RESEARCH ARTICLE | JUNE 03 2021

Hydrothermal synthesis of hierarchical boehmite (γ-AlOOH)

hollow microspheres with highly active surface
Fang Wang  ; Xue Yuan; Dengwu Wang 

AIP Advances 11, 065209 (2021)

https://doi.org/10.1063/5.0050294

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 AIP Advances ARTICLE scitation.org/journal/adv

Hydrothermal synthesis of hierarchical boehmite

(γ-AlOOH) hollow microspheres with highly active
surface
Cite as: AIP Advances 11, 065209 (2021); doi: 10.1063/5.0050294
Submitted: 13 March 2021 • Accepted: 16 May 2021 •
Published Online: 3 June 2021

Fang Wang,1,a) Xue Yuan,1 and Dengwu Wang2

AFFILIATIONS
1
Department of Chemistry and Chemical Engineering, Shaanxi Xueqian Normal University, Xi’an, Shaanxi 710100,
People’s Republic of China
2
College of Science, Xijing University, Xi’an, Shaanxi 710123, People’s Republic of China

a)
Author to whom correspondence should be addressed: 25014@snsy.edu.cn

ABSTRACT
In this study, hierarchical boehmite (γ-AlOOH) hollow microspheres with highly active surface were prepared by hydrothermal synthesis.

27 May 2024 04:05:40

Scanning electron microscopy images showed that the hierarchical structure of the product was composed of hexagonal nanoflake units.
Transmission electron microscopy images confirmed that the (010) plane was the main exposed surface of the crystal, and the ratio of the
(010) plane to the total surface area of the crystal units was about 91.5%. The (010) plane of γ-AlOOH is occupied by hydroxyl groups
with adsorption activity, which has a great influence on the adsorption performance of the materials. The possible mechanism of the prod-
uct was proposed. Cetyltrimethylammonium bromide, which was used as the structure inducer, broke the interlayer hydrogen bonds of
γ-AlOOH. As a result, the separated layers of the crystal formed thin flake-like structure units. The (010) crystal surface, which was usually
caught between the lattice layers, could be exposed on the surface with this unique morphology. The N2 adsorption–desorption experiment
showed that the specific surface area of the as-synthesized product was 43.5 m2 g−1 . The adsorption capacity test revealed that γ-AlOOH
hollow microspheres had an excellent adsorption performance, namely, the maximum adsorption capacity of the product for Congo red is
110 mg g−1 .
© 2021 Author(s). All article content, except where otherwise noted, is licensed under a Creative Commons Attribution (CC BY) license
(http://creativecommons.org/licenses/by/4.0/). https://doi.org/10.1063/5.0050294

I. INTRODUCTION charged anions in the solution. Therefore, the number of hydroxyl

Boehmite (γ-AlOOH) can be widely used as an adsorbent, a cat-
alyst, or their carrier due to its excellent physical property and high
chemical activity.1–9 It is traditionally considered that the adsorption
performance of γ-AlOOH mainly depends on the size, morphol-
ogy, specific surface area, and crystal plane characteristics of the
sample.10,11 To improve the adsorption performance of γ-AlOOH,
many researchers have devoted to developing efficient synthetic
routes to prepare nano-scale or micro-scale powders with various
morphologies and high specific surface area.12–17
The crystal of γ-AlOOH has a layered structure, and its (010)
crystal plane is covered with hydroxyl groups.18 The hydroxyl
groups exposed on the crystal surface can form hydrogen bonds
readily with hydrogen ions in the aqueous solution. Hence, the sur-
face of γ-AlOOH is positively charged and can adsorb negatively
groups on the crystal surface will affect the adsorption capacity of
γ-AlOOH. By increasing the exposure ratio of the (010) plane,
which is covered with hydroxyl groups, the adsorption capacity of
γ-AlOOH can be effectively improved. However, by conventional
synthesis methods, most of the (010) plane of γ-AlOOH is trapped
in the crystal lattice,19 and this limits the adsorption capacity of
the materials. In recent years, few references were reported about
increasing the exposure ratio of the active crystal plane of γ-AlOOH
to improve its adsorption capacity.
In this paper, we report a novel method to prepare γ-AlOOH
hierarchical hollow microspheres with a highly active surface by
hydrothermal synthesis under weak acidic conditions. During the
synthesis process, the surfactant cetyltrimethylammonium bromide
(CTAB) was used as a structure inducer to control the morphology
of the product. The crystal surface of the product is covered with a

