skip to main content

DOE PAGESDOE PAGES

Title: Synthetic control and empirical prediction of redox potentials for Co 4O 4 cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation

The oxo-cobalt cubane unit [Co 4O 4] is of interest as a homogeneous oxygen-evolution reaction (OER) catalyst, and as a functional mimic of heterogeneous cobalt oxide OER catalysts. The synthesis of several new cubanes allows evaluation of redox potentials for the [Co 4O 4] cluster, which are highly sensitive to the ligand environment and span a remarkable range of 1.42 V. The [Co III 4O 4] 4+/[Co III 3Co IVO 4 ]5+ and [Co III 3Co IVO 4] 5+/[Co III 2Co IV 2O 4] 6+ redox potentials are reliably predicted by the pKas of the ligands. Hydrogen bonding is also shown to significantly raise the redox potentials, by ~500 mV. The potential-p K a correlation is used to evaluate the feasibility of various proposed OER catalytic intermediates, including high-valent Co-oxo species. The synthetic methods and structure–reactivity relationships developed by these studies should better guide the design of new cubane-based OER catalysts.
Authors:
ORCiD logo [1] ;  [2] ; ORCiD logo [2] ; ORCiD logo [1] ;  [1]
  1. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  2. Univ. of California, Berkeley, CA (United States)
Publication Date:
Grant/Contract Number:
AC02-05CH11231
Type:
Accepted Manuscript
Journal Name:
Chemical Science
Additional Journal Information:
Journal Volume: 8; Journal Issue: 6; Journal ID: ISSN 2041-6520
Publisher:
Royal Society of Chemistry
Research Org:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
OSTI Identifier:
1379637

Nguyen, Andy I., Wang, Jianing, Levine, Daniel S., Ziegler, Micah S., and Tilley, T. Don. Synthetic control and empirical prediction of redox potentials for Co4O4 cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation. United States: N. p., Web. doi:10.1039/c7sc00627f.
Nguyen, Andy I., Wang, Jianing, Levine, Daniel S., Ziegler, Micah S., & Tilley, T. Don. Synthetic control and empirical prediction of redox potentials for Co4O4 cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation. United States. doi:10.1039/c7sc00627f.
Nguyen, Andy I., Wang, Jianing, Levine, Daniel S., Ziegler, Micah S., and Tilley, T. Don. 2017. "Synthetic control and empirical prediction of redox potentials for Co4O4 cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation". United States. doi:10.1039/c7sc00627f. https://www.osti.gov/servlets/purl/1379637.
@article{osti_1379637,
title = {Synthetic control and empirical prediction of redox potentials for Co4O4 cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation},
author = {Nguyen, Andy I. and Wang, Jianing and Levine, Daniel S. and Ziegler, Micah S. and Tilley, T. Don},
abstractNote = {The oxo-cobalt cubane unit [Co4O4] is of interest as a homogeneous oxygen-evolution reaction (OER) catalyst, and as a functional mimic of heterogeneous cobalt oxide OER catalysts. The synthesis of several new cubanes allows evaluation of redox potentials for the [Co4O4] cluster, which are highly sensitive to the ligand environment and span a remarkable range of 1.42 V. The [CoIII4O4]4+/[CoIII3CoIVO4]5+ and [CoIII3CoIVO4]5+/[CoIII2CoIV2O4]6+ redox potentials are reliably predicted by the pKas of the ligands. Hydrogen bonding is also shown to significantly raise the redox potentials, by ~500 mV. The potential-pKa correlation is used to evaluate the feasibility of various proposed OER catalytic intermediates, including high-valent Co-oxo species. The synthetic methods and structure–reactivity relationships developed by these studies should better guide the design of new cubane-based OER catalysts.},
doi = {10.1039/c7sc00627f},
journal = {Chemical Science},
number = 6,
volume = 8,
place = {United States},
year = {2017},
month = {4}
}