Falah 2016

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HAZMAT-17805; No. of Pages 11 ARTICLE IN PRESS

Journal of Hazardous Materials xxx (2016) xxx–xxx
Contents lists available at ScienceDirect
Journal of Hazardous Materials

journal homepage: www.elsevier.com/locate/jhazmat
New composites of nanoparticle Cu (I) oxide and titania in a novel

inorganic polymer (geopolymer) matrix for destruction of dyes and
hazardous organic pollutants
Mahroo Falah a , Kenneth J.D. MacKenzie a,∗ , Ruth Knibbe b , Samuel J. Page c ,
John V. Hanna c
a
MacDiarmid Institute for Advanced Materials and Nanotechnology, School of Chemical and Physical Sciences, Victoria University of Wellington, New
Zealand
b
Robinson Research Institute, Victoria University of Wellington, New Zealand
c
Department of Physics, Warwick University, Coventry CV4 7AL, United Kingdom
h i g h l i g h t s
• Synthesis reported of new photoactive nano-oxide composites in a geopolymer matrix.

• The novel aluminosilicate matrix is expanded with cetyltrimethylammonium bromide.
• The photoactive component consists of a Cu(I) oxide and titania heterostructure.
• Composites remove the model pollutant by both adsorption and photodegradation.
• These new photocatalysts are extremely efficient and ecologically friendly.
a r t i c l e i n f o a b s t r a c t
Article history: New photoactive composites to efficiently remove organic dyes from water are reported. These consist of
Received 1 April 2016 Cu2 O/TiO2 nanoparticles in a novel inorganic geopolymer matrix modified by a large tertiary ammonium
Received in revised form 15 May 2016 species (cetyltrimethylammonium bromide, CTAB) whose presence in the matrix is demonstrated by FTIR
Accepted 6 June 2016
spectroscopy. The CTAB does not disrupt the tetrahedral geopolymer structural silica and alumina units
Available online xxx
as demonstrated by 29 Si and 27 Al MAS NMR spectroscopy. SEM/EDS, TEM and BET measurements suggest
that the Cu2 O/TiO2 nanoparticles are homogenously distributed on the surface and within the geopolymer
Keywords:
pores. The mechanism of removal of methylene blue (MB) dye from solution consists of a combination
Photocatalysis
TiO2 /Cu2 O nanoparticles
of adsorption (under dark conditions) and photodegradation (under UV radiation). MB adsorption in
Modified geopolymers the dark follows pseudo second-order kinetics and is described by Freundlich-Langmuir type isotherms.
Organic pollutants The performance of the CTAB-modified geopolymer based composites is superior to composites based
on unmodified geopolymer hosts, the most effective composite containing 5 wt% Cu2 O/TiO2 in a CTAB-
modified geopolymer host. These composites constitute a new class of materials with excellent potential
in environmental protection applications.
© 2016 Elsevier B.V. All rights reserved.
1. Introduction the remediation of this problem is the use of photocatalysts to

