Effects of Silica Modification (Mg, Al, Ca, Ti, and Zr) on Supported Cobalt Catalysts for H 2 -Dependent CO 2 Reduction to Metabolic Intermediates.

Serpentinizing hydrothermal systems generate H ₂ as a reductant and harbor catalysts conducive to geochemical CO ₂ conversion into reduced carbon compounds that form the core of microbial autotrophic metabolism. This study characterizes mineral catalysts at hydrothermal vents by investigating the interactions between catalytically active cobalt sites and silica-based support materials on H ₂ -dependent CO ₂ reduction. Heteroatom incorporated (Mg, Al, Ca, Ti, and Zr), ordered mesoporous silicas are applied as model support systems for the cobalt-based catalysts. It is demonstrated that all catalysts surveyed convert CO ₂ to methane, methanol, carbon monoxide, and low-molecular-weight hydrocarbons at 180 °C and 20 bar, but with different activity and selectivity depending on the support modification. The additional analysis of the condensed product phase reveals the formation of oxygenates such as formate and acetate, which are key intermediates in the ancient acetyl-coenzyme A pathway of carbon metabolism. The Ti-incorporated catalyst yielded the highest concentrations of formate (3.6 mM) and acetate (1.2 mM) in the liquid phase. Chemisorption experiments including H ₂ temperature-programmed reduction (TPR) and CO ₂ temperature-programmed desorption (TPD) in agreement with density functional theory (DFT) calculations of the adsorption energy of CO ₂ suggest metallic cobalt as the preferential adsorption site for CO ₂ compared to hardly reducible cobalt-metal oxide interface species. The ratios of the respective cobalt species vary depending on the interaction strength with the support materials. The findings reveal robust and biologically relevant catalytic activities of silica-based transition metal minerals in H ₂ -rich CO ₂ fixation, in line with the idea that autotrophic metabolism emerged at hydrothermal vents.