Boosting Interfacial Charge Transfer with a Giant Internal Electric Field in a TiO₂ Hollow-Sphere-Based S-Scheme...

The construction of an S-scheme charge transfer pathway is considered to be a powerful way to inhibit charge recombination and maintain photogenerated carriers with high redox capacity to meet the kinetic requirements of the carbon dioxide (CO₂) photoreduction reaction. For an S-scheme heterojunction, an internal electric field (IEF) is regarded as the main driving force for accelerating the interfacial spatial transfer of photogenerated charges. Herein, we designed a TiO₂ hollow-sphere (TH)-based S-scheme heterojunction for efficient CO₂ photoreduction, in which WO₃ nanoparticles (WP) were applied as an oxidation semiconductor to form an intimate interfacial contact with the TH. The S-scheme charge transfer mode driven by a strong IEF for the TH/WP composite was confirmed by in situ X-ray photoelectron spectroscopy and ultraviolet photoelectron spectroscopy. As a result, abundant photogenerated electrons with strong reducing ability would take part in the CO₂ reduction reaction. The combination of surface photovoltage spectra and transient photocurrent experiments disclosed that the IEF intensity and charge separation efficiency of the fabricated TH/WP composite were nearly 16.80- and 1.42-fold higher, respectively, than those of the pure TH. Furthermore, sufficient active sites provided by the hollow-sphere structure also enhanced the kinetics of the catalytic reaction. Consequently, the optimized TH/WP composite showed a peak level of CO production of 14.20 μmol g^-1 in 3 h without the addition of any sacrificial agent. This work provides insights into the kinetic studies of the S-scheme charge transfer pathway for realizing high-performance CO₂ photoreduction.