纳米零价铁的制备及氧化还原技术的应用进展

doi:10.11949/0438-1157.20240351

化工学报 ›› 2024, Vol. 75 ›› Issue (9): 3041-3055.DOI: 10.11949/0438-1157.20240351

纳米零价铁的制备及氧化还原技术的应用进展

胡术刚¹(), 田国庆¹^,², 刘文娟³, 徐广飞⁴, 刘华清¹^,², 张建¹^,²^,⁵, 王艳龙¹^,²()

^1.山东科技大学安全与环境工程学院，山东青岛 266590
^2.山东科技大学黄河三角洲地表过程与生态完整性研究院，山东青岛 266590
^3.泗水县苗馆镇农业农村综合服务中心，山东济宁 273200
^4.山东正奇科技集团有限公司，山东临沂 276000
^5.山东师范大学地理环境学院，山东济南 250358

收稿日期:2024-03-29 修回日期:2024-05-24 出版日期:2024-09-25 发布日期:2024-10-10
通讯作者: 王艳龙
作者简介:胡术刚（1970—），男，博士，教授， husg8921@163.com
基金资助:
山东省自然科学基金青年项目(ZR2023QB132);青岛市自然科学基金青年项目(23-2-1-56-zyyd-jch)

Preparation of nanoscale zero-valent iron and its application of reduction and oxidation technology

Shugang HU¹(), Guoqing TIAN¹^,², Wenjuan LIU³, Guangfei XU⁴, Huaqing LIU¹^,², Jian ZHANG¹^,²^,⁵, Yanlong WANG¹^,²()

^1.College of Safety and Environmental Engineering, Shandong University of Science and Technology, Qingdao 266590, Shandong, China
^2.Institute of Yellow River Delta Earth Surface Processes and Ecological Integrity, Shandong University of Science and Technology, Qingdao 266590, Shandong, China
^3.Agricultural and Rural Comprehensive Service Center of Miaoguan Town, Sishui County, Jining 273200, Shandong，China
^4.Shandong Zhengqi Technology Group Co. , Ltd. , Linyi 276000, Shandong, China
^5.School of Geographical Environment, Shandong Normal University, Jinan 250358, Shandong, China

Received:2024-03-29 Revised:2024-05-24 Online:2024-09-25 Published:2024-10-10
Contact: Yanlong WANG

摘要/Abstract

摘要：

纳米零价铁（nZVI）因具有强还原能力和高吸附性能等特点，在环境污染修复中应用前景广阔。近年来，国内外学者开发了多种nZVI的合成方法，并在nZVI还原去除有机、无机污染物以及nZVI耦合高级氧化技术方面均有较大进展。本文综述了nZVI的物理、化学和绿色合成制备方法的原理及优缺点，分析了nZVI还原降解、吸附固定等作用去除有机、无机污染物的机制及影响因素，重点探讨了nZVI联用氧化剂（如分子氧、过氧化氢、过氧化钙和过硫酸盐等）构建类芬顿技术的机理及应用进展，并对nZVI修复技术的环境应用进行了展望，以期为nZVI的高效制备和环境修复领域的广泛应用提供参考。

关键词: 纳米材料, 材料制备, 还原, 氧化, 自由基, 环境修复

Abstract:

Nanoscale zero-valent iron (nZVI) has broad application prospects in environmental pollution remediation due to its strong reduction ability and high adsorption performance. In recent years, various synthesis methods have been developed and great promotion has been made in the reduction of nZVI to remove organic and inorganic pollutants, as well as advanced oxidation technologies based on nZVI. This review provided a comprehensive summary of the mechanisms and relative merits of the main methods for nZVI preparation, including physical, chemical, and green synthesis methods. The removal mechanisms of inorganic and organic contaminants by nZVI involving reduction, adsorption, and coprecipitation were described in detail; the mechanism and environmental application of nZVI coupled with oxidants (e.g., molecular oxygen, hydrogen peroxide, calcium peroxide, and persulfate) were emphatically introduced. Additionally, the research trends and development directions for the nZVI-based technology in environmental remediation are proposed, aiming to serve as a reference for the efficient preparation and widespread application of nZVI in environmental remediation.

Key words: nanomaterials, material preparation, reduction, oxidation, radical, environmental remediation

中图分类号:

胡术刚, 田国庆, 刘文娟, 徐广飞, 刘华清, 张建, 王艳龙. 纳米零价铁的制备及氧化还原技术的应用进展[J]. 化工学报, 2024, 75(9): 3041-3055.

