skip to main content
OSTI.GOV title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Electrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand

Authors:
 [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Department of Chemistry, Yale University, New Haven, Connecticut 06520, United States; Yale Energy Sciences Institute, Yale University, West Haven, Connecticut 06516, United States
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Argonne-Northwestern Solar Energy Research Center (ANSER)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1388131
DOE Contract Number:
SC0001059
Resource Type:
Journal Article
Resource Relation:
Journal Name: ACS Catalysis; Journal Volume: 7; Journal Issue: 5; Related Information: ANSER partners with Northwestern University (lead); Argonne National Laboratory; University of Chicago; University of Illinois, Urbana-Champaign; Yale University
Country of Publication:
United States
Language:
English
Subject:
catalysis (homogeneous), catalysis (heterogeneous), solar (photovoltaic), solar (fuels), photosynthesis (natural and artificial), bio-inspired, hydrogen and fuel cells, electrodes - solar, defects, charge transport, spin dynamics, membrane, materials and chemistry by design, optics, synthesis (novel materials), synthesis (self-assembly)

Citation Formats

Fisher, Katherine J., Materna, Kelly L., Mercado, Brandon Q., Crabtree, Robert H., and Brudvig, Gary W.. Electrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand. United States: N. p., 2017. Web. doi:10.1021/acscatal.7b00494.
Fisher, Katherine J., Materna, Kelly L., Mercado, Brandon Q., Crabtree, Robert H., & Brudvig, Gary W.. Electrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand. United States. doi:10.1021/acscatal.7b00494.
Fisher, Katherine J., Materna, Kelly L., Mercado, Brandon Q., Crabtree, Robert H., and Brudvig, Gary W.. Wed . "Electrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand". United States. doi:10.1021/acscatal.7b00494.
@article{osti_1388131,
title = {Electrocatalytic Water Oxidation by a Copper(II) Complex of an Oxidation-Resistant Ligand},
author = {Fisher, Katherine J. and Materna, Kelly L. and Mercado, Brandon Q. and Crabtree, Robert H. and Brudvig, Gary W.},
abstractNote = {},
doi = {10.1021/acscatal.7b00494},
journal = {ACS Catalysis},
number = 5,
volume = 7,
place = {United States},
year = {Wed Apr 12 00:00:00 EDT 2017},
month = {Wed Apr 12 00:00:00 EDT 2017}
}
  • Electrochemical water splitting requires efficient water oxidation catalysts to accelerate the sluggish kinetics of water oxidation reaction. Here in this paper, we report a promisingly dendritic core-shell nickel-iron-copper metal/metal oxide electrode, prepared via dealloying with an electrodeposited nickel-iron-copper alloy as a precursor, as the catalyst for water oxidation. The as-prepared core-shell nickel-iron-copper electrode is characterized with porous oxide shells and metallic cores. This tri-metal-based core-shell nickel-iron-copper electrode exhibits a remarkable activity toward water oxidation in alkaline medium with an overpotential of only 180 mV at a current density of 10 mA cm -2. The core-shell NiFeCu electrode exhibits pH-dependent oxygenmore » evolution reaction activity on the reversible hydrogen electrode scale, suggesting that non-concerted proton-electron transfers participate in catalyzing the oxygen evolution reaction. To the best of our knowledge, the as-fabricated core-shell nickel-iron-copper is one of the most promising oxygen evolution catalysts.« less
  • A nickel bis(diphosphine) complex containing proton relays in the second and outer coordination spheres, Ni(PCy2N(CH2)2OMe)2, (PCy2N(CH2)2OMe = 1,5-di(methoxyethyl)-3,7-dicyclohexyl-1,5-diaza-3,7-diphosphacyclooctane), is an electrocatalyst for hydrogen oxidation. The addition of hydrogen to the Ni(II) complex results in rapid formation of three isomers of the doubly protonated Ni(0) complex, [Ni(PCy2N(CH2)2OMe2H)2]2+. The three isomers show fast intramolecular interconversion at 40 °C, unique to this complex in this class of catalysts. Under conditions of 1.0 atm H2 using H2O as a base, catalytic oxidation proceeds at a turnover frequency of 5 s -1 and an overpotential of 720 mV, as determined from the potential at halfmore » of the catalytic current. Compared to the previously reported Ni(PCy2NBn)2 complex, the new complex operates at a faster rate and at a lower overpotential. The results of this study indicate that the presence of the pendant methoxy group in the outer coordination sphere of the catalyst plays a key role, facilitating intramolecular proton movement prior to intermolecular proton removal required to complete the catalytic cycle. 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.« less