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large number of active hydroxyl groups provided by the (010) plane,
which is the dominating plane on the surface. Moreover, the possi-
ble mechanism for the formation of the product and the role of the
structure inducer were also discussed. The adsorption capacity of the
product was evaluated by removing Congo red dye from the water.
II. EXPERIMENTAL SECTIONS
A. Preparation of γ-AlOOH
All reagents were analytical reagents without further purifica-
tion. In a typical synthesis, aluminum sulfate [Al2 (SO4 )3 , 4 mmol]
and CTAB (0.8 mmol) were dissolved in distilled water (35 ml). Sub-
sequently, urea was added into the mixture (followed as different
molar ratios of Al/urea). The mixed solution was stirred for 30 min
to form a transparent solution. Then, the obtained mixture solution
was transferred into a 50 ml Teflon-lined stainless autoclave and kept
at 165 ○ C for 24 h. After that, the autoclave was air-cooled to room
temperature. The precipitate was collected and washed repeatedly
with distilled water and absolute ethanol to remove by-products. The
resulting solid was dried under vacuum at 60 ○ C for 12 h.
B. Characterization of γ-AlOOH
The crystal structure of sample powders was identified with the
x-ray powder diffraction (XRD; Rigaku Max2200pc, Cu Kα radi-
ation). The morphology and structure were observed by a field
emission scanning electron microscope (FE-SEM; Zeiss, MERLIN
Compact) and a high-resolution transmission electron microscope
salt to urea, while all the other experimental variables remained
constant.
FESEM analyses have been carried out to further investigate
the influence of urea on the morphology of the products. When
the molar ratio of Al to urea is 4–12 during the synthetic process
[Fig. 1(a)], with all the other experimental variables remained con-
stant, the sample shows a severely agglomerated core–shell structure
and the shell presents an irregular fluffy shape.
When the sample is synthesized with the molar ratio of Al to
urea being increased to 4:15, from Figs. 1(b)–1(d), it can be seen that
the product exhibits a hollow microspherical appearance with uni-
form morphology, good dispersion, and consistent size. The average
diameter of the hollow microspheres is about 10 μm [Fig. 1(b)].
Figure 1(c) shows that the shell thickness of the hollow microspheri-
cal γ-AlOOH is about 1.6 μm. Figure 1(d) indicates that the product
has a hierarchical structure, which is formed by the self-assembly
of hexagonal nanoflake units. Since the nanoflake structural units,
which are perpendicular to the center of the hollow microspheres,
constitute the product through random distribution, both the inter-
nal and the external surfaces of the product are very loose and rough.
Therefore, the reactivity of the product can be greatly improved

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(HR-TEM; JEOL JEM-2100F), respectively. The spectrum of the
samples was identified by Fourier transform infrared spectroscopy
(FTIR; Nicolet, KBr disk) at room temperature. Thermogravimetric
analysis (TG) and differential scanning calorimetry (DSC) were
carried out in a simultaneous thermal analyzer (STA; NETZSCH,
STA449-F5). The specific surface area and textural information of
the samples were measured through an automatic multi-station
specific surface and pore analyzer (Microtracbel, BELSORP-max).
Before measurement, all the samples were degassed under vacuum
at 120 ○ C over 8 h.

C. Adsorption capacity evaluation of γ-AlOOH

The adsorption capacity of γ-AlOOH hierarchical hollow
microspheres was characterized by the removal rate of Congo red
dye in water. 110 mg l−1 of Congo red aqueous solution was used.
100 mg of γ-AlOOH hierarchical hollow microspheres was added
to the 100 ml solution, and the resulted mixture was magnetically
stirred. After some intervals, a part of the suspension was taken
out and passed through a 0.45 μm filter membrane to remove the
particles. The absorption spectrum of the resulted transparent solu-
tion was tested with the ultraviolet–visible spectrometer (UV–Vis;
Metash, UV-8000S), and absorbance near the maximum absorption
peak (∼497 nm) was monitored to reflect the adsorption capacity of
the powder.

III. RESULTS AND DISCUSSION

A. The effect of urea dosage on product morphology
In order to optimize the synthesis method, the products
have been investigated at different molar ratios of aluminum
FIG. 1. FESEM images of the samples with different molar ratios of Al to urea: (a)
Al2 (SO4 )3 /urea = 4:12, [(b)–(d)] Al2 (SO4 )3 /urea = 4:15, [(e) and (f)] Al2 (SO4 )3 /urea
= 4:17, and [(g) and (h)] Al2 (SO4 )3 /urea = 4:20.

