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Metal-oxoacid-mediated oxyhydroxide with proton acceptor to break adsorption energy scaling relation for efficient oxygen evolution

Journal of Energy Chemistry [2023]
Rongrong Zhang, Beibei Guo, Lun Pan, Zhen-Feng Huang, Chengxiang Shi, Xiangwen Zhang, Ji-Jun Zou
ABSTRACT

Metal oxyhydroxides (MOOH) generated from irreversible reconstructions of transition metal compounds are intrinsic active species for oxygen evolution reaction , whose activities are still constrained by sluggish deprotonation kinetics and inherent adsorption energy scaling relations. Herein, we construct a tunable proton acceptor (TPA) on oxyhydroxides by in-situ reconstruction of metal oxoacids such as NiC 2 O 4 to accelerate deprotonation and break adsorption energy scaling relations during OER. The modified C 2 O 4 2− as a TPA can easily extract H of *OH (forming *HC 2 O 4 intermediate) and then promote deprotonation by the transmitted hydrogen bond with *OOH along conjugated (H···)O C–O(–H) chain. As a result, NiOOH-C 2 O 4 shows non-concerted proton-electron transfer and improved deprotonation rate, and delivers a good OER activity (270 mV@10 mA cm −2 ). The conjugate acidity coefficient (p K a ) of the modified oxoacid group can be a descriptor for TPA selection. This TPA strategy can be universally applied to Co-, Fe-, and Ni-based oxyhydroxides to facilitate OER efficiency.

MATERIALS

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