Vacancy-induced catalytic mechanism for alcohol electrooxidation on nickel-based electrocatalyst.

Autor: Chen W; State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, National Supercomputer Centers in Changsha, Hunan University, Changsha, Hunan, 410082, P. R. China.; Greater Bay Area Institute for Innovation, Hunan University, Guangzhou, 511300, P. R. China., Shi J; State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, National Supercomputer Centers in Changsha, Hunan University, Changsha, Hunan, 410082, P. R. China., Wu Y; State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, National Supercomputer Centers in Changsha, Hunan University, Changsha, Hunan, 410082, P. R. China., Jiang Y; State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, National Supercomputer Centers in Changsha, Hunan University, Changsha, Hunan, 410082, P. R. China., Huang YC; Research Center for X-ray Science & Department of Physics, Tamkang University, 151 Yingzhuan Rd., New Taipei City, 25137, Taiwan., Zhou W; College of Materials Science and Engineering, Hunan University, Changsha, Hunan, 410082, P. R. China., Liu J; College of Materials Science and Engineering, Hunan University, Changsha, Hunan, 410082, P. R. China., Dong CL; Research Center for X-ray Science & Department of Physics, Tamkang University, 151 Yingzhuan Rd., New Taipei City, 25137, Taiwan., Zou Y; State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, National Supercomputer Centers in Changsha, Hunan University, Changsha, Hunan, 410082, P. R. China.; Greater Bay Area Institute for Innovation, Hunan University, Guangzhou, 511300, P. R. China., Wang S; State Key Laboratory of Chem/Bio-Sensing and Chemometrics, College of Chemistry and Chemical Engineering, National Supercomputer Centers in Changsha, Hunan University, Changsha, Hunan, 410082, P. R. China.; Greater Bay Area Institute for Innovation, Hunan University, Guangzhou, 511300, P. R. China.
Jazyk: angličtina
Zdroj: Angewandte Chemie (International ed. in English) [Angew Chem Int Ed Engl] 2024 Jan 22; Vol. 63 (4), pp. e202316449. Date of Electronic Publication: 2023 Dec 19.
DOI: 10.1002/anie.202316449
Abstrakt: Owing to outstanding performances, nickel-based electrocatalysts are commonly used in electrochemical alcohol oxidation reactions (AORs), and the active phase is usually vacancy-rich nickel oxide/hydroxide (NiO x H y ) species. However, researchers are not aware of the catalytic role of atom vacancy in AORs. Here, we study vacancy-induced catalytic mechanisms for AORs on NiO x H y species. As to AORs on oxygen-vacancy-poor β-Ni(OH) 2 , the only redox mediator is electrooxidation-induced electrophilic lattice oxygen species, which can only catalyze the dehydrogenation process (e.g., the electrooxidation of primary alcohol to carboxylic acid) instead of the C-C bond cleavage. Hence, vicinal diol electrooxidation reaction involving the C-C bond cleavage is not feasible with oxygen-vacancy-poor β-Ni(OH) 2 . Only through oxygen vacancy-induced adsorbed oxygen-mediated mechanism, can oxygen-vacancy-rich NiO x H y species catalyze the electrooxidation of vicinal diol to carboxylic acid and formic acid accompanied with the C-C bond cleavage. Crucially, we examine how vacancies and vacancy-induced catalytic mechanisms work during AORs on NiO x H y species.
(© 2023 Wiley-VCH GmbH.)
Databáze: MEDLINE
Externí odkaz: