Controllable Multicomponent Co-Assembly Approach to Ordered Mesoporous Zirconia Supported with Well-Dispersed Tungsten Oxide Clusters as High-Performance Catalysts

Article abstract of DOI:10.1002/cctc.202100385

Zirconia supported WO_x clusters with high acid strength and good stability are important solid acid catalysts in many reactions. However, conventional synthetic methods such as incipient-wetness impregnation and co-precipitation usually result

Full text of DOI:10.1002/cctc.202100385

The European Society Journal for Catalysis
Supported by
Accepted Article
Title: Controllable Multicomponent Co-Assembly Approach to Ordered
Mesoporous Zirconia Supported with Well-Dispersed Tungsten
Oxide Clusters as High-Performance Catalysts
Authors: Yonghui Deng, Jichun Li, Xuanyu Yang, Junhao Ma, Chenyi
Yuan, Yuan Ren, Abdulaziz A. Alghamdi, Fahad A. Alharthi,
and Xiaowei Cheng
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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To be cited as: ChemCatChem 10.1002/cctc.202100385
Link to VoR: https://doi.org/10.1002/cctc.202100385
01/2020

10.1002/cctc.202100385
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DOI: 10.1002/ ((please add manuscript number))
Article type: Full Paper
Controllable Multicomponent Co-Assembly Approach to Ordered Mesoporous Zirconia Supported
with Well-Dispersed Tungsten Oxide Clusters as High-Performance Catalysts
Jichun Lia, Xuanyu Yanga, Junhao Maa, Chenyi Yuana, Yuan Rena, Xiaowei Cheng*,a, Yonghui Deng*,a,b
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a Department of Chemistry, State Key Laboratory of Molecular Engineering of Polymers, Shanghai Key Laboratory of
Molecular Catalysis and Innovative Materials, Fudan University, Shanghai 200433, China
b State Key Lab of Transducer Technology, Shanghai Institute of Microsystem and Information Technology, Chinese
Academy of Sciences, Shanghai 200050, China
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* Email: xwcheng@fudan.edu.cn (X. Cheng), yhdeng@fudan.edu.cn (Y. Deng).
Keywords: Mesoporous materials, Multicomponent co-assembly, Solid acid, Tungsten oxide, Zirconia
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Zirconia supported WOx clusters with high acid strength and good stability are important solid acid
catalysts in many reactions. However, conventional synthetic methods such as incipient-wetness
impregnation and co-precipitation usually result in the products with low catalytic activity due to low
surface area, uncontrollable and non-homogeneous distribution of tungsten species. In this study, a facile
multicomponent co-assembly approach was utilized to straightforwardly synthesize ordered mesoporous
WOx/ZrO2 composites (OMWZr) with mesopore size over 17 nm, pore volume of 0.13 - 0.18 cm3/g and
surface area of 27.3 - 41.7 m2/g. The materials were composed of robust crystalline ZrO2 skeleton and
well-dispersed WOx clusters (polytungstates) in framework under the optimized conditions. The doped
tungsten species were well stabled by the crystallized skeletons of mesoporous ZrO2, which can inhibit
growth of tetragonal ZrO2 but facilitate crystallization of monoclinic ZrO2. The states of tungsten species
(monotungstates, polytungstates and crystalline WO3) can be precisely adjusted by their doping amount
in framework and calcination temperature as well, which can further tune the surface acidity of OMWZr
composites. Owing to the existence of numerous active surface WOx clusters generated over exposed
surface of mesoporous ZrO2, the OMWZr catalysts not only show great spatial homogeneity of accessible
Brönsted acid sites and feasible mass diffusion during catalytic reactions, but also display outstanding
acid-catalytic performance over hydrolysis reactions of benzaldehyde dimethyl acetal. The catalyst can
be reused for more than 10 cycles, without reduction of catalytic activity and selectivity to benzaldehyde.
1. Introduction
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As a kind of important industrial catalysts, solid acids are usually utilized in wide fields including fine
chemistry,[1] pharmaceutical synthesis,[2] biomass processing,[3] petrochemical industry,[4] and so on.
