Synergistic Effect of Metal Doping and Tethered Ligand Promoted High‐Selectivity Conversion of CO<sub>2</sub> to C<sub>2</sub> Oxygenates at Ultra‐Low Potential
Xiaowan Bai, Li Shi, Qiang Li, Chongyi Ling, Yixin Ouyang, Shiyan Wang, Jinlan Wang
Abstract
Effectively controlling the selectivity of C 2 oxygenates is desirable for electrocatalytic CO 2 reduction. Copper catalyst has been considered as the most potential for reducing CO 2 to C 2 products, but it still suffers from low C 2 selectivity, high overpotential, and competitive hydrogen evolution reaction (HER). Here, we propose a design strategy to introduce a second metal that weakly binds to H and a functional ligand that provides hydrogen bonds and protons to achieve high selectivity of C 2 oxygenates and effective suppression of HER on the Cu(100) surface simultaneously. Seven metals and eleven ligands are screened using first‐principles calculations, which shows that Sn is the most efficient for inhibiting HER and cysteamine (CYS) ligand is the most significant in reducing the limiting potential of *CO hydrogenation to *CHO. In the post C−C coupling steps, a so‐called “pulling effect” that transfers H in the CYS ligand as a viable proton donor to the C 2 intermediate to form an H bond, can further stabilize the OH group and facilitate the selection of C 2 products toward oxygenates. Therefore, this heterogeneous electrocatalyst can effectively reduce CO 2 to ethanol and ethylene glycol with an ultra‐low limiting potential of −0.43 V. This study provides a new strategy for effectively improving the selectivity of C 2 oxygenates and inhibiting HER to achieve advanced electrocatalytic CO 2 reduction.