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Benzimidazole-functionalized Zr-UiO-66 nanocrystals for luminescent sensing of Fe3+ in water
Journal of Solid State Chemistry 245 (2017) 160–163
Contents lists available at ScienceDirect
Journal of Solid State Chemistry journal homepage: www.elsevier.com/locate/jssc
Benzimidazole-functionalized Zr-UiO-66 nanocrystals for luminescent sensing of Fe3+ in water
crossmark
Yingying Donga, Hanzhuo Zhanga, Fan Leia, Mei Lianga, Xuefeng Qiana, Peilian Shena, ⁎ Hui Xub,⁎⁎, Zhihui Chena,c, , Junkuo Gaoa,⁎⁎, Juming Yaoa a The Key laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education, National Engineering Lab for Textile Fiber Materials and Processing Technology (Zhejiang), College of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, China b Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China c Key Lab of Advanced Transducers and Intelligent Control System, Ministry of Education and Shanxi Province, College of Physics and Optoelectronics, Taiyuan University of Technology, Taiyuan 030024, China
A R T I C L E I N F O
A BS T RAC T
Keywords: Metal-organic frameworks UiO-66 Nanocrystals Luminescent sensing
Zr-based MOF structure UiO-66 exhibits unprecedented high thermal and chemical stability, making it to be one of the most used MOFs in various applications. Yet, the poor photoluminescent (PL) properties of UiO-66 limit its applications in luminescent sensing. Herein, a new benzimidazole-functionalized UiO-66 nanocrystal (UiO-66-BI) was successfully fabricated via microwave synthesis. UiO-66-BI displayed octahedral nanocrystal morphology with a diameter smaller than 200 nm and could disperse well in water and common organic solvents. UiO-66-BI demonstrated extended optical absorption in the visible-light region and efficiently improved PL emission compared with UiO-66 pristine. The sensing properties of UiO-66-BI nanocrystals towards different ions were studied, and the results demonstrated that UiO-66-BI showed excellent selective luminescent sensing of Fe3+ ions in water.
1. Introduction In the past two decades, metal-organic frameworks (MOFs) or porous coordination polymers have attracted more and more attention due to their promising applications in gas storage and separation, catalysis, drug delivery, nonlinear optics and chemical sensors [1–19]. MOFs are ideal platforms as chemical sensors owning to their high porosity, large surface area, flexibility and tailorability [20–27]. The specific functional sites in MOFs, such as open metal sites, Lewis acidic/basic sites and organic groups can realize specific recognition with unprecedented selectivity through host–guest interactions. Fe3+ ion is one of the most essential elements in living biological systems [28]. The overload and deficiency of Fe3+ will result in various physiological disorders, such as anemia, insomnia and some iron metabolism disorder diseases [29–31]. Therefore, the identification and quantification of Fe3+ help us to rationalize the factors for the diseases, and provide clues for the treatment. Recently, MOFs have been widely used in the luminescent sensing of Fe3+ [10,32–34]. Yet, many reported MOFs can only be used for ion sensing in organic
solvents such as DMF and THF, mainly due the quenching effect of water or the unstability of MOFs in water [35–38]. The stable and efficient luminescent sensing of metal ions in aqueous solutions is still a challenge task. The coordination of Zr4+ with benzene-1,4-dicarboxylic acid (H2BDC) produce Zr-based MOF structure UiO-66 (UiO stands for the University of Oslo) with the formula of Zr6(μ3-O)4(μ3-OH)4(BDC)6, which is reported by Cavka et al in 2008 [39]. UiO-66 exhibits unprecedented high thermal and chemical stability. Importantly, UiO-66 is quite stable in strong acid and basic conditions. Also, the organic ligand BDC could be easily functionalized by various groups such as -NH2, -NO2, -Br, etc [40–42]. The unique features of UiO-66 make it to be one of the most used MOFs in various applications, such as gas storage and separation, catalysis, drug delivery, and so on [43– 51]. Here, we report the microwave synthesis of benzimidazole-functionalized UiO-66 nanocrystals. The introduction of benzimidazole group in the UiO-66 make it display strong photoluminescence emission in aqueous solution. Its luminescent sensing of Fe3+ ions in water was
⁎ Corresponding author at: The Key laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education, National Engineering Lab for Textile Fiber Materials and Processing Technology (Zhejiang), College of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, China. ⁎⁎ Corresponding authors. E-mail addresses: [email protected] (H. Xu), [email protected] (Z. Chen), [email protected] (J. Gao).
http://dx.doi.org/10.1016/j.jssc.2016.10.019 Received 14 September 2016; Received in revised form 14 October 2016; Accepted 17 October 2016 Available online 18 October 2016 0022-4596/ © 2016 Elsevier Inc. All rights reserved.