destroy harmful organic pollutants by converting them to harm-
Some of the most pressing present-day environmental problems less by-products using solar UV radiation. Falah et al. [1] have
arise from human activity, including pollution of the atmosphere previously reported the development of composites of copper (I)
from vehicle and industrial emissions, and pollution of water- oxide (Cu2 O) nanoparticles supported on ecologically-friendly alu-
ways by organic compounds, pesticides, etc. One approach for minosilicate inorganic geopolymers for the efficient removal of a
model organic compound (methylene blue (MB) dye) from solution.
Although Cu2 O has been much less extensively used as a pho-
∗ Corresponding author. tocatalyst than TiO2 , its direct bandgap of 2.2 eV compared with
E-mail addresses: Kenneth.mackenzie@vuw.ac.nz, k-a.mackenzie@xtra.co.nz that of TiO2 (∼3.2 eV) and its high optical absorption coefficient
(K.J.D. MacKenzie).
http://dx.doi.org/10.1016/j.jhazmat.2016.06.016
0304-3894/© 2016 Elsevier B.V. All rights reserved.
Please cite this article in press as: M. Falah, et al., New composites of nanoparticle Cu (I) oxide and titania in a novel
inorganic polymer (geopolymer) matrix for destruction of dyes and hazardous organic pollutants, J. Hazard. Mater. (2016),
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2 M. Falah et al. / Journal of Hazardous Materials xxx (2016) xxx–xxx
suggests that it is a potentially useful photocatalyst under both distilled water to remove residual acetate, glucose and NaOH. The
visible and UV radiation [2,3]. Previously-reported photoactive light orange product was then oven-dried at 50 ◦ C overnight.
composites with geopolymer hosts act in two ways; under dark The Cu2 O/TiO2 -geopolymer photocatalysts were prepared by
conditions the inorganic polymer matrix adsorbs the dye, while blending the uncured geopolymer mixture prepared as above, with
under UV irradiation, the photoactive oxide nanoparticles pho- 5, 10, 15 and 50 wt% of the Cu2 O/TiO2 nano-heterostructure, stirred
todegrade the dye [1]. Combination of the photoactive Cu2 O with for 15 min before transferring to cylindrical plastic moulds and
another photoactive oxide (P25 titania) has been found to result in vibrated for 15 min to remove entrained air. The composites were
geopolymer nanocomposites capable of even more efficient pho- then sealed in plastic, cured for 12 h at 40 ◦ C, then unsealed and
todestruction than can be achieved by the photocatalytic oxides dried for 12 h before being finely ground and stored in sealed plastic
separately [4]. These papers highlighted the important role played bags.
by the inorganic polymer matrix, and in particular the interac- In an alternative approach, an attempt was made to simplify
tion between the matrix and the photoactive oxide nanoparticles, the synthesis procedure by mixing the matrix and Cu2 O-forming
suggesting the possibility that improvements in the photoactive reagents in situ in a single step; this was abandoned however
performance of the composites might be achieved by modifying because of the high water content which militated against the for-
the structure of the inorganic polymer matrix. mation of a well-reacted geopolymer as determined by 27 Al and 29 Si
Aluminosilicate inorganic polymers, otherwise known as MAS NMR spectroscopy. For comparison, a parallel series of sam-
geopolymers, are composed of tetrahedral silicate and aluminate ples were prepared containing nanoparticle Cu2 O and P25 titania
structural units joined in a random configuration by sharing oxygen alone.
atoms [5]. The resulting structure is X-ray amorphous; the negative The samples are designated as GP (unmodified geopolymer),
charges on the aluminate units are compensated by the presence CTAB Gp (CTAB-modified Gp) and x% Cu2 O/TiO2 -CTAB Gp, where x%
of cations (typically monovalent alkali ions [5]). This arrangement refers to the weight% Cu2 O/TiO2 content of the CTAB-Gp composite.
is similar to zeolite structures, particularly with respect to cation
exchange behaviour of the charge-balancing cations [6], which 2.2. Sample characterization
in turn suggests a possible procedure for modifying the geopoly-
mer pore structure by inserting a large quaternary ammonium The as-synthesised Cu2 O/TiO nano heterostructure and
cation such as the cetyltrimethylammonium ion, introduced as Cu2 O/TiO2 -CTAB Gp samples were characterised using a JEOL
the bromide (CATB). CATB is extensively used to expand the basal 6500F field emission scanning electron microscope (FE-SEM) or
spacings of layer-lattice clay minerals such as montmorillonite a JEOL JSM-6610 LA SEM equipped with an electron dispersive
[7,8], rectorite [8] and kaolinite [9], but its use in conjunction with (EDS) detector. All samples were carbon coated with a 7–9 nm
geopolymers has not previously been reported. Here we investigate carbon layer. For EDS work the SEM was operated at 15 kV. The
the effect of CTAB on the aluminosilicate geopolymer structure, and Cu2 O/TiO2 -CTAB Gp samples were also characterised using a JEOL
the photocatalytic performance of composites of Cu2 O/TiO2 with 2100F transmission electron microscope (TEM) operated at 200 kV.
the CTAB-modified geopolymer matrix. The photodegradation of The samples were deposited on a gold grid with holey carbon film.
MB by the resulting composites was determined both in the dark The chemical compositions of all the samples were determined
and under UV irradiation, and the results compared with the pre- by XRF spectroscopy,
viously reported photocatalysts based on conventional unmodified X-ray diffraction (XRD) patterns were determined from 10 to 80◦
inorganic polymer matrices. 2␪ with a 0.013◦ step using a Bruker D8 Avance X-ray diffractometer
with Ni-filtered Cu K␣ radiation operated at 45 kV and 40 mA.
Nitrogen adsorption/desorption isotherms were recorded for
2. Experimental powdered samples using a Micrometrics model ASAP2010 ana-
lyzer at 77 K. The samples were degassed at ∼100 ◦ C overnight
2.1. Sample preparation prior to the measurement. The surface area was obtained by the
