Theoretical Study on CO_(2)Hydrogenation on In_(2)O_(3)(111)Supported Single-Atom Catalysts:Horiuti-Polanyi versus Non-Horiuti-Polanyi Mechanism  

In_(2)O_(3)(111)负载单原子催化剂表面CO_(2)加氢理论研究:Horiuti-Polanyi机理与非Horiuti-Polanyi机理对比

作　　者：Xiang Li Gang Fu 李香;傅钢(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,能源材料化学协同创新中心,厦门361005)

机构地区：[1]State Key Laboratory for Physical Chemistry of Solid Surfaces,Collaborative Innovation Center of Chemistry for Energy Materials,College of Chemistry and Chemical Engineering,Xiamen University,Xiamen 361005,China

出　　处：《Chinese Journal of Chemical Physics》2025年第1期54-62,I0055,I0056,共11页化学物理学报(英文)

基　　金：supported by the National Key Research and Development Program of Ministry of Sci-ence and Technology of China(No.2022YFA1504601);the National Natural Science Foundation of China(Nos.92045303,22132004,22121001,22072116,22072117,and 21773192).

摘　　要：In the field of catalytic hydro-genation,two primary mecha-nistic pathways,namely the Ho-riuti-Polanyi(HP)mechanism and the non-HP mechanism,have been extensively investi-gated.Current understandings suggested that the non-HP mechanism preferred to occur on the coinage metal surfaces,such as copper,silver,and gold,which exhibited low activity towards H_(2) dissociation.Herein,we offered a detailed theoretical investigation into the mechanisms of CO_(2)hydrogenation to formic acid on M_(1)-In_(2)O_(3)(111)surfaces,using density functional theory calculations.Our calculations provided novel in-sights into the preference of the non-HP mechanism on reduced single-atom noble metal cata-lysts,such as r-Rh_(1)-In_(2)O_(3)(111)and r-Ir_(1)-In_(2)O_(3)(111).In these cases,molecularly adsorbed H_(2) would be polarized into H^(δ−)-H^(δ+),thus facilitating the electrophilic attack to the O in CO_(2).Conversely,the H^(δ+)species,derived from heterolytically dissociated H_(2),exhibited a strong affinity on the adjacent oxygen site at the M-O-In interface.This strong adsorption resulted in a higher energy barrier for CO_(2)hydrogenation,thereby rendering the HP mechanism less viable than the non-HP one.Our results were anticipated to provide a deeper understanding of hydrogenation reactions on oxide-supported noble single-atom catalysts and theoretical guidance for the development of novel high-performance catalysts for catalytic hydrogena-tion reactions.在催化加氢领域,目前广泛研究了Horiuti-Polanyi(HP)和非HP两种主要的加氢机理。本文采用密度泛函理论系统研究了M1-In_(2)O_(3)(111)表面CO_(2)加氢生成甲酸的机理,发现贵金属单原子催化剂还原后,例如r-Rh_(1)-In_(2)O_(3)(111)和r-Ir_(1)-In_(2)O_(3)(111),表面CO_(2)加氢可能通过非HP加氢机理,计算表明,在非HP机理中,单原子位点上分子吸附的H_(2)会极化为H^(δ-)-H^(δ+),有利于对CO_(2)中氧位点的亲电进攻;而在HP机理中,H_(2)异裂解离生成的HH^(δ+)在邻近氧位点上具有很强的亲和力,导致后续CO_(2)加氢的能垒更高.本文的研究结果有望加深人们对氧化物负载贵金属单原子催化剂表面加氢机理的理解,并为新型高性能加氢反应催化剂的开发和制备提供理论指导.

关 键 词：Reduced single-atom catalysts CO_(2)hydrogenation Density functional theory calculation Heterolytic dissociation of H_(2) Molecular adsorption of H_(2) 

分 类 号：O64[理学—物理化学]