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 CSTR: 32189.14.10.15541/jim20220576

所属专题：【能源环境】污染物去除(202312)

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

参考文献 36

[1]	PODGORSKI J, BERG M. Global threat of arsenic in groundwater. Science, 2020, 368(6493): 845. DOI PMID
[2]	UNGUREANU G, SANTOS S, BOAVENTURA R, et al. Arsenic and antimony in water and wastewater: overview of removal techniques with special reference to latest advances in adsorption. Journal of Environmental Management, 2015, 151: 326. DOI PMID
[3]	ZHANG Y, LIU H, GAO F, et al. Application of MOFs and COFs for photocatalysis in CO₂ reduction, H₂ generation, and environmental treatment. EnergyChem, 2022, 4(4): 100078. DOI URL
[4]	LIU X, VERMA G, CHEN Z, et al. Metal-organic framework nanocrystal-derived hollow porous materials: synthetic strategies and emerging applications. The Innovation, 2022, 3(5): 100281. DOI URL
[5]	WANG X X, LI X, WANG J Q, et al. Recent advances in carbon nitride-based nanomaterials for the removal of heavy metal ions from aqueous solution. Journal of Inorganic Materials, 2020, 35(3): 260. DOI
[6]	ZHENG Y M, YU L, WU D, et al. Removal of arsenite from aqueous solution by a zirconia nanoparticle. Chemical Engineering Journal, 2012, 188: 15. DOI URL
[7]	SHEHZAD K, AHMAD M, XIE C, et al. Mesoporous zirconia nanostructures (MZN) for adsorption of As(III) and As(V) from aqueous solutions. Journal of Hazardous Materials, 2019, 373: 75. DOI PMID
[8]	HE X Y, DENG F, SHEN T T, et al. Exceptional adsorption of arsenic by zirconium metal-organic frameworks: engineering exploration and mechanism insight. Journal of Colloid and Interface Science, 2019, 539: 223. DOI PMID
[9]	SHAO P H, DING L, LUO J F, et al. Lattice-defect-enhanced adsorption of arsenic on zirconia nanospheres: a combined experimental and theoretical study. ACS Applied Materials & Interfaces, 2019, 11(33): 29736.
[10]	LATA S, SAMADDER S R. Removal of arsenic from water using nano adsorbents and challenges: a review. Journal of Environmental Management, 2016, 166: 387. DOI PMID
[11]	LUO J M, LUO X B, HU C Z, et al. Zirconia (ZrO₂) embedded in carbon nanowires via electrospinning for efficient arsenic removal from water combined with DFT studies. ACS Applied Materials & Interfaces, 2016, 8(29): 18912.
[12]	ADDO NTIM S, MITRA S. Adsorption of arsenic on multiwall carbon nanotube-zirconia nanohybrid for potential drinking water purification. Journal of Colloid and Interface Science, 2012, 375(1): 154. DOI PMID
[13]	SARKAR A, PAUL B. Evaluation of the performance of zirconia- multiwalled carbon nanotube nanoheterostructures in adsorbing As(III) from potable water from the perspective of physical chemistry and chemical physics with a special emphasis on approximate site energy distribution. Chemosphere, 2020, 242: 15.
[14]	SARKAR A, PAUL B. Analysis of the performance of zirconia- multiwalled carbon nanotube nanoheterostructures in adsorbing As(V) from potable water from the aspects of physical chemistry with an emphasis on adsorption site energy distribution and density functional theory calculations. Microporous and Mesoporous Materials, 2020, 302: 110191. DOI URL
[15]	YUAN P, TAN D Y, ANNABI-BERGAYA F. Properties and applications of halloysite nanotubes: recent research advances and future prospects. Applied Clay Science, 2015, 112: 75.
[16]	LVOV Y, WANG W, ZHANG L, et al. Halloysite clay nanotubes for loading and sustained release of functional compounds. Advanced Materials, 2016, 28(6): 1227. DOI URL
[17]	SMEDLEY P L, KINNIBURGH D G. A review of the source, behaviour and distribution of arsenic in natural waters. Applied Geochemistry, 2002, 17(5): 517. DOI URL
