基于锆-有机骨架的印染废水中Cr(VI)的荧光检测

doi:10.13475/j.fzxb.20201002307

纺织学报 ›› 2021, Vol. 42 ›› Issue (02): 122-128.doi: 10.13475/j.fzxb.20201002307

基于锆-有机骨架的印染废水中Cr(VI)的荧光检测

管斌斌¹^,², 李庆¹^,²(), 陈灵辉¹^,², 徐宇婷¹^,², 樊增禄³

1.西安工程大学西安市纺织化工助剂重点实验室, 陕西西安 710048
2.西安工程大学环境与化学工程学院, 陕西西安 710048
3.西安工程大学功能性纺织材料及制品教育部重点实验室, 陕西西安 710048

收稿日期:2020-10-12 修回日期:2020-11-21 出版日期:2021-02-15 发布日期:2021-02-23
通讯作者: 李庆
作者简介:管斌斌(1995—),男,硕士生。主要研究方向为功能性金属有机框架材料的构筑及其对染料废水的处理。
基金资助:
国家自然科学基金面上项目(22078253);国家级大学生创新训练计划项目(S202010709027);陕西省重点研发计划项目(2020GY-276);陕西省教育厅专项项目(19JC016);西安市科技计划项目(2019217114GXRC007CG008-GXYD7.1);西安市科技计划项目(BLKJ2020YYJS-0001);西安工程大学研究生创新基金项目(chx2020023)

Fluorescence detection of Cr(VI) from printing and dyeing wastewater by zirconium-organic framework

GUAN Binbin¹^,², LI Qing¹^,²(), CHEN Linghui¹^,², XU Yuting¹^,², FAN Zenglu³

1. Xi'an Key Laboratory of Textile Chemical Engineering Auxiliaries, Xi'an Polytechnic University, Xi'an, Shaanxi 710048, China
2. School of Environmental & Chemical Engineering, Xi'an Polytechnic University, Xi'an, Shaanxi 710048, China
3. Key Laboratory of Functional Textile Materials and Products, Ministry of Education, Xi'an Polytechnic University, Xi'an, Shaanxi 710048, China

Received:2020-10-12 Revised:2020-11-21 Online:2021-02-15 Published:2021-02-23
Contact: LI Qing

摘要/Abstract

摘要：

针对印染废水中重金属铬Cr(VI)离子造成的污染,采用氯化锆与2,2'-联喹啉-4,4'-二甲酸(H₂L)反应,合成了Zr-金属有机骨架(Zr-MOF)。经粉末X射线衍射表征证实Zr-MOF在水中和强酸/碱环境中具有结构稳定性。经荧光测试证明Zr-MOF的光致发光性能。对水中Cr(VI)离子的荧光传感检测结果表明,Zr-MOF在多种混合阴/阳离子的干扰下,可以对水中痕量的 $CrO 4 2 -$ 和$Cr_{2}O_{7}^{2-}$离子进行高选择性荧光淬灭识别和定量检测,其检出限分别为6.704和11.232 mg/L。并提出了Zr-MOF的光致发光和荧光淬灭检测机制。此外,经过7次连续的荧光检测循环后,Zr-MOF的荧光发射强度仍能维持在95%以上。

关键词: 印染废水, 铬(VI), Zr-金属有机骨架, 荧光检测, 抗干扰

Abstract:

Considering the pollution caused by heavy metal chromium ions in printing and dyeing wastewater, zirconium chloride and 2,2'-biquinoline-4,4'-dicarboxylic acid (H₂L) were used to synthesize Zr-metal organic framework (Zr-MOF). The structural stability in water and in strong acid/base environments and photoluminescence property of Zr-MOF were confirmed by powder X-ray diffraction and fluorescence tests. The results of fluorescence sensing detection of Cr(VI) ions show that Zr-MOF performs highly selective fluorescence quenching recognition and quantitative detection towards trace $CrO 4 2 -$ and $Cr_{2}O_{7}^{2-}$ ions in water, under the interference of a variety of mixed anion and ions. The detection limits are confirmed to be 6.704 and 11.232 mg/L for $CrO 4 2 -$ and $Cr_{2}O_{7}^{2-}$ ions, respectively. The photoluminescence and fluorescence quenching detection mechanisms of Zr-MOF are proposed. Furthermore, after 7 consecutive fluorescence detection cycles, the fluorescence emission intensity of Zr-MOF still retains at above 95%.

Key words: printing and dyeing wastewater, Cr(VI), Zr-organic framework, fluorescence detection, anti-interference

中图分类号:

TS190.2

管斌斌, 李庆, 陈灵辉, 徐宇婷, 樊增禄. 基于锆-有机骨架的印染废水中Cr(VI)的荧光检测[J]. 纺织学报, 2021, 42(02): 122-128.

