CoO_(x)/h-S-1催化剂制备及其催化硫醇氧化偶联合成二硫化物性能  

Preparation of CoO_(x)/h-S-1 Composite and Its Catalytic Performance in Aerobic Oxidative Coupling of Thiols to Disulfides

作　　者：陈铮 杨婷 厉晨豪 夏长久 彭欣欣 邢恩会 罗一斌 CHEN Zheng;YANG Ting;LI Chenghao;XIA Changjiu;PENG Xinxin;XING Enhui;LUO Yibin(State Key Laboratory of Petroleum Molecular&Process Engineering,SINOPEC Research Institute of Petroleum Processing Co.,Ltd.,Beijing 100083,China)

机构地区：[1]中石化石油化工科学研究院有限公司石油化工分子转化与反应工程全国重点实验室,北京100083

出　　处：《石油学报（石油加工）》2024年第5期1213-1222,共10页Acta Petrolei Sinica(Petroleum Processing Section)

基　　金：国家自然科学基金项目(21808244,22278441)资助。

摘　　要：以正硅酸乙酯为硅源、四丙基氢氧化铵为模板剂,引入具有撑层扩孔作用的N-苯基-3-氨基丙基三甲氧基硅烷,采用水热合成法制备多级孔分子筛h-S-1。通过浸渍法制备负载金属氧化物纳米簇的CoO_(x)/h-S-1复合催化剂,并将其用于催化硫醇氧化偶联反应。XRD、BET、XPS、SEM、TEM等表征结果表明,催化剂具有良好的MFI型拓扑结构,Co物种主要以Co_(3)O_(4)聚集体形式存在,在分子筛载体上分散良好,且CoO_(x)通过Co—O—Si键与分子筛存在较强相互作用。CoO_(x)/h-S-1对硫醇氧化偶联反应具有良好的催化活性,在优化条件:Co负载量3%、催化剂用量50 mg、溶剂2 mL甲醇、在60℃下反应6 h,以辛硫醇为探针分子,转化率达91%,二硫化物选择性100%。该催化剂硫醇底物适用范围广,且对于不同硫醇之间的交叉偶联反应制备不对称二硫化物也有较好的催化效果。报道了一条绿色高效的硫醇氧化偶联路径,对工业上硫资源的高价值利用和含硫精细化学品的绿色制备具有重要意义。Hierarchical Silicalite-1(h-S-1)zeolite was prepared by hydrothermal synthesis method using ethyl orthosilicate as silicon source,and tetrapropyl ammonium hydroxide as template;moreover,N-phenyl-3-amino-propyl trimethoxysilane was introduced,which played a role of supporting layer and expanding pore.Additionally,CoO_(x)/h-S-1 composite catalyst loaded with metal oxide nanoclusters was prepared by impregnation method,and then used to catalyze the thiol oxidation coupling reaction.The characterization results of XRD,BET,XPS,SEM and TEM show that this catalyst has good MFI-typed topological structure;the cobalt species are mainly in the form of Co_(3)O_(4) aggregates,and are well dispersed on the h-S-1 zeolite;there is a strong interaction between CoO_(x)and zeolite surface through Co—O—Si bonds.CoO_(x)/h-S-1 exhibits good catalytic activity for thiols oxidative coupling reaction.Under the optimized conditions of 50 mg 3%CoO_(x)/h-S-1 catalysts,2 mL methanol as the reaction solvent,and reaction at 60℃for 6 h,the conversion of thiols and the selectivity of disulfides can reach 91%and 100%,respectively.The catalyst has wide application range for thiol substrates.More importantly,CoO_(x)/h-S-1 shows excellent catalytic performance in the preparation of asymmetric disulfide by cross-coupling reaction between different thiols.This paper reports a green and efficient oxidative coupling pathway of thiols,which is of great significance for the high-value utilization of sulfur resources in industry and the green preparation of sulfur-containing fine chemicals.

关 键 词：硫醇 二硫化物 CoO_(x)/h-S-1 浸渍法 氧化偶联 

分 类 号：TQ218[化学工程—有机化工]