School of Environmental Science and Engineering, Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Sun Yat-Sen University, Guangzhou 510006, China.
School of Environmental Science and Engineering, Guangdong Provincial Key Laboratory of Environmental Pollution Control and Remediation Technology, Sun Yat-Sen University, Guangzhou 510006, China.
J Hazard Mater. 2023 Jun 15;452:131210. doi: 10.1016/j.jhazmat.2023.131210. Epub 2023 Mar 16.
Singlet oxygen (O), which is difficult to generate, plays an important role in chemosynthesis, biomedicine and environment. Molecular oxygen (O) is a green oxidant to produce O cost-effectively. However, O activation is difficult due to its spin-forbidden nature. Moreover, the main products of O activation are basically hydrogen peroxide (HO) and hydroxyl radical (•OH), but rarely O. Herein, we innovatively realize the selective generation of O via O activation by a facile molybdenum (Mo)/Cu system. In this system, Mo firstly reduces Cu in solution to low-valence Cu/Cu on its surface. Cu/Cu activates O to generate superoxide radical (O). Importantly, O can be captured immediately and oxidized to O by surface-bound Mo rather than reduced to HO. As a result, the Mo/Cu system can selectively produce O. Under air and O conditions, the degradation efficiency of ibuprofen by Mo/Cu 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 Cu 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 O for advanced oxidation processes.
单线态氧（O）难以生成，但在化学生物学、生物医药和环境科学等领域发挥着重要作用。分子氧（O）是一种绿色氧化剂，可以有效地产生 O。然而，由于其自旋禁阻性质，O 的活化较为困难。此外，O 活化的主要产物通常是过氧化氢（HO）和羟基自由基（•OH），而 O 很少见。在此，我们创新性地通过一种简便的钼（Mo）/铜（Cu）体系实现了 O 活化选择性生成 O 的目标。在该体系中，Mo 首先将溶液中的 Cu 还原为表面的低价态 Cu/Cu。Cu/Cu 活化 O 生成超氧自由基（O）。重要的是，表面结合的 Mo 可以立即捕获 O，并将其氧化为 O，而不是将其还原为 HO。因此，Mo/Cu 体系可以选择性地产生 O。在空气和 O 条件下，Mo/Cu 体系对布洛芬的降解效率分别为 67.2%和 76.6%。对双酚 A、罗丹明 B 和糠醇的降解效率分别为 77.1%、87.7%和 91.1%。Mo 和 Cu 的用量分别为 0.4 g/L 和 3 mM，反应时间为 2 h。有趣的是，经过 4 次循环后，Mo 的活性仅下降了 4.2%。因此，该研究为高级氧化工艺中选择性生成 O 提供了一种绿色途径。
