Hydrothermal synthesis of MnO2/SiC activated peroxymonosulfate for degradation of methylene blue
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摘要: 过渡金属活化过单硫酸盐(peroxymonosulfate，PMS)降解有机污染物在高级氧化领域有着重要的应用价值。通过水热法在碳化硅(SiC)表面负载二氧化锰(MnO2)制备出MnO2/SiC复合催化剂，用于活化PMS降解去除水体中的亚甲基蓝(methylene blue，MB)。实验结果表明：MnO2以颗粒的形式均匀附着在SiC表面，MnO2/SiC-PMS体系在40 min内对MB的降解效率达到99%；MnO2/SiC-PMS体系还可以在较宽的pH范围内(5.0~9.0)实现对MB较高的降解效率；5 mmol/L的Cl−与NO− 3对MnO2/SiC-PMS体系均无明显影响。磷酸盐与碳酸氢盐对氧化自由基具有猝灭作用，导致MnO2/SiC-PMS体系对MB的降解效率下降。自由基猝灭实验表明，MnO2/SiC-PMS体系中起主要作用的自由基为
$ {\text{O}}_{\text{2}}^{{-·}} $ 。此外，MnO2/SiC具有良好的循环使用性。Abstract: The degradation of organic pollutants by transition metal activated peroxymonosulfate (PMS) has important application value in the field of advanced oxidation. MnO2/SiC composite catalyst was prepared by hydrothermal method on the surface of silicon carbide (SiC), which was used to activate PMS to degrade and remove methylene blue (MB) from water. The results show that MnO2 is uniformly attached to the surface of SiC in the form of particles, and the removal rate of MB by MnO2/SiC-PMS system reaches 99% within 40 min. The MnO2/SiC-PMS system can achieve high degradation efficiency of MB over a wide pH range (5.0~9.0), while 5 mmol/L Cl−and NO− 3 had no significant effect on the MnO2/SiC-PMS system. Phosphate and bicarbonate have quenching effect on oxidative free radicals, leading to a decrease in the degradation efficiency of MB in the MnO2/SiC PMS system. The results of free radical quenching experiments indicate that$ {\text{O}}_{\text{2}}^{{-·}} $ plays a major role in the MnO2/SiC-PMS system. In addition, MnO2/SiC has good recyclability. -
图 1 样品MnO2/SiC的XRD谱及局部放大图
Figure 1. XRD patterns and local amplification diagrams of MnO2/SiC
图 2 SiC和MnO2/SiC-0.125的SEM图及MnO2/SiC-0.125元素面扫图
Figure 2. SEM images of SiC and MnO2/SiC-0.125 and elemental mapping patterns of MnO2/SiC-0.125
图 3 不同体系及不同物质的量比MnO2/SiC对降解MB的影响
Figure 3. Effect of different systems and molar ratios of MnO2/SiC on MB degradation
图 4 MnO2/SiC-0.125和PMS浓度对降解MB的影响
Figure 4. Effect of MnO2/SiC-0.125 and PMS concentrations on MB degradation
图 5 不同初始pH和共存阴离子对降解MB的影响
Figure 5. Effect of different initial pH and co-existing anions on MB degradation
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[1] 蒋婧, 程锦程. 多孔柱[5]芳烃聚合物的制备及其对有机污染物的吸附性能研究[J] . 铜陵学院学报,2018,17(6):113 − 117. [2] 张卡卡. 苯胺−磺酸基苯胺共聚物的制备及其对染料吸附性能的研究 [D]. 郑州: 郑州大学, 2014. [3] WU N, WANG S, LI L, et al. Degradation of organosulfur compound in wastewater of diesel refining by alkali heat activated persulfate[J] . Environmental Pollution & Control,2019,41(4):435 − 438, 444. [4] WANG Q, SHAO Y, GAO N, et al. Degradation kinetics and mechanism of 2, 4-Di-tert-butylphenol with UV/persulfate[J] . Chemical Engineering Journal,2016,304:201 − 208. doi: 10.1016/j.cej.2016.06.092 [5] DAN J, WANG Q, MU K, et al. Degradation of sulfachloropyridazine by UV-C/persulfate: kinetics, key factors, degradation pathway[J] . Environmental Science: Water Research & Technology,2020,6(9):2510 − 2520. [6] CAI A, DENG J, ZHU T, et al. Enhanced oxidation of carbamazepine by UV-LED/persulfate and UV-LED/H2O2 processes in the presence of trace copper ions[J] . Chemical Engineering Journal,2021,404:127119. doi: 10.1016/j.cej.2020.127119 [7] RAO Y F, QU L, YANG H S, et al. Degradation of carbamazepine by Fe(Ⅱ)-activated persulfate process[J] . Journal of Hazardous Materials,2014,268:23 − 32. doi: 10.1016/j.jhazmat.2014.01.010 [8] ZHU J P, LIN Y L, ZHANG T Y, et