Microporous and Mesoporous Materials 165 (2013) 613

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Microporous and Mesoporous Materials

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Post-synthesis of TiO2/MCM-41 from aqueous TiCl4 solution: Structure characteristics and epoxy catalytic activity
Lina Ma, Jianbing Ji , Fengwen Yu, Ning Ai, Hongtao Jiang
Zhejiang Province Key Laboratory of Biofuel, Zhejiang University of Technology, Hangzhou 310014, China

a r t i c l e

i n f o

a b s t r a c t
Titanium-containing mesoporous silica TiO2/MCM-41 (C) was prepared by impregnating MCM-41, pretreated by refrigeration at 278 K, with aqueous TiCl4 solution as titanium precursor. In addition, TiO2/ MCM-41 (H) was produced by same method but the support MCM-41 without refrigeration in order to investigate the inuence of unrefrigerated pretreatment on the structure of TiO2/MCM-41. The dispersion and nature of titanium species were characterized by inductively coupled plasma mass spectrometry (ICP-MS), powder X-ray diffraction (XRD), Fourier transform infrared spectroscopy (FT-IR), UVvisible diffuse reectance spectra (UV-vis DRS), standard BrunauerEmmnettTeller (BET), X-ray photoelectron spectra (XPS), scanning electron micrographs (SEM), transmission electron microscopy (TEM). The results indicate that TiO2/MCM-41 (C) showed better mesoscopic order, higher dispersion of titanium oxide species, stronger interaction with the MCM-41 support. But the pore size decreases from 3.4 to 2.4 nm when the titanium content increases to 76.6 mg/g. TiO2/MCM-41 (C2) exhibits more excellent catalytic performance than others, and the 97.6% conversion of methyl oleate (MO) and 93.1% selectivity to epoxidation methyl oleate (EMO) can be obtained at 353 K for 10 h. 2012 Elsevier Inc. All rights reserved.

Article history: Received 27 October 2011 Received in revised form 17 April 2012 Accepted 7 May 2012 Available online 3 August 2012 Keywords: TiO2/MCM-41 Mesoporous molecular sieves Post-synthesis Characterization Catalytic testing

1. Introduction Recently much attention has been paid on the olen epoxidation by various catalysis with various oxidants since epoxides are used in exible intermediates of many industrially signicant chemicals [14] such as drugs, agrochemicals, lubricants, biobased polymers, fuel additives, polymer stabilizer, and perfume materials. Several studies have been done to develop active catalytic systems for the epoxidation of different olens using a wide range of catalysts. Catalysts based on molybdenum [5], alumina [6], titanium [7] and tungsten [8,9] have been described for this reaction. Among them, Ti-containing catalysts enable many processes to be selectively, efciently, and environment-friendly conducted under mild condition. Usually Ti-containing catalyst is prepared by hydrothermal synthesis or post-synthesis. Post-synthesis has better industrialization prospect because its process is more easily to obtain than that of hydrothermal synthesis. Inumaru [10] prepared Ti/SiO2 catalysts by the chemical vapor deposition (CVD) method using TiCl4 as titanium source. And Lu and co-workers [11] optimized the CVD conditions and got the TiSBA-15 of Ti load of 4.62 wt.% with high epoxy selectivity and activity; Marchetti and co-workers [12] prepared Ti/MCM-41 samples by impregnation methods using Ti-tert Corresponding author. Tel./fax: +86 571 88320053.
E-mail address: jjb@zjut.edu.cn (J. Ji). 1387-1811/$ - see front matter 2012 Elsevier Inc. All rights reserved. http://dx.doi.org/10.1016/j.micromeso.2012.05.005

butoxide in isopropyl alcohol solution as titanium source and found that their catalytic activities were similar as that of the hydrothermal TiMCM-41. Yang and co-worker [13] investigated the synthesis of TiO2/SBA-15 materials via Ti-alkoxide hydrolysis in the support-isopropanol suspension; Stein and co-workers [14] and Sun and co-workers [15] used TiCl4 in hexane as titanium precursor to graft titania clusters into the pores of MCM-41. However, this process must be under nitrogen environment or TiCl4 hydrolyzes to TiO2 in an open atmosphere. In this work, we have investigated the post-synthesis of TiO2/ MCM-41 by grafting of titanium oxide onto the MCM-41 in air using an aqueous TiCl4 solution as precursor. And the comparison of the inuence of support with and without refrigerated pretreatment on the structure of TiO2/MCM-41 was investigated. The synthesized materials were characterized by various physical techniques. At the same time, their epoxy catalytic activities of MO were tested.

