三元水滑石负载的硫化纳米零价铁对铀的高效去除与机理研究

doi:10.15541/jim20190365

无机材料学报 ›› 2020, Vol. 35 ›› Issue (3): 381-389.DOI: 10.15541/jim20190365

所属专题： 2020年环境材料论文精选(一)放射性元素去除； 2019~2020年度优秀作者作品欣赏:环境材料；【虚拟专辑】放射性污染物去除(2020~2021)

三元水滑石负载的硫化纳米零价铁对铀的高效去除与机理研究

庞宏伟¹,唐昊¹,王佳琦²,王祥学^1,²,于淑君¹()

^1. 华北电力大学环境科学与工程学院, 资源环境系统优化教育部重点实验室, 北京 102206
^2. 华北电力大学环境科学与工程系, 燃煤电站烟气多污染物协同控制实验室, 保定 071003

收稿日期:2019-07-19 修回日期:2019-08-24 出版日期:2020-03-20 网络出版日期:2019-10-23
作者简介:庞宏伟(1994-), 男, 博士研究生. E-mail: panghw1994@163.com
基金资助:
国家自然科学基金(21906052);国家自然科学基金(21876048);中央高校基本科研业务费专项资金资助(2018ZD11);中央高校基本科研业务费专项资金资助(2018MS114)

Ternary Layered Double Hydroxide Supported Sulfide NZVI: Efficient U(VI) Elimination and Mechanism

PANG Hongwei¹,TANG Hao¹,WANG Jiaqi²,WANG Xiangxue^1,²,YU Shujun¹()

^1. MOE Key Laboratory of Resources and Environmental Systems Optimization, College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, China
^2. Heibei Key Lab of Power Plant Flue Gas Multi-Pollutants Control, Department of Environmental Science and Engineering, North China Electric Power University, Baoding 071003, China

Received:2019-07-19 Revised:2019-08-24 Published:2020-03-20 Online:2019-10-23
About author:PANG Hongwei(1994-), male, PhD candidate. E-mail: panghw1994@163.com
Supported by:
National Natural Science Foundation of China(21906052);National Natural Science Foundation of China(21876048);Special Funds for Basic Research Operating Costs of Central Colleges and Universities(2018ZD11);Special Funds for Basic Research Operating Costs of Central Colleges and Universities(2018MS114)

摘要/Abstract

摘要：

纳米零价铁材料(NZVI)被广泛用于环境中放射性核素U(VI)的去除, 但是单纯的NZVI存在稳定性差、去除效果差等不足。本研究结合表面钝化技术与负载技术制备得到Ca-Mg-Al水滑石负载的硫化纳米零价铁材料(CMAL-SNZVI), 并将其用于U(VI)的高效去除。结合宏观试验与光谱分析表征得到的结果表明, CMAL-SNZVI材料具有出色的理化性质与较高的活性, 对水溶液中U(VI)的去除具有优良的效果, 在2 h内可以达到反应平衡, 且最大吸附量可达175.7 mg·g ^-1。CMAL-SNZVI对U(VI)的去除主要是由吸附过程与氧化还原反应相结合的方式: 吸附过程中U(VI)与材料中的CMAL基底、SNZVI的表层通过内层表面络合作用结合; 还原过程中材料的NZVI内核将U(VI)还原成低毒难溶的U(IV)后去除。CMAL-SNZVI可为NZVI材料的改性方法提供新的研究方向, 同时, CMAL-SNZVI在污染物去除方面表现优异, 可以作为出色的环境修复材料。

关键词: 硫化纳米零价铁, 双金属氢氧化物, U(VI), 吸附, 还原

Abstract:

Nanoscale zero-valent iron (NZVI) has been widely applied to eliminate radionuclide U(VI). However, poor stability and low efficiency restrict the employment of pure NZVI. In this study, surface passivation and dispersion technology were employed together. Ca-Mg-Al layered double hydroxide supported sulfide NZVI (CMAL-SNZVI) was synthesized and applied for U(VI) elimination. Macroscopic and microscopic investigations demonstrate the outstanding physicochemical properties, high reactivity and excellent performance for U(VI) removal. The reaction process can be achieved equilibrium within 2 h and the maximum elimination capacity reaches 175.7 mg·g ^-1. The removal mechanism of U(VI) on CMAL-SNZVI is the synergistic effect between adsorption and reduction, through which U(VI) can be adsorbed by CMAL base and the SNZVI surface via inner-sphere surface complexation, U(VI) can be reduced into less toxic and insoluble U(IV) by Fe ⁰ inner core. Overall, the synthetization of CMAL-SNZVI can lead a new direction of NZVI modification. In the meantime, the outstanding performance of U(VI) removal indicate the potential of CMAL-SNZVI as excellent material for environment remediation.

Key words: SNZVI, layered double hydroxide, U(VI), adsorption, reduction

中图分类号:

X591

庞宏伟, 唐昊, 王佳琦, 王祥学, 于淑君. 三元水滑石负载的硫化纳米零价铁对铀的高效去除与机理研究[J]. 无机材料学报, 2020, 35(3): 381-389.

