Prebiotic Synthesis of Microdroplets from Formate over a Bimetallic Cobalt–Nickel Nanomotif

The hypothesis underlying the abiogenic origin of life suggests that the nonenzymatic synthesis of long-chain fatty acids led to the construction of vesicles for compartmentalization in an early stage during the transition from geochemistry to biochemistry. However, evidence for this theory remains elusive as C5+ carboxylic acids cannot be synthesized using current laboratory simulations. Here, we report the synthesis of long-chain carboxylic acids (C3–C7) with a 42 mmol/gCo+Ni yield and 87.7% selectivity from formate (an intermediate of the acetyl-CoA pathway) over a cobalt–nickel alloy under alkaline hydrothermal conditions and the subsequent formation of microdroplets from organics. Density functional theory (DFT) calculations confirmed that the synergistic effect of the bimetal catalyst is key for catalyzing C–C coupling. Investigations by infrared spectroscopy, electron paramagnetic resonance, and isotope-labeled experiments revealed that HCO* serves as a reaction intermediate and is involved in the subsequent elementary steps for synthesizing long-chain carboxylic acids from formate. Taken together, these findings may help explain how the first protocells emerged geochemically and provide support for the hypothesis of the abiogenic origin of life. The hydrothermal system developed may also be applicable for the sustainable synthesis of long-chain carboxylates from one-carbon substrates using nonnoble metal catalysts.