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Second‐Sphere Biomimetic Multipoint Hydrogen‐Bonding Patterns to Boost CO 2 Reduction of Iron Porphyrins
Author(s) -
Gotico Philipp,
Boitrel Bernard,
Guillot Régis,
Sircoglou Marie,
Quaranta Annamaria,
Halime Zakaria,
Leibl Winfried,
Aukauloo Ally
Publication year - 2019
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201814339
Subject(s) - overpotential , chemistry , carbon monoxide , hydrogen bond , molecule , adduct , porphyrin , catalysis , supramolecular chemistry , carbon monoxide dehydrogenase , hydrogen , photochemistry , selectivity , electrochemical reduction of carbon dioxide , coordination sphere , inorganic chemistry , crystallography , organic chemistry , electrochemistry , electrode
Inspired by nature's orchestra of chemical subtleties to activate and reduce CO 2 , we have developed a family of iron porphyrin derivatives in to which we have introduced urea groups functioning as multipoint hydrogen‐bonding pillars on the periphery of the porphyrinic ring. This structure closely resembles the hydrogen‐bond stabilization scheme of the carbon dioxide (CO 2 ) adduct in the carbon monoxide dehydrogenase (CODH). We found that such changes to the second coordination sphere significantly lowered the overpotential for CO 2 reduction in this family of molecular catalysts and importantly increased the CO 2 binding rate while maintaining high turnover frequency (TOF) and selectivity. Entrapped water molecules within the molecular clefts were found to be the source of protons for the CO 2 reduction.