Confinement Catalysis of Reaction Intermediates in Ag@Cu<sub>2</sub>O Cascade Nanoreactors toward Boosted Electrochemical C–C Coupling
Yonglian Lu, Honglin Li, Hongman Sun, Jiatai Zhao, Yu Zhang, Youhe Wang, Chuan-Yong Zhu, Dunfeng Gao, Yongxiao Tuo, Jingbin Zeng, De Chen, Zifeng Yan
Abstract
Cascade nanoreactors provide an ideal platform for multicomponent sequential reactions and synergistic transformations. However, the effects of morphology modulation on confinement catalysis, particularly regarding the generation, diffusion, and dimerization of reaction intermediates in CO 2 RR are less discerned. Herein, we synthesized a series of Ag@Cu 2 O cascade nanoreactors with tunable shell thicknesses by a two-step seeded growth method, observing an obvious volcano-type curve in C 2+ products generation. The variant with a medium shell thickness (Ag@Cu 2 O-40) achieved the highest Faradaic efficiency (FE) of C 2+ up to 78.5% at −1.6 V (vs RHE). In situ Raman and density functional theory (DFT) calculations indicate that CO generated on the Ag core spills over and becomes confined at the Cu 2 O shell, which is crucial in boosting C–C coupling rather than forming C 1 products (CO, CH 3 OH, and CH 4 ). Finite element method (FEM) simulations further reveal that the optimal thickness of the Cu 2 O shell accommodates CO 2 diffusion and CO confinement capabilities, thereby maximizing CO concentration for the formation of C 2+ products. Our findings exemplify the potential of rationally designed cascade nanoreactors for optimizing reaction intermediates through confinement catalysis.