Steering the Product Selectivity of CO <sub>2</sub> Electroreduction by Single Atom Switching in Isostructural Copper Nanocluster Catalysts
Chao Han, Tao Yang, Youqiong Fang, Yuanxin Du, Shan Jin, Lin Xiong, Manzhou Zhu
Abstract
Abstract Even single atom manipulation can cause drastic changes in catalytic activity and selectivity, especially in atomic‐level catalysts. However, it is challenging to accurately elucidate the influence of specific atoms on performance due to the intertwined factors in catalysts. Atomically precise isostructural nanoclusters (NCs) can serve as ideal platforms to uncover the impact of individual atoms on catalytic properties. Herein, a pair of isostructural Cu NCs ([Cu 13 (SC 6 H 3 F 2 ) 3 (P(PhF) 3 ) 7 H 10 ] 0 and [Cu 14 (SC 6 H 3 F 2 ) 3 (P(PhF) 3 ) 8 H 10 ] + namely as Cu 13 and Cu 14 ) were synthesized. In the electrochemical CO 2 reduction reaction, Cu 13 shows barely any activity toward only 2e product CO with a maximum 13% FE at −1.1 V. In contrast, Cu 14 can promote CO 2 deep reduction to hydrocarbons (CH 4 and C 2 H 4 ) with maximum FE of 54.3% at −1.2 V. Based on the crystallographic and computational analyses, the extra Cu at the top in Cu 14 squeezes the H connected with three core Cu into the center of the same plane, optimizing the electronic structure and thereby promoting CO 2 activation and H 2 O dissociation, which is further confirmed by comprehensive in situ characterizations, kinetic experiments, and theoretical calculations. This work provides a unique isostructural NCs system to gain fundamental insights into switching catalytic reactivity by single‐atom manipulation.