Characterization of platinum–iron catalysts supported on MCM-41 synthesized with rice husk silica and their performance for phenol hydroxylation

Mesoporous material RH-MCM-41 was synthesized with rice husk silica by a hydrothermal method. It was used as a support for bimetallic platinum−iron catalysts Pt–Fe/RH-MCM-41 for phenol hydroxylation. The catalysts were prepared by co-impregnation with Pt and Fe at amounts of 0.5 and 5.0 wt.%, respectively. The RH-MCM-41 structure in the catalysts was studied with x-ray diffraction, and their surface areas were determined by nitrogen adsorption. The oxidation number of Fe supported on RH-MCM-41 was + 3, as determined by x-ray absorption near edge structure (XANES) analysis. Transmission electron microscopy (TEM) images of all the catalysts displayed well-ordered structures, and metal nanoparticles were observed in some catalysts. All the catalysts were active for phenol hydroxylation using H₂O₂ as the oxidant at phenol : H₂O₂ mole ratios of 2 : 1, 2 : 2, 2 : 3 and 2 : 4. The first three ratios produced only catechol and hydroquinone, whereas the 2 : 4 ratio also produced benzoquinone. The 2 : 3 ratio gave the highest phenol conversion of 47% at 70 °C. The catalyst prepared by co-impregnation with Pt and Fe was more active than that prepared using a physical mixture of Pt/RH-MCM-41 and Fe/RH-MCM-41.     

Characterization of platinum–iron catalysts supported on MCM-41 synthesized with rice husk silica and their performance for phenol hydroxylation

Abstract

Mesoporous material RH-MCM-41 was synthesized with rice husk silica by a hydrothermal method. It was used as a support for bimetallic platinum?iron catalysts Pt–Fe/RH-MCM-41 for phenol hydroxylation. The catalysts were prepared by co-impregnation with Pt and Fe at amounts of 0.5 and 5.0 wt.%, respectively. The RH-MCM-41 structure in the catalysts was studied with x-ray diffraction, and their surface areas were determined by nitrogen adsorption. The oxidation number of Fe supported on RH-MCM-41 was + 3, as determined by x-ray absorption near edge structure (XANES) analysis. Transmission electron microscopy (TEM) images of all the catalysts displayed well-ordered structures, and metal nanoparticles were observed in some catalysts. All the catalysts were active for phenol hydroxylation using H₂O₂ as the oxidant at phenol : H₂O₂ mole ratios of 2 : 1, 2 : 2, 2 : 3 and 2 : 4. The first three ratios produced only catechol and hydroquinone, whereas the 2 : 4 ratio also produced benzoquinone. The 2 : 3 ratio gave the highest phenol conversion of 47% at 70 °C. The catalyst prepared by co-impregnation with Pt and Fe was more active than that prepared using a physical mixture of Pt/RH-MCM-41 and Fe/RH-MCM-41.     

不同偶联剂对介孔分子筛MCM-41的表面修饰及对MCM-41/环氧树脂性能的影响

使用2种硅烷偶联剂(KH550和KH792)对介孔分子筛MCM-41进行表面改性,采取氮气吸附-脱附、FTIR和TGA等进行表征,并采用原位聚合法制备了MCM-41/环氧树脂复合材料,研究了偶联剂种类和MCM-41用量等对复合材料固化过程及性能的影响。结果表明:硅烷偶联剂可与MCM-41表面的硅羟基反应,在分子筛内外表面接枝上功能化基团。经表面修饰的MCM-41比表面积下降为原来的1/5,KH550在MCM-41表面接枝率仅为KH792的一半。KH550与MCM-41外表面反应得更充分,KH792对MCM-41孔道内壁的修饰效果更强。固化动力学结果表明:KH792的功能化基团有伯胺和仲胺,与环氧树脂具有更高的反应活性,但不利于环氧大分子进入孔道,仅以球形粒子的形式添加在环氧树脂中;KH550表面修饰的MCM-41可使环氧大分子进入孔道内形成互穿结构。KH550表面修饰体系更多体现出MCM-41多孔的特征,形成了有机-无机互穿结构的复合体系,大幅度提高了储能模量和玻璃化转变温度。KH792表面修饰体系则呈常规球形纳米粒子的特征,其储能模量和玻璃化转变温度较纯环氧树脂有所提高但幅度不大。     

