The role of TiO2:SnO2 heterojunction for partial oxidation of methane by photoelectrocatalytic process at room temperature

Partial Oxidation of Methane into hydrocarbons using photoelectrochemical routes is attractive from a sustainability point of view owing to the possibility of using renewable energy (i.e., solar illumination) to activate this stable molecule. However, the process demands the development of novel catalysts that can promote methane activation and oxidation in a controlled manner to increase energy conversion efficiency. Herein, we demonstrated that semiconductor heterostructures improved charge separation compared to the individual materials alone. A more effortless transfer between bands favors the separation of the electron-hole (e ⁻/h ⁺ ) pairs generated by the photoelectrocatalytic system and prevents them from recombining. This process produces reactive oxygens, essential to driving methane oxidation conversion of the C–H bond cleavage. TiO ₂:SnO ₂ semiconductor heterojunction catalysts in film shape were investigated for methane oxidation via a photoelectrocatalytic process. The methane oxidation reactions were carried out in an inflow and sealed electrochemical system for 1 h. Liquid-state nuclear magnetic resonance revealed methanol and acetic acid as the main liquid products, where the TiO ₂:SnO ₂ heterojunction exhibited better performance with values of 30 and 8 µmol.cm ⁻².h ⁻¹, respectively. Compared to their materials alone, the superior performance of the TiO ₂:SnO ₂ heterojunction is attributed to the formation of heterostructure type II that enables a more effortless transfer between bands, facilitating the separation of the generated e ⁻/h ⁺ pairs under UV-Vis irradiation. The outcomes achieved here will motivate further studies for developing semiconductor heterojunction structure catalysts in photoelectrocatalysis to partially oxidize methane into valuable chemicals.