doped boehmite

are shown in Fig 2a, b, c. The figures show the TEM images of un-doped boehmite
(a), 3% doped (b) and 5% doped (c).
The figures clearly show that the boehmite is fibrous with very long narrow fibres
often exceeding 500 nm in length and with widths of between 2 and 6 nm. Many of
the fibres are curved or bent as may be observed in Fig. 2c for the 5% doped
boehmite.
96
(a) (b)
un
do
pe
bo
eh
mit
e
Fig. 1 (a) XRD patterns of undoped boehmite and 1% Cr-doped boehmite nanofibres
with different hydrothermal treatment time at 170 ºC. (b) XRD patterns of undoped
boehmite and various Cr % doped boehmite nanofibres, after hydrothermal
treatment at 170 ºC for 3 days.
(a) (b) (c)
Fig. 2 TEM images of the synthetic nanofibres with 3-day hydrothermal treatment:
(a) undoped boehmite, (b) 3% Cr-doped and (c)5% Cr-doped.
97
3.3 Thermo gravimetric analysis
The thermo gravimetric analysis and the differential thermo gravimetric analyses of
boehmite and Cr doped boehmite and their nanostructures with varying amounts of
Cr from 0 to 20% are shown in Figs 3a–3e. The results of the thermal analyses are
reported in Table 1.
Table 1 Results of the thermogravimetric analyses of the undoped and various % Cr

doped boehmite nanofibres.
The TG of the pure boehmite shows a strongly asymmetric curve with a peak
temperature of 406.5 °C and a mass loss of 15.8%. The thermal decomposition
occurs as follows: 2AlO(OH) → Al2O3 + H2O. This major decomposition step is
attributed to the dehydroxylation of the boehmite. Two low mass loss steps at 45 and
260 °C with mass losses of 1.5 and 1.7% are also observed. The first mass loss step
is assigned to the dehydration of boehmite (Column 1 in Table 1).
The thermal decomposition of 1% doped boehmite with 1 day hydrothermal

treatment shows three mass loss steps at 46, 311 and 403 °C with mass losses of 1.7,
6.6 and 11.0% (Fig. 3b). The asymmetry observed in Fig. 3a is no longer observed
but a second peak at 311 °C is found.
98
(a)
(b)
99
(c)
(d)
100
(e)
Fig. 3 Thermogravimetric analyses patterns of (a) undoped boehmite nanofibres and

1% Cr doped boehmite with different hydrothermal treatment time: (b) 1 day, (c) 3
days, (d) 5 days, and (e) 10 days.
The thermal decomposition of 1% doped boehmite with 3 day hydrothermal

treatment shows three mass loss steps at 50, 321 and 419.5 °C with mass losses of
1.0, 4.8 and 11.5% (Fig. 3c). The thermal decomposition of 1% doped boehmite with
5 day hydrothermal treatment shows three mass loss steps at 46, 311 and 403 °C with
mass losses of 0.8, 3.9 and 12.1% (Fig. 3d). With the 10 day hydrothermal
treatment, mass loss decomposition steps are observed at 54, 342 and 435 °C. The
mass losses at these temperatures are 0.7, 3.1 and 12.2%. The results of the 1% Cr
doped boehmite hydrothermally treated for 10 days (Fig. 3e) shows a large mass loss
step at 435 °C with a mass loss of 12.2%.
In addition two smaller mass loss steps at 54 and 342 °C with mass losses of 0.7 and
3.1% are observed. It is apparent that thermal decomposition temperature of the Cr
doped boehmite varies with the hydrothermal treatment time. This variation is
reported in Fig. 4.
101
Fig. 4 Dehydroxylation temperature of the dTG peak as a function of added Cr

content and with the hydrothermal treatment time.
The variation in the % Cr doping on the thermo gravimetric analyses patterns and
decomposition of boehmite is explored in Fig 5a to 5d. The thermo gravimetric
analyses patterns of 3% Cr doped boehmite hydrothermally treatment for 3 days
shows three mass loss steps at 46, 315 and 427 °C with mass losses of 1.1, 2.9, and
12.4%. The dehydroxylation peak at 427 °C is very narrow indication the
dehydroxylation occurs over a very narrow temperature range. For the 5% Cr doped
boehmite the dehydroxylation step is observed at 430.5 °C with a mass loss of
13.1%. For the 10% Cr doped boehmite hydrothermally treated for 3 days results in
a sharp mass loss peak at 433 °C with minor mass loss steps at 50 and 380 °C. The
temperature for the Cr 20% doped boehmite is 436.5 °C. The variation in the
temperature of the decomposition of boehmite as a function of % doping is reported
in Fig. 4. It is apparent that as the 5 of Cr is increased in the boehmite the
dehydroxylation temperature is increased and shifts from 406.5 °C to 436.5 °C.
102
(a)
(b)
103
(c)
(d)
Fig. 5 Thermo gravimetric analyses patterns of various % Cr-doped boehmite

nanofibres with 3-day hydrothermal treatment:(a) 3% , (b) 5%, (c)10%, and (d)
20%.
104
function of added Cr content.
function of the hydrothermal treatment time.
The variation of the dehydroxylation temperature and associated mass loss with the
% of Cr doping is shown in Fig. 6. As the dehydroxylation temperature increases
the mass loss from the dehydroxylation step decreases. The dehydroxylation
temperature increases significantly from 0% to 5% doping, after which the
dehydroxylation temperature shows a small steady increase up to the 20% doping
level. The associated mass loss decreases and then shows a constant mass loss.
The variation of mass loss and dehydroxylation temperature with hydrothermal
treatment time is illustrated in Fig. 7. The temperature of dehydroxylation increases
with time of hydrothermal treatment.
105
4. CONCLUSIONS
Boehmite and chromium doped boehmite were synthesised by low temperature

precipitation from aqueous solution and hydrothermally treated for differing time
intervals. Very long nanofibres were produced often exceeding 500 nm in length.
Normally at above the 5% doping level a mixture of nanofibres and nano-sheets are
produced.
ACKNOWLEDGEMENTS

Technology Inorganic Materials Research Program of the School of Physical and
Chemical Sciences is gratefully acknowledged. The Australian Research Council
(ARC) is thanked for funding the instrumentation.
106
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Journal of Thermal Analysis and Calorimetry, 2006. 86(1): p. 205-209.
23. Frost, R.L., M.L. Weier, and W. Martens, Thermal decomposition of

jarosites of potassium, sodium and lead. Journal of Thermal Analysis and
Calorimetry, 2005. 82(1): p. 115-118.
24. Frost, R.L., M.L. Weier, and W. Martens, Thermal decomposition of

liebigite: A high resolution thermogravimetric and hot-stage Raman
spectroscopic study. Journal of Thermal Analysis and Calorimetry, 2005.
82(2): p. 373-381.
25. Frost, R.L., et al., Thermal decomposition of ammonium jarosite

(NH4)Fe3(SO4)2(OH)6. Journal of Thermal Analysis and Calorimetry, 2006.
84(2): p. 489-496.
26. Frost, R.L., et al., Thermal decomposition of hydronium jarosite

(H3O)Fe3(SO4)2(OH)6. Journal of Thermal Analysis and Calorimetry,
2006. 83(1): p. 213-218.
27. Zhao, Y., et al., XRD, TEM and thermal analysis of Fe doped boehmite
nanofibres and nanosheets. Journal of Thermal Analysis and Calorimetry,
2007. 90(3): p. 755-760.
109
110
Chapter 6 Synthesis and characterisation of CrO(OH) nanoparticles
CHAPTER 6
SYNTHESIS AND
CHARACTERISATION OF
CHROMIUM OXYHYDROXIDE
CrO(OH) NANOPARTICLES
111
SYNOPSIS
Chromium doped aluminium oxyhydroxide nanofibres were successfully achieved as

mentioned in last chapter (Chapter 5). It would be interesting to take a further
investigation on the hydrothermal synthesis of pure chromium oxyhydroxide
nanomaterials. In this chapter, a similar hydrothermal synthesis procedure was
applied to fabricate chromium oxyhydroxide. This chapter consists of three published
articles.
Chromium oxyhydroxide has important application in catalyst industry; however, its

nanomaterials receive limited reports so far. In Chapter 6.1, it is reported that
well-crystalline chromium oxide hydroxide nano-plates with an average size of 11
nm were successfully synthesised. The synthetic CrO(OH) nanoparticles are uniform
in morphology and size. Detailed discussion is presented, particularly on the
controllable synthesis, as well as material structure, surface properties and their
thermal stabilities of the synthetic CrO(OH) nanomaterials. The aim of this research
is to investigate the influence of experimental procedures on the synthesis and
properties of chromium oxyhydroxide nanomaterials with controlled size and
morphology.
Raman spectroscopy allows the possibility of studying the structure at the molecular
level. The combination of Raman spectroscopy with a hot-stage lends itself as the
technique of choice for studying the chemical reactions during dehydration and
dehydroxylation. In Chapter 6.2 and 6.3, detailed hot-stage Raman spectroscopic
studies were presented on the thermal transition process of chromium oxide gel and
chromium oxyhydroxide nanomaterials to crystalline chromium oxide materials.
112
CHAPTER 6.1
SIZE-CONTROLLABLE
SYNTHESIS OF CHROMIUM
OXYHYDROXIDE
NANOMATERIALS USING A
SOFT CHEMICAL
HYDROTHERMAL ROUTE
Yang, J.; Baker, A. G.; Liu, H.; Martens, W. N.; Frost, R. L., " Size-controllable
synthesis of chromium oxyhydroxide nanomaterials using a soft chemical
hydrothermal route." Journal of Materials Science 2010, 45 (24), 6574-6585.
113

expertise;
academic unit, and
Size-controllable Synthesis of Chromium Oxyhydroxide Nanomaterials Using A Soft

Chemical Hydrothermal Route
Yang, J.; Baker, A. G.; Liu, H.; Martens, W. N.; Frost, R. L., Journal of Materials Science 2010,
45 (24), 6574-6585.

Adrian G. Baker Helped with experimental work and data presentation.

Hongwei Liu Conducted TEM and data analysis, manuscript editing.
and editing.

authorship.
____________________ ______________________ ____________________

Name Signature Date
114
RESEARCH HIGHLIGHTS
The article focuses on the synthesis and characterisation of chromium oxyhydroxide

nanomaterials. The best experimental method to control the size of the nanoparticles
was investigated, and CrO(OH) nanomaterials were found to form most easily with
an acidic precipitate process. The structure, morphology, specific surface analysis
were well characterised as a function of the experimental conditions of synthesis. A
detailed thermogravimetric study on samples synthesis in different conditions was
presented, which showed that the dehydroxylation of the dehydroxylation of the
synthetic chromium oxyhydroxides occurred at ~460 °C, while chromium hydroxide
impurities decomposed at ~400 °C.
115
SIZE-CONTROLLABLE SYNTHESIS OF
CHROMIUM OXYHYDROXIDE
NANOMATERIALS USING A SOFT CHEMICAL
HYDROTHERMAL ROUTE
Jing Yang, Adrian G. Baker, Hongwei Liu,

Wayde N. Martens and Ray L. Frost*

r.frost@qut.edu.au
Received: March 14, 2010

Accepted: June 28, 2010
Published Online: July 15, 2010
ABSTRACT
Chromium oxyhydroxide nanomaterials were synthesised through a simple soft

chemistry hydrothermal method. The chromium oxyhydroxide materials display
platelet morphology with clear edges, ~11 nm in diameter. CrO(OH) nanomaterials
synthesised under different conditions were fully characterised by X-ray diffraction
(XRD), transmission electron microscopy (TEM) combined with selected area
electron diffraction (SAED), scanning electron microscopy (SEM), BET specific
surface area analysis, X-ray photoelectron spectroscopy (XPS) and thermal
gravimetric analysis (TGA). Bonding of the trivalent chromium from the
oxyhydroxide nanomaterials was defined through the analysis of their high resolution
XPS spectra for Cr 2p3/2 and O 1s. The thermal stability of the nanomaterials
CrO(OH) were established. This research has developed methodology for the
synthesis of chromium oxyhydroxide nanoplates.
116
KEYWORDS
Chromium Oxyhydroxide; Grimaldiite; Nanomaterials; Nano-plates; XRD; SEM;