用稻壳灰为硅源合成有序介孔二氧化硅材料的研究

用稻壳灰为硅源,用十六烷基三甲基溴化铵作为模板剂,在酸性或碱性条件下均成功地合成了有序介孔SiO2材料MCM-41.利用XRD、N2吸附曲线、SEM、TEM等测试方法分别对稻壳灰及介孔SiO2样品进行了表征.结果表明,稻壳灰为非晶体,呈粒状的多孔结构,其比表面积为250m2/g;在酸性条件下合成的MCM-41具有周期性规则排列的介孔结构,最可几孔径为2.4nm,比表面积为1100m2/g.     

Preparation and characterization of epoxy composites filled with functionalized nano-sized MCM-41 particles

Mono-dispersed nano-sized MCM-41 (M (with template)) particles were synthesized by sol–gel reaction. The effect of interface modification on the properties of epoxy composites was investigated. Modifications were carried out either by substituting silanol groups on the surface or in the mesopore channels into amine (M-NH₂), calcinating mixture template in the mesopore channels (M(without template)), or recalcinating them at higher temperature to remove silanol groups (–OH) in the mesopore channels or on the surface (CM). Transmission electron micrograph results showed that the dispersing of MCM-41 nanoparticles was not influenced by the modification, while –NH₂ group indeed modified the mesopore channels or the surface of MCM-41 particle by using IR, XRD, and N₂ adsorption–desorption. In addition, tensile tests suggested that M-NH₂ nanoparticles could simultaneously provide epoxy matrix with strengthening and toughening effects. However, due to the different interfacial structures between the fillers and the matrix, the mechanical properties of the composites filled by M-NH₂ were much better than those of composites filled by MCM-41 (without template), MCM-41 (with mixture template), and CM.     

稻壳类生物沥青微观作用机理研究

为了探究稻壳类生物质油替代石油沥青的微观作用机理,以稻壳类生物质油和6种石油沥青为原材料,制备稻壳类生物沥青。采用针入度、软化点和延度指标评价稻壳类生物沥青的物理性能,通过傅里叶红外光谱实验(FTIR)和高温凝胶色谱实验(GPC)探究稻壳类生物沥青的微观作用机理。研究表明,稻壳类生物质油会使石油沥青的针入度和延度增大,同时使软化点略有降低;稻壳类生物质油与6种石油沥青的官能团相似,且生物沥青制备时未产生新的官能团;随着稻壳类生物质油的掺加,6种生物沥青中的小分子和中分子含量增加,大分子的含量变化不大,稻壳类生物质油小分子和中分子含量较多,生物沥青的数均分子量M_n和重均分子量M_w均降低。稻壳类生物质油的加入,使石油沥青的低温性能提高,流动性增大,高温性能稍有降低但并不会降低石油沥青的高温等级,稻壳类生物质油可以作为石油沥青的替代材料使用。     

Hollow MCM-41 microspheres derived from P(St-MMA)/MCM-41 core/shell composite particles

In soap-free latex media, poly(styrene-methyl methacrylate)/MCM-41 core/shell composite microspheres have been fabricated by adding silicate source in batches. In this process, silicate species and the surfactant micelles were self-assembled into 2-dimensional hexagonal arrangement on the surface of P(St-MMA) microspheres. Hollow MCM-41 microspheres were obtained via removing polymer core by solvent. XRD, TEM, IR and N₂ adsorption-desorption analysis were applied to characterize products. The results showed that average diameter and wall thickness of hollow MCM-41 microspheres is about 240 nm and 20 nm, respectively. Results of N₂ adsorption-desorption indicate that hollow MCM-41 microspheres possess a highly ordered mesoporous structure and a narrow pore distribution with a mean value of 2.34 nm.     

