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Synthesis of lathanum or La-B doped KIT-6 mesoporous materials and their application in the catalytic oxidation of styrene
ZHAN Wangcheng (), GUO Yanglong (), WANG Yanqin (), GUO Yun ( ), LU Guanzhong ()
(Key Laboratory for Advanced Materials, Research Institute of Industrial Catalysis, East China University of Science and Technology, Shanghai 200237, China) Received 11 January 2010; revised 12 April 2010

Abstract: La-doped and La-B-doped KIT-6 mesoporous materials were prepared by direct hydrothermal synthesis with pH-adjusting method and characterized by X-ray diffractometer (XRD), nitrogen sorption, FT-IR, UV-Vis, X-ray photoelectron spectroscopy (XPS) and ICP-AES. The catalytic performance for the oxidation of styrene by hydrogen peroxide, tert-butyl hydroperoxide or oxygen was investigated. The results showed that the introduction of heteroatoms did not destroy the mesostructure of KIT-6 with cubic Ia3d space group. La or B cations were incorporated into the framework of KIT-6 and the coexistence of B could hinder the dispersion or incorporation of La into the framework. La3+ species in the framework of La-KIT-6 promoted the catalytic performance of La-KIT-6 catalyst for the oxidation of styrene. H2O2 is the better oxidant for the oxidation of styrene than tert-butyl hydroperoxide and oxygen, in which the styrene conversion of 20.6% and the selectivity to benzaldehyde of 74.6% were achieved over La-KIT-6-0.02. Keywords: mesoporous materials; oxidation of styrene; benzaldehyde; styrene oxide; rare earths

Special attention is paid to KIT-6 mesoporous materials with the three-dimensional cubic Ia3d mesostructure, which consists of two interpenetrating bicontinuous networks of channels. This unique 3-D channel network provides a highly opened porous host with easy and direct access for guest species, so KIT-6 is generally used as a hard template for the synthesis of mesoporous metal oxide[15]. Furthermore, its channel network facilitates faster diffusion of reactants and products when used as the support for catalysts[69]. However, like other silicious mesoporous materials, the facile functionalization of KIT-6 is essential for the potential application as catalyst. For example, KIT-6 silica was developed as support for Co[8], Mo, CoMo[9], Ni[10], and nickel phosphide catalysts[11]. In addition, the direct incorporation of heteroatom into the cubic Ia3d mesostructure was also achieved by a hydrothermal synthesis, such as Ti[12], V[13], and Al[14]. Rare earth elements have some special chemical properties and have been efficiently introduced into MCM-41, MCM-48, and MSU-X mesoporous materials to provide catalytic active centers and to improve thermal stability[1523]. Moreover, the incorporation of two different heteroatoms might create materials with new redox or acidic properties. Synthesis and catalytic applications of such materials have already been reported[2427]. It is known that the catalytic properties of these materials depend on the localization and surrounding of the metal ions. For examples, Wu et al.[28] added the boron element during the synthesis of Ti-MCM-22 to decrease greatly the energy of Ti substitution, due to the

formation of a structure quite similar to the terminal silanol groups. In this paper, La-doped and La-B-doped KIT-6 mesoporous materials were prepared by direct hydrothermal synthesis with pH-adjusting method, and their applications for the catalytic oxidation of styrene by hydrogen peroxide, tert-butyl hydroperoxide and oxygen were investigated, which have not yet been reported.

1 Experimental
1.1 Synthesis of mesoporous materials A series of La-doped KIT-6 mesoporous materials were prepared by direct hydrothermal synthesis[29]: 6 g of pluronic P123 (EO20PO70EO20, MW=5800, Aldrich) was dissolved in 217 g of distilled water and 11.8 g of HCl (35%). To this, 6 g of butanol was added under stirring at 35 C. After stirring for 1 h, La(NO3)36H2O solution and 12.9 g of tetraethyl orthosilicate (TEOS) were added succedently at 35 C. The molar ratio of TEOS:P123:HCl:La:BuOH:H2O is 1:0.017: 1.83:x:1.31:195. The mixture was left under stirring for 24 h at 35 C, and subsequently heated in a Teflon container under static conditions at 100 C for 24 h. Then it was cooled to the room temperature and was adjusted to pH=8 by adding ammonia. After being kept continuously in the Teflon container at 100 C for 48 h, the solid particles produced were collected by filtration, dried overnight at 100 C, and calcined in air at 550 C for 6 h to remove the template. The

