Amino‐Induced CO2 Spillover to Boost the Electrochemical Reduction Activity of CdS for CO Production

Abstract A considerable challenge in CO 2 reduction reaction (CO 2 RR) to produce high‐value‐added chemicals comes from the adsorption and activation of CO 2 to form intermediates. Herein, an amino‐induced spillover strategy aimed at significantly enhancing the CO 2 adsorption and activation capabilities of CdS supported on N‐doped mesoporous hollow carbon sphere (NH 2 −CdS/NMHCS) for highly efficient CO 2 RR is presented. The prepared NH 2 −CdS/NMHCS exhibits a high CO Faradaic efficiency (FE CO ) exceeding 90% from −0.8 to −1.1 V versus reversible hydrogen electrode (RHE) with the highest FE CO of 95% at −0.9 V versus RHE in H cell. Additional experimental and theoretical investigations demonstrate that the alkaline −NH 2 group functions as a potent trapping site, effectively adsorbing the acidic CO 2 , and subsequently triggering CO 2 spillover to CdS. The amino modification‐induced CO 2 spillover, combined with electron redistribution between CdS and NMHCS, not only readily achieves the spontaneous activation of CO 2 to * COOH but also greatly reduces the energy required for the conversion of * COOH to * CO intermediate, thus endowing NH 2 −CdS/NMHCS with significantly improved reaction kinetics and reduced overpotential for CO 2 ‐to‐CO conversion. It is believed that this research can provide valuable insights into the development of electrocatalysts with superior CO 2 adsorption and activation capabilities for CO 2 RR application.