Manufactoring of sustainable fuels like methanol could make a great sense to carbon neutrality，but most of the catalysts failed to generate methanol in room-temperature electrochemical CO2 reduction reaction (CO2RR), which was contrast from thermal catalytic CO2 hydrogenation. As revealed by theoretical calculations, the methanol formation pathway on Cu-based catalyst by electrochemical CO2RR involves the adsorption of a key reaction intermediate (*OCH3) to form Cu–O–C interaction on Cu surface. The subsequent breaking of the Cu–O or O–C bond leads to the formation of *OCH3 or *CH3 intermediate, respectively. Whereas, compared to the Cu–O interaction (&gt; 450 kJ mol-1), the O–C bond has a much lower dissociation enthalpy (~ 377 kJ mol-1) and is easier to break and form *CH3 and then CH4, instead of *OCH3 toward CH3OH. Herein, inspired by the hard-soft-acid-base (HSAB) theory, we first proposed that the CO2 electro-reduction selectivity toward methanol or methane can be switched by tuning the local electron state around the Cu catalytic sites. With a delocalized electron state in Cu site, electrochemical CO2 reduction exhibits a superior methanol selectivity (70%) with one of the highest partial current density of −92.3 mA cm-2, corresponding to a record-high methanol electroproduction rate (1595 μmol s-1 m-2, 2.26 times higher than the highest report previously). Theoretical calculations show that delocalized Cu site demonstrates a much-reduced Cu–OCH3 interaction, thus favoring the release of *OCH3 for methanol formation. Our work suggests exciting opportunities of designing Cu-based catalysts for tuning selectivity and activity of CO2 electroreduction toward high value-added products.

Local electron state tuning in copper-based catalysts for sustainable methanol manufacturing

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