Multilayer‐Cavity Tandem Catalyst for Profiling Sequentially Coupling of Intermediate CO in Electrocatalytic Reduction Reaction of CO2 to Multi‐Carbon Products

Abstract Electrochemical CO 2 reduction reaction (CO 2 RR) is an effective approach to address CO 2 emission, promote recycling, and synthesize high‐value multi‐carbon (C 2+ ) chemicals for storing renewable electricity in the long‐term. The construction of multilayer‐bound nanoreactors to achieve management of intermediate CO is a promising strategy for tandem to C 2+ products. In this study, a series of Ag@Cu 2 O nanoreactors consisting of an Ag‐yolk and a multilayer confined Cu shell is designed to profile electrocatalytic CO 2 RR reactions. The optimized Ag@Cu 2 O‐2 nanoreactor exhibits a 74% Faradaic efficiency during the C 2+ pathway and remains stable for over 10 h at a bias current density of 100 mA cm −2 . Using the finite element method, this model determines that the certain volume of cavity in the Ag@Cu 2 O nanoreactors facilitates on‐site CO retention and that multilayers of Cu species favor CO capture. Density functional theory calculations illustrate that the biased generation of ethanol products may arise from the (100)/(111) interface of the Cu layer. In‐depth explorations in multilayer‐bound nanoreactors provide structural and interfacial guidance for sequential coupling of CO 2 RR intermediates for efficient C 2+ generation.