In:
Angewandte Chemie, Wiley, Vol. 136, No. 4 ( 2024-01-22)
Abstract:
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.
Type of Medium:
Online Resource
ISSN:
0044-8249
,
1521-3757
DOI:
10.1002/ange.202316449
Language:
English
Publisher:
Wiley
Publication Date:
2024
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