双金属合金团簇M12Ni（M=Pt,Sn,Cu）催化甲烷干法重整反应的理论研究  

Theoretical Study of Dry Reforming of Methane Catalyzed by Bimetallic Alloy Cluster M12Ni（M = Pt,Sn,Cu）

作　　者：陈涛 方镭 罗伟 孟跃[2] 薛继龙[1] 夏盛杰[1] 倪哲明[1] CHEN Tao;FANG Lei;LUO Wei;MENG Yue;XUE Jilong;XIA Shengjie;NI Zheming(College of Chemical Engineering,Zhejiang University of Technology,Hangzhou 310014,China;School of Life Sciences,Huzhou University,Huzhou 313000,China)

机构地区：[1]浙江工业大学化学工程学院,杭州310014 [2]湖州师范学院生命科学学院,湖州313000

出　　处：《高等学校化学学报》2019年第10期2135-2142,共8页Chemical Journal of Chinese Universities

基　　金：国家自然科学基金(批准号:21503188);浙江省自然科学基金(批准号:LQ15B030002)资助~~

摘　　要：利用密度泛函理论(DFT)研究了M12Ni(M=Pt,Sn,Cu)3种双金属合金团簇的电子活性和结构稳定性,并探讨了甲烷干法重整反应(DRM)在M12Ni双金属团簇表面的反应能量变化情况.经比较发现甲烷脱氢和二氧化碳活化过程在Pt12Ni团簇表面进行需克服的活化能垒最低,反应最易进行.Sn12Ni团簇上生成碳需要较高的活化能,说明Sn12Ni团簇能够有效抑制焦碳的生成,一定程度上克服了碳沉积导致的催化剂失活现象,并且Sn12Ni团簇在C*和CH*氧化过程中表现出最佳的催化活性.Cu12Ni团簇仅在甲烷脱氢过程中表现出较为优异的催化活性.The electronic activity and structural stability of three bimetallic alloy clusters of M12Ni(M=Pt,Sn,Cu)were studied by density functional theory(DFT).The change of the methane dry reforming reaction(DRM)on three clusters M12Ni(M=Pt,Sn,Cu)was also discussed.It is found that the methane dehydrogenation and carbon dioxide activation process exhibit the lowest activation energy barrier to be overcome on the surface of Pt12Ni cluster,so these two processes are the most potential to carry out over Pt12Ni cluster.The formation of carbon on the Sn12Ni cluster requires higher activation energy,indicating that the Sn12Ni cluster can effectively inhibit the formation of carbon.To some extent,it overcomes the catalyst deactivation caused by carbon deposition.And the Sn12Ni cluster exhibits the best catalytic activity during the oxidation of C*and CH*.The Cu12Ni cluster shows excellent catalytic activity only during the dehydrogenation of methane.

关 键 词：密度泛函理论 合金团簇 甲烷干法重整 能垒 

分 类 号：O641[理学—物理化学] O643[理学—化学]