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While exploring the process of CO/CO2 electroreduction (COxRR) is of great significance to achieve carbon recycling, deciphering reaction mechanisms so as to further design catalytic systems able to overcome sluggish kinetics remains challenging. In this work, a model single-Co-atom catalyst with well-defined coordination structure is developed and employed as a platform to unravel the underlying reaction mechanism of COxRR. The as-prepared single-Co-atom catalyst exhibits a maximum methanol Faradaic efficiency as high as 65% at 30 mA/cm2 in a membrane electrode assembly electrolyzer, while on the contrary, the reduction pathway of CO2 to methanol is strongly decreased in CO2RR. In-situ X-ray absorption and Fourier-transform infrared spectroscopies point to a different adsorption configuration of *CO intermediate in CORR as compared to that in CO2RR, with a weaker stretching vibration of the C–O bond in the former case. Theoretical calculations further evidence the low energy barrier for the formation of a H-CoPc-CO– species, which is a critical factor in promoting the electrochemical reduction of CO to methanol. Deciphering the reaction mechanisms of CO/CO2 electroreduction to methanol remains challenging. Here the authors report the higher electron density of single-Co-atom center, along with a different adsorption configuration of *CO, is crucial for promoting the CO electroreduction to methanol. [ABSTRACT FROM AUTHOR]

Electroreduction uses renewable energy to upgrade carbon dioxide to value-added chemicals and fuels. Renewable methane synthesized using such a route stands to be readily deployed using existing infrastructure for the distribution and utilization of natural gas. Here we design a suite of ligand-stabilized metal oxide clusters and find that these modulate carbon dioxide reduction pathways on a copper catalyst, enabling thereby a record activity for methane electroproduction. Density functional theory calculations show adsorbed hydrogen donation from clusters to copper active sites for the *CO hydrogenation pathway towards *CHO. We promote this effect via control over cluster size and composition and demonstrate the effect on metal oxides including cobalt(II), molybdenum(VI), tungsten(VI), nickel(II) and palladium(II) oxides. We report a carbon dioxide-to-methane faradaic efficiency of 60% at a partial current density to methane of 135 milliampere per square centimetre. We showcase operation over 18 h that retains a faradaic efficiency exceeding 55%. Electroreduction uses renewable energy to upgrade carbon dioxide to value-added chemicals and fuels. Here, the authors design a suite of ligand-stabilized metal oxide clusters to modulate the reduction pathways on a copper catalyst, enabling record activity for CO2-to-methane conversion. [ABSTRACT FROM AUTHOR]

While exploring the process of CO/CO 2 electroreduction (CO x RR) is of great significance to achieve carbon recycling, deciphering reaction mechanisms so as to further design catalytic systems able to overcome sluggish kinetics remains challenging. In this work, a model single-Co-atom catalyst with well-defined coordination structure is developed and employed as a platform to unravel the underlying reaction mechanism of CO x RR. The as-prepared single-Co-atom catalyst exhibits a maximum methanol Faradaic efficiency as high as 65% at 30 mA/cm 2 in a membrane electrode assembly electrolyzer, while on the contrary, the reduction pathway of CO 2 to methanol is strongly decreased in CO 2 RR. In-situ X-ray absorption and Fourier-transform infrared spectroscopies point to a different adsorption configuration of *CO intermediate in CORR as compared to that in CO 2 RR, with a weaker stretching vibration of the C-O bond in the former case. Theoretical calculations further evidence the low energy barrier for the formation of a H-CoPc-CO - species, which is a critical factor in promoting the electrochemical reduction of CO to methanol., (© 2023. The Author(s).)

Renewable CH 4 produced from electrocatalytic CO 2 reduction is viewed as a sustainable and versatile energy carrier, compatible with existing infrastructure. However, conventional alkaline and neutral CO 2 -to-CH 4 systems suffer CO 2 loss to carbonates, and recovering the lost CO 2 requires input energy exceeding the heating value of the produced CH 4 . Here we pursue CH 4 -selective electrocatalysis in acidic conditions via a coordination method, stabilizing free Cu ions by bonding Cu with multidentate donor sites. We find that hexadentate donor sites in ethylenediaminetetraacetic acid enable the chelation of Cu ions, regulating Cu cluster size and forming Cu-N/O single sites that achieve high CH 4 selectivity in acidic conditions. We report a CH 4 Faradaic efficiency of 71% (at 100 mA cm -2 ) with <3% loss in total input CO 2 that results in an overall energy intensity (254 GJ/tonne CH 4 ), half that of existing electroproduction routes., (© 2023. The Author(s).)