Journal of Solid State Chemistry 245 (2017) 160–163
Y. Dong et al.
Scheme 1. Synthesis of benzimidazole-functionalized UiO-66 nanocrystal.
Fig. 3. Nitrogen sorption isotherm of UiO-66-BI at 77 K.
Fig. 1. XRD pattern of UiO-66-BI nanocrystals and simulated XRD pattern of UiO-66.
Fig. 4. The solid state UV–vis diffuse reflectance spectra of UiO-66-BI and UiO-66.
Fig. 2. SEM image of UiO-66-BI nanocrystals.
studied in detail. 2. Experimental section
Fig. 5. The excitation (black) and PL spectra (blue) of the origin water solution of UiO66-BI, monitored and excited at 450 nm and 350 nm, respectively.
2.1. Materials and general methods Kubelka–Munk function: α/S=(1-R)2/2 R, in which R is the reflectance at a given wavelength, α is the absorption coefficient, and S is the scattering coefficient. The morphology was determined by a Hitachi S4800 scanning electron microscope (SEM). PL spectra were taken on a Hitachi F4600 fluorescence spectrometer.
The benzimidazole-functionalized organic ligand L1 were obtained from Jinan Henghua Company and used without further purification. All other chemicals were pursued from Alfa and TCI Company. Powder X-ray diffraction data were recorded on a Bruker D8 Advance diffractometer with a graphite-monochromatized Cu Ka radiation. The optical diffuse reflectance spectra were measured on a Perkin Elmer Hitachi U-4100H UV–Vis–NIR spectrometer equipped with an integrating sphere. BaSO4was used as the reference materials, and the polycrystalline samples were ground well before the measurement. The absorption (α/S) data were calculated from the reflectance using the
2.2. Synthesis 2.2.1. Microwave synthesis of UiO-66-BI A mixture of ZrCl4 (0.75 mmol, 0.175 g), L1 (0.75 mmol, 0.173 g), 161
Journal of Solid State Chemistry 245 (2017) 160–163
Y. Dong et al.
dispersed UIO66-BI nanocrystals in water. The results indicated that UiO-66-BI nanocrystals could be used as selective luminescent sensing of Fe3+. 4. Conclusions In conclusion, a new benzimidazole-functionalized UiO-66 nanocrystal (UiO-66-BI) was successfully fabricated via facile and fast microwave synthesis. UiO-66-BI displayed octahedral nanocrystal morphology with a diameter smaller than 200 nm and could disperse well in water and common organic solvents. UiO-66-BI demonstrated extended optical absorption in the visible-light region and efficiently improved PL emission compared with UiO-66 pristine. The sensing properties of UiO-66-BI nanocrystals towards different ions were studied, and the results demonstrated that UiO-66-BI showed excellent selective luminescent sensing of Fe3+ ions in water.
Fig. 6. The 450 nm emission intensities of the water solution of UiO-66-BI with 40 ppm of different metal ions (excited and monitored at 350 nm and 450 nm, respectively).
Acknowledgement
acetic acid (6 mL) and 50 mL DMF was put into a 100 mL Teflon-lined stainless-steel autoclave. Then, the vial was sealed with a septum and transferred to a microwave oven (CEM Discover) and heated to 120 °C with a power setting of 200 W for 1 h. After natural cooling to room temperature, the precipitates were isolated by centrifugation and washed several times with DMF and ethanol.
This work is supported by the National Natural Science Foundation of China (51402261, 51602301, 51672251, 11674239 and 61307069) and Science Foundation of Zhejiang Sci-Tech University (ZSTU) under Grant No. 13012138-Y. J. G. acknowledges the financial support from the Zhejiang Provincial Top Key Academic Discipline of Textile Science and Engineering. Z. C acknowledges the financial support from the Open Fund of Top priority disciplines in colleges and universities in Zhejiang Province, China (2015KF20).
