Structure and Oxygen Evolution Activity of β-NiOOH: Where Are the Protons?

Hu, Qi; Xue, Yufeng; Kang, Jianxin; Scivetti, Ivan; Teobaldi, Gilberto; Selloni, Annabella; Guo, Lin; Liu, Li-Min

doi:10.1021/acscatal.1c04647

Structure and Oxygen Evolution Activity of β-NiOOH: Where Are the Protons?

Journal Article · Wed Dec 15 00:00:00 EST 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.1c04647· OSTI ID:1838121

Hu, Qi ^[1]; Xue, Yufeng ^[2]; Kang, Jianxin ^[2]; ^[3]; ^[4]; ^[5]; ^[2]; ^[2]

Beijing Computational Science Research Center (China); Beihang Univ., Beijing (China); Princeton University
Beihang Univ., Beijing (China)
Science and Technology Facilities Council (STFC), Daresbury (United Kingdom). Daresbury Lab.; Univ. of Liverpool (United Kingdom)
Univ. of Southampton (United Kingdom); Science and Technology Facilities Council (STFC), Oxford (United Kingdom). Rutherford Appleton Lab. (RAL)
Princeton Univ., NJ (United States)

Ni oxides and oxyhydroxides (NiO_x) have been studied for a long time as cathode materials for alkaline batteries and electrocatalysts for the oxygen evolution reaction (OER). Yet, understanding of the connection between their atomic and electronic structures and electrochemical performance or stability is still incomplete. In this work, we use first-principles density functional theory (DFT) calculations to revisit the structure, electronic properties, and OER activity of β-NiOOH, the catalytically active phase of NiO_x. Following extensive DFTbased screening, we identify a hitherto overlooked structure characterized by a uniform distribution of H atoms on the NiO₂ layers. All the Ni³⁺ cations in this structure exhibit an identical t_g⁶e_g¹ electronic configuration with an occupied 3d_z2 orbital. Comparison of the calculated bond lengths with extended X-ray absorption fine structure (EXAFS) data unequivocally supports this structure relative to all other low-energy configurations. Based on this structure, we uncover and detail defect-dominated OER mechanisms on the basal β-NiOOH (001) surface, with overpotentials as low as 0.39 V. The present results should provide a valuable contribution to ongoing efforts for understanding and developing enhanced transition-metal hydroxide catalysts for the OER.

View Accepted Manuscript (DOE)

Research Organization:: Princeton Univ., NJ (United States)

Sponsoring Organization:: Beijing Natural Science Foundation; National Natural Science Foundation of China (NSFC); National Postdoctoral Program for Innovative Talents; Royal Society Newton Advanced Fellowship; USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: SC0007347

OSTI ID:: 1838121

Journal Information:: ACS Catalysis, Journal Name: ACS Catalysis Vol. 12; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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