Brunauer–Emmett–Teller (BET) method, and pore size distribution
The CTAB-modified geopolymer (CTAB Gp) was synthesised was calculated from the adsorption branch of the isotherm by the
by mixing together New Zealand kaolinite-type halloysite clay Barret–Joyner–Halenda (BJH) model.
(Imerys Premium Grade) dehydroxylated at 600 ◦ C for 24 h, sodium Fourier Transform Infrared (FTIR) spectroscopy was carried
hydroxide (BDH reagent grade) and sodium silicate solution out on powdered samples suspended in KBr pellets in the range
(FERNZ Chemical Co, NZ, Type “D”, Na2 O/SiO2 = 0.48, solids con- 400–4000 cm−1 using a Perkin-Elmer model 2000 FTIR spectrom-
tent = 41.1 mass%), in proportions such that the molar oxide eter.
ratio was SiO2 /Al2 O3 = 2.91, Na2 O/SiO2 = 0.34, Na2 O/Al2 O3 = 1.01, Solid-state 27 Al and 29 Si nuclear magnetic resonance spec-
H2 O/Na2 O = 10.18. A calculated amount of cetyltrimethylammo- troscopy with magic angle spinning MAS NMR was used to study
nium bromide (CTAB) (Merck) based on the cation exchange the chemical environment of these elements in the system before
capacity of the starting clay was added and the resulting paste and after their use as photocatalysts. The spectra were acquired at a
mixed with the photocatalytic component prior to curing. magnetic field of 11.7 T using a Bruker Avance III 500 spectrometer
The Cu2 O/TiO2 nanospheres were prepared by an alcohol- operating at a 27 Al frequency of 130.24 MHz and a 29 Si frequency of
aqueous based chemical precipitation method [10] as follows: 99.29 MHz. The 27 Al solid-state spectra were acquired using a 4 mm
A calculated amount of copper acetate (May and Baker AR grade) Doty MAS probe with a silicon nitride rotor spun at 10–12 kHz,
was dissolved in 100 mL absolute ethanol to form a deep green solu- a 1 ␮s pulse and a 1 s recycle time, the spectra referenced with
tion and stirred for ca. 30 min. Sufficient TiO2 (Degussa P25) was respect to Al(H2 O)6 3+ . The 29 Si spectra were acquired with a 5 mm
added to this solution to produce a 50:50 Cu2 O:TiO2 (mass ratio) Doty MAS probe and a zirconia rotor spun at ∼6 kHz. The excitation
mixture. The mixture was sonicated to achieve a uniform suspen- pulse for 29 Si was 7 ␮s with a recycle time of 30 s and the spectra
sion. 100 mL aqueous glucose solution was then added dropwise were referenced with respect to tetramethylsilane (TMS). The state
to the suspension heated at 60 ◦ C in a water bath, followed by the of the copper in the samples before and after their use as photo-
dropwise addition of 1.44 g of NaOH dissolved in 70 mL absolute catalysts was studied by 63 Cu NQR spectroscopy. 63 Cu (and 65 Cu)
ethanol and 50 mL distilled water. The resulting yellow precipitate quadrupole frequencies (Q ) were obtained at ambient tempera-
was centrifuged from the solvent and washed several times with ture through the use of a Chemagnetics CMX console pulsing into a
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M. Falah et al. / Journal of Hazardous Materials xxx (2016) xxx–xxx 3
Fig. 1. XRD patterns of (a) GP, (b) CTAB-GP, (c) 5 wt% Cu2 O/TiO2 -CTAB GP, (d) 10 wt% Cu2 O/TiO2 -CTAB GP, (e) 15 wt% Cu2 O/TiO2 -CTAB GP, (f) 50 wt% Cu2 O/TiO2 -CTAB GP, (g)
Cu2 O/TiO2 . Key: quartz (PDF no. 01-085-0930), cristobalite (PDF no. 00-039-1425) cuprous oxide (Cu2 O) (PDF no. 01-073-6237), anatase (PDF no. 00-021-1272), rutile (PDF
no. 04-006-1919).
probe arrangement that was well-removed from the magnet (>5 m) spectrum using an Agilent 8453 spectrophotometer operated in
and shielded from extraneous magnetic and radio frequency inter- single beam mode between 200 and 800 nm.
ference by a mumetal container. The quadrupole frequency range The dark and UV illumination experiments were conducted
scanned was determined from previous 63,65 Cu NQR and NMR stud- sequentially on the same composite sample. The sample was first
ies of two, three and four coordinate Cu (I) systems [11–15]. The held in the dark until the MB concentration in the solution decayed
location of both 63 Cu and 65 Cu isotope resonances (related by the to an equilibrium value, then the 150 W Xe UV source was switched
ratio Q(63Cu) /Q(65Cu) ) = 1.081) verified that true Cu NQR frequen- on and the photodegradation reaction allowed to come to comple-
cies were being observed. A scan of ∼±500 kHz around the central tion.
Cu2 O frequency was undertaken for each sample by stepping the The removal efficiency ␩, of the dye was then calculated by Eq.
spectrometer frequency in 100 kHz increments through this range (1):
and retuning the probe at each frequency. A Hahn echo (␪-␶-2␪-
(C0 − Ct )
␶-acquire) sequence with extended phase cycling was employed = × 100 (1)
C0
to obtain undistorted echoes, where the recycle delay was 0.5 s
and hard ␪/2␪ pulses of 2/4 s duration, respectively, were imple- where C0 and Ct are the concentration of the dye solution at the
mented. initial time and after time t of absorption. The amount of dye uptake
q is then given by:
C0 − C t
2.3. Photodegradation measurements q= ×V (2)
m
The photoactivity of the composites was evaluated by measur- where V is the volume of dye solution (mL) and m is the mass (g)
ing the bleaching of MB both in the dark and under UV illumination. of the adsorbent.
MB was chosen since its colour is stable at the high pH of the inor-
ganic polymer matrix. The photodegradation measurements were 3. Results and discussion
carried out by mixing 100 mg of the powdered composites with
100 mL of 0.1 mM aqueous MB solution in a round bottom flask with 3.1. Characterization of the photocomposites
magnetic stirring. After varying reaction periods, 5 mL aliquots of
the sample were taken and the suspension centrifuged off. The XRF major element analysis of the dried GP samples of vari-
concentration of the dye remaining in the solution was determined ous compositions shows a decrease in the Na concentration with
by measuring the absorbance maximum at 664 nm in the UV–vis increasing Cu and Ti concentration, confirming the incorporation of
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the Cu2 O-TiO2 heterostructure within the geopolymer matrix. The

