Cation‐Vacancy‐Enriched Nickel Phosphide for Efficient Electrosynthesis of Hydrogen Peroxides. Issue 16 (15th March 2022)

• Record Type: Journal Article
• Authors: Zhou, Zheng; Kong, Yuan; Tan, Hao; Huang, Qianwei; Wang, Cheng; Pei, Zengxia; Wang, Haozhu; Liu, Yangyang; Wang, Yihan; Li, Sai; Liao, Xiaozhou; Yan, Wensheng; Zhao, Shenlong
• Is Part Of: Advanced materials. Volume 34:Issue 16(2022)
• Page Start: n/a
• Page End: n/a
• Publication Date: 2022-03-15
• Subjects: cation vacancy engineering -- electrocatalysis -- green production -- hydrogen peroxide production -- oxygen reduction reaction; Materials -- Periodicals; Chemical vapor deposition -- Periodicals; 620.11
• DOI: 10.1002/adma.202106541
• Languages: English
• ISSNs: 0935-9648

Abstract

Abstract: Electrocatalytic hydrogen peroxide (H2 O2 ) synthesis via the two‐electron oxygen reduction reaction (2e ORR) pathway is becoming increasingly important due to the green production process. Here, cationic vacancies on nickel phosphide, as a proof‐of‐concept to regulate the catalyst's physicochemical properties, are introduced for efficient H2 O2 electrosynthesis. The as‐fabricated Ni cationic vacancies (VNi )‐enriched Ni2− x P‐VNi electrocatalyst exhibits remarkable 2e ORR performance with H2 O2 molar fraction of >95% and Faradaic efficiencies of >90% in all pH conditions under a wide range of applied potentials. Impressively, the as‐created VNi possesses superb long‐term durability for over 50 h, suppassing all the recently reported catalysts for H2 O2 electrosynthesis. Operando X‐ray absorption near‐edge spectroscopy (XANES) and synchrotron Fourier transform infrared (SR‐FTIR) combining theoretical calculations reveal that the excellent catalytic performance originates from the VNi ‐induced geometric and electronic structural optimization, thus promoting oxygen adsorption to the 2e ORR favored "end‐on" configuration. It is believed that the demonstrated cation vacancy engineering is an effective strategy toward creating active heterogeneous catalysts with atomic precision. Abstract : A cationic vacancy strategy is proposed for designing nickel‐phosphide‐based electrocatalysts for the two‐electron oxygen reduction reaction (2e ORR). The fabricated Ni2− x P‐VNi exhibits excellent electrocatalytic performance in 0.1 m KOH and high Faradaic efficiency in all pH solutions. Computational analysis and operando characterizations suggest that the oxygen adsorption on Ni2− x P‐VNi prefers to via an "end‐on" configuration, which facilitates the formation of the *OOH intermediate during the 2e ORR process.