TEM; BET; XPS; Thermal Analysis
1. INTRODUCTION
Transition metal oxides are important materials in industry as heterogenous catalysis,

which support materials as well as active components. Special attention has been
focused on the formation and properties of chromia (Cr2O3), which is important in
specific applied applications such as in high-temperature resistant materials, [1-3]
solar energy collectors, [4-6] liquid crystal displays, [7,8] and catalysts. [9-12] Rust
formed by corrosion of Cr-containing steels, Cr2O3 and CrO(OH) were also detected
and extensively studied. [13-16] Similar with the relationship of cobalt oxyhydroxide
to oxides, [17] chromium oxyhydroxide is a principal precursor for synthesis of
chromium oxides. The morphology and nanosize of the oxyhydroxide can be
retained through to the oxides through a topotactical relationship. [17-20] Therefore,
studies on controllable synthesis and characterisation for CrO(OH) nanomaterials are
important for the synthesis and application of Cr2O3 nanomaterials in industry.
It is reported that there are three currently known synthetic polymorphs of CrO(OH):
trigonal -CrO(OH) with a space group of R3m, orthorhombic -CrO(OH) with a
space group of Pnnm, and -CrO(OH) with a space group of Cmcm.[21] Approved in
1977 by the Commission on New Minerals and Mineral Names of the International
Mineralogical Association (IMA-CNMMN), the naturally occurring chromium
oxyhydrates include three species: bracewellite (orthorhombic CrO(OH)), guyanite
(orthorhombic β-CrO(OH)), and grimaldiite (trigonal CrO(OH)). [21] So far, limited
work has been devoted on the synthesis and industrial application of CrO(OH) and
Cr2O3 nanomaterials.
By reducing potassium chromate with hydrogen and then calcining the obtained
intermediate, which consists of Cr(OH)3·
nH2O and CrO(OH), the ultra-fine chromia
(Cr2O3) powder with a mean diameter of 0.3m has been prepared. [22] The
preparation of chromium oxide is of considerable interest since this compound is a
component of many oxide-type catalysts.
117
Cr(III)-Fe(III)-(oxy)hydroxides have been reported by Tang et al. [23] It is found

that the Cr end member sizing around 1 nm is likely to be amorphous with aspects of
local structure similar to -CrO(OH). Landau [24] and Rotter[9] reported catalytic
materials based on chromia aerogel, which consists of 1-2 nm CrO(OH) nanocrystals
with very high surface area. CrO(OH)·
2H2O nanocrystals of 3-5 nm in diameter were
prepared by critical CO2 extraction of the urea-assisted wet chromia gel mixture at
373 K in vacuum. [25,26] As reported, metal oxides can be formed through the
thermal dehydration of their corresponding oxyhydroxides, which can preserve the
texture of their precursors. [27,28,20,29] It is reported that hydrated chromium
oxides are mostly used as initial compounds for the synthesis of chromium oxides.
[30] As the important precursor for chromium oxides through thermal treating, the
thermal stability and decomposition process of chromium hydroxide or chromium
oxide hydroxide has been investigated. [30-35] However, not much work has been
done on the thermal study of nanoscaled CrO(OH) materials.
Possible industrial applications of CrO(OH) and Cr2O3 materials depend on their

chemical, physical and micro-/nano-structure properties. Generally the properties of
materials can be modified by their synthesis conditions. Therefore, researchers have
tried to establish the relation between the properties of chromium oxide materials and
synthesis conditions. In this study, a simple soft-chemical method is used and
well-crystalline chromium oxide hydroxide nano-plates with an average size of 11
nm were successfully synthesised. The synthetic CrO(OH) nanoparticles are very
uniform in morphology and size. Detailed discussion is presented in the text,
particularly on the controllable synthesis, as well as material structure, surface
properties and their thermal stabilities of the synthetic CrO(OH) nanomaterials. The
aim of this research is to investigate the influence of experimental procedures on the
synthesis and properties of chromium oxyhydroxide nanomaterials.
2. EXPERIMENTAL
2.1 Material synthesis
Typically, 15 g of Cr(NO3)3•9H2O was dissolved in 75 mL ultra pure water, and 28%

ammonia was diluted to 10% solution. At room temperature 10% ammonia solution
was added at a rate of 1 mL/min into Cr(NO3)3 solution with vigorous stirring.
118
Ammonia solution addition ceased when the pH of the reaction mixture reached the
desired values (5.0, 7.5 or 10.0). The reaction mixture was then kept stirring
constantly in air at room temperature for 0.5 h. The obtained gel was centrifuged and
washed at 13000 rpm for 10 mins, 3 times. The washed wet gel was transferred into a
glass beaker (25 mL). The beaker was placed into a Teflon vessel, 2 mL ultra pure
water was poured into the button of the Teflon vessel. The Teflon vessel was then
sealed and hydrothermally treated at 170 ºC for 12 h to 4 days. Ultra pure water was
added to the resultant product and then collected by centrifugation (at 13000 rpm for
10 mins). The washing process was repeated 3 times. Samples were dried at 65 ºC
overnight. Samples ID used in this paper and their preparation conditions are shown
in Table 1.
2.2 X-ray diffraction (XRD)
X-ray diffraction patterns were collected using a PANalytical X‟Pert PRO X-ray
diffractometer (radius: 240.0 mm). Incident X-ray radiation was produced from a line
focused PW3373/10 Cu X-ray tube, operating at 40 kV and 40 mA, with Cu K
radiation of 1.540596 Å. The incident beam passed through a 0.04 rad soller slit, a
1/2 °divergence slit, a 15 mm fixed mask, and a 1 °fixed antiscatter slit.
Table 1 Samples ID used in this paper and their preparation conditions.

pH for wet gel TGA
Sample ID HT temp. HT duration
precipitate products
ppt-5.0 5.0 - - -
ppt-7.5 7.5 - - -
ppt-10.0 10.0 - - -
CrO(OH)-5.0 5.0 170 °C 12 h -
gel-7.5-a 7.5 170 °C 12 h -
gel-10.0-a 10.0 170 °C 12 h -
CrO(OH)-7.5 7.5 170 °C 4 days -
CrO(OH)-10.0 10.0 170 °C 4 days -
ppt-5.0-TGA 5.0 - - Yes
CrO(OH)-5.0-TGA 5.0 170 °C 12 h Yes
CrO(OH)-7.5-TGA 7.5 170 °C 4 days Yes
CrO(OH)-10.0-TGA 10.0 170 °C 4 days Yes
119
2.3 Scanning electron microscopy (SEM)
The specimens were mounted on SEM mounts with carbon tape and coated with a
thin layer of evaporated gold. The secondary electron images were obtained using a
scanning electron microscope (FEI Quanta 200 SEM, FEI Company, Hillsboro,
Oregon, USA), operating at 30 kV.
2.4 Transmission electron microscopy (TEM)
A Philips CM20 transmission electron microscope (TEM) at 160 kV was used to

investigate the morphology of the as-prepared samples. All samples were
ultrasonically dispersed in absolute ethanol solution, and then dropped on copper
grids. Selected area electron diffraction (SAED) was performed via the same TEM.
2.5 Specific surface area analysis
Surface area analyses based upon N2 adsorption/desorption techniques were analysed

on a Micrometrics Tristar 3000 automated gas adsorption analyser. Before the
analysis, samples were pre-treated at 110 °C under the flow of N2 on a Micrometrics
Flowprep 060 degasser.
2.6 X-ray photoelectron spectroscopy (XPS)
Data was acquired using a Kratos Axis ULTRA X-ray Photoelectron Spectrometer
incorporating a 165 mm hemispherical electron energy analyser. The incident
radiation was Monochromatic Al Kα X-rays (1486.6 eV) at 150 W (15 kV, 10 mA)
and at 45 degrees to the sample surface. Photoelectron data was collected at take off
angle of theta = 90 o. Narrow high-resolution scans were run with 0.05 eV steps and
250 ms dwell time. Base pressure in the analysis chamber was 1.0×10-9 torr and
during sample analysis 1.0×10-8 torr. A small amount of each finely-powdered
sample was carefully applied to double sided adhesive tape on a standard Kratos
Axis Ultra sample bar. This was attached to the sample rod of the Load Lock system
for initial evacuation to ~1 × 10-6 torr. The sample bar was then transferred to the
UHV Sample Analysis Chamber (SAC) for collection of X-ray Photoemission
spectra. Spectra were subjected to a Shirley baseline. Various data handling
procedures were carried out using the CasaXPS version 2.3.14 software.
120
2.7 Thermal gravimetric analysis
Thermal decomposition of the samples was carried out in a TA ® Instruments

incorporated high-resolution thermo gravimetric analyser (series Q500) in a flowing
nitrogen atmosphere (60 cm3 min–1). Approximately 50 mg of each sample
underwent thermo gravimetric analyses, with a heating rate of 5 °C/min, with
resolution of 6 from 25 °C to 1000 °C. With the isothermal, isobaric heating program
of the instrument the furnace temperature was regulated precisely to provide a
uniform rate of decomposition in the main decomposition stage. The TGA
instrument was coupled to a Balzers (Pfeiffer) mass spectrometer for gas analysis.
Only water vapour, nitric oxide, carbon dioxide, and oxygen were analysed. In the
MS figures, e.g. Fig. 9, a background of broad peaks may be observed. This
background occurs for all the ion current curves. The background becomes more
prominent as the scale expansion is increased. It is considered that this background
may be due to the loss of chemicals which have deposited in the capillary which
connects the TA instrument to the MS.
3.1 Structure and morphology
The XRD patterns of the colloidal precipitation obtained under different pH values
and of the samples after being hydrothermally treated at 170 °C for 12 h are shown in
Fig. 1. Prior to the hydrothermal treatment, the colloidal chromium hydroxide
materials resulting from reaction of Cr(NO3)3 and NH4OH solutions, noted as
ppt-5.0, ppt-7.5 and ppt-10.0 separately, were amorphous. No XRD peaks were
observed for these precipitated samples. This agrees with literature, which reported
that the hydrogel obtained from the neutralisation of Cr3+ ions is usually amorphous
or poorly crystalline. [36,37] The conversion process from colloidal chromium
precipitate to crystalline CrO(OH) was found to be significantly affected by the
precipitation conditions. After a hydrothermal treatment at 170 °C for 12 h, only the
sample precipitated at pH = 5.0 was transformed to well crystalline phase, noted as
CrO(OH)-5.0; while the other two samples, which precipitated at pH 7.5 and 10.0,
remain amorphous, as shown in Fig. 1.
121
Fig .1 XRD patterns of ppt-5.0, ppt-7.5, ppt-10.0, CrO(OH)-5.0, gel-7.5-a and

gel-10.0-a. XRD pattern from literature: JCPDS card No. 01-070-0621 Grimaldiite.
A well defined XRD pattern for CrO(OH)-5.0 was observed and all diffraction peaks
were perfectly indexed to rhombohedral CrO(OH), which has the mineral name
Grimaldiite, with a space group of R3m (JCPDS card No. 01-070-0621).
The parameters of the rhombohedral unit cell of Grimaldiite are: a = 2.979 Å, c =

13.370 Å. [38] No XRD peaks representing other crystalline phases were detected,
indicating a high purity of the resultant crystalline solid by a hydrothermal
conversion process. Based on XRD results, the average crystallite size of sample
CrO(OH)-5.0 was 11 nm by application of the Scherrer equation. Scherrer equation
is D = Kλ/βcosθ, where D is the crystalline size (nm), K presents as Scherrer, which
has a value of 0.89, λ is the wavelength (nm), β is the observed peak width, and θ is
the diffraction angle.
122
Fig. 2 SEM images of (a) ppt-5.0 and (b) CrO(OH)-5.0.
Fig. 2 compares the SEM images of materials synthesised at pH = 5.0 before and
after the hydrothermal treatment at 170 °C. As shown in Fig. 2a, the colloidal
precipitate appears to be non-crystallized lumpy aggregates. A similar SEM
morphology of natural amorphous -CrO(OH) was reported by Shpachenko et al.
when they studied the genesis and compositional characteristics of natural
-CrO(OH). [21] After 12-hour hydrothermal treatment, the morphology of the
crystallized nanostructures of CrO(OH) was observed to be nano-particles (Fig. 2b).
The average diameter of these spherical nanoparticles was 50 nm.
As discussed above, after a hydrothermal treatment for 12h, only the precipitate
obtained at acidic conditions (pH = 5.0) transformed into crystalline CrO(OH)
material. In comparison, the precipitates obtained at pH = 7.5 and 10.0 were
hydrothermally treated for a longer period of time. The products after 4-day
treatment were characterised and shown to be CrO(OH) by XRD, Fig. 3. Peaks of
both XRD patterns can be well indexed and matched with the peaks of the
grimaldiite standard pattern (JCPDS card No. 01-070-0621). This indicates that a
much longer hydrothermal duration time is required to promote the conversion to
crystalline CrO(OH) from the precipitates obtained in neutral (pH = 7.5) and alkaline
(pH = 10) conditions. However the CrO(OH) product from alkaline precipitation
condition shows a much better crystallinity. On the basis of the broadening of
diffraction lines, it was estimated that the mean crystallite size of sample
CrO(OH)-10.0 was 12 nm.
123
Fig. 3 XRD patterns of CrO(OH)-10.0 and CrO(OH)-7.5. XRD pattern from

literature: JCPDS card No. 01-070-0621 Grimaldiite.
In the XRD pattern of CrO(OH)-7.5, low intensity of XRD reflections were found at
positions exactly corresponding to grimaldiite structure. However, diffraction peaks
were observed with lager full width at half-maximum (FWHM), which indicated that
the crystalline size of CrO(OH)-7.5 was much smaller than that of CrO(OH)-10.0,
even after 4-days hydrothermal treatment.
We note that particle size differs from crystallite size by definition; however, in the
case of very small particles their size is often comparable with the crystallite size, as
estimated by the Scherrer formula. Typical TEM images of the three crystalline
CrO(OH) materials synthesised under different conditions are shown in Fig. 4. The
resulting samples from acidic and alkaline conditions appear as nano-plates. The
average size in diameter for sample CrO(OH)-5.0 is measured to be 10 nm, while for
CrO(OH)-10.0 the average measured size is 12 nm. This slight increase in size is
considered to be due to longer hydrothermal crystal growth duration. It is noted that
size of the crystals observed under transmission electron microscope is in excellent
agreement with the results calculated by Scherrer equation determined by XRD data.
For a further study on the morphology of these CrO(OH) nanocrystals, high

resolution TEM (HRTEM) with a double tilt holder was utilised. Detailed high
resolution imaging micrographs were included in the supporting information.
124
Fig. 4c presents one HRTEM image for CrO(OH)-7.5 and the SAED of the
corresponding area has been inserted. It is revealed that no extra dimensionality of
the nano-platelets can be seen, which meant that the nanoparticles were in a plate
shape, instead of being bulk crystals. The particles size of CrO(OH)-7.5 derived from
this HRTEM image was measured to be 4 nm, which was in excellent agreement
with the results based on the Scherrer equation with presented XRD pattern.
Moreover, area was found showing no interference patterns under the HRTEM
detection, indicating there was an amorphous fraction in the sample. For
CrO(OH)-5.0 the selected area electron diffraction (SAED) pattern of the
corresponding area in Fig. 4a appears in rings, which indicates that the hydrothermal
synthesis yielded polycrystalline nanomaterials of CrO(OH).
Fig. 4 (a) TEM image of CrO(OH)-5.0; (b) SAED result of the corresponding area in
Fig.4 (a); (c) TEM image of CrO(OH)-7.5 and its SAED result (inset); (d) TEM
image of CrO(OH)-10.0 and its SAED result (inset).
125
The nano-plates of synthesised CrO(OH) exhibited excellent crystallinity, which is

confirmed by the results of the XRD investigation. The SAED pattern (Fig. 4b)
matched well with that in the XRD study, and the indexing of the ring pattern
indicated that the nano-plates possessed a crystal structure consistent with the
rhombohedral form of CrO(OH). It is observed that there are individual bright spots
in the rings, which indicate large and well formed crystals in the sample. This
observation is in harmony with the corresponding TEM image.
3.2 Surface analysis
3.2.1 N2 adsorption studies
Fig. 5 N2 adsorption/desorption isotherms for CrO(OH)-5.0, CrO(OH)-7.5 and