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Compared to conventional homogeneous acid catalysts (HCl, H2SO4, p-toluenesulfonic acid, etc.), solid
acids possess great advantages such as high safety in transport, outstanding catalytic activity, easy
separation and recyclability, no corrosion to reactor, and no discharge of wasted acid solution.[5-7]
Therefore, a large number of new type solid acids, such as zeolites, metal oxides, metal salts, ion exchange
resins, have been extensively developed and used as heterogeneous catalysts.[8-14] Among them, composite
metal oxides have attracted more and more attentions because of controllable introduction of acid sites
and enhancement of acid amount/strength through a synergistic effect of each component.[15-17]
Through incorporating tungsten on zirconia, the WOx/ZrO2 composites were first reported as novel
solid superacid catalysts for isomerization of butane and pentane.[18] Due to high acid strength and good
stability in comparison with sulfated zirconia, the WOx/ZrO2 composites also enable wide applications in
diverse acid-catalytic reactions.[19-26] Notably, the catalytic activity was demonstrated to be dependent on
surface acid density, which was closely associated with the density (W atoms/nm2) and dispersion
(electronic structure and domain size) of WOx species supported on ZrO2. Therefore, the surface acid
density of WOx/ZrO2 can be controlled by tuning tungsten amount, calcination temperature, and surface
area of ZrO2 supports.[8,27-31] However, conventional incipient-wetness impregnation and co-precipitation
methods usually result in WOx/ZrO2 composites with low surface area, uncontrollable and non-
homogeneous distribution of polytungstate species, and low catalytic activity.[26,32] Therefore, recent work
has been devoted to developing feasible strategies, such as microwave-assisted method,[25] two-phase
interface hydrolysis method,[33] and anionic exchange method,[34] in order to obtain WOx/ZrO2 catalysts
with higher specific surface area and desired exposed active sites. The rational design of mesoporous
WOx/ZrO2 materials with good pore connection and uniform W dispersion has been considered to be an
effective route, because they can facilitate mass transfer and suppress carbon deposition in catalytic
reactions involving large-size organic molecules. By using a one-pot synthesis method with Pluronic P123
triblock copolymer as template, tungsten and zirconium precursors were incorporated into the silica
framework of ordered mesoporous KIT-6.[35] The WZr-KIT-6 catalyst possesses strong Lewis/Brönsted
acid sites, exhibiting improved ethylene yields in ethanol dehydration. The mesoporous ceramic acid was
prepared by coating a uniform WZrOx layer onto the internal surface of mesoporous silica with extra-
large pores (such as FDU-12).[36] This mesoporous silica-supported WOx/ZrO2 solid acid exhibited
ordered mesostructure, strong Brönsted acid sites and high thermal stability, which also performed as a
good catalyst in ethanol dehydration. However, most of the reported mesoporous catalysts are supported
on mesoporous silica through a low-efficiency loading route. To the best of our knowledge, little work
has been reported on the direct synthesis of ordered mesoporous WOx/ZrO2 solid acids,[23,37] especially
those with large ordered mesopores, abundant exposed acid sites and highly crystallized pore walls.
Ordered mesoporous materials (OMMs) are a kind of porous materials with uniform pore diameters
between 2.0 and 50 nm, displaying unique physical/chemical properties, adjustable pore structure and
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high specific surface area,[38-44] they thus have been extensively applied in numerous emerging fields. In
general, soft-template and hard-template methods are developed for OMMs synthesis.[45-53] As a typical
soft-template approach, the controllable multicomponent co-assembly is flexible and universal for
synthesis of OMMs with diverse mesostructures and components. However, great challenges still remain
in directly synthesizing mesoporous WOx/ZrO2 composites by the traditional soft-template approach.[23]
For example, Pluronic F127 was used as template for synthesis, and the product showed high specific
surface area but disordered mesopores with confined WOx clusters, mainly due to mismatch of low glass
transition temperature of F127 with high crystallization temperature of ZrO2.[47] In past decade, using the
lab-made amphiphilic diblock copolymer of poly(ethylene oxide)-b-polystyrene (PEO-b-PS) with rich sp2
carbon and high glass transition temperature as template, our group has developed a facile and universal
strategy for the synthesis of several highly ordered mesoporous metal oxides with single or multiple
components.[54-62] But until now no work has been reported about the synthesis of ordered mesoporous
solid acids based on composite metal oxides.[19]
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Herein, by using a high molecular weight amphiphilic diblock copolymer (PEO114-b-PS221) as the
soft template, a controllable multicomponent co-assembly strategy was adopted to directly synthesize
ordered mesoporous WOx/ZrO2 solid acids (OMWZr) with tunable W contents and acid amounts. The
WOx clusters were well restrained as acid sites onto pore walls of mesoporous WOx/ZrO2, in which
highly-crystallized mesoporous ZrO2 provided a favorable rigid skeleton for uniform distribution and
stabilization of WOx clusters. The robust ordered mesostructure and acidic polytungstate species on pore
walls were well maintained even after calcination at 600 °C. To the best of our knowledge, this is the first
report about the successful synthesis of ordered mesoporous WOx/ZrO2 solid acids with a soft-template
method. The OMWZr composites showed ordered mesostructures with pore size over 17 nm, pore volume
of 0.13 - 0.18 cm3/g, surface area of 27.3 - 41.7 m2/g and tunable acid sites (0.026 - 0.118 mmol/g). The
intrinsic structural characteristics endow the OMWZr compositions with a particular potential application
as a high-efficiency solid acid catalyst in hydrolysis reaction of benzaldehyde dimethyl acetal with
excellent activity and recyclability.
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2. Results and discussion
Scheme 1 illustrates the procedure of one-pot controllable multicomponent co-assembly for
synthesis of ordered mesoporous WOx/ZrO2 composites. Amphiphilic diblock copolymer of PEO-b-PS
and two inorganic precursors were firstly dissolved in THF/EtOH solution. During evaporation of
THF/EtOH, spherical composite micelles were gradually formed through aggregation of PEO-b-PS,
which were composed of cores of hydrophobic PS blocks and shells of PEO blocks associated with
uniform inorganic zirconium and tungsten species by hydrogen bonding (Step 1). In order to decrease
surface free energy, the spherical micelles tended to closely pack into inorganic-polymer composites
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showing face-centered cubic (fcc) ordered mesostructures (Step 2). By calcination in N2 atmosphere at
350 °C, the polymer as template was partially carbonized, and residual carbon was performed as rigid
skeleton to support crystallized composite metal oxides at elevated temperatures. The template and
residual carbon were completely removed by calcination in air at 600 °C, and during this process,
framework crystallization was promoted to obtain the ordered mesoporous WOx/ZrO2 (OMWZr)
composites with large mesopores, crystallized pore walls and tunable W/Zr ratios (Step 3).
