Interfacial Electron Engineering of Palladium and Molybdenum Carbide for Highly Efficient Oxygen Reduction

Liang Huang; Xiliang Zheng; Ge Gao; He Zhang; Kai Rong; Jinxing Chen; Yongqin Liu; Xinyang Zhu; Weiwei Wu; Ying Wang; Jin Wang; Shaojun Dong

doi:10.1021/jacs.1c00656

Interfacial Electron Engineering of Palladium and Molybdenum Carbide for Highly Efficient Oxygen Reduction

J Am Chem Soc. 2021 May 12;143(18):6933-6941. doi: 10.1021/jacs.1c00656. Epub 2021 Apr 29.

Authors

Liang Huang^{1

2}, Xiliang Zheng¹, Ge Gao¹, He Zhang^{1

2}, Kai Rong^{1

2}, Jinxing Chen^{1

2}, Yongqin Liu¹, Xinyang Zhu^{1

2}, Weiwei Wu^{1

2}, Ying Wang³, Jin Wang⁴, Shaojun Dong^{1

2}

Affiliations

¹ State Key Laboratory of Electroanalytical Chemistry, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, China.
² University of Science and Technology of China, Hefei, Anhui 230026, China.
³ State Key Laboratory of Rare Earth Resource Utilization, Changchun Institute of Applied Chemistry, Chinese Academy of Sciences, Changchun, Jilin 130022, China.
⁴ Department of Chemistry and Physics, Stony Brook University, Stony Brook, New York 11794-3400, United States.

PMID: 33915042
DOI: 10.1021/jacs.1c00656

Abstract

Interfacial electron engineering between noble metal and transition metal carbide is identified as a powerful strategy to improve the intrinsic activity of electrocatalytic oxygen reduction reaction (ORR). However, this short-range effect and the huge structural differences make it a significant challenge to obtain the desired electrocatalyst with atomically thin noble metal layers. Here, we demonstrated the combinatorial strategies to fabricate the heterostructure electrocatalyst of Mo₂C-coupled Pd atomic layers (AL-Pd/Mo₂C) by precise control of metal-organic framework confinement and covalent interaction. Both atomic characterizations and density functional theory calculations uncovered that the strong electron effect imposed on Pd atomic layers has intensively regulated the electronic structures and d-band center and then optimized the reaction kinetics. Remarkably, AL-Pd/Mo₂C showed the highest ORR electrochemical activity and stability, which delivered a mass activity of 2.055 A mg_Pd^-1 at 0.9 V, which is 22.1, 36.1, and 80.3 times higher than Pt/C, Pd/C, and Pd nanoparticles, respectively. The present work has developed a novel approach for atomically noble metal catalysts and provides new insights into interfacial electron regulation.