Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen

Raugei, Simone; Helm, Monte L.; Hammes-Schiffer, Sharon; Appel, Aaron M.; O'Hagan, Molly J.; Wiedner, Eric S.; Bullock, R. Morris

doi:10.1021/acs.inorgchem.5b02262

Title: Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen

Journal Article · Tue Jan 19 00:00:00 EST 2016 · Inorganic Chemistry

DOI:https://doi.org/10.1021/acs.inorgchem.5b02262· OSTI ID:1236305

Raugei, Simone; Helm, Monte L.; Hammes-Schiffer, Sharon; Appel, Aaron M.; O'Hagan, Molly J.; Wiedner, Eric S.; Bullock, R. Morris

Understanding how to control the movement of protons and electrons is crucial to the design of fast, efficient electrocatalysts for hydrogen production and oxidation based on earth-abundant metals. Our work seeks to elucidate fundamental questions about proton movement. We have demonstrated that incorporating a pendant amine functioning as a proton relay in the second coordination sphere of a metal complex helps proton mobility, resulting in faster and more energy efficient catalysts. Proton transfer reactions are often rate limiting, and are influenced by several factors, such as pKa values, steric effects, hydrogen bonding, and solvation/desolvation of the exogenous base and acid employed. The presence of multiple protonation sites introduces branching points along the catalytic cycle, making less productive pathways accessible, or leading to the formation of stable off-cycle species. Using ligands with only one pendant amine mitigates this problem and results in catalysts with high rates for production of H2. For H2 oxidation catalysts, iron complexes with a high H2 binding affinity were developed. However, the improvement of H2 binding enthalpy resulted in a pKa mismatch between the protonated metal center and the protonated pendant amine, and consequently to rate-limiting intramolecular proton movement. Taken altogether, our results demonstrate the necessity of optimizing the entire catalytic cycle, as the optimization of a specific catalytic step can negatively influence another step, and not necessarily lead to better catalytic performance. We discuss a general procedure, based on thermodynamic arguments, which allows the simultaneous minimization of the free energy change of each catalytic step, yielding a nearly flat free energy surface, with no large barriers due to energy mismatches from either high- or low-energy intermediates. This research was supported as part of the Center for Molecular Electrocatalysis, an Energy Frontier Research Center funded by the U.S. Department of Energy, Office of Science, Office of Basic Energy Sciences. Pacific Northwest National Laboratory is operated by Battelle for DOE.

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Research Organization:: Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME); Pacific Northwest National Lab. (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1236305

Report Number(s):: PNNL-SA-114545; KC0307010

Journal Information:: Inorganic Chemistry, Vol. 55, Issue 2; ISSN 0020-1669

Publisher:: American Chemical Society (ACS)

Country of Publication:: United States

Language:: English

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Title: Experimental and Computational Mechanistic Studies Guiding the Rational Design of Molecular Electrocatalysts for Production and Oxidation of Hydrogen

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