Electrochemical reduction of carbon dioxide (CO2) into chemicals and fuels has recently attracted much interest, but normally suffers from a high overpotential and low selectivity. In this work, single P atoms were introduced into a N‐doped carbon supported single Fe atom catalyst (Fe‐SAC/NPC) mainly in the form of P−C bonds for CO2 electroreduction to CO in an aqueous solution. This catalyst exhibited a CO Faradaic efficiency of ≈97 % at a low overpotential of 320 mV, and a Tafel slope of only 59 mV dec−1, comparable to state‐of‐the‐art gold catalysts. Experimental analysis combined with DFT calculations suggested that single P atom in high coordination shells (n≥3), in particular the third coordination shell of Fe center enhanced the electronic localization of Fe, which improved the stabilization of the key *COOH intermediate on Fe, leading to superior CO2 electrochemical reduction performance at low overpotentials.

Electrochemical carbon dioxide (CO 2 ) conversion is promising to balance the carbon cycle for human society. However, an efficient electrocatalyst is the key to determine the selective conversion of CO 2 toward valuable products. We report herein an efficient La 2 CuO 4 perovskite catalyst for electrochemical CO 2 reduction. A high Faradaic efficiency of 56.3% with a partial current density of 117 mA cm −2 is achieved for methane production over this perovskite catalyst at −1.4 V (vs RHE). The results demonstrate that the structural evolution of La 2 CuO 4 perovskite takes place simultaneously during the cathodic CO 2 reduction process. Theoretical investigations further unravel that the emerging Cu/La 2 CuO 4 interface accounts for the CO 2 methanation behaviors. This work provides an effective perovskite electrocatalyst for ambient CO 2 methanation and offers a valuable understanding of the structure evolution and surface reconstruction of precatalysts in catalytic reactions for energy-relevant technologies.

The exploitation of highly efficient carbon dioxide reduction (CO2RR) electrocatalyst for methane (CH4) electrosynthesis has attracted great attention for the intermittent renewable electricity storage but remains challenging. Here, N‐heterocyclic carbene (NHC)‐ligated copper single atom site (Cu SAS) embedded in metal–organic framework is reported (2Bn‐Cu@UiO‐67), which can achieve an outstanding Faradaic efficiency (FE) of 81 % for the CO2 reduction to CH4 at −1.5 V vs. RHE with a current density of 420 mA cm−2. The CH4 FE of our catalyst remains above 70 % within a wide potential range and achieves an unprecedented turnover frequency (TOF) of 16.3 s−1. The σ donation of NHC enriches the surface electron density of Cu SAS and promotes the preferential adsorption of CHO* intermediates. The porosity of the catalyst facilitates the diffusion of CO2 to 2Bn‐Cu, significantly increasing the availability of each catalytic center.

The renewable energy-powered electrolytic reduction of carbon dioxide (CO2) to methane (CH4) using water as a reaction medium is one of the most promising paths to store intermittent renewable energy and address global energy and sustainability problems. However, the role of water in the electrolyte is often overlooked. In particular, the slow water dissociation kinetics limits the proton-feeding rate, which severely damages the selectivity and activity of the methanation process involving multiple electrons and protons transfer. Here, we present a novel tandem catalyst comprising Ir single-atom (Ir1)-doped hybrid Cu3N/Cu2O multisite that operates efficiently in converting CO2 to CH4. Experimental and theoretical calculation results reveal that the Ir1 facilitates water dissociation into proton and feeds to the hybrid Cu3N/Cu2O sites for the *CO protonation pathway toward *CHO. The catalyst displays a high Faradaic efficiency of 75% for CH4 with a current density of 320 mA cm–2 in the flow cell. This work provides a promising strategy for the rational design of high-efficiency multisite catalytic systems.

Single‐atom active‐site catalysts have attracted significant attention in the field of photocatalytic CO2 conversion. However, designing active sites for CO2 reduction and H2O oxidation simultaneously on a photocatalyst and combining the corresponding half‐reaction in a photocatalytic system is still difficult. Here, we synthesized a bimetallic single‐atom active‐site photocatalyst with two compatible active centers of Mn and Co on carbon nitride (Mn1Co1/CN). Our experimental results and density functional theory calculations showed that the active center of Mn promotes H2O oxidation by accumulating photogenerated holes. In addition, the active center of Co promotes CO2 activation by increasing the bond length and bond angle of CO2 molecules. Benefiting from the synergistic effect of the atomic active centers, the synthesized Mn1Co1/CN exhibited a CO production rate of 47 μmol g−1 h−1, which is significantly higher than that of the corresponding single‐metal active‐site photocatalyst.

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Precise design and tuning of the micro-atomic structure of single atom catalysts (SACs) can help efficiently adapt complex catalytic systems. Herein, we inventively found that when the active center of the main group element gallium (Ga) is downsized to the atomic level, whose characteristic has significant differences from conventional bulk and rigid Ga catalysts. The Ga SACs with a P, S atomic coordination environment display specific flow properties, showing CO products with FE of � 92 % at À 0.3 V vs. RHE in electrochemical CO 2 reduction (CO 2 RR). Theoretical simulations demonstrate that the adaptive dynamic transition of Ga optimizes the adsorption energy of the *COOH intermediate and renews the active sites in time, leading to excellent CO 2 RR selectivity and stability. This liquid single atom catalysts system with dynamic interfaces lays the foundation for future exploration of synthesis and catalysis.

Electrocatalytic conversion of carbon dioxide (CO2) is promising for balancing carbon cycles while producing value‐added feedstocks. Herein, ultrathin ZnIn2S4 nanosheets with abundant Zn vacancies are demonstrated for electrochemically reducing CO2 to formate. Specifically, a partial current density of 245 mA cm−2 with a near‐unity faradaic efficiency of 94 % for formate generation was achieved over the ultrathin ZnIn2S4 nanosheets in a flow cell configuration. Experimental and theoretical results revealed that abundant Zn vacancies in the ultrathin ZnIn2S4 nanosheets with a high electrochemically active surface area synergistically optimized the intermediate binding energy and contributed to the boosted selectivity and activity. This work may provide useful understandings in designing efficient catalysts for selective CO2 electroreduction.