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Selective Ligand Modification of Cobalt Porphyrins for Carbon Dioxide Electrolysis: Generation of a Renewable H2/CO Feedstock for Downstream Catalytic Hydrogenation

Journal Article · · Inorganica Chimica Acta
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Catalytic hydrogenation is an attractive approach to produce green fuels and chemicals. The building blocks for these processes may be effectively produced from renewable power via direct electrochemical reduction of carbon dioxide in an aqueous media. For the first time, the impact of increasing the local proton concentration of cobalt porphyrin was examined by synthesizing new cobalt porphyrins 2, Co(o-OCH3)TPP and cobalt porphyrin 3, Co(o-OH)TPP. Cobalt porphyrins coated on carbon paper converted carbon dioxide and water into a mixture of hydrogen and carbon monoxide in an aqueous electrolyte at near neutral pH. Increasing the local proton availability of the commercial cobalt porphyrin 1, accelerates hydrogen generation under heterogeneous conditions across the range of potentials tested (-0.85 to -1.5 V vs. Ag/AgCl) and demonstrates high Faradaic efficiencies (ca. 90%) at low over-potentials (ca. 540 mV). The culmination of this work can help identify key parameters that facilitate generation of sustainable reagents for catalytic hydrogenation under practical and scalable conditions.
Research Organization:
National Renewable Energy Laboratory (NREL), Golden, CO (United States)
Sponsoring Organization:
USDOE Office of Energy Efficiency and Renewable Energy (EERE)
DOE Contract Number:
AC36-08GO28308
OSTI ID:
1660083
Report Number(s):
NREL/JA-2700-77336; MainId:26282; UUID:93fc76fc-d53b-4825-ab8a-548ba6766c19; MainAdminID:14064
Journal Information:
Inorganica Chimica Acta, Journal Name: Inorganica Chimica Acta Vol. 507
Country of Publication:
United States
Language:
English

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Related Subjects

BIOMASS FUELS,INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
catalytic hydrogenation
electrocatalytic CO2 reduction
heterogeneous electrocatalysis
local proton source
modified ligand porphyrin