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Identifying the Transfer Kinetics of Adsorbed Hydroxyl as a Descriptor of Alkaline Hydrogen Evolution Reaction
Author(s) -
Mao Baoguang,
Sun Pingping,
Jiang Yan,
Meng Tao,
Guo Donglei,
Qin Jinwen,
Cao Minhua
Publication year - 2020
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.202006722
Subject(s) - kinetics , adsorption , chemistry , desorption , dissociation (chemistry) , catalysis , electron transfer , hydrogen , inorganic chemistry , photochemistry , organic chemistry , quantum mechanics , physics
The key descriptor that dominates the kinetics of the alkaline hydrogen evolution reaction (HER) has not yet been unequivocally identified. Herein, we focus on the adsorbed hydroxyl (OH ad ) transfer process (OH ad + e − ⇄ OH − ) and reveal its crucial role in promoting the overall kinetics of alkaline HER based on Ni/Co‐modified MoSe 2 model catalysts (Ni‐MoSe 2 and Co‐MoSe 2 ) that feature almost identical water dissociation and hydrogen adsorption energies, but evidently different activity trends in alkaline (Ni‐MoSe 2 ≫ Co‐MoSe 2 ) and acidic (Co‐MoSe 2 ≥ Ni‐MoSe 2 ) media. Experimental and theoretical calculation results demonstrate that tailoring MoSe 2 with Ni not only optimizes the hydroxyl adsorption, but also promotes the desorption of OH − and the electron‐involved conversion of OH ad to OH − , all of which synergistically accelerate the kinetics of OH ad + e − ⇄ OH − and thereby the overall kinetics of the alkaline HER.