A DFT Study on the Catalytic CO Oxidative Coupling to Dimethyl Oxalate on Al-Doped Core-Shell Pd Clusters

摘要：

　　A series of core-shell catalysts aiming at CO oxidative coupling to dimethyl oxalate(DMO)were constructed,and effects of the second metal doping and surface structures on the reaction activity and favorable reaction path were investigated by using the density functional theory(DFT)method.Pd13,Al@Pd12,and Ag@Pd12 were first studied to find the proper doping metal.Our results showed that the activity of CO oxidative coupling to DMO follows the order of Al@Pd12 > Pd13 > Ag@Pd12,and the same result was also obtained via the electronic analysis.In addition,Al6@Pd32 and Al13@Pd42 catalysts with higher doping ratio and lower cost than that of Al@Pd12 were selected to examine the influence of surface structure on the reaction activity.It showed that CO + CH3O → COOCH3 + CO → OCCOOCH3 + CH3O → DMO is the favorable pathway on the(100)surface of Al6@Pd32 catalyst,while CO + CH3O → CO + CH3O(COOCH3)→ COOCH3 + COOCH3 → DMO is the optimal pathway on the(111)surface of Al@Pd12 and Al13@Pd42,which indicated that the surface structure of catalysts affected the preferable pathway of DMO formation.Moreover,activities of CO oxidative coupling to DMO on AlPd core-shell catalysts followed the order of Al@ Pd12 > Al13@Pd42 > [e-mail] addition,Al13@Pd42 also exhibited a good selectivity between DMO and DMC.Thus,Al13@ Pd42 is a proper catalyst with high activity,high selectivity,and low cost because of high Al:Pd ratio.

作者: Xue Feng Lixia Ling Yueting Cao Riguang Zhang Maohong Fan Baojun Wang

作者单位: College of Chemistry and Chemical Engineering,Taiyuan University of Technology,Taiyuan,Shanxi 030024 College of Chemistry and Chemical Engineering,Taiyuan University of Technology,Taiyuan,Shanxi 030024 Key Laboratory of Coal Science and Technology,Taiyuan University of Technology,Ministry of Education Department of Chemical and Petroleum Engineering,University of Wyoming,1000 E. University Avenue,Lar

会议类型: 国内会议

会议名称: 第九届国际分子模拟与信息技术应用学术会议(ICMS&I2018)

会议地点: 太原

会议语种:英文

页码: 271-281

在线出版日期: 2018-05-01（万方平台首次上网日期，不代表论文的发表时间）