Journal of Textile Research ›› 2021, Vol. 42 ›› Issue (02): 122-128.doi: 10.13475/j.fzxb.20201002307

• Dyeing and Finishing & Chemicals • Previous Articles     Next Articles

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. 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 E-mail:liqingxpu1@163.com

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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

CLC Number: 

  • TS190.2

Fig.1

Fluorescence excitation and emission spectra of Zr-MOF"

Fig.2

Changes of Zr-MOF fluorescence intensity in deionized water (a) and aqueous solutions (b) with different pH values"

Fig.3

XRD patterns of Zr-MOF in deionized water and aqueous solutions with different pH values"

Tab.1

Fluorescence emission intensity of Zr-MOF in various anion/cation solutionsa.u."

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 NO2- 559
Na+ 770 Cu2+ 720 IO3- 658
K+ 733 Fe3+ 731 PO43- 873
Mg2+ 843 F- 789 HPO42- 853
Ni2+ 744 Cl- 930 SCN- 541
Pb2+ 802 Br- 854 C2H5O- 856
Co2+ 736 CO32- 786 CrO42- 20
Cr3+ 591 SO42- 806 Cr2O72- 5
Cd2+ 748 NO3- 733

Fig.4

Effect of different concentrations of Cr(VI) ion on fluorescence emission intensity of Zr-MOF. (a) Adding different concentrations of CrO42- with fluorescence quenching; (b) Stern-Volmer plot of I0/I versus concentrations of CrO42-; (c) Adding different concentrations of Cr2O72- with fluorescence quenching; (d) Stern-Volmer plot of I0/I versus concentrations of Cr2O72-"

Tab.2

Fluorescence emission intensity of Zr-MOF in mixed anion/cation aqueous solution before and after adding Cr(VI)"

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CrO42- 20
混合阴离子加Cr2O72- 23
混合阳离子 650
混合阳离子加CrO42- 10
混合阳离子加Cr2O72- 12

Fig.5

Cycle detection capability of Zr-MOF for CrO42-(a) and Cr2O72-(b) ions"

Fig.6

XRD patterns of Zr-MOF after seven cycles and after being treated with Cr(VI) ion"

Fig.7

Excitation and emission spectra of Zr-MOF and ultraviolet-visible absorption spectra ofCrO42- and Cr2O72- ions"

Fig.8

XPS spectra of Zr-MOF before and after immersed in Cr(VI) ions"

Fig.9

FT-IR spectra of Zr-MOF before and after immersed in Cr(VI) ions"

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