硅酸盐学报

FeS₂/高岭石复合材料活化过一硫酸盐降解苯并芘性能

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李春全 ¹ , 宁晓田 ¹ , 杨珊珊 ² , 尚海灵 ³ , 袁方 ¹ , 孙志明 ¹

硅酸盐学报 | 环境矿物材料专题—研究论文 2024,52(10): 3093-3105

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硅酸盐学报 |环境矿物材料专题—研究论文 2024 , 52 (10) : 3093 -3105

FeS₂/高岭石复合材料活化过一硫酸盐降解苯并芘性能

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李春全¹, 宁晓田¹, 杨珊珊², 尚海灵³, 袁方¹, 孙志明¹

作者信息

^1．中国矿业大学（北京）化学与环境工程学院，北京 100083

^2．中国地质大学（北京）水资源与环境学院，北京 100083

^3．内蒙古自治区水利科学研究院，呼和浩特 010052

通讯作者:

孙志明（1986—），男，博士，教授。

作者简介:

李春全（1992—），男，博士，副教授。

Performance of Activating Peroxymonosulfate to Remove Benzo[a]pyrene by FeS₂/Kaolinite Composite

Chunquan LI¹, Xiaotian NING¹, Shanshan YANG², Hailing SHANG³, Fang YUAN¹, Zhiming SUN¹

Affiliations

^1.School of Chemical and Environmental Engineering, China University of Mining and Technology (Beijing), Beijing 100083, China

^2.School of Water Resources and Environment, China University of Geosciences (Beijing), Beijing 100083, China

^3.Water Conservancy Science Research Institute of Inner Mongolia, Hohhot 010018, China

Corresponding Author:

SUN Zhiming (1986-), male, Ph.D., Professor. E-mail: zhimingsun@cumtb.edu.cn

LI Chunquan (1992-), male, Ph.D., Associate Professor. E-mail: chunquanli@cumtb.edu.cn

出版时间: 2024-10-20 doi: 10.14062/j.issn.0454-5648.20240237

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摘要

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苯并芘（B［a］p）作为典型多环芳烃化合物之一，具有强致癌、致畸及致突变作用，广泛分布在土壤、大气以及水体环境。基于过硫酸盐的高级氧化技术因其快速、简便以及高效等优点在环境治理领域一直是研究热点。尤其是铁基催化材料，因其环保、成本低和反应活性高等特性被广泛应用在过硫酸盐活化领域，但其在应用过程中存在易氧化、易团聚以及Fe（Ⅱ）再生能力差等缺陷。因此，本工作采用一步水热法制备了FeS₂/高岭石复合材料，用于高效活化过一硫酸盐（PMS）降解B［a］P。其在投加量为2.0 g/L，初始B［a］p浓度为20 mg/L，PMS剂量为2 mmol/L的条件下，15 min内对B［a］p的去除率达到93%，并证实了体系中¹O₂和O₂^•−起主导作用。此外，在土壤体系中，随着复合材料和PMS用量的增加，B［a］p的降解率逐渐增加；随着水土比（质量比）的增加，呈现出先增加后降低的趋势；而随着pH值的增加，降解效率反而呈现降低的趋势，选取催化剂用量50 mg/g，PMS用量80 mg/g，水土比3：1以及pH值为3的条件下进行实验，60 min内对B［a］p的去除率达到69.02%。

关键词

高岭石 / 二硫化铁 / 苯并芘 / 过硫酸盐活化 / 土壤修复

Abstract

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Introduction

Polycyclic aromatic hydrocarbons (PAHs) are hydrophobic aromatic compounds consisting of two or more condensed benzene rings, having greater teratogenicity, carcinogenicity, mutagenicity and toxicity. The most representative PAHs is benzo(a)pyrene (B[a]p), which is composed of five benzene rings, and is classified as a Group I carcinogen. The treatment technologies for B[a]p removal include bioremediation, physical remediation and chemical remediation. The advanced oxidation technology based on sulfate radicals becomes a recent research hotspot because of its high redox potential, high reactivity and environmental friendliness. Nevertheless, persulfate needs to be activated through various approaches to produce a series of reactive species, and iron-based materials are widely used due to the abundant reserves, environmental friendliness and excellent activation performance. In this paper, pyrite (FeS₂) was used as a cheap and non-toxic sulfide mineral, allowing for a slow release of Fe²⁺ as well as the cycling of Fe²⁺ and Fe³⁺. Kaolinite was chosen as a suitable carrier to solve the agglomeration of FeS₂ nanoparticles. A composite with FeS₂ and kaolinite was prepared to obtain efficient persulfate activation and B[a]p degradation.

Methods

Ferrous sulfate heptahydrate (FeSO₄·7H₂O), sodium thiosulfate (Na₂S₂O₃), cetyltrimethylammonium bromide and kaolinite were ultrasonically mixed and stirred for 30 min, and then the solution was transferred to a reactor for the hydrothermal reaction. At the end of the reaction, the solution was centrifuged and washed for three times, and then put into a vacuum oven for 12 h to obtain the composite catalyst.

The B[a]p solution, desired dosage of catalysts and peroxymonosulfate (PMS) solution were added in a centrifuge tube of 50.00 mL, and then conducted in a rotating mixer at room temperature. Before adding PMS solution, the adsorption-desorption equilibrium process was carried out under 30 min continuous stirring. Moreover, 1.00 mL of the mixture was taken at the setting time points and quenched with 0.50 mL of MeOH. Finally, the mixture was analyzed by high-performance liquid chromatography (HPLC) after filtration.

