3d-Orbital Occupancy Regulated Ir-Co Atomic Pair Toward Superior Bifunctional Oxygen Electrocatalysis
Abstract
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 dz2 orbital facilitates the electron acceptation from oxygen to form a stronger Co–O σ bond, thereby propelling faster reaction kinetics.
- Authors:
-
[4];
[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)
- Publication Date:
- Research Org.:
- Argonne National Lab. (ANL), Argonne, IL (United States)
- Sponsoring Org.:
- Natural Sciences and Engineering Research Council of Canada (NSERC); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1838926
- Grant/Contract Number:
- AC02-06CH11357; SC0012704
- Resource Type:
- Accepted Manuscript
- Journal Name:
- ACS Catalysis
- Additional Journal Information:
- Journal Volume: 11; Journal Issue: 14; Journal ID: ISSN 2155-5435
- Publisher:
- American Chemical Society (ACS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; active site; atomic pair; bifunctional oxygen electrocatalysis; orbital occupancy; spin polarization
Citation Formats
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, and Chen, Zhongwei. 3d-Orbital Occupancy Regulated Ir-Co Atomic Pair Toward Superior Bifunctional Oxygen Electrocatalysis. United States: N. p., 2021.
Web. doi:10.1021/acscatal.1c02165.
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. 3d-Orbital Occupancy Regulated Ir-Co Atomic Pair Toward Superior Bifunctional Oxygen Electrocatalysis. United States. https://doi.org/10.1021/acscatal.1c02165
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, and Chen, Zhongwei. Mon .
"3d-Orbital Occupancy Regulated Ir-Co Atomic Pair Toward Superior Bifunctional Oxygen Electrocatalysis". United States. https://doi.org/10.1021/acscatal.1c02165. https://www.osti.gov/servlets/purl/1838926.
@article{osti_1838926,
title = {3d-Orbital Occupancy Regulated Ir-Co Atomic Pair Toward Superior Bifunctional Oxygen Electrocatalysis},
author = {Xiao, Meiling and Zhu, Jianbing and Li, Shuang and Li, Gaoran and Liu, Wenwen and Deng, Ya-Ping and Bai, Zhengyu and Ma, Lu and Feng, Ming and Wu, Tianpin and Su, Dong and Lu, Jun and Yu, Aiping and Chen, Zhongwei},
abstractNote = {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 dz2 orbital facilitates the electron acceptation from oxygen to form a stronger Co–O σ bond, thereby propelling faster reaction kinetics.},
doi = {10.1021/acscatal.1c02165},
journal = {ACS Catalysis},
number = 14,
volume = 11,
place = {United States},
year = {Mon Jul 05 00:00:00 EDT 2021},
month = {Mon Jul 05 00:00:00 EDT 2021}
}
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