Title | Unifying the Hydrogen Evolution and Oxidation Reactions Kinetics in Base by Identifying the Catalytic Roles of Hydroxyl-Water-Cation Adducts |
Publication Type | Journal Article |
Year of Publication | 2019 |
Authors | Liu E, Li J, Jiao L, Doan HThi Thanh, Liu Z, Zhao Z, Huang Y, Abraham K.M, Mukerjee S, Jia Q |
Journal | Journal of the American Chemical Society |
Volume | 141 |
Issue | 7 |
Pagination | 3232-3239 |
Date Published | 02/2019 |
ISSN | 0002-7863 |
Abstract | Published on February 20th, 2019. Despite the fundamental and practical significance of the hydrogen evolution and oxidation reactions (HER/HOR), their kinetics in base remain unclear. Herein, we show that the alkaline HER/HOR kinetics can be unified by the catalytic roles of the adsorbed hydroxyl (OHad)-water-alkali metal cation (AM+) adducts, on the basis of the observations that enriching the OHad abundance via surface Ni benefits the HER/HOR; increasing the AM+ concentration only promotes the HER, while varying the identity of AM+ affects both HER/HOR. The presence of OHad-(H2O)x-AM+ in the double-layer region facilitates the OHad removal into the bulk, forming OH–-(H2O)x-AM+ as per the hard–soft acid–base theory, thereby selectively promoting the HER. It can be detrimental to the HOR as per the bifunctional mechanism, as the AM+ destabilizes the OHad, which is further supported by the CO oxidation results. This new notion may be important for alkaline electrochemistry. |
URL | https://doi.org/10.1021/jacs.8b13228 |
DOI | 10.1021/jacs.8b13228 |
Unifying the Hydrogen Evolution and Oxidation Reactions Kinetics in Base by Identifying the Catalytic Roles of Hydroxyl-Water-Cation Adducts
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