3. Results and discussion
Appendix A. Supplementary material
The reaction between ZrCl4 and benzimidazole-functionalized ligand L1 (Scheme 1) in DMF via microwave synthesis approach produced Zr-based MOF nanocrystals that had the same crystalline structure with UiO-66 (named as UiO-66-BI). The powder X-ray diffraction (PXRD) pattern of UiO-66-BI matches will with the simulated pattern of UiO-66, indicating the introduction of benzimidazole functional group did not alter the UiO-66 structure (Fig. 1). The morphology of UiO-66-BI was analyzed by SEM ( Fig. 2). UIO66-BI displayed a octahedral nanocrystal morphology with a diameter smaller than 200 nm. The N2 adsorption isotherm at 77 K measured on the synthesized UiO-66-BI was studied, as shown in Fig. 3. UiO-66-BI was found to retain large porosity, and the BET surface area is determined to be 518.7 m2 g-1. Yet, this value is smaller than the surface area of UiO-66 (1227.8 m2 g-1), due to the benzimidozole group introduced in the MOF structure which will reduce the free space. The optical properties of UiO-66-BI were investigated via UV– Vis–NIR diffuse reflectance spectra and photoluminescence (PL) spectra. As shown in Fig. 4, UiO-66-BI showed strong absorption in the visible region, while no absorption at wavelength larger than 400 nm was observed in UiO-66, indicating that the introduction of benzimidazole group into UiO-66 MOF could improve the optical absorption in the visible region. The PL spectra of UiO-66-BI and UiO-66 dispersed in water under 350 nm excitation were shown in Fig. 5. UiO-66-BI showed a strong PL emission with a peak at 450 nm, while there was almost no PL emission for UiO-66. Obviously, the benzimidozole group could efficiently enhance the PL emission of UiO-66. Also, the N atoms in the benzimidozole group may coordinate with metal ions, making UiO-66-BI nanocrystals a potential probe for luminescent sensing of metal ions in environmental or biological conditions. The sensing properties of UiO-66-BI nanocrystals towards different ions were studied via PL spectra. The addition of small amount of metal ions (40 ppm) has different effects on the luminescence intensity of the dispersed UiO-66-BI nanocrystals in water (Fig. 6). The analytes such as Ag+, Zn2+, Cd2+, Ca2+, Mg2+, Cu2+ and Ni2+ basically do not affect the luminescence intensity, while the Fe3+ ions have a significant quenching effect on the luminescence intensity of the
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163
Contents lists available at ScienceDirect
Journal of Solid State Chemistry journal homepage: www.elsevier.com/locate/jssc
Benzimidazole-functionalized Zr-UiO-66 nanocrystals for luminescent sensing of Fe3+ in water
crossmark
Yingying Donga, Hanzhuo Zhanga, Fan Leia, Mei Lianga, Xuefeng Qiana, Peilian Shena, ⁎ Hui Xub,⁎⁎, Zhihui Chena,c, , Junkuo Gaoa,⁎⁎, Juming Yaoa a The Key laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education, National Engineering Lab for Textile Fiber Materials and Processing Technology (Zhejiang), College of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, China b Institute of Coordination Bond Metrology and Engineering, College of Materials Science and Engineering, China Jiliang University, Hangzhou 310018, China c Key Lab of Advanced Transducers and Intelligent Control System, Ministry of Education and Shanxi Province, College of Physics and Optoelectronics, Taiyuan University of Technology, Taiyuan 030024, China
A R T I C L E I N F O
A BS T RAC T
Keywords: Metal-organic frameworks UiO-66 Nanocrystals Luminescent sensing
Zr-based MOF structure UiO-66 exhibits unprecedented high thermal and chemical stability, making it to be one of the most used MOFs in various applications. Yet, the poor photoluminescent (PL) properties of UiO-66 limit its applications in luminescent sensing. Herein, a new benzimidazole-functionalized UiO-66 nanocrystal (UiO-66-BI) was successfully fabricated via microwave synthesis. UiO-66-BI displayed octahedral nanocrystal morphology with a diameter smaller than 200 nm and could disperse well in water and common organic solvents. UiO-66-BI demonstrated extended optical absorption in the visible-light region and efficiently improved PL emission compared with UiO-66 pristine. The sensing properties of UiO-66-BI nanocrystals towards different ions were studied, and the results demonstrated that UiO-66-BI showed excellent selective luminescent sensing of Fe3+ ions in water.
