Coupling effects of Zn single atom and high curvature supports for improved performance of CO2 reduction

Zhongjing Hao; Junxiang Chen; Dafeng Zhang; Lirong Zheng; Yueming Li; Zi Yin; Gang He; Lei Jiao; Zhenhai Wen; Xiao-Jun Lv

doi:10.1016/j.scib.2021.04.020

Coupling effects of Zn single atom and high curvature supports for improved performance of CO₂ reduction

Sci Bull (Beijing). 2021 Aug 30;66(16):1649-1658. doi: 10.1016/j.scib.2021.04.020. Epub 2021 Apr 20.

Authors

Zhongjing Hao¹, Junxiang Chen², Dafeng Zhang³, Lirong Zheng⁴, Yueming Li⁵, Zi Yin⁶, Gang He⁷, Lei Jiao⁸, Zhenhai Wen⁹, Xiao-Jun Lv¹⁰

Affiliations

¹ State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004, China; Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
² CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Province Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China.
³ Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China; Department of Energy and Chemical Engineering, College of Chemistry and Chemical Engineering, Henan Key Laboratory of Coal Green Conversion, Henan Polytechnic University, Jiaozuo 454003, China.
⁴ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China.
⁵ State Key Laboratory of Metastable Materials Science and Technology, College of Materials Science and Engineering, Yanshan University, Qinhuangdao 066004, China. Electronic address: liyueming@ysu.edu.cn.
⁶ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing 100049, China; University of Chinese Academy of Sciences, Beijing 100049, China.
⁷ Key Laboratory of Cryogenics, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China.
⁸ Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China; University of Chinese Academy of Sciences, Beijing 100049, China.
⁹ CAS Key Laboratory of Design and Assembly of Functional Nanostructures, and Fujian Province Key Laboratory of Nanomaterials, Fujian Institute of Research on the Structure of Matter, Chinese Academy of Sciences, Fuzhou 350002, China. Electronic address: wen@fjirsm.ac.cn.
¹⁰ State Key Laboratory of Alternate Electrical Power System with Renewable Energy Sources, School of New Energy, North China Electric Power University, Beijing 102206, China; Key Laboratory of Photochemical Conversion and Optoelectronic Materials, Technical Institute of Physics and Chemistry, Chinese Academy of Sciences, Beijing 100190, China. Electronic address: xjlv@mail.ipc.ac.cn.

PMID: 36654299
DOI: 10.1016/j.scib.2021.04.020

Abstract

Single-atom catalysts (SACs) have emerged as one of the most competitive catalysts toward a variety of important electrochemical reactions, thanks to their maximum atom economy, unique electronic and geometric structures. However, the role of SACs supports on the catalytic performance does not receive enough research attentions. Here, we report an efficient route for synthesis of single atom Zn loading on the N-doped carbon nano-onions (ZnN/CNO). ZnN/CNO catalysts show an excellent high selectivity for CO₂ electro-reduction to CO with a Faradaic efficiency of CO (FE_CO) up to 97% at -0.47 V (vs. reversible hydrogen electrode, RHE) and remarkable durability without activity decay. To our knowledge, ZnN/CNO is the best activity for the Zn based catalysts up to now, and superior to single atom Zn loading on the two-dimensional planar and porous structure of graphene substrate, although the graphene with larger surface area. The exact role of such carbon nano-onions (CNO) support is studied systematically by coupling characterizations and electrochemistry with density functional theory (DFT) calculations, which have attributed such good performance to the increased curvature. Such increased curvature modifies the surface charge, which then changes the adsorption energies of key intermediates, and improves the selectivity for CO generation accordingly.

Keywords: Coupling effect; Electrocatalytic CO(2) reductions; High activity and selectivity; Highly curved substrate; Single-atom catalysts.