Affiliation:
1. School of Chemistry and Chemical Engineering Hunan University of Science and Technology Xiangtan 411201 P. R. China
2. Research Institute of HNU in Chongqing College of Materials Science and Engineering Hunan University Changsha 410082 P. R. China
3. Shanghai Institute of Applied Physics Chinese Academy of Science Shanghai 201204 P. R. China
4. University of Chinese Academy of Sciences Beijing 100049 P. R. China
5. Department of Polymer Materials and Engineering College of Materials & Metallurgy Guizhou University Guiyang 550025 P. R. China
6. Guangxi Key Laboratory of Petrochemical Resource Processing and Process Intensification Technology and School of Chemistry and Chemical Engineering Guangxi University Nanning 530004 P. R. China
7. State Key Laboratory of Chemo/Biosensing and Chemometrics Hunan Univeristy Changsha 410082 P. R. China
Abstract
AbstractChallenges in rational designing dual‐atom catalysts (DACs) give a strong motivation to construct coordination‐activity correlations. Here, thorough coordination‐activity correlations of DACs based on how the changes in coordination shells (CSs) of dual‐atom Cu,Co centers influence their electrocatalytic activity in oxygen reduction reaction(ORR), oxygen evolution reaction (OER), and hydrogen evolution reaction (HER) is constructed. First, Cu,Co DACs with different CSs modifications are fabricated by using a controlled “precursors‐preselection” approach. Three DACs with unique coordination environments are characterized as secondary S atoms that directly bond to Cu,Co‐N6 in lower CSs, indirectly bond in neighboring CSs, and are doped in higher CSs, respectively. Then, experimentally and theoretically, a coordination correlation resembling a planet‐satellite system, where satellite coordinated atoms (heteroatom N, S) surround Cu‐Co dual‐atom entity in various orbitals CSs. By evaluating electrocatalytic activity indicators, differences are identified in electronic structure and electrocatalytic performance of Cu and Co centers in ORR, OER, and HER. Interestingly, initial CSs modifications for DACs may not always be advantageous for electrocatalysis. This work offers valuable insight for designing DACs for diverse applications.
Funder
National Natural Science Foundation of China
Scientific Research Foundation of Hunan Provincial Education Department
Subject
Electrochemistry,Condensed Matter Physics,Biomaterials,Electronic, Optical and Magnetic Materials