New mechanistic insights into CO_(2) electroreduction to methane on penta-octa-graphene catalyst  

作　　者：Yirong Ma Jinbo Hao Baonan Jia Xinhui Zhang Chunling Zhang Ge Wu Changcheng Chen Yuanzi Li Zhiyuan Zhou Qiyu Li Pengfei Lu 

机构地区：[1]School of Science,Xi'an University of Architecture and Technology,Xi'an 710055,Shanxi,China [2]School of Automation and Electrical Engineering,University of Science and Technology Beijing,Beijing 100083,China [3]School of Integrated Circuits,Beijing University of Posts and Telecommunications,Beijing 100876,China

出　　处：《Journal of Energy Chemistry》2024年第12期529-540,共12页能源化学（英文版）

基　　金：supported by the Natural Science Basic Research Program of Shaanxi(2023-JC-YB-065,2024JC-YBMS-788);the Foundation of Laboratory of Computational Physics(6142A05QN22017)。

摘　　要：Electrocatalytic reduction of CO_(2) to produce high value-added products is an important way to achieve sustainable production of green energy,but it is limited by high complexity of the catalyst structure and reaction process,making the rational design of the catalyst and the targeted generation of specific products a huge challenge.Herein,based on the penta-octa-graphene(POG)with sp~2 and sp~3 hybrid as the prototype,we theoretically guide the design of CO_(2) electrocatalytic reduction(CO_(2)RR)catalyst over pure POG and TM doping POG(TM@POG).Our mechanistic study highlights two key factors in new pathway for CH_(4) production and catalytic performance,i.e.,TM provides electron transfer for the key intermediate*CHO,promoting the activation of CO_(2),and the type of protonation for CO_(2)RR is determined by the charge accumulation on the O atom of the intermediates.This reduces the complexity of the reaction and provides a predictive effect on the formation of intermediates.More importantly,the proper values of the Gibbs free energy indicate that TM@POG is an ideal catalyst candidate,especially the Fe@POG,which is superior to Cu(211)material.On this basis,three simple descriptors(Bader charge,d-band centerε_dand descriptorφ)based on the inherent properties of atoms were constructed to reveal the underlying causes of the improvement of catalytic activity.Our results provide a new understanding of the’structure-performance’relationship of carbon-based electrocatalysts,thus providing a useful strategy for the design of catalysts for CO_(2)RR.

关 键 词：Penta-octa-graphene Carbon dioxide reduction Catalytic descriptor First-principles calculation 

分 类 号：TQ221.11[化学工程—有机化工] O643.36[理学—物理化学] X701[理学—化学]