3d过渡金属单原子掺杂石墨烯缺陷电催化还原CO_(2)的第一性原理研究  

First-principles Investigation of Single 3d Transition Metals Doping Graphene Vacancies for CO_(2)Electroreduction

作　　者：靳宇翔 宋二红 朱永福 JIN Yuxiang;SONG Erhong;ZHU Yongfu(School of Materials Science and Engineering,Jilin University,Changchun 130025,China;Shanghai Institute of Ceramics,Chinese Academy of Sciences,Shanghai 200050,China)

机构地区：[1]吉林大学材料科学与工程学院,长春130025 [2]中国科学院上海硅酸盐研究所,上海200050

出　　处：《无机材料学报》2024年第7期845-852,I0012-I0014,共11页Journal of Inorganic Materials

基　　金：Science and Technology Commission of Shanghai Municipality(21ZR1472900,22ZR1471600)。

摘　　要：将CO_(2)高效转化为有价值的化学品(如CO和HCOOH等)是缓解环境问题、实现碳中和的重要措施。然而CO_(2)还原反应(CO_(2)RR)有着产物多样和路径复杂的特点,再加上目前难以确定影响CO_(2)RR活性的真正因素,使得设计对特定产物有高选择性和高活性的催化剂十分具有挑战性。本研究从第一性原理出发,系统研究了3d过渡金属单原子掺杂石墨烯单个空位(TM@CSV)和双空位(TM@CDV)电催化还原CO_(2)的潜力,具体涵盖基底的稳定性、中间产物热力学吸附以及与之竞争的析氢反应(HER)。通过对Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu和Zn掺杂石墨烯缺陷后形成的20种催化剂进行筛选,发现Sc原子掺杂石墨烯单个空位的Sc@CSV和Sc、Ti原子掺杂石墨烯双空位的Sc@CDV和Ti@CDV同时具备吸附CO_(2)分子和抑制HER的能力。其中Sc@CDV对HCOOH表现出最佳的活性和选择性,速率决定步骤的吉布斯自由能差仅为0.96 eV。最后,通过电子结构分析进一步揭示了Sc@CDV优于其他催化剂的原因是Sc@CDV调整了费米能级附近的活性电子态,从而实现对CO_(2)的高效还原。Among all options of carbon neutrality,conversion of CO_(2)into valuable chemicals by electrocatalytic reduction exhibit outstanding performance.However,due to the numerous products and complex pathways of CO_(2)electrocatalytic reduction,the exact factors affecting the activity of CO_(2)electrocatalytic reduction have not yet been identified.In addition,the CO_(2)electrocatalytic reduction process is often accompanied by hydrogen evolution reaction(HER).Therefore,it is still challenging to design a catalyst with high selectivity and high activity for specific product.Herein,this study systematically investigated the potential of 3d transition metal-based single-atom catalysts(SACs)positioned at graphene single vacancies(TM@CSV),as well as double vacancies(TM@CDV),for the CO_(2)reduction reaction(CO_(2)RR)using first-principles.The exploration encompassed substrate stability,CO2 adsorption,and the HER as the main competing reaction.Through the careful screening of 20 catalysts formed by Sc,Ti,V,Cr,Mn,Fe,Co,Ni,Cu and Zn doped graphene defects,several promising catalysts were identified:Sc@CSV situated on graphene single vacancies,Sc@CDV and Ti@CDV situated on graphene double vacancies.They could not only effectively adsorb CO_(2)molecules,but also inhibit HER,the main competing reaction.In assessing their performance in CO_(2)RR,all exhibited selectivity toward HCOOH.Notably,Sc@CDV demonstrated the best selectivity,requiring the lowestΔG(0.96 eV)for efficient CO_(2)conversion to HCOOH.Electronic structure analysis revealed that Sc@CDV outperforms due to its optimal balance betweenΔG of hydrogenation and the product desorption achieved through a moderate number of active electrons.

关 键 词：第一性原理 单原子催化剂 CO_(2)还原反应 HCOOH 碳中和 

分 类 号：TQ174[化学工程—陶瓷工业]