CrO(OH)-10.0.
126
The N2 adsorption-desorption measurement at a liquid N2 temperature of 77K was

applied to study the porosity and textural properties of the CrO(OH) nanomaterials
precipitated under different pH conditions. Fig. 5 depicts the N2
adsorption-desorption isotherms of all the samples, all of which exhibit a type IV
sorption behaviour, indicating the presence of mesoporous structural characteristic
according to the classification of IUPAC. [39] Type IV isotherm possesses a
hysteresis loop, the lower branch of which represents measurements obtained by
progressive addition of vapour to the system and the upper branch by progressive
withdrawal. [40] The apparent step in the adsorption branch combined with the sharp
decline in the desorption branch is an obvious verification of the present of
mesoporosity.
Fig. 6 Pore size distribution study for CrO(OH)-5.0, CrO(OH)-7.5 and

CrO(OH)-10.0.
127
As shown in Fig. 5, the adsorption of N2 of CrO(OH)-7.5 is much higher than that of

the other two samples, which indicates that CrO(OH)-7.5 possesses a higher specific
surface area. It is known that the specific surface area, pore volume and pore size
distribution can be calculated and compared from the N2 adsorption isotherms of
materials. [40] A pore size distribution is presented in Fig. 6, which shows that the
distribution of pore size is mostly in the mesopore region (pore size between 2 and
50 nm. The textural properties of CrO(OH)-7.5 synthesised under a neutral condition
are given in Table 2 as follows: a BET specific surface area of 384 m2∙g-1 with a BJH
mean pore diameter of 3.5 nm (within mesopore region) and desorption cumulative
pore volume of 0.33 cm3∙g-1.
Table 2 BET specific surface area (SBET), pore volume (Vp), and pore diameter for
synthesised CrO(OH) nanomaterials.
Mean D (nm)
2 -1 a 3 -1
Sample ID SBET (m g ) VP, (cm g )
BETb BJHc
CrO(OH)-5.0 119.09 0.25 8.5 6.7
CrO(OH)-10.0 114.63 0.26 8.9 6.9
CrO(OH)-7.5 384.14 0.33 3.8 3.5
a b
BJH desorption cumulative pore volume of pores between 1.7 and 300 nm in diameter.
c
Adsorption average pore diameter (4V/A by BET). Barrett-Joyner-Halenda (BJH)
desorption average pore diameter (4V/A).
CrO(OH)-5.0 and CrO(OH)-10.0, precipitated respectively under the acidic and

alkaline conditions, present similar patterns of N2 adsorption isotherm and pore size
distribution to those of sample CrO(OH)-7.5. However, their textural properties show
the following changes: CrO(OH)-5.0 has a BET specific surface area of 119 m2∙g-1
with a BJH mean pore diameter of 6.7 nm (within mesopore region) and desorption
cumulative pore volume of 0.25 cm3∙g-1, while CrO(OH)-10.0 has a BET specific
surface are of 115 m2∙g-1 with a BJH mean pore diameter of 6.9 nm (within mesopore
region) and desorption cumulative pore volume of 0.26 cm3∙g-1. These changes can
be attributed to the difference of the crystalline size for the nanomaterials: the
increase of the crystals/particle size leads to decrease in the specific surface area and
128
cumulative pore volume, but increase in the mean pore diameter. By comparison, the
calculated mean pore size of materials is found to be slightly smaller than the
crystalline size observed from XRD and TEM studies; since it is the inter crystalline
porosity that is studied by this N2 adsorption-desorption measurement.
3.2.2 X-ray photoelectron spectroscopy (XPS)
To further determine the surface chemical composition and the chemical states of the
prepared nanomaterials, X-ray photoelectron spectroscopy (XPS) analysis was
carried out. XPS has been widely applied for the investigation of the top few layers
of material surfaces with partially filled valence band. Spectral results from the
interaction with metal valence electrons can provide chemical environment
information about the metal ions. For the transition metal element chromium, high
resolution Cr 2p spectrum shows spin-orbit splitting into 2p1/2 and 2p3/2 components,
[41,42] and both components qualitatively contain the same chemical information.
Therefore, in this study only the higher intensity Cr 2p3/2 bands were curve-fitted and
discussed.
The high-resolution XPS spectra of Cr 2p3/2 and O1s of the chromium nanomaterials
synthesised under various conditions are compared in Fig. 7, and their curve-fitted
results are summarised in Table 3. All the spectra were referenced to the adventitious
carbon of binding energy (BE) 285.0 eV.
Table 3 Results for curve-fitted binding energies and their atomic contents (at.%) of
highly resolved Cr 2p3/2 and O 1s XPS spectra shown in Fig. 7 for sample ppt-5.0,
CrO(OH)-5.0, CrO(OH)-7.5and CrO(OH)-10.0.
Cr 2p3/2 (eV) O 1s (eV)
Samples
Cr1 Cr2 Cr3 O1 O2 O3
576.9 578.1 579.4 530.3 531.7 533.0
ppt-5.0
(40.8%) (44.7%) (14.5%) (7.0%) (45.6%) (47.4%)
576.2 577.4 578.6 530.2 531.4 532.4
CrO(OH)-5.0
(41.0%) (48.3%) (10.7%) (40.4%) (40.1%) (19.5%)
576.6 577.8 579.1 530.6 531.7 532.8
CrO(OH)-7.5
(38.5%) (48.7%) (12.8%) (28.7%) (42.9%) (28.4%)
576.4 577.6 579.1 530.4 531.6 532.6
CrO(OH)-10.0
(41.7%) (48.2%) (10.1%) (39.7%) (39.6%) (20.7%)
129
High resolution XPS spectra for Cr 2p are often involved because of the complex
multiplet and spin-orbit splitting; however their decomposition can reveal all the
component peaks. XPS spectra may be fitted in different ways and this may affect
the interpretation of the XPS data. Studies were performed on simple compounds to
obtain reference data for the proper peak assignment. [28]
In this study, as shown in Fig. 7, the precipitate sample ppt-5.0 and the three
hydrothermally treated samples: CrO(OH)-5,0, CrO(OH)-7.5 and CrO(OH)-10.0
exhibit XPS Cr 2p3/2 spectra that are very similar in nature to each other with
virtually identical peak profiles. Three peaks are required to curve fit the Cr 2p3/2
XPS spectra of all the 4 samples, which indicates that there were three chemical
states for chromium.
The first component (Cr 1) at around 576.4 eV used for curve fitting is assigned to
Cr3+ trivalent oxide state, a second one (Cr 2) at around 577.6 eV is associated to the
trivalent hydroxide state, which has been well documented. [43-45] The third fitted
binding energy with atomic content of ~10% is found at round 579.0 eV, which is
slightly higher than the reported binding energy for normal Cr (III) from chromium
hydroxide, and much lower than that for Cr (VI). [46,47] However, it is reported that
the binding energy for chromium could be slightly higher when the element has a
more complex load in the compound. [48,49] Therefore, the third fitted component
(Cr 3) observed in this study is considered to be trivalent chromium combined with
additional ligands, such as OH- and H2O ligands present in the surface of the
synthesised materials.
The observed slight increase in the Cr 2p3/2 binding energies for ppt-5.0 can also be
explained by the more complex load to chromium in this precipitate sample before
hydrothermal treatment. The atomic ratios for three kinds of fitting Cr components
are very close, where Cr 2 has the biggest portion.
130
Fig. 7 XPS high resolution spectra of Cr 2p3/2 and O 1s for ppt-5.0, CrO(OH)-5.0,
CrO(OH)-7.5 and CrO(OH)-10.0
As shown in Fig. 7, the O 1s spectrum for CrO(OH)-5.0 could also be fitted with
three peaks: O1 at 530.2 eV corresponding to O2- in CrO(OH), O2 at 531.4 eV
corresponding to OH- in oxyhydroxide or hydroxide, and a third peak, O3 at 532.4
eV corresponding to oxygen in water, which are in excellent agreement with the
values reported in literature. [50,47,51]
The qualitative analysis shows that O1 and O2 obtained similar ratios (40.0% and
40.1%) in the sample, which is consistent with their atom ratio of 1:1 in CrO(OH).
This illustrates the main composition in CrO(OH)-5.0 is chromium oxyhydroxide,
with minimal chromium hydroxide.
The O 1s spectrum for CrO(OH)-10.0 shows similar shape and curve fitted results as
CrO(OH)-5.0. The absence of significant binding energy shifts between these two
chromium nanomaterials suggests that the chemical nature of the elements in the
top-most surface layers is very similar, and that CrO(OH)-10.0 mainly contains
CrO(OH) as well.
131
In the O 1s spectra for ppt-5.0 and CrO(OH)-7.5, three peaks can also be fitted and
assigned to O2-, OH- and H2O, respectively. Their binding energies are slightly
higher than that of CrO(OH)-5.0.
However, a decrease of atomic contents for O1 and an increase of atomic contents

for O2 are observed in CrO(OH)-7.5, which suggests a lower content of CrO(OH) in
the sample. One possible interpretation of this CrO(OH) content variation is that the
amorphous precipitates obtained at neutral condition (pH = 7.5) require longer
hydrothermal treatment to form a better CrO(OH) phase. This finding is consistent
with the XRD and TEM observations, which reflect the fact that CrO(OH)-7.5
contains non-CrO(OH) amorphous phase which is not very well crystalline.
Moreover, in the O 1s spectrum for ppt-5.0, a low atomic content of O1 is observed

(7%), while the atomic percentage for O2 is 45.6%. Therefore, without hydrothermal
treatment, at pH=5.0, the formula of the amorphous materials is represented by
CrO0.13(OH)1.87. High atomic contents for O2 from OH- and O3 from H2O are
observed, which confirm that the precipitate contains large amounts of hydroxide and
water in the structure.
3.3 Thermo gravimetric analysis
The thermogravimetric and differential thermogravimetric analysis of the synthesised

chromium materials are presented in Fig. 8, which shows the TG and dTG curves for
samples obtained in different conditions: (a) pH = 5.0, precipitate without
hydrothermal treatment (HT), noted as sample A; (b) pH = 5.0, HT for 12h, noted as
sample B; (c) pH = 7.5, HT for 4 days, noted as sample C; (d) pH = 10.0, HT for 4
days, noted as sample D. Thermal decomposition properties of the synthesised
materials are discussed in details as follows.
Fig. 8a shows the thermal decomposition of amorphous chromium hydroxide gel

precipitated under pH = 5.0 at room temperature (A). Two sharp dTG peaks are
observed at 149 °C and 177 °C with mass losses of 6.94% and 21.54%, respectively.
These two mass loss steps are attributed to the loss of water in the structure.
132
(a)
(b)
133
(c)
(d)
Fig.8 Thermogravimetric analyses (TGA) of (a) ppt-5.0, (b) CrO(OH)-5.0, (c)