GUAN Binbin, LI Qing, CHEN Linghui, XU Yuting, FAN Zenglu. Fluorescence detection of Cr(VI) from printing and dyeing wastewater by zirconium-organic framework[J]. Journal of Textile Research, 2021, 42(02): 122-128.

图/表 11

图1

图2

图3

表1

Zr-MOF在各种阴/阳离子溶液中的荧光发射强度"

离子种类	荧光发射强度	离子种类	荧光发射强度	离子种类	荧光发射强度
空白	850	Al³⁺	596	N $O 2 -$	559
Na⁺	770	Cu²⁺	720	I $O 3 -$	658
K⁺	733	Fe³⁺	731	P $O 4 3 -$	873
Mg²⁺	843	F^-	789	HP $O 4 2 -$	853
Ni²⁺	744	Cl^-	930	SCN^-	541
Pb²⁺	802	Br^-	854	C₂H₅O^-	856
Co²⁺	736	C $O 3 2 -$	786	Cr $O 4 2 -$	20
Cr³⁺	591	S $O 4 2 -$	806	Cr₂ $O 7 2 -$	5
Cd²⁺	748	N $O 3 -$	733

表1

图4

表2

加入Cr(VI)前后的混合阴/阳离子水溶液中Zr-MOF的荧光发射强度"

离子种类	荧光发射强度/a.u.
空白	850
混合阴离子	680
混合阴离子加Cr $O 4 2 -$	20
混合阴离子加Cr₂ $O 7 2 -$	23
混合阳离子	650
混合阳离子加Cr $O 4 2 -$	10
混合阳离子加Cr₂ $O 7 2 -$	12

表2

图5

图6

图7

图8

图9

参考文献 15

[1]	HE T, ZHANG Y Z, KONG X J, et al. Zr(IV)-based metal organic framework with T-shaped ligand: unique structure, high stability, selective detection, and rapid adsorption of Cr₂O₇^2-in water [J]. ACS Applied Materials & Interfaces, 2018,10(19):16650-16659. pmid: 29733570
[2]	LI W, XUE X. Effects of boron oxide addition on chromium distribution and emission of hexavalent chromium in stainless-steel slag[J]. Industrial & Engineering Chemistry Research, 2018,57(13):4731-4742.
[3]	YAO Z Q, LI G Y, XU J, et al. A water-stable luminescent ZnII metal-organic framework as chemosensor for high-efficiency detection of Cr(VI)-anions (Cr₂O₇^2-and CrO₄^2-) in aqueous solution [J]. Chemistry: A European Journal, 2018,24(13):3192-3198.
[4]	JIAO C Q, SUN M, LIU F, et al. Terbium oxalatopho-sphonate as efficient multiresponsive luminescent sensors for chromate anions and tryptophan molecules[J]. ACS Omega, 2018,3(12):16735-16742. pmid: 31458303
[5]	LIU J, JI G, XIAO J, et al. Ultrastable 1D europium complex for simultaneous and quantitative sensing of Cr(III) and Cr(VI) ions in aqueous solution with high selectivity and sensitivity[J]. Inorganic Chemistry, 2017,56(7):4197-4205. pmid: 28318248
[6]	肖平平, 邓满兰, 胡红武, 等. 基于光波导技术的水中六价铬离子痕量检测[J]. 光子学报, 2017,46(1):159-164.
	XIAO Pingping, DENG Manlan, HU Hongwu, et al. Detection of trace amounts of hexavalent chromium ion in water based on optical waveguide analysis techno-logy[J]. Acta Photonica Sinica, 2017,46(1):159-164.
[7]	初红涛, 姚冬, 陈嘉琪, 等. 金属有机骨架材料作为荧光探针的研究进展[J]. 材料导报, 2020,34(13):13114-13120.
	CHU Hongtao, YAO Dong, CHEN Jiaqi, et al. Research progress of metal-organic framework materials as fluorescent probes[J]. Materials Reports, 2020,34(13):13114-13120.
[8]	LI Q, XUE D X, ZHANG Y F, et al. A dual-functional indium-organic framework towards organic pollutant decontamination via physically selective adsorption and chemical photodegradation[J]. Journal of Materials Chemistry A, 2017,5(27):14182-14189.
[9]	HU Z, DEIBERT B J, LI J. Luminescent metal-organic frameworks for chemical sensing and explosive detec-tion[J]. Chemical Society Reviews, 2014,43(16):5815-5840. pmid: 24577142
[10]	李庆, 樊增禄, 张洛红, 等. 锆-有机骨架对水中染料的高选择性可循环吸附[J]. 纺织学报, 2019,40(2):141-146.
	LI Qing, FAN Zenglu, ZHANG Luohong, et al. High selectivity and cyclic adsorption of dyes in water by zirconium-organic framework[J]. Journal of Textile Research, 2019,40(2):141-146.
[11]	LUSTING W P, MUKHERJEE S, RUDD N D, et al. Metal-organic frameworks: functional luminescent and photonic materials for sensing applications[J]. Chemical Society Reviews, 2017,46(11):3242-3285. doi: 10.1039/c6cs00930a pmid: 28462954
[12]	DANG S, MA E, SUN Z M, et al. A layer-structured Eu-MOF as a highly selective fluorescent probe for Fe ³⁺ detection through a cation-exchange approach [J]. Journal of Materials Chemistry, 2012,22(33):16920.
[13]	ZHOU J M, SHI W, LI H M, et al. Experimental studies and mechanism analysis of high-sensitivity luminescent sensing of pollutional small molecules and ions in Ln₄O₄ cluster based microporous metal-organic frameworks[J]. The Journal of Physical Chemistry C, 2013,118(1):416-426.
[14]	SINGH M, SENTHILKUMAR S, RAJPUT S, et al. Pore-functionalized and hydrolytically robust Cd(II)-metal-organic framework for highly selective, multicyclic CO₂ adsorption and fast-responsive luminescent monitoring of Fe(III) and Cr(VI) ions with notable sensitivity and reusability[J]. Inorganic Chemistry, 2020,59(5):3012-3025. doi: 10.1021/acs.inorgchem.9b03368 pmid: 32052632
[15]	CAO C S, HU H C, XU H, et al. Two solvent-stable MOFs as a recyclable luminescent probe for detecting dichromate or chromate anions[J]. Cryst Eng Comm, 2016,18(23):4445-4451.

