Sol-gel synthesis of mesoporous spherical zirconia

Article abstract of DOI:10.1039/c5ra23782c

Mesoporous spherical zirconia (ZrO₂) with a surface area of 113 m² g^-1 and average pore size of 5.0 nm is prepared by a sol-gel method with ZrOCl₂·8H₂O precursors and Sodium Dodecyl Sulfonate (SDS) templates with subsequent annealing at 500 °C in air. After calcination at 700 °C, the tetragonal phase transfers to monoclinic zirconia and the surface area is reduced to 26 m² g^-1. The mesoporous spherical structure, which is assembled by aggregation of the ZrO₂ nanoparticles, is confirmed by characterization using low and wide-angle X-ray diffraction, Transmission Electron Microscopy (TEM) and Scanning Electron Microscopy (SEM). Mesoporous ZrO₂ with a surface area of 113 m² g^-1 has a higher adsorption for Cs ion (357 mg g^-1). For the 700 °C calcinated ZrO₂, the absorption capacity at equilibrium is only 188 mg g^-1.

Full text of DOI:10.1039/c5ra23782c

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RR SS CC AA dd vv aa nn cc ee ss
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DOI: 10.1039/C5RA23782C
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ARTICLE
Sol-gel Synthesis of Mesoporous Spherical Zirconia
a
c
a
b
b
a
Yulei Chang, Chen Wang, Tongxiang Liang,* Chunsong Zhao, Xi Luo, Ting Guo, Jianghong
b
b
Gong, Hui Wu*
2
Mesoporous spherical zirconia (ZrO
2
) with the surface area of 113 m /g and the average pore size of 5.0 nm is
·8H O precursors and Sodium Dodecyl Sulfonate (SDS) templates with subsequent
annealing at 500 C in air. After calcinating at 700
prepared by sol-gel method with ZrOCl
2
2
o
o
C
,
tetragonal phase transfers to monoclinic zirconia and the surface
area is reduced to 26 m /g. The mesoporous spherical structure, which is assembled by aggregation of ZrO
nanoparticles, is confirmed by the characterizations of low and wide-angle X-ray Diffraction, Transmission Electron
2
2
2
Microscopy (TEM), Scanning Electron Microscope (SEM). The mesoporous ZrO
o
higher adsorption for Cs ion (357 mg/g). For the 700 C calcinated ZrO
2
with the surface area of 113 m /g has a
2
, the absorption capacity at equilibrium is only
1
88 mg/g.
1
5
neighboring materials, irradiation resistance should be considered
.
Introduction
ZrO
2
, MgO, MgAl
2
O
4
and Y
Al O12 are usually considered as inert
3 5
matrix for inert matrix fuel (IMF), among which, ZrO
2
is a promising
Inorganic nanomaterials with mesoporous structure have
received great attentions due to large surface areas, easy
candidate because of its excellent mechanical properties, including
high strength, high hardness and high fracture toughness. Currently
1
,2
functionalization, possibilities for applications in catalysis and
other favourable characteristics. Mesoporous materials with
controllable morphologies, pore sizes, and variable composition is
ZrO
route, the first step is the production of ZrO
method, and then the calcinated ZrO2 kernels are immersed in
2
–Minor Actinides (MA) fuel is manufactured by infiltration
2
kernels using sol-gel
3
highly desired for their advanced applications . While silica of
1
6
4
,5
actinide solution so that the infiltrated kernels are obtained . This
infiltration method does have two limitations, 1) the ratio of MA to
the matrix is too low and cannot be chosen freely, i.e., the content
of MA, that can be infiltrated, is determined by the porosity of the
kernels. 2) The size and distribution of pores in the ZrO2 after
calcinated are heterogeneous, resulting in the maldistribution of
MA. The uneven distribution of MA further degrades properties of
mesoporous structure was successfully applied in many fields,
synthesis of mesoporous materials of a board range of transition
metal oxides have aroused scientists’ interests for multiple
6
,7
applications , since transition metal oxides can be effectively
8
,9
10,11
applied as catalyst supports , chemical sensors
, solid oxide fuel
has better ion transfer
performance and the concentration of oxygen vacancy because it
has both acid sites and basic sites on surface. ZrO can acts as not
1
2
13
cells and photocatalystic materials . ZrO
2
2
fuels. Nevertheless the ZrO with mesoporous structure have a
2
promising to enhance volume and homogeneity of adsorption for
MA.
only the carrier but the catalyst for some reactions. Introducing a
mesoporous structure into the transition metal oxides is a promising
route to upgrade the properties.