Foundation item: Project supported by the National Basic Research Program of China (2010CB732300), Education Commission of Shanghai Municipality (2008CG35), and Science and Technology Commission of Shanghai Municipality (09ZR1408200) Corresponding author: GUO Yanglong (E-mail: [email protected], [email protected]; Tel.: +86-21-64252923) DOI: 10.1016/S1002-0721(09)60105-8

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samples prepared were designated La-KIT-6-X where X is the La/Si molar ratio in the synthesis gel, i.e. 0.02, 0.03, or 0.04. Pure silica KIT-6 (designated Si-KIT-6) was prepared by the above procedure in the absence of La(NO3)36H2O. Furthermore, La-B-doped KIT-6 samples were also prepared by the similar procedure to La-KIT-6-X. 6 g of Pluronic P123 was dissolved in 217 g of distilled water and 11.8 g of HCl (35%). To this mixture, 6 g of butanol was added under stirring at 35 C. After stirring for 1 h, this solution was divided into two equal parts, to one of which La(NO3)36H2O solution was added under vigorous stirring, and to the other 4 g of H3BO3 solution was added. After stirring for 0.5 h, the two solutions were then mixed together and 12.9 g of TEOS were added gradually to the solutions. Further stirring for 1 h was allowed to form homogeneous gels with a molar ratio of TEOS:0.017 P123:1.83 HCl:1.04 H3BO3:xLa:1.31 BuOH:195 H2O. The resulting gel was left under stirring for 24 h at 35 C and the following procedure was the same as the synthesis of La-KIT-6. The samples prepared were designated LaB-KIT-6-X where X is the La/Si molar ratio in the synthesis gel, i.e. 0.02, 0.03, or 0.04. 1.2 Characterization of mesoporous materials Powder X-ray diffraction (XRD) patterns were recorded on a Rigaku D/max-2550VB/PC diffractometer operated at 40 kV, 100 mA (Cu K radiation, =0.15406 nm). The diffraction patterns were taken in the Braggs angle (2) range from 1 to 70 at room temperature. N2 adsorption-desorption isotherms were measured at 77 K on a Micromeritics ASAP 2020M surface area and pore size analyzer. Prior to the measurements, all samples were degassed at 573 K until a stable vacuum of ca. 0.6665 Pa was reached. The pore size distribution curves were calculated from the adsorption branch using the Barrett-Joyner-Halenda (BJH) method. The specific surface area was assessed using the BET method from adsorption data. FT-IR spectra were recorded on a Nicolet Nexus 670 FT-IR spectrometer in the range of 4004000 cm1. The samples were ground with KBr and pressed into thin wafers to measure the IR adsorption of the groups. UV-Vis spectra were recorded on a Varian Cary 500 UV-Vis-NIR spectrophotometer in the range of 200800 nm, and BaSO4 was used as reference. XPS spectra were recorded on a Thermo ESCALAB 250 spectrometer

with a monochromatized Al K X-ray source (1486.6 eV) and a passing energy of 20 eV, operated at 15 kV and 150 W. C1s (binding energy of 284.6 eV) of adventitious carbon was used as reference. Elemental analysis of the samples was done by inductively coupled-plasma atomic emission spectroscopy (ICP-AES) using a TJA IRIS ADVANTAG 1000 instrument. 1.3 Oxidation of styrene The oxidation of styrene was carried out in the flask reactor with 5 mmol of styrene, 5 mmol of H2O2 (30 wt.%), 0.1 g of catalyst, 4.5 ml of acetonitrile (MeCN), and 0.5 ml of dimethylformamide (DMF). The reaction temperature was 60 oC and reaction time was 24 h. After the reaction was finished, the catalyst was separated by centrifugation. The concentrations of the oxidation products were analyzed by a Perkin-Elmer Clarus 500 gas chromatograph equipped with a PE-2 capillary column (25 m0.32 mm1.0 m) and a FID detector. Cyclooctane was used as an internal standard substance. Temperature of both the injector and the detector was 220 C, and the temperature of the column oven increased as programmed from 100 to 180 C at the rate of 10 C/min. Furthermore, the effect of various oxidants on the oxidation of styrene, viz., tert-butyl hydroperoxide (TBHP, 70% aq., Alfa Aesar) and oxygen (O2), were also investigated. In the reaction under oxygen pressure of 0.5 MPa, a 100 ml autoclave was employed and the mixture of 0.1 g catalyst, 5 mmol styrene, 4.5 ml MeCN and 0.5 ml DMF was stirred at 60 C for 24 h.

