硫化协同老化零价铁增效去除水中Cr（Ⅵ）的作用机制

doi:10.11949/0438-1157.20230042

摘要/Abstract

摘要：

为缓解零价铁（AZVI）的老化失活，考察了硫化对老化零价铁去除水中Cr（Ⅵ）性能的影响，并借助拉曼光谱、X射线光电子能谱（XPS）以及电化学等方法探究了硫化对老化零价铁除污增效的作用机制。以水中Cr（Ⅵ）为目标污染物，研究结果表明，AZVI在老化周期为0.5~1 d内反应速率从0.0024 min^-1降低至失活，而硫化的AZVI（AZVI^S）在0.5~14 d内仍能维持高反应活性。基于结构表征技术手段以及相关性分析，明确了空间硫（S^2-/S $2 2 -$ ）能够改善AZVI的电子转移能力以实现Cr（Ⅵ）的增效去除，解析了反应前后Fe和Cr的价态及含量变化，进一步揭示了表层Fe₃O₄耦合嵌层FeS/FeS₂介导内核Fe⁰电子传递以实现AZVI^S高效还原除污的反应机理。

关键词: 零价铁, 失活, 硫化, 动力学模型, 电化学, 电子转移

Abstract:

To resolve the deactivation of zero-valent iron (ZVI) by aging effect, the sulfidation was proposed in this work to improve the reactivity of aged ZVI (AZVI). In addition, the coupled effects of sulfidation and aging on the improved performance of ZVI were explored with the help of Raman spectroscopy, X-ray photoelectron spectroscopy (XPS) and electrochemistry. Taking the Cr(Ⅵ) as the targeted contaminant, the results showed that the reaction rate of AZVI decreased from 0.0024 min^-1 to 0 within an aging period of 0.5—1 d, while the sulfated AZVI (AZVI^S) maintained the high reactivity within 0.5—14 d. Based on structural characterization techniques and correlation analysis, it is clear that steric sulfur (S^2-/S $2 2 -$ ) can improve the electron transfer ability of AZVI to achieve the synergistic removal of Cr(Ⅵ), and analyze the valence states of Fe and Cr before and after the reaction. In the subshell of AZVI^S at 20 nm, the correlation coefficients of S^2-/S $2 2 -$ with lgk_SA were greater than 0.63, further demonstrating that sulfidation can modulate the reactivity of AZVI through the roles of spatial sulfurs (S^2-/S $2 2 -$ ). In addition, this work further revealed that the surface Fe₃O₄ could couple the embedded FeS/FeS₂ to mediate the electron transfer from Fe⁰ core for efficient reduction of Cr(Ⅵ) by AZVI^S. In general, this study not only helps to guide the interface reconstruction of ZVI, but also is expected to provide theoretical support for the development of ZVI-based technology for water treatment.

Key words: zero-valent iron, deactivation, sulfidation, kinetic modeling, electrochemistry, electronic transfer

中图分类号:

X 703.5

王承泽, 顾凯丽, 张晋华, 石建轩, 刘艺娓, 李锦祥. 硫化协同老化零价铁增效去除水中Cr（Ⅵ）的作用机制[J]. 化工学报, 2023, 74(5): 2197-2206.

Chengze WANG, Kaili GU, Jinhua ZHANG, Jianxuan SHI, Yiwei LIU, Jinxiang LI. Sulfidation couples with aging to enhance the reactivity of zerovalent iron toward Cr(Ⅵ) in water[J]. CIESC Journal, 2023, 74(5): 2197-2206.

