Engineering Catalytic Interfaces in Cu^δ+/CeO₂-TiO₂ Photocatalysts for Synergistically Boosting CO₂ Reduction to...

Photocatalytic CO₂ conversion into a high-value-added C₂ product is a highly challenging task because of insufficient electron deliverability and sluggish C-C coupling kinetics. Engineering catalytic interfaces in photocatalysts provides a promising approach to manipulate photoinduced charge carriers and create multiple catalytic sites for boosting the generation of C₂ product from CO₂ reduction. Herein, a Cu^δ+/CeO₂-TiO₂ photocatalyst that contains atomically dispersed Cu^δ+ sites anchored on the CeO₂-TiO₂ heterostructures consisting of highly dispersed CeO₂ nanoparticles on porous TiO₂ is designedly constructed by the pyrolytic transformation of a Cu²⁺-Ce³⁺/MIL-125-NH₂ precursor. In the designed photocatalyst, TiO₂ acts as a light-harvesting material for generating electron-hole pairs that are efficiently separated by CeO₂-TiO₂ interfaces, and the Cu-Ce dual active sites synergistically facilitate the generation and dimerization of *CO intermediates, thus lowering the energy barrier of C-C coupling. As a consequence, the Cu^δ+/CeO₂-TiO₂ photocatalyst exhibits a production rate of 4.51 μmol^-1·g_cat^-1·h^-1 and 73.9% selectivity in terms of electron utilization for CO₂ to C₂H₄ conversion under simulated sunlight, with H₂O as hydrogen source and hole scavenger. The photocatalytic mechanism is revealed by operando spectroscopic methods as well as theoretical calculations. This study displays the rational construction of heterogeneous photocatalysts for boosting CO₂ conversion and emphasizes the synergistic effect of multiple active sites in enhancing the selectivity of C₂ product.