Chemoselective Reduction of α,β‐Unsaturated Carbonyls over Novel Mesoporous CoHMA Molecular Sieves under Hydrogen Transfer Conditions

Chemoselective reduction of α,β‐unsaturated carbonyls to the corresponding alcohols was achieved by a catalytic transfer hydrogenation (CTH) method using cobalt(II)‐substituted hexagonal mesoporous aluminophosphate (CoHMA) molecular sieve catalyst. Further, the catalyst was found to be promising as a heterogeneous catalyst as the yield was practically unchanged after up to six cycles.     

铁取代介孔磷铝分子筛的合成、表征及其催化性能

以水热晶化法合成了Fe取代介孔磷铝分子筛,并用XRD, FT-IR, N2吸附等对其进行了表征. 结果表明,合成的分子筛为缺乏长程有序的介孔结构,具有较高的比表面积. 在焙烧后的分子筛中,Fe3+离子主要以四配位的形式存在于骨架中. 该分子筛能有效催化氧化水溶液中苯酚,在反应温度60℃、苯酚起始浓度3 mmol/L、加入45 mmol/L H2O2、溶液起始pH值4.5的条件下,4 h后苯酚去除率达99.5%,COD去除率达87.9%,且催化剂性能稳定,反应过程中有极少量Fe3+离子流失.     

Redox solid catalysts for the selective oxidation of cyclohexane in air

The selective oxidation of cyclohexane to cyclohexanol, cyclohexanone and adipic acid using molecular oxygen as the oxidant and at moderate temperatures (403 K) has been investigated over four different cobalt‐containing aluminophosphate (AlPO) molecular sieves. There is a correlation between catalytic activity and the fraction of (framework) Co(II) ions that is first oxidised to Co(III) in air. CoAlPO‐36 (pore aperture 6.5 x 7.5 Å) exhibits significant activity for the oxidation of cyclohexane in contrast to CoAlPO‐18, which, although it has the highest fraction of oxidisable cobalt, does not show any activity chiefly because of its smaller pores.     

介孔磷酸铝分子筛的研究进展

从合成方法、特性和应用三个方面综述了介孔磷酸铝分子筛(AlPO4)的国内外研究进展,分析了水热或溶剂热在合成介孔AlPO4分子筛工艺上的特点,介绍了介孔AlPO4分子筛的结构组成和在化工领域中的一些应用。     

镧改性磷酸铝介孔分子筛的合成及表征

以十八胺为模板剂,导向剂法合成磷酸铝镧介孔分子筛..采用电感耦合等离子体质谱(ICP-MS)、红外光谱(FT-IR)、N2吸附-脱附、NH3程序升温脱附(NH3-TPD)、小角度X射线衍射分析(XRD)等方法对所得样品的组成、结构和性质进行了表征.结果表明,镧修饰磷酸铝介孔分子筛与修饰前相比,比表面积略有降低,酸量和酸...     

Synthesis, Characterization and Catalytic Properties of Vanadium Substituted Hexagonal Mesoporous Aluminophosphate Molecular Sieves

Vanadium substituted hexagonal mesoporous aluminophosphate (VHMA) molecular sieves were synthesized hydrothermally. Various physicochemical studies, viz., XRD, TEM, DRUV–VIS, EPR, N₂ sorption were used to find the location of vanadium ions in the VHMA matrix and to check the mesoporosity of the sample. The catalytic activity of VHMA was evaluated, under mild reaction conditions, for the oxidation of cyclohexane reaction, which mainly gave cyclohexanol and cyclohexanone along with a very small amount of a secondary product, viz., cyclohexyl acetate. A comparative study, with other vanadium containing molecular sieves, viz., VMCM-41, VAPO-5 and VS-1, on the application of VHMA catalyst reveal that the latter exhibits excellent activity, selectivity and stability to leaching for the oxidation reaction of cycloalkanes, including bulkier molecules such as cyclododecane.     

Titanium substituted hexagonal mesoporous aluminophosphates: Highly efficient and selective heterogeneous catalysts for the oxidation of phenols at room temperature

A remarkable para-selectivity was achieved, for the first time, for the oxidation of phenol over novel titanium substituted hexagonal mesoporous aluminophosphate molecular sieves at room temperature, and that the catalysts also showed excellent activity for alkyl substituted phenols.     

Synthesis,characterization and catalytic properties of hexagonal mesoporous vanadium aluminophosphate molecular sieves

Novel vanadium containing hexagonal mesoporous aluminophosphate molecular sieve (VHMA) have been synthesized. XRD and TEM analysis confirm the phase purity of the synthesized samples. FT-IR analysis suggests the incorporation of V⁴⁺ in the aluminophosphate framework. ESR, UV–Vis spectroscopic techniques and cyclic voltammetric studies confirm the incorporation of vanadium and reveal its presence of tetrahedral and square pyramidal environments in the as-synthesized samples. Cyclic voltammetry reveals the presence of two redox couples in VHMA. This catalyst is found to be a good oxidation catalyst.     