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Scheme 1. Illustration of the one-pot controllable multicomponent co-assembly pathway for ordered
mesoporous WOx/ZrO2 composites. Step 1: co-assembly of tungsten precursors, zirconium precursors
and PEO-b-PS into composite spherical micelles with cores of hydrophobic PS segments and shells of
PEO segments during THF/EtOH evaporation; Step 2: the spherical composites further pack into fcc
ordered mesostructures after complete evaporation of solvent and thermosetting at 100 °C for further
solidification; Step 3: carbonization of the ordered mesostructured composites under N2 atmosphere and
pyrolysis in air, resulting in ordered mesoporous WOx/ZrO2 composites.
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Crystallographic structures of OMWZr composites were identified by using wide-angle X-ray
diffraction (XRD) in the range of 20 - 80°/2θ (Figure 1A). First, the obtained mesoporous ZrO2 displays
four primary diffraction peaks at 30.1, 35.2, 50.1, 60.1°/2θ (Figure S1A), which are indexed to (111),
(110), (112) and (121) reflections of tetragonal ZrO2 (JCPDS No. 50-1089), respectively. For comparison,
two new diffraction peaks appear at 28.2 and 31.4°/2θ in OMWZr composites (Figure 1A), which are
well attributed to (-111) and (111) reflections of monoclinic ZrO2 (JCPDS No. 37-1484) respectively,
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suggesting partial transformation of tetragonal ZrO2 to monoclinic ZrO2 caused by in situ insertion of
WOx species into the framework of OMWZr composites. With W/Zr ratios increasing from 0.03 to 0.10,
the peak intensity of monoclinic ZrO2 increases, while that of tetragonal ZrO2 decreases (Figure 1A-a to
c), indicating that introduction of WOx species can inhibit growth of tetragonal ZrO2 and facilitate
crystallization of monoclinic ZrO2. Besides, no diffraction peaks belonged to crystalline WO3 are
observed in these XRD patterns, demonstrating that WOx species are well dispersed on pore walls of the
OMWZr composites when W content is below 10 mol%. However, diffraction peaks at 22.9, 23.5,
24.2°/2θ appear in meso-0.15WOx/ZrO2 (Figure 1A-d), which are assigned to (002), (020) and (200)
reflections of monoclinic WO3 (JCPDS No. 43-1035, Figure S1-B) respectively, suggesting that the
doped WOx species easily crystallize into isolated WO3 when W content is over 15 mol%. Raman
spectroscopy was applied to further investigate fine structure of the obtained OMWZr composites (Figure
1B). The absorption peaks at around 469 and 631 cm-1 correspond to tetragonal ZrO2, while monoclinic
ZrO2 can be well distinguished from the Raman bands at about 273, 331, 378, and 560 cm-1, indicating
that all the OMWZr composites show two crystalline phases including tetragonal and monoclinic ZrO2.[63]
In addition, the Raman spectrum of meso-0.15WOx/ZrO2 catalyst displays two additional distinct bands
attributed to monoclinic WO3 at 714 and 808 cm-1 (Figure 1B-d),[23] in good agreement with its XRD
pattern (Figure 1A-d). Each sample of OMWZr composites shows broad bands associated with WOx-O-
Zr bridging bonds around 920 - 980 cm-1.[48] Moreover, meso-0.03WOx/ZrO2 exhibit a band at around
1000 cm-1, corresponding to isolated surface monotungstates. Besides of this band, meso-0.07WOx/ZrO2
shows an additional band at about 1020 cm-1, attributed to surface polytungstates (WOx clusters), which
are the main sources of acid sites in WOx/ZrO2 composites, revealing coexistence of monomeric and
polymeric tungsten species in this sample.[63] The band about monotungstates completely disappears in
meso-0.10WOx/ZrO2 and meso-0.15WOx/ZrO2, but the band about polytungstates can still be observed,
indicating that tungsten species in both samples exist as polytungstates. Therefore, the state of WOx
species is closely dependent on the contents of W species in OMWZr composites. When W amount is
below 3 mol%, it primarily exists as surface monotungstate species. When W amount increases to 7 mol%,
both monotungstate species and polymetric WOx clusters are dispersed in the composites. When W
amount is up to 10 mol%, monotungstate species are completely replaced by polymetric WOx clusters.
When W content further increases over 15 mol%, polymetric WOx clusters and crystalline WO3 particles
coexist in OMWZr composites.
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Figure 1. (A) XRD patterns and (B) Raman spectra of ordered mesoporous WOx/ZrO2 composites with
different W/Zr mole ratios: (a) meso-0.03WOx/ZrO2, (b) meso-0.07WOx/ZrO2, (c) meso-0.10WOx/ZrO2,
and (d) meso-0.15WOx/ZrO2.
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Transmission electron microscopy (TEM) images of the OMWZr composites taken along [110]
direction show that meso-0.03WOx/ZrO2, meso-0.07WOx/ZrO2 and meso-0.10WOx/ZrO2 possess ordered
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face-centered cubic (fcc) mesostructure (Fm3m symmetry) (Figure 2A to 2C), in which average pore size
is estimated to be about 20.0 nm, consistent with the molecular size of PEO114-b-PS221. Field-emission
scanning electron microscope (FESEM) images further confirm their ordered mesoporous structures over
a large domain composed of rigid skeletons in thickness of ~ 4.0 nm (Figure 2D to 2F). Pure mesoporous
ZrO2 and WO3 materials were also synthesized for comparison, exhibiting the same ordered
mesostructures with OMWZr composites (Figure S2A and S2B). However, the sample of meso-
0.15WOx/ZrO2 displays worm-like mesostructures with low ordering (Figure 2C), mainly caused by the
formation of large WO3 nanocrystals in WOx/ZrO2 composites and collapse of ordered mesopores when
W content is as high as 15 mol%.
