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Title: Reversing the Tradeoff between Rate and Overpotential in Molecular Electrocatalysts for H2 Production

Abstract

A longstanding challenge in molecular electrocatalysis is to design catalysts that break away from the tradeoff between rate and overpotential arising from electronic scaling relationships. In this paper, we report an inversion of the rate–overpotential correlation through system-level design of [Ni(PR2NR'2)2]2+ electrocatalysts for the production of H2. The overpotential is lowered by an electron-withdrawing ligand, while the turnover frequency is increased by controlling the catalyst structural dynamics, using both ligand design and solvent viscosity. The cumulative effect of controlling each of these system components is an electrocatalyst with a turnover frequency of 70000 s–1 and an overpotential of 230 mV, corresponding to a 100-fold rate enhancement and a 170 mV reduction in overpotential in comparison to the parent nickel catalyst. Molecular Tafel plot analysis reveals that the new catalysts reported here are substantially more efficient than other leading molecular electrocatalysts for the production of H2.

Authors:
 [1];  [2]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
  2. Pacific Northwest National Lab. (PNNL), Richland, WA (United States); State Univ. of New York, Fredonia, NY (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Battelle Memorial Institute, Columbus, OH (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1566354
Grant/Contract Number:  
AC05-76RL01830
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 4; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; catalysis (homogeneous); catalysis (heterogeneous); solar (fuels); bio-inspired; energy storage (including batteries and capacitors); hydrogen and fuel cells; charge transport; materials and chemistry by design; synthesis (novel materials); electrocatalysis; hydrogen; scaling relation; overpotential; nickel; proton relay; viscosity

Citation Formats

Klug, Christina M., Cardenas, Allan Jay P., Bullock, R. Morris, O’Hagan, Molly, and Wiedner, Eric S. Reversing the Tradeoff between Rate and Overpotential in Molecular Electrocatalysts for H2 Production. United States: N. p., 2018. Web. doi:10.1021/acscatal.7b04379.
Klug, Christina M., Cardenas, Allan Jay P., Bullock, R. Morris, O’Hagan, Molly, & Wiedner, Eric S. Reversing the Tradeoff between Rate and Overpotential in Molecular Electrocatalysts for H2 Production. United States. doi:10.1021/acscatal.7b04379.
Klug, Christina M., Cardenas, Allan Jay P., Bullock, R. Morris, O’Hagan, Molly, and Wiedner, Eric S. Wed . "Reversing the Tradeoff between Rate and Overpotential in Molecular Electrocatalysts for H2 Production". United States. doi:10.1021/acscatal.7b04379. https://www.osti.gov/servlets/purl/1566354.
@article{osti_1566354,
title = {Reversing the Tradeoff between Rate and Overpotential in Molecular Electrocatalysts for H2 Production},
author = {Klug, Christina M. and Cardenas, Allan Jay P. and Bullock, R. Morris and O’Hagan, Molly and Wiedner, Eric S.},
abstractNote = {A longstanding challenge in molecular electrocatalysis is to design catalysts that break away from the tradeoff between rate and overpotential arising from electronic scaling relationships. In this paper, we report an inversion of the rate–overpotential correlation through system-level design of [Ni(PR2NR'2)2]2+ electrocatalysts for the production of H2. The overpotential is lowered by an electron-withdrawing ligand, while the turnover frequency is increased by controlling the catalyst structural dynamics, using both ligand design and solvent viscosity. The cumulative effect of controlling each of these system components is an electrocatalyst with a turnover frequency of 70000 s–1 and an overpotential of 230 mV, corresponding to a 100-fold rate enhancement and a 170 mV reduction in overpotential in comparison to the parent nickel catalyst. Molecular Tafel plot analysis reveals that the new catalysts reported here are substantially more efficient than other leading molecular electrocatalysts for the production of H2.},
doi = {10.1021/acscatal.7b04379},
journal = {ACS Catalysis},
number = 4,
volume = 8,
place = {United States},
year = {2018},
month = {3}
}

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  • DOI: 10.1039/c8fd00164b

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  • Chemical Science, Vol. 10, Issue 8
  • DOI: 10.1039/c8sc05247f

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  • DOI: 10.1039/c9cc06916j

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