CrO(OH)-7.5 and (d) CrO(OH)- 10.0.
134
A second mass loss step is observed at 439 °C with a mass loss of 5.75%, which is
attributed to the dehydroxylation of the compound. A minor mass loss observed at 77
°C is attributed to the desorption of water. Ratnasamy and Leonard [36] reported that
below 200 °C water molecules were eliminated from the amorphous hydroxide
precursor precipitated from Cr(NO3)3 solution with NH4OH, and a crystalline Cr2O3
phase was produced at 400 °C. This finding is in excellent agreement with the results
in this study. In the dTG curve of this experiment, the shoulder at 401 °C can be
assigned to the dehydration of the small amount of amorphous chromium hydroxide
to chromium oxide.
After the hydrothermal treatment of the chromium hydroxide gel, the product (noted
as sample B) shows a totally different thermal decomposition pattern in Fig. 8b. As
confirmed from XRD (Fig. 1), this hydrothermal product is crystalline CrO(OH)
nanomaterial. In the thermal study, the major mass loss steps occur at 444 °C and
463 °C with a total mass loss of 10.52%. These mass loss steps are attributed to the
dehydroxylation of the compound according to the reaction 2CrO(OH) → Cr2O3 +
H2O. The theoretical mass loss for this reaction is 10.59%, which is consistent with
our experimental mass loss of 10.52%. The minor mass losses observed below 110
°C are possible attributed to desorption of water.
Fig. 8c presents the thermo gravimetric analyses of CrO(OH) obtained after 4-days
of hydrothermal treatment from precipitate at pH = 7.5, which is noted as sample C.
The dTG curve shows a large band at 396 °C with two broad shoulders. The main
mass loss of sample C at 396 °C is attributed to the dehydroxylation of amorphous
chromium hydroxide to crystalline chromium oxide, as discussed above. The
shoulder at 276 °C is attributed to the formation of CrO(OH) from chromium
hydroxide which was X-ray amorphous.
It is suggested that surface formation of CrO(OH) during the heating of chromium

hydroxide at lower temperatures occur. [30] Another shoulder peak in the dTG curve
of sample C appears at 438 °C. This mass loss is assigned to the dehydroxylation of a
small amount of chromium oxy-hydroxide to crystalline chromium oxide.
135
Fig. 9 Mass spectrometric analysis associated with the thermal decomposition

process for sample CrO(OH)-10.0.
Sample D synthesised at pH 10.0 shows a similar dTG pattern as sample B. XRD

showed these samples had a more crystalline CrO(OH) phase. The dTG curve of
sample D shown in Fig. 8d, and the associated mass spectrometric analysis is
reported in Fig. 9. The main mass losses at 436 °C and 458 °C are attributed to the
dehydroxylation of CrO(OH) to Cr2O3, which is confirmed by the maxima for ion
current curves for H2O, OH, and O (Fig. 9). A small mass loss of 0.91% at 238 °C is
observed, which is attributed to the decomposition of nitrate impurity. Such
decomposition is confirmed by the ion current curves of NO where a maximum at
238 °C is observed. The mass loss step at 318 °C is assigned to the release of CO2,
confirmed by the ion current curves of CO2 and C.
136
Table 4 Summary of peaks shown in dTG curves for synthesised chromium materials.
ppt-5.0 CrO(OH)-5.0 CrO(OH)-7.5 CrO(OH)-10.0
77 °C 45 °C, 84 °C, 109 °C 40 °C 50 °C, 80 °C
149 °C, 177 °C
276 °C 238 °C
315 °C 318 °C
401 °C 396 °C
439 °C 444 °C, 463 °C 438 °C 436 °C, 458 °C
643 °C
Peaks shown in dTG curves of the four samples are summarised in Table 4. The four
samples all present a dTG peak at around 440 °C, at which CrO(OH) losses hydroxyl
groups which form Cr2O3.
Sample B and D, are more crystalline (XRD), show an additional dehydroxylation

peak at around 460 °C associated with CrO(OH). Sample A and C show peaks at
around 400 °C, which are assigned to the dehydroxylation of amorphous chromium
hydroxide.
These samples were obtained by precipitation at room temperature from chromium

nitrate and ammonia. Similar gel materials have been reported by Milligan [37] and
Ratnasamy [36]. Milligan‟s study found that there was a certain amount of chromium
trihydroxide (Cr(OH)3) in the sample. A mass loss at around 315 °C for sample B
and D, but not for sample C, is assigned to the release of CO2 (identified by MS)
from an impurity.
137
Fig. 10 XRD patterns of products after TGA from ppt-5.0, CrO(OH)-5.0,

CrO(OH)-7.5 and CrO(OH)-10.0. XRD patterns from literature: JCPDS card No.
01-084-1616 Cr2O3.
The thermo gravimetric analyses of the samples up to 1000 °C all were found to
transform to a well crystalline Cr2O3 phase (XRD), as shown in Fig. 10. All the
diffraction peaks of products were well indexed using a rhombohedral system of
lattice for Cr2O3, with space group of R-3c (JCPDS card, No. 01-084-1616).
It is noticed that all these thermal products have very high crystallinity and purity,
even from the colloidal precipitate (sample A). It is reported that when chromium
hydroxide materials are heated, the amorphous material can be converted into
crystalline Cr2O3 of around 400 °C. [36,52]
However, the thermal product from sample C has a slightly lower crystallinity. It is
suggested that the pH value that the sample precipitates at can affect the crystallinity
of the synthesised material.
138
4. CONCLUSIONS
Chromium oxyhydroxide nanomaterials were obtained by soft-chemistry methods

under various conditions. A combination of techniques were used to study
morphology and structure of the as-prepared nanomaterials, including XRD, SEM,
TEM, BET specific surface area analysis, XPS and thermo gravimetric analyses. The
pH value in precipitate process was proven to be critical for the formation and
crystallinity of the synthesised nanomaterials.
The CrO(OH) nanomaterials were found to form most easily with an acidic
precipitate process. The synthetic chromium oxyhydroxide was identified with a
plate-like morphology of ~11 nm in size. N2 adsorption study is proven as a facile
way to provide information on textural properties of the synthesised compounds.
XPS measurements for the as-prepared chromium oxyhydroxide nanomaterials allow
us to develop a view to determine spectral characteristics and to identify element
chemical environment in the compounds. It is also reported that the dehydroxylation
of the synthetic chromium oxyhydroxides occurs at ~460 °C, while chromium
hydroxide impurities decomposed at ~400 °C.
ACKNOWLEDGEMENTS

Technology Inorganic Materials Research Program of the School of Physical and
Chemical Sciences is gratefully acknowledged. The Australian Research Council
(ARC) is thanked for funding the instrumentation. One of the authors (JY) thanks
the Queensland University of Technology for a postgraduate doctoral scholarship.
Thanks are also given to Dr. B. Wood for technical and computing support in the
XPS study.
139
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143
SUPPORTING INFORMATION
A double tilt holder was utilised to take the HRTEM images of sample
CrO(OH)-10.0. The holder can be tilted in two directions:  and . The following
images of one area were taken from the positions of different tilted angles:
(a)  = 0°, = 0°
(b)  = 0°, = 10°
(c)  = -20°, = 0°
(d)  = -60°, = 0°
144
CHAPTER 6.2
TRANSITION OF SYNTHETIC
CHROMIUM OXIDE GEL TO
CRYSTALLINE CHROMIUM
OXIDE: A HOT-STAGE RAMAN
SPECTROSCOPIC STUDY
Yang, J.; Martens, W. N.; Frost, R. L., "Transition of synthetic chromium oxide gel to
crystalline chromium oxide: a hot-stage Raman spectroscopic study." Journal of
Raman Spectroscopy 2010, in press. DOI:10.1002/jrs.2794.
145

expertise;
academic unit, and
Transition of Synthetic Chromium Oxide Gel to Crystalline Chromium Oxide: A

Hot-stage Raman Spectroscopic Study
Yang, J.; Cheng, H. F.; Martens, W. N.; Frost, R. L., Journal of Raman Spectroscopy 2010, in
press. DOI:10.1002/jrs.2794.

Hongfei Cheng Aided in data presentation and manuscript revising.

and editing.

authorship.
____________________ ______________________ ____________________

Name Signature Date
146
RESEARCH HIGHLIGHTS
The article studied the transition of synthetic chromium oxide gel to crystalline
chromium oxide using Raman spectra at different temperatures based on the results
of thermogravimetric analysis. The evolution of the Raman spectra versus
temperature was carefully described as well as band assignments. Two bands were
observed at 849 and 735 cm-1, which were separately assigned to symmetric
stretching modes of O-CrIII-OH and O-CrIII-O. With the temperature increased, the
intensity of these bands changed, which was attributed to the loss of OH groups and
formation of O-CrIII-O units in the material structure. The thermal product of the
synthetic chromium oxide gel in N2 atmosphere was found to be crystalline Cr2O3.
147
TRANSITION OF SYNTHETIC CHROMIUM

OXIDE GEL TO CRYSTALLINE CHROMIUM
OXIDE: A HOT-STAGE RAMAN
SPECTROSCOPIC STUDY
Jing Yang, Hongfei Cheng, Wayde N. Martens and Ray L. Frost*

r.frost@qut.edu.au
Received: July 6, 2010

Accepted: August 02, 2010
Published Online: September 21, 2010
ABSTRACT
Chromium oxide gel material was synthesised and appeared to be X-ray amorphous.
The changes in the structure of the synthetic chromium oxide gel were investigated
using hot-stage Raman spectroscopy based upon the results of thermogravimetric
analysis. The thermally decomposed product of the synthetic chromium oxide gel in
nitrogen atmosphere was confirmed to be crystalline Cr2O3 as determined by the
hot-stage Raman spectra. Two bands were observed at 849 and 735 cm-1 in the
Raman spectrum at 25 °C, which were attributed to the symmetric stretching modes
of O-CrIII-OH and O-CrIII-O. With temperature increase, the intensity of the band at
849 cm-1 decreased, while the band at 735 cm-1 increased. These changes in intensity
are attributed to the loss of OH groups and formation of O-CrIII-O units in the
structure. A strongly hydrogen bonded water H-O-H bending band was found at
1704 cm-1 in the Raman spectrum of the chromium oxide gel, however this band
shifted to around 1590 cm-1 due to destruction of the hydrogen bonds upon thermal
treatment. Six new Raman bands were observed at 578, 540, 513, 390, 342 and 303
cm-1 attributed to the thermal decomposed product Cr2O3.
148
The use of the hot-stage Raman microscope enabled low-temperature phase changes
brought about through dehydration and dehydroxylation to be studied.
KEYWORDS
Hot-stage; Raman Spectroscopy; Chromium Oxide Gel; Grimaldiite; Chromium

Oxide; Eskolaite
1. INTRODUCTION
Because of their high surface area, chemical and thermally stable properties and
mesoporous properties, transition metal oxides have been extensively used as carriers
and support for a variety of industrial catalysts at high temperature as well as low
temperature.1-3 Special attention has been focused on the formation and properties
of chromium oxide (Cr2O3), which is a mineral known as eskolaite. Chromium oxide
is important in high-temperature resistant materials,4, 5
liquid crystal displays,6, 7
catalysts,1, 3
and so on. A solid catalyst usually requires thermal treatment for
attributing the desired specific structural and textural character to be finished catalyst
which is also related to be activity and stability.8 Therefore it is important to
understand the thermal transformation for precipitated chromium gel material, which
is a precursor for Cr2O3 catalyst materials.
Raman spectroscopy has proven to be a very useful tool for studying materials.9-11
Raman spectroscopy allows the possibility of studying the structure at the molecular
level. Many minerals both natural and synthetic lend themselves to analysis by
Raman spectroscopy.10, 12-14
The combination of Raman spectroscopy with a
hot-stage lends itself as the technique of choice for studying the chemical reactions
during dehydration and dehydroxylation. The advantage of this technique is that the
changes in molecular structure can be followed in situ and at the elevated
temperatures. Spectroscopic studies with a hot-stage to reveal the thermal transition
from chromium oxide gel material to chromium oxides are limited. Our interest in
materials for industrial applications led our motivation for this research, as did the
search for fundamental knowledge of thermal stability of materials using hot-stage
Raman spectroscopy.15-17
149
This paper is a part of a vibrational spectroscopic investigation on synthetic

transition metal catalyst materials. The aim of this paper is to study the thermal
transition process of amorphous chromium oxide gel to crystalline chromium oxide
materials. Hot-stage Raman spectroscopy allows us to monitor the changes occurring
in the molecular structure during the thermal transition procedure. In the present
work, the authors report the hot-stage Raman spectra of a synthetised chromium
oxide gel as a function of temperature, and determine the transition to chromium
oxide, thus relating the spectra to the structure of the materials.
2. EXPERIMENTAL
2.1 Synthesis of chromium oxide gel
15 g of Cr(NO3)3•9H2O (laboratory reagent) was dissolved in 75 mL ultrapure water,

and 28% ammonia (analytical reagent) was diluted into 10% solution. At room
temperature, the ammonia solution (10%) was added at a rate of 1 mL min-1 into the
chromium ion solution with vigorous stirring. Ammonia solution addition ceased
when the pH of the reaction mixture reached 5.0. The reaction mixture was kept
stirring constantly in the air at room temperature for 0.5 h. The obtained gel-like
mixture was centrifuged and washed at 13000 rpm for 10 mins, 3 times. The
washed gel was dried at 65 ºC overnight, and denoted as “chromium oxide gel”.

from a line focused PW3373/10 Cu X-ray tube, operating at 40 kV and 40 mA, with
Cu K radiation of 1.540596 Å. The incident beam passed through a 0.04 rad soller
slit, a 1/2 °divergence slit, a 15 mm fixed mask, and a 1 °fixed antiscatter slit.
and sputter-coated with a thin layer of gold.
150
The synthetic chromium oxide gel was placed on the stage of an Olympus BHSM
microscope, equipped with 10x and 50x objectives and part of a Renishaw 1000
Raman microscope system, which also includes a monochromator, a filter system
and a Charge Coupled Device (CCD). Raman spectra were excited by a 633 nm laser
at a resolution of 4 cm-1 in the range between 100 and 4000 cm-1. Repeated
acquisition using the highest magnification was accumulated to improve the
signal-to-noise ratio. Spectra were calibrated using the 520.5 cm-1 line of a silicon
wafer. Details of the technique have been published by the authors.18-23
Spectra at elevated temperatures were obtained using a Linkam thermal stage

