Defective high-entropy rocksalt oxide with enhanced metal-oxygen covalency for electrocatalytic oxygen evolution

doi:10.1016/S1872-2067(21)63794-4

Abstract

Abstract:

High-entropy materials are emerging electrocatalysts by integrating five or more elements into one single crystallographic phase to optimize the electronic structures and geometric environments. Here, a rocksalt-type high-entropy oxide Mg_0.2Co_0.2Ni_0.2Cu_0.2Zn_0.2O (HEO) is developed as an electrocatalyst towards the oxygen evolution reaction (OER). The obtained HEO features abundant cation and oxygen vacancies originating from the lattice mismatch of neighboring metal ions, together with enlarged Co/Ni-O covalency due to the introduction of less electronegative Mg and Zn. As a result, the HEO exhibits superior intrinsic OER activities, delivering a turnover frequency (TOF) 15 and 84 folds that of CoO and NiO at 1.65 V, respectively. This study provides a mechanistic understanding of the enhanced OER on HEO and demonstrates the potential of high-entropy strategy in developing efficient oxygen electrocatalysts by elaborately incorporating low-cost elements with lower electronegativity.

Key words: High-entropy material, Rocksalt oxide, Oxygen evolution reaction, Electrocatalyst, Defect, Metal-oxygen covalency

Fangming Liu, Meng Yu, Xiang Chen, Jinhan Li, Huanhuan Liu, Fangyi Cheng. Defective high-entropy rocksalt oxide with enhanced metal-oxygen covalency for electrocatalytic oxygen evolution[J]. Chinese Journal of Catalysis, 2022, 43(1): 122-129.

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URL: https://www.cjcatal.com/EN/10.1016/S1872-2067(21)63794-4

https://www.cjcatal.com/EN/Y2022/V43/I1/122

Figures/Tables 5

Fig. 1. Schematic of the synthetic process and the morphological evolution of the HEO.

Fig. 2. HRTEM image (a) and SAED pattern (b) of the HEO; (c) Magnified HRTEM image of the M zone indicated by the carmine rectangle in panel b, with inset showing the profile plot of the atoms array indicated by the cyan rectangle; (d) HAADF STEM image and the corresponding elemental mapping images of the HEO.

Fig. 3. Co K-edge (a) and Ni K-edge (b) XANES spectra of the materials; Fourier transforms (FT) of Co K-edge (c) and Ni K-edge (d) EXAFS spectra of the materials; Contour plots of Morlet WT of Co K-edge (e) and Ni K-edge (f) EXAFS spectra of the materials.

Fig. 4. Co 2p (a), Ni 2p (b), O 1s (c) XPS spectra and EPR (d) spectra of CoO, NiO and HEO.

Fig. 5. The LSV curves (a) and corresponding Tafel plots (b) of the catalysts in 1 M KOH saturated with O2; (c) Nyquist plots recorded at 1.6 V with the equivalent circuit in the inset; (d) Potential-dependent TOF curves of the catalysts; (e) Nightingale rose diagram showing multi-angle comparisons of the catalysts, with the TOF, mass activities and specific activities evaluated at 1.65 V; (f) Chronopotentiometry profile of HEO at a current density of 10 mA cm-2.

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