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through this unique structure. The products in Figs. 1(b)–1(d) have
been indexed to be boehmite by XRD (Fig. 2).
When the sample is synthesized with the molar ratio of Al to
urea being increased to 4:17, it can be seen from Fig. 1(e) that the
product still maintains the hollow microspherical structure on the
whole. However, after zooming in, Fig. 1(f) shows that the shape
of the structural units has become irregular and their aspect ratio
has increased. When the molar ratio of Al to urea increases to 4:20
[Figs. 1(g) and 1(h)], the hollow microspherical structure has been
completely decomposed and the structural unit has changed from
a flake-like structure to a needle-like structure. Since the product
synthesized with a molar ratio of Al to urea of 4:15 has obvious
structural advantages, its performance will be further characterized.
B. Crystal structure of the product
Figure 2 shows the typical XRD pattern of the synthesized prod-
uct, in which the molar ratio of Al to urea is 4:15 during the synthesis
process.
Figure 2 shows the typical XRD pattern of the sample prepared
by the hydrothermal method. In the pattern, all the sharp and strong
reflection peaks are readily indexed as orthorhombic boehmite
(γ-AlOOH, JCPDS Card No. 74-1895). There is no diffraction peak
that belongs to impurities, indicating that the purity of the prod-
uct γ-AlOOH is very high. The intensity of each diffraction peak is
larger, and the half-width is smaller, showing that the product is well
crystallized.
The crystal of the sample belongs to the orthorhombic sys-
tem, and the cell parameters are a = 0.2859 nm, b = 1.224 nm, and
c = 3.691 nm. The crystal of γ-AlOOH has a typical layered struc-
ture with its b axis ([010] crystal orientation) perpendicular to the
layered surface. The (020) plane is an important interlayer plane of
the crystal. Generally, L020 represents the vertical distance between
layers, and this interplanar distance can represent the average crys-
tal grain size.20 Whole pattern fitting was performed on the resulted
XRD pattern, and the average grain size of the product γ-AlOOH
FIG. 2. XRD pattern of the as-synthesized γ-AlOOH prepared by the hydrothermal
method.
AIP Advances 11, 065209 (2021); doi: 10.1063/5.0050294
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(that is, the interplanar distance of the L020 crystal plane) was about
13.8 nm, calculated by the Scherrer formula.
C. TEM characterization of the product
Figure 3 provides the TEM images of the as-synthesized
γ-AlOOH synthesized when the molar ratio of Al to urea is 4:15.
Figure 3(a) is consistent with Fig. 1(d), and both of them show
that the shells of the product are self-assembled by hexagonal
nanoflake structural units. It can be observed that the thickness of
the nanoflake is ∼14 nm [Fig. 3(b)], and this is almost consistent with
the thickness of the L020 crystal plane calculated by the XRD pat-
tern. The length and width of the nanoflake are ∼900 and ∼200 nm,
respectively [Fig. 3(d)]. The inset of Fig. 3(c) shows the high-
resolution transmission electron microscopy (HRTEM) of the side
face of the nanoflake structure unit. In Fig. 3(c), the lattice fringes
are clear and the interplanar distance is 0.612 nm, which is consistent
with the interplanar distance of the (020) crystal plane of γ-AlOOH.
The inset of Fig. 3(d) shows that the selected area electron diffrac-
tion pattern of the front of the nanoflake (the red circled area) always
exhibits the same single-crystal structure.
It is well known that γ-AlOOH has a layered structure. Under
weak acid or neutral conditions, the γ-AlOOH crystal grows mainly
along the [001] directions and then forms hexagonal nanoflake
units.21 The (020) plane is the interlayer plane of the crystal. The
model of the crystal plane of the hexagonal nanoflake structure unit
is shown in Fig. 4. After calculation, the proportion of the (010)
crystal plane in the total surface area of the crystal is ∼91.5% and
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the proportion of the (001) crystal plane and (101) crystal plane is
∼6.4 and ∼2.1%, respectively. It can be seen that γ-AlOOH obtained
in this study exposes a very high proportion of the (010) crystal
plane on its surface. Therefore, the crystal surface of the product is
covered by a large amount of hydroxyl groups, and it should have
FIG. 3. TEM images of the as-synthesized γ-AlOOH prepared by the hydrothermal
method.
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FIG. 4. Model of the crystal plane of γ-AlOOH hexagonal nanoflake units.
high chemical activity and an excellent adsorption performance in
water.
D. FT-IR spectrum of the product
The structure of the sample has been corroborated by the FT-
IR spectrum when the synthetic molar ratio of aluminum to urea is
4:15 (Fig. 5). The spectrum shows the typical characteristic absorp-
tion peaks of γ-AlOOH.22 In addition to this, the peaks in Fig. 5 also
indicate the absorption of the infrared wave due to adsorbed water,
AlOOH, methyl (CH3 ), and methylene (CH2 ).
The strong peaks at 3307 and 3094 cm−1 are mainly caused
by the asymmetric and symmetric stretching vibration mode
of (Al)O–H of boehmite, respectively.23 This spectrum band is
expanded by the association between the hydrogen bonds, which
are formed by the hydroxyl groups on the surface of the boehmite,
and is reinforced by superposition with the stretching vibration
peak of adsorbed water, which normally appear in the range of
3400–3500 cm−1 . The bending vibration peak of the adsorbed water
appears at 1639 cm−1 . Peaks at 1151 and 1067 cm−1 are due to
the asymmetric and symmetric deformation vibration mode of
FIG. 5. FT-IR spectrum of the product γ-AlOOH.
AIP Advances 11, 065209 (2021); doi: 10.1063/5.0050294
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Al–O–H.24 The peaks at 743, 615, and 475 cm−1 are due to the twist-
ing vibration, stretching vibration, and bending vibration of Al–O,
respectively.25 The translation and rotation of molecules in the crys-
tal lattice will cause the vibration of the crystal lattice. The weaker
peaks at 2095 and 1971 cm−1 belong to the spectral combination
band, which is constituted by the lattice vibration and other original
vibration modes.14
Two weak peaks that appear at 2927 and 2856 cm−1 belong to
the asymmetric and symmetric stretching vibration mode of CH2 ,
respectively. Similarly, the peak at 1468 cm−1 is formed by the scis-
sor vibration of CH2 . The appearance of the above characteristic
absorption peaks reveals that the surfactant CTAB remains on the
γ-AlOOH surface. This indicates that CTAB and γ-AlOOH are
bound together so firmly that the former cannot be removed by
washing. The symmetric deformation vibration peak of CH3 appears
at 1397 cm−1 and is blue-shifted obviously. This blue-shift is usu-
ally caused by the reduced binding force between the CH3 groups
at the end of the molecule structure and nitrogen.26 In the CTAB
molecule, nitrogen is sp3 hybridized. One hybrid orbital of nitrogen
is occupied by lone pair electrons, which can form hyperconjugation
with the σ-bond (C–H) of the surrounding CH3 group. Because, in
the product, the nitrogen in CTAB can be stably bound to the sur-
face of γ-AlOOH by chemical bonds, the hyperconjugation effect
is partially destroyed and the CH3 group stays away from nitro-
gen. Therefore, the symmetric deformation vibration peak of CH3
exhibits blue-shift.
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E. Thermal properties of the product
Thermal properties of the as-synthesized γ-AlOOH were eval-
uated by STA when the synthetic molar ratio of aluminum to urea is
4:15. In a nitrogen environment, the product was heated from 100 to
1250 ○ C at a rate of 20 K min−1 . It is well known that γ-AlOOH can
be converted to Al2 O3 by releasing H2 O,
2AlOOH → Al2 O3 + H2 O.
The theoretical weight loss in this process should be 14.2%. The plot
of TG-DSC is shown in Fig. 6.
FIG. 6. TG-DSC plot of the as-synthesized γ-AlOOH.
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The TG-DSC plot of the product with a molar ratio of alu-

