羟基氧化铟团簇与二氧化碳和甲烷作用的密度泛函理论研究  

Density-functional Theoretical Study on the Interaction of Indium Oxyhydroxide Clusters with Carbon Dioxide and Methane

作　　者：何鸿锐 夏文生[1] 张庆红[1] 万惠霖[1] HE Hongrui;XIA Wensheng;ZHANG Qinghong;WAN Huilin(State Key Laboratory of Physical Chemistry of Solid State Surface,National Engineering Laboratory for Green Chemical Productions of Alcohols-Ethers-Esters,Fujian Province Key Laboratory of Theoretical and Computational Chemistry,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China)

机构地区：[1]厦门大学化学化工学院,固体表面物理化学国家重点实验室,醇醚酯化工清洁生产国家工程实验室,福建省理论与计算化学重点实验室,厦门361005

出　　处：《高等学校化学学报》2022年第8期237-247,共11页Chemical Journal of Chinese Universities

基　　金：国家重点研发计划项目(批准号:2019YFE04400);国家自然科学基金(批准号:21373169);教育部创新团队发展计划项目(批准号:IRT1036)资助。

摘　　要：二氧化碳(CO_(2))和化石能源气体燃料甲烷(CH_(4))均是化学稳定、温室效应较大的分子,因而对其活化、转化和利用的研究具有显著的理论和实际意义.本文采用密度泛函理论方法,计算研究了羟基氧化铟团簇与CO_(2),CH_(4)和(CO_(2)+CH_(4))的作用.结果表明,氧化铟团簇通过其活性位点—In—O(桥氧)—对CO_(2)和CH_(4)分子进行[2+2]加成活化,而羟基的引入调变了氧化铟团簇活性位点上的局部电荷,显著降低了其与CO_(2)和CH_(4)分子作用的活化自由能垒,使得CO_(2)和CH_(4)分子的活化变得容易进行.活性位点—In—O(桥氧)—中的In,O上的局部电荷差值(q_(In)-q_(O))越大,其对CO_(2)和CH_(4)分子作用的活化自由能垒越低.羟基氧化铟与CO_(2)和CH_(4)分子作用时,电子由羟基氧化铟流向CO_(2)和CH_(4)分子(亲核活化);而羟基引入前的氧化铟与CO_(2)和CH_(4)分子作用时,电子则由CO_(2)和CH_(4)分子流向氧化铟(亲电活化).Both carbon dioxide(CO_(2))and methane(CH_(4))as fossil energy gas fuel are chemically stable molecules with a large greenhouse effect,so it is theoretical and practical significance to investigate their activation,transforma⁃tion and utilization.The density functional theory(DFT)method were used to investigate computationally the interaction of indium oxide clusters with CO_(2),CH_(4) and CO_(2)+CH_(4).The results show that,indium oxide clusters activate CO_(2) and CH_(4) via-In-O(bridge)-with[2+2]addition mode,and the presence of hydroxyl changes the local charge of the active site of indium oxide clusters,leading to significantly decrease of activation free barrier for their interaction with CO_(2) and CH_(4),and then making the activation be easily proceeded.Interestingly,the difference of local charges between In and O(q_(In)-q_(O))of the active site-In-O-correlates well with the activation of CO_(2) and CH_(4),i.e.,the greater the q_(In)-q_(O),the lowest the activation free barrier for their interaction with CO_(2) and CH_(4).For activation of CO_(2) and CH_(4) by indium oxyhydroxide clusters,electrons transfer to CO_(2) and CH_(4) from the clusters(nucleophilic activation),and for that by indium oxide clusters without hydroxyl,the opposite transfer of electrons occurs(electro⁃ philic activation).

关 键 词：羟基氧化铟 二氧化碳 甲烷 密度泛函理论 

分 类 号：O643[理学—物理化学]