Molecular‐Level Control of the Intersheet Distance and Electronic Coupling between 2D Semiconducting and Metallic Nanosheets: Establishing Design Rules for High‐Performance Hybrid Photocatalysts

Hybridization with conductive nanospecies has attracted intense research interest as a general effective means to improve the photocatalytic functionalities of nanostructured materials. To establish universal design rules for high-performance hybrid photocatalysts, correlations between versatile roles of conductive species and interfacial interaction between hybridized species are systematically investigated through fine-control of intersheet distance between photocatalytically active TiO2 and metallic reduced graphene oxide (rGO)/RuO2 nanosheets. Molecular-level tailoring of intersheet distance and electronic coupling between 2D nanosheets can be successfully achieved by restacking of colloidal nanosheet mixture with variable-sized organic intercalants. While the shortest intersheet distance between restacked TiO2 and rGO nanosheets leads to the highest visible-light-driven photocatalytic activity, the best UV-vis photocatalyst performance occurs for moderate intersheet spacing. These results highlight the greater sensitivity of photoinduced electronic excitation to the intersheet distance than that of interfacial charge transfer. The rGO nanosheet can function as effective charge transport pathway and cocatalyst within ≈1.7 nm distance from the semiconducting nanosheet, and as efficient stabilizer for hybridized photocatalyst within ≈1.8 nm. The present study underscores that the intercalative restacking of colloidal nanosheet mixture with intercalants enables molecular-level control of distance between 2D inorganic/graphene nanosheets, which provides a rational design strategy for high-performance hybrid photocatalysts.