碳热还原法制备的碳载零价铁对水中U(VI)的去除研究

doi:10.15541/jim20190378

无机材料学报 ›› 2020, Vol. 35 ›› Issue (3): 373-380.DOI: 10.15541/jim20190378

所属专题： 2020年环境材料论文精选(一)放射性元素去除；优秀作者论文集锦； 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)

碳热还原法制备的碳载零价铁对水中U(VI)的去除研究

王佳琦¹,庞宏伟²,唐昊²,于淑君²,朱洪涛¹,王祥学^1,^2,³()

^1. 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
^2. 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
^3. 西南科技大学核废物与环境安全国防重点学科实验室, 绵阳 621010

收稿日期:2019-07-23 修回日期:2019-09-05 出版日期:2020-03-20 网络出版日期:2019-10-23
作者简介:王佳琦(1996-), 男, 硕士研究生. E-mail:wjqncepu@163.com
基金资助:
国家自然科学基金(21876048);国家自然科学基金(21906052);国家自然科学基金(21836001);中央高校基本科研业务费专项资金(2018ZD11);中央高校基本科研业务费专项资金(2018MS114);核废物与环境安全国防重点学科实验室开放基金(17kfhk01)

Carbothermic Synthesis of Carbon-supported Zero-valent Iron Material for Removal of U(Ⅵ) from Aqueous Solution

WANG Jiaqi¹,PANG Hongwei²,TANG Hao²,YU Shujun²,ZHU Hongtao¹,WANG Xiangxue^1,^2,³()

^1. Hebei Key Lab of Power Plant Flue Gas Multi-Pollutants Control, Department of Environmental Science and Engineering, North China Electric Power University, Baoding 071003, China
^2. MOE Key Laboratory of Resources and Environmental Systems Optimization, College of Environmental Science and Engineering, North China Electric Power University, Beijing 102206, China
^3. Fundamental Science on Nuclear Wastes and Environmental Safety Laboratory, Southwest University of Science and Technology, Mianyang 621010, China

Received:2019-07-23 Revised:2019-09-05 Published:2020-03-20 Online:2019-10-23
About author:WANG Jiaqi(1996-), male, Master candidate. E-mail: wjqcepu@163.com
Supported by:
National Natural Science Foundation of China(21876048);National Natural Science Foundation of China(21906052);National Natural Science Foundation of China(21836001);The Fundamental Research Funds for the Central Universities(2018ZD11);The Fundamental Research Funds for the Central Universities(2018MS114);The Open Foundation of Fundamental Science on Nuclear Waste and Environmental Security Laboratory(17kfhk01)

摘要/Abstract

摘要：

随着核电的发展, 放射性污染物流入环境, 污染水土资源。纳米零价铁(nZVI)材料因还原性强、去除效率高等优势, 被广泛应用于水资源污染修复。本研究以海藻酸钠(SA)为碳源, 采用一步碳热还原法制备碳载零价铁(Fe-CB)材料, 并将其用于水溶液中放射性核素U(Ⅵ)的去除。采用微观光谱和宏观实验研究Fe-CB对U(Ⅵ)的吸附性能和作用机理。研究发现Fe-CB具有丰富的官能团(如-OH和-COOH)及较高的比表面积, 弥补了纳米零价铁(nZVI)分散性差和去除效果低的不足。在298 K时, Fe-CB对U(Ⅵ)的吸附去除在3 h内达到平衡, 最大吸附量为77.3 mg·g ^-1, 是能够自发进行的化学吸附。X射线光电子能谱分析仪(XPS)分析发现Fe-CB对U(Ⅵ)的去除主要是通过吸附和还原的协同作用来实现的, 吸附过程是U(Ⅵ)与Fe-CB发生表面络合, 还原过程是通过零价铁的还原性将U(Ⅵ)还原成U(Ⅳ)。研究结果表明Fe-CB材料可作为优良的吸附剂, 在环境污染治理领域具有良好的应用前景。

关键词: 零价铁, 碳材料, 铀, 吸附, 还原

Abstract:

With the development of nuclear power, radioactive pollutants discharge into the environment and then contaminate soil and water resources. Nanoscale zero-valent iron (nZVI) materials are widely used in water remediation due to their strong reducibility and high removal efficiency. A carbon-based zero-valent iron material (Fe-CB) was prepared in this work. Fe-CB was fabricated using sodium alginate (SA) as a carbon source via one-step carbothermic method and then applied to eliminate U(Ⅵ) from aqueous solution. Its mechanism and adsorption properties of Fe-CB and U(VI) were studied by spectroscopic analyses and macroscopic experiments. The results illustrated that Fe-CB possessed of ample functional groups (such as -OH and -COOH) and high BET surface area, which made up for the dispersibility and low removal efficiency of nanoscale zero-valent iron (nZVI). The removal of U(VI) by Fe-CB achieved equilibrium in 3 h and the maximum sorption capacity was 77.3 mg·g ^-1 at 298 K. XPS analyses indicated that the U(Ⅵ) removal by Fe-CB was a synergistic effect of reductive adsorptive processes. Adsorption process resulted from surface complexation and the reduction process was dominated by U(VI) reduction to U(IV) by nZVI. The results show that Fe-CB can be used as an inexpensive and highly efficient pollutant scavenger, which has great potential for environment pollution management.

