负载型磷化镍催化剂的空气表面改性法制备及其加氢脱氧性能

以MCM-41为载体,采用先前驱体氢气低温(673 K)还原、空气表面改性的方法制备了高活性的Ni2P/M CM-41催化剂,并采用XRD、BET、SEM、TEM、XPS和CO吸附等手段对催化剂进行了表征。以苯并呋喃(BF)加氢脱氧(HDO)为探针反应,考察了空气表面改性对Ni2P/M CM-41催化剂结构和HDO性能的影响。结果表明,空气表面改性得到的催化剂,活性相为单一的Ni2P;空气表面改性能够降低催化剂表面P物种的集聚,有助于小尺寸、高分散的Ni2P活性相的生成。在573 K、3.0 M Pa、质量空速为4.0 h-1、H2/油体积比为500的条件下,Ni2P/M CM-41催化剂上BF转脱氧产物收率高达88%,较程序升温还原法制备的催化剂高50%。     

Effects of trifluoromethanesulfonic acid ligand on the Zinc-based catalysts for the acetylene hydration

Developing an efficient Zn-based catalyst modified with Trifluoromethanesulfonic acid (TfOH) ligand is extremely desirable for the acetylene hydration reaction. In this paper, with the use of a simple impregnation method, a series of Zn-TfOH/AC catalysts were synthesized, and the Zn-1.5TfOH/AC catalyst demonstrated the optimal catalytic performance with 96% acetylene conversion in the hydration of acetylene. The X-ray absorption fine structure (XAFS) spectra of the fresh Zn-1.5TfOH/AC catalysts demonstrated the establishment of the Zn-O4 coordination structure. According to the characterization results, TfOH ligands effectively inhibited carbon accumulation and Zinc loss, improved acidic sites and the dispersion of active metal, and produced more catalytic active site. Furthermore, the hydration reaction mechanism of Zn-TfOH/AC catalyst with Zn(OTf)₂, TfO-ZnCl, and TfO-ZnOH complex configurations was explored by the Density Functional Theory (DFT) method, which showed that the activation barrier increased sequentially TfO-ZnOH < Zn(OTf)₂ < TfO-ZnCl. Importantly, the OH⁻ in TfO-ZnOH is involved in the reaction and regenerated by the dissociation of H₂O, which lowers the energy barrier. This will provide a reference to design more efficient nonmercury catalysts for acetylene hydration.     

Preparation and Acid Catalytic Activity of TiO2 Grafted Silica MCM-41 with Sulfate Treatment

TiO2 grafted silica MCM-41 catalyst with and without sulfate treatment were prepared. The structural and acid properties of these materials were investigated by XRD, N2 adsorption-desorption, element analysis, thermal analysis, Raman and FTIR measurements. Their acid-catalytic activities were evaluated using the cyclization reaction of pseudoionone. It was found that the obtained materials possess well-ordered mesostructure, and the grafted TiO2 components were in highly dispersed amorphous form. T/MCM41 without sulfation contained only Lewis acid sites, while Br?nsted and Lewis acidities were remarkably improved for the sulfated materials ST/MCM41 and d-ST/MCM41. T/MCM-41 was not active for the cyclization reaction of pseudoionone, but ST/MCM-41 and d-ST/MCM-41 possessed favorable catalytic activities. The catalytic performance of ST/MCM-41 was comparable with that of the commercial solid acid catalyst of Amberlyst-15, and better than that of d-ST/MCM-41, although the latter underwent a second TiO2 grafting process and accordingly had higher Ti and S content. The specific surface structure of Si-O-Ti-O-S=O in ST/MCM-41 and the bilateral induction effect of Si and S=O on Si-O-Ti bonds were speculated to account for its higher acid catalytic activity.     