图/表 6

图1 不同体系下零价铁除Cr(Ⅵ)反应动力学

Fig.1 Kinetics of Cr(Ⅵ) removal by ZVI in different reaction systems

图2 AZVIS的SEM图像

Fig.2 SEM images of AZVIS

图3 AZVIS的拉曼光谱(a)及20 nm深度处S 2p的XPS能谱(b)

Fig.3 Raman spectra (a) and S 2p XPS spectra at 20 nm (b) of AZVIS samples

图4 AZVIS的腐蚀动力学

Fig.4 Corrosion kinetics of AZVIS

图5 AZVIS与Cr(Ⅵ) 反应后Cr(a)，反应前Fe(b)，反应后Fe 2p (c)的XPS能谱

Fig.5 XPS depth profiling spectra of Cr after reaction (a), Fe before reaction (b), and Fe 2p after reaction (c)

图6 AZVIS除Cr(Ⅵ)的比表面积归一化常数与其20 nm深度处S含量的相关性分析

Fig.6 Correlation analysis of the normalization constant of the specific surface area of AZVIS for the removal of Cr(Ⅵ) and its S content at a depth of 20 nm

参考文献 31

1	王兴润, 张艳霞, 王琪, 等. 铬污染建筑废物不同清洗剂的作用效果比较[J]. 化工学报, 2012, 63(10): 3255-3261.
	Wang X R, Zhang Y X, Wang Q, et al. Comparison of different washing agents for disposal of chromium-contaminated construction waste[J]. CIESC Journal, 2012, 63(10): 3255-3261.
2	朱文会, 李志涛, 王夏晖, 等. 不同异位修复工艺对高浓度铬渣污染土壤中Cr的去除特性[J]. 化工学报, 2018, 69(6): 2730-2736.
	Zhu W H, Li Z T, Wang X H, et al. Characteristics of chromium removing using different ex-situ remediations in soil seriously contaminated by chromite ore processing residue[J]. CIESC Journal, 2018, 69(6): 2730-2736.
3	程治良, 全学军, 代黎, 等. 水力喷射空气旋流器用于含Cr(Ⅵ)废水处理[J]. 化工学报, 2014, 65(4): 1403-1410.
	Cheng Z L, Quan X J, Dai L, et al. Treatment of Cr(Ⅵ)-containing wastewater in a water-sparged aerocyclone[J]. CIESC Journal, 2014, 65(4): 1403-1410.
4	Zafar A M, Javed M A, Hassan A A, et al. Groundwater remediation using zero-valent iron nanoparticles (nZVI)[J]. Groundwater for Sustainable Development, 2021, 15: 100694.
5	Vollprecht D, Krois L M, Sedlazeck K P, et al. Removal of critical metals from waste water by zero-valent iron[J]. Journal of Cleaner Production, 2019, 208: 1409-1420.
6	Guan X H, Sun Y K, Qin H J, et al. The limitations of applying zero-valent iron technology in contaminants sequestration and the corresponding countermeasures: the development in zero-valent iron technology in the last two decades (1994—2014)[J]. Water Research, 2015, 75: 224-248.
7	Xie Y, Cwiertny D M. Influence of anionic cosolutes and pH on nanoscale zerovalent iron longevity: time scales and mechanisms of reactivity loss toward 1, 1, 1, 2-tetrachloroethane and Cr(Ⅵ)[J]. Environmental Science & Technology, 2012, 46(15): 8365-8373.
8	Sun Y K, Li J X, Huang T L, et al. The influences of iron characteristics, operating conditions and solution chemistry on contaminants removal by zero-valent iron: a review[J]. Water Research, 2016, 100: 277-295.
9	曹贝, 李锦祥, 关小红. 弱磁场强化零价铁对水中U(Ⅵ)去除效能[J]. 化工学报, 2017, 68(8): 3282-3290.
	Cao B, Li J X, Guan X H. Enhancing reactivity of zerovalent iron toward U(‍Ⅵ) by weak magnetic field[J]. CIESC Journal, 2017, 68(8): 3282-3290.
10	Su Y M, Adeleye A S, Keller A A, et al. Magnetic sulfide-modified nanoscale zerovalent iron (S-nZVI) for dissolved metal ion removal[J]. Water Research, 2015, 74: 47-57.
11	Liu T X, Li X M, Waite T D. Depassivation of aged Fe₀ by divalent cations: correlation between contaminant degradation and surface complexation constants[J]. Environmental Science & Technology, 2014, 48(24): 14564-14571.
12	Liu T X, Li X M, Waite T D. Depassivation of aged Fe⁰ by ferrous ions: implications to contaminant degradation[J]. Environmental Science & Technology, 2013, 47(23): 13712-13720.
13	Liu T X, Li X M, Waite T D. Depassivation of aged Fe⁰ by inorganic salts: implications to contaminant degradation in seawater[J]. Environmental Science & Technology, 2013, 47(13): 7350-7356.