Shugang HU, Guoqing TIAN, Wenjuan LIU, Guangfei XU, Huaqing LIU, Jian ZHANG, Yanlong WANG. Preparation of nanoscale zero-valent iron and its application of reduction and oxidation technology[J]. CIESC Journal, 2024, 75(9): 3041-3055.

图/表 11

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98	Li S, Tang J C, Yu C, et al. Efficient degradation of anthracene in soil by carbon-coated nZVI activated persulfate[J]. Journal of Hazardous Materials, 2022, 431: 128581.
99	Zhou L, Wang Y C, Li D Q, et al. Efficient degradation of phenanthrene by biochar-supported nano zero-valent iron activated persulfate: performance evaluation and mechanism insights[J]. Environmental Science and Pollution Research International, 2023, 30(60): 125731-125740.
100	Yuan X H, Li T L, He Y Y, et al. Degradation of TBBPA by nZVI activated persulfate in soil systems[J]. Chemosphere, 2021, 284: 131166.
101	Chen M L, Yao X W, Diao Z H, et al. Oxalic acid enhanced removal of heavy metal and pesticide by peroxymonosulphate activation with a green biochar iron composite: reactivity and mechanism[J]. Separation and Purification Technology, 2023, 327: 125013.
102	Zhang Y C, Zhao L, Yang Y K, et al. Degradation of norfloxacin in an aqueous solution by the nanoscale zero-valent iron-activated persulfate process[J]. Journal of Nanomaterials, 2020, 2020: 3286383.
103	Huang S T, Lei Y Q, Guo P R, et al. Degradation of Levofloxacin by a green zero-valent iron-loaded carbon composite activating peroxydisulfate system: reactivity, products and mechanism[J]. Chemosphere, 2023, 340: 139899.
104	Wang Z, Qiu W, Pang S Y, et al. Relative contribution of ferryl ion species (Fe(Ⅳ)) and sulfate radical formed in nanoscale zero valent iron activated peroxydisulfate and peroxymonosulfate processes[J]. Water Research, 2020, 172: 115504.
105	Ji Q Q, Li J, Xiong Z K, et al. Enhanced reactivity of microscale Fe/Cu bimetallic particles (mFe/Cu) with persulfate (PS) for p-nitrophenol (PNP) removal in aqueous solution[J]. Chemosphere, 2017, 172: 10-20.
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制备方法		具体过程	优点	缺点
物理法
	机械球磨法	球磨机中钢球撞击并研磨铁粉，通过固态反应或原子扩散生成不规则nZVI	nZVI产率大，无多余副产物	nZVI粒径不均，易混合杂质，易团聚胶结，设备能耗高
	深度塑性变形法	施加准静态压力细化含铁物质以制得nZVI	nZVI粒度均匀，致密性好	生产成本高，制备周期长
	物理气相沉积法	加热含铁气化物或等离子体后急速冷凝，制得晶粒超细的nZVI	nZVI粒径小，表面清洁，颗粒分散性好	设备能耗大，生产成本高
	冷冻干燥法	低温冻结含铁溶液形成固溶体，低压升华溶剂，留下难挥发铁成分，形成nZVI	nZVI粒径小	制备周期长，冻干效率低
化学法
	液相还原法	利用硼氢化钠、硼氢化钾、水合肼等还原剂，在溶液体系中还原铁离子制得nZVI	合成路线简单，反应条件温和，nZVI纯度高，粒径分布均匀	nZVI易团聚，还原试剂价格昂贵
	蒸发冷凝法	激光加热铁靶至铁原子蒸发，在惰性气体中快速凝结形成nZVI	可控制粒径大小，nZVI纯度高，化学活性强	制备时间长，设备价格昂贵
	碳热还原法	含碳物质与氯化亚铁混合物高温热解，铁离子在保护气的高温环境中被碳还原，得到nZVI	原料便宜易得，nZVI纯度高	制备条件苛刻，设备能耗高
	热分解法	含铁有机金属分子高温热分解，铁元素被还原，形成nZVI	可调控粒径分布	制备条件苛刻，设备能耗高
	电化学法	利用电解法，使铁离子在阴极上沉积，生成nZVI	nZVI活性高，nZVI不易团聚	制备条件苛刻
	超声辅助法	利用超声作用促进传质，抑制液相还原制备的nZVI	可调控粒径分布	nZVI易高温氧化
绿色还原合成法	多以植物提取物作为原料	利用植物（如薄荷叶、大戟叶、葡萄籽、芒果皮、茶叶类）提取物与铁离子溶液混合加热还原制备nZVI	制备成本低，原料来源广，无有害废物产生	铁离子还原不彻底且nZVI会形成团聚体

