锌硫功能生物炭活化过二硫酸盐降解亚甲基蓝

doi:10.19965/j.cnki.iwt.2023-1055

摘要/Abstract

摘要：

以入侵物种水葫芦为原料，七水硫酸锌（ZnSO₄·7H₂O）溶液作为培养基，采用简单环保的植物富集法结合一步热解法制备了锌（Zn）硫（S）功能生物炭（Zn/S-BC），并利用SEM、BET、FT-IR、XRD和XPS等对其形貌和结构等进行了表征。以亚甲基蓝（MB）为主要污染物，考察了不同体系、Zn/S-BC投加量、过二硫酸盐（PDS）投加量、初始pH、共存阴离子和不同质量浓度MB等对Zn/S-BC活化PDS降解MB的影响，并探索了体系降解MB起主导作用的活性物种。实验结果表明：在溶液初始pH为7.08、Zn/S-BC投加量为0.2 g/L、PDS投加量为0.3 mmol/L、MB初始质量浓度为50 mg/L和反应温度为25 ℃条件下，体系对MB的降解率达98.7%，Zn/S-BC-PDS体系对高质量浓度MB（100、500、1 000 mg/L）及甲基橙（MO）和四环素（TC）也有很好的降解效果。在MB降解过程中硫酸盐自由基（SO₄ ^·-）、羟基自由基（·OH）和单线态氧（¹O₂）是参与MB降解的主要活性物质，催化剂表面的含氧官能团C—O、吡啶氮、石墨氮和噻吩硫等也会参与对MB的降解。Zn/S-BC-PDS体系具有很好的抗干扰性和稳定性。该研究为绿色高效催化剂的制备及其催化PDS降解有机污染物提供了参考。

关键词: 植物富集法, 锌硫功能生物炭, 过二硫酸盐, 催化氧化, 亚甲基蓝

Abstract:

Zinc (Zn) and sulfur (S) functional biochar (Zn/S-BC) was prepared by simple and environmental friendly plant enrichment method combined with one-step pyrolysis method using invasive species water hyacinth as raw material and zinc sulfate heptahydrate (ZnSO₄·7H₂O) solution as culture medium. The morphology and structure of Zn/S-BC were characterized by SEM, BET, FT-IR, XRD, and XPS. Taking methylene blue (MB) as the main pollutant, the effects of different systems, Zn/S-BC dosage, PDS dosage, initial pH, coexisting inorganic anions and different mass concentrations of MB on the degradation of MB by Zn/S-BC activated peroxydisulfate (PDS) were investigated, and the dominant active substances playing a leading role in the degradation of MB in the system were explored. The experimental results showed that the degradation rate of MB in the system was 98.7% at the condition of initial pH of 7.08, 0.2 g/L Zn/S-BC, 0.3 mmol/L PDS, 50 mg/L MB and 25 ℃. The Zn/S-BC-PDS system also showed good degradation effects on high mass concentrations of MB (100, 500, 1 000 mg/L), methyl orange (MO) and tetracycline (TC). Sulfate radicals (SO₄ ^·-), hydroxyl radicals (·OH) and singlet oxygen (¹O₂) were the dominant active substances in the MB degradation process. In addition, the oxygen-containing functional groups C—O, pyridine-N, graphite-N and thiophenic sulfur on the surface of the catalyst would also participate in the removal of MB. Zn/S-BC-PDS system had good anti-interference and stability. This study provided a reference for the preparation of green and efficient catalysts and the catalytic degradation of organic pollutants by PDS.

Key words: plant enrichment method, zinc and sulfur functional biochar, peroxydisulfate, catalytic oxidation, methylene blue

中图分类号:

X52
X703

覃毅雪, 王盛, 张兵兵, 陈蔚洁, 安明泽, 杨照, 秦舒浩. 锌硫功能生物炭活化过二硫酸盐降解亚甲基蓝[J]. 工业水处理, 2024, 44(11): 82-92.

Yixue QIN, Sheng WANG, Bingbing ZHANG, Weijie CHEN, Mingze AN, Zhao YANG, Shuhao QIN. Degradation of methylene blue using peroxydisulfate activated by zinc and sulfur functional biochar[J]. Industrial Water Treatment, 2024, 44(11): 82-92.

https://www.iwt.cn/CN/Y2024/V44/I11/82

图/表 14

图1 BC和Zn/S-BC的制备

Fig.1 Preparation of BC and Zn/S-BC

图2 样品的SEM及EDS表征（a）BC的SEM；（b）BC的局部放大SEM；（c）BC的EDS；（d）Zn/S-BC的SEM；（e）Zn/S-BC的局部放大SEM；（f）Zn/S-BC的EDS。

Fig.2 SEM and EDS characterization of samples

图3 N₂吸附-脱附等温线和孔径分布

Fig.3 N₂ adsorption-desorption isotherms and pore size distribution

表1 BC和Zn/S-BC的比表面积、平均孔径和总孔隙容积

Table 1 Specific surface area，average pore size and total pore volume of BC and Zn/S-BC

催化剂	比表面积/（m²·g^-1）	平均孔径/nm	总孔隙容积/（cm³·g^-1）
BC	9.836	3.794	0.039 39
Zn/S-BC	42.413	1.766	0.048 99

图4 BC和Zn/S-BC的FT-IR谱图

Fig.4 FT-IR spectra of BC and Zn/S-BC

图5 BC和Zn/S-BC的XRD谱图

Fig.5 XRD spectra of BC and Zn/S-BC

图6 BC和Zn/S-BC的XPS精细谱图（a）BC和Zn/S-BC的XPS总谱图；（b）BC的C 1s；（c）BC的O 1s；（d）BC的N 1s；（e）BC的S 2p；（f）Zn/S-BC的C 1s；（g）Zn/S-BC的O 1s；（h）Zn/S-BC的N 1s；（i）Zn/S-BC的S 2p；（j）Zn/S-BC的Zn 2p。

Fig.6 XPS fine spectra of BC and Zn/S-BC

图7 不同体系降解MB的性能

Fig.7 MB degradation in different systems

图8 不同因素对体系降解MB的影响

Fig.8 Effects of different factors on the degradation of MB in the system

图9 不同自由基清除剂对Zn/S-BC活化PDS降解MB的影响

Fig.9 Effects of different free radical scavengers on the degradation of MB by Zn/S-BC activated PDS

图10 MB降解实验反应后Zn/S-BC的晶体结构和元素价态

Fig.10 Crystal structure and elemental valence states of Zn/S-BC after MB degradation experiment

图11 Zn/S-BC活化PDS降解MB的机理示意

Fig.11 Schematic diagram of the mechanism of Zn/S-BC activated PDS degrading MB

图12 Zn/S-BC的循环使用性能

Fig.12 Recycle performance of Zn/S-BC

图13 Zn/S-BC-PDS体系对不同有机污染物的降解效果

Fig.13 Degradation effect of Zn/S-BC-PDS system on different organic pollutants

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