Water-assisted proton delivery and removal in bio-inspired hydrogen production catalysts
Abstract
Electrocatalysts for H2 production are envisioned to play an important role in renewable energy utilization systems. Nickel-based catalysts featuring pendant amines functioning as proton relays in the second coordination sphere of the metal center have led to catalysts achieving turnover frequencies as high as 107 s–1 for H2 production. The fastest rates are observed when water is present in solution, with rates up to 103 times faster than those found in dry solvent. The focus of this paper is to provide mechanistic insight into the unexpected enhancement due to water. Addition of H2 to [Ni(PCy2NR'2)2]2+ was previously shown to give three isomers of a Ni(0) product with two protonated amines, where the N–H can be endo or exo to the Ni. By investigating the deprotonation of these two N-protonated Ni(0) intermediates resulting from the addition of H2 to [Ni(PCy2NR'2)2]2+, we observe by NMR spectroscopy studies an enhancement in the rate of deprotonation for protons positioned on the pendant amine next to the metal (endo) vs. protons that are positioned away from the metal (exo). Further, computational studies suggest that for smaller bases, the desolvation energy of the exogenous base is the primary contribution limiting the rate of endo deprotonation, whilemore »
- Authors:
-
- Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
- Publication Date:
- Research Org.:
- Energy Frontier Research Centers (EFRC) (United States). Center for Molecular Electrocatalysis (CME)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Biological and Environmental Research (BER)
- OSTI Identifier:
- 1386953
- Grant/Contract Number:
- AC05-76RL01830
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Dalton Transactions
- Additional Journal Information:
- Journal Volume: 44; Journal Issue: 24; Related Information: CME partners with Pacific Northwest National Laboratory (lead); University of Illinois, Urbana-Champaign; Pennsylvania State University; University of Washington; University of Wyoming; Journal ID: ISSN 1477-9226
- Publisher:
- Royal Society of Chemistry
- 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)
Citation Formats
Ho, Ming-Hsun, O'Hagan, Molly, Dupuis, Michel, DuBois, Daniel L., Bullock, R. Morris, Shaw, Wendy J., and Raugei, Simone. Water-assisted proton delivery and removal in bio-inspired hydrogen production catalysts. United States: N. p., 2015.
Web. doi:10.1039/C5DT00782H.
Ho, Ming-Hsun, O'Hagan, Molly, Dupuis, Michel, DuBois, Daniel L., Bullock, R. Morris, Shaw, Wendy J., & Raugei, Simone. Water-assisted proton delivery and removal in bio-inspired hydrogen production catalysts. United States. https://doi.org/10.1039/C5DT00782H
Ho, Ming-Hsun, O'Hagan, Molly, Dupuis, Michel, DuBois, Daniel L., Bullock, R. Morris, Shaw, Wendy J., and Raugei, Simone. Tue .
"Water-assisted proton delivery and removal in bio-inspired hydrogen production catalysts". United States. https://doi.org/10.1039/C5DT00782H. https://www.osti.gov/servlets/purl/1386953.
@article{osti_1386953,
title = {Water-assisted proton delivery and removal in bio-inspired hydrogen production catalysts},
author = {Ho, Ming-Hsun and O'Hagan, Molly and Dupuis, Michel and DuBois, Daniel L. and Bullock, R. Morris and Shaw, Wendy J. and Raugei, Simone},
abstractNote = {Electrocatalysts for H2 production are envisioned to play an important role in renewable energy utilization systems. Nickel-based catalysts featuring pendant amines functioning as proton relays in the second coordination sphere of the metal center have led to catalysts achieving turnover frequencies as high as 107 s–1 for H2 production. The fastest rates are observed when water is present in solution, with rates up to 103 times faster than those found in dry solvent. The focus of this paper is to provide mechanistic insight into the unexpected enhancement due to water. Addition of H2 to [Ni(PCy2NR'2)2]2+ was previously shown to give three isomers of a Ni(0) product with two protonated amines, where the N–H can be endo or exo to the Ni. By investigating the deprotonation of these two N-protonated Ni(0) intermediates resulting from the addition of H2 to [Ni(PCy2NR'2)2]2+, we observe by NMR spectroscopy studies an enhancement in the rate of deprotonation for protons positioned on the pendant amine next to the metal (endo) vs. protons that are positioned away from the metal (exo). Further, computational studies suggest that for smaller bases, the desolvation energy of the exogenous base is the primary contribution limiting the rate of endo deprotonation, while steric accessibility and facile proton movement also contribute. For more bulky bases, steric accessibility can play the dominant role. The significant reduction in these barriers observed in the presence of water has important implications for disfavoring less productive catalytic pathways and increasing catalytic rates.},
doi = {10.1039/C5DT00782H},
journal = {Dalton Transactions},
number = 24,
volume = 44,
place = {United States},
year = {Tue Apr 21 00:00:00 EDT 2015},
month = {Tue Apr 21 00:00:00 EDT 2015}
}
Web of Science
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