2. Experimental 2.1. Catalyst preparation 2.1.1. Preparation of MCM-41 The pure mesoporous silica MCM-41 was synthesized according to the reported procedure [16] by using of cetyltrimethylammonium bromide (CTAB, 99%) as the cationic surfactant under alkaline

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conditions. Briey, a solution of CTAB/NaOH/H2O/TEOS = 1/2.7/ 9820/8.7 (mole ratio) was prepared and stirred for 10 h at 353 K. The solid product was ltered off, and then dried overnight at 373 K. Mostly occluded surfactant was removed by calcinations at 853 K for 0.5 h in air, yielding the mesoporous molecular MCM-41 material. The MCM-41 (BET surface area: 1437 m2/g, average pore diameter: 3.41 nm, total pore volume: 1.35 cm3/g) was used in preparation of TiO2/MCM-41 samples support. 2.1.2. Preparation of TiO2/MCM-41 2.1.2.1. Aqueous TiCl4 solution. TiCl4 (above 99%) was used without any further purication. The aqueous TiCl4 solutions, the titanium precursor, were prepared by slowly adding, drop-wise, a given amount of water into a certain amount of TiCl4. When water contacts with TiCl4 excess heat explosively generating from the exothermic reaction was removed by constantly shaking in ice-water bath. And the white smoke was collected and absorbed by 2 N alkali liquor. The color of aqueous TiCl4 solution changed from pale yellow to lemon and then to colorless. The concentration of colorless aqueous TiCl4 solutions was 0.3 and 0.4 mol/L. And the aqueous TiCl4 solutions were kept in ice-water bath. 2.1.2.2. TiO2/MCM-41 (C). MCM-41 was dried at 373 K and then refrigerated in refrigerator at 278 K for overnight before impregnation. Following the simple impregnation to incipient wetness of 0.5 g MCM-41 with 2 ml above solutions at 278 K for two days in air the samples were dried at 373 K, separately. And then the samples were calcined in air at 823 K for 2 h at a heating rate of 2 K/ min to obtain TiO2/MCM-41 (C1), and TiO2/MCM-41 (C2) samples. 2.1.2.3. TiO2/MCM-41 (H). MCM-41 was dried at 373 K and cooled at room temperature for 2 h. With the same impregnation to incipient wetness and same nishing procedure as described above TiO2/MCM-41 (H1) and TiO2/MCM-41 (H2) samples were obtained. 2.2. Characterizations The titanium contents in TiO2/MCM-41 samples were determined by ICP-MS (PerkinElmer Elan DRC-e). For ICP-MS studied, 0.025 g of the samples was digested with 3 mL HNO3 and 1 mL of HF in digestion high-pressure tank at 333 K for 5 h, 25 ml boric acid neutralized after cooled down and then diluted to 250 mL, respectively. The titanium concentrations of samples were determined from a calibration plot made previously. XRD measurements were performed at room temperature using a PNAlytical XPert PRO powder diffractometer with Cu Ka (k = 1.5404 ) radiation. The diffractometer was operated at 40 kV and 40 mA and scanned between 1.5 and 8 (2h) with a step size of 0.0083 and between 10 and 70 (2h) using steps of 0.033. FT-IR spectra were recorded on a Nicolet 6700 FT-IR spectrometer using 0.5 mm KBr pellets containing 2.5 wt.% samples. The UVvis DRS in the UV vis range with BaSO4 as reference were recorded using a Shimadzu UV-2550 spectrometer equipped with an integration sphere attachment. XPS were acquired recorded on Kratos AXIS Ultra DLD spectrometer equipped with a dual X-ray source, of which the AlKa (1486.6 eV) anode and a hemispherical energy analyzer were used. The background pressure during data acquisition was kept below 7.4 107 Pa. Measurements were performed at pass energy of 160.0 eV to ensure sufcient sensitivity for the acquisition scan, while pass energy of 40.0 eV was used for the scanning of the narrow spectra of Ti 2p and C 1s to ensure sufcient resolution. All the binding energies were calibrated by referencing to the contaminant carbon (C 1s) 284.8 eV. The surface morphological details of catalysts were studied by SEM (Hitachi S-4700 II). The catalyst samples were mounted directly on the holders and covered with sputtered gold and then observed in SEM. TEM images were