1. Introduction In the past two decades, metal-organic frameworks (MOFs) or porous coordination polymers have attracted more and more attention due to their promising applications in gas storage and separation, catalysis, drug delivery, nonlinear optics and chemical sensors [1–19]. MOFs are ideal platforms as chemical sensors owning to their high porosity, large surface area, flexibility and tailorability [20–27]. The specific functional sites in MOFs, such as open metal sites, Lewis acidic/basic sites and organic groups can realize specific recognition with unprecedented selectivity through host–guest interactions. Fe3+ ion is one of the most essential elements in living biological systems [28]. The overload and deficiency of Fe3+ will result in various physiological disorders, such as anemia, insomnia and some iron metabolism disorder diseases [29–31]. Therefore, the identification and quantification of Fe3+ help us to rationalize the factors for the diseases, and provide clues for the treatment. Recently, MOFs have been widely used in the luminescent sensing of Fe3+ [10,32–34]. Yet, many reported MOFs can only be used for ion sensing in organic
solvents such as DMF and THF, mainly due the quenching effect of water or the unstability of MOFs in water [35–38]. The stable and efficient luminescent sensing of metal ions in aqueous solutions is still a challenge task. The coordination of Zr4+ with benzene-1,4-dicarboxylic acid (H2BDC) produce Zr-based MOF structure UiO-66 (UiO stands for the University of Oslo) with the formula of Zr6(μ3-O)4(μ3-OH)4(BDC)6, which is reported by Cavka et al in 2008 [39]. UiO-66 exhibits unprecedented high thermal and chemical stability. Importantly, UiO-66 is quite stable in strong acid and basic conditions. Also, the organic ligand BDC could be easily functionalized by various groups such as -NH2, -NO2, -Br, etc [40–42]. The unique features of UiO-66 make it to be one of the most used MOFs in various applications, such as gas storage and separation, catalysis, drug delivery, and so on [43– 51]. Here, we report the microwave synthesis of benzimidazole-functionalized UiO-66 nanocrystals. The introduction of benzimidazole group in the UiO-66 make it display strong photoluminescence emission in aqueous solution. Its luminescent sensing of Fe3+ ions in water was
⁎ Corresponding author at: The Key laboratory of Advanced Textile Materials and Manufacturing Technology of Ministry of Education, National Engineering Lab for Textile Fiber Materials and Processing Technology (Zhejiang), College of Materials and Textiles, Zhejiang Sci-Tech University, Hangzhou 310018, China. ⁎⁎ Corresponding authors. E-mail addresses: [email protected] (H. Xu), [email protected] (Z. Chen), [email protected] (J. Gao).
http://dx.doi.org/10.1016/j.jssc.2016.10.019 Received 14 September 2016; Received in revised form 14 October 2016; Accepted 17 October 2016 Available online 18 October 2016 0022-4596/ © 2016 Elsevier Inc. All rights reserved.
Journal of Solid State Chemistry 245 (2017) 160–163
Y. Dong et al.
Scheme 1. Synthesis of benzimidazole-functionalized UiO-66 nanocrystal.
Fig. 3. Nitrogen sorption isotherm of UiO-66-BI at 77 K.
Fig. 1. XRD pattern of UiO-66-BI nanocrystals and simulated XRD pattern of UiO-66.
Fig. 4. The solid state UV–vis diffuse reflectance spectra of UiO-66-BI and UiO-66.
Fig. 2. SEM image of UiO-66-BI nanocrystals.
studied in detail. 2. Experimental section
Fig. 5. The excitation (black) and PL spectra (blue) of the origin water solution of UiO66-BI, monitored and excited at 450 nm and 350 nm, respectively.
2.1. Materials and general methods Kubelka–Munk function: α/S=(1-R)2/2 R, in which R is the reflectance at a given wavelength, α is the absorption coefficient, and S is the scattering coefficient. The morphology was determined by a Hitachi S4800 scanning electron microscope (SEM). PL spectra were taken on a Hitachi F4600 fluorescence spectrometer.
The benzimidazole-functionalized organic ligand L1 were obtained from Jinan Henghua Company and used without further purification. All other chemicals were pursued from Alfa and TCI Company. Powder X-ray diffraction data were recorded on a Bruker D8 Advance diffractometer with a graphite-monochromatized Cu Ka radiation. The optical diffuse reflectance spectra were measured on a Perkin Elmer Hitachi U-4100H UV–Vis–NIR spectrometer equipped with an integrating sphere. BaSO4was used as the reference materials, and the polycrystalline samples were ground well before the measurement. The absorption (α/S) data were calculated from the reflectance using the
2.2. Synthesis 2.2.1. Microwave synthesis of UiO-66-BI A mixture of ZrCl4 (0.75 mmol, 0.175 g), L1 (0.75 mmol, 0.173 g), 161