minum to urea of 4:15 is shown in Fig. 6. The TG curve shows
that the sample has two major weight loss events. The first weight
loss event below 500 ○ C is mainly due to the thermal decomposi-
tion of γ-AlOOH to Al2 O3 in the heating process. At this stage,
the actual weight loss is about 16.07 wt. %, which is slightly greater
than the theoretical value. The possible reason for this phenomenon
is that the weight loss is due to not only the thermal decomposi-
tion of γ-AlOOH to Al2 O3 but also the thermal decomposition of
absorbed water and the residual organic groups, which are released
by surfactant CTAB. The corresponding DSC curve has an exother-
mic peak at 416.23 ○ C, which is related to the decomposition of
γ-AlOOH,27 and an endothermic peak at 495.04 ○ C, which is related
to the thermal decomposition of residual organic groups in the sam- FIG. 7. Schematic formation mechanism of the hierarchical γ-AlOOH hollow
ple.28 The endothermic peak confirms that the surfactant CTAB is microsphere with a highly active surface.
tightly bound to the hydrothermal product γ-AlOOH and cannot
be completely removed by washing, which is consistent with the
conclusion of the FT-IR analysis. by layer to form a plate-like structure by hydrogen bonds. By con-
As the temperature increases above 500 ○ C during the thermal trast, under acidic conditions, the reaction solution contains a large
process, the TG curve also maintains a slight decrease and the weight amount of protons, which will combine with the oxygen lone pairs of
loss is about 3.66 wt. % at this stage. The possible reason for this the hydroxyl and destroy the layered structure. In order to maintain
weight loss is that the heating rate is too fast to completely decom- a stable existence by reducing the surface energy, the separated lay-
pose the sample in the previous process, and then, γ-AlOOH contin- ers subsequently curl to form a rod-like structure via the scrolling-
ues to thermally decompose to Al2 O3 . The DSC curve has another growth route.22,34,35 It can be seen that no matter what the pH is,
endothermic peak at 845.92 ○ C. Since there is no significant weight the hydroxyl groups are caught between the lattice layers. Conse-
change present in the corresponding TG curve, the endothermic quently, the amount of hydroxyl groups exposed on the crystal sur-
peak may be caused by the crystal transformation of Al2 O3 .29 face is limited, which directly decreases the adsorption performance

