噻吩在MoS_2活性相上的反应化学研究  

Study on hydrodesulfurization reaction chemistry of thiophene on MoS_2

作　　者：赵晓光[1] 王薇[1] 李会峰[1] 周涵[1] 李明丰[1] 

机构地区：[1]中国石化石油化工科学研究院,北京100083

出　　处：《计算机与应用化学》2017年第4期291-294,共4页Computers and Applied Chemistry

基　　金：国家重点基础研究发展计划"973"资助项目(2012CB224802)

摘　　要：针对常规实验方法对硫化物加氢脱硫机理研究存在的不足,本文研究中运用分子模拟方法,建立了较为合理的MoS_2簇结构模型,在此基础上对MoS_2上几种主要活性位的加氢脱硫反应进行了比较系统的量子化学计算。计算结果表明,在噻吩加氢脱硫的过程中,Mo边和角位主要起加氢作用,主要生成2,5-二氢噻吩;而S边空位是主要的脱硫活性位,不仅接收Mo边和角位转移来的二氢噻吩并按加氢途径(HYD)脱硫,还可以吸附噻吩分子按直接脱硫途径(DDS)脱硫。但是1-己烯在三种活性中心上都可以发生加氢饱和反应。因此,对于MoS_2活性相而言,适当减少Mo边和角位的比例、增加S边的比例将有助于加氢脱硫活性和选择性的提高。As conventional experimental techniques have not given definite answers to the mechanism of hydrodesulfurization, molecu-lar simulation method and quantum chemistry calculation were used in this paper to study the reactions of thiophene on a more reasona-ble cluster model. After a comprehensive analysis of thiophene HDS processing on MoS2, it could be concluded that Mo edge and cor- ner site were more inclined to hydrogenate thiophene into 2, 5-dihydrothiophene （2, 5-DHT）, and 2, 5-DHT would subsequently transfer to S vacancy at S edge to desulfurize by hydrogenation （HYD） route, while S vacancy could not only remove sulphur of 2, 5-DHT by HYD route but also remove sulphur ofthiophene by direct desulfurization（DDS） route. For the reaction of 1-hexene hydrogenation, Mo edge had the highest activity, S vacancy took the second place, and comer site was the last. So increasing the ratio of S edge and decreasing the ratio of Mo edge may improve the activity and selectivity of the unpromoted-MoS2 catalyst.

关 键 词：MoS2催化剂 量子化学计算 噻吩 

分 类 号：TQ015.9[化学工程] TP391.9[自动化与计算机技术—计算机应用技术]