Design of heterogenous catalyst of Cu4/CeO2(111) for high-efficiency CO2 electroreduction: Tetrahedral Cu4 or Planar Cu4?

• Explore the heterogenous structure of tetrahedral Cu 4 (T d -Cu 4 ) and planer Cu 4 (pl-Cu 4 )supported by CeO 2 (111) as the CO 2 RR catalyst. • The oxidation state of loaded metal clusters can be improved by spillover of lattice oxygen atom from the oxide surface . • The catalytic efficiency and selectivity can be increased the dynamic change of the Cu 4 structure, composition and oxidation state. • The symmetric *CO + *CO route was confirmed to be both thermodynamically favorable and kinetically feasible on the pl-Cu4@CeO2. Based on the density-functional theory (DFT) calculations, we designed a heterogeneous catalyst of Cu 4 cluster supported by CeO 2 (111) surface for electrocatalytic CO 2 reduction reaction (CO 2 RR) and compared the structural stabilities, electronic properties and the catalytic performance of tetrahedral Cu 4 (T d -Cu 4 ) and planar Cu 4 (pl-Cu 4 ) supported on. Our results show that the pl-Cu 4 @CeO 2 exhibits higher structural stability and superior CO 2 RR catalytic performances compared with T d -Cu 4 @CeO 2 . However, during the CO 2 RR with end-on adsorption of CO 2 , the pl-Cu 4 reconstructs to tetrahedral Cu 4 O structure (T d -Cu 4 O) by the spontaneous spillover of the lattice oxygen from the CeO 2 (111) surface. Such dynamic changes of the catalyst structure and composition alter the coordination environment and oxidation states of Cu atoms, further enhancing the catalytic activity and selectivity for CH 4 and CH 3 OH products. In addition, the pl-Cu 4 @CeO 2 also presents high-efficiency catalytic activity for the *CO-*CO coupling in terms of thermodynamics and kinetics. This theoretical study deepens our understanding of how oxide supports determine and change the structure, composition and catalytic activity of supported metal cluster under realistic reaction conditions, and provides new perspectives for the design of cost-effective CO 2 RR catalysts with high efficiency and selectivity. The Cu 4 clusters (Tetrahedral Cu 4 vs Planar Cu 4 ) supported on the surface of CeO 2 (111) were theoretically explored as high-performance CO 2 RR catalyst for both C 1 and C 2 products. The higher oxidation states induced by the dynamic reconstruction from pl-Cu 4 to T d -Cu 4 O under the oxygen spillover during the reaction promise the great increase of the catalytic performance in efficiency and selectivity.