Organo-functionalized mesoporous supports for Jacobsen-type catalyst: Laponite versus MCM-41

In order to exploit the different textural properties of Laponite and MCM-41, specifically in terms of their external versus internal surface areas, in the covalent anchoring of a chiral Mn(III) salen complex, these materials were functionalized with 3-aminopropyltriethoxysilane (APTES), subsequently activated with sodium ethoxide, and finally used to anchor the Jacobsen catalyst derivative C1. All the materials were characterized by nitrogen elemental analysis, XPS, PXRD, nitrogen adsorption at −196 °C, FTIR and for those with the immobilized complex, they were additionally characterized by Mn AAS. The APTES anchored at the edges of the Laponite single crystals and inside the MCM-41 pores. Moreover, under the same preparative conditions, higher amount of APTES was anchored onto MCM-41 than onto Laponite, which is due to the higher surface area of MCM-41 compared to Laponite, as well as to its more exposed SiO₄ tetrahedra. Activation of the two organo-functionalized materials with sodium ethoxide originated anionic nitrogen groups as deduced by the increase of surface sodium content of these materials and N1s binding energy changes, but led to a small decrease in N bulk content as a result of some APTES leaching. Moreover, for MCM-41 some disruption of the silica framework occurred as a consequence of the basic treatment, as suggested by XPS, PXRD, and nitrogen adsorption study. The APTES functionalized Laponite and MCM-41 materials, as well as the activated analogs, were able to anchor C1 through axial coordination of the metal centre to the grafted surface nitrogen atoms. APTES functionalized MCM-41 presented similar complex content to Laponite analog, what points out for the fact that, at least for the bulky complex used in this work, there was no clear benefit in using a material of high internal area; for the ethoxide activated analogs, Laponite showed the highest complex content of all materials, but MCM-41 was able to anchor the lowest complex quantity, probably as a consequence of damaging effect caused by the basic treatment within its porous structure. Electronic supplementary material  The online version of this article (doi:) contains supplementary material, which is available to authorized users.     

Functionalization of mesoporous MCM-41 for the delivery of curcumin as an anti-inflammatory therapy

In this study, mesoporous silica nanoparticles (MSNs) composed of MCM-41 were synthesized and modified with amine groups (i.e., NH₂) to form NH_2/MCM-41, which was loaded with curcumin (CUR) to form CUR@NH₂/MCM-41 to create an efficient carriers in drug delivery systems (DDSs). The three samples (i.e., pure MCM-41, NH₂/MCM-41, and CUR@NH₂/MCM-41) were characterized using X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET) surface area, Fourier-transform infrared spectroscopy (FT-IR), scanning electron microscopy (SEM), energy-dispersive X-ray spectroscopy (EDX), transition electron microscopy (TEM), and a thermogravimetric analyzer (TGA). The study investigated the effect of the carrier dose, CUR concentration, pH, and contact time on the drug loading efficiency (DLE%) by adsorption. The best DLE% for MCM-41 and NH₂/MCM-41 was found to be 15.78 and 80%, respectively. This data demonstrated that the Langmuir isotherm had a greater correlation coefficient (R²) of 0.9840 for MCM-41 and 0.9666 for NH₂/MCM-41 than the Freundlich and Temkin isotherm models. A pseudo-second-order kinetic model seems to fit well with R² = 0.9741 for MCM-41 and R² = 0.9977 for NH₂/MCM-41. A phosphate buffer solution (PBS) with a pH of 7.4 was utilized to study CUR release behavior. As a result, the full release after 72 h was found to have a maximum of 74.1% and 29.95% for pure MCM-41 and NH₂/MCM-41, respectively. The first-order, Weibull, Hixson-Crowell, Korsmeyer-Peppas, and Higuchi kinetic release models were applied to releasing CUR from CUR@MCM-41 and CUR@NH₂/MCM-41. The Weibull kinetic model fit well, with R² = 0.944 and 0.96912 for pure MCM-41 and NH₂/MCM-41, respectively.     