al. Modelling of iohexol degradation in a Fe(Ⅱ)-activated persulfate system[J] . Chemical Engineering Journal,2019,367:86 − 93. doi: 10.1016/j.cej.2019.02.120 [9] ANIPSITAKIS G P, DIONYSIOU D D. Degradation of organic contaminants in water with sulfate radicals generated by the conjunction of peroxymonosulfate with cobalt[J] . Environmental Science & Technology,2003,37(20):4790 − 4797. [10] LI Z Y, WANG L, LIU Y L, et al. Unraveling the interaction of hydroxylamine and Fe(Ⅲ) in Fe(Ⅱ)/Persulfate system: A kinetic and simulating study[J] . Water Research,2020,168:115093. doi: 10.1016/j.watres.2019.115093 [11] JIANG C, GARG S, WAITE T D. Hydroquinone-mediated redox cycling of iron and concomitant oxidation of hydroquinone in oxic waters under acidic conditions: Comparison with iron-natural organic matter interactions[J] . Environmental Science & Technology,2015,49(24):14076 − 14084. [12] LI T, ZHAO Z, WANG Q, et al. Strongly enhanced Fenton degradation of organic pollutants by cysteine: An aliphatic amino acid accelerator outweighs hydroquinone analogues[J] . Water Research,2016,105:479 − 486. doi: 10.1016/j.watres.2016.09.019 [13] 王一凡, 李小蝶, 侯美茹, 等. 锰基氧化物活化过硫酸盐降解水中有机污染物的研究进展[J] . 环境科学研究,2021,34(8):1899 − 1908. doi: 10.13198/j.issn.1001-6929.2021.04.02 [14] MORKOÇ H, STRITE S, GAO G B, et al. Large-band-gap SiC, III–V nitride, and II–VI ZnSe-based semiconductor[J] . Journal of Applied Physics,1994,76(3):1363 − 1398. doi: 10.1063/1.358463 [15] Goldberg Y, LEVINSHTEIN M E, RUMYANTSEV S L. Properties of advanced semiconductor materials: GaN, AlN, SiC, BN, SiC, SiGe [M]. Lexington: ScienceOpen, 2001: 93–148. [16] PRESSER V, NICKEL K G. Silica on silicon carbide[J] . Critical Reviews in Solid State and Materials Sciences,2008,33(1):1 − 99. doi: 10.1080/10408430701718914 [17] OHTANI N, TAKAHASHI J, KATSUNO M, et al. Development of large single-crystal SiC substrates[J] . Electronics and Communications in Japan,1998,81(6):8 − 19. [18] ZIEGLER G, LANIG P, THEIS D, WEYRICH C. Single crystal growth of SiC substrate material for blue light emitting diodes[J] . IEEE Transactions on Electron Devices,1983,30(4):277 − 281. doi: 10.1109/T-ED.1983.21117 [19] FALK A L, BUCKLEY B B, CALUSINE G, et al. Polytype control of spin qubits in silicon carbide[J] . Nature Communication,2013,4:1819. doi: 10.1038/ncomms2854 [20] PEDERSEN H, LEONE S, KORDINA O, et al. Chloride-based CVD growth of silicon carbide for electronic applications[J] . Chemical Reviews,2012,112(4):2434 − 2453. doi: 10.1021/cr200257z [21] 杨俊晖, 张惠灵, 梁俊杰, 等. 壳聚糖/磁性榴莲生物炭对亚甲基蓝的吸附研究[J] . 环境科学与技术,2021,44(12):7 − 12. doi: 10.19672/j.cnki.1003-6504.1877.21.338 [22] KHAN A, ZHANG K K, SUN P, et al. High performance of the α-Mn2O3 nanocatalyst for persulfate activation: Degradation process of organic contaminants via singlet oxygen[J] . Journal of Colloid and Interface Science,2021,584:885 − 899. doi: 10.1016/j.jcis.2020.10.021 [23] ZHOU X, LUO H P, SHENG B, et al. Cu2+/Cu+ cycle promoted PMS decomposition with the assistance of Mo for the degradation of organic pollutant[J] . Journal of Hazardous Materials,2021,411:125050. doi: 10.1016/j.jhazmat.2021.125050 [24] GOVINDAN K, RAJA M, NOEL M, et al. Degradation of pentachlorophenol by hydroxyl radicals and sulfate radicals using electrochemical activation of peroxomonosulfate, peroxodisulfate and hydrogen peroxide[J] . Journal of Hazardous Materials,2014,272:42 − 51. doi: 10.1016/j.jhazmat.2014.02.036 -
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