Investigation of the performance and reaction mechanism of tetracycline degradation by LaMnO3/GA composites activated PMS
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摘要: 本研究采用溶胶凝胶法和水热法制备了石墨烯气凝胶(GA)负载的LaMnO3复合催化剂，研究了其对过一硫酸盐(PMS)降解四环素(TC)的催化性能。采用SEM、TEM、XPS、拉曼光谱等手段对样品的形貌结构、元素组成和化学形态进行了表征，结果显示构成了LaMnO3/GA复合催化剂。实验结果表明，与LaMnO3纯样相比(降解率为58%)，LaMnO3/GA25复合材料活化PMS降解TC的催化性能可提高至83%以上。这种增强效果可归因于GA的引入，加快了电荷的迁移速率并提升了活性位点的电荷浓度。自由基捕获试验验证了O2•−, 1O2, •OH作为活性物质在TC降解过程中的重要性。此外，通过探究LaMnO3/GA25/PMS体系对多种无机阴离子(如${{\text{H}}_{\text{2}}}\text{PO}_{\text{4}}^{{-}} $, $\text{SO}_{\text{4}}^{{2-}} $, Cl−, Urea, $\text{HCO}_{\text{3}}^{{-}} $)和腐殖酸(HA)的抗干扰活性以及和循环使用性能，证明了LaMnO3/GA25/PMS体系用于复杂水体中污染物处理的可行性，并为充分利用锰矿资源解决环境污染问题提供了新的思路。Abstract: Graphene aerogel (GA)-loaded LaMnO3 perovskite-type oxides were prepared by sol-gel and hydrothermal methods and their catalytic performance for the degradation of tetracycline (TC) by peroxymonosulfate (PMS) was investigated. SEM, TEM, XPS, and Raman spectroscopy were employed to analyze the morphological structure, elemental composition, and chemical morphology. Characterization results showed the successful preparation of LaMnO3 and LaMnO3/GA crystalline phase heterojunction. The experimental results indicated that, when compared with the pure LaMnO3 (58% degradation rate), the catalytic performance of the LaMnO3/GA25 composites for the PMS activation for TC degradation improved to be more than 83%. This enhancement was mainly attributed to GA complexation, which promotes the charge transfer rate and increases the charge concentration at the reactive sites. The vital roles of •OH and SO4•− were certified by free radical trapping assays. In addition, the catalytic activity of the LaMnO3/GA25/PMS system in complex aqueous (HA, ${{\text{H}}_{\text{2}}}\text{PO}_{\text{4}}^{{-}} $, $\text{SO}_{\text{4}}^{{2-}} $, Cl−, Urea, $\text{HCO}_{\text{3}}^{{-}} $) environments were also explored. This work demonstrated the feasibility of the LaMnO3/GA25/PMS system for wastewater treatment and provided a novel way to make full use of manganese resources to solve the problem of environmental pollution.
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Key words:
- LaMnO3 /
- Graphene aerogel /
- Peroxymonosulfate /
- Tetracycline hydrochloride /
- Catalysis
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图 1 SEM图像(a) 石墨烯气凝胶(GA)；(b) LaMnO3；(c-d) LaMnO3/GA25；(e) LaMnO3/GA25的TEM图像和(f) HRTEM图像
Figure 1. SEM images of (a) graphene aerogel (GA); (b) LaMnO3; (c-d) LaMnO3/GA25; (e) TEM images and (f) HRTEM images of LaMnO3/GA25
图 2 (a) 制备的LaMnO3/GA样品图；LaMnO3、GA和LaMnO3/GA25的(b) XRD谱图(c) 拉曼光谱图；(d) N2吸附-脱附曲线和孔径分布图像(插图)
Figure 2. (a) Diagram of prepared LaMnO3/GA samples; (b) XRD spectra (c) Raman spectra of LaMnO3, GA and LaMnO3/GA25; (d) N2 adsorption-desorption curves and pore size distribution images (insert)
图 3 LaMnO3/GA25的XPS高分辨测量谱图：(a) La 3d；(b) Mn 2p；(c) O 1s
Figure 3. XPS high-resolution measurement spectra of LaMnO3/GA25: (a) La 3d; (b) Mn 2p; (c) O 1s
图 4 (a) TC在不同催化剂下的降解曲线；(b) 相关动力学速率常数；(c) 不同体系的TOC去除效率(实验条件：催化剂用量为0.1 g/L；PMS用量为0.2 g/L；初始TC浓度为0.02 g/L)
Figure 4. (a) Degradation curves of TC under different conditions; (b) associated kinetic rate constants; (c) TOC removal efficiency of different systems (experimental conditions: catalyst dosage of 0.1 g/L; PMS dosage of 0.2 g/L; initial TC concentration of 0.02 g/L)
图 5 TC降解活性的影响规律：(a) LaMnO3/GA25浓度的影响；(b)PMS浓度的影响；(c) 初始TC浓度的影响；(d) 溶液pH值的影响；实验条件：[LaMnO3/GA25] = 0.1 g/L (b, c, d); [PMS] = 0.2 g/L (a, c, d); [TC] = 100 mL 0.02 g/L (a, b, d)
Figure 5. Patterns of influence of TC degradation activity: (a) effect of LaMnO3/GA25 concentration; (b) effect of PMS concentration; (c) effect of initial TC concentration; (d) effect of solution pH. experimental conditions: [LaMnO3/GA25] = 0.1 g/L (b, c, d); [PMS] = 0.2 g/L (a, c, d); [TC] = 100 mL 0.02 g/L(a, b, d)
图 6 无机阴离子和有机物的影响(a) HA；(b) ${{\text{H}}_{\text{2}}}\text{PO}_{\text{4}}^{{-}} $；(c) $\text{SO}_{\text{4}}^{{2-}} $；(d) Cl−；(e) Urea；(f) HCO3−；实验条件：[LaMnO3/GA25] = 0.1 g/L;[PMS] = 0.2 g/L; [TC] = 100 mL 0.02 g/L
Figure 6. Effects of inorganic anions and organic matter (a) HA; (b) ${{\text{H}}_{\text{2}}}\text{PO}_{\text{4}}^{{-}} $; (c) $\text{SO}_{\text{4}}^{{2-}} $; (d) Cl−; (e) Urea; (f) HCO3−. Experimental conditions:[LaMnO3/GA25] = 0.1 g/L; [PMS] = 0.2 g/L; [TC] = 100 mL 0.02 g/L
图 7 不同催化体系下的(a) LSV曲线；(b) 电化学阻抗谱；(c) Tafel极化曲线
Figure 7. (a) LSV curves; (b) electrochemical impedance spectra; (c) Tafel polarisation curves for different systems
图 8 牺牲剂存在下LaMnO3/GA25对TC的降解效果图Fig. 8 Plot of the degradation effect of LaMnO3/GA25 on TC in the presence of sacrificial agent
图 9 (a-c) LaMnO3/GA25在DMPO和TEMP自旋捕获下不同时间间隔的EPR图谱
Figure 9. (a-c) EPR profiles of LaMnO3/GA25 at different time intervals under DMPO and TEMP spin trapping
图 10 在LaMnO3/GA25/PMS体系中TC的降解过程
Figure 10. Degradation process of TC in the LaMnO3/GA25/PMS system
图 11 LaMnO3/GA25的催化机制示意图
Figure 11. Schematic representation of the catalytic mechanism of LaMnO3/GA25
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