(Scientific Instruments Ltd., Waterford Surrey, England). Spectra were taken from
room temperature (25 ºC) up to a temperature of 550 ºC in a flowing nitrogen
atmosphere. Temperatures for the Raman spectroscopic study were selected based
on our previous studies on the thermogravimetric analysis of the synthetic chromium
oxide gel.
Spectral Manipulation such as baseline adjustment, smoothing and normalisation was

performed using GRAMS® software package (Galactic Industries Corporation
Salem, NH, USA).
bands used for the fitting process.
The Lorentz-Gauss ratio was maintained at values greater than 0.7 and fitting was
undertaken until reproducible results were obtained with squared correlations of r2
greater than 0.997.
151
3.1 Phase and Raman studies of the precipitated Cr-gel
The chromium oxide gel material was obtained by recovering the precipitate from
the reaction of Cr(NO3)3 and NH4OH solutions at pH 5.0.
No peaks were observed for this precipitated material in its XRD study (Fig. 1a),
which indicated that the precipitated chromium oxide gel was X-ray non-diffracting.
This agreed with published results, which reported that the material obtained from
the neutralisation of Cr3+ ions was usually amorphous or poorly crystalline.24, 25
Fig. 1b displays the SEM image of the Cr oxide-gel material, which appeared to be a
non-crystalline lumpy aggregate.
(a) (b)
Fig. 1 (a) XRD pattern of the precipitated Cr-gel material and a reference pattern:
JCPDS card No. 01-070-0621 CrO(OH) and (b) SEM image of the precipitated
Cr-gel material
In the region between 2000 and 100 cm-1 shown as Fig. 2, the Raman spectrum taken
at room temperature (25 °C) of the synthetic chromium oxide gel was characterised
by a sharp intense band at 849 cm-1. The band was assigned to be the symmetric
stretching mode of O-CrIII-OH bonds.
152
100 to 2000 cm-1 at 25 °C
The presence of a shoulder at 735 cm-1 was due to the symmetric stretching modes of
O-CrIII-O. These two bands were too low in wavenumber to be associated with
[CrVIO4] units, which were reported at around 899 cm-1 by Maslar et al.26-28
In the lower wavenumber region, a band at 439 cm-1 was observed and assigned to be
antisymmetric stretching modes of O-CrIII-O. The band at 258 cm-1 observed for this
Cr-gel material was probably attributable to the bending/deformation modes of
[CrIIIO6] units in the structure. A Raman band was reported at 269 cm-1 for [CrIIIO6]
units in a study on selected chromate minerals.29
It is well known that gel materials are highly hydrated and as such both water and
hydroxyls play a significant role in the structure of gels. It is common for water to
play a major role in the degree of polymerization because of the asymmetric nature
of hydrogen bonding systems.30-33 Water may bond to the interstitial cation or may
simply be held in the structure through hydrogen bonding in the chromium oxide gel
net-work.
A broad band was found at 1704 cm-1 in the Raman spectrum at 25 °C of the
synthetic Cr-gel material. This band is attributed to be H-O-H bending mode of the
very strongly hydrogen-bonded water.
153
The band shifted to lower wavenumbers in the Raman spectra taken at higher
temperatures, which indicated that the hydrogen bonds were destroyed as the
temperature increased.
Another band was observed at 1006 cm-1, which is considered to be due to O-H
deformation modes according to the Raman study on minerals as reported in the
previous work.34, 35 A weak band at 1309 cm-1 is understood to be a combination or
overtone of band at lower wavenumbers.
3.2 Hot-stage Raman spectroscopy for the thermal transition

process
One method of studying the thermal decomposition of precipitated chromium oxide

gel is through the changes in the structure caused by dehydration of the material. The
use of Raman spectroscopy in conjunction with a hot-stage enables the molecular
structural changes to be observed.
Fig. 3 shows the spectra of the Cr-gel material in the region of 2000 to 100 cm-1 as a
function of temperature. The results of the band component analysis of these spectra,
comparing with the spectrum taken at room temperature, are reported in Table 1.
The band at 1704 cm-1, at 25 °C assigned to be very strongly hydrogen-bonded water

H-O-H bending mode, could not be observed in the Raman spectra above 100 °C,
which indicated that after 100 °C a significant amount of water was removed from
the structure as water vapour. Instead, a new band was found at 1579 cm-1 at 130 °C.
This band was proposed to be water H-O-H bending mode of non-hydrogen-bonded
water.
The band intensity decreased significantly when temperature above 130 °C and it is
understood to be due to the escape of H2O trapped in the pores and vacant sites of the
chromium oxide gel structural network when the temperature increased. This band
shifted to higher wavenumbers as the temperature increased, to 1597 cm-1 at 350 °C.
The position of non-hydrogen-bonded H-O-H bending mode in Raman spectrum
reported in this study was in good agreement with that published by Frost and his
co-workers36 in the study of the Zn-Al hydrotalcite.
154
The band attributed to the O-H deformation modes at around 1008 cm-1 can be found
in all the Raman spectra at 25 to 350 °C, before the chromium oxide gel material
completely thermal decomposed to be metal oxide.
Bands at around 845 and 740 cm-1 assigned to be symmetric stretching of O-CrIII-OH
and O-CrIII-O modes showed obvious changes in the Raman spectra at 25 °C to 350
°C. The band at 845 cm-1 decreased, while the band at 740 cm-1 increased in their
relative intensity with the increase of temperature. It is proposed to due that the
O-CrIII-OH vibration modes were transformed to O-CrIII-O vibration modes because
of the dehydroxylation in the structure. This is in accordance with the results from
the thermo gravimetric analyses of this chromium oxide gel, which showed that there
were two large mass loss steps observed at 150 °C and 180 °C due to the dehydration
of the material.
A band at around 435 cm-1, ascribed to the antisymmetric stretching modes of

O-CrIII-O, can also be found in similar positions in all hot-stage Raman spectra from
130 to 350 °C.
The weak, broad band remained in the region of 260-240 cm-1 in all the Raman
spectra at 25 to 350 °C, which is proposed to be associated with the bending modes
of [CrIIIO6] units in the chromium oxide gel structural network. The band increased
in intensity with temperature, which meant that more [CrIIIO6] units in the structure
formed resulted from the dehydroxylation of the Cr-gel material as temperature
increased. More overtone and combination bands were found at 1969, 1858, 1792
and 1195 cm-1 in the Raman spectrum at 350 °C.
155
Fig. 3 Hot-stage Raman spectra of the precipitated Cr-gel material in the region of
100 to 2000 cm-1 from 130 to 350 °C
156
Table 1 Summary of Raman shifts (cm-1) and their assignment for synthetic Cr-gel
and its thermal-decomposed product Cr2O3 in the hot-stage Raman spectroscopic
study.
550 °C
25 °C 130 °C 160 °C 250 °C 350 °C Assignment
(Cr2O3)
1969,
Combinations
1858,
& overtones
1792
Water H-O-H
1704 bending (strongly
hydrogen bonded)
Water H-O-H
1579 1590 1594 1597
bending
1504, 1530, 1544, 1551, Combinations
1309
1335 1288 1330 1195 & overtones
O-H
1006 1009 1007 1009 1008
deformation
578 (Eg)
540 (A1g)
849 841 843 845 842 s (O-CrIII-OH) 513 (Eg)
735 734 740 749 747 s (O-CrIII-O) 390 (Eg)
439 448 435 434 430 as (O-CrIII-O) 342 (Eg)
258 246 249 239 241  ( [CrIIIO6] ) 303 (A1g)

s (symmetric stretching);
as (anti-symmetric stretching);
 (bending/deformation).
157
For a better understanding to the phase identification after heating to this

temperature, XRD was applied to study the samples at this transition stage. Fig. 4
shows the XRD pattern of product from Cr-gel material heated at 350 °C for 4 h. A
crystalline phase was found with the diffraction pattern indexed to rhombohedral
Cr2O3 (JCPDS No. 01-084-0314). This suggests that the nucleation and growth of
Cr2O3 crystals occurred at this stage.
Yet no typical bands of Cr2O3 were observed in the obtained hot-stage Raman
spectrum at 350 °C (Fig. 3), which indicating the material at 350 °C is a mixed phase
of Cr-gel thermal transition species and crystalline Cr2O3 at an early stage of
crystallisation. However the transition species is amorphous or in low concentration
and could not be detected by XRD.
material and a reference pattern: JCPDS card No. 01-084-0314 (Cr2O3).
3.3 Phase, structure and morphology of Cr2O3
The Raman spectrum of the Cr-gel material heated at 550 °C in nitrogen atmosphere
is presented in Fig. 5, which was identical to a typical Raman spectrum of Cr2O3.37, 38
It is understood that thermally treated product in N2 from the Cr-gel was proved to be
crystalline Cr2O3, as confirmed by XRD (Fig. 6).
158
It is important to understand that rhombohedral Cr2O3 has the corundum-type

structure of a space group R-3c, with hexagonal close-packed layers of oxygen atoms
and two thirds of the octahedral holes in between filled by chromium atoms.39, 40 As
shown in the molecular model of Cr2O3 (Fig. 7), there are 6 formula units in the
hexagonal unit cell. It is reported38 that the chromium oxide belongs to the D63d space
group, and the irreducible representations for the optical modes in the crystal are
2A1g + 2A1u+ 3A2g + 2A2u + 5Eg + 4Eu.
Vibrations with symmetry A1g and Eg are Raman active, which means there are seven
Raman-active modes. Only five bands were found in most of the previous works of
Raman studies on chromium oxide37, 38, 41 However, six bands were revealed in this
study, and another weak mode42 below 250 cm-1 was not observed. The most intense
peak at 540 cm-1 was corresponding to the 1 (A1g) vibration mode of chromia.43
Another two sharp peaks at 578 and 342 cm-1, as well as two weak peaks at 513 and
342 cm-1 were due to the Eg vibration modes. A sharp peak at 303 cm-1 was attributed
to A1g mode.
100 to 2000 cm-1 at 550 °C
159
material and a reference pattern: JCPDS card No. 01-084-0314 (Cr2O3).
Fig. 7 Schematic of Cr2O3 in rhombohedral structure (space group R-3c)
160
4. CONCLUSIONS
The chromium oxide gel material was obtained by precipitation from the reaction of
Cr(NO3)3 and NH4OH solutions at pH 5.0. The transition of the synthetic chromium
oxide gel to crystalline Cr2O3 was followed by hot-stage Raman spectroscopy up to
550 °C. The changes in the structure of the material in the dehydration and
dehydroxylation processes were determined in detail by hot-stage Raman
spectroscopy.
The Raman spectrum of the synthetic Cr oxide-gel material was characterised by an

intense peak at 849 cm-1 with a shoulder at 735 cm-1. These two bands were
separately assigned to be O-CrIII-OH and O-CrIII-O symmetric stretching modes.
These bands changed in their relative intensity with the temperature increase and the
loss of hydroxyl units. Part of the water in the synthetic Cr-gel network structure
was released before 100 °C with the Raman band shift for water H-O-H bending
modes from 1704 to round 1590 cm-1. In the low-wavenumber region, a band at 439
cm-1 was ascribed to the anti-symmetric stretching modes of O-CrIII-O, and a band at
258 cm-1 was due to the bending modes of [CrIIIO6] units of the chromium oxide gel
structural network. These bands were observed up to 350 °C.
Raman spectroscopy confirmed that the synthetic Cr-gel material was converted to
be crystalline Cr2O3 after thermally treated up to 550 °C. Six typical bands were
observed for the thermal product Cr2O3 at Raman shifts (cm-1) of 578 (Eg), 540 (A1g),
513 (Eg), 390 (Eg), 342 (Eg) and 303 (A1g).
ACKNOWLEDGMENTS

Technology Chemistry Discipline is gratefully acknowledged. The Australian
Research Council (ARC) is thanked for funding the instrumentation. One of the
authors (JY) is grateful to the Queensland University of Technology Chemistry
Discipline for the award of an international doctoral scholarship.
161
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164
CHAPTER 6.3
TRANSITION OF CHROMIUM
OXYHYDROXIDE
NANOMATERIALS TO
CHROMIUM OXIDE: A
HOT-STAGE RAMAN
SPECTROSCOPIC STUDY
Yang, J.; Martens, W. N.; Frost, R. L., "Transition of chromium oxyhydroxide

nanomaterials to chromium oxide: a hot-stage Raman spectroscopic study." Journal
of Raman Spectroscopy 2010, in press. DOI: 10.1002/jrs.2773.
165

expertise;
academic unit, and
Transition of Chromium Oxyhydroxide Nanomaterials to Chromium Oxide: A Hot-stage

Raman Spectroscopic Study
Yang, J.; Martens, W. N.; Frost, R. L., Journal of Raman Spectroscopy 2010, in press. DOI:
10.1002/jrs.2773.


and editing.

authorship.
____________________ _____________________ ____________________

Name Signature Date
166
RESEARCH HIGHLIGHTS
The article reports the transition of chromium hydroxide nanomaterials to chromium

oxide using XRD, TEM and hot-stage Raman spectroscopy. Good quality Raman
spectra displayed the structure revolution of the synthetic CrO(OH) nanomaterials
during heating from room temperature to 550 ºC. Raman spectrum of CrO(OH) was
characterised by two intense bands at 823 and 630 cm-1 attributed to CrIII-O symmetric
stretching mode and the band at 1179 cm-1 due to CrIII-OH deformation mode. Upon
heating to 350 ºC, new Raman bands were observed at 599, 542, 513, 396, 344 and 304
cm-1, which were typical bands of Cr2O3.
167
TRANSITION OF CHROMIUM
OXYHYDROXIDE NANOMATERIALS TO
CHROMIUM OXIDE: A HOT-STAGE RAMAN
SPECTROSCOPIC STUDY
Jing (Jeanne) Yang, Wayde N. Martens and Ray L. Frost*

r.frost@qut.edu.au
Received: May 31, 2010

Accepted: July 08, 2010
Published Online: August 28, 2010
ABSTRACT
The transition of disc-like chromium hydroxide nanomaterials to chromium oxide

nanomaterials has been studied by hot-stage Raman spectroscopy. The structure
and morphology of -CrO(OH) synthesised using hydrothermal treatment was
confirmed by X-ray diffraction and transmission electron microscopy. The Raman
spectrum of -CrO(OH) is characterised by two intense bands at 823 and 630 cm-1
attributed to ν1 CrIII-O symmetric stretching mode, bands at 1179 cm-1 attributed to
CrIII-OH δ deformation modes. No bands are observed above 3000 cm-1. The absence
of characteristic OH vibrational bands may be due to short hydrogen bonds in the
-CrO(OH) structure. Upon thermal treatment of -CrO(OH), new Raman bands
are observed at 599, 542, 513, 396, 344 and 304 cm-1, which are attributed to Cr2O3.
This hot-stage Raman study shows that the transition of -CrO(OH) to Cr2O3
occurs before 350 °C.
168
KEYWORDS
Raman Spectroscopy; Hot-Stage Raman; Chromium Oxyhydroxide; Chromium