Key words: zero-valent iron, carbon material, uranium, adsorption, reduction

中图分类号:

X591

王佳琦, 庞宏伟, 唐昊, 于淑君, 朱洪涛, 王祥学. 碳热还原法制备的碳载零价铁对水中U(VI)的去除研究[J]. 无机材料学报, 2020, 35(3): 373-380.

WANG Jiaqi, PANG Hongwei, TANG Hao, YU Shujun, ZHU Hongtao, WANG Xiangxue. Carbothermic Synthesis of Carbon-supported Zero-valent Iron Material for Removal of U(Ⅵ) from Aqueous Solution[J]. Journal of Inorganic Materials, 2020, 35(3): 373-380.

图/表 10

图1 Fe-CB的SEM图片(a), 元素分布图(b)与EDS能谱分析(c)

Fig. 1 SEM image (a), element mapping (b) and EDS pattern(c) of Fe-CB

图2 SA、nZVI与Fe-CB的XRD图谱(a)和N2吸附脱附等温线(b); SA与Fe-CB的红外光谱图(c)和Fe-CB的磁滞回线(d)

Fig. 2 XRD patterns (a) and N2 adsorption-desorption isotherm (b) of SA, nZVI and Fe-CB; FT-IR spectra (c) of SA and Fe-CB; magnetization curve (d) of Fe-CB

表1 nZVI、SA和Fe-CB的BET结果

Table 1 BET results of nZVI, SA and Fe-CB

Material	Specific surface area/(m²·g^-1)	Pore diameter/nm
nZVI	4.1	1.03
SA	0.2	2.12
Fe-CB	346.6	20.12

图3 不同接触时间对Fe-CB吸附U(Ⅵ)的影响(a)、准一阶动力学拟合模型(b)和准二阶动力学拟合模型(c)

Fig. 3 Effect of contact time on the sorption of U(VI) by Fe-CB (a), and corresponding simulation of kinetics data by pseudo-first-order model (b) and pseudo-second-order model (c)

表2 Fe-CB对U(Ⅵ)吸附动力学的拟合参数

Table 2 Kinetic model parameters for remove of U(Ⅵ) by Fe-CB

Pseudo-first-order model			Pseudo-second-order model
k₁/min^-1	Q_e/(mg·g^-1)	R₁²	k₂/(g·mg^-1·min^-1)	Q_e/(mg·g^-1)	R₂²
0.4388	57.3	0.489	0.0026	64.3	0.998

图4 Fe-CB对U(Ⅵ)的吸附等温线(a)和lnKd-Ce的线性图(b)

Fig. 4 Adsorption isotherms (a) and linear plots of lnKd against Ce (b) for the elimination of U(Ⅵ) by Fe-CB at 328, 313 and 298 K

表3 Fe-CB对U(Ⅵ)吸附等温线的拟合参数

Table 3 Fitting parameters of adsorption isotherms for U(Ⅵ) on Fe-CB

T/K	Langmuir model			Freundlich model
T/K	Q_m/(mg·g^-1)	k_L/(L·mg^-1)	R₁²	k_F/(mg^1-ⁿ·Lⁿ·g^-1)	n	R₂²
298	77.3	1.40	0.971	62.6	18.62	0.788
313	89.7	1.54	0.970	71.1	16.29	0.884
328	103.7	1.25	0.959	76.4	12.15	0.901

表4 不同温度下的热力学拟合数据

Table 4 Thermodynamic parameters at different temperatures

T/K	ΔG^θ/(kJ·mol^-1)	ΔS^θ/(J·K^-1·mol^-1)	ΔH^θ/(kJ·mol^-1)
298	-5.74	34.84	4.64
313	-6.61
328	-7.72

图5 pH(a)与离子强度(b)对Fe-CB吸附能力的影响; pH对Fe-CB表面电势的影响(c), 以及U(Ⅵ)在不同pH水溶液中的物种分布(d)

Fig. 5 Effect of pH (a) and ionic strength (b) on U(Ⅵ) sorption by Fe-CB, Zeta-potential of Fe-CB (c), and relative distribution of U(VI) species in different pH (d)

图6 Fe-CB吸附U(Ⅵ)前后的XPS图谱 (a), U4f (b), Fe2p (c), O1s (d)高分辨XPS图谱

Fig. 6 XPS survey spectra of Fe-CB before and after reaction with U(Ⅵ) (a), high resolution XPS spectrum of U4f (b), and deconvolution analyses of Fe2p (c); O1s (d) for Fe-CB before and after U(Ⅵ) adsorption

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碳热还原法制备的碳载零价铁对水中U(VI)的去除研究

Carbothermic Synthesis of Carbon-supported Zero-valent Iron Material for Removal of U(Ⅵ) from Aqueous Solution

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