presence of bromide from the CTAB decreased after addition of the
nanoparticles, resulting from the removal of the bromide ions in
the washing step accompanying the insertion of the nanoparticles.
Fig. 1 shows representative XRD patterns of CTAB-GP, the
Cu2 O/TiO2 -CTAB Gp composites containing varying geopoly-
mer/nanoparticle ratios and the starting Cu2 O/TiO2 nano-
heterostructure. CTAB-GP (Fig. 1b) shows a broad amorphous
background feature at about 27–29◦ 2␪ which is identical to a
well-formed unmodified geopolymer (Fig. 1a) with superimposed
sharp reflections of crystalline quartz (JCPDF file no. 01-078-2076)
and cristobalite (PDF no. 01-075-0923) arising from impurities in
the starting halloysite. The XRD pattern of the Cu2 O/TiO2 nano-
heterostructure (Fig. 1g) contains the expected reflections of the
major TiO2 phase anatase (JCPDF file no. 00-021-1272), TiO2 rutile
phase (JCPDF file no. 04-006-1919) and cubic Cu2 O (JCPDF file
no. 01-073-6237), while the patterns of the Cu2 O/TiO2 -CTAB Gp
composites (Fig. 1c–f) contain all the reflections of the crystalline
components, with no additional products or impurity phases. Con-
sistent with the composition of P25 titania, this contains ca. 70%
anatase and 30% rutile. The XRD patterns of these samples are
unchanged after UV irradiation.
Backscattered electron (BSE) micrographs of the Cu2 O/TiO2 -
CTAB Gp composites show bright regions on a light grey
background (Fig. 2a,b). The lighter regions are from the higher
atomic number TiO2 and Cu2 O, which is confirmed by EDS elemen-
tal mapping of Cu and Ti (Fig. c,d). The particles are homogenously
dispersed on the geopolymer surface with no obvious Cu or Ti
aggregation. Using EDS no impurities are found in the sample. As
reported previously [4] the Cu2 O grains are considerably larger than
the TiO2 grains (ca. 25 nm).
Representative TEM images of the 10% Cu2 O/TiO2 -CTAB Gp com-
posite (Fig. 3a,c) suggest the efficient penetration of the Cu2 O/TiO2
nano-hetrostructures into the modified geopolymer. This is sup-
ported by the BET measurements which indicate that the average
pore diameters decrease from 43 nm in CTAB-GP to 30 nm in 10%
Cu2 O/TiO2 -CTAB GP and 15% Cu2 O/TiO2 -CTAB Gp (see below).
Incorporation of the nanoparticles into the GP matrix is expected
as the nanoparticles are added to the GP matrix prior to set-
ting, making penetration into the developing pores more likely.
The specific surface areas of the composites formed using the
CTAB-modified geopolymer matrix, derived from N2 adsorption-
desorption isotherms, show increased surface areas from 17.0 m2 /g
in the matrix alone to 34.8 m2 /g and 33.6 m2 /g in the composites
containing 10 and 15 wt% Cu2 O/TiO2 respectively. Similar trends
are found in the BET surface areas and the cumulative surface
areas of the pores calculated by the BJH method, suggesting the
Cu2 O/TiO2 has been incorporated into the CTAB-GP matrix pore
structure, consequently increasing the relative surface areas. This
hypothesis is further confirmed by the BET pore diameter anal-
ysis. The average BET pore diameter decreases from 43.1 nm in
the CTAB-modified geopolymer matrix to 29.7 nm in the compos-
ite containing 10 wt% Cu2 O, remaining approximately constant at
27.9 nm in the composite containing 15 wt% Cu2 O. It is suggested
that the incorporation of the Cu2 O/TiO2 into the CTAB-GP matrix
pore structure has decreased the average pore size.
Fig. 3b shows a high-resolution micrograph of a TiO2 nanoparti-
cle with the corresponding fast fourier transform (inset) indicating
this TiO2 nanoparticle has a (121) growth direction. The lattice
spacings of 0.23 nm are directly measured from the diffraction pat-
tern.
Fig. 2. (a,b) Backscattered SEM micrographs of 15 wt% Cu2 O/TiO2 -CTAB GP, (c) Cu
The d-spacings corresponding to the well-defined diffraction EDS elemental map, (d) Ti EDS elemental map.
rings of the Selected Area Electron Diffraction pattern (SAED)
(Fig. 3d) are in agreement with the anatase phase of tetragonal TiO2
(JCPDF file no. 00-021-1272) and the cubic Cu2 O (JCPDF file no. 01-
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Fig. 3. TEM micrographs of 10 wt% Cu2 O/TiO2 -CTAB GP (a,c) Overview micrograph, (b) High-resolution micrograph of TiO2 nanoparticle with inset Fast Fourier Transform of
nanoparticle, (d) SAED with corresponding lattice fringes.
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Fig. 4. FTIR spectra of (a) pure CTAB, (b) GP, (c) CTAB-GP, (d) 5 wt% Cu2 O/TiO2 -CTAB GP, (e) 10 wt% Cu2 O/TiO2 -CTAB GP, (f) 15 wt% Cu2 O/TiO2 -CTAB GP, (g) 50 wt% Cu2 O/TiO2 -
CTAB GP.
073-6237) and are assigned as the (101), (211) planes of tetragonal The 29 Si MAS NMR spectra of the geopolymer matrix and com-
anatase and the (111) and (200) planes of the cubic Cu2 O phase. posites (Fig. 5) are typical of unmodified geopolymer composites
Fig. 4 shows the FTIR spectra of pure CTAB (Fig. 4a), GP (Fig. 4b), [4], with a small additional resonance at about −107 ppm corre-
and CTAB-GP (Fig. 4c). Of particular significance is the presence of sponding to SiO4 units. The presence of the CTAB in the geopolymer
the bands at 2918–2929 cm−1 in CTAB-GP, which correspond to matrix slightly broadens the spectral envelope at about −70 ppm
the CH2 stretching vibration of the CTAB, confirming the presence suggesting that the insertion of CTAB into the geopolymer results
of the CTAB on the surface or the inside pores of the CTAB-modified in the formation of a small number of Q0 monosilicate units [18].
geopolymer. The FTIR spectra of the Cu2 O/TiO2 -CTAB GP com- The corresponding 27 Al MAS NMR spectra (Fig. 6) are typ-
posites (Fig. 4d–g) and CTAB-GP (Fig. 4c) contain bands in three ical of well-developed geopolymers [1] with a principal sharp
principal regions: (a) 3439–3463 cm−1 , (b) 1644–1652 cm−1 and
(c) 1002–1008 cm−1 .
Region (a) arises from the (OH) stretching vibration of H-bonded
water in the geopolymer structure [16] and appears in all the
Cu2 O/TiO2 -CTAB GP samples, but is shifted to higher frequencies
with increasing Cu2 O/TiO2 loading. In literature it is reported that,
the addition of CTAB decreases the hydrogen bonding strength in
CTAB-treated clays [16,17], changing their surface from hydrophilic
to hydrophobic by replacing the hydrated cations with CTAB
thereby reducing the strength of the H-bonding [17]. This facilitates
the entry of Cu2 O and TiO2 into the CTAB-modified geopolymer
pores, which consequently further weakens the H-bonds and shifts
the O H stretching band to higher wavenumbers.
Region (b) arises from H O H bending vibrations and is shifted
to higher wavenumbers in the presence of the CTAB compared
with unmodified GP [4], reflecting the increased hydrophobic-
ity of the CTAB-modified materials [17]. Region (c) arises from
the typical Si O Si and Si O Al asymmetric stretching vibra-
tions of an aluminosilicate geopolymer [5]. At lower wavenumbers
(444–798 cm−1 ) the geopolymer Si O Si symmetric stretching
vibrations appear, while other bands at 576–615 cm−1 arise from
the Cu/Ti O Cu/Ti photoactive species [1]. Fig. 5. 11.7 T 29 Si MAS NMR spectra of (a) GP, (b) CTAB-GP, (c) 10 wt% Cu2 O/TiO2 -
CTAB GP, (d) 15 wt% Cu2 O/TiO2 -CTAB GP, (e) 50 wt% Cu2 O/TiO2 -CTAB GP.
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kinetics (g mg−1 min−1 ). The present adsorption data were fitted to

