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Title: Theoretical Design of Molecular Electrocatalysts with Flexible Pendant Amines for Hydrogen Production and Oxidation

Abstract

The design of hydrogen oxidation and production catalysts is important for the development of alternative renewable energy sources. The overall objective is to maximize the turnover frequency and minimize the overpotential. In an effort to assist in the design of such catalysts, we use computational methods to examine a variety of nickel-based molecular electrocatalysts with pendant amines. Our studies focus on the proton-coupled electron transfer (PCET) process involving electron transfer between the complex and the electrode and intramolecular proton transfer between the nickel center and the nitrogen of the pendant amine. The concerted PCET mechanism, which tends to require a lower overpotential, is favored by a smaller equilibrium Ni-N distance and a more flexible pendant amine ligand, thereby decreasing the energetic penalty for the nitrogen to approach the nickel center for proton transfer. These calculations provide design principles that will be useful for developing the next generation of hydrogen catalysts. 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.

Authors:
; ;
Publication Date:
Research Org.:
Pacific Northwest National Lab. (PNNL), Richland, WA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1117064
Report Number(s):
PNNL-SA-92343
KC0307010
DOE Contract Number:  
AC05-76RL01830
Resource Type:
Journal Article
Journal Name:
The Journal of Physical Chemistry Letters, 4(3):542-546
Additional Journal Information:
Journal Name: The Journal of Physical Chemistry Letters, 4(3):542-546
Country of Publication:
United States
Language:
English

Citation Formats

Fernandez, Laura, Horvath, Samantha, and Hammes-Schiffer, Sharon. Theoretical Design of Molecular Electrocatalysts with Flexible Pendant Amines for Hydrogen Production and Oxidation. United States: N. p., 2013. Web. doi:10.1021/jz3020277.
Fernandez, Laura, Horvath, Samantha, & Hammes-Schiffer, Sharon. Theoretical Design of Molecular Electrocatalysts with Flexible Pendant Amines for Hydrogen Production and Oxidation. United States. doi:10.1021/jz3020277.
Fernandez, Laura, Horvath, Samantha, and Hammes-Schiffer, Sharon. Thu . "Theoretical Design of Molecular Electrocatalysts with Flexible Pendant Amines for Hydrogen Production and Oxidation". United States. doi:10.1021/jz3020277.
@article{osti_1117064,
title = {Theoretical Design of Molecular Electrocatalysts with Flexible Pendant Amines for Hydrogen Production and Oxidation},
author = {Fernandez, Laura and Horvath, Samantha and Hammes-Schiffer, Sharon},
abstractNote = {The design of hydrogen oxidation and production catalysts is important for the development of alternative renewable energy sources. The overall objective is to maximize the turnover frequency and minimize the overpotential. In an effort to assist in the design of such catalysts, we use computational methods to examine a variety of nickel-based molecular electrocatalysts with pendant amines. Our studies focus on the proton-coupled electron transfer (PCET) process involving electron transfer between the complex and the electrode and intramolecular proton transfer between the nickel center and the nitrogen of the pendant amine. The concerted PCET mechanism, which tends to require a lower overpotential, is favored by a smaller equilibrium Ni-N distance and a more flexible pendant amine ligand, thereby decreasing the energetic penalty for the nitrogen to approach the nickel center for proton transfer. These calculations provide design principles that will be useful for developing the next generation of hydrogen catalysts. 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.},
doi = {10.1021/jz3020277},
journal = {The Journal of Physical Chemistry Letters, 4(3):542-546},
number = ,
volume = ,
place = {United States},
year = {2013},
month = {2}
}