超临界CO_2中MCM-41-g-PHEMA介孔复合物的制备及性能

以甲基丙烯酸羟乙酯(HEMA)为单体,用乙烯基三乙氧基硅烷改性的介孔分子筛MCM-41为载体,偶氮二异丁腈为引发剂,在超临界二氧化碳中通过沉淀聚合,成功合成了聚甲基丙烯酸羟乙酯-二氧化硅介孔复合材料(MCM-41-gPHEMA)。考察了反应物配比、反应时间和反应压力对所制复合物形貌与产率的影响。对所合成的复合物进行红外光谱分析、比表面积、小角X射线衍射、扫描电镜、透射电镜、热重分析等表征。研究了复合物的溶胀性及在不同pH下对牛血清白蛋白(BSA)水溶液的吸附性能与吸附动力学。结果表明,MCM-41-g-PHEMA的孔径约为6.3nm,热稳定性明显提高,复合物对BSA的吸附动力学符合伪二级速率方程,最大吸附量为35mg/g。     

硅烷修饰对环氧树脂/纳米介孔MCM-41复合材料性能的影响

用偶联剂将纳米介孔MCM-41粉体修饰后与环氧树脂溶液共混,制备出环氧树脂/MCM-41纳米复合材料.研究了偶联剂的含量和不同溶剂的修饰对纳米介孔MCM-41粉体分散性和复合材料力学性能的影响.结果表明,加入适量的偶联剂和在极性较小的介质中修饰,可制备出单分散的纳米介孔MCM-41颗粒增强的新型网络复合材料.偶联剂中的有机基团-(CH2)3-NH2不仅进入孔道、修饰了MCM-41的孔壁,而且使介孔分子筛保持了有序的孔道结构.环氧树脂高分子链与偶联修饰后的MCM-41颗粒的内、外表面以强烈的化学键结合,使MCM-41颗粒均匀分散在聚合物基体中,提高了材料的力学性能,其拉伸强度比基体树脂提高了69%,杨氏模量提高了90%.     

The investigation of MCM-48-type and MCM-41-type mesoporous silica as oral solid dispersion carriers for water insoluble cilostazol

Objective: To explore the suitable application of MCM-41 (Mobil Composition of Matter number forty-one)-type and MCM-48-type mesoporous silica in the oral water insoluble drug delivery system.

Methods: Cilostazol (CLT) as a model drug was loaded into synthesized MCM-48 (Mobil Composition of Matter number forty-eight) and commercial MCM-41 by three common methods. The obtained MCM-41, MCM-48 and CLT-loaded samples were characterized by means of nitrogen adsorption, thermogravimetric analysis, ultraviolet-visible spectrophotometry, scanning electron microscopy, transmission electron microscopy, differential scanning calorimetry and powder X-ray diffractometer.

Results: It was found that solvent evaporation method was preferred according to the drug loading efficiency and the maximum percent cumulative drug dissolution. MCM-48 with 3D cubic pore structure and MCM-41 with 2D long tubular structure are nearly spherical particles in 300–500?nm. Nevertheless, the silica carriers with similar large specific surface areas and concentrating pore size distributions (978.66?m²/g, 3.8?nm for MCM-41 and 1108.04?m²/g, 3.6?nm for MCM-48) exhibited different adsorption behaviors for CLT. The maximum percent cumulative drug release of the two CLT/silica solid dispersion (CLT-MCM-48 and CLT-MCM-41) was 63.41% and 85.78% within 60?min, respectively; while in the subsequent 12?h release experiment, almost 100% cumulative drug release were both obtained. In the pharmacokinetics aspect, the maximum plasma concentrations of CLT-MCM-48 reached 3.63?mg/L by 0.92?h. The AUC_0–∞ values of the CLT-MCM-41 and CLT-MCM-48 were 1.14-fold and 1.73-fold, respectively, compared with the commercial preparation.