2 Results and discussion

2.1 Characterization of mesoporous materials 2.1.1 XRD Figs. 1 and 2 show the powder XRD patterns of La-KIT-6 and LaB-KIT-6 samples. As shown in Figs. 1 and 2, the XRD patterns of these samples agree well with those of other cubic Ia3d mesoporous materials[2931]. The most intense (211) diffraction peak of KIT-6 appears at 2 0.8 along with a distinct shoulder peak of (220) at 21.0. Another low intense diffraction peak of higher order appears at 21.5. The diffraction peaks of La-KIT-6 samples shift to smaller angles marginally with an increase in La content. The

Fig. 1 Small-angle and wide-angle XRD patterns of Si-KIT-6 (1), La-KIT-6-0.02 (2), La-KIT-6-0.03 (3) and La-KIT-6-0.04 (4)

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Fig. 2 Small-angle and wide-angle XRD patterns of Si-KIT-6 (1), LaB-KIT-6-0.02 (2), LaB-KIT-6-0.03 (3) and LaB-KIT-6-0.04 (4)

effects of La content on the d spacing and cubic unit cell constant (ao) of the samples are summarized in Table 1. The results show that the d spacing and ao value of La-KIT-6 increase with an increase in La content. Similar results were reported for the incorporation of other metal ions into the silicate framework[20,21,32]. Because the cation radius of La3+ is larger than that of Si4+, its unit cell constant increases when La cations are incorporated into the framework of KIT-6, which confirms that La cations have been incorporated into the framework of KIT-6. However, the d spacing and ao value of LaB-KIT-6 is not larger than that of Si-KIT-6, and the d spacing and ao value of B-KIT-6 is much small. This is because B coexistence in the framework sites has an adverse effect on the lattice parameters due to its smaller cation radius and the contents of La and B increase simultaneously in the LaB-KIT-6 samples. On the other hand, the intensity of diffraction peaks of La-KIT-6 and LaB-KIT-6 decreases, which indicates a relatively disordered mesostructure due to the La loading or La and B loading. As shown in Fig. 2, the diffraction peak at 2=29.0 appears in the wide-angle XRD patterns of LaB-KIT-6, indicating the presence of La2O3. However, with the same La content in the samples, the diffraction peak of La2O3 does not exist in the wide-angle XRD patterns of La-KIT-6 samples. This difference indicates that the coexistence of B in the samples can hinder the dispersion or incorporation of La into the framework. To detect the content of heteroatoms in KIT-6 mesoporous

materials, an elemental analysis by ICP-AES was carried out for the calcined samples, and the results are listed in Table 1. These results indicate that the La content in the solid samples is similar to that in the synthesis solution. For example, the molar ratio of La/Si in La-KIT-6-0.02, La-KIT-6-0.03 and La-KIT-6-0.04 is 0.021, 0.030 and 0.044, respectively. As for B-KIT-6, the content of B in the products is close to that in the gel with the molar ratio of B/Si of 1.04. However, the content of B in LaB-KIT-6 is much lower than that in the gel. The further research is needed. 2.1.2. N2 Sorption Figs. 3 and 4 show the nitrogen adsorption-desorption isotherms of La-KIT-6 and LaB-KIT-6 samples. All isotherms show the typical IV type isotherms of mesoporous materials with a hysteresis loop in the relative pressure range of 0.70.9. Textural properties of La-KIT-6 and LaB-KIT-6 samples are listed in Table 1. The results show that the BET surface areas of La-KIT-6 and LaB-KIT-6 samples decrease with an increase of La content in the samples. This is because the incorporation of La perturbs the mesostructure of KIT-6, as shown in XRD. On the other hand, it is remarkable that the incorporation of La increases the pore size of La-KIT-6 and LaB-KIT-6 samples, which is similar to the incorporation of La into the MSU-X mesoporous materials[15]. However, the incorporation of B decreases the pore size, leading to the smaller pore size of LaB-KIT-6 than that of La-KIT-6 with the same La content.