[18]	STYBLO M, DEL RAZO L M, VEGA L, et al. Comparative toxicity of trivalent and pentavalent inorganic and methylated arsenicals in rat and human cells. Archives of Toxicology, 2000, 74(6): 289. DOI PMID
[19]	CAI N, DAI Q, WANG Z L, et al. Toughening of electrospun poly(L-lactic acid) nanofiber scaffolds with unidirectionally aligned halloysite nanotubes. Journal of Materials Science, 2015, 50(3): 1435. DOI URL
[20]	ZHENG P W, DU Y Y, MA X F. Selective fabrication of iron oxide particles in halloysite lumen. Materials Chemistry and Physics, 2015, 151: 14. DOI URL
[21]	SEREDYCH M, BANDOSZ T J. Effects of surface features on adsorption of SO₂on graphite oxide/Zr(OH)₄ composites. Journal of Physical Chemistry C, 2010, 114(34): 14552. DOI URL
[22]	SHEHZAD K, AHMAD M, HE J Y, et al. Synthesis of ultra-large ZrO₂ nanosheets as novel adsorbents for fast and efficient removal of As(III) from aqueous solutions. Journal of Colloid and Interface Science, 2019, 533: 588. DOI URL
[23]	HE Q, YANG D, DENG X L, et al. Preparation, characterization and application of N-2-pyridylsuccinamic acid-functionalized halloysite nanotubes for solid-phase extraction of Pb(II). Water Research, 2013, 47(12): 3976. DOI URL
[24]	SONG Y R, YUAN P, DU P X, et al. A novel halloysite-CeO_x nanohybrid for efficient arsenic removal. Applied Clay Science, 2020, 186: 10.
[25]	SONG X L, ZHOU L, ZHANG Y, et al. A novel cactus-like Fe₃O₄/halloysite nanocomposite for arsenite and arsenate removal from water. Journal of Cleaner Production, 2019, 224: 573. DOI URL
[26]	ARCIBAR-OROZCO J A, AVALOS-BORJA M, RANGEL-MENDEZ J R. Effect of phosphate on the particle size of ferric oxyhydroxides anchored onto activated carbon: As(V) removal from water. Environmental Science & Technology, 2012, 46(17): 9577. DOI URL
[27]	HE Z L, TIAN S L, NING P. Adsorption of arsenate and arsenite from aqueous solutions by cerium-loaded cation exchange resin. Journal of Rare Earths, 2012, 30(6): 563. DOI URL
[28]	LI C H, XU W, JIA D M, et al. Removal of arsenic from drinking water by using the Zr-loaded resin. Journal of Chemical and Engineering Data, 2013, 58(2): 427. DOI URL
[29]	WU Z X, LI W, WEBLEY P A, et al. General and controllable synthesis of novel mesoporous magnetic iron oxide@carbon encapsulates for efficient arsenic removal. Advanced Materials, 2012, 24(4): 485. DOI URL
[30]	CHANDRA V, PARK J, CHUN Y, et al. Water-dispersible magnetite-reduced graphene oxide composites for arsenic removal. ACS Nano, 2010, 4(7): 3979. DOI PMID
[31]	SETYONO D, VALIYAYEETTIL S. Chemically modified sawdust as renewable adsorbent for arsenic removal from water. ACS Sustainable Chemistry & Engineering, 2014, 2(12): 2722.
[32]	MA J, ZHU Z L, CHEN B, et al. One-pot, large-scale synthesis of magnetic activated carbon nanotubes and their applications for arsenic removal. Journal of Materials Chemistry A, 2013, 1(15): 4662. DOI URL
[33]	FENG C, ALDRICH C, EKSTEEN J J, et al. Removal of arsenic from alkaline process waters of gold cyanidation by use of gamma- Fe₂O₃@ZrO₂nanosorbents. Hydrometallurgy, 2017, 174: 71. DOI URL
[34]	LIANG Q W, LUO H J, GENG J J, et al. Facile one-pot preparation of nitrogen-doped ultra-light graphene oxide aerogel and its prominent adsorption performance of Cr(VI). Chemical Engineering Journal, 2018, 338: 62. DOI URL
[35]	LI R, YANG W, SU Y, et al. Ionic potential: a general material criterion for the selection of highly efficient arsenic adsorbents. Journal of Materials Science & Technology, 2014, 30(10): 949.
[36]	SUN T Y, ZHAO Z W, LIANG Z J, et al. Efficient removal of arsenite through photocatalytic oxidation and adsorption by ZrO₂- Fe₃O₄ magnetic nanoparticles. Applied Surface Science, 2017, 416: 656. DOI URL