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Figure 2. TEM images of (A) meso-0.03WOx/ZrO2, (B) meso-0.07WOx/ZrO2, (C) meso-0.10WOx/ZrO2;
and SEM images of (D) meso-0.03WOx/ZrO2, (E) meso-0.07WOx/ZrO2, (F) meso-0.10WOx/ZrO2.
High-resolution TEM (HRTEM) image of meso-0.10WOx/ZrO2 (Figure 3A) clearly displays crystal
lattice of tetragonal ZrO2 ((011) lattice plane) and monoclinic ZrO2 ((111) and (-111) lattice plane) within
mesopore walls, and no crystalline WO3 phase appears around mesopore skeletons, in good consistence
with the XRD and Raman results (Figure 1). Owing to serious effect of tungsten precursors in large
amount on the co-assembly process, disordered mesopores and highly-crystallized ZrO2 walls are formed
in meso-0.15WOx/ZrO2 (Figure S2C and S3A). The regular spotted diffraction rings in selected area
electron diffraction (SAED) patterns further confirm polycrystalline walls of meso-0.10WOx/ZrO2 and
meso-0.15WOx/ZrO2 (Figure 3B and S3B), containing both tetragonal and monoclinic ZrO2. Moreover,
high-angle annular dark-field scanning transmission electron microscopy (HAADF-STEM) images show
ordered mesoporous structures with average pore size of 17.7 nm and wall thickness of 4.2 nm (Figure
3C). The corresponding energy dispersive X-ray (EDX) element mappings prove uniform distributions of
W, O and Zr elements over large domains (Figure 3D). The W/Zr mole ratio of meso-0.10WOx/ZrO2 is
calculated to be about 0.17, slightly higher than its chemical mole ratio (0.10), indicating that WOx species
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as acid sites show an enrichment potential on surface of the OMWZr composites. Small-angle X-ray
scattering (SAXS) patterns of the OMWZr composites (Figure 4A) display scattering peak assigned to
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111 reflection of ordered fcc mesostructure with space group of Fm3m.[58] In contrast, well-dispersed
WOx species in monotungstate or polytungstate states are very small, in consequence, they have almost
no effects on unit cell parameters of OMWZr composites when W content is below 10 mol% (Figure 4A-
a to c), which show ordered mesostructures and uniform dispersion of WOx species. Nitrogen adsorption-
desorption isotherms of the OMWZr composites display type-IV curves with H1-type hysteresis loops
and sharp capillary condensation at high relative pressure (Figure 4B), suggesting that all the samples
possess uniform and large ordered mesopores. In addition, meso-0.03WOx/ZrO2, meso-0.07WOx/ZrO2
and meso-0.10WOx/ZrO2 present relatively narrow pore size distribution derived from the adsorption
branches, showing mean pore size centered at about 17.6, 17.1 and 23.8 nm, respectively (Figure 4C and
Table 1). However, doping excessive tungsten species in framework gives rise to formation of crystalline
WO3 and partial collapse of mesostructures, exhibiting wider pore size distribution and larger pore size
(27.5 nm) in meso-0.15WOx/ZrO2. Brunauer-Emmett-Teller (BET) surface area and pore volume of
OMWZr composites are in the range of 27.3 - 41.7 m2/g and 0.133 - 0.182 cm3/g, respectively, and the
relatively low surface area of OMWZr materials is mainly due to the large mesopore size (> 17 nm) and
the high density of ZrO2 skeletons and WOx species. (Table 1). Meso-0.15WOx/ZrO2 owns the lowest
BET surface area among the OMWZr composites, further proving collapse of ordered mesopores during
calcination process.
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Figure 3. (A) HRTEM image, (B) SAED pattern, and (C) HAADF-STEM image of meso-0.10WOx/ZrO2,
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and (D) the corresponding elemental mapping images of Zr, W and O elements.
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Figure 4. (A) SAXS patterns, (B) nitrogen sorption isotherms, and (C) pore size distribution curves of
ordered mesoporous WOx/ZrO2 catalysts. (a, b, c and d represent meso-0.03WOx/ZrO2, meso-
0.07WOx/ZrO2, meso-0.10WOx/ZrO2 and meso-0.15WOx/ZrO2, respectively.)
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X-ray photoelectron spectroscopy (XPS) was conducted to capture detailed information about
surface elements of mesoporous WOx/ZrO2 composites (Figure 5). Taking meso-0.10WOx/ZrO2 as an
example, the Zr 3d XPS spectrum shows two well-resolved peaks at 182.6 and 185.0 eV (Figure 5A),
which are assigned to Zr4+ 3d5/2 and Zr4+ 3d7/2,[64] respectively. In addition, valence states of W species in
meso-0.10WOx/ZrO2 are analysed by the W 4f XPS spectrum (Figure 5B), where peaks at 38.0 and 35.9
eV are assigned to W6+ 4f5/2 and W6+ 4f7/2 respectively,[57] demonstrating the existence of hexavalent
tungsten in polytungstates of WOx clusters that perform as acid sites in catalytic reactions. The results
further indicate that introduction of W species in mesoporous skeletons does not affect the valence states
of Zr species. However, they greatly influence the crystallization behaviour of ZrO2 with a partial
transformation from tetragonal phase to monoclinic phase. Meanwhile, the presence of ZrO2 does not
affect the valence states of W species, which performs as an appreciate support for uniform dispersion
and stabilization of WOx clusters under an appropriate doping amount. Although crystalline WO3 is
formed from excess doped W precursors in meso-0.15WOx/ZrO2, the Zr 3d and W 4f XPS spectra of the
sample are quite similar with those of meso-0.10WOx/ZrO2 (Figure S4).