Oxide; Nanomaterials
1. INTRODUCTION
In recent years, nano-scaled inorganic materials, particularly transition metal based

materials, have received more and more attention in industry, in heterogenous
catalysis, as support materials as well as active components. Because of their high
surface area, chemical and thermally stable properties and mesoporous properties,
metal oxides have been extensively used as carriers and support for a variety of
industrial catalysts at high temperature as well as low temperature. Novel
1, 2 3 4, 5
nanomaterials may be based upon boehmite, titania, gallium oxyhydroxide
and designed clay minerals.6, 7 Special attention has been focused on the formation
and properties of chromium oxyhydroxides (CrO(OH)) and chromia (Cr2O3), which
are important in specific applied applications such as in high-temperature resistant
materials,8, 9 liquid crystal displays,10, 11 catalysts,12, 13 and so on. It is well known
that intrinsic properties of inorganic materials are mainly determined by their
composition, structure, crystallinity, size and morphology; great efforts have been
devoted to the investigation of different chromium oxide materials synthesis.14-16 3-5
nm CrO(OH) nanocrystals have been prepared by critical CO2 extraction of the
urea-assisted wet chromia gel mixture,17 and smaller CrO(OH) crystals with size of
1-2 nm were obtained in Chromia aerogel as well.13 To our best knowledge, 10 nm
CrO(OH) synthesised in this work is the biggest hydrothermally synthetic
CrO(OH) nanocrystal size so far.
As the development of all kinds of nanomaterials, technologies meet big challenge to

achieve perfect control on nanoscale-related properties. Modern Raman instruments
offer great advantages to assess some properties that are characteristic of the
nanoscale. Many minerals both natural and synthetic lend themselves to analysis by
Raman spectroscopy.18-21 The combination of Raman spectroscopy and a hot-stage
22-24
has been proved to be a powerful tool for studying the chemical reactions during
dehydration and dehydroxylation. The advantage of this technique is that the changes
in molecular structure can be followed in situ and at the elevated temperatures.
169
The purpose of this study is to elucidate the use of hot-stage Raman spectroscopy to
assess the thermal stability of chromium oxyhydroxide nanomaterials, and to
determine the changes in the molecular structure of the nano-scaled materials as the
chromium oxyhydroxide is thermally treated. In the present work, the authors report
the hot-stage Raman spectra of synthetic chromium oxyhydroxide nanomaterial, and
the transition of CrO(OH) to Cr2O3 relating the spectra to the structure of the
synthesised materials.
2. EXPERIMENTAL
2.1 Synthesis of CrO(OH) nanomaterial
15 g of Cr(NO3)3•9H2O was dissolved in 75 mL ultrapure water, and 28% ammonia

was diluted into 10% solution. At room temperature, the ammonia solution (10%)
was added at a rate of 1 mL/min into the chromium ion solution with vigorous
stirring. Ammonia solution addition ceased when the pH of the reaction mixture
reached 5.0. The reaction mixture was kept stirring constantly in the air at room
temperature for 0.5 h. The obtained gel-like mixture was centrifuged and washed at
13000 rpm for 10 mins, 3 times. The washed wet gel was transferred into a glass
beaker (25 mL). The beaker was placed into a Teflon vessel; 2 mL pure water was
poured into the button of the Teflon. The Teflon vessel was then sealed and placed in
a 170 ºC oven to process a 12 h steam-assisted hydrothermal treatment. Ultra pure
water was added to the resultant product and then collected by centrifugation (at
13000 rpm for 10 mins). The washing process was repeated for 3 times. Sample was
dried at 65 ºC overnight.

from a line focused PW3373/10 Cu X-ray tube, operating at 40 kV and 40 mA, with
Cu K radiation of 1.540596 Å. The incident beam passed through a 0.04 rad soller
slit, a 1/2 °divergence slit, a 15 mm fixed mask, and a 1 °fixed antiscatter slit.
170
2.3 Transmission electron microscopy
A Philips CM20 transmission electron microscope (TEM) at 160 kV was used to

investigate the morphology of the as-prepared sample. The sample was ultrasonically
dispersed in absolute ethanol solution, and then dropped on copper grid, which dried
in the air.
The crystals of CrO(OH) were placed and oriented on the stage of an Olympus
BHSM microscope, equipped with 10x and 50x objectives and part of a Renishaw
1000 Raman microscope system, which also includes a monochromator, a filter
system and a Charge Coupled Device (CCD). Raman spectra were excited by a 633
nm laser at a resolution of 2 cm-1 in the range between 100 and 4000 cm-1.
Repeated acquisition using the highest magnification was accumulated to improve
the signal-to-noise ratio. Spectra were calibrated using the 520.5 cm-1 line of a silicon
22-27
wafer. Details of the technique have been published by the authors. Spectra at
elevated temperatures were obtained using a Linkam thermal stage (Scientific
Instruments Ltd., Waterford Surrey, England). Spectra were taken from room
temperature (25 ºC) up to a temperature of 550 ºC in a flowing nitrogen atmosphere.
Spectral Manipulation such as baseline adjustment, smoothing and normalisation was
performed using GRAMS® software package (Galactic Industries Corporation
Salem, NH, USA).
bands used for the fitting process. The Lorentz-Gauss ratio was maintained at values
greater than 0.7 and fitting was undertaken until reproducible results were obtained
with squared correlations of r2 greater than 0.996.
171
3.1 Phase structure and morphology of the synthetic -CrO(OH)

nanomaterial
X-ray diffraction (XRD) was used to determine the phase structure of the
hydrothermally synthesised material. It is reported that chromium oxyhydroxides can
crystallised in three polymorphs, ,  and .28 The -CrO(OH) phase has a layer
crystal structure with trigonal symmetry (space group R-3m or R3m).29 -CrO(OH)
has a different structure from -CrO(OH) and consist of a distorted rutile-type
structure with orthorhombic symmetry (space group Pnnm or P21nm).30 -CrO(OH)
was reported to be X-ray amorphous28 and assumed to have the same structure as
boehmite,  -AlO(OH).31, 32 -CrO(OH) is found as grimaldiite a naturally occurring
mineral, while -CrO(OH) is found as guyanite, another mineral phase.33
Fig. 1 presents the typical XRD pattern of the resultant material. All diffraction peaks
in this pattern are well indexed and in good agreement with the standard JCPDS card
No. 01-085-1374 (Grimaldiite). No impurity peaks are observed, indicating that the
resultant material was a single crystalline phase, -CrO(OH).
Fig. 1 XRD pattern for the synthetic -CrO(OH) and a reference pattern: JCPDS
card No. 01-085-1374 (Grimaldiite).
172
The rhombohedral unit cell of -CrO(OH) (space group R3m) is shown in Fig. 2a,
presenting a three-layered structure. The parameters for this unit cell are: a = b =
2.979 Å, c = 13.70 Å.34 As reported by Christensen34 and Fujihara35, in the structure
of -CrO(OH) , layers of Cr atoms perpendicular to the trigonal axis are sandwiched
between two parallel sheets of oxygen atoms, which are joined by short hydrogen
bonds aligned along the trigonal axis (Fig. 2a). It is easily observed in the structure
(Fig. 2b) that 6 oxygen atoms are octahedrally coordinated about each chromium
atom, and each oxygen atom was coordinated by three chromium atoms. Hydrogen
atoms are assumed to be involved in a disordered structure.
(a)
(b)
Fig. 2 Schematic of the synthetic -CrO(OH) in rhombohedral structure (space

group R3m) observed from different directions. The hexagonal unit cells are shown.
173
Fig. 3 TEM image of the synthetic -CrO(OH) nanomaterial
Morphology of the synthetic -CrO(OH) material was examined using transmission

electron microscopy (TEM), as shown in Fig. 3. Because of the high surface energy
of nano-particles, nanocrystals in the TEM image are aggregated. However we can
still observe that the synthetic -CrO(OH) crystals have an overall shape of discs
with average size of 10 nm in diameter. The size of synthetic -CrO(OH)
nanocrystals observed from TEM is in accordance with the result estimated by
Scherrer equation from the XRD data, which was 11 nm.
3.2 Hot-stage Raman spectroscopy
3.2.1 Raman spectra of -CrO(OH)
In order to study the changes in the spectra of -CrO(OH) as the nanomaterial is

thermally treated, it is necessary to describe the spectra collected at low temperature.
According to the previous thermogravimetric study published by the authors, the
dehydration of -CrO(OH) was observed from 120 °C. Therefore, this study reported
the spectra before and after 120 °C and will discussion the structure change of the
material during the thermal decomposition process.
174
Fig. 4 Hot-stage Raman spectra of the synthetic -CrO(OH) nanomaterial in the 200
to 1800 cm-1 region at 25 and 100 °C
Fig. 4 depicts the Raman spectra at 25 and 100 °C of -CrO(OH) nanomaterial in the
region of 200 to 1800 cm-1. The spectra are characterised by two intense bands at 823
and 630 cm-1.
As discussed above, -CrO(OH) adopts the sheet structure built from [CrIIIO6]
octahedra. Bands at 823 and 630 cm-1 are attributed to the ν1 CrIII-O symmetric
stretching vibration. An additional band is found at 558 cm-1. This band is
attributed to the ν3 CrIII-O anti-symmetric stretching vibration. A low intensity band
is observed at 452 cm-1, which is assigned to the O-CrIII-O bending modes. This is in
good agreement with the reports by Maslar et al.36
Low intensity Raman bands are found at the 985-889 cm-1 region, however this
wavenumber range is too high to due to CrIII-O vibrational modes, and is assumed to be
the CrVI-O stretching modes or mixed CrIII/CrVI –O vibrational modes as reported by
Maslar et al..37, 38
Maslar published Raman studies on chromium coupons, and
-CrO(OH) was identified as a corrosion product. It is possible to detected trace of
Cr (VI) in the resultant sample due to the hydrothermal treatment, where little
175
portion of Cr (III) material can be oxidised to Cr (IV) compounds in the high

temperature and high pressure conditions. Raman spectroscopy once again shows its
advantage as a powerful tool to examine the phases trace in the samples, when the
content of materials is too little to be detected by bulk technique, such as XRD.
In the region of 1000 to 1200 cm-1, the Raman spectra at 25 and 100 °C are
composed of broad low intensity bands. These bands are assigned to CrIII-OH δ
deformation modes. Raman spectra of some crystalline oxyhydroxides exhibit OH
stretching modes in the region above 3000 cm-1. However, no obvious bands are
observed in this wavenumber range. This lack of characteristic OH vibrational bands
is possible due to the short hydrogen bonds in the -CrO(OH) structure. This
observation is accordant with the reports made by Christensen28, which revealed no
OH absorption was found in an infrared study.
An intense band at 1607 cm-1 is presented in the Raman spectrum of 25 °C, which
shifts to 1593 cm-1 in the 100 °C spectrum. These bands are assumed to the bending
modes of absorbed water in the -CrO(OH) layered structure.
3.2.2 Thermal transition from -CrO(OH) to Cr2O3 nanomaterials
The hot-stage Raman spectroscopy of the transition of -CrO(OH) to Cr2O3 in the

region of 200 to 1800 cm-1 over the temperature range ambient to 550 °C is studied
in this work.
The Raman spectrum at 350 °C shows different features from that at low
temperatures (25 and 100 °C) in Fig. 5. Bands at 1607, 1171, 823, 630, 556 and 425
cm-1 are not observed anymore. New Raman bands at 602, 544, 518, 389, 348 and
304 cm-1 are found, which are attributed to the new phase (Cr2O3) formed by the
thermal decomposition of chromium oxyhydroxide. It is reported that Cr2O3 adopts
the corundum (Al2O3) structure consisting of vertex-, edge-, and face-sharing
[CrIIIO6] octahedral.36 Kemdehoundja et al. discussed that there are five vibrational
modes for chromia, four Eg modes and one A1g mode.39 Chen et al. reported as well
that Cr2O3 presented the most intense A1g band at 540 cm-1, with another two lower
intensity bands at 291 and 335 cm-1.40 A sharp band was observed at 1009 cm-1 with
a shoulder at 997 cm-1. These bands are assumed to due to O-H deformation modes.
176
Fig. 5 Raman spectra of the synthetic -CrO(OH) nanomaterial in the 200 to 1800
cm-1 region at 350 and 550 °C
Broad bands are observed in the region of 620-830 cm-1, which are assigned to the
vibrations of CrVI-O bridging bonds. It is reported that CrVI is probably present in
bridging bonds but not in polychromate structures.36 In such structures, CrVI is
incorporated into the CrIII-O surface network rather than being present as a
monochromate or polychromate. There is a small band found at 1363 cm-1 at the
temperature of 350 °C, which is assigned to be the combination band.
The Raman spectrum at 550 °C is very similar with what that at 350 °C, which
indicated the thermal decomposition product from -CrO(OH) nanomaterial is
Cr2O3. Bands in 620-830 cm-1 region show the loss of intensity at 550 °C. The
combination band at 1363 cm-1 disappeared at 550 °C. No intensity of OH stretching
bands remained at 550 °C, which reveals that -CrO(OH) had totally transformed to
Cr2O3. This agrees with the results of thermal gravimetric analysis reported in
somewhere else by the authors, which showed no sample mass loss above 550 °C.
All the peaks and their assignment are summarised in Table 1.
177
Table 1 Summary of Raman shifts (cm-1) and their assignment for -CrO(OH) and
Cr2O3 nanomaterials in the hot-stage Raman spectroscopic study.
-CrO(OH) nanomaterial Cr2O3 nanomaterial

