埃洛石纳米管负载锆氧化物吸附水中砷的研究

doi:10.15541/jim20220576

无机材料学报 ›› 2023, Vol. 38 ›› Issue (5): 529-536.DOI: 10.15541/jim20220576

所属专题：【能源环境】水体污染物去除(202309)

埃洛石纳米管负载锆氧化物吸附水中砷的研究

郭春霞(), 陈伟东(), 闫淑芳, 赵学平, 杨傲, 马文

内蒙古工业大学材料科学与工程学院, 内蒙古自治区薄膜与涂层重点实验室, 呼和浩特 010051

收稿日期:2022-09-29 修回日期:2022-12-15 出版日期:2022-12-28 网络出版日期:2022-12-28
通讯作者: 陈伟东, 教授. E-mail: weidongch@163.com
作者简介:郭春霞(1991-), 女, 博士研究生, 讲师. E-mail: chunchun123.cool@imut.edu.cn
基金资助:
国家自然科学基金(51964035);国家自然科学基金(62264013);内蒙古工业大学科学研究项目(ZY201806)

Adsorption of Arsenate in Water by Zirconia-halloysite Nanotube Material

GUO Chunxia(), CHEN Weidong(), YAN Shufang, ZHAO Xueping, YANG Ao, MA Wen

Inner Mongolia Key Laboratory of Thin Film and Coatings, College of Materials Science and Engineering, Inner Mongolia University of Technology, Hohhot 010051, China

Received:2022-09-29 Revised:2022-12-15 Published:2022-12-28 Online:2022-12-28
Contact: CHEN Weidong, professor. E-mail: weidongch@163.com
About author:GUO Chunxia (1991-), female, PhD candidate, lecturer. E-mail: chunchun123.cool@imut.edu.cn
Supported by:
National Natural Science Foundation of China(51964035);National Natural Science Foundation of China(62264013);Science Project of Inner Mongolia University of Technology(ZY201806)

摘要/Abstract

摘要：

长期饮用砷污染的水会严重危害人类的健康, 因此亟待开发一种高效且便于分离的除砷吸附剂。本研究采用水热法构建了一种新型高效的除砷吸附材料——埃洛石纳米管负载锆氧化物材料(ZrO₂/HNT)。使用不同手段对制备的复合材料的组成、结构和形貌进行表征, 发现氧化锆纳米颗粒均匀分布在埃洛石纳米管外壁上, 晶型为单斜结构。研究表明, ZrO₂/HNT可快速、有效地去除溶液中的As(V), 吸附反应在30 min内达到平衡。在25 ℃, As(V)的最高吸附容量为27.46 mg/g, 吸附容量随溶液pH升高而降低, 共存离子(除PO₄^3-离子外)对As(V)的吸附性能影响不大。ZrO₂/HNT对As(V)的吸附动力学数据符合准二级动力学模型。吉布斯自由能计算结果和Dubinin-Radushkevich(D-R)等温模型拟合结果表明, As(V)去除过程是吸热、化学吸附反应。傅里叶变换红外光谱(FT-IR)和X射线光电子能谱(XPS)研究表明, As(V)的去除机制主要是As(V)与ZrO₂/HNT吸附材料中ZrO₂表面的羟基发生配体交换, 最终形成稳定的内层配合物。本研究表明合成的ZrO₂/HNT吸附剂可用于去除水溶液中的As(V)。

关键词: 埃洛石纳米管, 氧化锆, 吸附, 砷

Abstract:

Drinking water contaminated with arsenic for a long time will inevitably lead to serious human health problems. Suitable adsorbent for arsenic removal from water is an urgent but a challenging task. In this study, halloysite nanotubes-supported ZrO₂ (ZrO₂/HNT), a novel and efficient arsenate adsorbent, was prepared using a straightforward hydrothermal method. Its morphology and structure were characterized. ZrO₂ nanoparticles with monoclinic phase were well dispersed on the outer walls of halloysite nanotubes. And the ZrO₂/HNT could effectively remove As(V), achieving adsorption equilibrium within 30 min. The saturation As(V) adsorption capacity was 27.46 mg/g at 25 ℃. Its adsorption capacity decreased with the increase of the solution’s pH. Coexistent ions (except phosphate) showed little effect on adsorption performance of As(V). The As(V) adsorption kinetics fitted well with pseudo-second-order modeland the As(V) removal processes were endothermic which was verified as chemisorption reactions based on calculation of Gibbs free energy and Dubinin-Radushkevich (D-R) isotherm model. Fourier transform infrared (FT-IR) and X-ray photoelectron spectrometer (XPS) study indicated that the As(V) adsorption processes mainly proceeded through ligand exchange between As(V) and hydroxyl groups on the surface of ZrO₂ in the ZrO₂/HNT and formation of inner-sphere surface complexes. This study suggest that the as-synthesized ZrO₂/ HNT is a potential candidate for practical applications of As(V) removal from water.

Key words: halloysite, zirconia, adsorption, arsenate

中图分类号:

郭春霞, 陈伟东, 闫淑芳, 赵学平, 杨傲, 马文. 埃洛石纳米管负载锆氧化物吸附水中砷的研究[J]. 无机材料学报, 2023, 38(5): 529-536.

GUO Chunxia, CHEN Weidong, YAN Shufang, ZHAO Xueping, YANG Ao, MA Wen. Adsorption of Arsenate in Water by Zirconia-halloysite Nanotube Material[J]. Journal of Inorganic Materials, 2023, 38(5): 529-536.