Deoxydesulfurization of dibenzothiophene sulfone over cesium/MCM-41 catalysts

Dibenzothiophene sulfone, one of the products of the oxidative desulfurization of heavy oil, can be utilized through catalytic cracking. The object of the present study is to provide Cs/MCM-41 catalysts for the removal of sulfur dioxide from dibenzothiophene sulfone. Cesium oxide was deposited via an impregnation method on MCM-41, and the catalytic performances of the samples were investigated during the deoxydesulfurization of dibenzothiophene sulfone to biphenyl and sulfur dioxide gas. The influence of cesium loading on the basic properties of MCM-41 was estimated by the temperature-programmed desorption of carbon dioxide. The dibenzothiophene sulfone conversions of the MCM-41, Cs(1 wt%)/MCM-41, Cs(3 wt%)/MCM-41 and Cs(10 wt%)/MCM-41 catalysts were 38.5, 52.1, 72.4 and 40.9%, respectively, which implies that the Cs(3 wt%)/MCM-41 catalyst has the highest activity. This result agrees with the finding of the basicity enhancement of MCM-41 with the addition of cesium, in which Cs(3 wt%)/MCM-41 exhibited a maximum number of basic sites.     

One-pot synthesis of nitrogen and sulfur co-doped activated carbon supported AuCl3 as efficient catalysts for acetylene hydrochlorination

Commercialization of acetylene hydrochlorination using AuCl₃ catalysts has been impeded by its poor stability. We have been studying that nitrogen-modified Au/NAC catalyst delivered a stable performance which can improve acetylene hydrochlorination activity and has resistance to catalytic deactivation. Here we show that nitrogen and sulfur co-doped activated carbon supported AuCl₃ catalyst worked as efficient catalysts for the hydrochlorination of acetylene to vinyl chloride. Au/NSAC catalyst demonstrated high activity comparative to Au/AC catalyst. Furthermore, it also delivered stable performance within the selectivity of acetylene, reaching more than 99.5%, and there was only a 3.3% C₂H₂ conversion loss after running for 12 h under the reaction conditions of a temperature of 180℃ and a C₂H₂ hourly space velocity of 1480 h 1. The presence of the sulfur atoms may serve to immobilize/anchor the Au and also help prevent reduction and sintering of the Au and hence improve the catalytic activity and stability. The excellent catalytic performance of the Au/NSAC catalyst demonstrated its potential as an alternative to mercury chloride catalysts for acetylene hydrochlorination.     

不同有机胺修饰MCM-41的CO2吸附性能和热稳定性

将乙二胺(EDA,60 g/mol)、四乙烯五胺(TEPA,189 g/mol)和两种聚乙烯亚胺600(PEI600g/mol; PEI1800g/mol)分别负载在MCM-41上制备氨基功能化介孔材料,研究其对CO₂的吸附性能和热稳定性.结果表明,除了EDA-MCM41,其他三种材料随着胺分子量增大CO₂吸附性能下降,但是热稳定性却有所提高,其中,TEPA-MCM41的吸附容量最大,达到2.7 mmol/g.同时发现,乙二胺在制备过程中随溶剂挥发而难以完全负载在MCM-41上.在纯N₂气氛和再生温度100 ℃条件下,经10次循环实验后,TEPA-MCM41的吸附能力下降了7.4%,而PEI600-MCM41和PEI1800-MCM41吸附能力保持不变,且质量变化在1%以内,表现出良好的再生稳定性.采用80%CO₂/20%N₂对吸附饱和的材料进行再生,四种材料的再生温度将提高到160 ℃以上,高分子量PEI600-MCM41和PEI1800-MCM41相比于TEPA-MCM41具有更好的热稳定性.     

介孔分子筛MCM-41固载多氮杂环席夫碱与偏钒酸钠共催化氧化苯一步制备苯酚

2-苯基-1,2,3-三唑醛和喹喔啉醛通过亚胺键固载到介孔分子筛MCM-41上,得到6种MCM-41固载多氮杂环席夫碱(L1~L6),用FT-IR、XRD和SEM等技术手段对所制得的固载席夫碱进行表征。 研究了以MCM-41固载多氮杂环席夫碱和金属盐偏钒酸钠为共同催化剂,过氧化氢为氧源,直接催化氧化苯合成苯酚,用气相色谱快速检测苯酚产率。 系统地考察了配体、金属盐、温度、溶剂、催化剂用量、反应时间、氧化剂等因素对反应的影响,产率最佳可达23.9%,选择性大于90%。 对催化剂扩大5倍量进行试验,得到23%的产率和93%的选择性,并且催化剂重复使用3次仍能达到19%的产率和90%以上的选择性。     

HPW and supported HPW catalyzed condensation of aromatic aldehydes with aniline: Synthesis of DATPM derivatives