14	Lipczynska-Kochany E, Harms S, Milburn R, et al. Degradation of carbon tetrachloride in the presence of iron and sulphur containing compounds[J]. Chemosphere, 1994, 29(7): 1477-1489.
15	Kim E J, Kim J H, Azad A M, et al. Facile synthesis and characterization of Fe/FeS nanoparticles for environmental applications[J]. ACS Applied Materials & Interfaces, 2011, 3(5): 1457-1462.
16	Li J X, Zhang X Y, Liu M C, et al. Enhanced reactivity and electron selectivity of sulfidated zerovalent iron toward chromate under aerobic conditions[J]. Environmental Science & Technology, 2018, 52(5): 2988-2997.
17	Li D, Mao Z, Zhong Y, et al. Reductive transformation of tetrabromobisphenol A by sulfidated nano zerovalent iron[J]. Water Research, 2016, 103: 1-9.
18	Wang B, Dong H R, Li L, et al. Influence of different co-contaminants on trichloroethylene removal by sulfide-modified nanoscale zero-valent iron[J]. Chemical Engineering Journal, 2020, 381: 122773.
19	Dong H R, Zhang C, Deng J M, et al. Factors influencing degradation of trichloroethylene by sulfide-modified nanoscale zero-valent iron in aqueous solution[J]. Water Research, 2018, 135: 1-10.
20	Xu J, Cao Z, Zhou H, et al. Sulfur dose and sulfidation time affect reactivity and selectivity of post-sulfidized nanoscale zerovalent iron[J]. Environmental Science & Technology, 2019, 53(22): 13344-13352.
21	Semerád J, Filip J, Ševců A, et al. Environmental fate of sulfidated nZVI particles: the interplay of nanoparticle corrosion and toxicity during aging[J]. Environmental Science: Nano, 2020, 7(6): 1794-1806.
22	Fan D M, Johnson G O, Tratnyek P G, et al. Sulfidation of nano zerovalent iron (nZVI) for improved selectivity during in-situ chemical reduction (ISCR)[J]. Environmental Science & Technology, 2016, 50(17): 9558-9565.
23	Cao Z, Li H, Xu X H, et al. Correlating surface chemistry and hydrophobicity of sulfidized nanoscale zerovalent iron with its reactivity and selectivity for denitration and dechlorination[J]. Chemical Engineering Journal, 2020, 394: 124876.
24	Liang L P, Guan X H, Shi Z, et al. Coupled effects of aging and weak magnetic fields on sequestration of selenite by zero-valent iron[J]. Environmental Science & Technology, 2014, 48(11): 6326-6334.
25	Xu H Y, Sun Y K, Li J X, et al. Aging of zerovalent iron in synthetic groundwater: X-ray photoelectron spectroscopy depth profiling characterization and depassivation with uniform magnetic field[J]. Environmental Science & Technology, 2016, 50(15): 8214-8222.
26	Ling J F, Qiao J L, Song Y D, et al. Influence of coexisting ions on the electron efficiency of sulfidated zerovalent iron toward Se(Ⅵ) removal[J]. Chemical Engineering Journal, 2019, 378: 122124.
27	Li J X, Zhang X Y, Sun Y K, et al. Advances in sulfidation of zerovalent iron for water decontamination[J]. Environmental Science & Technology, 2017, 51(23): 13533-13544.
28	Mangayayam M C, Perez J P H, Dideriksen K, et al. Structural transformation of sulfidized zerovalent iron and its impact on long-term reactivity[J]. Environmental Science: Nano, 2019, 6(11): 3422-3430.
29	Gu Y W, Gong L, Qi J L, et al. Sulfidation mitigates the passivation of zero valent iron at alkaline pHs: experimental evidences and mechanism[J]. Water Research, 2019, 159: 233-241.
30	Gu Y W, Wang B B, He F, et al. Mechanochemically sulfidated microscale zero valent iron: pathways, kinetics, mechanism, and efficiency of trichloroethylene dechlorination[J]. Environmental Science & Technology, 2017, 51(21): 12653-12662.
31	Xu J, Wang Y, Weng C, et al. Reactivity, selectivity, and long-term performance of sulfidized nanoscale zerovalent iron with different properties[J]. Environmental Science & Technology, 2019, 53(10): 5936-5945.