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F. The possible mechanism of the formation
During the hydrothermal reaction, urea can be hydrolyzed to
produce NH+4 , HCO−3 , and OH− . Among the products, OH− can
adjust the pH value of the reaction system.30 The pH of the sys-
tem was determined to be ∼6.5 after the reaction. In the reac-
tion process, first, urea can be hydrolyzed at the high tempera-
ture in the hydrothermal process [Eq. (1)]. Second, Al3+ derived
from Al2 (SO4 )3 reacts with OH− hydrolyzed from urea to pro-
duce AlOOH [Eq. (2)]. Finally, the Al(OH)3 colloid will be further
transformed into γ-AlOOH [Eq. (3)],
of γ-AlOOH.
In this study, hierarchical γ-AlOOH hollow microspheres with
a highly active surface were synthesized under weakly acidic con-
ditions. The introduction of the surfactant CTAB as a structure
inducer leads to the formation of this unique and highly active struc-
ture. On the basis of the known mechanism, one possible mechanism
for the formation of hierarchical γ-AlOOH hollow microspheres is
presented in Fig. 7. Under weak acid conditions, the γ-AlOOH crys-
tal was grown mainly along the [100] and [001] directions and then

CO(NH2 )2 + 3H2 O → 2NH+4 + HCO−3 + OH− , (1)

Al3+ + 3OH− → Al(OH)3 (colloid), (2)

Al(OH)3 (colloid) → γ − AlOOH + H2 O. (3)

It is well known that boehmite crystals have an Al–O octahe-

dral structure, in which aluminum atoms are located in the center
of the octahedron and oxygen atoms are located in the lobes.31 The
flake-like structure of linked octahedral AlO6 units can form an infi-
nite plane perpendicular to the [010] direction. Since the (010) plane
of boehmite has the lowest interfacial tension, it is the basal face
in the crystal growth.32 The surfaces of the (010) crystal plane are
occupied by the hydroxyl groups, in which the lone pair electrons of
oxygen atoms are directed outward. The resulting layers are weakly
bound together by hydrogen bonds.33 This characteristic structure
of γ-AlOOH can be attributed to the pH-controlled growth mech-
FIG. 8. N2 adsorption–desorption isotherm of the product.
anism.19 In basic solutions, (010) crystal planes are stacked layer