these two equations by a nonlinear method with successive interac-
tions calculated by the Levenberg-Marquardt algorithm [20] using
OriginPro 2015 software. The resulting plots of the data are only
poorly fitted by the pseudo-first-order model but very good fits
are obtained to the pseudo-second-order model (Fig. 8) for which
the correlation coefficients R2 are all >0.90 (Table 1) except for the
composite containing 15% Cu2 O/TiO2 . Moreover, comparison of the
experimental values of the amount of dye adsorbed (qexp ) with the
qe values calculated from Eqs. (2) and (3) (Table 1) confirms that
the pseudo-second-order model delivers a better fit to the experi-
mental data under dark conditions. This was also previously found
to be the case for nanoparticle oxide composites with unmodified
geopolymer matrices [4].
The relationship between the amount of MB adsorbed and the
concentration of the solution at a given constant temperature
can also be described by adsorption isotherms such as the Lang-
muir, Frendlich, and Langmuir-Freundlich isotherms. The Langmuir
Fig. 6. 11.7 T 27 Al MAS NMR spectra of (a) GP, (b) CTAB-GP, (c) 10 wt% Cu2 O/TiO2 -
CTAB GP, (d) 15 wt% Cu2 O/TiO2 -CTAB GP, (e) 50 wt% Cu2 O/TiO2 -CTAB GP.
isotherm (Eq. (5)) assumes that the adsorption process occurs at
specific homogeneous sites within the adsorbent [21]. The Fre-
undlich isotherm (Eq. (6)) is an empirical equation used to describe
resonance at about 59 ppm corresponding to tetrahedral AlO4 units. heterogeneous systems, while the Langmuir-Freundlich isotherm
The small broad feature in some of the samples arises from Al-O (Eq. (7)) provides a more flexible analytical model by the use of
in octahedral coordination [18] from a trace of unreacted dehy- a three-parameter equation that may give a better fit to the data.
droxylated halloysite starting material. These spectra confirm that These isotherms can be written:
aluminosilicate geopolymer composites are successfully formed in
the presence of CTAB and are unchanged by the presence of the (Qs kC)
Langmuir : q = (5)
nanosized Cu2 O/TiO2 photoactive component. 1 + kC
3.2. Adsorption and degradation of methylene blue (MB) dye by Freundlich : q = kCn (6)
these composites
Qs kCn
Langmuir-Freundlich : q = n
(7)
A previous study [4] has shown that unmodified geopoly- 1 + kC
mers are efficient absorbers of organic dyes in their own right,
since their surface hydroxyl groups can attract and hold cationic where q is the adsorbed amount of the dye (mg/g), C is the equi-
organic species [19]. Photoactive composites based on an unmod- librium concentration of the dye in solution (mg/L), Qs is the
ified geopolymer matrix were shown to remove MB from solution adsorption capacity (mg/g), k is a constant related to the free energy
by adsorption on the matrix (in the dark) and by a combination of adsorption (L/mg) and n is a constant specifying the extent of the
of adsorption and photodegradation under UV illumination, under adsorption and the degree of nonlinearity between the solution
which conditions the two mechanisms cannot be distinguished [4]. concentration and the adsorption.
In contrast, the use of the CTAB-modified geopolymer as the matrix Adsorption under dark conditions by the CTAB-GP matrix is fit-
has proved to allow the two processes to be distinguished. Under ted well by both the Langmuir and Freundlich isotherms, with R2
dark conditions, rapid initial adsorption of the dye by the matrix values >0.995, whereas the Cu2 O/TiO2 -CTAB-GP composites con-
alone (Fig. 7) is related to the availability of the active surface taining 5, 10 and 50 wt.% of the photoactive components are fitted
sites initially available for adsorption, which become saturated at best by the three-parameter Langmuir-Freundlich model, giving
longer adsorption times. Incorporation of 5 and 15 wt% Cu2 O/TiO2 higher correlation coefficients (R2 ) values of 0.990, 0.993 and 0.961
nanoparticles into the geopolymer matrix results in a signifi- respectively. These results are similar to those found for photoac-
cant increase in the rate of dye adsorption, suggesting that the tive geopolymer composites based on an unmodified geopolymer
nanoparticles are entering the geopolymer matrix, facilitating matrix [4].
access of the dye to the internal adsorption sites. Adsorption by As described in Section 2.3, destruction of MB dye by these
the Cu2 O/TiO2 heterostructures and their component oxides alone composites under UV radiation can be distinguished by allowing
is much less significant, (Fig. 7), reflecting their poorer adsorption the adsorption reaction to come to equilibrium in the dark before
properties. exposing the composites to UV irradiation (Fig. 9). This behaviour is
Two kinetic models, pseudo-first-order (Eq. (3)) and pseudo- in contrast to composites based on unmodified geopolymer matri-
second-order (Eq. (4)) have previously been used [1,4] to analyse ces in which the adsorption and photodegradation processes could
the kinetics of MB dye adsorption under dark conditions on unmod- not be separated due to the pH changing continuously throughout
ified geopolymer substrates: the adsorption process [1,4]. Modification of the pore surfaces by
the CTAB produces a matrix of stable pH by acting as a pH buffer
q = qe (1 − exp (−k1 t)) (3)
and allowing the two dye removal processes to be separated.

