Rh_(1)-ZSM-5分子筛催化乙烷选择性氧化反应的理论研究  

Theoretical investigation of ethane selective oxidation catalyzed with Rh_(1)-ZSM-5 zeolite

作　　者：郝聪 吴安安 谭凯 吕鑫 HAO Cong;WU An'an;TAN Kai;LÜ Xin(Fujian Provincial 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,福建省理论与计算化学重点实验室,福建厦门361005

出　　处：《厦门大学学报（自然科学版）》2022年第1期13-17,共5页Journal of Xiamen University：Natural Science

基　　金：国家自然科学基金(91545105,21273177,21773193)。

摘　　要：采用密度泛函理论(DFT)对单核铑负载的沸石催化剂(Rh_(1)-ZSM-5)上铑活性氧(Rh-oxo)物种与CO和H_(2)O的吸附行为及其催化的乙烷氧化反应进行理论研究.结果表明:CO和H_(2)O可共吸附在Rh-oxo物种形成四配位铑配合物Rh(O)(CO)(H_(2)O);与Rh-oxo物种催化甲烷氧化不同,在乙烷的选择性氧化反应中,羰基化产物丙酸的生成在热力学和动力学上均是不利的,反应产物是以乙醇为主的C_(2)氧化产物.The adsorption behavior of CO and H_(2)O on rhodium reactive oxygen(Rh-oxo)species and the selective oxidation of ethane catalyzed by mononuclear rhodium supported zeolite catalyst(Rh_(1)-ZSM-5)were investigated using the density functional theory(DFT).Our calculations reveal that CO and H_(2)O can be readily co-adsorbed on Rh-oxo species,leading to a stable four-coordination adspecies Rh(O)(CO)(H_(2)O).In the ethane selective oxidation,the formation of propionic acid(as a carbonylation product)is both thermodynamically and kinetically unfavorable and the main product is predicted to be C_(2)oxidation product,which is different from methane selective oxidation catalyzed with Rh-oxo species.

关 键 词：Rh_(1)-ZSM-5 过渡金属活性氧物种 乙烷选择性氧化 密度泛函理论 

分 类 号：O643.12[理学—物理化学]