Mechanistic insight into molecular catalysts during electrocatalytic reduction of oxygen and carbon dioxide
Physical Chemistry of Molecules, Liquids and Interfaces, Biophysical Chemistry
Final Report Abstract
The electrocatalytic reduction of oxygen, protons and carbon dioxide are key processes for the sustainable production and conversion of green fuels. In nature, enzymes with atomically defined active sites catalyze these reactions. In these systems, the catalytic centers often have a so-called "second coordination sphere", which enables them to interact with a second metal atom and/or other protonatable groups during catalysis. As part of the project "Mechanistic insights into molecular catalysts in the electrocatalytic reduction of oxygen and carbon dioxide", the influence of such a second coordination sphere on electrocatalytic reduction reactions of molecular porphyrin complexes was investigated. For this purpose, porphyrin complexes with different metal centres, linker molecules and functional groups were synthesized and investigated. It was shown that the presence of a second coordination sphere could improve the catalytic activity by a factor of up to 100. The catalysts were also immobilized on specifically functionalized electrodes and their structure analyzed under electrochemical potential using Raman spectrochemistry. The results not only provided information on the interaction of molecular compounds with different electrode materials, but also identified intermediate stages in the catalytic conversion of small molecules. The results presented here can therefore contribute to the development of optimized catalytic systems in the future.
Publications
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Influence of Mesityl and Thiophene Peripheral Substituents on Surface Attachment, Redox Chemistry, and ORR Activity of Molecular Iron Porphyrin Catalysts on Electrodes. Inorganic Chemistry, 58(16), 10637-10647.
Götz, Robert; Ly, Khoa H.; Wrzolek, Pierre; Dianat, Arezoo; Croy, Alexander; Cuniberti, Giancarlo; Hildebrandt, Peter; Schwalbe, Matthias & Weidinger, Inez M.
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An Iron Porphyrin Complex with Pendant Pyridine Substituents Facilitates Electrocatalytic CO2 Reduction via Second Coordination Sphere Effects. ChemCatChem, 13(18), 3934-3944.
Ramuglia, Anthony R.; Budhija, Vishal; Ly, Khoa H.; Marquardt, Michael; Schwalbe, Matthias & Weidinger, Inez M.
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Structural Determination of an Unusual CuI‐Porphyrin‐π‐Bond in a Hetero‐Pacman Cu‐Zn‐Complex. Chemistry – A European Journal, 27(12), 3991-3996.
Marquardt, Michael; Cula, Beatrice; Budhija, Vishal; Dallmann, André & Schwalbe, Matthias
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Understanding active sites in molecular (photo)electrocatalysis through complementary vibrational spectroelectrochemistry. Chemical Communications, 57(19), 2328-2342.
Ly, Khoa H. & Weidinger, Inez M.
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Potential Induced Protonation of the Second Coordination Sphere in a Hangman-type Iron Porphyrin Complex Promotes HER: Insights via in Situ Raman Spectroelectrochemistry. Inorganic Chemistry, 62(26), 10232-10240.
Ramuglia, Anthony R.; Göbel, Markus; Budhija, Vishal; Werheid, Matthias; Ly, Khoa H.; Schwalbe, Matthias & Weidinger, Inez M.
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Proton Activation in the Presence of a Weak Acid Facilitated by Second Coordination Sphere Effects in Iron Porphyrins**. ChemElectroChem, 10(23).
Ramuglia, Anthony R.; Budhija, Vishal; Ly, Khoa H.; Schwalbe, Matthias & Weidinger, Inez M.
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Synthesis, Properties and Reactivity Studies of a Hetero‐dicopper Complex Consisting of a Porphyrin and a Bispyridylamine Moiety Connected by a Xanthene Backbone. European Journal of Inorganic Chemistry, 26(14).
Budhija, Vishal; van Langevelde, Phebe H.; Krause, Konstantin B.; Cula, Beatrice; Hetterscheid, D. G. H. & Schwalbe, Matthias
