Unusual Role of Point Defects in Perovskite Nickelate Electrocatalysts

Guo, Hongquan; Huang, Jijie; Zhou, Hua; Zuo, Fan; Jiang, Yifeng; Zhang, Kelvin L.; Fu, Xianzhu; Bu, Yunfei; Cheng, Wei; Sun, Yifei

doi:10.1021/acsami.1c04903

Unusual Role of Point Defects in Perovskite Nickelate Electrocatalysts

Journal Article · Tue May 18 00:00:00 EDT 2021 · ACS Applied Materials and Interfaces

DOI:https://doi.org/10.1021/acsami.1c04903· OSTI ID:1840015

Guo, Hongquan ^[1]; Huang, Jijie ^[2]; ^[3]; Zuo, Fan ^[4]; Jiang, Yifeng ^[5]; ^[1]; ^[6]; Bu, Yunfei ^[7]; Cheng, Wei ^[1]; Sun, Yifei ^[1]

Xiamen Univ. (China)
Sun Yat-Sen Univ., Guangdong (China)
Argonne National Lab. (ANL), Lemont, IL (United States)
Indiana State Univ., Terre Haute, IN (United States)
Runner (Xiamen) Corp., Xiamen (China)
Shenzhen Univ. (China)
Nanjing Univ. of Information Science and Technology (NUIST) (China)

Low-cost transition-metal oxide is regarded as a promising electrocatalyst family for an oxygen evolution reaction (OER). The classic design principle for an oxide electrocatalyst believes that point defect engineering, such as oxygen vacancies (VO^..) or heteroatom doping, offers the opportunities to manipulate the electronic structure of material toward optimal OER activity. Oppositely, in this work, we discover a counterintuitive phenomenon that both VO^.. and an aliovalent dopant (i.e., proton (H⁺)) in perovskite nickelate (i.e., NdNiO₃ (NNO)) have a considerably detrimental effect on intrinsic OER performance. Detailed characterizations unveil that the introduction of these point defects leads to a decrease in the oxidative state of Ni and weakens Ni-O orbital hybridization, which triggers the local electron-electron correlation and a more insulating state. Evidenced by first-principles calculation using the density functional theory (DFT) method, the OER on nickelate electrocatalysts follows the lattice oxygen mechanism (LOM). The incorporation of point defect increases the energy barrier of transformation from OO*(V_O) to OH*(V_O) intermediates, which is regarded as the rate-determining step (RDS). Furthermore, this work offers a new and significant perspective of the role that lattice defects play in the OER process.

View Accepted Manuscript (DOE)

Research Organization:: Argonne National Laboratory (ANL), Argonne, IL (United States)

Sponsoring Organization:: National Natural Science Foundation of China (NSFC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357

OSTI ID:: 1840015

Alternate ID(s):: OSTI ID: 1823161
OSTI ID: 1787764

Journal Information:: ACS Applied Materials and Interfaces, Journal Name: ACS Applied Materials and Interfaces Journal Issue: 21 Vol. 13; ISSN 1944-8244

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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