25 °C 100 °C Assignment 350 °C 550 °C Assignment
1634
1593 1607 Water H-O-H
1537 1537 bending
Combinations
1504 1387
& overtones
Combinations
1363
& overtones
O-H
1179, 1153 1171, 1129
deformation
O-H
1009, 997 1007, 997
deformation
981 985, 938
CrVI-O
889 889
817
771 770
CrVI-O
729 719
823 823 683 684
1 (O-CrIII-O)
630 630
558 556 3 (O-CrIII-O) 602 599 Cr2O3
544, 518 542, 513 Cr2O3

452 452 2 (O-CrIII-O) 477 CrVI-O
389 396 Cr2O3
348 344 Cr2O3
304 304 Cr2O3
1 (O-CrIII-O symmetric stretching);
2 (O-CrIII-O symmetric bending);
3 (O-CrIII-O anti-symmetric stretching)
178
4. CONCLUSIONS
Disc-like of -CrO(OH) nanomaterial was synthesised by using hydrothermal

techniques without surfactants at low temperatures. The phase composition was
proven by X-ray diffraction and TEM showed a10 nm size of the nanocrystals. The
conversion of -CrO(OH) to Cr2O3 nanomaterial was achieved by thermal
treatment up to 350 °C. The transition of -CrO(OH) to Cr2O3 was studied by
hot-stage Raman spectroscopy; upon thermally treating the synthetic -CrO(OH)
nanomaterial at 550 °C.
The structure of synthetic nanomaterials, -CrO(OH) and Cr2O3, are deduced

from their Raman spectra. Intense bands at 823 and 630 cm-1, as well as relatively
weaker peaks at 558 and 452 cm-1 were observed in the Raman spectra of
rhombohedral-CrO(OH). These bands are attributed to O-CrIII-O vibrations. Bands
at 1179 cm-1 are assigned to CrIII-OH δ deformation modes.
Upon thermal treatment of -CrO(OH) at 350 °C, new Raman bands at 599, 542, 513,
396, 344 and 304 cm-1 are found. The Raman spectrum of resultant Cr2O3 is
characterised by an intense sharp peak at 542 cm-1, which was due to the A1g band.
ACKNOWLEDGMENTS

Technology Inorganic Materials Research Program is gratefully acknowledged. The
Australian Research Council (ARC) is thanked for funding the instrumentation.
One of the authors (JY) is grateful to the Queensland University of Technology
Inorganic Materials Research Program for the award of an international doctoral
scholarship.
179
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182
Chapter 7 Synthesis and characterisation of CoO(OH) nanodiscs
CHAPTER 7
SYNTHESIS AND
CHARACTERISATION OF
COBALT HYDROXIDE, COBALT
OXYHYDROXIDE AND COBALT
OXIDE NANODISCS
Yang, J.; Liu, H.; Martens, W. N.; Frost, R. L.,"Synthesis and characterization of
cobalt hydroxide, cobalt oxyhydroxide, and cobalt oxide nanodiscs." The Journal of
Physical Chemistry C 2010, 114 (1), 111-119.
183
SYNOPSIS
CoO(OH) has more oxidation state (Co3+) than Co3O4, and is considered to be a
potential better nanosensors than Co3O4. CoO(OH) and Co3O4 materials can be
prepared from the precursor Co(OH)2, which itself is well known as additives of
alkaline secondary batteries and also important starting materials of heterogeneous
catalysts.
Hydrothermal treatment proves to be a facile method to fabricate desired

nanomaterials as mentioned in the previous chapters. A similar synthesis procedure
was applied to produce cobalt oxyhydroxide nanomaterials in this chapter. Co(OH)2
nanomaterial with hexagonal nanostructure was synthesised. CoO(OH) and Co3O4
nanomaterials were produced from the as-prepared Co(OH)2 nanomaterial. The size
and disc-like morphology was successfully kept between these materials. The
resultant Co(OH)2, CoO(OH) and Co3O4 materials were systematically studied by
XRD, TEM, SEM, XPS, Raman and thermogravimetric techniques. The aim of this
research is to controllably synthesise a series of cobalt hydroxide, oxyhydroxide and
oxide nanomaterials with disc-like morphology by simple route and to investigate
their intrinsic properties for potential applications.
184

expertise;
academic unit, and
Synthesis and Characterisation of Cobalt Hydroxide, Cobalt Oxyhydroxide, and Cobalt

Oxide Nanodiscs
Yang, J.; Liu, H. W.; Martens, W. N.; Frost, R. L., The Journal of Physical Chemistry C 2010,
114 (1), 111-119.

Hongwei Liu Conducted TEM and data analysis, manuscript editing.

and editing.

authorship.
____________________ ______________________ ____________________

Name Signature Date
185
RESEARCH HIGHLIGHTS
The article presents a soft chemistry method for synthesis of cobalt hydroxide, cobalt
oxyhydroxide and cobalt oxide nanodiscs. A detailed survey of the morphology,
structure and properties of the synthesised materials was given, combining XRD,
SEM, TEM, XPS, etc. The synthesised Co(OH)2 displayed hexagonal morphology
with clear edges of 20 nm long, and this morphology and nanosize were retained to
Co3O4 through a topotactical relationship. Analysis of the high resolution XPS
spectra on pure components allows the identification of the chemical environment
change of cobalt element during the synthesis process. Raman spectra were
compared to provide information on structure of the synthesised nanomaterials. It
was also found that the dehydroxylation of Co(OH)2 happened at 130 ºC and
CoO(OH) decomposed at 252 ºC.
Due to copyright restrictions, this article is

not available here. Please consult the
hardcopy thesis available from QUT Library
or view the published version online at:
http://dx.doi.org/10.1021/jp908548f
186
CHAPTER 8
GENERAL DISCUSSION &

FUTURE WORK
215
1. GENERAL DISCUSSION
This thesis has increased our fundamental knowledge of the synthesis and
characteristic properties of metal oxyhydroxides, oxide and hydroxide nanomaterials.
Facile soft chemistry routes, including hydrothermal techniques, were utilised to
synthesise the desired nanomaterials without using any surface directing agents.
Hydrothermal treatment offers the advantages of high purity, good dispersion, and
high crystallinity, as well as uniform and controllable morphology. All the
synthesised nanomaterials were fully characterised using XRD, TEM/SAED, SEM,
N2 adsorption/desorption study, XPS, TGA-MS, Raman, infrared, as well as
hot-stage Raman and infrared emission spectroscopy.
The main conclusions of this thesis are list below. More detailed discussion is
presented in the following paragraphs.
(1) Oxyhydroxide and hydroxide nanomaterials of Group IIIA elements (Al &
In). Well-crystalline and uniform boehmite (aluminium oxyhydroxide)
nanofibres of 500 nm long were achieved under hydrothermal treatment without
the assistance of any surfactants or structure directing agents. Under the similar
hydrothermal synthesis route, instead of indium oxyhydroxide, indium hydroxide
was obtained, which appeared to be nanocubes of 350 nm in size. Infrared
emission spectroscopy has proven to be very useful technique to study in situ the
dehydration, dehydroxylation behavior, and other thermal structure changes of
nanomaterials.
(2) Transition elements doped boehmite nanomaterials. Chromium (III) ions were
successfully doped into boehmite nanostructures through facile hydrothermal
treatment. By controlling the reaction pH and reaction duration, it was possible to
obtain desired Cr dopant amounts and Cr doped boehmite nanostructures. It was
found that doping with Cr enhanced the thermal stability of boehmite nanofibres
(~500 nm long) by increasing their dehydroxylation temperatures.
(3) Chromium oxyhydroxides (CrO(OH)) nanomaterials. Through hydrothermal

treatment, amorphous chromium oxide gels were easily converted to CrO(OH)
nanomaterials (4-12 nm) with high surface area. The particle size of CrO(OH)
nanomaterials could be controlled by adjusting the pH and hydrothermal treatment
216
duration. Hot-stage Raman spectroscopy has shown its advantages in monitoring

material structural changes during the thermal decomposition process of Cr oxide
gel and CrO(OH) nanoparticles.
(4) Cobalt-based nanomaterials. Well-crystalline cobalt oxyhydroxide, cobalt

hydroxide and cobalt oxide nanodiscs (40 nm) were achieved and a “topological
relationship” was found between these nanomaterials. Morphology of other
cobalt-based nano-/micro-materials can be controlled to be nano-needles,
nano-rings, nano-flowers, and other nano-morphologies.
1.1 Aluminum oxyhydroxide (boehmite) nanofibres and indium

hydroxide nanocubes
One dimensional (1D) nanomaterials with high aspect ratio show wide applications
in catalysis, adsorption, ceramic separation membranes and other applications.1-5 1D
boehmite nanomaterials, such as nanofibres, nanotubes and nanorods have attracted
extensive interest because of their particular morphology and high surface areas. In
Chapter 3, boehmite nanofibres with very surface areas 133 m2 g-1 were reported.
The nanofibres appear in bundles under the SEM, and were found to be 500 nm long
and between 4-6 nm wide. The IES spectra indicated the dehydroxylation of boehmite
nanofibres started from 250 ºC and was completed by 450 ºC. The synthesis of
boehmite nanofibres was achieved under hydrothermal conditions at 170 ºC for 48
hours at pH 5, based on Shen‟s work.6 This synthesis route without use of any
surfactants or structure directing agents showed its advantages in manufacturing 1D
boehmite nanofibres in large quantities environmental friendly, facilely and
economically.
Since the elements aluminium and indium are both in Group IIIA, which have 3
valence electrons and are in the main trivalence compounds. Indium is expected to
show similar chemistry with aluminium, therefore, I am interested in fabricating
indium oxyhydroxide nanomaterials through the similar hydrothermal synthesis route
for boehmite (aluminium oxyhydroxide) nanofibres. As reported in Chapter 4,
surprisingly, instead of indium oxyhydroxide (InO(OH)), indium hydroxide (In(OH)3)
nanocubes (300-400 nm) were found after 2-day hydrothermal treatment at both 100
ºC and 180 ºC.
217
This may be explained by the Ralph Pearson‟s HSAB theory, which assigns the terms
“hard” or “soft”, and “acid” or “base” to chemical species. Aluminium ions are small,
have high charge states, and can be classified as “hard” species, while indium presents
to be “soft” because of its large ionic radium. The “hard” aluminium species were
more easily to form oxyhydroxides through hydrothermal treatment. However, under
the similar hydrothermal synthesis conditions, the “soft” indium species tended to
form its hydroxides instead of oxyhydroxides. Interestingly, a trace of InO(OH) specie
was found in the product synthesised at 100 ºC, which indicates that it is possible to
obtain InO(OH) nanomaterials by hydrothermal methods. This needs further
investigation.
Thermal analysis showed the transition of the synthetic In(OH)3 to In2O3 nanocubes
occurred mainly at 219 °C. SEM showed there was a topotactical relationship
between the of In(OH)3 nanocubes and its oxide thermal decomposition product
In2O3.
1.2 Transition metals doped boehmite nanomaterials
Transition metal doping is a promising method to modify properties and increase the
applications of nanomaterials. Since long and uniform boehmite nanofibres were
successfully obtained through a facile hydrothermal route, chromium and cobalt were
used as dopants to modify boehmite nanofibres. The project of cobalt doped
boehmite nanofibres proved more difficult and requires further research, because that
the starting Co (II) species are required to be oxidised to Co (III) first before they can
be applied to substitute the Al ions in the boehmite structure to form Co doped
materials. However, in the case of chromium doped boehmite nanofibres, Cr (III)
species were utilised directly as dopants. In Chapter 5, I demonstrated the first report
of chromium doped boehmite nanofibres prepared by a hydrothermal method under a
range of conditions. Chromium was successfully doped into boehmite nanostructure,
and the nanofibre (~500 nm) morphology was retained with a low amount of Cr
doping. In this chapter, the thermal stability of the synthetic Cr doped boehmite
nanofibres was detailed. It is found that doping with chromium resulted in an
increase in the main dehydroxylation temperature of boehmite nanofibres from 406.5
°C to 436.5 °C.
218
The dehydroxylation temperature rose with the increased hydrothermal treatment

period. It was also found that as the dehydroxylation temperature increased the
mass loss from the dehydroxylation step decreases.
More detailed studies have been undertaken on (a) optimizing synthesis parameters to
enhance the efficiency of doping into boehmite crystal structures and (b) how doping
affected the morphology of nanomaterials. However these results are not published yet
or included as a chapter in this thesis. The main findings are: (i) 1% Cr was doped in
the time dependent series study, and the hydrothermal duration varied from 1 day to 10
days. The increase of hydrothermal treatment duration resulted in better crystallinity
and larger nanofibres. this was attributed to the Ostwald ripening process. (ii) 1% -
20% Cr was applied in the added Cr amount dependent series. Nanofibres were formed
when the added Cr was less than 10%. When 20% Cr was added, nanorods were found.
(iii) Detected Cr amount in the resultant samples was less than 2%. When 10% Cr was
added, 2% Cr was detected, which is more than that in the 20% Cr sample. However, it
was noticed that there was large Cr loss under these synthesis conditions. The Cr loss
was assumed to be due to the oxidisation of Cr(III) to Cr(IV) in hydrothermal
conditions by NO3-, which was induced by the starting materials. After washing NO3-
off carefully before hydrothermal treatment, one can detect much more Cr doped into
the boehmite nanofibres. (iv) It was found that alkaline hydrothermal conditions can
increase Cr doped amount. 9.5% Cr was detected in the 10% Cr added sample when
certain amount of ammonia solution was applied during the hydrothermal treatment.
However, the increase of detected Cr in doped samples resulted morphology change
from uniform nanofibres to very short rods and broken nanoparticles.
1.3 Chromium oxyhydroxide nanoparticles
As found in the system of chromium doped boehmite nanofibres, when 2% Cr was