k2 qe 2t The greater photoactivity of the 10 wt% Cu2 O/TiO2 composites
q= (4) under both dark and UV conditions is attributed to the disper-
(1 + k2 qe t)
sion of the Cu2 O/TiO2 within the CTAB-GP matrix rather than on
where q is the amount of dye adsorbed (mg/g) at time t (min), its surface, as suggested by the SEM/TEM evidence and porosity
qe is the amount of dye adsorbed at equilibrium (mg/g), k1 is the measurements. After equilibration in the dark, UV illumination pro-
equilibrium rate constant for pseudo-first-order kinetics (min−1 ) duces significant photodegradation in all the samples (Fig. 9), most
and k2 is the equilibrium rate constant for pseudo-second-order particularly at a concentration of 5 wt% Cu2 O/TiO2 .
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Fig. 7. Residual MB dye concentration (C/C0 ) vs. time in the presence of CTAB GP, Cu2 O/TiO2 -CTAB GP and the photoactive (Cu2 O/TiO2 ) components alone, monitored at
664 nm in the dark.
Fig. 8. Experimental kinetic curves for the adsorption of MB dye in the dark on CTAB GP and its composites fitted to pseudo second-order kinetic model (broken lines).
These points are illustrated more clearly by comparing MB phodestruction. This is illustrated by the experiments under dark
removal after 60 min by the CTAB-GP composites containing dif- conditions, in which the dye is absorbed (but not photodestroyed)
ferent percentages of Cu2 O/TiO2 and the metal oxide components until equilibrium is reached; at this point adsorption ceases and
alone, both in the dark and under UV irradiation (Fig. 10). The when the system is subjected to UV irradiation, further dye removal
adsorption step of MB removal is most efficient in the composites occurs by photodestruction (Fig. 9). Since these processes are facili-
containing 5–15 wt% Cu2 O/TiO2 (Fig. 10B–D) by comparison with tated by modifying the host matrix with CTAB, is suggested that the
the CTAB-GP matrix alone (Fig. 10A), and the Cu2 O (Fig. 10F), TiO2 adsorption step might enhance the photodestruction step by trap-
(Fig. 10H) and Cu2 O/TiO2 (Fig. 10G) photoactive elements alone. ping and holding the dye molecules in proximity to the photoactive
Thus, the performance of all the composites, in both the adsorption oxides.
and photodegradation steps, is superior to that of the oxides when 63 Cu NQR spectroscopy was used to seek information about pos-
they are not combined with the geopolymer matrix. sible changes in the state of the Cu2 O resulting from its insertion
Thus, the mechanism for the removal of the dye from solution by into the geopolymer matrix and in the photodegradation process.
these geopolymer-based composites occurs both by adsorption and The 63 Cu NQR spectra (Fig. 11) show the expected single line for
Table 1
Kinetic parameters for MB dye adsorption on samples based on CTAB-modified geopolymer matrices under dark conditions.
Sample Kinetic model qexp (mg/g) qe (mg/g) k1 (min−1 ) k2 (g/mg/min) R2
CTAB GP 1st-order 13.76 12.87 240.78 – 0.97

