Heterojunction and homojunction engineering on multi-shelled confinement structure for CO2 photoreduction to CH4

Abstract

The underdeveloped CO2 photo-reduction solid-gas mode still relies on precious metals to produce CH4. Fine-tuned ingenious structure and morphology with nonprecious metal can enable better performance with lower cost. We have synthesized and modified a TiO2 with a three-stage cavity and a three-shelled layer, loaded with In2S3 flakes only on the outermost layer. The porous hollow multi-shelled structure can give a sequence of gas diffusion from inside to outside or vice versa. Due to the confinement effect, products generated by the core can only be transferred from the inside to the outside in a unidirectional manner. The In2S3/TiO2 catalysts exhibited high performance comparable to that of conventional noble metal catalysts (e.g., Au-Ag-Pt), with a selectivity of up to 98.28 % for CH4 and a rate of 296.87 μmol·g−1·h−1 without using any co-catalyst or sacrificial agent. Systematic fundamental characterization, as well as in situ characterization and DFT calculations show that homo-junctions consisting of two crystalline phases of TiO2 contribute to the production of more *Hads and *CO. Desorbed CO can be captured and catalyzed by the outer shell In2S3/TiO2 S-scheme heterojunction during diffusion for methanation via formaldehyde intermediate. A series of photoelectrochemical characterizations also confirms that the In2S3/TiO2 hetero-junction improves light absorption and charge separation efficiency. This work provides insight into the future rational design of hollow semiconductors for artificial photosynthesis systems and selective solar fuel production.