Conclusion: Our findings suggest that MCM-41-type and MCM-48-type mesoporous silica have great promise as solid dispersion carriers for sustained and immediate release separately.     

Characterization of Zr-based MCM-41 mesoporous molecular sieves obtained by microwave irradiation or hydrothermal method

Zr-based MCM-41 mesoporous molecular sieves (ZrMCM-41) were successfully synthesized by microwave irradiation method and hydrothermal method, respectively. The obtained samples were characterized by XRD, TEM, FT-IR and N₂ physical adsorption. The results show that the samples synthesized by the two different methods both possess typical hexagonal mesoporous structure of MCM-41 and high specific surface areas (over 800 m²/g). After calcination at 750°C for 3 h or hydrothermal treatment at 100°C for 6 days, the mesoporous structure of the samples still retained, however, the mesoporous ordering is poor. Under the comparable conditions, the reaction time required in the synthesis of ZrMCM-41 by microwave irradiation method was greatly reduced, and microwave irradiation method is eco-friendly and is easy to operate.     

Comparative study on the structural and catalytic properties of mesoporous hexagonal silica anchored with H3PW12O40: Green synthesis of benzoic acid from benzaldehyde

Mesoporous silica anchored with 25 wt.% 12-tungstophosphoric acid (H₃PW₁₂O₄₀, HPW) were comparatively characterized on their structures and catalytic activities for benzaldehyde oxidation with H₂O₂. The results revealed that the mesoporous materials retained the typical hexagonal mesopores for the supports of HPW. It was found that HPW exhibited higher dispersion within MCM-41 than those within SBA-15 and other mesoporous molecular sieves. Moreover, the as-prepared materials were found to be the efficient catalysts for the green synthesis of benzoic acid. In particular, HPW/MCM-41 exhibited the best catalytic properties due to its suitable textural and structural characteristics.     

SiC-dopped MCM-41 materials with enhanced thermal and hydrothermal stabilities

SiC-dopped MCM-41 mesoporous materials were synthesized by the in situ hydrothermal synthesis, in which a small amount of SiC was added in the precursor solvent of molecular sieve before the hydrothermal treatment. The materials were characterized by X-ray diffraction, transmission electron microscopy, X-ray photoelectron spectroscopy, N₂ physical adsorption and thermogravimetric analysis, respectively. The results show that the thermal and hydrothermal stabilities of MCM-41 materials can be improved obviously by incorporating a small amount of SiC. The structure collapse temperature of SiC-dopped MCM-41 materials is 100 °C higher than that of pure MCM-41 according to the differential scanning calorimetry analysis. Hydrothermal treatment experiments also show that the pure MCM-41 will losses it's ordered mesoporous structure in boiling water for 24 h while the SiC-dopped MCM-41 materials still keep partial porous structure.     

Compatibilizing effect of mesoporous fillers on the mechanical properties and morphology of polypropylene and polystyrene blend

Polypropylene(PP)/Polystyrene(PS) (PP/PS = 80/20) blend with different types of fillers were prepared by using melt method. Four different types of fillers, namely mesoporous MCM-41 (without template), nano-SiO₂, Polymethylmethacrylate (PMMA)/MCM-41 and PMMA/SiO₂ were considered. For PMMA/MCM-41 filler, the synthesis of the filler consisting of entrapped strand of PMMA within the pores of mesoporous MCM-41 (without template) was described. The mechanical properties of the blend determined as the nano-fillers contents and the different types of blend were found to vary with the different interface between fillers and the matrix. SEM revealed a good interaction between the matrix phases and PMMA/MCM-41 or MCM-41 (without template). The decreased T_g of PS implied that the good adhesion between PP and PS blend was obtained by adding PMMA/MCM-41 nano-filler.     

