Nitrate is a pervasive aquatic contaminant of global environmental concern. In nature, the most effective nitrate reduction reaction (NRR) is catalyzed by nitrate reductase enzymes at neutral pH, using a highly‐conserved Mo center ligated mainly by oxo and thiolate groups. Mo‐based NRR catalysts mostly function in organic solvents with a low water stability. Recently, an oxo‐containing molybdenum sulfide nanoparticle that serves as an NRR catalyst at neutral pH was first reported. Herein, in a nanoparticle‐catalyzed NRR system a pentavalent MoV(=O)S4 species, an enzyme mimetic, served as an active intermediate for the NRR. Potentiometric titration analysis revealed that a redox synergy among MoV−S, S radicals, and MoV(=O)S4 likely play a key role in stabilizing MoV(=O)S4, showing the importance of secondary interactions in facilitating NRR. The first identification and characterization of an oxo‐ and thiolate‐ligated Mo intermediates pave the way to the molecular design of efficient enzyme mimetic NRR catalysts in aqueous solution.

Abiotic CO2 reduction on transition metal minerals has been proposed to account for the synthesis of organic compounds in alkaline hydrothermal systems, but this reaction lacks experimental support, as only short-chain hydrocarbons (<C5) have been synthesized in artificial simulation. This presents a question: What particular hydrothermal conditions favor long-chain hydrocarbon synthesis? Here, we demonstrate the hydrothermal bicarbonate reduction at ∼300 °C and 30 MPa into long-chain hydrocarbons using iron (Fe) and cobalt (Co) metals as catalysts. We found the Co0 promoter responsible for synthesizing long-chain hydrocarbons to be extraordinarily stable when coupled with Fe−OH formation. Under these hydrothermal conditions, the traditional water-induced deactivation of Co is inhibited by bicarbonate-assisted CoOx reduction, leading to honeycomb-native Co nanosheets generated in situ as a new motif. The Fe−OH formation, confirmed by operando infrared spectroscopy, enhances CO adsorption on Co, thereby favoring further reduction to long-chain hydrocarbons (up to C24). These results not only advance theories for an abiogenic origin for some petroleum accumulations and the hydrothermal hypothesis of the emergence of life but also introduce an approach for synthesizing long-chain hydrocarbons by nonnoble metal catalysts for artificial CO2 utilization.

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The development of denitrification catalysts which can reduce nitrate and nitrite to dinitrogen is critical for sustaining the nitrogen cycle. However, regulating the selectivity has proven to be a challenge, due to the difficulty of controlling complex multielectron/proton reactions. Here we report that utilizing sequential proton-electron transfer (SPET) pathways is a viable strategy to enhance the selectivity of electrochemical reactions. The selectivity of an oxo-molybdenum sulfide electrocatalyst toward nitrite reduction to dinitrogen exhibited a volcano-type pH dependence with a maximum at pH 5. The pH-dependent formation of the intermediate species (distorted Mo(V) oxo species) identified using operando electron paramagnetic resonance (EPR) and Raman spectroscopy was in accord with a mathematical prediction that the pK of the reaction intermediates determines the pH-dependence of the SPET-derived product. By utilizing this acute pH dependence, we achieved a Faradaic efficiency of 13.5% for nitrite reduction to dinitrogen, which is the highest value reported to date under neutral conditions.