Local Structure Insight into Hydrogen Evolution Reaction with Bimetal Nanocatalysts

Qiang Li; He Zhu; Xiaoyu Chen; Hui Liu; Yang Ren; Yanan Chen; Koji Ohara; Lihui Zhou; Jun Chen; Jinxia Deng; Jun Miao; Kun Lin; Xiaojun Kuang; Xianran Xing

doi:10.1021/jacs.2c07844

Local Structure Insight into Hydrogen Evolution Reaction with Bimetal Nanocatalysts

J Am Chem Soc. 2022 Nov 9;144(44):20298-20305. doi: 10.1021/jacs.2c07844. Epub 2022 Oct 27.

Authors

Qiang Li¹, He Zhu¹, Xiaoyu Chen², Hui Liu³, Yang Ren⁴, Yanan Chen⁵, Koji Ohara⁶, Lihui Zhou⁷, Jun Chen³, Jinxia Deng¹, Jun Miao¹, Kun Lin¹, Xiaojun Kuang⁸, Xianran Xing¹

Affiliations

¹ Beijing Advanced Innovation Center for Materials Genome Engineering, Institute of Solid State Chemistry, University of Science and Technology Beijing, Beijing 100083, China.
² College of Materials Science and Engineering, Shenzhen University, Shenzhen 518071, China.
³ Beijing Advanced Innovation Center for Materials Genome Engineering, University of Science and Technology Beijing, Beijing 100083, China.
⁴ Department of Physics, City University of Hong Kong, Kowloon 999077, Hong Kong, China.
⁵ School of Materials Science and Engineering, Key Laboratory of Advanced Ceramics and Machining Technology of Ministry of Education, Tianjin Key Laboratory of Composite and Functional Materials, Tianjin University, Tianjin 300072, China.
⁶ SPring-8, Japan Synchrotron Radiation Research Institute, Sayo-gun, Hyogo 679-5148, Japan.
⁷ Key Laboratory for Advanced Materials and Joint International Research Laboratory of Precision Chemistry and Molecular Engineering, Feringa Nobel Prize Scientist Joint Research Center, School of Chemistry and Molecular Engineering, East China University of Science and Technology, Shanghai 200237, China.
⁸ College of Chemistry and Bioengineering, Guilin University of Technology, Guilin 541006, China.

PMID: 36300893
DOI: 10.1021/jacs.2c07844

Abstract

The revelation of the atomic 3D structure of sub-5 nm bimetal nanocatalysts challenges the limitations of conventional methods. Notably, the identification of the cooperative relationship between the active sites and nearby coordination environment during catalytic reactions depends on the stereo distribution of local phases and chemical composition within a short range. As a model nanocatalyst in our investigation, we studied the ordered PtFe bimetals in hydrogen evolution reactions (HER). By combining pair distribution functions with reverse Monte Carlo, local-range phase symmetry, chemical composition, and atom distribution were determined. The segregation of local phase segments as disordered Pt-rich A1 and Pt₃Fe L1₂ phases can be attributed to the marked improvement of HER activity and stability in Pt₅₆Fe₄₄. Following the etching of the outermost-surface Fe, the remaining disordered segregation offered a large number of active Pt sites for discharge and electrochemical desorption reactions. It resulted in local-bonding Pt pairs that made it easier for adsorbed hydrogen atoms to recombine. The current research will provide structural insight into the local range for bimetal nanocatalysts and be valuable for the creation of new, low-cost nanocatalysts.