Cu 2 O@Cu@NiAl‐LDH with Cu 0 /Cu + Valence Synergy and Core‐Shell Structure for Highly Selective Generation of C 2 H 6

Abstract Photocatalytic CO 2 reduction to produce C 2 products remains a challenge. Herein, Cu 2 O@Cu@NiAl‐LDH composites with three‐dimensional ordered core‐shell structures were successfully prepared, and the effects of Cu 2 O with different exposed surfaces on CO 2 photoreduction were investigated. The synergistic effect of zero‐valent Cu and Cu + as intermediate electron mediators retains more photogenerated electrons and the Z‐scheme heterojunction formed between Cu 2 O and NiAl‐LDH leads to the enhancement of C 2 selectivity. The best sample, Cu 2 O@Cu@NiAl‐LDH‐2, achieved a C 2 H 6 yield of 22.17 μmol g −1 h −1 with 63.89 % electron selectivity. The evolution pathways and photocatalytic mechanisms of CO 2 were investigated by in‐situ DRIFTS and theoretical calculations. This study provides references and suggestions for the further development of experimental and theoretical calculations of Cu 2 O‐based photocatalysts for the reduction of CO 2 to C 2 products.