Metrics

Viewed

Full text

Abstract

Cited

Shared

Discussed

基于锆-有机骨架的印染废水中Cr(VI)的荧光检测

Fluorescence detection of Cr(VI) from printing and dyeing wastewater by zirconium-organic framework

RichHTML

PDF (PC)

摘要/Abstract

引用本文

使用本文

图/表 11

参考文献 15

相关文章 15

Metrics

本文评价

推荐阅读 0

[1]	李庆, 管斌斌, 王雅, 刘天卉, 张洛红, 樊增禄. 光敏剂敏化Cu-有机骨架对活性深蓝K-R的高效光催化降解[J]. 纺织学报, 2020, 41(10): 87-93.
[2]	赵芷芪, 李秋瑾, 孙月静, 巩继贤, 李政, 张健飞. 磁性氧化石墨烯/聚丙烯胺盐酸盐微胶囊在染料吸附中的应用[J]. 纺织学报, 2020, 41(07): 109-116.
[3]	陈冬芝, 杨晓刚, 陈艳霞, 刘琳, 陈彬, 崔科丛, 张勇. 亚麻废纱制备纤维素基絮凝材料及其混凝工业废水性能[J]. 纺织学报, 2020, 41(01): 88-95.
[4]	徐春霞, 降帅, 韩阜益, 徐芳, 刘丽芳. 纤维素纳米纤丝气凝胶制备及其对亚甲基蓝的吸附性能[J]. 纺织学报, 2019, 40(10): 20-25.
[5]	辛民岳, 郑强, 吴江丹, 梁列峰. 同轴静电纺多孔氧化锌薄膜制备及其光催化性能[J]. 纺织学报, 2019, 40(10): 42-47.
[6]	张兰河, 张明爽, 高伟围, 李正, 贾艳萍, 高敏, 凌良雄. 铝酸钴/蜂窝陶瓷催化剂的制备及其在印染废水处理中的应用[J]. 纺织学报, 2019, 40(03): 125-132.
[7]	周存李叶燃马悦王闻宇金欣肖长发. 二氧化钛负载聚酯织物的制备及其光催化性能[J]. 纺织学报, 2018, 39(11): 91-95.
[8]	王建坤郭晶张昊郑帼. 交联氨基淀粉对亚甲基蓝染料的吸附性能[J]. 纺织学报, 2018, 39(11): 103-110.
[9]	贾艳萍姜成郭泽辉张兰河张海丰. 印染废水深度处理及回用研究进展[J]. 纺织学报, 2017, 38(08): 172-180.
[10]	刘桂萍祝杏王明杰王丽多. 有机无机复合型混凝剂在印染废水中的应用[J]. 纺织学报, 2013, 34(4): 98-103.
[11]	龚安华, 孙岳玲. 基于混凝-吸附-氧化法的印染废水处理[J]. 纺织学报, 2012, 33(4): 95-99.
[12]	隋智慧;赵欣;刘安军. 季铵盐型高分子絮凝剂的制备及其在印染废水处理中的应用[J]. 纺织学报, 2008, 29(11): 92-96.
[13]	汪木兰;朱昊;左健民. 针织机电气控制系统抗干扰设计[J]. 纺织学报, 2007, 28(4): 111-115.
[14]	刘梅红. 印染废水处理技术研究进展[J]. 纺织学报, 2007, 28(1): 116-119.
[15]	吕彤;吴赞敏;曹明华;陈雷;彭晓军. 高取代度阳离子淀粉在印染废水处理中的应用[J]. 纺织学报, 2005, 26(6): 53-56.