UV-Vis Activated Cu₂O/SnO₂/WO₃ Heterostructure for Photocatalytic Removal of Pesticides

A three-steps sol-gel method was used to obtain a Cu₂O/SnO₂/WO₃ heterostructure powder, deposited as film by spray pyrolysis. The porous morphology of the final heterostructure was constructed starting with fiber-like WO₃ acting as substrate for SnO₂ development. The SnO₂/WO₃ sample provide nucleation and grew sites for Cu₂O formation. Diffraction evaluation indicated that all samples contained crystalline structures with crystallite size varying from 42.4 Å (Cu₂O) to 81.8 Å (WO₃). Elemental analysis confirmed that the samples were homogeneous in composition and had an oxygen excess due to the annealing treatments. Photocatalytic properties were tested in the presence of three pesticides-pirimicarb, S-metolachlor (S-MCh), and metalaxyl (MET)-chosen based on their resilience and toxicity. The photocatalytic activity of the Cu₂O/SnO₂/WO₃ heterostructure was compared with WO₃, SnO₂, Cu₂O, Cu₂O/SnO₂, Cu₂O/WO₃, and SnO₂/WO₃ samples. The results indicated that the three-component heterostructure had the highest photocatalytic efficiency toward all pesticides. The highest photocatalytic efficiency was obtained toward S-MCh (86%) using a Cu₂O/SnO₂/WO₃ sample and the lowest correspond to MET (8.2%) removal using a Cu₂O monocomponent sample. TOC analysis indicated that not all the removal efficiency could be attributed to mineralization, and by-product formation is possible. Cu₂O/SnO₂/WO₃ is able to induce 81.3% mineralization of S-MCh, while Cu₂O exhibited 5.7% mineralization of S-MCh. The three-run cyclic tests showed that Cu₂O/SnO₂/WO₃, WO₃, and SnO₂/WO₃ exhibited good photocatalytic stability without requiring additional procedures. The photocatalytic mechanism corresponds to a Z-scheme charge transfer based on a three-component structure, where Cu₂O exhibits reduction potential responsible for O₂ production and WO₃ has oxidation potential responsible for HO· generation.