Au4团簇上甲酸分解反应机理的理论研究  

Theoretical Study on Decomposition Mechanism of Formic Acid on Au Clusters

作　　者：张可欣 杨春晓 张艳琨 李粉吉 杨云汉 高倩 吕振东 李相华 夏福婷 贾丽娟 ZHANG Ke-xin;YANG Chun-xiao;ZHANG Yan-kun;LI Fen-ji;YANG Yun-han;GAO Qian;LU Zhen-dong;LI Xiang-hua;XIA Fu-ting;JIA Li-juan(School of Chemistry and Environment,Yunnan Minzu University,Key Laboratory of Resource Clean Conversion in Ethnic Regions,Education Department of Yunnan,Kunming 650500,China)

机构地区：[1]云南民族大学化学与环境学院,云南省高校民族地区资源清洁转化重点实验室,云南昆明650500

出　　处：《分子催化》2020年第6期534-545,I0002,共13页Journal of Molecular Catalysis(China)

基　　金：云南省教育厅科学研究基金项目(2020Y0263);国家自然科学基金(21966033,51968075,21567030)。

摘　　要：采用密度泛函理论方法对Au4团簇上甲酸分解反应的机理进行了研究,并考察了Au4团簇的两个催化活性位点.在路径Ⅰ和路径Ⅱ中,HCOOH分解的产物是CO2和H2.在路径Ⅲ和路径Ⅳ中,HCOOH分解的最终产物为CO和H2O.此外,我们还研究了CO2、H2和CO、H2O两种产物的相互转化,即路径Ⅴ和路径Ⅵ.研究表明,路径Ⅰ和路径Ⅱ的活化自由能垒较低,即在Au4团簇上HCOOH更易分解得到CO2和H2,此外两种产物之间不容易转化.进一步研究发现团簇的大小及CeO2载体对HCOOH分解脱氢路径的活化自由能垒有一定的影响.The decomposition mechanism of HCOOH on Au4 clusters was studied using density functional theory and two catalytic active sites of Au4 cluster were investigated.In pathⅠand pathⅡ,the decomposed products of HCOOH are CO2 and H2.In pathⅢand pathⅣ,the final decomposed products of HCOOH are CO and H2O.In addition,the transformation of two kinds of products,named pathⅤand pathⅥwas studied.It is showed that the activation energy barrier of pathⅠand pathⅡare low,which means that HCOOH on Au4 clusters is likely to be decomposed to CO2 and H2.Moreover the conversation of the two kinds of products is not easy to happen.Further study finds that cluster size and CeO2 support have certain influence on the activation free energy barrier of dehydrogenation path of HCOOH decomposition.

关 键 词：HCOOH分解 密度泛函理论 反应机理 Au4团簇 

分 类 号：O643.12[理学—物理化学]