Palladium-modified cuprous(i) oxide with {100} facets for photocatalytic CO₂ reduction

Using metal as a photohole capturer can promote the photoelectron of p-type copper(i) oxide (Cu₂O) substrate for efficient carbon dioxide reduction. However, palladium-decorated Cu₂O (Cu₂O-Pd) is seldom reported due to their mismatching band arrangement. Herein, we have successfully established a matched band alignment between Pd nanoparticles and Cu₂O with exposed {100} facets (100Cu₂O). The high work function of 100Cu₂O originating from T_1u symmetry vibration facilitates the photohole transferring to Pd nanoparticles, which leads to a three-fold increase in the photocatalytic generation of carbon monoxide (100Cu₂O-0.1Pd, 0.13 μmol g^-1 h^-1) than that with pristine 100Cu₂O (0.04 μmol g^-1 h^-1). Besides, the incorporation of Pd can relieve the photocorrosion of 100Cu₂O, thus promoting its photocatalytic stability. As a contrast, 111Cu₂O (Cu₂O exposed to {111} facets) with low-work function was also synthesized and no charge migration was observed between 111Cu₂O and Pd species, which verified the important role of the crystal surface regulation. All experimental phenomena were certified by the crystal surface analysis and energy band structure construction. Moreover, CO₂ adsorption capacity tests indicated that the incorporation of Pd is beneficial for the capture of CO₂ molecules. We hope that this work to some extent will enrich the subject of photocatalytic CO₂ reduction.