The Hallmarks of Copper Single Atom Catalysts in Direct Alcohol Fuel Cells and Electrochemical CO₂ Fixation

Single‐atom catalysts (SACs) are highly enviable to exploit the utmost utilization of metallic catalysts; their efficiency by utilizing nearly all atoms to often exhibit high catalytic performances. To architect the isolated single atom on an ideal solid support with strong coordination has remained a crucial trial. Herein, graphene functionalized with nitrile groups (cyanographene) as an ideal support to immobilize isolated copper atoms G(CN)‐Cu with strong coordination is reported. The precisely designed mixed‐valence single atom copper (G(CN)‐Cu) catalysts deliver exceptional conversions for electrochemical methanol oxidation (MOR) and CO 2 reduction (CO 2 RR) targeting a “closed carbon cycle.” An onset of MOR and CO 2 RR are obtained to be ≈0.4 V and ≈−0.7 versus Ag/AgCl, respectively, with single active sites located in an unsaturated coordination environment, it being the most active Cu sites for both studied reactions. Moreover, G(CN)‐Cu exhibited significantly lower resistivity and higher current density toward MOR and CO 2 RR than observed for reference catalysts.