Table 1 Textural properties of La-KIT-6-X and LaB-KIT-6-X samples*

Samples Si-KIT-6 B-KIT-6 La-KIT-6-0.02 La-KIT-6-0.03 La-KIT-6-0.04 LaB-KIT-6-0.02 LaB-KIT-6-0.03 LaB-KIT-6-0.04 0.021 0.030 0.044 0.018 0.031 0.046 0.30 0.49 0.57 0.97 La/Si a B/Si a d211 spacing/nm 10.22 8.86 10.52 10.93 11.26 9.97 10.14 10.22 ao b/nm 25.03 21.70 25.77 26.77 27.58 24.42 24.84 25.03 Surface area/(m2/g) 558 852 514 467 435 521 443 406
c

Pore volume/(cm3/g) 1.38 0.94 1.34 1.34 1.35 1.32 1.42 1.32

Pore size c/nm 7.23 5.54 7.80 8.65 8.83 7.24 7.72 7.78

* a Determined by ICP-AES; b average unit cell parameter (ao) calculated using ao = d211

6 ; pore size obtained from BJH analysis of desorption data

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2.1.3 UV-Vis Spectroscopy Fig. 5 shows UV-Vis spectra of Si-KIT-6, B-KIT-6, La-KIT-6 and LaB-KIT-6 samples. Si-KIT-6 has strong absorption peaks at 205 nm while La-KIT-6 samples display two strong absorption peaks at 205 and 247 nm, and the intensity of absorption peak at 247 nm increases with an increase in La content of the samples. According to the position of absorption peak that is related to the charge transfer transitions of O2La3+, the absorption peak at 205 nm is ascribed to Si-O while the absorption peak at 247 nm is ascribed to the presence of the

Fig. 3 Nitrogen adsorption-desorption isotherms of Si-KIT-6 (1), La-KIT-6-0.02 (2), La-KIT-6-0.03 (3) and La-KIT-6-0.04 (4)

La3+ ions with tetra-coordination in the framework. Furthermore, LaB-KIT-6 samples almost display the same absorption peaks as La-KIT-6, except the intensity of absorption peak at 247 nm is stronger than that of La-KIT-6. Since B-KIT-6 has another strong absorption peak at 245 nm besides at 205 nm, the absorption peak at 247 nm is due to the conjunct effect of the presence of La and B, which results in a strong absorption peak at 245 nm. 2.1.4 FT-IR Spectroscopy Fig. 6 shows FT-IR spectra of Si-KIT-6 and La-KIT-6 samples. The IR absorption peak at 1083 cm1 is due to vas(Si-O-Si) vibrations of silica framework of Si-KIT-6, and the peak at 805 cm1 is due to vs(Si-O-Si) vibrations[19,26]. As for La-KIT-6 samples, a progressive blue shift of 48 cm1 appears in the peak at 1083 cm1, the higher La content in the sample, the more blue shift of this absorption peak, which indicates that the definite perturbation of absorption peak is due to the incorporation of La into the framework[27]. The absorption peak at 968 cm1 for Si-KIT-6 sample is usually assigned to the stretching vibrations of SiO in the SiOR+ groups and it is as(SiOH) or as(SiOLa) vibration for La-KIT-6 samples. With an increase in La content of the samples, the absorbance intensity of this peak at 968 cm1 increases progressively. This result is generally regarded as a evidence of the metal cation incorporated into the framework of mesoporous silicates[21,27,33]. Fig. 7 shows FT-IR spectra of B-KIT-6 and LaB-KIT-6

Fig. 4 Nitrogen adsorption-desorption isotherms of B-KIT-6 (1), LaBKIT-6-0.02 (2), LaB-KIT-6-0.03 (3) and LaB-KIT-6-0.04 (4)

Fig. 6 FT-IR spectra of Si-KIT-6 (1), La-KIT-6-0.02 (2), La- KIT6-0.03 (3), and La-KIT-6-0.04 (4)

Fig. 5 UV-Vis spectra of Si-KIT-6 (1), B-KIT-6 (2), La-KIT-60.02 (3), La-KIT-6-0.03 (4), La-KIT-6-0.04 (5), LaB-KIT6-0.02 (6), LaB-KIT-6-0.03 (7) and LaB-KIT-6-0.04 (8)