Catalytic Oxidation of Alkylaromatics over Mesoporous (Cr)MCM-41

Liquid-phase catalytic oxidation of certain alkylaromatics over mesoporous (Cr)MCM-41 molecular sieves in the presence of chlorobenzene and tertiary butylhydroperoxide showed high substrate conversion and excellent product selectivity. The high catalytic activity of the materials is attributed to the complete oxidation of chromium ions to hexavalent chromium and the absence of pentavalent chromium in the mesoporous matrix.     

含钛中孔分子筛Ti-MSU的合成、表征与催化氧化性能

分别以两种非离子表面活性剂C₁₈(EO)₁₀、C₁₂Ph(EO)₁₀为模板剂,硅酸四乙酯（TEOS）为硅源,钛酸四丁酯（TBOT）为钛源,乙醇、异丙醇为溶剂分别合成了两种含钛中孔分子筛Ti-MSU-1和Ti-MSU-2.采用XRD、FT-IR、UV-Vis、元素分析（ICP）法、N₂吸附-脱附等方法对合成的分子筛进行了结构测试和表征.将得到的Ti-MSU-1分子筛前体在高压釜中进行水热处理后,其孔道对称性或有序性显著增强,焙烧过程中热诱导的晶层收缩不再明显,而同样条件的热处理对Ti-MSU-2分子筛孔道结构改性不大.两种Ti-MSU分子筛均对苯乙烯具有催化氧化性能.苯乙烯转化率随中孔分子筛中含钛量的增大而增大.Ti-MSU-1分子筛与Ti-MSU-2分子筛在催化性能上没有太大差别,这与其结构的相似性是一致的.     

沸石和磷酸盐分子筛晶体的空间生长

沸石晶体是应用领域最广的分子筛材料.基于这一原因,长期以来人们几乎把"沸石"一词等同于分子筛.沸石晶体不仅可应用于催化、吸附、分离等过程,还可用于微型激光器、非线性光学材料及纳米器件等新兴领域.因此,分子筛材料的合成和晶体生长引起科学界和工业部门越来越浓厚的研究兴趣.1982年美国联合碳化物公司首次合成了新型磷酸铝分子筛,打破了分子筛由硅氧四面体和铝氧四面体组成的传统观念,此后许多AlPO4-n分子筛不断涌现.由于在地面上难以生长出较大尺度的沸石晶体,因而,自20世纪80年代以来,沸石晶体的合成已成为空间材料科学的研究热点之一.前苏联、欧洲、日本和美国已在空间完成了多次沸石和磷酸铝晶体生长试验.本文将首先介绍微重力环境对于分子筛晶体生长的有利条件.然后,简述国际上已完成的空间实验,包括:前苏联PHOTO返回卫星实验、欧洲和日本CASIMIR飞行实验、欧洲EURECA空间飞行平台实验、美国STS航天飞机实验、国际空间站(ISS)实验.最后综述空间实验的主要研究结果.     

催化氧化脱硫分子筛催化剂研究进展

综述了催化氧化脱硫分子筛催化剂的研究进展。介绍了TS分子筛催化剂、SBA分子筛催化剂、HMS分子筛催化剂、MCM分子筛催化剂、ZSM-5分子筛催化剂和磷酸铝分子筛催化剂上油品的氧化脱硫方法,其中SBA、HMS、MCM和磷酸铝介孔分子筛催化剂对大分子的硫化物脱除率较高,具有很好的发展前景。今后分子筛催化氧化脱硫技术研究的重要方向是进一步开发通用性好的大孔径分子筛,研究脱硫机理和降低成本。     

Selective crystallization of CoAPO-34 and VAPO-5 molecular sieves under microwave irradiation in an alkaline or neutral condition

Syntheses of cobalt- and vanadium-incorporated aluminophosphate molecular sieves (CoAPO and VAPO) with AFI and CHA structures have been studied using an alkaline or neutral gel under microwave irradiation and conventional hydrothermal heating. Microwave synthesis gives rise to the selective crystallization of CoAPO-34 with a CHA structure and VAPO-5 with an AFI structure, while the conventional hydrothermal crystallization brings CoAPO-5 and VAPO-34 through the gradual transformation of CoAPO-34 and VAPO-5, respectively, as the crystallization time increases. These results reveal that the relative stabilities of metal-incorporated aluminophosphate (MeAPO) molecular sieves between AFI and CHA structures depend on the type of incorporated metal ions. This work also suggests that microwave syntheses of MeAPO molecular sieves preferentially induce a kinetically favorable MeAPO phase in a short period of crystallization time. The synthesis of VAPO-5 in an alkaline condition is for the first time reported in this work.     

