Cu2O@Cu@NiAl‐LDH with Cu0/Cu+ Valence Synergy and Core‐Shell Structure for Highly Selective Generation of C2H6

Photocatalytic CO2 reduction to produce C2 products remains a challenge. Herein, Cu2O@Cu@NiAl‐LDH composites with three‐dimensional ordered core‐shell structures were successfully prepared, and the effects of Cu2O with different exposed surfaces on CO2 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 Cu2O and NiAl‐LDH leads to the enhancement of C2 selectivity. The best sample, Cu2O@Cu@NiAl‐LDH‐2, achieved a C2H6 yield of 22.17 μmol g‐1h‐1 with 63.89% electron selectivity. The evolution pathways and photocatalytic mechanisms of CO2 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 Cu2O‐based photocatalysts for the reduction of CO2 to C2 products.