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forms hexagonal nanoflakes. After CTAB was dissolved in water, it
could anchor to the surface of γ-AlOOH by chemical bonds.34,36,37
The separated layers formed a thin flake-like structure with the
dominating (010) crystal instead of curling to a rod-like structure
because the distance between the layers of the γ-AlOOH crystals
was increased. Finally, by Ostwald ripening, the flake-like struc-
ture units were self-assembled to form hollow microspheres. In this
unique morphology, the surface of the γ-AlOOH crystal was cov-
ered by a large amount of active hydroxyl groups of the(010) plane,
which could effectively improve the adsorption performance of the
material.
G. Textural analysis of the product
The textural information of the as-synthesized product with a
molar ratio of aluminum to urea of 4:15 was obtained from nitrogen
adsorption–desorption isotherms.
Figure 8 presents the typical N2 adsorption–desorption
isotherm of the product. It can be seen that the isotherm of the
sample is identified as a type V isotherm. In the low-pressure range
(p/p0 < 0.6), the N2 adsorption isotherm and desorption isotherm of
the samples overlap. When the relative pressure is in the range from
0.6 to 1.0 (0.6 < p/p0 < 1.0), the isotherm is identified to be a hystere-
sis of type H3, which reveals that the product is composed of flake-
like granular materials. The amount of adsorption rises rapidly in the
high-pressure range, indicating that the sample particle has uniform
size distribution. The calculation indicates that the specific surface
area of the hollow sphere is 43.5 m2 g−1 by Brunauer–Emmett–Teller
(BET).
H. Adsorption capacity test of the product
In recent years, the treatment of printing/dyeing wastewater
has received extensive attention from scientists. Congo red is one
of the most commonly used benzidine azo anionic dyes in the print-
ing/dyeing industry. When Congo red is discharged into the water, it
can be hydrolyzed to form toxic aromatic amines, which will pollute
the environment and threaten the survival of the living creatures. γ-
AlOOH can be used to reduce environmental pollution caused by
Congo red. In water, the hydroxyl groups on the crystal surface of
γ-AlOOH can combine with hydrogen ions by hydrogen bonds, so
the surface is positively charged. By electrostatic force, the negatively
charged Congo red can be adsorbed on the surface of γ-AlOOH and
then removed by filtration.
AIP Advances 11, 065209 (2021); doi: 10.1063/5.0050294
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FIG. 9. Adsorption analysis of Congo red
by the γ-AlOOH hollow microspheres:
(a) absorption spectra of Congo red
aqueous solution in the presence of the
as-synthesized product at different time
intervals and (b) absorption rate curve
of Congo red by the as-synthesized
product.
γ-AlOOH synthesized with the molar ratio of aluminum to urea
of 4:15 was activated by HCl (0.02 mol l−1 ) and dried again in order
to remove the remaining surfactant CTAB. 100 mg of γ-AlOOH
hollow microspheres was added to 100 ml of Congo aqueous solu-
tion (110 mg l−1 ) and stirred to form a suspension solution. After
some intervals, the ultraviolet–visible absorption spectrum of the
Congo red aqueous solution was measured. The results are pre-
sented in Fig. 9. From Fig. 9(a), it can be seen that the maximum
absorption wavelength of the Congo red solution appears at 497 nm.
Figures 9(b) and 9(a) both show that the intensity of the maximum
absorption peak decreases rapidly with the increase in time, and
it disappears at ∼60 min. That is to say, the maximum adsorption
capacity of the product for Congo red is 110 mg g−1 .
27 May 2024 04:05:40
By this test, it is shown that γ-AlOOH hollow microspheres
with highly active surface have excellent adsorption performance,
although it has a limited specific surface area. This fully confirms
that the performance of micro–nano-materials is not only related to
its specific surface area but also closely related to the characteristics
of the crystal plane exposed by its unique morphology.
IV. CONCLUSION
In summary, we present a facile method to prepare hierarchi-
cal γ-AlOOH hollow microspheres with a highly active surface by