中孔分子筛材料的研究进展

介绍了中孔分子筛MCM系列、HMS系列、MSU系列、SBA系列等在合成方法和改性方法上的研究进展;评述了掺入杂原子、引入有机基团、硅源前处理、混合模板剂等赋予中孔分子筛新的催化性能和选择性氧化性能及其应用前景。     

Characterization and catalytic evaluation of mesoporous and microporous molecular sieves containing niobium

The synthesis and characterization of the novel microporous aluminophosphate NbAPO-5 is described. The novel material has been studied by X-ray powder diffraction, SEM, TG/DTA-MS, electron spin resonance, and ultraviolet-visible (UV-Vis) spectroscopy The catalytic properties have been tested in the epoxidation of 1-hexene and cyclohexene, respectively, in comparison with niobium-containing silicalite-1 and NbMCM-41. The results of the physical characterization indicate that it is possible to prepare niobium-containing aluminophosphates, where isolated Nb(V) species are connected to framework defect sites via formation of Nb–O–P or Nb–O–Al bonds. The results of this study allow the preparation of microporous and mesoporous niobium-containing molecular sieves which are active catalysts in oxidation reactions.     

Catalytic Oxidation of Oleic Acid in Supercritical Carbon Dioxide Media with Molecular Oxygen

Oxidation of oleic acid was performed over various ordered porous catalysts containing transition metal in supercritical carbon dioxide (scCO₂) media with molecular oxygen. Oleic acid was completely decomposed into mono- and dicarboxylic acids over porous catalysts, viz., mesoporous molecular sieves (CrMCM-41, MnMCM-41, CoMCM-41) and microporous molecular sieves (CrAPO-5, CoMFI, MnMFI) using scCO₂ at 353 K for 8 h. Among the different catalysts studied, microporous and mesoporous catalysts containing chromium, in presence of scCO₂ showed high distribution of azelaic and pelargonic acids as compared to their analogs containing cobalt or manganese. The presence of scCO₂ medium with the catalysts increased the distribution of azelaic and pelargonic acids. The effect of CO₂ pressure, reaction temperature and reaction time on oxidation of oleic acid over CrMCM-41 was also investigated. Additionally it is noticed that the catalyst can be recycled with negligible loss of catalytic activity.     

杂原子AlPO-n分子筛的制备及应用研究进展

通过在AlPO-n分子筛中掺杂不同的金属或非金属元素制备杂原子AlPO-n分子筛,不仅具有AlPO-n分子筛的规整结构、良好热稳定和水热稳定性,还具有可调控的酸性质、离子交换位点、催化活性中心和择形性,使杂原子AlPO-n分子筛在催化、气体吸附和化学分离等方面展现巨大潜力。综述近年来杂原子AlPO-n分子筛的研究进展,介绍杂原子掺杂的制备方法、模板剂效应和取代性能变化,描述杂原子AlPO-n分子筛的应用前景。     

气相法制备沸石分子筛的研究进展

综述了气相法,包括气相转移法和干胶法在合成沸石分子筛、磷铝分子筛和其它杂原子分子筛及分子筛膜方面的研究进展。介绍了合成过程中一些影响因素,如时间、温度、干胶组分或有机模板剂对合成的影响。并且对气相法制备分子筛成型体作了简单介绍。     

Mesoporous Silicates with Spherical Morphology Modified with Vanadium Highly Active in Oxidation of Cyclohexene with H2O2

Vanadium-containing mesoporous molecular sieves have been prepared by hydrothermal treatment at 373 K. These materials showed spherical morphology with a narrow particle size distribution between 2 and 4 μm. The techniques used for their physicochemical characterization were: XRD, AAS, N₂ physisorption, SEM, TEM and DR–UV–Vis spectroscopy. All the materials presented high specific surface area (>900 m²/g), characteristic of MCM-41 materials. A well-defined mesoporous structure was observed by TEM measures although there was no one-dimensional ordering of pores characteristic of such materials. Additionally, secondary mesoporosity domains were determined in the BJH size distribution. The sample synthesized with the highest content of V presented marked differences in their structural characteristics, which were attributed to the blockage of channels by the presence of nano-clusters and/or V_xO_y nano-oxides. From the DR–UV–Vis analysis, a successful incorporation of V ions to silica structure in tetrahedral coordination with oxygen of the network could be inferred. The catalytic activity of these materials was evaluated in the test reaction of cyclohexene oxidation using H₂O₂ as oxidizing agent, showing a high conversion of about 93% respect to the maximum, resulting dominant the radicalary mechanism over the direct oxidation mechanism. Apparently, the isolated V ions incorporated into the silica structure would be responsible for the high catalytic activity of these materials.     

Mesoporous (Cr)MCM-41 and (Cr)MCM-48 Molecular Sieves: Promising Heterogeneous Catalysts for Liquid Phase Oxidation Reactions

Chromium-containing mesoporous MCM-41 and MCM-48 silicate molecular sieves were synthesized and characterized. Unlike the chromium-containing microporous materials, the mesoporous analogues show significant activity for the chosen (ethylbenzene oxidation) reaction even after several recycling or washing treatments.