Permeation of solvents through disk type rice husk silica membrane modified with alkyl silylation reagents

Rice husk silica (RHS) which was obtained with thermal treatment of rice husk has the size of approximately 10 micrometer with 4-5 nm pore. RHS can be mold to a disk type membrane. The membrane may have submicron pore originated from the space among the particles, and the nano pores of the rice husk silica (RHS pore). Even it is difficult to adjust the size of the pores, we can suggest that the membrane shows different permeability for the organic/inorganic solvents if the affinity between the surface of the pores and the permeating molecule is changed. In this study, we investigated the permeation of the typical solvents such as water, ethanol and toluene to the RHS membranes sintered at 1100 degrees C, 1150 degrees C and 1200 degrees C and modified with triethoxymethyl silane (CH3)Si(C2H5O)3, diethoxydiemethyl silane (CH3)2Si(C2H5O)2 and ethoxytriemethyl silane (CH3)3Si (C2H5O). The result showed that permeability of original membranes for water (e.g., 1100 degrees C, 2.87 x 10(-3) mol/m2 s Pa) was larger than ethanol (1100 degrees C, 5.51 x 10(-4) mol/m2 s Pa) and toluene (1100 degrees C, 3.09 x 10(-4) mol/m2 s Pa) at the sintering temperatures. For the silane modified membranes, the permeability for water decreased drastically while those for ethanol and toluene increased.     

配合物[Fe(bipy)2]3+修饰的MCM-41的合成与表征

以γ－氨丙基修饰介孔分子筛ＭＣＭ－４１内孔壁,将引入的γ－氨丙基与金属配位离子［Ｆｅ（ｂｉｐｙ）_２］^３＋通过配位键首次合成了金属配位化合物修饰的ＭＣＭ－４１（ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２）．通过ＸＲＤ,７７Ｋ氮气吸附－脱附曲线,固体ＵＶ－ｖｉｓ漫反射光谱和循环伏安曲线表征了复合物ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２。由于［Ｆｅ（ｂｉｐｙ）_２］^３＋的引入,使 ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２的结晶度降低, ＢＥＴ比表面积、孔容和最可几孔径急剧下降．γ－氨丙基与Ｆｅ^３＋的配位而使其ＵＶ－ｖｉｓ漫反射吸收光谱与ＭＣＭ－Ｆｅ（ｂｉｐｙ）_２不同;循环伏安特性曲线表明ＭＣＭ－ａｐ－Ｆｅ（ｂｉｐｙ）_２在电化学上比浸渍法制备的ＭＣＭ－Ｆｅ（ｂｉｐｙ）_２稳定．     

Synthesis and characterization of super-microporous material with enhanced hydrothermal stability

Super-microporouos silicon material with high hydrothermal stability denoted as MCM-41-T has been prepared from mesoporous MCM-41 by high temperature treatment. The structural and chemical property of MCM-41-T has been characterized by X-ray diffraction, transmission electron microscopy, N₂ adsorption-desorption, infrared spectroscopy and ²⁹Si MAS NMR. The characteristic results show that Si-OH groups are forced to condense by high temperature treatment, and the pore size of MCM-41-T is around 1.5 nm in the super-microporous range. Compared with the original material MCM-41, the hydrothermal stability of MCM-41-T has been significantly enhanced.     

杂原子MCM-41分子筛的合成和催化性能

采用水热合成法合成了金属原子(Zn,Ni,Fe,Al,Cu,Ce)掺杂的MCM-41介孔分子筛(简称T-MCM-41),并将其应用于邻苯二甲酸二(2-乙基已)酯(DOP)的合成反应,研究了不同原子的掺杂对T-McM-41的结构,比表面积和孔径、酸性及催化性能的影响.结果表明,所制备的T-McM-41仍然具有六方有序排列结构,比表匝f积较高(550-900 m2/g)、孔径大(3 nm左右),杂原子的引入使T-MCM-41产生了酸中心,从而使其对DOP的合成具有很好的催化活性和选择性.用T-MCM-41(T=Zn,Fe,Al,Cu)催化DOP的合成反应,在5 h的反应时间内苯酐的转化率可以达到95.5%以上,DOP的选择性可达到96.5%以上.T-MCM-41催化剂具有很好的稳定性,Al-MCM-41在重复使用5次后仍具有较好的催化活性.