文献类型：期刊文献

英文题名：Theory-guided engineering well-defined Ni-pyrrolic-N4 catalysts with modulable nonmetal-coordinated nitrogen for efficiently synergistic CO2 electroreduction

作者：Xu, Hui[1];Zhao, Yan[1];Zheng, Hongbing[1];Wang, Minxuan[1];Dai, Bingyuan[1];Yang, Can[1];Liu, Zhe[1];Ma, Cheng[1];Qiao, Wenming[1];Ling, Licheng[1];Zhang, Yayun[1];Wang, Jitong[1]

机构：[1]East China Univ Sci & Technol, State Key Lab Chem Engn, Shanghai 200237, Peoples R China

年份：2025

卷号：379

外文期刊名：APPLIED CATALYSIS B-ENVIRONMENT AND ENERGY

收录：;EI(收录号：20253118871929);WOS:【SCI-EXPANDED(收录号:WOS:001584300900005)】；

基金：This work is supported by the National Natural Science Foundation of China (No. U21A2060, No. 22178116, No. 22008073, 22478123) , Natural Science Foundation of Shanghai (No. 22ZR1417400) , Funda-mental Research Funds for the Central Universities (No. 222201817001, No. 50321041918013, No. JKA01221601) , Shanghai Sailing Program (No. 20YF1410600) , and Shanghai Talent Development Fund (2021026) .

语种：英文

外文关键词：CO 2 RR; Theoretical prediction; Nonmetal-coordinated pyridinic-N; Ni-pyrrolic-N 4; Large scale synthesis

摘要：Carbon-supported single-atom catalysts exhibit significant potential for efficient electrochemical reduction of CO2 to CO. However, achieving scalable synthesis and precise engineering the metal-ligand coordination environment to optimize metal-nonmetal synergy remain challenges. Herein, Density Functional Theory (DFT) was employed to identify Ni-pyrrolic-N4 as the optimal coordination, which facilitates the formation of *COOH and desorption of *CO. Furthermore, the precise grafting of nonmetal-coordinated pyridinic-N was confirmed to reduce the proton availability around the Ni-pyrrolic-N4, further mitigating Hydrogen Evolution Reaction (HER). Based on theoretical simulation, a model Ni single-atom catalyst (Ni/PCNTs4) was constructed, which featured the well-defined Ni-pyrrolic-N4 coordination by utilizing the porphyrin structure and achieved adjustable content of nonmetal-coordinated pyridinic-N by regulating the ratio of raw materials. The non-pyrolysis synthesis method avoided the generation of unfavorable reaction sites and readily achieved scalable synthesis on a scale of several hundred grams. The synergistic effects of the unique coordination and the microenvironment modulation of nonmetal-coordinated pyridinic-N enable Ni/PCNTs4 to exhibit ultra-high selectivity. In the flow cell, the Faraday Efficiency (FECO) of Ni/PCNTs4 exceeds 99.7 % at current densities ranging from 100 to 600 mA cm- 2, which is attributed to the strong adsorption of protons by nonmetal-coordinated pyridinic-N at high current densities, significantly inhibiting the HER. Notably, even at an industrial-grade low CO2 concentration (10 %), Ni/PCNTs4 can also achieve FECO of 99.8 % at 200 mA cm- 2. This work provides critical mechanistic insights to guide the rational design of advanced CO2 catalysts for industrial electrocatalytic reduction of CO2.