Water Steam Bathed FeS<sub>2</sub> for Highly Efficient Fenton Degradation of Alachlor

Citation: Jizhou Jiang, Lianglang Yu, Fangyi Li, Wenming Deng, Cong Pan, Haitao Wang, Jing Zou, Yaobin Ding, Fengxia Deng, Jia Huang. Water Steam Bathed FeS₂ for Highly Efficient Fenton Degradation of Alachlor[J]. Acta Physico-Chimica Sinica, 2023, 39(3): 220903. doi: 10.3866/PKU.WHXB202209033 shu

水蒸汽浴FeS₂高效Fenton降解甲草胺

江吉周 ^1, ,
余良浪 ^1, ,
李方轶 ^1, ,
邓文明 ^1, ,
潘聪 ^2, ,
王海涛 ^{1,
,} ,
邹菁 ^1, ,
丁耀彬 ^2, ,
邓凤霞 ^3, ,
黄佳 ^{1,
,}

1.
武汉工程大学, 环境生态与生物工程学院, 化学与环境工程学院, 化工与制药学院, 绿色化工程教育部重点实验室, 磷资源开发利用教育部工程研究中心, 新型催化材料湖北省工程研究中心, 武汉 430205
2.
中南民族大学, 资源与环境学院, 武汉 430074
3.
哈尔滨工业大学, 环境学院, 城市水资源与水环境国家重点实验室, 哈尔滨 150090

通讯作者: 王海涛, wanghaitao@wit.edu.cn
黄佳, 21070201@wit.edu.cn

基金项目:
国家自然科学基金 62004143

国家自然科学基金 21876209

湖北省重点研发计划 2022BAA084

湖北省自然科学基金 2021CFB133

中央引导地方科技发展专项基金 2020ZYYD033

能量转换与存储材料化学教育部重点实验室开放基金 2021JYBKF05

磷资源开发利用教育部工程研究中心创新项目 LCX2021003

武汉工程大学绿色化工程教育部重点实验室开放基金 GCP202101

摘要: 由于硫化铁在自然环境中的丰富性，其生成活性氧和降解各种有机污染物的类Fenton活性已被广泛研究。然而，由于表面含铁活性位点的暴露有限，它们的类Fenton活性通常不高。在本研究中，以黄铁矿(FeS₂)为例，基于水蒸汽对FeS₂的热处理，开发了一种提高硫化铁矿物Fenton活性的新策略，研究发现经水蒸汽热处理后的FeS₂ (Heat-FeS₂)对甲草胺(ACL)的非均相Fenton活性比由水热反应制备的母体FeS₂ (Fresh-FeS₂)更高。在初始pH为6.3时，Heat-FeS₂-Fenton体系对ACL的降解速率为0.48 min⁻¹，约为Fresh-FeS₂-Fentton体系的23倍。电子自旋共振分析和苯甲酸探针实验证实，与Fresh-FeS₂-Fenton体系相比，在Heat-FeS₂-Fenton体系中产生更多的羟基自由基(•OH)和超氧自由基(•O₂⁻)。Heat-FeS₂的Fenton活性大幅增强主要可归因于含量增加的高活性表面Fe²⁺/Fe³⁺组份、较高的Fe²⁺浸出量和最佳的反应pH条件。扫描电镜，透射电镜，X射线光电子能谱(XPS)和傅里叶变换红外光谱等一系列表征结果表明，热处理可显著促进晶格Fe²⁺向表面活性Fe²⁺的转化，同时增强表面SO₄²⁻的生成，从而形成高酸性表面。此外，热处理后Fresh-FeS₂表面Fe²⁺在表面总铁中的百分比从13%提高到了Heat-FeS₂的29%，而且Heat-FeS₂的Fe²⁺浸出量(0.23 mmol·L⁻¹)也远高于Fresh-FeS₂的Fe²⁺浸出量(< 0.02 mmol·L⁻¹)。为了进一步阐明Heat-FeS₂材料ACL降解活性增强的机理，我们通过XPS技术监测类Fenton反应前后Heat-FeS₂表面Fe和S物种的变化关系。结果表明，H₂O₂反应后，Fresh-FeS₂和Heat-FeeS₂中Fe²⁺和Fe³⁺的表面含量显著增加，而S₂²⁻物种的表面浓度则相对下降，证实了S₂²⁻物种在Fe³⁺还原为Fe²⁺循环中的关键作用。重要的是，本研究不仅加深了对FeS₂氧化转化、腐蚀及其对天然环境中有毒有机物转化与降解的认识，而且还提供了一种基于硫化铁矿物的高效Fenton氧化方法。

关键词:

English

Water Steam Bathed FeS₂ for Highly Efficient Fenton Degradation of Alachlor

1.
School of Environmental Ecology and Biological Engineering, School of Chemistry and Environmental Engineering, School of Chemical Engineering and Pharmacy, Key Laboratory of Green Chemical Engineering Process of Ministry of Education, Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education, Novel Catalytic Materials of Hubei Engineering Research Center, Wuhan Institute of Technology, Wuhan 430205, China
2.
College of Resources and Environmental Science, South-Central Minzu University, Wuhan 430074, China
3.
State Key Laboratory of Urban Water Resources and Environment, School of Environment, Harbin Institute of Technology, Harbin 150090, China

Corresponding author: Haitao Wang, wanghaitao@wit.edu.cn Jia Huang, 21070201@wit.edu.cn

Received Date: 21 September 2022
Accepted Date: 25 October 2022
Revised Date: 14 October 2022
Available Online: 15 March 2023
Fund Project:

Abstract: Fenton-like activity of iron sulfides for the generation of reactive oxygen species and degradation of various organic pollutants has been extensively investigated due to its abundance in the natural environment. However, their Fenton-like activity is usually unsatisfactory due to the limited exposure of surface ferrous reactive sites. In this work, a new strategy to enhance the Fenton-like activity of iron sulfides, using pyrite (FeS₂) as a model, was developed based on the heat treatment of FeS₂ by water steam. It was found that the FeS₂ heat-treated by water steam (Heat-FeS₂) exhibited much higher heterogeneous Fenton activity in the degradation of alachlor (ACL) than its parent FeS₂ prepared from hydrothermal reaction (Fresh-FeS₂). At an initial pH of 6.3, the rate of degradation of ACL by Heat-FeS₂ Fenton system was 0.48 min⁻¹, which is ~23 times higher than that of Fresh-FeS₂ Fenton system. Electron spin resonance analysis and benzoic acid probe experiments confirmed the production of more hydroxyl (•OH) and superoxide radicals (•O₂⁻) in Heat-FeS₂ Fenton system than Fresh-FeS₂ Fenton system. The increased Fenton-like activity of Heat-FeS₂ can be attributed to the increased content of highly reactive surface bonded Fe²⁺/Fe³⁺ species, higher amount of leached Fe²⁺, and optimal reaction pH due to stronger acidification of Heat-FeS₂. Characterization studies by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy (XPS), and Fourier-transform infrared spectroscopy showed that heat treatment remarkably promoted the transformation of lattice Fe²⁺ to surface reactive Fe²⁺, allowing the exposure of more surface reactive Fe²⁺ and leaching of Fe²⁺; simultaneously, heat treatment enhanced the generation of surface SO₄²⁻, creating a highly acidic surface. The surface Fe²⁺ percentage in the surface total iron was raised from 13% in Fresh-FeS₂ to 29% in Heat-FeS₂. Fe²⁺ leaching from Heat-FeS₂ was 0.23 mmol·L⁻¹, much higher than that (< 0.02 mmol·L⁻¹) for Fresh-FeS₂. The change in the surface Fe and S species in the Heat-FeS₂ system during the Fenton-like reaction was monitored by XPS to elucidate the enhanced Fenton oxidation mechanism. The characterization results showed that after Fenton reaction with H₂O₂, the surface contents of Fe²⁺ and Fe³⁺ species on Fresh-FeS₂ and Heat-FeS₂ were remarkably raised, while the surface content of S₂²⁻ species was reduced, confirming the crucial role of S₂²⁻ in the reductive cycle of Fe³⁺ to Fe²⁺. These findings increase understanding of the oxidative transformation and corrosion of iron sulfides and its relevant transformation and degradation of toxic organics in natural environments. The results of this work also provide an efficient Fenton-like oxidation method based on iron sulfides for highly efficient degradation of organic pollutants (e.g. ACL) in aqueous solution.

Key words:

1. [1]
  Tyohemba, R. L.; Humphries, M. S.; Schleyer, M. H.; Porter, S. N. Environ. Pollut. 2022, 294, 118665. doi: 10.1016/j.envpol.2021.118665
2. [2]
  Lou, Y. Y.; Geneste, F.; Soutrel, I.; Amrane, A.; Fourcade, F. Sep. Purif. Technol. 2020, 232, 115936. doi: 10.1016/j.seppur.2019.115936
3. [3]
  Lerro, C. C.; Andreotti, G.; Koutros, S.; Lee, W. J.; Hofmann, J. N.; Sandler, D. P.; Parks, C. G.; Blair, A.; Lubin, J. H.; Freeman, L. E. B. JNCI-J. Natl. Cancer Inst. 2018, 110, 950. doi: 10.1093/jnci/djy005
4. [4]
  Pipi, A. R. F.; De Andrade, A. R.; Brillas, E.; Sires, I. Sep. Purif. Technol. 2014, 132, 674. doi: 10.1016/j.seppur.2014.06.022
5. [5]
  Gil, F. N.; Goncalves, A. C.; Jacinto, M. J.; Becker, J. D.; Viegas, C. A. Environ. Toxicol. Chem. 2011, 30, 2506. doi: 10.1002/etc.640
6. [6]
  Kidak, R.; Dogan, S. Chem. Eng. Process. 2015, 89, 19. doi: 10.1016/j.cep.2014.12.010
7. [7]
  Pérez, M. H.; Vega, L. P.; Zúñiga-Benítez, H.; Peñuela, G. A. Water Air Soil Poll. 2018, 229, 346. doi: 10.1007/s11270-018-3996-6
8. [8]
  Ghosh, A.; Meshram, N. K.; Saha, R. Environ. Sci. Pollut. Res. Int. 2019, 26, 11951. doi: 10.1007/s11356-019-04621-4
9. [9]
  Vanraes, P.; Wardenier, N.; Surmont, P.; Lynen, F.; Nikiforov, A.; Van Hulle, S. W. H.; Leys, C.; Bogaerts, A. J. Hazard. Mater. 2018, 354, 180. doi: 10.1016/j.jhazmat.2018.05.007
10. [10]
  De Luna, M. D. G.; Rivera, K. K. P.; Suwannaruang, T.; Wantala, K. Desalin. Water Treat. 2016, 57, 6712. doi: 10.1080/19443994.2015.1011706
11. [11]
  Paul, B.; Martens, W. N.; Frost, R. L. J. Colloid. Interface Sci. 2011, 360, 132. doi: 10.1016/j.jcis.2011.04.055
12. [12]
  Palanisamy, B.; Babu, C. M.; Sundaravel, B.; Shanthi, K.; Murugesan, V. Sci. Adv. Mater. 2015, 7, 746. doi: 10.1166/sam.2015.1914
13. [13]
  Huang, X.; Hou, X.; Jia, F.; Song, F.; Zhao, J.; Zhang, L. ACS Appl. Mater. Interfaces 2017, 9, 8751. doi: 10.1021/acsami.6b16600
14. [14]
  Xin, Y.; Liu, H.; Han, L.; Zhou, Y. J. Hazard. Mater. 2011, 192, 1812. doi: 10.1016/j.jhazmat.2011.07.005
15. [15]
  Lauga, B.; Girardin, N.; Karama, S.; Menach, K. L.; Budzinski, H.; Duran, R. Environ. Sci. Pollut. Res. Int. 2013, 20, 1089. doi: 10.1007/s11356-012-0999-5
16. [16]
  Qiang, Z.; Liu, C.; Dong, B.; Zhang, Y. Chemosphere 2010, 78, 517. doi: 10.1016/j.chemosphere.2009.11.037
17. [17]
  Cheng, D.; Yuan, S.; Liao, P.; Zhang, P. Environ. Sci. Technol. 2016, 50, 11646. doi: 10.1021/acs.est.6b02833
18. [18]
  Zhang, P.; Yuan, S. Geochim. Cosmochim. Acta 2017, 218, 153. doi: 10.1016/j.gca.2017.08.032
19. [19]
  贾晓庆, 白晓宇, 吉喆喆, 李轶, 孙妍, 秘雪岳, 展思辉. 物理化学学报, 2021, 37, 2010042. doi: 10.3866/PKU.WHXB202010042Jia, X.; Bai, X.; Ji, Z.; Li, Y.; Sun, Y.; Mi, X.; Zhan, S. Acta Phys. -Chim. Sin. 2021, 37, 2010042. doi: 10.3866/PKU.WHXB202010042
20. [20]
  Tabasum, A.; Bhatti, I. A.; Nadeem, N.; Zahid, M.; Rehan, Z. A.; Hussain, T.; Jilani, A. Water Sci. Technol. 2020, 81, 178. doi: 10.2166/wst.2020.098
21. [21]
  Shen, W.; Kang, H.; Ai, Z. J. Hazard. Mater. 2018, 357, 408. doi: 10.1016/j.jhazmat.2018.06.029
22. [22]
  Zheng, J.; Gao, Z.; He, H.; Yang, S.; Sun, C. Chemosphere 2016, 150, 40. doi: 10.1016/j.chemosphere.2016.02.001
23. [23]
  Yang, X.; Xu, X.; Xu, J.; Han, Y. J. Am. Chem. Soc. 2013, 135, 16058. doi: 10.1021/ja409130c
24. [24]
  李艳, 胡星盛, 黄静伟, 王磊, 佘厚德, 王其召. 物理化学学报, 2021, 37, 2009022. doi: 10.3866/PKU.WHXB202009022Li, Y.; Hu, X.; Huang, J.; Wang, L.; She, H.; Wang, Q. Acta Phys. -Chim. Sin. 2021, 37, 2009022. doi: 10.3866/PKU.WHXB202009022
25. [25]
  Feng, H.; Ju, Y.; Chen, B.; Fang, W.; Zhu, H.; Li, W.; Ju, L.; Qiao, P. J. Nanosci. Nanotechnol. 2021, 21, 246. doi: 10.1166/jnn.2021.18744
26. [26]
  Kantar, C.; Oral, O.; Urken, O.; Oz, N. A. J. Hazard. Mater. 2019, 373, 160. doi: 10.1016/j.jhazmat.2019.03.065
27. [27]
  Matta, R.; Hanna, K.; Chiron, S. Sci. Total Environ. 2007, 385, 24. doi: 10.1016/j.scitotenv.2007.06.030
28. [28]
  Che, H.; Bae, S.; Lee, W. J. Hazard. Mater. 2011, 185, 1355. doi: 10.1016/j.jhazmat.2010.10.055
29. [29]
  Kantar, C.; Oral, O.; Oz, N. A. Chemosphere 2019, 237, 124440. doi: 10.1016/j.chemosphere.2019.124440
30. [30]
  Liu, W.; Wang, Y.; Ai, Z.; Zhang, L. ACS Appl. Mater. Interfaces 2015, 7, 28534. doi: 10.1021/acsami.5b09919
31. [31]
  Sun, L.; Hu, D.; Zhang, Z.; Deng, X. Int. J. Environ. Res. Public Health 2019, 16, 4773. doi: 10.3390/ijerph16234773
32. [32]
  Ye, Y.; Shan, C.; Zhang, X.; Liu, H.; Wang, D.; Lv, L.; Pan, B. Environ. Sci. Technol. 2018, 52, 10657. doi: 10.1021/acs.est.8b01693
33. [33]
  Fathinia, S.; Fathinia, M.; Rahmani, A. A.; Khataee, A. Appl. Surf. Sci. 2015, 327, 190. doi: 10.1016/j.apsusc.2014.11.157
34. [34]
  Nie, W.; Mao, Q.; Ding, Y.; Hu, Y.; Tang, H. J. Hazard. Mater. 2019, 364, 59. doi: 10.1016/j.jhazmat.2018.09.078
35. [35]
  Zhao, L.; Chen, Y.; Liu, Y.; Luo, C.; Wu, D. Chemosphere 2017, 188, 557. doi: 10.1016/j.chemosphere.2017.09.019
36. [36]
  Khataee, A.; Gholami, P.; Vahid, B.; Joo, S. W. Ultrason. Sonochem. 2016, 32, 357. doi: 10.1016/j.ultsonch.2016.04.002
37. [37]
  Kantar, C.; Oral, O.; Urken, O.; Oz, N. A.; Keskin, S. Environ. Pollut. 2019, 247, 349. doi: 10.1016/j.envpol.2019.01.017
38. [38]
  Atalla, S. L.; Toledo-Pereyra, L. H.; MacKenzie, G. H.; Cederna, J. P. Transplantation 1985, 40, 584. doi: 10.1097/00007890-198512000-00002
39. [39]
  Phulkar, S.; Rao, B.; Schuchmann, H.; Sonntag, C. Z. für Naturforschung B 1990, 45, 1425. doi: 10.1515/znb-1990-1012