The mesoporous Si-MCM-41 was synthesized by hydrothermal method and various wt.% (20 and 30 wt.%) of HPW were loaded on Si-MCM-41 by wet impregnation method. The synthesized Si-MCM-41 and HPW-loaded catalysts were characterized by XRD, BET surface area, FT-IR, TEM and TGA–DTG techniques. The catalytic activity of the catalyst was tested over the condensation reaction of aniline with various aromatic aldehydes at refluxing temperature under liquid-phase condition, which yields highly commercial product namely diamino triphenyl methanes (DATPMs). The effects of various parameters like catalyst, mole ratio, solvents and substituent effect on the formation of DATPMs were optimized. The catalytic activity of the catalysts showed the following order: H₃PW₁₂O₄₀·nH₂O > H₃PMo₁₂O₄₀·nH₂O > H₄SiW₁₂O₄₀·nH₂O > 20 wt.% HPW/MCM-41 > 30 wt.% HPW/MCM-41 > HM (12) > Hβ (8) > HY (4) > HZSM-5 (15) > Al-MCM-41 (25). The results showed that mole ratio of 4:1 (aniline:aldehyde) gave higher yield than the other mole ratios. Acetonitrile and ethyl acetate shows better activity especially in the supported materials than toluene was used as a solvent. The product thus obtained was analyzed by ¹H NMR, FT-IR techniques.     

MCM-41 and SBA-15 supported Cp2ZrCl2 catalysts for the preparation of nano-polyethylene fibres via in situ ethylene extrusion polymerization

Under atmospheric pressure, nano-polyethylene fibres were prepared via in situ ethylene extrusion polymerization, with MCM-41 and SBA-15 supported zirconocene dichloride (Cp₂ZrCl₂) catalytic systems, respectively. The effects of the geometrical structures and surface properties of MCM-41 and SBA-15 on the morphology of the resultant polyethylene, catalytic activity and polymerization rate were investigated and compared in various polymerization conditions. The possible formation mechanism of nano-polyethylene fibres with MCM-41 and SBA-15 supported Cp₂ZrCl₂ as catalyst was discussed.     

功能化MCM-41负载双齿氮钯催化剂的制备及其在Suzuki偶联中的应用

首先胺功能化修饰介孔材料MCM-41,再与二-(吡啶-2-基-)甲酮缩合成席夫碱,最后通过Pd(OAc)2配位制备了MCM-41负载双齿氮钯配合物,采用X射线衍射(XRD)以及X射线光电子能谱(XPS)对其结构表征.该负载催化剂在以二甲苯为溶剂,K2CO3为碱以及n-Bu4NF用作添加剂的Suzuki偶联中表现出优越的催化性能.     

Synthesis and catalytic performance of bimetallic NiMo- and NiW-ZSM-5/MCM-41 composites for production of liquid biofuels

This work presents a synthesis of bimetallic NiMo and NiW modified ZSM-5/MCM-41 composites and their heterogeneous catalytic conversion of crude palm oil( CPO) to biofuels. The ZSM-5/MCM-41 composites were synthesized through a self-assembly of cetyltrimethylammonium bromide( CTAB) surfactant with silica-alumina from ZSM-5 zeolite,prepared from natural kaolin by the hydrothermal technique. Subsequently,the synthesized composites were deposited with bimetallic NiMo and NiW by impregnation method. The obtained catalysts presented a micro-mesoporous structure,confirmed by XRD,SEM,TEM,EDX,NH_3-TPD,XRF and N_2 adsorption-desorption measurements. The results of CPO conversion demonstrate that the catalytic activity of the synthesized catalysts decreases in the series of NiMo-ZSM-5/MCM-41 NiW-ZSM-5/MCM-41 Ni-ZSM-5/MCM-41 Mo-ZSM-5/MCM-41 W-ZSM-5/MCM-41 NiMo-ZSM-5 NiW-ZSM-5 ZSM-5/MCM-41 ZSM-5 MCM-41. It was found that the bimetallic NiMo-and NiW-ZSM-5/MCM-41 catalysts give higher yields of liquid hydrocarbons than other catalysts at a given conversion. Types of hydrocarbon in liquid products,identified by simulated distillation gas chromatography-flame ionization detector( SimDis GC-FID),are gasoline( 150-200 ℃; C5-12),kerosene( 250-300 ℃; C5-20) and diesel( 350 ℃; C7-20).Moreover,the conversion of CPO to biofuel products using the NiMo-and NiW-ZSM-5/MCM-41 catalysts offers no statistically significant difference( P 0.05) at 95% confidence level,evaluated by SPSS analysis.     

