Steering Catalytic Activity and Selectivity of CO2 Photoreduction to Syngas with Hydroxy‐Rich Cu2S@ROH‐NiCo2O3 Double‐Shelled Nanoboxes.

Simultaneous transformation of CO2 and H2O into syngas (CO and H2) using solar power is desirable for industrial applications. Herein, an efficient photocatalyst based on double‐shelled nanoboxes, with an outer shell of hydroxy‐rich nickel cobaltite nanosheets and an inner shell of Cu2S (Cu2S@ROH‐NiCo2O3), is prepared via a multistep templating strategy. The high performance of Cu2S@ROH‐NiCo2O3 (7.1 mmol g−1 h−1 for CO; 2.8 mmol g−1 h−1 for H2) is attributed to the hierarchical hollow geometry and p–n heterojunction to promote light absorption and charge separation. Spectroscopic and theoretical analyses elucidate that the ROH‐NiCo2O3 surface enhances *CO2 adsorption and lowers energy barriers for CO2‐to‐CO. Therefore, modulating the hydroxy contents of ROH‐NiCo2O3 can achieve broad CO/H2 ratios from 0.51 to 1.24. This work offers in‐depth insights into adjustable syngas photosynthesis and generalized concepts of selective heterogeneous CO2 photoreduction beyond cobalt‐based oxides. [ABSTRACT FROM AUTHOR]