Improving Photocatalytic Stille Coupling Reaction by CuPd Alloy-Doped Ordered Mesoporous TiO2

Abstract

Rational surface engineering of noble metal-doped photocatalysts is essential for the efficient conversion of solar energy into chemical energy, but it is still challenging to perform. Herein, we reported an effective strategy for structuring alloyed CuPd (CP) nanoclusters on the ordered mesoporous TiO2 (CPT) by a pore confinement effect. The resultant CPT exhibited an extraordinary photocatalytic activity during Stille reaction under visible light. The X-ray photoelectron spectroscopy spectra, the field emission scanning electron microscope (FESEM) images, and the aberration-corrected high-angle annular dark scanning transmission electron microscopy (HAADF-STEM) images demonstrated that CP nanoclusters were anchored in the mesoporous pore wall of TiO2, and the atomic ratio as well as densities of CP could be precisely modulated via the coordination configuration. As the atomic ratio of CP to TiO2 increased to a certain extent, their photocatalytic activity during Stille reaction increased. A mechanistic investigation suggested that the CP alloy could absorb visible light and its conduction electrons gained energy, which were available at the surface Pd sites. This allowed the Pd sites to become electron-rich and to accelerate the rate-determining step of the Stille reaction. As a result, the efficiency of the photocatalytic Stille coupling reaction was extraordinary enhanced.