doped into the boehmite structure, the morphology was nanofibres; while 9.5% Cr
was detected in the boehmite material, the morphology of the material converted to
be nanorods, even nanoparticles. Obviously, the Cr dopant amount into the boehmite
structure can affect the morphology of doped boehmite nanomaterials. Therefore, it
is worthwhile to investigate further the properties of pure chromium oxyhydroxide
nanomaterials.
219
In Chapter 6, chromium oxyhydroxide nanomaterials were achieved after a

hydrothermal treatment to chromium oxide gel precipitations obtained from the
reaction of Cr(NO3)3 and NH4OH solutions at various pHs. The pH value during
precipitation was critical for the growth and crystallinity of the synthesised
nanomaterials: CrO(OH) nanomaterials were formed most easily under an acidic
precipitate process. The CrO(OH) nanomaterials synthesised both from acidic and
alkaline precipitates were identified with a plate-like morphology of ~11 nm in
diameter under TEM. Round particles with 50 nm in size were observed by SEM,
which were considered to be the aggregates of the CrO(OH) nanoplatelets. The
CrO(OH) nanomaterials possess BET specific surface area of ~120 m2 g-1.
However, the CrO(OH) nanomaterial obtained from neutral precipitate show smaller
size as 4 nm and larger surface area of 380 m2 g-1. XPS measurements for the
as-prepared chromium oxyhydroxide nanomaterials allow us to develop a view to
determine spectral characteristics and to identify element chemical environment in
the compounds. It is also observed that the dehydroxylation of the synthetic
chromium oxyhydroxides occurs at ~460 °C.
1.4 Cobalt-based nanomaterials
Cobalt hydroxide, oxyhydroxide and their oxides are important transition metal
compounds because of their wide applications as semiconductors, catalysts, gas
sensor, and so on. In Chapter 7, well-crystalline Co(OH)2 nanodiscs (~40 nm) were
prepared through a soft chemistry method. CoO(OH) nanodiscs were easily
achieved through the oxidisation of the synthetic Co(OH)2 with the assistance of
H2O2; while Co3O4 nanodiscs can be obtained by calcination of Co(OH)2 and
CoO(OH). There was a so-called topological relationship among these as-prepared
cobalt compounds, which means their size and shape remain similar. Raman
spectroscopy proves as a facile way to provide information on structure of the
synthesized compounds. The dehydroxylation of the synthetic cobalt hydroxide
happened at 130 °C, while cobalt oxyhydroxide decomposed at 252 °C.
Several morphology control studies on cobalt-based nanomaterials were undertaken

during the course of PhD research. The Co(OH) 2 nanodiscs was precipitated in 45
°C sand bath from the reaction between cobalt nitrate and sodium hydroxide
solutions, and it is found that the sand bath temperature can affect growth of
220
nanomaterials. With low concentrations of the starting solutions, very uniform

Co(OH)2 singlets were prepared. However as reported in Chapter 7, a higher
concentration results Co(OH)2 doublets along with some broken particles. The discs
appear in pairs, which may be due to a surface-edge charge as is found in kaolinite
platelets. An alternative explanation is ascribed in terms of magnetism. The Co(OH)2
platelets are magnetic and the platelets may have a +/- relationship. Co(OH)2
nanorings were found after a much longer hydrothermal duration or with the
assistance of PEO surfactants. Cobalt hydroxy carbonate Co2CO3(OH)2
nano-needles and nano-flowers were achieved with the assistance of urea and
Na3PO4. These nanomaterials can all be the precursor of cobalt oxides, which are
widely applied transition metal oxides. Because of the topological relationship
happened during calcination, one can control the morphology of cobalt oxides by
controlling the desired cobalt-based nanomaterial precursors.
1.5 Hot-stage Raman and infrared emission spectroscopic studies

on the synthesised nanomaterials
Hot-stage Raman and infrared emission spectroscopy (IES) enabled in situ

monitoring of the structural changes at the molecular level through the thermal
decomposition process. Extensive studies on the application of hot-stage Raman and
IES to synthetic nanomaterials were included in this thesis.
The transition of the precipitated chromium oxide gel (before hydrothermal

treatment) to crystalline Cr2O3 was followed by hot-stage Raman spectroscopy up to
550 °C. The Raman spectrum was characterised by an intense peak at 849 cm-1,
s(O-CrIII-OH), with a shoulder at 735 cm-1, s(O-CrIII-O). These two bands changed
in relative intensity with the temperature increase because of the loss of hydroxyl
units. Part of the water in the synthetic Cr-gel network structure was released
before 100 °C with the Raman band of the water H-O-H bending modes shifting
from 1704 to round 1590 cm-1. The conversion of CrO(OH) nanoparticles to Cr2O3
was studied by hot-stage Raman spectroscopy upon 550 °C. Intense bands at 823 and
630 cm-1, as well as relatively weaker peaks at 558 and 452 cm-1 were observed in
the Raman spectra of rhombohedralCrO(OH). Upon thermal treatment of CrO(OH)
at 350 °C, new Raman bands appear characterised to Cr2O3.
221
The transition of In(OH)3 to In2O3 was studied by hot-stage Raman spectroscopy and
thermogravimetric analysis. An Intense Raman band at 309 cm-1 is assigned to the
ν1(In(OH)3), and two bands at 3079 and 3240 cm-1 are attributed to OH stretching
band. Raman spectroscopy shows that the transition of In(OH)3 to In2O3 occurs in the
200 to 225 °C temperature range.
In the infrared emission spectrum of the synthetic In(OH)3 nanocubes at 100 °C,
OInO vibrational modes are observed at 771 and 853 cm-1. Bands at 1063, 1139 and
1156 (sharp) cm-1 are assigned to be In(OH) bending modes, and the OH stretching
modes are observed at 3123 and 3247 cm-1. The intensity of these bands nearly
reaches zero above 200 °C, which indicates that almost all the OH units are lost in
the structure. However, new weak bands were found at 915 and 3437 cm-1 in infrared
emission spectra from 250 to 450 °C, which are assumed to due to OH bending and
stretching modes separately. This observation shows the releasing and transfer of
protons and formation of transition new OH bonds upon calcination.
2. FUTURE WORK
2.1 Doping with other elements for new functional materials
In this study, I have successfully synthesised chromium doped boehmite, and

introduced a better thermal stability for boehmite nanofibres and created the
photoluminescence properties of chromium doped alumina nanofibres. Therefore, it
is viable to create novel properties of boehmite nanofibres by doping elements into
its structure. New nanomaterials will be designed using other transition metal
elements, such as cobalt, cerium and lanthanides.
2.2 Doping mechanism
Further investigation into the chromium doped boehmite nanomaterials formation

mechanism is needed. This involves the examination of samples produced over a
matrix of hydrothermal conditions by systematically altering many parameters, such
pH value, temperature, aging, washing, etc. In the study of chromium
oxyhydroxide nanoparticles, it is found the pH value of the precipitation before
hydrothermal treatment crucially influenced the particle size of products.
222
Therefore, it is worthwhile to take a detailed study if the pH values for precipitation

affect the chromium doping into boehmite nanofibre structure. Under the help of
different analysis techniques, evidence would be collected and mechanism of doping
and nanostructure formation will be proposed.
2.3 Application studies: catalyst, gas sensors
As discussed previously, nanomaterials exhibit large surface area and high surface
activity because of the size effect of nanoparticles. This shows great potential for the
synthetic nanomaterials to be used as catalysts or gas sensors. The reaction efficiency
needs to be studied for the further modification of the nanomaterials.
2.4 Environment friendly study
Finally, to be on the environment safe side, further studies on the leaching of

elements of the nanomaterials need to be researched, especially for the element
chromium, cobalt, etc.
223
REFERENCES
[1] M. Sumetsky, Y. Dulashko, A. Hale, Optics Express 2004, 12, 3521-3531.

[2] G. S. Wu, T. Xie, X. Y. Yuan, B. C. Cheng, L. D. Zhang, Materials Research
Bulletin 2004, 39, 1023-1028.
[3] E. A. Stach, P. J. Pauzauskie, T. Kuykendall, J. Goldberger, R. He, a. P. Yang,
Nano Letters 2003, 3, 867-869.
[4] C. Mao, D. J. Solis, B. D. Reiss, S. T. Kottmann, R. Y. Sweeney, A. Hayhurst,
G. Georgiou, B. Iverson, A. M. Belcher, Science 2004, 303, 213.
[5] S. Sharma, M. K. Sunkara, Jounal of the American Chemical Society 2002,
124, 12288-12293.
[6] S. C. Shen, Q. Chen, P. S. Chow, G. H. Tan, X. T. Zeng, Z. Wang, R. B. H.
Tan, the Journal of Physical Chemistry C 2007, 111, 700-707.
224

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SYNTHESIS AND

JING (JEANNE) YANG

A thesis submitted to the Queensland University of Technology, in

In this work, a range of nanomaterials have been synthesised based on metal

The synthesised nanomaterials were fully characterised by X-ray diffraction (XRD),

RESEARCH HIGHLIGHTS ................................................................................ 167

Table 1 Results of the thermogravimetric analyses of the undoped and various % Cr

Table 4 Summary of peaks shown in dTG curves for synthesised chromium

Table 1 Curve-fitted XPS binding energies of as-prepared cobalt hydroxide, cobalt

Table S1 Results of Raman spectra of Co(OH)2, CoO(OH) and Co3O4 in comparison

Fig. 1 XRD pattern of the synthetic boehmite nanofibres, after hydrothermal

Fig. 3 IES spectra of the synthetic boehmite nanofibres, collected at an interval of

Fig. 4 Raman spectra of the synthetic boehmite nanofibres, after hydrothermal

Fig. 1 Thermo gravimetric analyses of synthetic In(OH)3 nanocubes. ...................... 54

Fig. 2 Schematic of In(OH)3 in cubic structure (space group Im 3 ) ........................ 75

Fig.3 Infrared absorption spectrum (curve-fitted) of the synthetic In(OH)3 nanocubes

Fig. 3 Thermogravimetric analyses patterns of (a) undoped boehmite nanofibres and

Fig. 4 Dehydroxylation temperature of the dTG peak as a function of added Cr

Fig. 5 Thermo gravimetric analyses patterns of various % Cr-doped boehmite

Fig .1 XRD patterns of ppt-5.0, ppt-7.5, ppt-10.0, CrO(OH)-5.0, gel-7.5-a and

Fig. 3 XRD patterns of CrO(OH)-10.0 and CrO(OH)-7.5. XRD pattern from

Fig. 5 N2 adsorption/desorption isotherms for CrO(OH)-5.0, CrO(OH)-7.5 and

Fig. 6 Pore size distribution study for CrO(OH)-5.0, CrO(OH)-7.5 and

Fig.8 Thermogravimetric analyses (TGA) of (a) ppt-5.0, (b) CrO(OH)-5.0, (c)

Fig. 9 Mass spectrometric analysis associated with the thermal decomposition

Fig. 10 XRD patterns of products after TGA from ppt-5.0, CrO(OH)-5.0,

Fig. 7 Schematic of Cr2O3 in rhombohedral structure (space group R-3c).............. 160

Fig. 2 Schematic of the synthetic -CrO(OH) in rhombohedral structure (space

Fig. 3 TEM image of the synthetic -CrO(OH) nanomaterial ................................ 174

Fig. 7 Thermo-gravimetric analyses of (a) Co(OH)2, (b) CoO(OH) nanomaterials. 206

PUBLICATION AND CONFERENCE

LIST OF PUBLICATIONS AS A RESULT OF THIS PROJECT

1. Yang, J.; Frost, R. L., "Synthesis and characterization of boehmite nanofibres."

9. Yang, J.; Frost, R. L.; Martens, W. N., "Thermogravimetric analysis and

LIST OF OTHER PUBLICATIONS IN WHICH I WAS A CO-AUTHOR

LIST OF CONFERENCES ATTENDED IN THIS COURSE OF STUDY

Oral presentation: "Raman spectroscopy of the transition of chromium

2. 21st Australian Clay Minerals Society Conference

Oral presentation: "Facile self-assembly synthesis of high-quality disc-like

3. 5th International Conference on Advanced Vibrational Spectroscopy

Poster: "Hot-stage Raman spectroscopic study of cubic indium hydroxide", Jing

4. 21st International Conference of Raman Spectroscopy (ICORS)

 "Thermo-Raman spectroscopy study of the transition of alpha GaO(OH) to

XRD X-ray diffraction

TEM Transmission electron microscopy

SAED Selected area electron diffraction

EDX Energy dispersive X-ray spectroscopy

SEM Scanning electron microscopy

XPS X-ray photoelectron spectroscopy

TGA Thermogravimetric analysis

IES Infrared emission spectroscopy

UV-vis Ultraviolet-visible spectroscopy

ICP Inductively coupled plasma

VOC Volatile organic compounds

Jing (Jeanne) Yang

 My supervisors: Prof. Ray L. Frost, Dr. Wayde N. Martens and Prof.

 Dr. Barry Wood from UQ for your help with XPS.

2. DESCRIPTION OF SCIENTIFIC PROBLEMS

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