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

Klug, Christina M.; Cardenas, Allan Jay P.; Bullock, R. Morris; O’Hagan, Molly; Wiedner, Eric S.

doi:10.1021/acscatal.7b04379

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

Journal Article · Wed Mar 07 00:00:00 EST 2018 · ACS Catalysis

DOI:https://doi.org/10.1021/acscatal.7b04379· OSTI ID:1566354

Klug, Christina M. ^[1]; Cardenas, Allan Jay P. ^[2];

^[1]; O’Hagan, Molly ^[1];

^[1]

Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Pacific Northwest National Lab. (PNNL), Richland, WA (United States); State Univ. of New York, Fredonia, NY (United States)

A long-standing challenge in molecular electrocatalysis is to design catalysts that break away from the tradeoff between rate and overpotential arising from electronic scaling relationships. Here we report an inversion of the rate-overpotential correlation through system-level design of new [Ni(P^R₂N^R'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. Here, the cumulative effect of controlling each of these system components is an electrocatalyst with a turnover frequency of 70,000 s^–1 and an overpotential of 230 mV, corresponding to a 100-fold rate enhancement and a 170 mV reduction in overpotential compared to the parent nickel catalyst. The success of this system-level approach originates from the detailed mechanistic understanding of these catalysts, which enabled modifications of the catalyst and solvent to disfavor non-productive pathways.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Battelle Memorial Institute, Columbus, OH (United States); Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: AC05-76RL01830

OSTI ID:: 1566354

Alternate ID(s):: OSTI ID: 1842948

Report Number(s):: PNNL-SA-130125

Journal Information:: ACS Catalysis, Vol. 8, Issue 4; ISSN 2155-5435

Publisher:: American Chemical Society (ACS)Copyright Statement

Country of Publication:: United States

Language:: English

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Cited by: 66 works

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

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