2
There are different ways to compound mesoporous ZrO ,
1
7,18
broadly separated into hydrothermal synthesis
, non-hydration
As nuclear energy is developed rapidly nowadays, radioactive
waste has become a big problem. Many countries are devoted to
1
9
20,21
22
method , sol-gel method
and soft or hard template method .
2
3
1
4
Hudson and Knowles et al. use CTMAB (Hexadecyl trimethyl
ammonium Bromide) as template and ZrOCl2 as the source of
zirconium to react in the alkaline aqueous solution and then the
precursor was calcinated in hydrothermal synthesis reactor to
researching into ADS (accelerator driven systems) reactor which is
designed to accomplish the high level radioactive waste (HLW)
disposal. When choosing the matrix used in the ADS fuel to absorb
radioactive waste, the thermal and mechanical properties,
activation with neutrons, and chemical compatibility with
2
4
compound mesoporous ZrO
dihydrogen phosphate as template and Zirconium (IV) Ethoxide as
the source of zirconium to prepare mesoporous ZrO in acid
2
. Pacheco et al. used dodecyl
2
2
5
isopropyl alcohol solution. Dong et al. invented a hard template
method to prepare mesoporous oxide and the process was
described as followed. Firstly, uniform mesoporous silica spheres
2
6
prepared by Unger’s method are used as the template for the
formation of mesoporous carbon sphere by the nanocasting
2
7
technology
2
, and then mesoporous ZrO are obtained by
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templating the specific precursor with carbon sphere whereafter. Lu using a BEL Japan Inc. Belsorp-HP surface area analyser at 77 K. The
2
8
et al. use sol-gel method to synthesis yttria-stabilized mesoporous surface areas are calculated by the Brunauer-Emmett-Teller (BET)
ZrO . However, a facile technique that is easy to practice and method and the pore size distributions are calculated by the
2
inexpensive to synthesis uniform and high surface area sphere- Barrett-Joyner-Halenda
shaped ZrO with inner mesoporous structure is still lacking. In this adsorption/desorption isotherm. The samples are prepared by
work, we present a simple and practicable facile sol-gel approach ultrasonic dispersing the material in methanol and then dripped
(BJH)
method
from
the
2
with the aid of structure-directing surfactant to synthesize ZrO
2
one drop on a carbon coated copper grid when doing TEM.
nanoparticles with mesoporous structure. We use low-cost material
ZrOCl2 (zirconium oxychloride) and CO(NH2)2 (carbamide) as raw
Adsorption experiments
+
2
9
The cesium ion (Cs ) adsorption on ZrO
2
is investigated. Cesium
materials to prepare mesoporous zirconia by sol-gel method with
3
0
is supplied as cesium chloride from Sigma–Aldrich Company. Stock
solutions of the test reagent are prepared by dissolving CsCl in
distilled water, the initial concentration is 150 mg/L, and the initial
pH is adjusted to the value of 7.0 using dilute solution of sodium
the aid of SDS (sodium dodecyl sulfate) as template. Moreover, a
novel and interesting structure is found in the ZrO powders. An
amount of zirconia spheres are obtained and mesopore spreading
on sphere. The specific surface area of mesoporous ZrO is quite
2
2
hydroxide. 40mg of ZrO
2
adsorbent is added into the solution at 25
high comparing with samples of the precious methods and becomes
higher after aging in ammonia solution.
Experimental
o
C
. Then, the suspension is stirred for 5 hours. After centrifugation,
+
the residual quantity of Cs is determined by ICP-AES. The
absorption capacity q (mg/g) at equilibrium is calculated: q = (C
)V/W, where C (mg/L) and C (mg/L) are the concentrations of Cs
(≥99.0%), SDS (Sodium Dodecyl Sulfonate), at initial and equilibrium, respectively. V(L) and W(g) are the volume
2 2
) (≥99.0%) (Carbamide) and Ammonia solution (25%- of solution and the mass of adsorbent, respectively.
e
e
0
-
+
Chemicals
C
e
0
e
ZrOCl
CO(NH
8%) are purchased from Sinopharm Chemical reagent Co. Ltd.
2
2
Results and Discussion
All chemicals are used as received without further purification.
