期刊
ACS NANO
卷 12, 期 11, 页码 11625-11631出版社
AMER CHEMICAL SOC
DOI: 10.1021/acsnano.8b06896
关键词
metastable; nickel; hexagonal-close-packed; doping; hydrogen evolution reaction
类别
资金
- Ministry of Science and Technology [2016YFA0204100, 2017YFA0208200]
- National Natural Science Foundation of China [21571135, 21522305]
- Young Thousand Talented Program
- Jiangsu Province Natural Science Fund for Distinguished Young Scholars [BK20150045, BK20170003]
- Natural Science Foundation of Jiangsu Higher Education Institutions [17KJB150032]
- project of scientific and technologic infrastructure of Suzhou [SZS201708]
- Soochow University
- Priority Academic Program Development of Jiangsu Higher Education Institutions (PAPD)
- U.S. Department of Energy, Office of Science, Basic Energy Sciences, Materials Science and Engineering Division
- Center for Functional Nanomaterials [DESC0012704]
Exploring high-performance and cost-efficient electrocatalysts with unusual metastable phase offers opportunities for improving the electrochemical hydrogen generation, while it remains a great challenge to achieve them with desirable activity and stability. Herein, we report that the doping engineering in a metastable, hexagonal-close-packed nickel (hcp Ni) electrocatalyst is a largely unrevealed yet important factor in achieving an extremely active and stable electrocatalyst toward alkaline hydrogen evolution reaction (HER). Theoretical predications and experimental results suggest that, while the stability of metastable hcp Ni electrocatalyst can be largely improved via the manganese (Mn) doping due to the lower formation energy and lattice stabilization, the MnO/hcp Ni surface promotes the HER via intrinsic favorable H2O adsorption and fast dissociation kinetics. Consequently, the Mn-doped hcp Ni electrocatalyst shows a small overpotential of 80 mV at 10 mA/cm(2) and a low Tafel slope of 68 mV/dec. The result is even approaching that of the commercial Pt/C, being one of the best reported non-noble metal HER electrocatalysts in alkaline media. Under long-term chronopotentiometry measurement, such electrocatalyst can endure at least 10 h with negligible activity decay and structure change. The present work demonstrates the dimension in boosting the electrocatalysis by doping engineering of metastable electrocatalysts.
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