制备方法		具体过程	优点	缺点
物理法
	机械球磨法	球磨机中钢球撞击并研磨铁粉，通过固态反应或原子扩散生成不规则nZVI	nZVI产率大，无多余副产物	nZVI粒径不均，易混合杂质，易团聚胶结，设备能耗高
	深度塑性变形法	施加准静态压力细化含铁物质以制得nZVI	nZVI粒度均匀，致密性好	生产成本高，制备周期长
	物理气相沉积法	加热含铁气化物或等离子体后急速冷凝，制得晶粒超细的nZVI	nZVI粒径小，表面清洁，颗粒分散性好	设备能耗大，生产成本高
	冷冻干燥法	低温冻结含铁溶液形成固溶体，低压升华溶剂，留下难挥发铁成分，形成nZVI	nZVI粒径小	制备周期长，冻干效率低
化学法
	液相还原法	利用硼氢化钠、硼氢化钾、水合肼等还原剂，在溶液体系中还原铁离子制得nZVI	合成路线简单，反应条件温和，nZVI纯度高，粒径分布均匀	nZVI易团聚，还原试剂价格昂贵
	蒸发冷凝法	激光加热铁靶至铁原子蒸发，在惰性气体中快速凝结形成nZVI	可控制粒径大小，nZVI纯度高，化学活性强	制备时间长，设备价格昂贵
	碳热还原法	含碳物质与氯化亚铁混合物高温热解，铁离子在保护气的高温环境中被碳还原，得到nZVI	原料便宜易得，nZVI纯度高	制备条件苛刻，设备能耗高
	热分解法	含铁有机金属分子高温热分解，铁元素被还原，形成nZVI	可调控粒径分布	制备条件苛刻，设备能耗高
	电化学法	利用电解法，使铁离子在阴极上沉积，生成nZVI	nZVI活性高，nZVI不易团聚	制备条件苛刻
	超声辅助法	利用超声作用促进传质，抑制液相还原制备的nZVI	可调控粒径分布	nZVI易高温氧化
绿色还原合成法	多以植物提取物作为原料	利用植物（如薄荷叶、大戟叶、葡萄籽、芒果皮、茶叶类）提取物与铁离子溶液混合加热还原制备nZVI	制备成本低，原料来源广，无有害废物产生	铁离子还原不彻底且nZVI会形成团聚体

材料	污染物和其降解效率	降解产物	降解机制	文献
100.0 g/L nZVI 800.0 ml/min O₂	10.0 mg/L双氯芬酸 21.3%	—	氧化	[67]
3.5 g/L ZVI >0.1 mg/L O₂	50.0 mg/L硝基苯 39.0%	丁烯二酸	氧化	[56]
0.4 g/L nZVI O₂（连通大气）	10.0 mg/L 2,4-二氯苯酚 46.7%	—	氧化、吸附	[68]
0.2 g/L nZVI O₂（连通大气）	40.0 mg/L 硝基苯 81.0%	二氧化碳、水	氧化	[69]
1.0 g/L nZVI 8.7 g/L O₂	20.0 mg/L Sb(Ⅲ) 86.8%	—	氧化、吸附	[65]
0.01 g nZVI 0.2 m³/h O₂	5.0 mg/L 罗丹明B 91.2%	—	氧化	[70]

材料	污染物和其降解效率	降解产物	降解机制	文献
100.0 g/L nZVI 800.0 ml/min O₂	10.0 mg/L双氯芬酸 21.3%	—	氧化	[67]
3.5 g/L ZVI >0.1 mg/L O₂	50.0 mg/L硝基苯 39.0%	丁烯二酸	氧化	[56]
0.4 g/L nZVI O₂（连通大气）	10.0 mg/L 2,4-二氯苯酚 46.7%	—	氧化、吸附	[68]
0.2 g/L nZVI O₂（连通大气）	40.0 mg/L 硝基苯 81.0%	二氧化碳、水	氧化	[69]
1.0 g/L nZVI 8.7 g/L O₂	20.0 mg/L Sb(Ⅲ) 86.8%	—	氧化、吸附	[65]
0.01 g nZVI 0.2 m³/h O₂	5.0 mg/L 罗丹明B 91.2%	—	氧化	[70]

