Atomic-Level Modulation of Electronic Density at Cobalt Single-Atom Sites Derived from Metal-Organic Frameworks: Enhanced Oxygen Reduction Performance

Yuanjun Chen; Rui Gao; Shufang Ji; Haijing Li; Kun Tang; Peng Jiang; Haibo Hu; Zedong Zhang; Haigang Hao; Qingyun Qu; Xiao Liang; Wenxing Chen; Juncai Dong; Dingsheng Wang; Yadong Li

doi:10.1002/anie.202012798

Atomic-Level Modulation of Electronic Density at Cobalt Single-Atom Sites Derived from Metal-Organic Frameworks: Enhanced Oxygen Reduction Performance

Angew Chem Int Ed Engl. 2021 Feb 8;60(6):3212-3221. doi: 10.1002/anie.202012798. Epub 2020 Dec 10.

Authors

Yuanjun Chen¹, Rui Gao², Shufang Ji¹, Haijing Li³, Kun Tang⁴, Peng Jiang¹, Haibo Hu⁴, Zedong Zhang¹, Haigang Hao², Qingyun Qu¹, Xiao Liang¹, Wenxing Chen⁵, Juncai Dong³, Dingsheng Wang¹, Yadong Li¹

Affiliations

¹ Department of Chemistry, Tsinghua University, Beijing, 100084, China.
² College of Chemistry and Chemical Engineering, Inner Mongolia University, Hohhot, 010021, China.
³ Beijing Synchrotron Radiation Facility, Institute of High Energy Physics, Chinese Academy of Sciences, Beijing, 100049, China.
⁴ School of Physics and Materials Science, Anhui University, Hefei, 230601, China.
⁵ Materials and Green Applications, School of Materials Science and Engineering, Beijing Institute of Technology, Beijing, 100081, China.

PMID: 33124719
DOI: 10.1002/anie.202012798

Abstract

Demonstrated here is the correlation between atomic configuration induced electronic density of single-atom Co active sites and oxygen reduction reaction (ORR) performance by combining density-functional theory (DFT) calculations and electrochemical analysis. Guided by DFT calculations, a MOF-derived Co single-atom catalyst with the optimal Co₁ -N₃ PS active moiety incorporated in a hollow carbon polyhedron (Co₁ -N₃ PS/HC) was designed and synthesized. Co₁ -N₃ PS/HC exhibits outstanding alkaline ORR activity with a half-wave potential of 0.920 V and superior ORR kinetics with record-level kinetic current density and an ultralow Tafel slope of 31 mV dec^-1 , exceeding that of Pt/C and almost all non-precious ORR electrocatalysts. In acidic media the ORR kinetics of Co₁ -N₃ PS/HC still surpasses that of Pt/C. This work offers atomic-level insight into the relationship between electronic density of the active site and catalytic properties, promoting rational design of efficient catalysts.

Keywords: cobalt; density-functional calculations; heterogeneous catalysis; metal-organic frameworks; oxygen reduction.

Abstract

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