The ground‐state deprotection of a simple alkynylsilane is studied under vibrational strong coupling to the zero‐point fluctuations, or vacuum electromagnetic field, of a resonant IR microfluidic cavity. The reaction rate decreased by a factor of up to 5.5 when the Si−C vibrational stretching modes of the reactant were strongly coupled. The relative change in the reaction rate under strong coupling depends on the Rabi splitting energy. Product analysis by GC‐MS confirmed the kinetic results. Temperature dependence shows that the activation enthalpy and entropy change significantly, suggesting that the transition state is modified from an associative to a dissociative type. These findings show that vibrational strong coupling provides a powerful approach for modifying and controlling chemical landscapes and for understanding reaction mechanisms.

Life builds its molecules from CO2 and breaks them down to CO2 again through the intermediacy of just five metabolites that act as the hubs of biochemistry.1 However, how core biological metabolism initiated and why it uses the intermediates, reactions and pathways that it does remains unclear. Here, we describe a purely chemical reaction network promoted by Fe2+ in which aqueous pyruvate and glyoxylate, two products of abiotic CO2 reduction,2–4 build up nine of the eleven Krebs (tricarboxylic acid, TCA) cycle intermediates, including all five universal metabolic precursors. The intermediates simultaneously break down to CO2 in a life-like regime resembling biological anabolism and catabolism.5 Adding hydroxylamine6–8 and Fe0 into the system produces four biological amino acids in a manner paralleling biosynthesis. The observed network significantly overlaps the Krebs and glyoxylate cycles9,10 and may represent a prebiotic precursor to these core metabolic pathways.

Autotrophic theories for the origin of life propose that CO2 was the carbon source for primordial biosynthesis. Among the six known CO2 fixation pathways in nature, the acetyl CoA (or Wood-Ljungdahl) pathway is the most ancient, and relies on transition metals for catalysis. Modern microbes that use the acetyl CoA pathway typically fix CO2 with electrons from H2, which requires complex flavin-based electron bifurcation. This presents a paradox: How could primitive metabolic systems have fixed CO2 before the origin of proteins? Here we show that native transition metals (Fe0, Ni0, Co0) selectively reduce CO2 to acetate and pyruvate, the intermediates and end-products of the AcCoA pathway, in near mM levels in water over hours to days using 1-40 bar CO2 and at temperatures from 30-100 °C. Geochemical CO2 fixation from native metals could have supplied critical C2 and C3 metabolites before the emergence of enzymes.

Three iron minerals found in alkaline hydrothermal vents are shown to convert CO2 and H2 into formate, acetate and pyruvate in water, suggesting that such reactions could have paved the way for early metabolism.