TY - JOUR
T1 - Climbing the Volcano of Electrocatalytic Activity while Avoiding Catalyst Corrosion
T2 - Ni3P, a Hydrogen Evolution Electrocatalyst Stable in Both Acid and Alkali
AU - Laursen, Anders B.
AU - Wexler, Robert B.
AU - Whitaker, Marianna J.
AU - Izett, Edward J.
AU - Calvinho, Karin U.D.
AU - Hwang, Shinjae
AU - Rucker, Ross
AU - Wang, Hao
AU - Li, Jing
AU - Garfunkel, Eric
AU - Greenblatt, Martha
AU - Rappe, Andrew M.
AU - Dismukes, G. Charles
N1 - Funding Information:
Research at Rutgers was jointly funded by the National Science Foundation, Division of Chemical, Bioengineering, Environmental, and Transport Systems (CBET), and the U.S. Department of Energy, Office of Energy Efficiency and Renewable Energy, Fuel Cell Technologies Office, award number CBET-1433492. A.B.L. thanks Rutgers University for fellowship support. Research at Penn was supported by the Department of Energy, Division of Basic Energy Sciences, award number DE-FG02-07ER15920. The authors also acknowledge computational support from the High-Performance Computing Modernization Office and the National Energy Research Scientific Computing Center.
Publisher Copyright:
© 2018 American Chemical Society.
PY - 2018/5/4
Y1 - 2018/5/4
N2 - We report microcrystalline Ni3P as a noble-metal-free electrocatalyst for the H2 evolution reaction (HER) with high activity just below those of Ni5P4 and Pt, the two most efficient HER catalysts known. Ni3P has previously been dismissed for the HER, owing to its anticipated corrosion and its low activity when formed as an impurity in amorphous alloys. We observe higher activity of single-phase Ni3P crystallites than for other nickel phosphides (except Ni5P4) in acid, high corrosion tolerance in acid, and zero corrosion in alkali. We compare its electrocatalytic performance, corrosion stability, and intrinsic turnover rate to those of different transition-metal phosphides. Electrochemical studies reveal that poisoning of surface Ni sites does not block the HER, indicating P as the active site. Using density functional theory (DFT), we analyze the thermodynamic stability of Ni3P and compare it to experiments. DFT calculations predict that surface reconstruction of Ni3P (001) strongly favors P enrichment of the Ni4P4 termination and that the H adsorption energy depends strongly on the surface reconstruction, thus revealing a potential synthetic lever for tuning HER catalytic activity. A particular P-enriched reconstructed surface on Ni3P(001) is predicted to be the most stable surface termination at intermediate P content, as well as providing the most active surface site at low overpotentials. The P adatoms present on this reconstructed surface are more active for HER at low overpotentials in comparison to any of the sites investigated on other terminations of Ni3P(001), as they possess nearly thermoneutral H adsorption. To our knowledge this is the first time reconstructed surfaces of transition-metal phosphides have been identified as having the most active surface site, with such good agreement with the experimentally observed catalytic current onset and Tafel slope. The active site geometry achieved through reconstruction identified in this work shows great similarity to that reported for Ni2P(0001) and Ni5P4(0001) facets, serving as a general design principle for the future development of even more active transition-metal phosphide catalysts and further climbing the volcano plot.
AB - We report microcrystalline Ni3P as a noble-metal-free electrocatalyst for the H2 evolution reaction (HER) with high activity just below those of Ni5P4 and Pt, the two most efficient HER catalysts known. Ni3P has previously been dismissed for the HER, owing to its anticipated corrosion and its low activity when formed as an impurity in amorphous alloys. We observe higher activity of single-phase Ni3P crystallites than for other nickel phosphides (except Ni5P4) in acid, high corrosion tolerance in acid, and zero corrosion in alkali. We compare its electrocatalytic performance, corrosion stability, and intrinsic turnover rate to those of different transition-metal phosphides. Electrochemical studies reveal that poisoning of surface Ni sites does not block the HER, indicating P as the active site. Using density functional theory (DFT), we analyze the thermodynamic stability of Ni3P and compare it to experiments. DFT calculations predict that surface reconstruction of Ni3P (001) strongly favors P enrichment of the Ni4P4 termination and that the H adsorption energy depends strongly on the surface reconstruction, thus revealing a potential synthetic lever for tuning HER catalytic activity. A particular P-enriched reconstructed surface on Ni3P(001) is predicted to be the most stable surface termination at intermediate P content, as well as providing the most active surface site at low overpotentials. The P adatoms present on this reconstructed surface are more active for HER at low overpotentials in comparison to any of the sites investigated on other terminations of Ni3P(001), as they possess nearly thermoneutral H adsorption. To our knowledge this is the first time reconstructed surfaces of transition-metal phosphides have been identified as having the most active surface site, with such good agreement with the experimentally observed catalytic current onset and Tafel slope. The active site geometry achieved through reconstruction identified in this work shows great similarity to that reported for Ni2P(0001) and Ni5P4(0001) facets, serving as a general design principle for the future development of even more active transition-metal phosphide catalysts and further climbing the volcano plot.
KW - HER
KW - electrocatalysis
KW - energy storage
KW - hydrogen evolution
KW - renewable energy
KW - water splitting
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U2 - 10.1021/acscatal.7b04466
DO - 10.1021/acscatal.7b04466
M3 - Article
AN - SCOPUS:85046648537
VL - 8
SP - 4408
EP - 4419
JO - ACS Catalysis
JF - ACS Catalysis
SN - 2155-5435
IS - 5
ER -