文献速递|重庆大学WR:利用两性氧化物调制增强过氧酮反应，高效净化具有挑战性的废水：性能比较、经济评估和试点规模实施

第一作者：Yi-Shuo Zhang, Xin-Jia Chen

通讯作者：陈飞 教授

通讯单位：重庆大学环境与生态学院

DOI:10.1016/j.watres.2024.123058

Fig. 1. Degradation efficiency of ATZ by O3, O3/H2O2, and ZnO/O3/H2O2 at pH=5.0, 7.0, and 9.0 (a). Degradation rates of ATZ by O3, O3/PMS, and ZnO/O3/PMS systems at pH=5.0, 7.0, and 9.0 (b). Mineralization rates of ATZ in different systems (c). Control experiment for Zn2+ (d). Changes in pH of the ZnO/O3/H2O2 reaction under different initial pH conditions (e). Degradation efficiency in the presence of buffer salts (f). Catalytic effect of commercial MnO2 on O3/H2O2 (PMS) (g). The cycling experiment of ZnO/O3/H2O2 (h). XRD of ZnO before and after reaction (i). FTIRD of ZnO before and after reaction (j). ICP of different systems (k). Conditions: [ATZ]0 = 5 mg•L-1, [H2O2] = 0.05 mM, [PMS] = 0.05 mM, [O3] = 15.05 mg•L-1, ZnO = 20 mg, flow rate = 200 mL•min-1, T = 20 ± 2 °C. For (c), "O" represents O3, "OH" represents O3/H2O2, "ZOH" represents ZnO/O3/H2O2, "OP" represents O3/PMS, and "ZOP" represents ZnO/O3/PMS. For (d), [Zn2+]=0.75 mM. For (g), "MOH" represents MnO2/O3/H2O2, and "MOP" represents MnO2/O3/PMS. For (k), "ZOH-5, ZOH-7, ZOH-9″ respectively represent the reaction of ZnO/O3/H2O2 under pH=5.0, 7.0, and 9.0 conditions.

Fig. 2. Capture experiments of different catalytic systems (a). ESR of different systems (b). NB probe experiment (c). BA probe experiment (d). Contribution of •OH in the ZnO/O3/H2O2 system (e). Contribution of·•OH and SO4·•-in the ZnO/O3/PMS system (f). The variation of O3 concentration in different systems during the reaction process (g). Utilization rate of oxidants in different systems (h). Conditions: [ATZ]0 = 5 mg•L-1, [H2O2] = 0.05 mM, [PMS] = 0.05 mM, [O3] = 15.05 mg•L-1, ZnO = 20 mg, flow rate = 200 mL•min-1, TBA = MeOH = 40 mM, [NB]0 = [BA]0 = 5 mg•L-1, T = 20 ± 2 °C. For (b), "ZOH-1, ZOH-3, ZOP-1, ZOP-3″ represent the signals collected by the ZnO/O3/H2O2 and ZnO/O3/PMS systems at reaction times of 1 min and 3 min, respectively; ZOH-A and ZOP-A "respectively represent the signals collected after adding ATZ to two reaction systems.

Fig. 3. EDTA shielding Zn site experiment (a). XPS of Zn 2p in ZnO before and after the reaction (b). In situ Raman spectroscopy of the ZnO/O3/H2O2 system (c). In situ Raman spectroscopy of the ZnO/O3/PMS system (d). The adsorption effect of ZnO on oxidants (e). Open circuit potential of ZnO/O3/H2O2 system (f). I-t curve of ZnO/O3/H2O2 system (g) LSV curve of ZnO/O3/H2O2 system (h). Binding energy calculation for reaction steps (i). Mechanistic diagram of ZnO catalyzed O3/H2O2 (PMS) (j). Conditions: [ATZ]0 = 5 mg•L-1, [H2O2] = 0.05 mM, [PMS] = 0.05 mM, [O3] = 15.05 mg•L-1, ZnO = 20 mg, flow rate = 200 mL•min-1, T = 20 ± 2 °C.

Fig. 4. Effect of different ions (a) and water quality (b) on ZnO/O3/H2O2. Effect of different Cl- and SO42- concentrations on ZnO/O3/H2O2 (c). Effect of different pairs of pH on ATZ removal using ZnO/O3/H2O2 (d). Degradation rates under different water quality conditions (e). Effect of HA concentration on ZnO/O3/H2O2 (f). Comparison of kinetic constants for different pollutants in different systems (g). TOC degradation experiment of 50 L actual coking wastewater (h). Conditions: [H2O2] = 0.05 mM, [PMS] = 0.05 mM, [O3] = 15.05 mg•L-1, ZnO = 20 mg, flow rate = 200 mL•min-1, [Ions]=5 mM (for a), [pollutants]= 5 mg•L-1 (except h), reaction time = 18 min (except h).

Fig. 5. HOMO and LUMO distributions (a), Chemical structure, molecular electrostatic potential (ESP) (b) of ATZ. The common degradation pathway of ATZ by ZnO/O3/H2O2 and ZnO/O3/PMS systems (c). The additional unique degradation pathway of ZnO/O3/PMS system (d). The f-, f+, f0 of each atom in ATZ (e). Zebrafish toxicity experiment (f). E. coli. culture experiment (g). Wheat seed germination experiment (h).

Fig. 6. ZnO catalyzed degradation of ATZ by O3/PAA and O3/PI (a), different commercial metal oxides catalyze O3/H2O2 and O3/PMS (b), comparison of degradation effects with traditional Fenton and Fenton-like systems (c), comparison of EE/O among different systems (d), relative environmental impacts of O3/H2O2, O3/PMS, Fenton, ZnO/O3/H2O2, and ZnO/O3/PMS processes on the degradation of 5 mg•L-1 ATZ using environmental descriptors (e), technical prospects of ZnO/O3/H2O2 (PMS) process (f). Conditions: For (e), "0.33 L" and "50 L" represent processing volumes of 0.33 L and 50 L, respectively.