[1]	金正浩, 封立杰, 李舒宏. 氨水溶液交叉型再吸收式热泵的能量及分析[J]. 化工学报, 2023, 74(S1): 53-63.
[2]	王阳, 戴永强, 曾炜. 2，5-二羟基苯磺酸增强离子水凝胶材料热电性能的研究[J]. 化工学报, 2023, 74(9): 3946-3955.
[3]	程业品, 胡达清, 徐奕莎, 刘华彦, 卢晗锋, 崔国凯. 离子液体基低共熔溶剂在转化CO₂中的应用[J]. 化工学报, 2023, 74(9): 3640-3653.
[4]	李锦潼, 邱顺, 孙文寿. 煤浆法烟气脱硫中草酸和紫外线强化煤砷浸出过程[J]. 化工学报, 2023, 74(8): 3522-3532.
[5]	胡亚丽, 胡军勇, 马素霞, 孙禹坤, 谭学诣, 黄佳欣, 杨奉源. 逆电渗析热机新型工质开发及电化学特性研究[J]. 化工学报, 2023, 74(8): 3513-3521.
[6]	张琦钰, 高利军, 苏宇航, 马晓博, 王翊丞, 张亚婷, 胡超. 碳基催化材料在电化学还原二氧化碳中的研究进展[J]. 化工学报, 2023, 74(7): 2753-2772.
[7]	张蒙蒙, 颜冬, 沈永峰, 李文翠. 电解液类型对双离子电池阴阳离子储存行为的影响[J]. 化工学报, 2023, 74(7): 3116-3126.
[8]	葛加丽, 管图祥, 邱新民, 吴健, 沈丽明, 暴宁钟. 垂直多孔碳包覆的FeF₃正极的构筑及储锂性能研究[J]. 化工学报, 2023, 74(7): 3058-3067.
[9]	屈园浩, 邓文义, 谢晓丹, 苏亚欣. 活性炭/石墨辅助污泥电渗脱水研究[J]. 化工学报, 2023, 74(7): 3038-3050.
[10]	张谭, 刘光, 李晋平, 孙予罕. Ru基氮还原电催化剂性能调控策略[J]. 化工学报, 2023, 74(6): 2264-2280.
[11]	李艳辉, 丁邵明, 白周央, 张一楠, 于智红, 邢利梅, 高鹏飞, 王永贞. 非常规服役超临界锅炉的微纳尺度腐蚀动力学模型建立及应用[J]. 化工学报, 2023, 74(6): 2436-2446.
[12]	周继鹏, 何文军, 李涛. 异形催化剂上乙烯催化氧化失活动力学反应工程计算[J]. 化工学报, 2023, 74(6): 2416-2426.
[13]	郭旭, 张永政, 夏厚兵, 杨娜, 朱真珍, 齐晶瑶. 碳基材料电氧化去除水体污染物的研究进展[J]. 化工学报, 2023, 74(5): 1862-1874.
[14]	张正, 何永平, 孙海东, 张荣子, 孙正平, 陈金兰, 郑一璇, 杜晓, 郝晓刚. 蛇形流场电控离子交换装置用于选择性提锂[J]. 化工学报, 2023, 74(5): 2022-2033.
[15]	李瑞康, 何盈盈, 卢维鹏, 王园园, 丁皓东, 骆勇名. 电化学强化钴基阴极活化过一硫酸盐的研究[J]. 化工学报, 2023, 74(5): 2207-2216.