双杂原子掺杂生物质基碳材料电催化CO_(2)还原性能理论模拟研究  

Theoretical Simulation of Electrocatalytic CO_(2) Reduction Performance of Dual Heteroatom-doped Biomass-based Carbon Materials

作　　者：赵钰莹 范孟孟 孙康[1] 蒋剑春[1,2] ZHAO Yuying;FAN Mengmeng;SUN Kang;JIANG Jianchun(Institute of Chemical Industry of Forest Products,CAF,Key Lab.of Biomass Energy and Material,Jiangsu Province,Key Lab.of Chemical Engineering of Forest Products,National Forestry and Grassland Administration,National Engineering Research Center of Low-Carbon Processing and Utilization of Forest Biomass,Jiangsu Co-Innovation Center of Efficient Processing and Utilization of Forest Resources,Nanjing 210042,China;International Innovation Center for Forest Chemicals and Materials,Nanjing Forestry University,Nanjing 210037,China)

机构地区：[1]中国林业科学研究院林产化学工业研究所,江苏省生物质能源与材料重点实验室,国家林业和草原局林产化学工程重点实验室,林木生物质低碳高效利用国家工程研究中心,江苏省林业资源高效加工利用协同创新中心,江苏南京210042 [2]南京林业大学林产化学与材料国际创新高地,江苏南京210037

出　　处：《林产化学与工业》2025年第2期87-95,共9页Chemistry and Industry of Forest Products

基　　金：国家自然科学基金资助项目(32371810);江苏省自然科学基金面上项目(BK20221338);中国博士后科学基金(2023M731702)。

摘　　要：为增强杂原子掺杂碳材料在电催化二氧化碳还原反应(CO_(2)RR)中的性能,揭示双杂原子掺杂的影响及其作用机理,通过密度泛函理论(DFT)模拟,围绕CO_(2)RR反应机制,研究最优的双杂原子掺杂策略,探讨了不同双杂原子掺杂构型对CO_(2)RR催化性能的影响,进一步明确最优双杂原子掺杂构型。研究结果表明:设计的系列氟-氮、氯-氮、硼-氮、磷-氮、硫-氮、硼-磷,以及硼-硫双杂原子掺杂石墨烯结构,B-N双杂原子掺杂碳材料(BNC)具有较高的稳定性和催化活性,有最低的形成能(3.72 eV)和较低的吉布斯自由能(ΔG, 0.53 eV)。吡啶氮(PyN)、吡咯氮(PyrrN)和石墨氮(GrN)3种N构型中,含有PyN-B构型的双杂原子掺杂碳材料可以促进CO_(2)还原为CO,其中N原子作为最佳的活性位点,ΔG值低至0.47 eV,展现出最优的催化性能。PyN引入的给电子性能与B的失电子性能形成双电荷效应,这种协同作用增强了材料对CO_(2)的吸附和活化作用,有效降低了CO_(2)RR的反应能垒,从而提高了催化剂的选择性和反应速率。To enhance the performance of heteroatom-doped carbon-based catalysts in electrocatalytic carbon dioxide reduction reaction(CO_(2) RR)and elucidate the effects and mechanisms of dual heteroatom doping,the optimal dual heteroatom doping strategy was studied by density functional theory(DFT)simulations around the CO_(2) RR reaction mechanism.Focusing on the CO_(2) RR reaction mechanism,the influence of various dual heteroatom doping types on CO_(2) RR performance was investigated with the aim of identifying the optimal dual heteroatom doping strategy.The results showed that the designed series of fluorine-nitrogen chlorine-nitrogen,boron-phosphorus,and boron-sulfur dual heteroatom-doped graphene structures,B-N dual heteroatom-doped carbon materials(BNC)had high stability and catalytic activity,with the lowest formation energy(3.72 eV)and lower Gibbs free energy(ΔG,0.53 eV).Among the three N configurations of pyridine nitrogen(PyN),pyrrole nitrogen(PyrrN)and graphite nitrogen(GrN),the dual heteroatom-doped carbon material containing the PyN-B configuration could promote the reduction of CO_(2) to CO.Among them,the N atom was the best active site,and theΔG value was as low as 0.47 eV,showing the best catalytic performance.This synergistic interaction enhanced the adsorption and activation of CO_(2),effectively reduced the reaction barrier for CO_(2) RR,thus improved the selectivity and reaction rate of the catalyst.

关 键 词：碳基催化剂 B、N共掺杂 吡啶N-B 电催化CO_(2)还原 密度泛函理论 

分 类 号：TQ35[化学工程]