Ni_2P/Zr-MCM-41催化剂的制备及其对麻风树油加氢脱氧的催化性能

采用水热法合成MCM-41和Zr-MCM-41,由Ni(NO_3)_2和(NH_4)2HPO_4溶液共浸渍、高温焙烧、氢气还原和钝化制备了负载型Ni_2P/Zr-M CM-41催化剂。采用XRD、TEM、氮气吸附、CO吸附、吡啶吸附红外和XPS等方法对催化剂进行了表征,并在高压反应釜中研究了其对麻风树油加氢脱氧(HDO)的催化性能。结果表明,氢气还原温度为650℃、Ni2P负载量为20%(质量分数)、Ni2P物相呈晶型时,Ni_2P/Zr-M CM-41催化剂的活性最佳;较低的Ni2P负载量有利于其在Zr-M CM-41载体表面均匀分散,而负载量高于25%(质量分数)时,活性组分少量团聚,易导致孔道堵塞。催化剂表面存在部分因钝化而形成的Ni O。对于麻风树油加氢脱氧,Ni2P负载量为20%(质量分数)Ni_2P/Zr-M CM-41表现出优异的催化性能;脱氧率高达93.90%,直链烷烃含量高达85.36%,其中柴油组分产率较高,C15~20组分占直连烷烃组分50%以上。     

Amine functionalized MCM-41: An active and reusable catalyst for Knoevenagel condensation reaction

This paper reports preparation, characterization of amine modified mesoporous crystalline MCM-41 and its application in Knoevenagel condensation reaction. Amine modified MCM-41 was prepared by co-condensation and post-synthesis methods. The samples were characterized by X-ray powder diffraction, Fourier-transfer infrared spectroscopy (FTIR), thermo gravimetric analysis (TGA), differential thermal analysis (DTA), scanning electron micrograph (SEM), ²⁹Si magic-angle spinning (MAS), nuclear magnetic resonance (NMR), diffuse reflectance spectra (DRS), nitrogen adsorption–desorption and CHN analysis. X-ray diffraction patterns indicate that the modified materials retain the standard MCM-41 structure. SEM study exhibits that the arrangement of particles for 12.8% amine modified MCM-41 is well ordered and spherical in nature. CHN analysis supports that complete hydrolysis of ethoxy groups take place in 12.8% amine modified sample. From the NMR study it is confirmed that the surface coverage is 40% in 12.8% amine modified sample. The base catalytic activity of hybrid MCM-41 materials such as amine (post-synthesis and co-condensation methods) and surfactant functionalized materials for condensation reaction between benzaldehyde and diethyl malonate in solvent free, room temperature synthesis of cinnamic acid was evaluated and correlated with the surface and textural properties. Sample containing 12.8 wt% amine loaded by co-condensation method showed highest malonic ester conversion (92%) and selectivity (98%) for cinnamic acid.     

Characterizations and Catalytic Properties of V-MCM-41 Synthesized by Template-ion Exchange Method

Much attention has been paid to the use of the new mesoporous material, MCM-41,as catalyst or catalyst support^[1,2]. Recently, we focus our study on the design of catalytically active sites such as vanadium species inside the mesopore of MCM-41. V-MCM-41 is generally synthesized by direct hydrothermal method in the literature, but a large part of vanadium sites seems difficult to be accessed during the catalytic reactions by this method. We have developed a novel method to introduce vanadium species by a template-ion exchange (TIE) method, i.e., by exchanging the template cation in the uncalcined MCM-41 with VO²⁺ ion in aqueous solution. Here, the results of the characterizations of such synthesized V-MCM-41 and its catalytic properties in oxidative dehydrogenation of propane are described.     