obtained on a Tecnai G2 F30 S-Twin microscope operated at 300 kV. The samples were dispersed in ethanol in an ultrasonic bath for several minutes, and then deposited on a Cu grid and dried by infrared heat lamp for the experiment. The specic surface area was calculated using the standard BET method. Nitrogen adsorption/desorption isotherms were measured at 77 K using micromeritics ASAP 2010 of samples. The total pores volume was estimated from the amount of nitrogen adsorbed at a relative pressure p/p0 of 0.99, assuming complete surface saturation with nitrogen, where p and p0 denote the adsorption size distribution curves were calculated from the adsorption branches of the isotherms using BarettJoynerHalenda (BJH) method. 2.3. Activity test 2.3.1. Materials Methyl oleate (MO), the substrate for catalytic tests, was a colorless liquid obtained from vegetable tallow by esterication, transesterication with methanol and following rectication. FAME mixture was qualitative analyzed by Agilent 9790A/5875C gas chromatographymass spectrometry (GCMS). And the composition is (wt.%) MO (84.5), methyl linoleate (2.5), methyl stearate (1.6), methyl palmitate (9.5), others (1.9) quantitative analyzed by Fuli GC 9790 with a HP-INNOWAX column (30 m 0.25 mm 0.25 lm) with a ame ionization detector (FID). 2.3.2. Catalytic tests The activity test was performed at 353 K for 10 h with magnetic stirring in a round bottomed ask with MO, aqueous tert-butylhydroperoxide (TBHP, 75%) as oxygen donor and ethyl acetate as solvent. The analysis method was same as above. 3. Results and discussion 3.1. Characterization of TiO2/MCM-41 The amount of titanium present on the support is determined by using ICP-MS. Table 1 shows the amounts of titanium, expressed in mg/g of product. Small-angle powder X-ray diffraction patterns of TiO2/MCM-41 (H1, H2), TiO2/MCM-41 (C1, C2) samples and pure MCM-41 are shown in Fig. 1. TiO2/MCM-41 (C1, C2) samples and pure MCM41 exhibit three well-resolved peaks indexed to d100, d110, and d200 Bragg reection, indicating that good microscopic order and the characteristic hexagonal features of MCM-41 are maintained (Fig. 1a, d, and e). However, the d110 and d200 reection peaks of TiO2/MCM-41 (H1, H2) samples become very weak and even disappear when the content of titanium reached 73.8 mg/g. Obviously, the incorporation process of using refrigerated pretreatment support does not lead to disorder the hexagonal structure. The intensity of the d100 reection diffraction peaks at 23 decrease moderately with the titanium content increasing as compared with the corresponding pure MCM-41. In addition, the reection positions of peaks shift in different level to larger diffraction angle and become slightly broader, especially for TiO2/MCM-41 (C1,
Table 1 Titanium content of TiO2/MCM-41 samples analyzed by ICP-MS. Samples TiO2/MCM-41 TiO2/MCM-41 TiO2/MCM-41 TiO2/MCM-41 (H1) (H2) (C1) (C2) Ti (mg/g) 62.2 73.8 63.3 76.6

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Fig. 1. Small-angle powder XRD patterns of samples: (a) Pure MCM-41, (b) TiO2/ MCM-41 (H1), (c) TiO2/MCM-41 (H2), (d) TiO2/MCM-41 (C1), (e) TiO2/MCM-41 (C2).

Fig. 3. FT-IR spectra of samples: (a) Pure MCM-41, (b) TiO2/MCM-41 (H1), (c) TiO2/ MCM-41 (H2), (d) TiO2/MCM-41 (C1), (e) TiO2/MCM-41 (C2).

Fig. 2. Wide-angle powder XRD patterns of samples: (a) TiO2/MCM-41 (H2), (b) TiO2/MCM-41 (H1), (c) TiO2/MCM-41 (C2), (d) TiO2/MCM-41 (C1).