X-ray diffraction
Preparation
The following synthesis procedure is employed for the
preparation of mesoporous zirconia nanoparticles. 1) 3.759 g SDS is
dissolved in 400ml deionized water. The SDS solution is then stirred
on the magnetic stirring apparatus for about 3h until SDS is totally
dissolved in H O as solution A. 2) 0.25mol (15.02 g) carbamide and
2
0
2
.1mol (32.21 g) ZrOCl are dissolved in 100ml deionized water as
solution B. 3) We inject solution B into solution A using injection
pump in a rate of 0.6 ml/min, meanwhile, the mixture solution is
o
heated in water bath to 75
C. After injecting all the solution B into
A, solution C is obtained with 28.0 mmol/L SDS and 0.5 mol/L
carbamide and 0.2mol/L ZrOCl . 4) The C solution is turned to be
2
o
viscous sol after reacting for 12 h at 75
C. Afterward, the viscous sol
o
is dried for 24h at 80
C in air atmosphere under atmospheric
pressure to obtain a porous solid mass (xerogel). 5) The porous solid
o
o
mass is calcinated under air at 500
C and 700 C for 5 h and
naturally cooled under air condition to remove the SDS surfactant
and then the desired mesoporous ZrO particles are obtained.
2
Characterization
The X-ray diffraction (XRD) analyses are used to identify the
crystalline phase of the sample, which are performed on a SmartLab
diffractometer (Cu Kα radiation, λ=1.5406 A) with an operating
voltage of 40 kv and
a current of 40 mA. Morphological
characterization is obtained by means of scanning electron
microscope (SEM) using MERLIN VP Compact with an accelerating
voltage of 1.0 kV. When conducting the SEM analyses, a small
2
quantity of ZrO powder was dispersed in ethyl alcohol under
ultrasound so that the nanoparticle can be dispersed
homogeneously. Transmission electron microscopy (TEM) is
2
Fig. 1(a) XRD pattern of the synthesized mesoporous-assembled ZrO nanoparticles;
accomplished using Tecnai G2 TEM with the operating voltage of (b) XRD pattern in the low angle range of the synthesized mesoporous-assembled
2
ZrO nanoparticles.
2
00kV. Nitrogen adsorption/desorption isotherms are obtained
2
|
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As we can see in Fig. 1(a), the as-synthesized particles are that ZrO
ARTICLE
3
3
2
particles are formed in two step mechanism . First, ZrO
2
amorphous. Two phase transformations are observed with precursors are hydrolyzed and polymerized to form small primary
increasing calcination temperature. The first one is a transformation particles in the size range of 1–10 nm, and then aggregate to form
from the amorphous state to crystalline tetragonal zirconia, which the final particles. As diffusion-limited aggregation mostly leads to
o
C
finished at about 500
. The second phase transformation is from disordered particles with no structural porosity, in Fig.2, one
tetragonal to monoclinic zirconia, which occurred after calcination spherical particle is composed of many tiny particles, thus, the
o
at 700
tetragonal phase and then to the thermodynamically stable aggregation.
monoclinic phase only after heating at higher temperatures is Fig.3 is the TEM and SAED images of ZrO2 spherical
C. This transition from the amorphous to the metastable present reaction is believed to proceed via reaction-limited
3
1,32
o
common and has been reported for zirconia particles
. For the particles after calcinated at 500 C. As shown in Fig. 3(a) and
first phase transformation, it is commonly accepted that the short- (b), the particle is obviously spherical and many pores (about
range order in the amorphous phase is more similar to the 5.0 nm in the length scale) spreading over the spheres, each
3
2
tetragonal rather than the monoclinic phase
.
Thus, initial sphere is composed of hundreds of individual tiny
o
crystallization at 500
C yields the metastable tetragonal phase, its nanoparticles with an average diameter of about 5 nm, it can
XRD pattern correspond to the well crystallized with tetragonal be conclude that the mesopore is created by assembly of zirconia
o
phases (PDF number：89-6976), the primary crystal size is 6.4 nm nanoparticles. During calcination at 500
C, amorphous zirconia
as calculated by applying the Scherrer equation on the (011) transfers to tetragonal phase, rearrangement of the individual
diffraction peak. It has been reported that below a critical grain nanoparticles could occur, which results in the formation of strong
size, tetragonal rather than monoclinic becomes the covalent bridges between the particles. This covalent bonding
thermodynamically preferred phase due to differences in the between particles could be responsible for the high thermal
surface energies of the polymorphs. This critical size has been stability of the mesoporous ZrO2 nanoparticles. Thus, ZrO2
3
1
reported to be typically of the order of 10–20 nm
Small-angle diffraction of ZrO calcinated at 500
is done for the purpose of testing if there is mesoporous
structure in this sample. The result is shown in Fig. 1(b). After
.
nanocrystallites assembled to form thick mesoporous walls.
o
2
C and
o
7
00 C
o
calcinated at 500 C, there is a peak and the beginning of the
pattern which means there are mesopores in the material. But
the peak intensity is reduced when the sample is calcinated at
o
700
C,
this means some mesopores disappeared.
