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Title: Chemical Pressure-Driven Enhancement of the Hydrogen Evolving Activity of Ni2P from Nonmetal Surface Doping Interpreted via Machine Learning

Journal Article · · Journal of the American Chemical Society
DOI:https://doi.org/10.1021/jacs.8b00947· OSTI ID:1489143
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [1]
  1. Univ. of Pennsylvania, Philadelphia, PA (United States). Dept. of Chemistry
  2. Princeton Univ., Princeton, NJ (United States). Dept. of Mechanical and Aerospace Engineering
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The activity of Ni2P catalysts for the hydrogen evolution reaction (HER) is currently limited by strong H adsorption at the Ni3-hollow site. We investigate the effect of surface nonmetal doping on the HER activity of the Ni3P2 termination of Ni2P(0001), which is stable at modest electrochemical conditions. Using density functional theory (DFT) calculations, we find that both 2p nonmetals and heavier chalcogens provide nearly thermoneutral H adsorption at moderate surface doping concentrations. We also find, however, that only chalcogen substitution for surface P is exergonic. For intermediate surface concentrations of S, the free energy of H adsorption at the Ni3-hollow site is -0.11 eV, which is significantly more thermoneutral than the undoped surface (-0.45 eV). We use the regularized random forest machine learning algorithm to discover the relative importance of structure and charge descriptors, extracted from the DFT calculations, in determining the HER activity of Ni2P(0001) under different doping concentrations. Here, we discover that the Ni–Ni bond length is the most important descriptor of HER activity, which suggests that the nonmetal dopants induce a chemical pressure-like effect on the Ni3-hollow site, changing its reactivity through compression and expansion.

Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC)
Sponsoring Organization:
USDOE
OSTI ID:
1489143
Journal Information:
Journal of the American Chemical Society, Vol. 140, Issue 13; ISSN 0002-7863
Publisher:
American Chemical Society (ACS)Copyright Statement
Country of Publication:
United States
Language:
English
Citation Metrics:
Cited by: 114 works
Citation information provided by
Web of Science

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Stable Active Sites on Ni 12 P 5 Surfaces for the Hydrogen Evolution Reaction journal May 2019
A flower-like Zn 3 V 2 O 8 /Ag composite with enhanced visible light driven photocatalytic activity: the triple-functional roles of Ag nanoparticles journal January 2019
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