Fig. 7 FT-IR spectra of Si-KIT-6 (1), B-KIT-6 (2), LaB-KIT-60.02 (3), LaB-KIT-6-0.03 (4) and LaB-KIT-6-0.04 (5)

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samples. There are two differences from that of La-KIT-6. Firstly, no obvious blue shift is observed for the absorption peak of vas (SiOSi) vibrations for LaB-KIT-6 samples, due to the coexistence of B in the framework of silica materials. Secondly, an additional absorption peak at 1405 cm1 appears for LaB-KIT-6 and B-KIT-6 samples, which is attributed to B-O vibrations. 2.1.5 XPS Table 2 shows the binding energies and surface atom concentration of La-KIT-6-0.02 and LaB-KIT-6-0.02 samples determined by XPS. The binding energy of La3d3/2 and La 3d5/2 is 852 and 835 eV, respectively, which agrees well with the standard XPS spectra data of La3d[34], and thus confirms the existence of La3+ cations only[35]. The results also show that the La content on the surface of LaB-KIT-60.02 is higher than that of La-KIT-6-0.02, due to the presence of La2O3 on the surface of LaB-KIT-6-X samples confirmed by XRD results. 2.2 Oxidation of styrene 2.2.1 Oxidation with H2O2 as oxidant Table 3 shows the catalytic performances of La-KIT-6 and LaB-KIT-6 for the oxidation of styrene with H2O2 as oxidant. The results show that Si-KIT-6, La2O3, and B-KIT-6 display a low styrene conversion similar to that of the blank test. When La-KIT-6 was used as catalyst, a high conversion of styrene (>20%) was obtained with the main product of benzaldehyde and a little amount of styrene oxide. It indicates that La3+ species in the framework of La-KIT-6 has a high catalytic activity for the oxidation of styrene. Moreover, the conversion of styrene and the selectivity to benzaldehyde increase with an increasing La content of La-KIT-6 samples. It indicates that higher amount of La3+ cations in the framework is favourable for improving the catalytic performance of La-KIT-6 catalyst. On the other hand, the conversion of styrene over La-KIT-6 is higher than that over La-MCM-48 with the similar La content, reported in our previous work[22]. This is because larger pore size of La-KIT-6 is favourable for faster diffusion of reactants and products through the pore channels. As shown in Table 3, LaB-KIT-6 behaves much lower styrene conversion than La-KIT-6 with similar product selectivity, which is ascribed to La2O3 nanocrystallites on the surface of LaB-KIT-6 catalysts. It has proved that La2O3 is less active for the oxidation of styrene than La3+ cations in the tetrahedral framework and hexacoordinated La3+ cations dispersed highly in the extraframework[22]. Therefore, the presence of La2O3 nanocrystallites prevented the reactants from reacting with the active sites in the framework, and
Table 2 Binding energies (eV) and surface atom concentration (%) of La-KIT-6-0.02 and LaB-KIT-6-0.02 samples determined by XPS
Samples La-KIT-6-0.02 LaB-KIT-6-0.02 O1s BE 531.55 531.5 At/% 96.49 78.92 191.64 4.76 B1s BE At/% La3d5/2 BE 835.41 835.73 At/% 3.51 16.32

Table 3 Catalytic performance of La-KIT-6-X and LaB-KIT-6- X catalysts in the oxidation of styrene with H2O2 as oxidationa *
Catalysts Blank La2O3 La(NO3)36H2O Si-KIT-6 B-KIT-6 La-KIT-6-0.02 La-KIT-6-0.03 La-KIT-6-0.04 LaB-KIT-6-0.02 LaB-KIT-6-0.03 LaB-KIT-6-0.04 *
a

Styrene conversion/% 3.8 5.0 3.8 4.1 6.5 20.6 25.2 28.0 7.3 8.6 9.5

Product selectivity/% BzA b 69.3 84.1 100.0 87.8 82.6 74.6 80.5 83.1 68.0 74.7 85.2 SO c 30.7 15.9 12.2 17.4 25.4 19.5 16.9 32.0 25.3 14.8

Reaction conditions: catalyst 100 mg, styrene 5 mmol, H2O2 (30 wt.%)