“ 2nd-order “ 14.91 – 0.52 0.97
5% Cu2 O/TiO2 -CTAB Gp 1st-order 19.70 18.54 87.30 – 0.79
““ 2nd-order “ 20.11 – 0.003 0.98
““ 2nd-order “ 18.38 – 0.002 0.96
““ 2nd-order “ 16.70 – 5.96e−04 0.92
G Model
Fig. 9. Residual concentration (C/C0 ) of MB dye vs. time in the presence of the CTAB GP, the geopolymer-Cu2 O/TiO2 composites and the photoactive components alone,
monitored at 664 nm after equilibration in the dark followed by UV illumination.
pure Cu2 O [12] (Fig. 11e) and 10 wt% Cu2 O/TiO2 -CTAB GP before presence of the CTAB-modified matrix are worth further investiga-
UV irradiation (Fig. 11d). However, after UV irradiation of this sam- tion, but are beyond the scope of this paper.
ple, the single 63 Cu line disappears (Fig. 11c), unlike the 63 Cu results
for composites containing Cu2 O alone in an unmodified geopoly- 3.3. Comparative performance of the CTAB-modified and
mer matrix [1] in which the copper NQR resonance is unaffected by unmodified matrix composites
UV irradiation. This is unlikely to be due to the complete oxidation
of the Cu2 O since the XRD results suggest no loss of Cu2 O or forma- Comparison of the photocatalytic behaviour under UV illumi-
tion of CuO. Since the only difference between the present samples nation of the Cu2 O/TiO2 -CTAB Gp composites with those based
and those reported in Ref. [1] is the modification of the present on an unmodified geopolymer matrix is shown in Fig. 12. All the
geopolymer matrix structure by CTAB and the presence of TiO2 , it composite samples presented contain 10 wt% nanoparticles and are
is possible that the Cu2 O is adsorbed more deeply into the internal measured under the same experimental conditions. The results for
pores of the CTAB matrix, or that some of the Ti4+ in proximity to the two matrices alone (i.e. no nanoparticle addition) (Fig. 12A)
the Cu species is being reduced to paramagnetic Ti3+ (or that both
these effects may be operating). The loss of the 63 Cu line from the
unirradiated 15 wt% Cu2 O/TiO2 -CTAB GP sample (Fig. 11b) is more
difficult to explain, but may reflect a saturation of the NQR sig-
nal arising from the increased concentration of photoactive Ti and
Cu species. The effect of interactions between the Ti and Cu in the
Fig. 10. Comparative destruction of MB dye solution after 60 min in the dark and
under UV irradiation by composites based on CTAB-modified inorganic polymer Fig. 11. 63 Cu NQR spectra of (a) 15 wt% Cu2 O/TiO2 -CTAB GP after UV irradiation, (b)
matrices and the photoactive oxides alone. (A) CTAB GP, (B) 5 wt% Cu2 O/TiO2 -CTAB- 15 wt% Cu2 O/TiO2 -CTAB GP before UV irradiation, (c) 10 wt% Cu2 O-CTAB GP after
GP, (C) 10 wt% Cu2 O/TiO2 -CTAB GP, (D) 15 wt% Cu2 O/TiO2 -CTAB GP, (E) 50 wt% UV irradiation, (d) 10 wt% Cu2 O-CTAB GP before UV irradiation, (e) as-synthesised
Cu2 O/TiO2 -CTAB GP, (F) Cu2 O, (G) Cu2 O/TiO2 , (H) TiO2 . Cu2 O.
G Model
of MB by these CTAB-modified composites follows pseudo second-

