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Title: Development of Earth-Abundant Transition Metal Compounds for Water Oxidation

Abstract

Our initial work on this project posited that late 3d transition metals such as Co could be be used as catalysts for water oxidation when bound to fluorinated, oxygen-donor ligands. Prior work had focused primarily on hydrogenated N-donor ligands and precious metals such as Ru and Ir. The O-donor environment is well-known from Photosystem II in green plants and from bulk oxides used as heterogeneous water-oxidation catalysis, but, except for Mn, lacked small molecule models to decipher the chemistry. Fluorinated ligands provide an oxidation-resistant “teflon” coating of the pre-catalysts, so that the O-donating surroundings can be maintained under strongly oxidizing conditions. Our work has been successful in several important areas: (i) synthesis of a large and flexible family of water-soluble, late transition metal, perfluoropinacolate (pinF) compounds, (ii) structural characterization of five-coordinate water adducts for Co and Ni, (iii) demonstration of homogeneous electrochemical water oxidation catalysis by the [Co(OHx)(pinF)2]n- system, (iv) development of new strategy for inhibition of heterogeneous MOx formation by using the complex ligand as the buffer, (v) comparative spectroscopic and electrochemical studies of the [Ni(OHx)(pinF)2]n- system, and (vi) discovery of water and nitrate reduction catalysis from [Cu(pinF)2]2-.

Authors:
ORCiD logo
Publication Date:
Research Org.:
Boston University
Sponsoring Org.:
USDOE
OSTI Identifier:
1489778
Report Number(s):
DE-SC0007055
DOE Contract Number:  
SC0007055
Resource Type:
Technical Report
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Doerrer, Linda H. Development of Earth-Abundant Transition Metal Compounds for Water Oxidation. United States: N. p., 2019. Web. doi:10.2172/1489778.
Doerrer, Linda H. Development of Earth-Abundant Transition Metal Compounds for Water Oxidation. United States. doi:10.2172/1489778.
Doerrer, Linda H. Tue . "Development of Earth-Abundant Transition Metal Compounds for Water Oxidation". United States. doi:10.2172/1489778. https://www.osti.gov/servlets/purl/1489778.
@article{osti_1489778,
title = {Development of Earth-Abundant Transition Metal Compounds for Water Oxidation},
author = {Doerrer, Linda H},
abstractNote = {Our initial work on this project posited that late 3d transition metals such as Co could be be used as catalysts for water oxidation when bound to fluorinated, oxygen-donor ligands. Prior work had focused primarily on hydrogenated N-donor ligands and precious metals such as Ru and Ir. The O-donor environment is well-known from Photosystem II in green plants and from bulk oxides used as heterogeneous water-oxidation catalysis, but, except for Mn, lacked small molecule models to decipher the chemistry. Fluorinated ligands provide an oxidation-resistant “teflon” coating of the pre-catalysts, so that the O-donating surroundings can be maintained under strongly oxidizing conditions. Our work has been successful in several important areas: (i) synthesis of a large and flexible family of water-soluble, late transition metal, perfluoropinacolate (pinF) compounds, (ii) structural characterization of five-coordinate water adducts for Co and Ni, (iii) demonstration of homogeneous electrochemical water oxidation catalysis by the [Co(OHx)(pinF)2]n- system, (iv) development of new strategy for inhibition of heterogeneous MOx formation by using the complex ligand as the buffer, (v) comparative spectroscopic and electrochemical studies of the [Ni(OHx)(pinF)2]n- system, and (vi) discovery of water and nitrate reduction catalysis from [Cu(pinF)2]2-.},
doi = {10.2172/1489778},
journal = {},
number = ,
volume = ,
place = {United States},
year = {2019},
month = {1}
}