Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

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
; ; ; ; ;
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

References (23)

Directing Clostridium ljungdahlii fermentation products via hydrogen to carbon monoxide ratio in syngas journal May 2019
Recent Advances in Inorganic Heterogeneous Electrocatalysts for Reduction of Carbon Dioxide journal March 2016
Mechanisms of carbon monoxide hydrogenation yielding formaldehyde catalyzed by the representative strong mineral acid, H 2 SO 4 , and Lewis–Brønsted superacid, HF/AlF 3 journal January 2017
Electrochemical CO 2 Reduction to Hydrocarbons on a Heterogeneous Molecular Cu Catalyst in Aqueous Solution journal June 2016
Water Facilitated Electrochemical Reduction of CO 2 on Cobalt-Porphyrin Catalysts journal March 2019
DFT Study on the Mechanism of the Electrochemical Reduction of CO 2 Catalyzed by Cobalt Porphyrins journal February 2016
Making quantitative sense of electromicrobial production journal May 2019
Enhanced Catalytic Activity of Cobalt Porphyrin in CO 2 Electroreduction upon Immobilization on Carbon Materials journal May 2017
A new mechanism for the selectivity to C1 and C2 species in the electrochemical reduction of carbon dioxide on copper electrodes journal January 2011
Efficient electrocatalytic CO 2 reduction with a molecular cofacial iron porphyrin dimer journal January 2015
Catalysis of the Electrochemical Reduction of Carbon Dioxide by Iron(0) Porphyrins:  Synergystic Effect of Weak Brönsted Acids journal January 1996
Influence of Supporting Electrolyte on the Electrocatalysis of CO2 Reduction by Cobalt Protoporphyrin journal October 2018
Ultraefficient homogeneous catalyst for the CO 2 -to-CO electrochemical conversion journal October 2014
Molecular Catalysis of Electrochemical Reactions. Mechanistic Aspects journal July 2008
Catalysts and Reaction Pathways for the Electrochemical Reduction of Carbon Dioxide journal September 2015
Rh-Catalyzed Hydrogenation of CO 2 to Formic Acid in DMSO-based Reaction Media: Solved and Unsolved Challenges for Process Development journal October 2018
Status and perspectives of CO2 conversion into fuels and chemicals by catalytic, photocatalytic and electrocatalytic processes journal January 2013
Reticular Electronic Tuning of Porphyrin Active Sites in Covalent Organic Frameworks for Electrocatalytic Carbon Dioxide Reduction journal January 2018
Improving methanol synthesis from carbon-free H2 and captured CO2: A techno-economic and environmental evaluation journal March 2018
Ultraefficient selective homogeneous catalysis of the electrochemical reduction of carbon dioxide by an iron(0) porphyrin associated with a weak Broensted acid cocatalyst journal June 1994
High-Performance Carbon Dioxide Electrocatalytic Reduction by Easily Fabricated Large-Scale Silver Nanowire Arrays journal May 2018
Metal–organic framework-mediated strategy for enhanced methane production on copper nanoparticles in electrochemical CO2 reduction journal May 2019
Thermodynamic theory of multi-electron transfer reactions: Implications for electrocatalysis journal September 2011

Similar Records

Covalent organic frameworks comprising cobalt porphyrins for catalytic CO2 reduction in water
Journal Article · Wed Aug 19 20:00:00 EDT 2015 · Science · OSTI ID:1370752
Electrocatalysis of oxygen reduction. 5. Oxygen to hydrogen peroxide conversion by cobalt(II) tetrakis(N-methyl-4-pyridyl)porphyrin
Journal Article · Tue Nov 05 23:00:00 EST 1985 · Inorg. Chem.; (United States) · OSTI ID:6035976
Conductive polymeric porphyrin films: Application in the electrocatalytic oxidation of hydrazine
Journal Article · · Chemistry of Materials; (United States) · OSTI ID:7115561

Related Subjects

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