the hydrothermal method. The average diameter and shell thick-
ness of the hollow microspheres are ∼10 and ∼1.6 μm, respectively.
The product has a hierarchical structure, which is constituted from
hexagonal nanoflake units. The thickness of the nanoflake is ∼14 nm,
and the length and width are ∼900 and ∼200 nm, respectively. The
structure inducer CTAB plays a key role in controlling the mor-
phology of the product. The crystal surface of the product is mainly
covered by active hydroxyl groups provided by the (010) plane. The
ratio of the (010) crystal plane exposed by this unique morphol-
ogy to the total surface area of the crystal units is about 91.5%.
The product has a good application prospect in the sewage treat-
ment. The adsorption performance test shows that the maximum
adsorption capacity of the product for Congo red is 110 mg g−1 ,
although its specific surface area is only 43.5 m2 g−1 . In addition,
the as-synthesized product with a highly active surface has a poten-
tial application value in catalysis, carrier of catalyst or adsorbent,
and other fields. The test result also reveals that the performance of
micro–nano-materials is not only related to its specific surface area
but also related to the characteristics of the crystal plane exposed by
its unique morphology.
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ACKNOWLEDGMENTS
This work was supported by the National College Stu-
dent Innovation and Entrepreneurship Training Program (Grant
No. 201614390024) and the College Research Fund (Grant No.
2014YBKJ030) of Shaanxi Xueqian Normal University.
DATA AVAILABILITY
The data that support the findings of this study are available
from the corresponding author upon reasonable request.
REFERENCES
1 23
X. Yu, J. Yu, B. Cheng et al., “Synthesis of hierarchical flower-like AlOOH
and TiO2 /AlOOH superstructures and their enhanced photocatalytic properties,”
J. Phys. Chem. C 113(40), 17527–17535 (2009).
2 24
S. Liu, C. Chen, Q. Liu et al., “Two-dimensional porous γ-AlOOH and
γ-Al2 O3 nanosheets: Hydrothermal synthesis, formation mechanism and catalytic
performance,” RSC Adv. 5(88), 71728–71734 (2015).
3 25
M. Zhang and B. Gao, “Removal of arsenic, methylene blue, and phos-
phate by biochar/AlOOH nanocomposite,” Chem. Eng. J. 226(12), 286–292
(2013).
4
Y. Wei, R. Yang, Y.-X. Zhang et al., “High adsorptive γ-AlOOH(boehmite)
@SiO2 /Fe3 O4 porous magnetic microspheres for detection of toxic metal ions in
drinking water,” Chem. Commun. 47(39), 11062–11064 (2011).
5
G. Hota, B. R. Kumar, W. J. Ng et al., “Fabrication and characterization of a
boehmite nanoparticle impregnated electrospun fiber membrane for removal of
metal ions,” J. Mater. Sci. 43(1), 212–217 (2008).
6
W. Cai, S. Chen, J. Yu et al., “Template-free solvothermal synthesis of hierarchi-
cal boehmite hollow microspheres with strong affinity toward organic pollutants
in water,” Mater. Chem. Phys. 138(1), 167–173 (2013).
7
M. Digne, P. Sautet, P. Raybaud et al., “Use of DFT to achieve a rational under-
standing of acid-basic properties of γ-alumina surfaces,” J. Catal. 226(1), 54–68
(2004).
8 30
A. Navrotsky, “Nanomaterials in the environment, agriculture, and technology
(NEAT),” J. Nanopart. Res. 2(3), 321–323 (2000).
9 31
Y. Yang, X. Jiao, B. Chen et al., “Preparation of fine-grained α-alumina powder
from seeded boehmite,” J. Nanopart. Res. 15(8), 1855 (2013).
10
J. Zhang, S. Wei, J. Lin et al., “Template-free preparation of bunches of aligned
boehmite nanowires,” J. Phys. Chem. B 110(43), 21680–21683 (2006).
11
Z. Zhu, H. Liu, H. Sun et al., “Surfactant assisted hydrothermal and ther-
mal decomposition synthesis of alumina microfibers with mesoporous structure,”
Chem. Eng. J. 155(3), 925–930 (2009).
12
Z. Wang, H. Du, J. Gong et al., “Facile synthesis of hierarchical flower-like
γ-AlOOH films via hydrothermal route on quartz surface,” Colloids Surf., A 450,
76–82 (2014).
13
J. Zhang, S. Liu, J. Lin et al., “Self-assembly of flowerlike AlOOH boehmite 3D
nanoarchitectures,” J. Phys. Chem. B 110(29), 14249–14252 (2006).
14
Y. Feng, W. Lu, L. Zhang et al., “One-step synthesis of hierarchical cantaloupe-
like AlOOH superstructures via a hydrothermal route,” Cryst. Growth Des. 8(4),