C2) samples, indicating narrowed unit cell. Wide-angle powder Xray diffraction patterns of various samples are shown in Fig. 2. None of the typical diffraction peaks form crystalline titanium oxide species are observed, only a broad peak resulting from amorphous silica centered at 2 = 23 for TiO2/MCM-41 (C1, C2) samples (Fig. 2c and d). While for TiO2/MCM-41 (H1, H2) samples which support without refrigerated pretreatment with very week characteristic peaks of crystalline anatase appear (Fig. 2a and b). Besides, the intensity of reection peaks strengthens and the number of peaks increases along with the increase of titanium content. This above result may be explained by the following two considerations: (i) titanium oxide species is totally incorporated into the lattice of the MCM-41 for TiO2/MCM-41 (C) samples and (ii)

for TiO2/MCM-41 (H1, H2) samples, the formation of partial anatase species causes destruction and partial blocking of the pore system. And this nding could be conrmed by SEM and TEM images and showed in context. In order to evaluate the formation of titanium oxide in the catalyst framework, FTIR, XPS and UVvis DRS were carried out. The FT-IR spectra of pure MCM-41 and TiO2/MCM-41 samples are shown in Fig. 3. Four characteristic absorption bands are observed. All the samples exhibit the symmetric stretching vibration band of SiOSi bridges at around 810 cm1, the anti-symmetric vibration band at around 1100 cm1 with a shoulder at 1220 cm1 for the tetrahedral SiO4 structure units. Finally, for Ti-containing molecular sieve the important band at 960 cm1 is to be regarded as a consequence of stretching vibrations of SiOTi bonds. And its increase in intensity along with the content is generally considered as a evidence of the incorporating of titanium into the framework [17,18] as the stretching SiO vibration mode perturbed by the neighboring metal ions. Pure MCM-41 shows very mild band (Fig. 3a). For TiO2/MCM-41 (C1, C2) samples, characteristic intensity band strengthens with the increase of titanium loading. While no typical intensity increase of IR band located at around 960 cm1 can be observed for TiO2/MCM-41 (H1, H2) samples. UVvis DRS is a very sensitive probe for the presence of extraframe Ti in molecular sieves. The UVvis DRS spectra of TiO2/ MCM-41 (C1, C2, H1, H2) samples and anatase are given in Fig. 4. There is no peak for pure MCM-41 (not show in gure). TiO2/ MCM-41 (C1, C2) (Fig. 4d and e) samples have an absorption maximum band at about 210240 nm, which is assigned to the ligandto-metal charge transfer involving isolated titanium atoms in tetrahedral coordination, in which two water molecules form part of the metal coordination sphere. Although there is not obvious peak at about 280 nm, the broad peak mean that there is probably a very weak shoulder at about 280 nm for TiO2/MCM-41 (C1, C2) samples. The shoulder at 280 nm probably corresponds to partially polymerized Ti species (ve- and six-coordinate) in small titania nanodomains [19]. While TiO2/MCM-41 (H1, H2) samples (Fig. 4b and c) show an intense band centered at 230260 nm, probably containing peaks at 210230 and 260270, together with a shoulder at 310 nm. The shoulder at 310 nm, being obvious for anatase

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Fig. 6. Ti 2p photoelectron spectra of samples: (a) TiO2/MCM-41 (C2), (b) TiO2/ MCM-41 (H2). Fig. 4. UVvis DRS patterns of samples: (a) Anatase, (b) TiO2/MCM-41 (H2), (c) TiO2/MCM-41 (H1), (d) TiO2/MCM-41 (C2), (e) TiO2/MCM-41 (C1).

(shown in the Fig. 4a), indicates that bulk titania is formed [20]. Fig. 5 outlines the reaction scheme of potential structures resulting from the grafting procedure. Solution can reach internal pore (Fig. 5a) derived mainly by capillary force and titania is anchored to the silica framework via reaction with terminal SiOH groups on the pore surface (Fig. 5b) under the slow volatilization of HCl for TiO2/MCM-41 (C) samples. And the titanium species forming a smooth layer which coats the pore surface leads to narrow pore. Besides, with the increasing of content of titanium, polymerized Ti

Fig. 5. Schematic of the grafting procedure and potential results. Only a single pore is shown. The color darkens with the increase of concentration of titanium. (a) A single pore of pure MCM-41. (b) A smooth layer of titanium oxide species coats the pore surface. (c) Small polymerized titanium oxide species partially form. (d) (TiO2)n nanoclusters partially form. (e) Bulk (TiO2)n nanoclusters and isolated TiO2 unites form.