图/表 15

图1 (a)HNT和(b)ZrO2/HNT的SEM照片

Fig. 1 SEM images of (a) HNT and (b) ZrO2/HNT composite

图2 HNT和ZrO2/HNT的形貌及元素分布图

Fig. 2 Morphologies and element distribution of HNT and ZrO2/HNT (a, b) TEM images of HNT (a) and ZrO2/HNT (b); (c) HRTEM image of ZrO2/HNT; (d-i) TEM-EDS mapping images of ZrO2/HNT-As(V) (d), Al (e), Si (f), O (g), Zr (h), and As (i)

图3 (a) ZrO2/HNT和(b) HNT的XRD图谱

Fig. 3 XRD patterns of (a) ZrO2/HNT and (b) HNT

图4 HNT、ZrO2/HNT和ZrO2/HNT-As(V)的FT-IR光谱图

Fig. 4 FT-IR spectra of HNT, ZrO2/HNT, and ZrO2/HNT-As(V)

图5 HNT和ZrO2/HNT对As(V)的吸附动力学

Fig. 5 Adsorption kinetics for As(V) adsorption on HNT and ZrO2/HNT

表1 ZrO2/HNT对As(V)的吸附动力学拟合参数

Table 1 Adsorption kinetics parameters for As(V) adsorption on ZrO2/HNT

Model	Parameter
Psedo-first-order	Q_e/(mg•g^-1)	K₁/min^-1	R²
Psedo-first-order	20.49	0.6985	0.924
Psedo-second-order	Q_e/(mg•g^-1)	K₂/(g•mg^-1•min^-1)	R²
Psedo-second-order	21.16	0.0548	0.984

图6 ZrO2/HNT吸附剂吸附As(V)的等温线

Fig. 6 Adsorption isotherms of As(V) on ZrO2/HNT under different temperatures

表2 ZrO2/HNT吸附剂对As(V)的吸附等温线拟合参数

Table 2 Fitting results of isotherms for As(V) adsorption onto ZrO2/HNT

Isotherm model	Parameter	Temperature/℃
Isotherm model	Parameter	25	35	45
Langmuir model	Q_m/(mg•g^-1)	27.45819	30.03619	31.59709
	k_L/(L•mg^-1)	1.75844	2.36858	3.45464
	R²	0.9972	0.9994	0.9999
Freundlich model	n	9.30552	9.26368	9.98317
	k_F/(mg^1-(1/ⁿ⁾•L^1/ⁿ•g^-1)	17.15745	18.92668	20.52261
	R²	0.7370	0.76954	0.74909
D-R model	q_m/(mol•g^-1)	8.09×10^-4
	β/(mol²•kJ^-2)	4.42×10^-9
	E/(kJ•mol^-1)	10.64
	R²	0.94213

表3 不同吸附剂去除As(V)的效能比较

Table 3 Comparison of ZrO2/HNT with other reported similar adsorbents for As(V) adsorption

Adsorbent	pH	Adsorption capacity/ (mg•g^-1)	Ref.
ZrO₂/multiwall carbon nanotube	6	5	[12]
Ferric oxyhydroxides/ activated carbon	7	5	[26]
Cerium-loaded cation exchange resin	5-6	1.03	[27]
Hydrous zirconium oxide/D401	3.16	11.84	[28]
Magnetic iron oxide/ carbon encapsulates	7	17.9	[29]
Fe₃O₄-MnO₂/graphite	2-12	12.2	[30]
ZrO₂/sawdust	3-11	12	[31]
Iron oxide/carbon nanotubes	5.5	9.74	[32]
γ-Fe₂O₃ cores coated with ZrO₂	9	18.3	[33]
ZrO₂/HNT	3	27.46	This study

表4 ZrO2/HNT对As(V)吸附的热力学计算结果

Table 4 Temperature-dependent thermodynamic characteristics of As(V) adsorption on ZrO2/HNT

	Thermodynamic parameter
Temperature/℃	ΔG°/ (kJ•mol^-1)	ΔH°/ (kJ•mol^-1)	ΔS°/ (kJ•mol^-1•K^-1)
25	-20.41	37.75	0.19
35	-21.96
45	-24.33

图7 溶液pH对ZrO2/HNT材料吸附As(V)性能及Zeta电位的影响

Fig. 7 Effect of pH on Zeta potential and adsorption capacity of ZrO2/HNT for As(V)

图8 常见共存离子对ZrO2/HNT吸附剂去除As(V)效能的影响

Fig. 8 Effects of co-existing ions on adsorption of As(V) by ZrO2/HNT

图9 ZrO2/HNT材料吸附As(V)(1)前(2)后的(a) XPS总谱图, (b) As3d和(c) Zr3d XPS分谱图

Fig. 9 (a) Survey, (b) As3d, and (c) Zr3d XPS spectra of (1) ZrO2/HNT and (2) ZrO2/HNT-As(V)

图S1 D-R等温吸附模型中lnqe和ε2的拟合直线

Fig. S1 D-R isotherm plots obtained for the adsorption of As(V) on ZrO2/HNT

图S2 热力学计算中lnKd和1/T的拟合直线

Fig. S2 Plot of lnKd versus 1/T obtained for the adsorption of As(V) on ZrO2/HNT

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埃洛石纳米管负载锆氧化物吸附水中砷的研究

Adsorption of Arsenate in Water by Zirconia-halloysite Nanotube Material

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