Iron sulfide-catalyzed gaseous CO2 reduction and prebiotic carbon fixation in terrestrial hot springs

Understanding abiotic carbon fixation provides insights into early Earth's carbon cycles and life's emergence in terrestrial hot springs, where iron sulfide (FeS), similar to cofactors in metabolic enzymes, may catalyze prebiotic synthesis. However, the role of FeS-mediated carbon fixation in such conditions remains underexplored. Here, we investigate the catalytic behaviors of FeS (pure and doped with Ti, Ni, Mn, and Co), which are capable of H2-driven CO2 reduction to methanol under simulated hot spring vapor-zone conditions, using an anaerobic flow chamber connected to a gas chromatograph. Specifically, Mn-doped FeS increases methanol production five-fold at 120 degrees C, with UV-visible light (300-720 nm) and UV-enhanced light (200-600 nm) further increasing this activity. Operando and theoretical investigations indicate the mechanism involves a reverse water-gas shift with CO as an intermediate. These findings highlight the potential of FeS-catalyzed carbon fixation in early Earth's terrestrial hot springs, effective with or without UV light. Simulation experiments conducted at 80-120 degrees C under UV-visible light demonstrate FeS-catalyzed gaseous CO2 reduction, providing new insights into prebiotic carbon fixation mechanisms and the origins of life in terrestrial hot spring environments.