species form (Fig. 4c). While for TiO2/MCM-41 (H) samples, much of TiCl4 has formed (TiO2)n nanoclusters (Fig. 5d) or isolated TiO2 unites (Fig. 5e) when TiCl4 penetrates the pore in carrier and grafts onto pore surface because of the quick volatition of HCl. After obtaining information about the chemical nature and coordination states of the titanium species in the samples, we investigated the oxidation state of the species presents on their surface using XPS analysis. Fig. 6 shows the Ti 2p spectra of TiO2/ MCM-41 (C2, H2) samples. The deconvoluted XPS spectra of the two samples show the presence of three different Ti species with their Ti2p3/2 binding energies which can be tted with three symmetric cures which distinguish titanium oxide species in different chemical states according to published binding energy (BE) shifts for TiO2, SiO2, TiO2/SiO2mixed oxide systems, TS-1 and TiMCM41 [14,2124]. The rst species with the lowest binding energies arising at 457.8 0.2 eV is characteristic of octahedral titanium species. The proportion of peak at 457.8 0.2 eV of TiO2/MCM-41 (C2) sample is far less than that of TiO2/MCM-41 (H2) sample. The largest peak at 460.0 0.2 eV for TiO2/MCM-41 (C2) sample, as same as that observed on TS-1, is attributable to tetrahedral coordinated Ti species which is referred to titanium accommodated into the silica framework. TiO2/MCM-41 (H2) sample showing a maximum peak at 459 0.2 eV is consistent with titanium in the octahedral environment of anatase and probably originates from the anatase particles that are present on the external surface. The SEM and TEM micrographs of TiO2/MCM-41 (C) are shown in Figs. 7 and 8, respectively. The ball-rod-like structure of TiO2/ MCM-41 (C2) sample (Fig. 7a) is about 300 nm in diameter and about 650 nm in length. And each particle consists of well-ordered hexagonal nano-channels (Fig. 8a and b) of one-dimensional mesopores. Anatase crystallites are not present at external MCM-41 surfaces in sample, demonstrating titanium oxide species are well dispersed in MCM-41 channels. However, for the TiO2/MCM-41 (H2) sample, the scaly-like structure is shown in Fig. 7b. TEM images of TiO2/MCM-41 (H2) sample (Fig. 8c and d) show the degradation and rupture of the MCM-41 mesostructure, which are consistent with the small-angle XRD results. The amorphous zones and even anatase agglomerate species were blocked in the channels and formed on the external surface.

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Fig. 7. SEM images of samples: (a) TiO2/MCM-41 (C2), (b) TiO2/MCM-41 (H2).

Fig. 8. TEM images of samples: (a) and (b) TiO2/MCM-41 (C2); (c) and (d) TiO2/MCM-41 (H2).

The nitrogen adsorptiondesorption isotherms and typical pore size distributions for TiO2/MCM-41 (C2, H2) samples and ungrafted MCM-41 are shown in Fig. 9. And the average pore volume, diameter and BET surface area are listed in Table 2. Compared with MCM-41, TiO2/MCM-41 (C2, H2) samples have lower surface areas obviously caused by deposition of titanium oxide species. There is a noticeable difference in the shape of the isotherms and a significant decrease of pore size with Ti loading for the TiO2/MCM-41 (C2) sample compared to MCM-41, attributed to lling of pores with titanium oxide species. The nitrogen sorption isotherm for TiO2/MCM-41 (H2) sample exhibits the shape of type IV cures, typical of mesoporous material, but combined with above results it

can be seen that no signicant decrease of the pore size with Ti loading which suggest that mostly titanium oxide species located on external surface instead of incorporating with MCM-41. 3.2. Catalytic results The catalytic performance of TiO2/MCM-41 catalysts is shown in Fig. 10. For the purpose of comparison, the catalysts were used in these experiments containing the same amount of MO/Ti moral ratio. Furthermore, pure MCM-41 or TiO2 show no transformation toward the reaction (not shown here), while those grafted titanium species on the MCM-41 support show substantial activity and yield

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Fig. 9. Nitrogen adsorption/desorption isotherms at 77 K and BJH pore size distribution of samples: h Calcined, pure MCM-41, 4 TiO2/MCM-41 (H2), O TiO2/MCM-41 (C2).

