Insight into the metal-free electrocatalysis of heteroatom-doped carbon nanocages in competitive CO_(2) reduction and H_(2) evolution  

作　　者：Liu Jiao Chenghui Mao Biao Feng Fengfei Xu Shuo Li Jun Zhong Mingqi Xia Ruonan Cui Xizhang Wang Lijun Yang Qiang Wu Zheng Hu 

机构地区：[1]Key Laboratory of Mesoscopic Chemistry of Ministry of Education(MOE)and Jiangsu Provincial Laboratory for Nanotechnology,School of Chemistry and Chemical Engineering,Nanjing University,Nanjing 210023,China [2]Institute of Functional Nano and Soft Materials Laboratory(FUNSOM),Jiangsu Key Laboratory of Advanced Negative Carbon Technologies,Soochow University,Suzhou 215123,China

出　　处：《Nano Research》2025年第2期255-262,共8页纳米研究(英文版)

基　　金：This work was jointly supported by the National Key Research and Development Program of China(No.2021YFA1500900);the National Natural Science Foundation of China(No.52071174);the Natural Science Foundation of Jiangsu Province,Major Project(No.BK20212005)。

摘　　要：Metal-free carbon-based catalysts exhibit diverse electrocatalytic performances in CO_(2) reduction reaction(CO_(2)RR),but the attributions and contributions of active sites are still confusing to date.Herein,the hierarchical carbon nanocages(hCNC)doped with different heteroatoms(B,N,P,S)are prepared to examine the impact of dopants on the competitive CO_(2)RR and hydrogen evolution reaction(HER).The hCNC and P-doped hCNC show little CO_(2)RR activity,B-and S-doped hCNC show weak CO_(2)RR activity,while N-doped hCNC presents high CO_(2)RR activity.The CO Faradaic efficiency(FECO)of N-containing hCNC increases almost linearly with increasing the N content,even with the co-existing B or P.S and SN-doped hCNC more facilitate the HER.16 doping configurations are constructed,and up to 53 sites are examined CO_(2) H2O H2 CO*H*COOH*CO for the electrochemical activities with a constant potential modelling method.The pyridinic-N(N^(*))is the best active site for CO_(2)RR to CO,while CBO_(2)H_(2)-1(αC^(*)),CBO_(2)H_(2)-2(γC^(*)),NO-1(βC^(*)),PO_(2)H-3(αC^(*))and SO_(3)H-3(δC^(*))are active for HER.The optimized FECO achieves 83.6%for N-doped hCNC with 9.54 at.%nitrogen,and S-doped hCNC reaches ca.30 mA·cm^(-2) current density for HER.This study unveils the structure-performance correlation of heteroatom-doped hCNC,which is conducive to the rational design of advanced metal-free carbon-based catalysts.

关 键 词：heteroatom-doping metal-free carbon-based catalyst CO_(2)reduction reaction hydrogen evolution reaction active sites density functional theory(DFT) 

分 类 号：O64[理学—物理化学]