Subsurface‐Carbon‐Induced Local Charge of Copper for an On‐Surface Displacement Reaction

Transition‐metal carbides have sparked unprecedented enthusiasm as high‐performance catalysts in recent years. Still, the catalytic properties of copper carbide remain unexplored. By introducing subsurface carbon to Cu(111), a displacement reaction of a proton in a carboxyl acid group with a single Cu atom is demonstrated at the atomic scale and room temperature. Its occurrence is attributed to the C‐doping‐induced local charge of surface Cu atoms (up to +0.30 e/atom), which accelerates the rate of on‐surface deprotonation via reduction of the corresponding energy barrier, thus enabling the instant displacement of a proton with a Cu atom when the molecules adsorb on the surface. This well‐defined and robust Cuδ+ surface based on subsurface‐carbon doping offers a novel catalytic platform for on‐surface synthesis. By subsurface doping with carbon, local charge is introduced to the surface Cu atoms of Cu(111), which enables an instant on‐surface displacement reaction. The well‐defined and robust Cuδ+ surface offers a novel catalytic platform for on‐surface synthesis. The strategy based on subsurface doping with non‐metal atoms provides an efficient path to improve the catalytic performance of the parent metal.