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Homogeneous Photocatalytic Reduction of CO 2 to CO Using Iron(0) Porphyrin Catalysts: Mechanism and Intrinsic Limitations
Author(s) -
Bonin Julien,
Chaussemier Marie,
Robert Marc,
Routier Mathilde
Publication year - 2014
Publication title -
chemcatchem
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.497
H-Index - 106
eISSN - 1867-3899
pISSN - 1867-3880
DOI - 10.1002/cctc.201402515
Subject(s) - catalysis , porphyrin , photocatalysis , selectivity , photochemistry , tetraphenylporphyrin , chemistry , homogeneous catalysis , turnover number , solvent , degradation (telecommunications) , organic chemistry , telecommunications , computer science
A photochemical catalytic reduction of CO 2 was performed in an organic solvent with iron(0) porphyrins as homogeneous molecular catalysts under visible light irradiation. With modified tetraphenylporphyrins consisting of internal phenolic groups, the photochemical process led to the production of CO, with H 2 as a minor product. High catalytic selectivity for CO formation and turnover numbers up to 30 were obtained. Degradation of the catalyst occurred at longer irradiation times, along with decreased selectivity. Furthermore, addition of a weak acid, which increased the reduction efficiency under electrochemical conditions, led to rapid deactivation of the catalyst. With the unmodified tetraphenylporphyrin as catalyst, we observed lower performance and higher proportion of H 2 , which highlighted differences in the reduction pathways followed. A combination of a spectroscopic study and product analysis performed under various conditions led to detailed reduction mechanisms and helped pave the way for designing durable photocatalytic systems.