Confined Synthesis of Noble Metal Clusters Assisted by Liquid Film for Photocatalytic CO 2 Reduction.

The important concept of confined synthesis is considered a promising strategy for the design and synthesis of definable nanostructured materials with controllable compositions and specific morphology, such as highly loaded single-atom catalysts capable of providing abundant active sites for photocatalytic reactions. In recent years, researchers have been working on developing new confined reaction systems and searching for new confined spaces. Here, we present for the first time the concept of a bubble liquid film as a novel confined space. The liquid film has a typical sandwich structure consisting of a water layer, sandwiched between the upper and lower surfactant layers, with the thickness of the intermediate water layer at the micro- and nanometer scales, which can serve as a good confinement. Based on the above understanding and combined with the photodeposition method, we successfully confined synthesized Ag/TiO2 , Au/TiO2 , and Pd/TiO2 photocatalysts in liquid film. By HAADF-STEM, it can be seen that the noble metal morphologies are all nanoclusters of about 1 nm and are highly uniformly dispersed on the TiO2 surface. Compared with photodeposition in solution, we believe that the surfactant molecular layer restricts a limited amount of precursor to the liquid film, avoiding the accumulation of noble metals and the formation of large particle size nanoparticles. The liquid film, meanwhile, restricts the migration path of noble metal precursors, allowing for thorough in situ photodeposition and enables the complete and uniform dispersion of noble metal precursors, greatly reducing the photodeposition time. The uniform loading of the three noble metals proved the universality of the method, and the catalysts showed high activity for photocatalytic CO2 reduction. The rates of reduction of CO2 to CO over the Ag/TiO2 photocatalytic reached 230 μmol g-1 h-1 .This study provides a new idea for the expansion of the confined reaction system and a reference for the study of liquid film as the confined space.