Design of molecular MNC dual-atom catalysts for nitrogen reduction starting from surface state analysis

Yuefeng Zhang; Zixun Yu; Fangxin She; Li Wei; Zhiyuan Zeng; Hao Li

doi:10.1016/j.jcis.2023.03.033

Design of molecular MNC dual-atom catalysts for nitrogen reduction starting from surface state analysis

J Colloid Interface Sci. 2023 Jun 15:640:983-989. doi: 10.1016/j.jcis.2023.03.033. Epub 2023 Mar 8.

Authors

Yuefeng Zhang¹, Zixun Yu², Fangxin She³, Li Wei⁴, Zhiyuan Zeng⁵, Hao Li⁶

Affiliations

¹ Department of Materials Science and Engineering, and State Key Laboratory of Marine Pollution, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong 999077, China.
² Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai 980-8577, Japan; School of Chemical and Biomolecular Engineering, The University of Sydney, Darlington, New South Wales 2006, Australia.
³ School of Chemical and Biomolecular Engineering, The University of Sydney, Darlington, New South Wales 2006, Australia.
⁴ School of Chemical and Biomolecular Engineering, The University of Sydney, Darlington, New South Wales 2006, Australia. Electronic address: l.wei@sydney.edu.au.
⁵ Department of Materials Science and Engineering, and State Key Laboratory of Marine Pollution, City University of Hong Kong, 83 Tat Chee Avenue, Kowloon, Hong Kong 999077, China; Shenzhen Research Institute, City University of Hong Kong, Shenzhen 518057, China. Electronic address: zhiyzeng@cityu.edu.hk.
⁶ Advanced Institute for Materials Research (WPI-AIMR), Tohoku University, Sendai 980-8577, Japan. Electronic address: li.hao.b8@tohoku.ac.jp.

PMID: 36913836
DOI: 10.1016/j.jcis.2023.03.033

Abstract

Under electrocatalytic conditions, the state of a catalyst surface (e.g., adsorbate coverage) can be very different from a pristine form due to the existing conversion equilibrium between water and H- and O-containing adsorbates. Dismissing the analysis of the catalyst surface state under operating conditionsmay lead to misleading guidelines for experiments. Given that confirming the actual active site of the catalyst under operating conditions is indispensable to providing practical guidance for experiments, herein, we analyzed the relations between the Gibbs free energy and the potential of a new type of molecular metal-nitrogen-carbon (MNC) dual-atom catalysts (DACs) with a unique 5 N-coordination environment, by spin-polarized density functional theory (DFT) and surface Pourbaix diagram calculations. Analyzing the derived surface Pourbaix diagrams, we screened out three catalysts, N₃-Ni-Ni-N₂, N₃-Co-Ni-N₂, and N₃-Ni-Co-N₂, to further study the activity of nitrogen reduction reaction (NRR). The results display that N₃-Co-Ni-N₂ is a promising NRR catalyst with a relatively low ΔG of 0.49 eV and slow kinetics of the competing hydrogen evolution. This work proposes a new strategy to guide DAC experiments more precisely: the analysis of the surface occupancy state of the catalysts under electrochemical conditions should be performed before activity analysis.

Keywords: Dual-atom catalyst; Nitrogen reduction; Surface states; surface Pourbaix diagrams.