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Title: Electroactive Co( iii ) salen metal complexes and the electrophoretic deposition of their porous organic polymers onto glassy carbon

Abstract

We discuss the CO 2 electroreduction properties of three bis-bromo Co(III) salen metal complexes and their Porous Organic Polymers (POPs) as a platform for using the salen core as a multi-electron reducing agent. Although Co(III) salen metal complexes have been studied extensively for their chemical catalysis with CO 2, their electrochemical behaviour, particularly their reduction, in the presence of CO 2 is much less explored. The discrete Co(III) complexes enabled the reduction of CO 2 to CO in faradaic efficiencies of up to 20%. The reductive electrochemical processes of Co(III) salen complexes are relatively unknown; therefore, the mechanism of reduction for the complexes was investigated using IR and UV-Vis-NIR spectroelectrochemical (SEC) techniques. The discrete bis-bromo salen complexes were incorporated into POPs with tris-(p-ethynyl)-triphenylamine as a co-ligand and were characterised using solid state NMR, IR, UV-Vis-NIR and Field Emission Scanning Electron Microscopy (FE-SEM). The POP materials were electrophoretically deposited onto glassy carbon under milder conditions than those previously reported in the literature. Direct attachment of the POP materials to glassy carbon enabled improved solid state electrochemical analysis of the samples. The POP materials were also assessed via SEC techniques, where a Co(II/I) process could be observed, but further reductions associated withmore » the imine reduction compromised the stability of the POPs.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]; ORCiD logo [1]; ORCiD logo [1]
  1. School of Chemistry, The University of Sydney, New South Wales 2006, Australia
  2. NMR Facility, Mark Wainwright Analytical Centre, The University of New South Wales, Australia
  3. Department of Chemistry and Biochemistry, University of California, San Diego, USA
Publication Date:
Research Org.:
Univ. of California, San Diego, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); Commonwealth Scientific and Industrial Research Organisation (CSIRO); National Science Foundation (NSF)
OSTI Identifier:
1458795
Alternate Identifier(s):
OSTI ID: 1547354
Grant/Contract Number:  
FG02-08ER46519; CHE-1145893
Resource Type:
Published Article
Journal Name:
RSC Advances
Additional Journal Information:
Journal Name: RSC Advances Journal Volume: 8 Journal Issue: 43; Journal ID: ISSN 2046-2069
Publisher:
Royal Society of Chemistry (RSC)
Country of Publication:
United Kingdom
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Solomon, Marcello B., Rawal, Aditya, Hook, James M., Cohen, Seth M., Kubiak, Clifford P., Jolliffe, Katrina A., and D'Alessandro, Deanna M. Electroactive Co( iii ) salen metal complexes and the electrophoretic deposition of their porous organic polymers onto glassy carbon. United Kingdom: N. p., 2018. Web. doi:10.1039/C8RA04385J.
Solomon, Marcello B., Rawal, Aditya, Hook, James M., Cohen, Seth M., Kubiak, Clifford P., Jolliffe, Katrina A., & D'Alessandro, Deanna M. Electroactive Co( iii ) salen metal complexes and the electrophoretic deposition of their porous organic polymers onto glassy carbon. United Kingdom. doi:10.1039/C8RA04385J.
Solomon, Marcello B., Rawal, Aditya, Hook, James M., Cohen, Seth M., Kubiak, Clifford P., Jolliffe, Katrina A., and D'Alessandro, Deanna M. Mon . "Electroactive Co( iii ) salen metal complexes and the electrophoretic deposition of their porous organic polymers onto glassy carbon". United Kingdom. doi:10.1039/C8RA04385J.
@article{osti_1458795,
title = {Electroactive Co( iii ) salen metal complexes and the electrophoretic deposition of their porous organic polymers onto glassy carbon},
author = {Solomon, Marcello B. and Rawal, Aditya and Hook, James M. and Cohen, Seth M. and Kubiak, Clifford P. and Jolliffe, Katrina A. and D'Alessandro, Deanna M.},
abstractNote = {We discuss the CO2 electroreduction properties of three bis-bromo Co(III) salen metal complexes and their Porous Organic Polymers (POPs) as a platform for using the salen core as a multi-electron reducing agent. Although Co(III) salen metal complexes have been studied extensively for their chemical catalysis with CO2, their electrochemical behaviour, particularly their reduction, in the presence of CO2 is much less explored. The discrete Co(III) complexes enabled the reduction of CO2 to CO in faradaic efficiencies of up to 20%. The reductive electrochemical processes of Co(III) salen complexes are relatively unknown; therefore, the mechanism of reduction for the complexes was investigated using IR and UV-Vis-NIR spectroelectrochemical (SEC) techniques. The discrete bis-bromo salen complexes were incorporated into POPs with tris-(p-ethynyl)-triphenylamine as a co-ligand and were characterised using solid state NMR, IR, UV-Vis-NIR and Field Emission Scanning Electron Microscopy (FE-SEM). The POP materials were electrophoretically deposited onto glassy carbon under milder conditions than those previously reported in the literature. Direct attachment of the POP materials to glassy carbon enabled improved solid state electrochemical analysis of the samples. The POP materials were also assessed via SEC techniques, where a Co(II/I) process could be observed, but further reductions associated with the imine reduction compromised the stability of the POPs.},
doi = {10.1039/C8RA04385J},
journal = {RSC Advances},
number = 43,
volume = 8,
place = {United Kingdom},
year = {2018},
month = {1}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
DOI: 10.1039/C8RA04385J

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