Enhanced charge separation of Cu-BTC@CuSe@TiO2 hollow octahedrons for efficient CO2 photoreduction with superior CO selectivity

Solar-driven photocatalytic conversion of CO2 into high-value-added fuels has attracted widespread attention. However, the relatively low conversion efficiency and product yield severely limited photocatalytic applications. In this work, binary Cu-BTC@TiO2 catalysts with adjustable inner cavity were prepared using copper-based metal organic framework (Cu-BTC) octahedrons as substrate via a solvothermal reaction. In this process, the inner Cu-BTC octahedrons can be controllably etched into a hollow octahedral structure in the presence of HF. Subsequently, the Cu-BTC@CuSe@TiO2 hollow octahedrons (HOs) were fabricated by selenization reaction and exhibited various properties such as abundant active sites for CO2 adsorption and reduction reactions, shortened charge transfer distance to prevent electron-hole recombination, and internal reflection/scattering effects to improve solar light utilization. Moreover, the formed dual p-n heterostructures between p-type CuSe and n-type semiconductors (Cu-BTC and TiO2) effectively promote spatial separation and migration of charge carriers. The synergistic effect of these advantages makes the optimized Cu-BTC@CuSe@TiO2 HO catalyst exhibit remarkable CO2 photoreduction performance with a CO production rate of 72.3 μmol h−1 g−1 and near 100 % selectivity. This work opens a new pathway for designing highly active photocatalysts with excellent product selectivity.