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Figure 5. XPS spectra of meso-0.10WOx/ZrO2 in the vicinity of (A) Zr 3d, and (B) W 4f.
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Figure 6. (A) NH3-TPD curves of (a) meso-0.10WOx/ZrO2, and (b) bulk-0.10WOx/ZrO2, (B) total acidity
of WOx/ZrO2 composites with different amount of W species, (C) pyridine-adsorbed DRIFT spectra of
(a) meso-0.10WOx/ZrO2, and (b) bulk-0.10WOx/ZrO2.
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NH3-TPD profiles are used to compare the acid density and strength of meso-0.10WOx/ZrO2 and
bulk-0.10WOx/ZrO2 composites (Figure 6A). From the integration areas it can be observed that meso-
0.10WOx/ZrO2 possesses higher acid amount than bulk-0.10WOx/ZrO2. Meanwhile, each sample shows
one broad NH3 desorption peak centered at about 120 °C, belonged to weakly bounded NH3, suggesting
that mesoporous and bulk WOx/ZrO2 composites possess the acid sites with similar acid strength.
Moreover, through calibrating the integration areas of NH3 desorption peaks, the acid amount of OMWZr
composites increases from 0.026 to 0.118 mmol/g when W content increases from 3 to 10 mol%, and then
decreases to 0.098 mmol/g when W content is up to 15 mol% (Figure 6B and Table 1), due to formation
of crystalline WO3 of excess tungsten species in meso-0.15WOx/ZrO2, further proving that polymeric
WOx clusters supported on ZrO2 are the acid sites of OMWZr composites. In order to understand better
the relationship between acid property and tungsten content, WOx density (W per nm2) was calculated by
the equation as follows:[65]
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The W surface densities of OMWZr catalysts were 2.23, 5.53, 8.03 and 13.78 W/nm2, respectively (Table
1), demonstrating that isolated monotungstates species existed in meso-0.03WOx/ZrO2 and the formation
of polytungstates occurred in OMWZr catalysts with W content over 0.03. Notably, crystalline WO3 co-
existed with polytungstates species in meso-0.15WOx/ZrO2 with a tungsten density (13.78 W/nm2) over
8 W/nm2, according to the growth mode of tungstate species over zirconia, which has been previously
studied in depth.[28] Moreover, the W density of meso-0.10WOx/ZrO2 was calculated as 8.03 W/nm2,
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indicating the saturation of polytungstate over meso-0.10WOx/ZrO2, therefore, meso-0.10WOx/ZrO2
owns the highest acidity of OMWZr catalysts. The existence form of tungsten species in OMWZr
composites inferred from tungsten density is in good agreement with the results of Raman analysis, which
well explains the acidity change of OMWZr catalysts with the increase of W content. Pyridine-adsorbed
DRIFT spectra captured at 100 oC of bulk-0.10WOx/ZrO2 and meso-0.10WOx/ZrO2 show bands around
1449, 1490 and 1545 cm-1 (Figure 6C). The band at 1449 cm-1 is attributed to molecular pyridine
coordinated to Lewis acid (L acid) sites, and peak at 1545 cm-1 is responsible for Brönsted acid (B acid)
sites, while the band at 1485 cm-1 is a combined one originating from pyridine bonded to both B and L
acid sites.[29] The results suggest that both meso-0.10WOx/ZrO2 and bulk-0.10WOx/ZrO2 composites
possess L and B acid sites. While the 1545 cm-1 band of bulk-0.10WOx/ZrO2 is weaker than that of meso-
0.10WOx/ZrO2, indicating that meso-0.10WOx/ZrO2 possesses more B acid sites than bulk-
0.10WOx/ZrO2, because WOx clusters mainly bring B acid sites to the catalyst,[29] which are very stable
and difficult to migrate and crystallize into large particles on the surface of meso-0.10WOx/ZrO2 with
mesostructure of three-dimensional connected spherical pores. Moreover, peak areas at 1545 cm-1 of both
meso-0.10WOx/ZrO2 and bulk-0.10WOx/ZrO2 change little with purge temperature increasing from 100
to 400 °C (Figure S6), revealing high stability of B acid sites in WOx/ZrO2 composites. Considering the
unique mesostructures and surface acid properties, the obtained OMWZr composites were used as
heterogeneous catalysts for deprotection of benzaldehyde dimethyl acetal (BDA), a typical acid-catalytic
probe reaction and an important step for protection amd deprotection of aldehyde groups (Figure 7A).[66-
67]
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Figure 7. (A) Reaction equation of hydrolysis of benzaldehyde dimethyl acetal to benzaldehyde catalyzed
by Brönsted acid, (B) conversion of benzaldehyde dimethyl acetal, and (C) selectivity to benzaldehyde
over ordered mesoporous WOx/ZrO2 catalysts and bulk-0.10WOx/ZrO2 at the reaction time of 2 h (a, b, c,
d, e and f represent blank system (without catalyst), meso-0.03WOx/ZrO2, meso-0.07WOx/ZrO2, meso-
0.10WOx/ZrO2, meso-0.15WOx/ZrO2 and bulk-0.10WOx/ZrO2, respectively), (D) conversion of
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benzaldehyde dimethyl acetal and selectivity to benzaldehyde over meso-0.10WOx/ZrO2 calcined at
different temperatures (500, 600 and 700 °C) for 2 h.
