Homolytic versus Heterolytic Hydrogen Evolution Reaction Steered by a Steric Effect

Autor:	Xiaojun Guo, Ni Wang, Rui Cao, Shuping Ding, Xialiang Li, Wanjie Ren, Jianfeng Li, Ulf-Peter Apfel, Gelun Xu, Jianping Zhao, Zongyao Zhang, Wei Zhang
Rok vydání:	2020
Předmět:	Steric effects 010405 organic chemistry Rational design General Chemistry General Medicine 010402 general chemistry Photochemistry Electrocatalyst 01 natural sciences Porphyrin Heterolysis Catalysis 0104 chemical sciences Homolysis chemistry.chemical_compound chemistry Trifluoroacetic acid
Zdroj:	Angewandte Chemie. 132:9026-9031
ISSN:	1521-3757 0044-8249
Popis:	Several H-H bond forming pathways have been proposed for the hydrogen evolution reaction (HER). Revealing these HER mechanisms is of fundamental importance for the rational design of catalysts and is also extremely challenging. Now, an unparalleled example of switching between homolytic and heterolytic HER mechanisms is reported. Three nickel(II) porphyrins were designed and synthesized with distinct steric effects by introducing bulky amido moieties to ortho- or para-positions of the meso-phenyl groups. These porphyrins exhibited different catalytic HER behaviors. For these Ni porphyrins, although their 1e-reduced forms are active to reduce trifluoroacetic acid, the resulting Ni hydrides (depending on the steric effects of porphyrin rings) have different pathways to make H2 . Understanding HER processes, especially controllable switching between homolytic and heterolytic H-H bond formation pathways through molecular engineering, is unprecedented in electrocatalysis.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::4aca5b3a02f13abc29ac530e07fd256f https://doi.org/10.1002/ange.202002311 Zobrazit plný text záznamu Plný text ve formátu PDF Plný text ve formátu HTML
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