Effects of Cu Doping on the Microstructure, Room-Temperature Desulfurization Performance and Reaction Mechanism of...

A nano-CuO/ZnO desulfurizer was successfully prepared via a homogeneous precipitation method, and the effects of Cu doping on its microstructure, oxygen species, desulfurization performance, and reaction mechanism were systematically investigated. The results show that an appropriate Cu doping amount (TZ2, Cu:Zn = 1:18.40) significantly reduces the particle size (to ~10.9 nm) compared with pure ZnO (14.3 nm), leading to an increased number of surface-active sites. XPS and TG analyses reveal that Cu incorporation increases the proportion of lattice oxygen and decreases the concentration of oxygen vacancies, indicating that the modification effect of Cu dominates over the particle size effect in regulating surface oxygen species. Despite the reduced oxygen vacancy concentration, the desulfurization performance is markedly enhanced, with TZ2 exhibiting the longest breakthrough time under oxygen-free conditions at room temperature. This improvement is attributed to the strong interaction between highly dispersed Cu species and the ZnO matrix, which promotes H₂S adsorption and activation. Mechanistic studies demonstrate that, unlike pure nano-ZnO, where oxygen vacancy-mediated reactions dominate, the CuO/ZnO system follows a chemisorption-driven pathway involving the formation of copper sulfides and highly reactive polysulfide intermediates. Furthermore, the presence of oxygen significantly influences the reaction behavior, with an optimal oxygen concentration (~10%) maximizing desulfurization performance by balancing the generation of reactive oxygen species and sulfur intermediates. This work provides new insights into the design of high-performance ZnO-based desulfurizers and highlights the critical role of Cu-induced mechanism transformation.