The blank system in absence of catalysts shows only 1% conversion of BDA even after reaction for
4 h (Figure 7B-a), and similar results appeare when the reaction is catalyzed over mesoporous ZrO2
(Figure S7A), indicating that hydrolysis rate of BDA is very slow under spontaneous reaction and pure
mesoporous ZrO2 provides hardly catalytic active sites. Though mesoporous WO3 has slight catalytic
effect on the hydrolysis of BDA, it exhibits poor selectivity to benzaldehyde (Figure S7B). All the
investigated WOx/ZrO2 composites display catalytic activity toward the hydrolysis of BDA, and the
conversion gradually increases as a function of reaction time (Figure 7B-b to f). Moreover, for the
OMWZr catalysts, the conversion of BDA at the same reaction time of 2 h increases in the order as meso-
0.03WOx/ZrO2 < meso-0.07WOx/ZrO2 < meso-0.15WOx/ZrO2 < meso-0.10WOx/ZrO2, in consistence
with that of the acid amount (Figure 6B), further confirming that the BDA hydrolysis is an acid-catalytic
reaction. Meso-0.10WOx/ZrO2 shows the best catalytic activity, reaching as high as 99.1% conversion of
BDA at 2 h (Figure 7B-d). In spite of that meso-0.03WOx/ZrO2 owns the largest surface area, it shows
the lowest acid amount (0.026 mmol/g) and catalytic activity, due to existence of monotungstates but no
polytungstates at the surface of mesoporous skeletons.[29] In addition, although the content of W species
in meso-0.15WOx/ZrO2 is higher than that of meso-0.10WOx/ZrO2, the former catalyst exhibits lower
catalytic efficiency before 2 h, probably because of partially crystallized WO3 on ZrO2 support from
excess W species and slightly lower acid amount (0.098 mmol/g) in meso-0.15WOx/ZrO2. For comparison,
the hydrolysis reaction was also conducted over the counterpart sample of bulk-0.10WOx/ZrO2 with
comparable acid amount (0.103 mmol/g) but low specific surface area (9.6 m2/g) and high tungsten
density (13.78 W/nm2), showing lower catalytic activity than meso-0.10WOx/ZrO2 (Figure 7B-f).
Therefore, under the same W content and close acid amount, meso-0.10WOx/ZrO2 presents improved
catalytic activity compared to bulk-0.10WOx/ZrO2, attributed to faster diffusion of reactants and products
within well-developed mesopores, more appropriate W density (8.03 W/nm2) and easily accessible acid
sites especially rich Brönsted acid in meso-0.10WOx/ZrO2. The same conclusion can also be drawn by
comparing other mesoporous and bulk WOx/ZrO2 catalysts (Figure S8). Furthermore, all the WOx/ZrO2
catalysts show the selectivity to benzaldehyde higher than 97% (Figure 7C), in which meso-
0.10WOx/ZrO2 owns the highest selectivity of 98.9%, further proving its outstanding catalytic
performance in BDA hydrolysis. Meso-0.10WOx/ZrO2 with polytungstate species of WOx clusters on
ZrO2 surface shows the highest TOF value of 1.110-2 s-1 among all the obtained WOx/ZrO2 composites
(Table 1), in good agreement with the excellent catalytic performance of meso-0.10WOx/ZrO2. The
influence of calcination temperatures on catalytic performance of meso-0.10WOx/ZrO2 solid acids was
also studied (Figure 7D). The sample calcined at 600 °C shows the highest catalytic activity. The
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conversion of BDA over meso-0.10WOx/ZrO2-500 composed of low-crystallized tetragonal ZrO2 (Figure
S5B) is as low as 59%, due to low content of acid amount and existence of a little of residual carbon on
surface after calcination at 500 °C for 2 h (Figure S9A). Once calcination temperature further increases
to 700 °C, the conversion of BDA decreases to 91.3% as the acid amount reduced by formation of
monoclinic WO3 crystals (Figure S5D). Therefore, the calcination temperature of 600 °C favors the
formation of polytungstate WOx species as active acid sites, which further facilitate the improvement of
BDA hydrolysis. Moreover, the catalysts calcined at different temperatures show close selectivity to
benzaldehyde at about 99%, indicating that calcination temperatures have weak effects on the catalytic
selectivity. In addition, the long-term stability and recyclability of meso-0.10WOx/ZrO2 were also tested
(Figure S10), and the catalytic activity decreased slightly as reaction cycles going on. The XRD pattern
and Raman spectrum (Figure S11) of the recycled meso-0.10WOx/ZrO2 after 10-cycles catalytic reactions
show similar results to those of the fresh catalyst, and no peaks indexed to crystalline WO3 are observed,
suggesting that polymeric WOx clusters didn’t crystallize into WO3 particles in the mesopore channels
during recycling process. The TEM and SEM images of the recycled catalysts (Figure S12) retained
ordered mesostructure, indicating that the mesoporous ZrO2 skeleton can be well maintained during the
catalytic reactions. In addition, the average crystallite sizes of the fresh and the recycled meso-
0.10WOx/ZrO2 measured by TEM observation were around 5.5 and 6.5 nm, respectively, agreeing well
with XRD results. The recycled meso-0.10WOx/ZrO2 possesses surface area of 32.6 m2/g and pore size
of 20.2 nm (Figure S13A and B), which were slightly reduced in comparison with that of the fresh catalyst,
mainly originated from the slight growth of grain size. The acid amount of the recycled catalyst was
calculated as 0.093 mmol/g from NH3-TPD profile (Figure S13C), lower than 0.118 mmol/g of the fresh
catalyst possibly due to the leaching of W species, which is responsible for the decrease of acid-catalytic
performance. Nevertheless, the conversion was still preserved higher than 85% and the selectivity to
benzaldehyde was over 97% even after ten cycles. Therefore, meso-0.10WOx/ZrO2 with ordered
mesostructure and moderate loading amount of W species calcined at 600 ℃exhibits the optimal catalytic
performance, due to numerous WOx clusters dispersed on pore walls of rigid mesoporous ZrO2, which
provide a large number of accessible Brönsted acid sites.
