Insights into the activity of nickel boride/nickel heterostructures for efficient methanol electrooxidation

Yanbin Qi; Yue Zhang; Li Yang; Yuhan Zhao; Yihua Zhu; Hongliang Jiang; Chunzhong Li

doi:10.1038/s41467-022-32443-5

Insights into the activity of nickel boride/nickel heterostructures for efficient methanol electrooxidation

Nat Commun. 2022 Aug 6;13(1):4602. doi: 10.1038/s41467-022-32443-5.

Authors

Yanbin Qi^#^{1

2}, Yue Zhang^#³, Li Yang⁴, Yuhan Zhao², Yihua Zhu², Hongliang Jiang⁵, Chunzhong Li^{6

7}

Affiliations

¹ Key Laboratory for Ultrafine Materials of Ministry of Education, School of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China.
² Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China.
³ Institutes of Physical Science and Information Technology, Anhui University, Hefei, 230601, China.
⁴ Institutes of Physical Science and Information Technology, Anhui University, Hefei, 230601, China. lyang@ahu.edu.cn.
⁵ Key Laboratory for Ultrafine Materials of Ministry of Education, School of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China. jhlworld@ecust.edu.cn.
⁶ Key Laboratory for Ultrafine Materials of Ministry of Education, School of Chemical Engineering, East China University of Science and Technology, Shanghai, 200237, China. czli@ecust.edu.cn.
⁷ Shanghai Engineering Research Center of Hierarchical Nanomaterials, School of Materials Science and Engineering, East China University of Science and Technology, Shanghai, 200237, China. czli@ecust.edu.cn.

^# Contributed equally.

Abstract

Designing efficient catalysts and understanding the underlying mechanisms for anodic nucleophile electrooxidation are central to the advancement of electrochemically-driven technologies. Here, a heterostructure of nickel boride/nickel catalyst is developed to enable methanol electrooxidation into formate with a Faradaic efficiency of nearly 100%. Operando electrochemical impedance spectroscopy and in situ Raman spectroscopy are applied to understand the influence of methanol concentration in the methanol oxidation reaction. High concentrations of methanol inhibit the phase transition of the electrocatalyst to high-valent electro-oxidation products, and electrophilic oxygen species (O* or OH*) formed on the electrocatalyst are considered to be the catalytically active species. Additional mechanistic investigation with density functional theory calculations reveals that the potential-determining step, the formation of *CH₂O, occurs most favorably on the nickel boride/nickel heterostructure rather than on nickel boride and nickel. These results are highly instructive for the study of other nucleophile-based approaches to electrooxidation reactions and organic electrosynthesis.

Abstract

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