3d-Orbital Occupancy Regulated Ir-Co Atomic Pair Toward Superior Bifunctional Oxygen Electrocatalysis

Xiao, Meiling; Zhu, Jianbing; Li, Shuang; Li, Gaoran; Liu, Wenwen; Deng, Ya-Ping; Bai, Zhengyu; Ma, Lu; Feng, Ming; Wu, Tianpin; Su, Dong; Lu, Jun; Yu, Aiping; Chen, Zhongwei

doi:10.1021/acscatal.1c02165

Title: 3d-Orbital Occupancy Regulated Ir-Co Atomic Pair Toward Superior Bifunctional Oxygen Electrocatalysis

Journal Article · Mon Jul 05 00:00:00 EDT 2021 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.1c02165· OSTI ID:1838926

Xiao, Meiling ^[1]; Zhu, Jianbing ^[1]; Li, Shuang ^[1]; Li, Gaoran ^[1]; Liu, Wenwen ^[1]; Deng, Ya-Ping ^[1]; Bai, Zhengyu ^[2]; Ma, Lu ^[3];

^[4]; Wu, Tianpin ^[3];

^[5];

^[3];

^[1];

^[1]

Univ. of Waterloo, ON (Canada). Waterloo Institute for Nanotechnology, Waterloo Institute for Sustainable Energy
Henan Normal Univ., Xinxiang (China). Collaborative Innovation Center of Henan Province for Green Manufacturing of Fine Chemicals, Key Laboratory of Green Chemical Media and Reactions
Argonne National Lab. (ANL), Lemont, IL (United States)
Jilin Normal Univ., Changchun (China). Key Laboratory of Functional Materials Physics and Chemistry
Chinese Academy of Sciences (CAS), Beijing (China). Inst. of Physics. Beijing National Lab. for Condensed Matter Physics (BNLCP-CAS)

Atomically dispersed metal catalysts are hailed as the most promising catalyst category for oxygen electrocatalysis. However, the challenges in regulating electronic configuration and unveiling the mechanism on the atomic scale are hindering their practical implementation. Herein, we modulate the Co d-orbital electron configuration by constructing the Ir–Co atomic pair toward boosted bifunctional activity. The as-developed dual-atom IrCo–N–C catalyst displays unprecedented activity with a half-wave potential of 0.911 V for oxygen reduction reaction and only 330 mV overpotential at 10 mA cm^–2 for oxygen evolution reaction, outperforming the single-atom counterparts as well as the commercial Pt/C and Ir/C benchmarks. The impressive bifunctionality is also verified in a Zn–air battery prototype with an ultra-high cyclability over 450 cycles. Furthermore, theoretical calculations are performed to shed light on the synergetic effects of the atomic pair site, where the incorporation of Ir atom alters the d-orbital energy level of Co and thus induces the re-arrangement of d-electron toward intensified spin polarization. As a result, the lower occupancy of d_z² orbital facilitates the electron acceptation from oxygen to form a stronger Co–O σ bond, thereby propelling faster reaction kinetics.

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

Sponsoring Organization:: Natural Sciences and Engineering Research Council of Canada (NSERC); USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC02-06CH11357; SC0012704

OSTI ID:: 1838926

Journal Information:: ACS Catalysis, Vol. 11, Issue 14; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
active site
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spin polarization

Title: 3d-Orbital Occupancy Regulated Ir-Co Atomic Pair Toward Superior Bifunctional Oxygen Electrocatalysis

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