Table 2 Textural properties of TiO2/MCM-41 (C2, H2) samples. Sample TiO2/MCM-41 (C2) TiO2/MCM-41 (H2) BET surface area (m2/g) 882 840 Pore volume (cm3/g) 0.44 0.78 Average pore diameter (nm) 2.44 3.31

in the epoxidation reaction, which indicates that the titanium species loaded on the mesoporous MCM-41 act as active centers for the selective epoxidation of MO. Their catalytic selectivity of EMO is above 90%. This result suggests that the titanium species loaded on the mesoporous MCM-41 material act as active centers for the epoxidation of MO. As shown in Fig. 10, the TiO2/MCM-41 (C) catalysts show excellent catalytic activity as compared with the TiO2/MCM-41 (H) for this reaction. Furthermore, catalysts of

TiO2/MCM-41 (C2, H2) display better catalytic performance than that of TiO2/MCM-41 (C1, H1), which means that the catalytic performance is decided by the content and nature of titanium oxide species. To get more information on the activity of these two kinds catalysts, the effect of TBHP/MO and Ti/MO molar ratio have been carried out and results are shown in Figs. 11 and 12. The effect of TBHP/MO molar ratio (from 1.1/1 to 2.2/1) (Fig. 11) was investigated under 358 K, reaction time 10 h, MO/ Ti [TiO2/MCM-41 (H2)] = 8.8, mass ratio of ethyl acetate/MO = 20. We observe that the conversion of MO increases with the increasing of TBHP/MO molar ratio. And a maximum is obtained by using TBHP/MO molar ratio of 1.55 giving a conversion 78%. Then the effect of MO/Ti molar ratio was investigated under 358 K, reaction time 10 h, TBHP/ MO = 1.55, mass ratio of ethyl acetate/MO = 20 in Fig. 12. In aggregate TiO2/MCM-41 (C2) shows remarkable higher catalytic activity

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Fig. 10. Epoxidation performance of the selective epoxidation of MO over catalysts: I. TiO2/MCM-41 (C2); II. TiO2/MCM-41 (C1); III. TiO2/MCM-41 (H2); IV. TiO2/MCM41 (H1). Reaction time 10 h, reaction temperature 358 K, mole ratio of MO/TBHP/ TiO2 = 100:160:6, mass ratio of ethyl acetate/MO = 20.

Fig. 12. Effect of MO/Ti molar ratio on the epoxidation conversion of MO and yield of EMO. Reaction time 10 h, reaction temperature 358 K, mole ratio of TBHP/ MO = 1.5, mass ratio of ethyl acetate/MO = 20.

Fig. 11. Effect of TBHP/MO molar ratio on the reaction conversion using catalyst TiO2/MCM-41 (H2). Reaction time 10 h, reaction temperature 358 K, mole ratio of MO/ Ti = 8.8, mass ratio of ethyl acetate/MO = 20.

Fig. 13. Effect of MO/Ti molar ratio on the epoxidation conversion of MO with TiO2/ MCM-41 (C2) under solvent-free condition. Reaction time 10 h, reaction temperature 358 K, mole ratio of TBHP/MO = 1.6.

than TiO2/MCM-41 (H2). The range of conversion increases for TiO2/MCM-41 (H2) is bigger than that of TiO2/MCM-41 (C2) when the MO/Ti molar ratio changes from 15 to 7, but the maximum conversion of TiO2/MCM-41 (H2) still lower than that of TiO2/MCM-41 (C2). Besides, the solvent-free selective epoxidation of MO over TiO2/ MCM-41 (C2) was investigated. In Fig. 13, the conversion of MO for the high active catalyst TiO2/MCM-41 (C2) is below 70% even the MO/Ti reaching 8. As we could see, the activity of the catalyst at 358 K is strongly dependent upon the surface properties of the catalyst, MO/Ti molar ratio, as well as the solvent existing.

4. Conclusion TiO2/MCM-41 (C) and TiO2/MCM-41 (H) had been prepared by post-synthesis step via aqueous TiCl4 solution in the support with and without refrigeration pretreatment, respectively, and characterized by several physical techniques. The results show that using MCM-41 pretreated by refrigeration as the support is favor of reducing surface temperature, resulting in no anatase formation on the MCM-41 surface. TiO2/MCM-41 (C) show better mesoscopic order, higher dispersion of titanium oxide species, stronger interaction with the MCM-41 support. It is revealed that the refrigera-

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tion pretreatment is of crucial importance for the nature of catalyst. MO with highest loaded Ti retaining the ordered mesostructure showed 98% conversion with 92% selectivity for EMO, and even got 67% conversion of MO under solvent-free condition. References
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