Low-valent copper on molybdenum triggers molecular oxygen activation to selectively generate singlet oxygen for...

Singlet oxygen (¹O₂), which is difficult to generate, plays an important role in chemosynthesis, biomedicine and environment. Molecular oxygen (O₂) is a green oxidant to produce ¹O₂ cost-effectively. However, O₂ activation is difficult due to its spin-forbidden nature. Moreover, the main products of O₂ activation are basically hydrogen peroxide (H₂O₂) and hydroxyl radical (•OH), but rarely ¹O₂. Herein, we innovatively realize the selective generation of ¹O₂ via O₂ activation by a facile molybdenum (Mo)/Cu²⁺ system. In this system, Mo firstly reduces Cu²⁺ in solution to low-valence Cu⁰/Cu⁺ on its surface. Cu⁰/Cu⁺ activates O₂ to generate superoxide radical (O₂^•-). Importantly, O₂^•- can be captured immediately and oxidized to ¹O₂ by surface-bound Mo⁶⁺ rather than reduced to H₂O₂. As a result, the Mo/Cu²⁺ system can selectively produce ¹O₂. Under air and O₂ conditions, the degradation efficiency of ibuprofen by Mo/Cu²⁺ system is 67.2 % and 76.6 %, respectively. The degradation efficiencies of bisphenol A, rhodamine B and furfuryl alcohol are 77.1 %, 87.7 % and 91.1 %, respectively. The dosages of Mo and Cu²⁺ are 0.4 g/L and 3 mM, respectively, and the reaction time is 2 h. Interestingly, the activity of Mo decreased by only 4.2 % after 4 cycles. Therefore, this study provides a green pathway to selectively generate ¹O₂ for advanced oxidation processes.