1426–1429 (2008).
15
Y. Liu, D. Ma, X. Han et al., “Hydrothermal synthesis of microscale
boehmite and gamma nanoleaves alumina,” Mater. Lett. 62(8-9), 1297–1301
(2008).
16
G. Li, Y. Liu, D. Liu et al., “Synthesis of flower-like boehmite (AlOOH) via a sim-
ple solvothermal process without surfactant,” Mater. Res. Bull. 45(10), 1487–1491
(2010).
AIP Advances 11, 065209 (2021); doi: 10.1063/5.0050294
© Author(s) 2021
ARTICLE scitation.org/journal/adv
17
C. F. Diniz, K. Balzuweit, and N. D. S. Mohallem, “Alumina nanotubes: Prepa-
ration and textural, structural and morphological characterization,” J. Nanopart.
Res. 9(2), 293–300 (2007).
18
J. Karger-Kocsis and L. Lendvai, “Polymer/boehmite nanocomposites: A
review,” J. Appl. Polym. Sci. 135(24), 45573 (2017).
19
X. Y. Chen and S. W. Lee, “pH-dependent formation of boehmite (γ-AlOOH)
nanorods and nanoflakes,” Chem. Phys. Lett. 438(4-6), 279–284 (2007).
20
M. P. B. van Bruggen, “Preparation and properties of colloidal core–shell rods
with adjustable aspect ratios,” Langmuir 14(9), 2245–2255 (1998).
21
X. Zhang, W. Cui, K. Page et al., “Size and morphology controlled synthesis of
boehmite nanoplates and crystal growth mechanisms,” Cryst. Growth Des. 18(6),
3596–3606 (2018).
22
H. Hou, Y. Xie, Q. Yang et al., “Preparation and characterization of γ-AlOOH
nanotubes and nanorods,” Nanotechnology 16(6), 741–745 (2005).
S. Ram, “Infrared spectral study of molecular vibrations in amorphous,
nanocrystalline and AlO(OH)⋅αH2 O bulk crystals,” Infrared Phys. Technol. 42(6),
547–560 (2001).
R. L. Frost, J. T. Kloprogge, S. C. Russell et al., “Vibrational spectroscopy and
dehydroxylation of aluminum (oxo)hydroxides: Gibbsite,” Appl. Spectrosc. 53(4),
423–434 (1999).
S. A. Dickie and A. J. Mcquillan, “In-situ infrared spectroscopic stud-
ies of adsorption processes on boehmite particle films: Exchange of surface
hydroxyl groups observed upon chelation by acetylacetone,” Langmuir 20(26),
11630–11636 (2004).
26
W. Wang, L. Li, and S. Xi, “A FT-IR spectroscopic study on conformation of
the hydrocarbon chains of crystallized cetyltrimethylammonium bromide,” Chin.
J. Chem. Phys. 6(6), 553–558 (1993).
27
J. T. Kloprogge, H. D. Ruan, and R. L. Frost, “Thermal decomposition of baux-
ite minerals: Infrared emission spectroscopy of gibbsite, boehmite and diaspore,”
J. Mater. Sci. 37(6), 1121–1129 (2002).
27 May 2024 04:05:40
28
M. Ocaña, V. Fornés, and C. J. Serna, “A simple procedure for the preparation
of spherical oxide particles by hydrolysis of aerosols,” Ceram. Int. 18(2), 99–106
(1992).
29
C. Hai, G. Zhang, J. Liu et al., “ζ-potential variations of micro-nano sized
hexagram-like α-Al2 O3 particles,” J. Nanopart. Res. 22(3), 65 (2020).
F. Wang, J. Zhu, and H. Liu, “Urea controlled hydrothermal synthesis of
ammonium aluminum carbonate hydroxide rods,” AIP Adv. 8(3), 035103 (2018).
P. Pardo, F. J. Serrano, O. Vallcorba et al., “Enhanced lateral to basal surface
ratio in boehmite nanoparticles achieved by hydrothermal aging,” Cryst. Growth
Des. 15(7), 3532–3538 (2015).
32
J.-P. Jolivet, C. Froidefond, A. Pottier et al., “Size tailoring of oxide nanoparticles
by precipitation in aqueous medium. A semi-quantitative modelling,” J. Mater.
Chem. 14(21), 3281–3288 (2004).
33
A. F. Popa, S. Rossignol, and C. Kappenstein, “Ordered structure and preferred
orientation of boehmite films prepared by the sol–gel method,” J. Non-Cryst.
Solids 306(2), 169–174 (2002).
34
B. S. Gevert and Z.-S. Ying, “Formation of fibrillar boehmite,” J. Porous Mater.
6(1), 63–67 (1999).
35
M. Zhang, R. Zhang, G. Xi et al., “From sheets to fibers: A novel approach to
gamma-AlOOH and gamma-A12 O3 1D nanostructures,” J. Nanosci. Nanotech-
nol. 6(5), 1437–1440 (2006).
36
D. J. Maclachlan and K. R. Morgan, “Phosphorus-31 solid-state NMR stud-
ies of the structure of amine-intercalated α-zirconium phosphate: Reaction of
α-zirconium phosphate with excess amine,” J. Phys. Chem. 94, 7656–7661 (1990).
37
D. J. Maclachlan and K. R. Morgan, “Phosphorus-31 solid-state NMR stud-
ies of the structure of amine-intercalated α-zirconium phosphate. 2. Titration of
α-zirconium phosphate with n-propylamine and n-butylamine,” J. Phys. Chem.
96, 3458–3464 (1992).
11, 065209-7