材料	污染物及其降解效率	降解产物	降解机制	文献
0.1 g/L nZVI 20.0 mmol/L H₂O₂	50.0 mg/L 四环素 9.8%	二氧化碳、水、小分子有机物（草酸、甲酸）	氧化	[9]
0.5 g/L ZVI 1.0 mmol/L H₂O₂	10.0 mg/L 诺氟沙星 56.7%	—	氧化	[82]
0.4 g/L nZVI 0.05% H₂O₂	50.0 mg/L 五氯苯酚 57.0%	—	氧化、吸附	[78]
1.5 mmol/L nZVI 5.0 mmol/L H₂O₂	100.0 mg/kg 萘 <60.0%	二氧化碳、水	氧化	[83]
2.0 g/L nZVI 2.5 ml/L H₂O₂	有机卤素 85.0%	—	氧化	[53]
1∶2 膨润土负载nZVI/FeS₂ 2.0 mmol/L H₂O₂	0.04 mmol/L阿特拉津 98.0%	二氧化碳、水、无机氮（氯）	氧化	[75]
4.0 g/L聚丙烯腈包覆nZVI 1.0 mmol/L H₂O₂	50.0 mg/L罗丹明B 98.3%	二氧化碳、水	氧化、吸附	[84]
0.02 g/L nZVI 1.0 mmol/L H₂O₂	10.0 mg/L磺胺乙嗪 99.0%	—	氧化	[85]

纳米零价铁的制备及氧化还原技术的应用进展

Preparation of nanoscale zero-valent iron and its application of reduction and oxidation technology

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材料	污染物及其降解效率	降解产物	降解机制	文献
0.02 g/L CaO₂ 0.02 g/L FeS	19.6 mg/L三氯乙烯 9.3%	二氧化碳、氯离子	氧化	[92]
0.05 g/L聚乙烯包覆CaO₂ 0.02 g/L FeS	19.6 mg/L三氯乙烯 11.0%	—	氧化	[70]
0.09 g/L FeS 0.02 g/L 纳米CaO₂	19.6 mg/L三氯乙烯 <20.0%	—	氧化	[93]
5.0 g/L CaO₂ 1.0%（质量分数）黄铁矿	0.1 mmol/L对氨基苯磺酰胺 80.0%	—	氧化	[94]
0.1 g/L FeS₂ 0.07 g/L CaO₂	10.0 mg/L邻苯二甲酸二乙酯 100.0%	二氧化碳	氧化	[95]
0.04 g/L CaO₂ 0.04 g/L 铁基泡沫	19.6 mg/L 三氯乙烯 100.0%	—	氧化	[96]

材料	污染物及其降解效率	降解产物	降解机制	文献
1.8 g/kg nZVI 30.0 g/kg 过硫酸盐	0.1 g/kg蒽 <25.0%	二氧化碳、水	氧化	[98]
0.6 g/L nZVI 1.6 mmol/L 过硫酸盐	1.0 mg/L菲 70.4%	二氧化碳、水	吸附、氧化	[99]
0.5 g/L 膨润土负载nZVI 1.0 mmol/L 过硫酸盐	0.1 mmol/L苯酚 71.5%	儿茶酚、1,4-苯醌、丙酸、甲酸	氧化	[31]
3.0 g/kg nZVI 25.0 mmol/L过硫酸盐	5.0 mg/kg 四溴双酚A 78.3%	—	氧化	[100]
1.0 g/L生物碳负载ZVI 0.5 mmol/L 过一硫酸氢盐	10.0 mg/L 阿特拉津 79.3%	二氧化碳、水、无机氮、氯离子	氧化	[101]
0.1 g/L nZVI 12.0 mmol/L 过硫酸盐	100.0 mg/L诺氟沙星 93.8%	短链酸、二氧化碳、水	氧化	[102]
1.0 g/L 生物炭负载nZVI 0.8 mmol/L 过硫酸盐	10.0 mg/L 双酚A 98.0%	二氧化碳、水	氧化	[27]
0.8 g/L 碳包覆ZVI 1.0 mmol/L 过硫酸氢盐	40.0 mg/L左氧氟沙星 99.0%	二氧化碳、水	吸附、氧化	[103]

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