Scanning electron microscope (SEM) and Transmission Electron
Microscopy (TEM)
Fig. 2 shows that the obtained material is spherical
particles with the size ranged from 100 nm to 300 nm. The
inset of Fig.2 indicates that the surface of particles is not
smooth and the spherical particles are agglomerates, i.e., they
are composed of many tiny particles.
2
Fig. 3 (a) Low magnification TEM image of ZrO sphere shows that big sphere is
consist of tiny particle; (b) In the low magnification TEM image, the space between
tiny particle is mesopore size; (c) High magnification TEM images of some particles;
(
2
d) SAED image of multicrystal ZrO .
Fig. 3(c) is the high magnification TEM image of some
particles. As we can see in the picture, the pore wall is
multicrystal and the lattice space of 0.3 nm assigned to the
interplanar distance of the (101) planes of the sample. The
corresponding Selected Area Electron Diffraction (SAED) pattern
(Fig. 3(d)) of the spherical aggregates of ZrO2 nanoparticles is
indicative of high nanocrystallinity of the formed product and can
be assigned to the tetragonal phase, the concentric Debye-
Scherrer rings which can be indexed to the (011), (110), (020)
and (121) planes. The d-spacing corresponding to the diffraction
o
Fig. 2 SEM image of synthesized particles after calcinated at 500
sphere morphologically.
C, showing regular
2
The shape and size of ZrO nanoparticles are controlled by rings of the SAED pattern are in good agreement with the
3
2
synthesis method, stabilizer or surfactant , it is generally accepted tetragonal phases of ZrO nanocrystal.
2
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Surface area and porosity
Zr(OH)4-x(OOH)
(4)
x 2 2 2
ꢀ ZrO (amorphous) ꢀ t-ZrO or m-ZrO
o
After calcinated at 500
2
C, the spherical ZrO nanoparticle
8
+
scaffold exhibits a mesoporous channel system, displaying high
[Zr (OH) (H O)16] in aqueous solution generates Zr(OH)4-
4 8 2
surface areas and narrow pore size distribution. Fig. 4 shows N2 x(OOH)x nanoparticles and grows slowly because of the slow
-
adsorption-desorption isotherm of the sample calcinated at introduction of OH from the release of carbamide, and these
o
C
500
, in which pore structure is confirmed clearly. The nanoparticles are adhere to the surface of SDS surfactant
.
isotherm displays the typical type IV curve, which is usually During drying of the solvent, the surfactant induces cooperative
attributed to the predominance of mesopores. The presence of a assembly of functionalized nanoparticles to attain packing, results
pronounced hysteresis loop in the isotherm curve is indicative for a in the formation of large spherical particles. When the SDS
3
D intersection network of the pores, which also goes well with the template is removed from the particles, the mesopores are
TEM observation. Moreover, the isotherms possess evident formed.
hysteresis loop with an evident increase in adsorbed N
volume in the relative pressure range of 0.45–0.90. This
indicates the capillary condensation of N molecules inside the
2
2
sufficiently pores of small sizes. The average size of the mesopore
is calculated to be about 5.0 nm.
o
The spherical ZrO
2
nanoparticle calcinated at 500
C
exhibits
2
1
13 m /g of surface area by a nitrogen Brunauer-Emmett-Teller
(
BET) measurement, which is rather high comparing with
2
0
previous result. Qibing Chang synthesized mesoporous ZrO
2
2
with the surface area of 43 m /g. After calcinated at 700
o
C
, the
2
nanoparticle reduced to 26 m /g. In bulk
surface area of ZrO
2
zirconia, phase transformation from tetragonal to monoclinic is
accompanied by volume expansion of 3–5%. This volume
2
Fig.5. Mechanism for the forming of mesoporous spherical ZrO particles
a
expansion will result in the collapse and disappear of mesopores.
Adsorption of Cesium Ions on ZrO
2
It is known that pH is important factor for the adsorption of
metal ions on adsorbents, because it affects the solution chemistry
of the solute as well as the functional groups present in the sorbent.