MCM-41 Supported Nickel Catalysts for Carbon Dioxide Reforming of Methane

There has been an increasing interest in the conversion of methane and carbon dioxide into synthesis gas^[1]. High performance Ni-based catalysts have attracted much attention^[2-4]. In this study, MCM-41 supported nickel were used as catalysts for carbon dioxide reforming of methane. It is found that the obtained catalyst exhibited high activity for getting syngas with its ratio of unity.In contrast to the performance of other nickel-based catalysts; Ni/MCM-41 has higher conversion and yield at lower temperature. The effects of nickel loading, particle size, GHSV, and calcination temperature on catalytic activities were also investigated.     

Ruthenium deposited on MCM-41 as efficient catalyst for hydrolytic dehydrogenation of ammonia borane and methylamine borane

Ultrafine Ru nanoparticles are successfully deposited on MCM-41 by using a simple liquid impregnationreduction method, and further investigated for catalytic hydrolysis of ammonia borane and methylamine borane. Among all the catalysts tested, 1.12 wt% Ru/MCM-41 exhibits the highest catalytic activity, with turnover frequency value of 288 min^-1.     

PtSn/Al2O3/MCM-41催化剂的丙烷脱氢催化性能

用微型催化反应装置评价, 并结合X射线粉末衍射(XRD)、表面积和孔结构测试、程序升温还原(TPR)、氢化学吸附和热重分析等方法研究了负载型PtSn/γ-Al2O3, PtSn/MCM-41和PtSn/Al2O3/MCM-41催化剂的丙烷脱氢反应催化性能. 发现PtSn/Al2O3/MCM-41催化剂具有较PtSn/MCM-41催化剂高的丙烷脱氢反应活性和较PtSn/γ-Al2O3催化剂高的反应稳定性. 实验结果表明, 纯硅MCM-41载体表面的锡物种因与载体相互作用较弱故易被还原, 导致铂金属分散度和催化剂的丙烷脱氢活性较低. 用Al2O3修饰MCM-41可以增强Sn物种与Al2O3/MCM-41载体之间的相互作用, 提高PtSn/Al2O3/MCM-41催化剂铂金属分散度和丙烷脱氢催化活性. 并且, 积炭后的PtSn/Al2O3/MCM-41催化剂具有较高的铂金属表面裸露度, 故具有较高的丙烷脱氢反应稳定性. PtSn/Al2O3/MCM-41催化剂优良的丙烷脱氢催化性能可能不仅与Sn-载体Al2O3/MCM-41较强的相互作用有关, 而且与Al2O3/MCM-41载体的介孔结构有关.     

Aza-Michael addition reactions between nitroolefins and benzotriazole catalyzed by MCM-41 immobilized heteropoly acids in water

MCM-41 supported heteropoly acids(HPAs) catalysts were synthesized,characterized and their catalytic activity was evaluated in an aza-Michael addition reaction between nitroolefins and benzotriazole in water at room temperature.50 wt% PW/MCM-41 showed the highest activity(up to 96% yield).The catalyst was used in six consecutive experiments without obvious loss of activity, confirming the success of the anchoring process and the catalyst stability.     

新型MCM-41固载化铌酸催化氧化环戊烯制备戊二醛

通过可溶的草酸配合物将铌酸固载到中孔分子筛MCM-41上,得到含催化氧化活性中心的Nb₂O₅/MCM-41负载型催化剂,并用XBD,BET,N₂吸附等手段进行了表征.该催化剂在环戊烯催化氧化制备戊二醛的反应中表现出优良的催化性能,环戊烯的转化率高达100%,戊二醛收率达到50%,展现了良好的应用前景.     

Hβ/MCM-41复合分子筛催化剂上苯甲醚与乙酸酐酰化反应研究

以β沸石为硅源,制备了不同硅铝比的Hβ/MCM-41复合分子筛,考察了该复合分子筛对苯甲醚与乙酸酐酰化反应的催化效果,并与介孔MCM-41、微孔Hβ分子筛的催化效果进行了比较,研究了分子筛硅铝比、酸性及孔道结构对酰化反应催化性能的影响。结果表明,对于苯甲醚和乙酸酐酰化反应,Hβ/MCM-41复合分子筛具有较好的催化稳定性,反应过程中的积炭量较少,积炭的碳氢比较低。该复合分子筛不仅具有微孔沸石的强酸性,而且具有较大孔径的介孔,产物分子能及时从孔道中扩散出来,催化活性位不易中毒失活。