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

Angew Chem Int Ed Engl. 2021 Oct 18;60(43):23123-23127. doi: 10.1002/anie.202108712. Epub 2021 Sep 21.

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.

Keywords: carbon doping; catalysis; displacement reactions; local charge; on-surface synthesis.