5 mmol, MeCN 4.5 ml, DMF 0.5 ml, at 60 C for 24 h; b BzA = benzaldehyde; c SO=styrene oxide

thus resulted in a low styrene conversion over LaB-KIT-6 catalyst. 2.2.2 Oxidation with TBHP or O2 as oxidant Table 4 shows the effect of different oxidants on the catalytic performances of La-KIT-6-0.02 and LaB-KIT-6-0.02 for the oxidation of styrene. The results show that the styrene conversion over La-KIT-6 with TBHP as oxidant is much lower than that with H2O2 as oxidant. However, regardless of oxidants, the styrene conversions are low over LaB-KIT-6 catalyst. Due to the stronger oxidizing capability of TBHP than H2O2, a little amount of by-products were produced with TBHP as oxidant[36]. When O2 was used as oxidant, the lowest styrene conversion with the highest selectivity to benzaldehyde was achieved over both La-KIT-6-0.02 and LaB-KIT-6-0.02 catalysts. The lowest styrene conversion may be due to the direct attack of O2 to styrene, an endothermic reaction, and as a consequence the activation process is highly difficult[37]. Figs. 8 and 9 show the effect of reaction temperature on the catalytic performance of La-KIT-6-0.02 for the oxidation
Table 4 Effect of different oxidants on the oxidation of styrene over La-KIT-6-0.02 and LaB-KIT-6-0.02 catalystsa *
Catalysts Styrene conversion/% H2O2 b TBHP b O2 b H2O2 c TBHP O2 c
c

Product selectivity/% BzA d 74.6 70.8 100 68.0 77.8 98.4 SO e 25.4 27.2 32.0 20.1 1.6 Others f 2.0 2.1

20.6 5.4 1.0 7.3 5.6 4.0

* a Reaction conditions: catalyst 100 mg, styrene 5 mmol, oxidant (H2O2 or TBHP) 5 mmol or O2 0.5 MPa, MeCN 4.5 ml, DMF 0.5 ml, at 60 C for 24 h; b La-KIT-60.02 as catalyst; c LaB-KIT-6-0.02 as catalyst; d BzA=benzaldehyde; e SO=styrene oxide; f Phenylacetaldehyde and phenylethanediol

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styrene conversion increased gradually with an increase in the reaction temperature with TBHP or O2 as oxidant, the selectivity to benzaldehyde and styrene oxide decreased gradually, due to the deep oxidation arising from the higher reaction temperature. Thus it is concluded that H2O2 is the better oxidant for the oxidation of styrene than tert-butyl hydroperoxide and oxygen.

References:
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Fig. 8 Effect of reaction temperature on the catalytic performance of La-KIT-6-0.02 in the oxidation of styrene (reaction conditions: catalyst 100 mg, styrene/MeCN/DMF=5 mmol/4.5 ml/ 0.5 ml, 5 mmol TBHP, 24 h)

Fig. 9 Effect of reaction temperature on the catalytic performance of La-KIT-6-0.02 in the oxidation of styrene (reaction conditions: catalyst 100 mg, styrene/MeCN/DMF=5 mmol/4.5 ml/ 0.5 ml, 0.5 MPa O2, 24 h)

of styrene with TBHP or O2 as oxidant. As shown in Figs. 8 and 9, the styrene conversion increases gradually regardless of TBHP or O2 as oxidant with an increasing reaction temperature. However, the selectivity to benzaldehyde and styrene oxide decreased, due to the deep oxidation arising from the higher reaction temperature. Therefore H2O2 is the best oxidant for the oxidation of styrene because of simplicity in handling, environmentally benign nature of by-product.

3 Conclusions
La-doped and La-B-doped KIT-6 mesoporous materials were prepared by direct hydrothermal synthesis with pH-adjusting method. The results showed that La or B cations have been incorporated into the framework of KIT-6 and the coexistence of B hindered the dispersion or incorporation of La into the framework. La3+ species in the framework of La-KIT-6 was favourable to improve the catalytic performance of La-KIT-6 for the oxidation of styrene. When H2O2 was used as oxidant, LaB-KIT-6 behaved much lower styrene conversion than La-KIT-6 catalyst with similar product selectivity, which was ascribed to La2O3 nanocrystallites on the surface of LaB-KIT-6 catalysts. Although the

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