3
4
According to reference , zirconia contains hydroxyl groups which
can act role in ion-exchange reaction through the substitution of its
protons by cesium ion, the reactions is:
+
+
nCs + Zr(-OH)
m
↔ Zr(-O-Cs)m-n + nH (1)
+
Where -OH is hydroxyl group, nH is number of protons
released, and Zr refers to the zirconia surface. The adsorption
process is influenced by pH, contact time and temperature. The
highest removal efficiency of zirconia for cesium ion was obtained
3
5
at pH 7.0 . In this paper we fix the experimental parameters as:
pH=7, Temperature=25°, the purpose is to compare the
adsorption capacity of several kinds of powder on Cs ion. The
adsorption equilibrium is reached within 2 hours. Table 1 shows the
o
Fig. 4.
N
2
adsorption-desorption isotherm of ZrO
2
calcinated at 500 C
To explain the special morphology of mesoporous, in Fig.5,
adsorption capacity of Cs ion on ZrO
2
, where Z5 means ZrO
2
we suppose a model for the forming of mesoporous spherical ZrO
8
2
+
o
o
calcinated at 500
C, Z7 means ZrO calcinated at 700 C, and R is the
2
particles. When ZrOCl
2
8H
2
O is dissolved in water [Zr
4
(OH)
8
(H
2
O)16
+
]
data from reference [35].
4
complexation is formed, and carbamide is hydrolyzed to NH and
-
-
OH , then Zr(OH)4-x(OOH)
finally ZrO is produced during the subsequent heating. The whole
reaction formula can be expressed as:
x
, is precipitated by the action of OH ,
2
surface area (m /g)
Sample
q
e
(mg/g)
357
2
Z5
Z7
R
113
26
-
8
]
+
-
+
188
130
4
ZrOCl
2
8H
2
O ꢀ [Zr
4
(OH)
8
(H
2
O)16
+8Cl + 8H
(
1)
+
4
-
CO(NH ) + 3H O ꢀ 2NH + 2OH + CO
(2) Table 1. The adsorption capacity of Cs ion
2
2
2
2
8
]
+
-
–(2+2x)
x
-
[
(
Zr
3)
4
(OH)
8
(H
2
O)16
+ 8xOH ꢀ4Zr(OH)4-x(OOH)
+ (24+8x)OH
Our result indicates that the mesoporous ZrO
2
has a
higher adsorption for Cs ion. Future work includes: adding Y to
stable ZrO2 phase, improving the specific surface area,
4
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ARTICLE
studying the effect of monoclinic and tetragonal phase on the
adsorption behaviour, surface modification to improve the
adsorption or selective adsorption capacity, and the
adsorption behaviour of other radionuclides, etc..
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Courcot, Electron Paramagnetic Resonance investigation of
the nature of active species involved in carbon black
In this work, we produce mesoporous sphere of zirconia
from a simple sol-gel processing. Carbamide will release OH-
o
-
when heated to 70
group of ZrO precursor. After calcinated at the temperature
under air condition, the sample exhibit regular
C
in acid solution and OH is the essential
oxidation on ZrO and Cu/ZrO catalysts, Catal. Commun.,
2 2
17, 64–70 (2012).
2
o
of 500
C
9
X. Zhang, H. Su, and X. Yang, Catalytic performance of a three-
dimensionally ordered macroporous Co/ZrO catalyst in
Fischer–Tropsch synthesis, J. Mol. Catal. A: Chem., 360, 16–
5 (2012).
nanospheriacle which consists of tiny particles. The space
between these tiny particles is mesopore size and the surface
2
area is as higher as 113 m /g. The adsorption for Cs ion on this
2
2
kind of mesoporous spherical ZrO
o
2
is 357 mg/g. When
tetragonal phase transfers to monoclinic 10
calcinating at 700
C
,
T. Liu, L. Li, and J. Yu, An electrochemical sulfur sensor based
on ZrO (MgO) as solid electrolyte and ZrS + MgS as
auxiliary electrode, Sens. Actuators B: Chem., 139, 501–504
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2
zirconia and the surface area is reduced to 26 m /g, the
adsorption for Cs ion is only 188 mg/g.
2
2
(
1
1
R. Zhang, X. Zhang, and S. Hu, High temperature and pressure
chemical sensors based on Zr/ZrO electrode prepared by
nanostructured ZrO film at Zr wire, Sens. Actuators B:
Acknowledgements
2
This work is supported by the National Natural Science
Foundation of China (Grand No. 21271114 and No. 91326203);
Tsinghua University independent research and development
fund (20111080982) and Program for Changjiang Scholars and
Innovative Research Team in University (IRT13026).
2
Chem., 149, 143–154 (2010).
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