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

RichHTML

PDF (PC)

可视化

摘要/Abstract

引用本文

使用本文

图/表 15

参考文献 36

相关文章 15

编辑推荐

Metrics

本文评价

[1]	吴光宇, 舒松, 张洪伟, 李建军. 接枝内酯基活性炭增强苯乙烯吸附性能研究[J]. 无机材料学报, 2024, 39(4): 390-398.
[2]	谢天, 宋二红. 弹性应变对C、H、O在过渡金属氧化物表面吸附的影响[J]. 无机材料学报, 2024, 39(11): 1292-1300.
[3]	晁少飞, 薛艳辉, 吴琼, 伍复发, MUHAMMAD Sufyan Javed, 张伟. MXene异质结Ti-O-H-O电子快速通道促进高效率储钾[J]. 无机材料学报, 2024, 39(11): 1212-1220.
[4]	马晓森, 张丽晨, 刘砚超, 汪全华, 郑家军, 李瑞丰. 13X@SiO₂合成及其甲苯吸附性能[J]. 无机材料学报, 2023, 38(5): 537-543.
[5]	王世怡, 冯爱虎, 李晓燕, 于云. Fe₃O₄负载Ti₃C₂T_x对Pb(II)的吸附性能研究[J]. 无机材料学报, 2023, 38(5): 521-528.
[6]	张万文, 罗建强, 刘淑娟, 马建国, 张小平, 杨松旺. 氧化锆间隔层的低温喷涂制备及其三层结构钙钛矿太阳能电池应用性能[J]. 无机材料学报, 2023, 38(2): 213-218.
[7]	于业帆, 徐玲, 倪忠斌, 施冬健, 陈明清. 普鲁士蓝/生物炭材料的制备及其氨氮吸附机理[J]. 无机材料学报, 2023, 38(2): 205-212.
[8]	凌洁, 周安宁, 王文珍, 贾忻宇, 马梦丹. Cu/Mg比对Cu/Mg-MOF-74的CO₂吸附性能的影响[J]. 无机材料学报, 2023, 38(12): 1379-1386.
[9]	汤亚, 孙盛睿, 樊佳, 杨庆峰, 董满江, 寇佳慧, 刘阳桥. 粉煤灰衍生水合硅酸钙PEI改性及吸附去除Cu(II)与催化降解有机污染物[J]. 无机材料学报, 2023, 38(11): 1281-1291.
[10]	戴洁燕, 冯爱虎, 米乐, 于洋, 崔苑苑, 于云. NaY沸石分子吸附涂层对典型空间污染物的吸附机制研究[J]. 无机材料学报, 2023, 38(10): 1237-1244.
[11]	王红宁, 黄丽, 清江, 马腾洲, 黄维秋, 陈若愚. 有机-无机氧化硅空心球的合成及VOCs吸附应用[J]. 无机材料学报, 2022, 37(9): 991-1000.
[12]	王亚宁, 张玉琪, 宋索成, 陈若梦, 刘亚雄, 段玉岗. 氧化锆陶瓷扫描光固化成形与脱脂烧结工艺研究[J]. 无机材料学报, 2022, 37(3): 303-309.
[13]	刘城, 赵倩, 牟志伟, 雷洁红, 段涛. 新型铋基SiOCNF复合膜对放射性气态碘的吸附性能[J]. 无机材料学报, 2022, 37(10): 1043-1050.
[14]	周帆, 毕辉, 黄富强. 用稻壳制备亚甲基蓝高吸附容量的超高比表面积活性炭[J]. 无机材料学报, 2021, 36(8): 893-903.
[15]	余祥坤, 刘坤, 李志鹏, 赵雨露, 沈锦优, 茆平, 孙爱武, 蒋金龙. 铜/凹凸棒石复合材料高效吸附放射性碘离子性能[J]. 无机材料学报, 2021, 36(8): 856-864.