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3. Conclusion
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In summary, a facile and controllable multicomponent co-assembly approach was utilized to successfully
synthesize a series of ordered mesoporous WOx/ZrO2 (OMWZr) catalysts with tunable W contents for the
first time, by which loading-efficiency and dispersion of W species were promoted. The obtained OMWZr
catalysts possess robust ordered mesostructures with interconnected large mesopores even after
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calcination at 600 °C. Besides, the materials show favorable rigid skeletons composed of highly
crystalline ZrO2 for uniform dispersion and stabilization of WOx clusters, leading to the production of
great numbers of exposed accessible Brönsted acid sites. Consequently, the OMWZr catalysts show
outstanding acid-catalytic performance for hydrolysis of benzaldehyde dimethyl acetal. Detailed structure
characterizations and mechanism analysis reveal that large mesopores and active polymeric WOx clusters
result in rich surface Brönsted acid sites, which contribute to superior acid-catalytic activity and excellent
recyclability of the OMWZr catalysts. It is believed that the synthesized OMWZr catalysts can be used
for various solid acid-catalyzed reactions, and through the similar controllable multicomponent co-
assembly, a variety of ordered mesoporous metal oxides with high porosity, rich interfaces, different
components and functionalities can be readily synthesized for diverse applications, such as petrochemical
heterogeneous catalysis, chemical sensing and energy conversion.
Table 1. Textural and catalytic properties of ordered mesoporous WOx/ZrO2 composites with different
amount of loaded W species and bulk-0.10WOx/ZrO2.
TOF#
(s-1)
W density
(W/nm2)
BET surface Pore volume
Pore size Acidity
Sample
area (m2/g)
(cm3/g)
(nm)
(mmol/g)
7.2  10-3
8.7  10-3
1.1  10-2
2.23
5.53
meso-0.03WOx/ZrO2
meso-0.07WOx/ZrO2
meso-0.10WOx/ZrO2
meso-0.15WOx/ZrO2
bulk-0.10WOx/ZrO2
41.7
35.7
0.182
0.133
17.6
17.1
0.026
0.074
33.7
27.3
9.6
0.162
0.161
0.032
23.8
27.5
13.6
0.118
0.098
0.103
8.03
5.1  10-3
7.9  10-3
13.78
20.60
# TOF: the conversion mole number of benzaldehyde dimethyl acetal at a single active site per unit time.
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10.1002/cctc.202100385
ChemCatChem
4. Experimental section
Chemicals and Materials. Monomethyl poly(ethylene oxide) (Mw: 5000 g/mol) was
purchased from Aldrich. N,-N,-N’,-N”,-N”-Pentamethyl diethylenetriamine
(PMDETA) was purchased from Acros Corp. Zirconium(IV) acetylacetonate
(Zr(acac)4), tungsten(VI) hexachloride (WCl6) and decane were purchased from
Aladdin Corp. Benzaldehyde dimethyl acetal (BDA) was purchased from TCI
Development Co., Ltd. Other chemicals including tetrahydrofuran (THF), ethanol
(EtOH), concentrated hydrochloric acid (HCl, 37 wt.%), acetic acid, pyridine, styrene,
toluene, benzaldehyde, ethylether, CuBr, petroleum ether (b.p. 30 - 60 °C) were
purchased from Sino-Pharm Chemical Reagent Co., Ltd. All the chemicals were of
analytical grade and used as received without further purification.
Synthesis of Ordered Mesoporous WOx/ZrO2 Catalysts. In a typical synthesis of
mesoporous WOx/ZrO2, 37.5 mg lab-made amphiphilic diblock copolymer (PEO114-b-
PS221, Mn = 27960 g/mol) was dissolved in 4 mL THF to obtain solution A. Zr(acac)4
of 0.15 g was dissolved in 1 mL ethanol, in which 75 μL concentrated hydrochloric
acid and 75 μL acetic acid were added, and then different amount of WCl6 was added
to form solution B to adjust the content of WOx species. Afterwards, solution A and
solution B were mixed under stirring and yellow transparent solution was formed after
further stirring for 2 h, which was then poured onto Petri dishes. After slow solvent
evaporation under room temperature for 24 h, sequential heating at 40 °C for 24 h to
completely remove solvent and aging at 100 °C for another 24 h, the inorganic-polymer
composites were formed as a thin film on Petri dishes. The film was scraped off and
crushed into fine powder, and then calcined at 350 °C for 2 h in nitrogen (heating rate
= 1 °C/min), followed by calcination at 600 °C in air for another 2 h (heating rate =
5 °C/min), resulting in white powder of mesoporous WOx/ZrO2 (OMWZr). Pure
mesoporous zirconia (ZrO2) was also synthesized in the same way, during which WCl6
was not added in solution B. For comparison, bulk WOx/ZrO2 catalysts were
synthesized in the same way without addition of PEO114-b-PS221. The final ordered
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10.1002/cctc.202100385
ChemCatChem
mesoporous catalysts and bulk catalysts were denoted as meso-pWOx/ZrO2 and bulk-
pWOx/ZrO2 respectively, where p stands for feed mole ratio of W to Zr. For instance,
meso-0.10WOx/ZrO2 means the sample that 10 mol% WCl6 was added during synthesis.
As a note, loading amount of tungsten is defined as mole of nominal W species per
mole of ZrO2 support.
