Wächtershäuser’s proposal of the autotrophic origin of life theory and subsequent laboratory demonstrations of relevant organic reactions have opened a new gate for the exploration of the origin of life. However, this scenario remains controversial because, at present, it requires a high pressure of CO as a source of carbon and reducing energy, although CO must have been a trace C species on the Hadean Earth. We show that, simulating a geoelectrochemical environment in deep-sea hydrothermal fields, CO production with up to ~40% Faraday efficiency was attainable on CdS in CO₂-saturated NaCl solution at ≤–1 V (versus the standard hydrogen electrode). The threshold potential is readily generated in the H₂-rich, high-temperature, and alkaline hydrothermal vents that were probably widespread on the early komatiitic and basaltic ocean crust. Thus, Wächtershäuser’s scenario starting from CO₂ was likely to be realized in the Hadean ocean hydrothermal systems.

Prebiotic organic synthesis catalyzed by Earth-abundant metal sulfides is a key process for understanding the evolution of biochemistry from inorganic molecules, yet the catalytic functions of sulfides have remained poorly explored in the context of the origin of life. Past studies on prebiotic chemistry have mostly focused on a few types of metal sulfide catalysts, such as FeS or NiS, which form limited types of products with inferior activity and selectivity. To explore the potential of metal sulfides on catalyzing prebiotic chemical reactions, here, the chemical diversity (variations in chemical composition and phase structure) of 304 natural metal sulfide minerals in a mineralogy database was surveyed. Approaches to rationally predict the catalytic functions of metal sulfides are discussed based on advanced theories and analytical tools of electrocatalysis such as proton-coupled electron transfer, structural comparisons between enzymes and minerals, and in situ spectroscopy. To this end, we introduce a model of geoelectrochemistry driven prebiotic synthesis for chemical evolution, as it helps us to predict kinetics and selectivity of targeted prebiotic chemistry under “chemically messy conditions”. We expect that combining the data-mining of mineral databases with experimental methods, theories, and machine-learning approaches developed in the field of electrocatalysis will facilitate the prediction and verification of catalytic performance under a wide range of pH and Eh conditions, and will aid in the rational screening of mineral catalysts involved in the origin of life.

Significance: Molybdenum sulfide (MoS ₂ ) is the most studied two-dimensional (2D) material bar graphene. Current research on crystal-phase engineering focuses almost exclusively on the improvement of catalytic activity. However, the potential advantages of phase engineering toward regulation of selectivity control during multistep catalytic processes remain unexplored. Here, we report atomic-scale evidence on how metallic MoS ₂ shows significantly higher selectivity compared to the semiconducting phase during multielectron reduction of nitrite to nitrous oxide. Namely, a reaction intermediate specific to metallic MoS ₂ increases the selectivity by decoupling the proton and electron transfer steps. This has previously been shown to be a universal mechanism to enhance selectivity, and therefore, our work opens directions of the application of 2D materials toward selective electrocatalysis.