order kinetics and Freundlich-Langmuir type isotherms and the
most effective composite in photodegrading the dye under UV irra-
diation is the 5 wt% Cu2 O/TiO2 -CTAB modified geopolymer. The
performance of these composites is superior to that of previously-
reported Cu2 O/TiO2 composites based on unmodified geopolymer
matrices [4]. These results demonstrate that composites of nano-
sized Cu2 O particles combined with photoreactive TiO2 supported
by an aluminosilicate geopolymer matrix modified with CTAB con-
stitute extremely efficient new and novel materials with potential
environmental protection applications to remove organic pollu-
tants from water or the atmosphere.
Acknowledgements
We are indebted to Grant O’sullivan for supplying the halloysite

Fig. 12. Comparative removal of MB dye from solution after 90 min UV irradiation,
by composites based on CTAB-modified inorganic polymer matrices and unmodified clay, to David Flynn for assistance with the electron microscopy
matrices. (A) GP matrix, (B) 10 wt% Cu2 O/TiO2 -GP, (C)10 wt% Cu2 O/GP, (D) 10 wt% and to Diego del Puerto for the BET measurements. Mahroo Fallah
TiO2 -GP. Data for the unmodified matrix composites are taken from Ref. [4]. acknowledges the financial support of a PhD Fellowship from the
MacDiarmid Institute for Advanced Materials and Nanotechnology.
JVH thanks the University of Warwick, EPSRC and the Birmingham
correspond to their MB adsorption characteristics, and indicate that
Science City for contribution to the solid state NQR instrumentation
the CTAB-GP matrix is a more efficient adsorber. The difference
used in this research. The latter was partially supported through the
between the two matrices is much more pronounced in compos-
Birmingham Science City Advanced Materials Project 1: Creating
ites containing the photoactive Cu2 O/TiO2 nano-heterostructure
and Characterising Next Generation Materials Project, with support
(Fig. 12B) with around 55% and 97% MB dye removal by the
from Advantage West Midlands (AWM) and partial funding from
Cu2 O/TiO2 -GP and Cu2 O/TiO2 -CTAB GP composites respectively.
the European Regional Development Fund (ERDF).
However, modification of the geopolymer matrix by CTAB has
little effect on the photodegradation characteristics of the com-
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HAZMAT-17805; No. of Pages 11 ARTICLE IN PRESS

Contents lists available at ScienceDirect

Journal of Hazardous Materials

New composites of nanoparticle Cu (I) oxide and titania in a novel

• Synthesis reported of new photoactive nano-oxide composites in a geopolymer matrix.

1. Introduction the remediation of this problem is the use of photocatalysts to

the Cu2 O-TiO2 heterostructure within the geopolymer matrix. The

kinetics (g mg−1 min−1 ). The present adsorption data were ﬁtted to

Sample Kinetic model qexp (mg/g) qe (mg/g) k1 (min−1 ) k2 (g/mg/min) R2

CTAB GP 1st-order 13.76 12.87 240.78 – 0.97

of MB by these CTAB-modiﬁed composites follows pseudo second-

We are indebted to Grant O’sullivan for supplying the halloysite

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