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

Abstract

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.

Rational Manipulation of Intermediates on Copper for CO2 Electroreduction Toward Multicarbon Products

“…Because of the lattice mismatch between the dopant and Cu, the strain generated at the interface adjusts the electronic structure and the intermediate adsorption strength for CO 2 RR. Doping by p-block elements with higher electronegativity than Cu will induce the presence of oxidation states without a phase change [105][106][107]. In addition, the dopants with strong oxygen affinity facilitate the breaking of C-O bonds in *OCHCH 2 ; this condition thermodynamically favors the generation of ethylene and ethane but inhibits the formation of ethanol [108].…”