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通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

水蒸汽浴FeS₂高效Fenton降解甲草胺

通讯作者: 王海涛, wanghaitao@wit.edu.cn
黄佳, 21070201@wit.edu.cn

English

Water Steam Bathed FeS₂ for Highly Efficient Fenton Degradation of Alachlor

Corresponding author: Haitao Wang, wanghaitao@wit.edu.cn Jia Huang, 21070201@wit.edu.cn

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通讯作者: 陈斌, bchen63@163.com

中国化学会秘书处

水蒸汽浴FeS2高效Fenton降解甲草胺

通讯作者: 王海涛, wanghaitao@wit.edu.cn 黄佳, 21070201@wit.edu.cn

English

Water Steam Bathed FeS2 for Highly Efficient Fenton Degradation of Alachlor

Corresponding author: Haitao Wang, wanghaitao@wit.edu.cn Jia Huang, 21070201@wit.edu.cn

CCS Chemistry：嵌段共聚物自组装成 “三明治”二维有机材料，实现纳米级压力传感功能

CCS Chemistry：颜徐州、鲍哲南： 你的皮肤可能是一片SPMs

CCS Chemistry：工作高效不疲劳，只须让催化剂动起来

CCS Chemistry：静电组装导向聚合- 聚电解质纳米凝胶量化制备新策略

CCS Chemistry：金黄色葡萄球菌醛基脱氢酶是如何识别特异性底物的？

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水蒸汽浴FeS₂高效Fenton降解甲草胺

通讯作者: 王海涛, wanghaitao@wit.edu.cn
黄佳, 21070201@wit.edu.cn

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