Metal–N4 model single-atom catalyst with electroneutral quadri-pyridine macrocyclic ligand for CO2 electroreduction

Jian-Zhao Peng1; Yin-Long Li1; Yao-Ti Cheng1; Fu-Zhi Li1; Bo Cao1; Qing Wang2; Xian Yue1; Guo-Tao Lai1; Yang-Gang Wang1; Jun Gu1

2024-02-15

10.1002/cey2.506

Carbon Energy   影响因子和分区

2637-9368

Metal-N-C single-atom catalysts, mostly prepared from pyrolysis of metal-organic precursors, are widely used in heterogeneous electrocatalysis. Since metal sites with diverse local structures coexist in this type of material and it is challenging to characterize the local structure, a reliable structure-property relationship is difficult to establish. Conjugated macrocyclic complexes adsorbed on carbon support are well-defined models to mimic the single-atom catalysts. Metal-N-4 site with four electroneutral pyridine-type ligands embedded in a graphene layer is the most commonly proposed structure of the active site of single-atom catalysts, but its molecular counterpart has not been reported. In this work, we synthesized the conjugated macrocyclic complexes with a metal center (Co, Fe, or Ni) coordinated with four electroneutral pyridinic ligands as model catalysts for CO2 electroreduction. For comparison, the complexes with anionic quadri-pyridine macrocyclic ligand were also prepared. The Co complex with the electroneutral ligand expressed a turnover frequency of CO formation more than an order of magnitude higher than that of the Co complex with the anionic ligand. Constrained ab initio molecular dynamics simulations based on the well-defined structures of the model catalysts indicate that the Co complex with the electroneutral ligand possesses a stronger ability to mediate electron transfer from carbon to CO2.

ab initio molecular dynamics CO2 reduction electrocatalysis model catalyst single-atom catalyst

SCI ; EI

英语

第一 ; 通讯

National Natural Science Foundation of China["22272073","22373045"] ; Shenzhen Science and Technology Program["JCYJ20210324104414039","JCYJ20220818100410023","KCXST20221021111207017"] ; Guangdong Basic and Applied Basic Research Foundation["2021A1515110360","2022A1515011976"] ; China Postdoctoral Science Foundation[2022M721469] ; null[2021ZT09C064]

Chemistry ; Energy & Fuels ; Science & Technology - Other Topics ; Materials Science

Chemistry, Physical ; Energy & Fuels ; Nanoscience & Nanotechnology ; Materials Science, Multidisciplinary

WOS:001162706700001

WILEY

人工提交

1.Department of Chemistry, Southern University of Science and Technology, Shenzhen, Guangdong, China
2.Institute for Catalysis, Hokkaido University, Sapporo, Japan

Jian-Zhao Peng,Yin-Long Li,Yao-Ti Cheng,等. Metal–N4 model single-atom catalyst with electroneutral quadri-pyridine macrocyclic ligand for CO2 electroreduction[J]. Carbon Energy,2024.

Jian-Zhao Peng.,Yin-Long Li.,Yao-Ti Cheng.,Fu-Zhi Li.,Bo Cao.,...&Jun Gu.(2024).Metal–N4 model single-atom catalyst with electroneutral quadri-pyridine macrocyclic ligand for CO2 electroreduction.Carbon Energy.

Jian-Zhao Peng,et al."Metal–N4 model single-atom catalyst with electroneutral quadri-pyridine macrocyclic ligand for CO2 electroreduction".Carbon Energy (2024).