Water-Assisted Proton Delivery and Removal in bio-inspired Hydrogen Production Catalysts

Ho, Ming-Hsun; O'Hagan, Molly J.; Dupuis, Michel; DuBois, Daniel L.; Bullock, Ronald M.; Shaw, Wendy J.; Raugei, Simone

doi:10.1039/C5DT00782H

Water-Assisted Proton Delivery and Removal in bio-inspired Hydrogen Production Catalysts

Journal Article · Sun Jun 28 04:00:00 EDT 2015 · Dalton Transactions

DOI:https://doi.org/10.1039/C5DT00782H· OSTI ID:1770161

Ho, Ming-Hsun ^[1]; ^[2]; ^[2]; DuBois, Daniel L. ^[2]; ^[2]; ^[2]; Raugei, Simone ^[2]

MULTIPLE CONTRACTORS
BATTELLE (PACIFIC NW LAB)

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 a 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 102 times faster than dry conditions. The focus of this paper is to provide mechanistic insight into the unexpected enhancement due to water. Addition of H2 to [Ni(PR2NR´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 two N-protonated Ni(0) intermediates resulting from H2 addition to to [Ni(PR2NR´2)2]2+, we observe 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). Computational studies suggest that steric accessibility and desolvation energy of the deprotonating base are responsible for limiting endo deprotonation. The significant reduction in this barrier observed in the presence of water has important implications for disfavoring less productive catalytic pathways and increasing catalytic rates. 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 the U.S. Department of Energy.

Research Organization:: Pacific Northwest National Laboratory (PNNL), Richland, WA (United States)

Sponsoring Organization:: USDOE

DOE Contract Number:: AC05-76RL01830

OSTI ID:: 1770161

Report Number(s):: PNNL-SA-108272

Journal Information:: Dalton Transactions, Journal Name: Dalton Transactions Journal Issue: 24 Vol. 44

Country of Publication:: United States

Language:: English

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