Iron-sulfur (Fe-S) clusters are an emerging class of compounds that facilitate the reduction of C 1 substrates such as CO, CO 2 , and CN – into hydrocarbons. In this work, we report heterogeneous materials composed of the synthetic Fe-S cluster Fe 4 S 4 (STip) 2 (tmtu) 2 (Tip = 2,4,6- i Pr 3 C 6 H 2 , tmtu = tetramethylthiourea) supported on bipyridine-functionalized periodic mesoporous organosilica. Under 1 atm of CO at ambient temperature, using H 2 O as a proton source and SmI 2 as a reducing agent, these hybrid materials catalyzed the conversion of CO into hydrocarbons with an efficiency of 21% based on SmI 2 , and they outperformed the Fe 4 S 4 precursor. While the hybrid materials showed limited catalytic activity for the conversion of CO 2 into hydrocarbons, their combination with rhenium-carbonyl complexes immobilized on bipyridine-functionalized silica achieved ~8% efficiency in CO 2 -to-hydrocarbon conversion. The silica-supported Fe-S clusters remained active for at least four catalytic runs in the CO reduction. • Catalytic CO reduction by a silica-supported iron-sulfur (Fe-S) cluster • Immobilization of an Fe 4 S 4 cluster on bipyridine-functionalized PMO • CO 2 -to-hydrocarbon conversion using immobilized Fe 4 S 4 and Re-carbonyl catalysts • Catalytic activity retained over at least four catalytic runs
Jayakumar et al. (Fri,) studied this question.