Also, 4.00 g B[a]p-contaminated soil, desired dosage of catalysts and PMS were added in a centrifuge tube of 50.00 mL, and then conducted in a rotating mixer for 60 min at room temperature. After 60 min reaction, the supernatant was poured after centrifugation, and then the soil sample with an extraction fluid (MeOH and acetonitrile in a volume ratio of 1∶1) was ultrasonicated for 60 min to obtain 20.00 mL of soil extract. Finally, the supernatant was withdrawn and filtered for HPLC to test the residual B[a]p concentration in soil samples after centrifugation.

Results and discussion

According to the analysis by scanning electron microscopy and energy dispersive spectroscopy, a composite with kaolinite and layered FeS₂, can be prepared. The specific surface area of FeS₂/kaolinite slightly increases, and the particle size of FeS₂/kaolinite is smaller than that of FeS₂, which is attributed to the elimation of the agglomeration via the introduction of kaolinite and the improvement of the dispersibility of FeS₂, resulting in the superior catalytic performance for PMS activation and B[a]p removal.

The results show that the B[a]p removal rate is 93.00% (liquid-phase) and 69.02% (soil) under the optimum conditions (i.e., 2.0 g/L catalyst, 20 mg/L B[a]p concentration, 2 mmol/L PMS concentration (liquid-phase) and 50 mg/g catalyst, 80 mg/g PMS, 3∶1 water/soil ratio (in mass), respectively). The acidic and neutral conditions are more suitable for the PMS activation and B[a]p removal. Also, the B[a]p removal is affected in the presence of H₂PO₄^2- and HCO₃^-. The existence of Cl^- and NO₃^- promotes the B[a]p degradation efficiency. Based on the quenching experiments, the reactive species including ¹O₂, SO₄^•- and O₂^•- are proved to be involved in the process of PMS activation and B[a]p degradation, and ¹O₂ and O₂^•- are further confirmed to be the dominant reactive species.

Based on the mechanism of PMS activation in FeS₂/kaolinite/PMS, the content of Fe²⁺, S₂^2- and S⁰ is decreased after the catalytic reaction, indicating that Fe²⁺ is the main driving force for the PMS activation to generate ¹O₂, SO₄^•- and O₂^•-, and the cycling of Fe²⁺ and Fe³⁺ is facilitated in the presence of S₂^2- and S⁰ possessing reductivity. In addition, the oxygen-containing functional groups contained in kaolinite can be also beneficial to the PMS activation.

Conclusions

A composite of FeS₂/kaolinite was synthesized by an one-step hydrothermal method for PMS activation and B[a]p degradation. The degradation results demonstrated that 93.00% B[a]p was removed within 15 min under the optimized conditions (i.e., 2.0 g/L FeS₂/kaolinite, 20 mg/L B[a]p concentration, and 2 mmol/L PMS concentration). ¹O₂ and O₂^•- played a dominant role in FeS₂/kaolinite/PMS for PMS activation and B[a]p degradation. The excellent catalytic performance of FeS₂/kaolinite was also confirmed in the degradation experiment of B[a]p removal in soil, with 69.02% B[a]p degradation efficiency under the optimized conditions (i.e., 50 mg/g FeS₂/kaolinite, 80 mg/g PMS, 3∶1 water/soil ratio and pH value 3). The high catalytic performance of FeS₂/kaolinite was mainly due to the cycling of Fe²⁺ and Fe³⁺ as well as the reduction reaction between Fe³⁺ and S₂^2-/S⁰.

Key words

kaolinite / ferrous disulfide / benzo(a)pyrene / persulfate activation / soil remediation

引用本文

李春全, 宁晓田, 杨珊珊, 尚海灵, 袁方, 孙志明. FeS₂/高岭石复合材料活化过一硫酸盐降解苯并芘性能. 硅酸盐学报, 2024 , 52 (10) : 3093 -3105 . DOI: 10.14062/j.issn.0454-5648.20240237

Chunquan LI, Xiaotian NING, Shanshan YANG, Hailing SHANG, Fang YUAN, Zhiming SUN. Performance of Activating Peroxymonosulfate to Remove Benzo[a]pyrene by FeS₂/Kaolinite Composite[J]. Journal of the Chinese Ceramic Society, 2024 , 52 (10) : 3093 -3105 . DOI: 10.14062/j.issn.0454-5648.20240237

基金

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国家自然科学基金项目(52304310)

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2024年第52卷第10期

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文章信息

doi: 10.14062/j.issn.0454-5648.20240237

接收时间：2024-03-25
首发时间：2026-10-22
出版时间：2024-10-20

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收稿日期：2024-03-25
修回日期：2024-04-29

基金

国家自然科学基金项目(52304310)

作者信息

^1．中国矿业大学（北京）化学与环境工程学院，北京 100083

^2．中国地质大学（北京）水资源与环境学院，北京 100083

^3．内蒙古自治区水利科学研究院，呼和浩特 010052

通讯作者:

孙志明（1986—），男，博士，教授。

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https://castjournals.cast.org.cn/joweb/gsyxb/CN/10.14062/j.issn.0454-5648.20240237

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2种不同金属材料的力学参数

科 Family	属数 Number of genus	种数 Number of species	占总种数比例 Percentage of total species (%)	属 Genus	种数 Number of species	占总种数比例 Percentage of total species (%)
鹅膏菌科Amanitaceae	2	11	5.26	鹅膏菌属 Amanita	10	4.78
小菇科 Mycenaceae	2	12	5.74	丝盖伞属 Inocybe	5	2.39
多孔菌科 Polyporaceae	8	14	6.70	蜡蘑属 Laccaria	5	2.39
红菇科 Russulaceae	3	23	11.00	小皮伞属 Marasmius	6	2.87
				小菇属 Mycena	11	5.26
				光柄菇属 Pluteus	5	2.39
				红菇属 Russula	17	8.13
				栓菌属 Trametes	5	2.39

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