PANG Hongwei, TANG Hao, WANG Jiaqi, WANG Xiangxue, YU Shujun. Ternary Layered Double Hydroxide Supported Sulfide NZVI: Efficient U(VI) Elimination and Mechanism[J]. Journal of Inorganic Materials, 2020, 35(3): 381-389.

图/表 9

图1 NZVI(A)、SNZVI(B)、CMAL(C)与CMAL-SNZVI(E)的SEM照片; CMAL(D)与CMAL-SNZVI(F)的TEM照片

Fig. 1 SEM images of NZVI (A), SNZVI (B), CMAL (C) and CMAL-SNZVI (E); TEM images of CMAL (D) and CMAL- SNZVI (F)

图2 CMAL-SNZVI中Ca(A), Mg(B), Al(C), Fe(D), S(E), O(F)元素的分布图与EDS能谱分析(G)

Fig. 2 Element mapping of Ca(A), Mg(B), Al(C), Fe(D), S(E), and O(F), and EDS pattern (G) of CMAL-SNZVI

图3 CMAL-SNZVI、CMAL和SNZVI的XRD图谱(A), CMAL-SNZVI的N2吸附-脱附等温线(B)与磁滞回线(C)

Fig.3 XRD patterns (A) of CMAL-SNZVI, CMAL and SNZVI, N2 adsorption-desorption isotherm (B)and magnetization curve (C) of CMAL-SNZVI

表1 CAML与CMAL-SNZVI对U(VI)去除的相关动力学参数

Table 1 Kinetic modeling of U(VI) adsorption on CMAL and CMAL-SNZVI

Material	Pseudo-first-order model			Pseudo-second-order model
Material	k₁/min^-1	Q_e/(mg·g^-1)	R²	k₂/(g·mg^-1·min^-1)	Q_e/(mg·g^-1)	R²
CMAL	0.049	62.62	0.95	0.0015	65.36	0.99
CMAL-SNZVI	0.121	87.60	0.94	0.0036	90.09	0.99

图4 CMAL-SNZVI与CMAL去除U(VI)的吸附动力学(A), 拟一阶动力学模型(B)与拟二阶动力学模型(C)拟合情况以及25 ℃时的吸附等温线(D)

Fig. 4 Adsorption kinetics (A), pseudo-first-order (B) and pseudo-second-order kinetic plots (C), adsorption isotherms (D) of U(VI) adsorption on CMAL-SNZVI and CMAL

表2 25 ℃下CAML与CMAL-SNZVI对U(VI)去除的等温线拟合及其相关参数

Table 2 Parameters calculated from the Langmuir and Freundlich models for U(VI) adsorption on CMAL-SNZVI at 25 ℃

Adsorbents	Langmuir model			Freundlich model
Adsorbents	Q_max/(mg·g^-1)	K_L/(L·mg^-1)	R²	K_F/(mg^1-ⁿ·Lⁿ·g^-1)	n	R²
CMAL	129.8	0.36	0.975	51.5	3.89	0.877
CMAL	175.7	0.95	0.954	89.5	4.60	0.933
-SNZVI	175.7	0.95	0.954	89.5	4.60	0.933

表3 不同吸附材料对U(VI)的去除效果对比

Table 3 Comparison of CMAL-SNZVI with other typical adsorbents for U(VI) decontamination

Adsorbents	pH	Equilibrium time/h	Removal capacity /(mg·g^-1)	Ref.
nZVI/C composite	4.0	Not given	103.1	[25]
g-C₃N₄@Ni-Mg-Al-LDH	5.0	6	99.7	[26]
Ca-Mg-Al-LDH	5.0	24	132.5	[27]
GO@LDH	4.5	10	159.7	[28]
Magnetic biochar	3.0	12	54.4	[29]
CMAL	5.0	2	129.8	This study
CMAL-SNZVI	5.0	2	175.7	This study

图5 背景溶液pH(A)与离子浓度(C)对CMAL-SNZVI与CMAL的U(VI)去除效率的影响, pH对CMAL-SNZVI的Zeta电势值的影响(B), 通过Visual MINTEQ软件对不同pH下U(VI)在水溶液中的物种分布模拟图(D)

Fig. 5 Effect of pH (A) and ionic strength (C) on U(VI) adsorption of CMAL-SNZVI and CMAL, Zeta potential values of CMAL-SZVI as a function of pH (B), species distribution of U(VI) as a function of pH by Visual MINTEQ (D)

图6 吸附前后CMAL-SNZVI材料的总XPS图谱(A)以及U4f (B), Fe2p (C), S2p (D), Ca2p (E), Mg1s (F)与Al2p (G)的高分辨率XPS图谱; CMAL-SNZVI对U(VI)去除的反应机理示意图(H)

Fig. 6 XPS survey spectra of CMAL-SNZVI (before and after U(VI) adsorption) (A), High -resolution XPS spectra of U4f (B), Fe2p (C), S2p (D), Ca2p (E), Mg1s (F) and Al2p (G), and removal mechanisms of U(VI) on CMAL-SNZVI (H)

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三元水滑石负载的硫化纳米零价铁对铀的高效去除与机理研究

Ternary Layered Double Hydroxide Supported Sulfide NZVI: Efficient U(VI) Elimination and Mechanism

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