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- Title
Catalytic CO<sub>2</sub> Reduction with Heptacoordinated Polypyridine Complexes: Switching the Selectivity via Metal Replacement.
- Authors
Droghetti, Federico; Amati, Agnese; Pascale, Fabien; Crochet, Aurélien; Pastore, Mariachiara; Ruggi, Albert; Natali, Mirco
- Abstract
The discovery of molecular catalysts for the CO2 reduction reaction (CO2RR) in the presence of water, which are both effective and selective towards the generation of carbon‐based products, is a critical task. Herein we report the catalytic activity towards the CO2RR in acetonitrile/water mixtures by a cobalt complex and its iron analog both featuring the same redox‐active ligand and an unusual seven‐coordination environment. Bulk electrolysis experiments show that the cobalt complex mainly yields formate (52 % selectivity at an applied potential of −2.0 V vs Fc+/Fc and 1 % H2O) or H2 (up to 86 % selectivity at higher applied bias and water content), while the iron complex always delivers CO as the major product (selectivity >74 %). The different catalytic behavior is further confirmed under photochemical conditions with the [Ru(bpy)3]2+ sensitizer (bpy=2,2'‐bipyridine) and N,N‐diisopropylethylamine as electron donor, where the cobalt complex leads to preferential H2 formation (up to 89 % selectivity), while the iron analog quantitatively generates CO (up to 88 % selectivity). This is ascribed to a preference towards a metal‐hydride vs. a metal‐carboxyl pathway for the cobalt and the iron complex, respectively, and highlights how metal replacement may effectively impact on the reactivity of transition metal complexes towards solar fuel formation.
- Subjects
ELECTRON donors; CATALYTIC reduction; IRON; ELECTROLYSIS; TRANSITION metal complexes; METALS; CATALYTIC activity
- Publication
ChemSusChem, 2024, Vol 17, Issue 4, p1
- ISSN
1864-5631
- Publication type
Article
- DOI
10.1002/cssc.202300737