Measurement and Characterization. Nitrogen adsorption-desorption isotherms were
measured at 77 K on a Micromeritics Tristar 3020 analyzer. Before determination, the
samples were degassed in vacuum at 180 °C for longer than 6 h. The Brunauer-Emmett-
Teller (BET) method was used to calculate specific surface areas of the samples. By
using Barrett-Joyner-Halenda (BJH) model, total pore volume (Vtotal) was calculated
from the adsorbed amount of nitrogen at P/P0 = 0.995 and pore size distribution curve
was obtained from the adsorption branch of isotherms. Transmission electron
microscope (TEM) images were taken on JEM-2100F microscope (JEOL, Japan).
Scanning electron microscopy (SEM) images were recorded on Hitachi S4800 FESEM
(Japan). High-resolution TEM (HRTEM) images were taken on FEI Field Emission
Transmission Electron Microscope (America). Small-angle X-ray scattering (SAXS)
patterns were collected on Bruker Nanostar U small angle X-ray scattering system
(Germany) using Cu Kα radiation (40 kV, 40 mA). X-ray power diffraction (XRD)
measurements were carried out on Bruker D4 X-ray diffractometer (Germany)
equipped with Ni-filtered Cu Kα radiation (40 kV, 40 mA). X-ray photoelectron
spectroscopy (XPS) was conducted on RBD 147 upgraded PHI 5000C ESCA system
with a dual X-ray source. The pyridine adsorbed Fourier transform infrared (FT-IR)
spectroscopy was conducted on NICOLET NEXUS 470 (US THERMO). A certain
amount of sample was firstly pressed into in-suit cell and purified at 400 °C for 2 h
under vacuum. The saturated pyridine vapor was absorbed on materials at 35 °C for 10
min, and then the spectra was obtained when pyridine was removed by vacuum for 5
min at 100, 200, 300 and 400 °C, respectively. NH3-temperature programmed
desorption (NH3-TPD) measurement was conducted on Micromeritics AutoChem II
2920 (America) equipped with a thermal conductivity detector (TCD). The catalysts of
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10.1002/cctc.202100385
ChemCatChem
about 100 mg were charged into a quartz U-type tube at ambient temperature and
o
o
degassed in helium atmosphere at 600 C for 3 h before test. After cooled to 110 C,
NH3 gas was poured into the quartz U-type tube immediately, which was held for 2 h
to make the sample chemically adsorb NH3 adequately. Then the temperature was
o
o
o
increased from 120 C to 600 C at the rate of 10 C/min to release NH3. Gas
chromatography-mass spectrum (GC-MS) was used to analyze catalytic products and
recorded on Shimadzu GCMS-QP2020 (Japan) equipped with SH-Rxi-5Sil capillary.
Acid-catalysis Tests. The acid-catalyzed deprotection of benzaldehyde dimethyl acetal
to benzaldehyde was performed to evaluate the activity of mesoporous WOx/ZrO2
catalysts. In a typical procedure, the catalytic reaction was carried out in a two-neck
round bottom flask, and toluene of 5 mL was used as solvent. Benzaldehyde dimethyl
acetal of 150 μL, deionized water of 40 μL and catalyst of 20 mg were charged into the
flask, and the mixture was then heated in an oil bath at 90 °C for 4 h. The reaction was
performed under vigorous stirring (700 rpm) at atmospheric pressure. Liquid sample of
0.1 mL was withdrawn periodically at 30-minute or 60-minute intervals from the
reactor with a syringe in order to separate the solid catalyst from the solution. The
withdrawn liquid was cooled down to room temperature and diluted in 1 mL toluene,
and the solution was analyzed by GC-MS. In addition, in order to confirm the effect of
acid catalysts on conversion of benzaldehyde dimethyl acetal and selectivity to
benzaldehyde, a blank experiment in absence of any catalysts was conducted under the
same conditions for comparison.
Supporting Information
Supporting Information is available from the Wiley Online Library or from the
author.
Acknowledgements
This work was financially supported by the NSF of China (52073064, 21875044,
22005058, 22005057), National Key R&D Program of China (2020YFB2008600), Key
Basic Research Program of Science and Technology Commission of Shanghai
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10.1002/cctc.202100385
ChemCatChem
Municipality (20JC1415300), Program of Shanghai Academic Research Leader
(19XD1420300), China Postdoctoral Science Foundation (2020M670973,
BX20200085), and the state key laboratory of Transducer Technology of China (Grant
no. SKT1904).
Received: ((will be filled in by the editorial staff))
Revised: ((will be filled in by the editorial staff))
Published online: ((will be filled in by the editorial staff))
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A multicomponent co-assembly approach was utilized to controllably synthesized
ordered mesoporous ZrO2 with stably supported and well dispersed WOx clusters,
which possess easily accessible Brönsted acid sites, and well-connected pore structure
and thus exhibit outstanding acid-catalytic performance in hydrolysis of benzaldehyde
dimethyl acetal.
Keyword Mesoporous materials, Multicomponent co-assembly, Solid acid, Tungsten
oxide, Zirconia
Jichun Lia, Xuanyu Yanga, Junhao Maa, Chenyi Yuana, Yuan Rena, Xiaowei Cheng*,a,
Yonghui Deng*,a,b
Controllable Multicomponent Co-Assembly Approach to Ordered Mesoporous
Zirconia Supported with Well-Dispersed Tungsten Oxide Clusters as High-
Performance Catalysts
ToC figure
Copyright WILEY-VCH Verlag GmbH & Co. KGaA, 69469 Weinheim, Germany,
2016.
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