Nanoflower-like TiO₂/CoAl-layered double hydroxide direct Z-scheme for boosted photocatalytic CO₂ conversion

Direct Z-scheme heterojunction (DZH) has promising potential in photocatalytic carbon dioxide reduction (PCR) owing to its unusual charge transfer pathway, exceptional charge separation efficiency, and high redox ability. Herein, ultrathin TiO2 nanosheets (NSs) have been employed as a substrate for the in-situ growth of CoAl layered double hydroxide (LDH) NSs to fabricate nanoflower-like TiO2/CoAl-LDH (TCA) DZH. The unconsolidated heterostructure is beneficial for active site exposure and mass transfer, and the inherent alkalinity of CoAl-LDH promoted the adsorption of CO2, synergistically boosting the process of PCR reaction in the TCA system. Simulated calculation and in-situ analysis jointly demonstrate the unique electron transfer processes during hybridization and photoexcitation. The resulting (-)TiO2/(+)CoAl-LDH interfacial electric field and DZH further lead to efficient separation of photogenerated charges of TCA. In the solid-gas system, the optimized TCA heterojunction exhibits a competitive PCR activity (76.18 mu mol g- 1h- 1 for CO production rate) increase of 31.6 and 20.3 times compared to TiO2 and CoAl-LDH, respectively.