Journal of Solid State Chemistry 245 (2017) 160–163
Y. Dong et al.
dispersed UIO66-BI nanocrystals in water. The results indicated that UiO-66-BI nanocrystals could be used as selective luminescent sensing of Fe3+. 4. Conclusions In conclusion, a new benzimidazole-functionalized UiO-66 nanocrystal (UiO-66-BI) was successfully fabricated via facile and fast microwave synthesis. UiO-66-BI displayed octahedral nanocrystal morphology with a diameter smaller than 200 nm and could disperse well in water and common organic solvents. UiO-66-BI demonstrated extended optical absorption in the visible-light region and efficiently improved PL emission compared with UiO-66 pristine. The sensing properties of UiO-66-BI nanocrystals towards different ions were studied, and the results demonstrated that UiO-66-BI showed excellent selective luminescent sensing of Fe3+ ions in water.
Fig. 6. The 450 nm emission intensities of the water solution of UiO-66-BI with 40 ppm of different metal ions (excited and monitored at 350 nm and 450 nm, respectively).
Acknowledgement
acetic acid (6 mL) and 50 mL DMF was put into a 100 mL Teflon-lined stainless-steel autoclave. Then, the vial was sealed with a septum and transferred to a microwave oven (CEM Discover) and heated to 120 °C with a power setting of 200 W for 1 h. After natural cooling to room temperature, the precipitates were isolated by centrifugation and washed several times with DMF and ethanol.
This work is supported by the National Natural Science Foundation of China (51402261, 51602301, 51672251, 11674239 and 61307069) and Science Foundation of Zhejiang Sci-Tech University (ZSTU) under Grant No. 13012138-Y. J. G. acknowledges the financial support from the Zhejiang Provincial Top Key Academic Discipline of Textile Science and Engineering. Z. C acknowledges the financial support from the Open Fund of Top priority disciplines in colleges and universities in Zhejiang Province, China (2015KF20).
3. Results and discussion
Appendix A. Supplementary material
The reaction between ZrCl4 and benzimidazole-functionalized ligand L1 (Scheme 1) in DMF via microwave synthesis approach produced Zr-based MOF nanocrystals that had the same crystalline structure with UiO-66 (named as UiO-66-BI). The powder X-ray diffraction (PXRD) pattern of UiO-66-BI matches will with the simulated pattern of UiO-66, indicating the introduction of benzimidazole functional group did not alter the UiO-66 structure (Fig. 1). The morphology of UiO-66-BI was analyzed by SEM ( Fig. 2). UIO66-BI displayed a octahedral nanocrystal morphology with a diameter smaller than 200 nm. The N2 adsorption isotherm at 77 K measured on the synthesized UiO-66-BI was studied, as shown in Fig. 3. UiO-66-BI was found to retain large porosity, and the BET surface area is determined to be 518.7 m2 g-1. Yet, this value is smaller than the surface area of UiO-66 (1227.8 m2 g-1), due to the benzimidozole group introduced in the MOF structure which will reduce the free space. The optical properties of UiO-66-BI were investigated via UV– Vis–NIR diffuse reflectance spectra and photoluminescence (PL) spectra. As shown in Fig. 4, UiO-66-BI showed strong absorption in the visible region, while no absorption at wavelength larger than 400 nm was observed in UiO-66, indicating that the introduction of benzimidazole group into UiO-66 MOF could improve the optical absorption in the visible region. The PL spectra of UiO-66-BI and UiO-66 dispersed in water under 350 nm excitation were shown in Fig. 5. UiO-66-BI showed a strong PL emission with a peak at 450 nm, while there was almost no PL emission for UiO-66. Obviously, the benzimidozole group could efficiently enhance the PL emission of UiO-66. Also, the N atoms in the benzimidozole group may coordinate with metal ions, making UiO-66-BI nanocrystals a potential probe for luminescent sensing of metal ions in environmental or biological conditions. The sensing properties of UiO-66-BI nanocrystals towards different ions were studied via PL spectra. The addition of small amount of metal ions (40 ppm) has different effects on the luminescence intensity of the dispersed UiO-66-BI nanocrystals in water (Fig. 6). The analytes such as Ag+, Zn2+, Cd2+, Ca2+, Mg2+, Cu2+ and Ni2+ basically do not affect the luminescence intensity, while the Fe3+ ions have a significant quenching effect on the luminescence intensity of the
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