Constructing Gold Single‐Atom Catalysts on Hierarchical Nitrogen‐Doped Carbon Nanocages for Carbon Dioxide Electroreduction to Syngas

Abstract Precious‐metal single‐atom catalysts (SACs), featured by high metal utilization and unique coordination structure for catalysis, demonstrate distinctive performances in the fields of heterogeneous and electrochemical catalysis. Herein, gold SACs are constructed on hierarchical nitrogen‐doped carbon nanocages (hNCNC) via a simple impregnation‐drying process and first exploited for electrocatalytic carbon dioxide reduction reaction (CO 2 RR) to produce syngas. The as‐constructed Au SAC exhibits the high mass activity of 3319 A g −1 Au at −1.0 V (vs reversible hydrogen electrode, RHE), much superior to the Au nanoparticles supported on hNCNC. The ratio of H 2 /CO can be conveniently regulated in the range of 0.4–2.2 by changing the applied potential. Theoretical study indicates such a potential‐dependent H 2 /CO ratio is attributed to the different responses of HER and CO 2 RR on Au single‐atom sites coordinating with one N atom at the edges of micropores across the nanocage shells. The catalytic mechanism of the Au active sites is associated with the smooth switch between twofold and fourfold coordination during CO 2 RR, which much decreases the free energy changes of the rate‐determining steps and promotes the reaction activity.