Differentiation of Fe(III) and Cr(VI) Ions in Aqueous Solution

Transcription

1 Zinc Metal-Organic Framework for Selective Detection and Differentiation of Fe(III) and Cr(VI) Ions in Aqueous Solution Rui Lv, Hui Li, Jian Su, Xin Fu, Boyi Yang, Wen Gu,* Xin Liu* College of Chemistry, Key Laboratory of Advanced Energy Materials Chemistry (MOE), Tianjin Key Laboratory of Metal and Molecule Based Material Chemistry, Collaborative Innovation Center of Chemical Science and Engineering, Nankai University, Tianjin , P. R. China. liuxin64@nankai.edu.cn, guwen68@nankai.edu.cn This file includes Figures S1-S21 and Tables S1-S7 Figure S1 FT-IR spectra of Zn-MOF. Figure S2 PXRD patterns of Zn-MOF and Eu upon the treatment with water. Figure S3 TG curve of Zn-MOF in N 2 condition. Figure S4 The XPS spectrum of Eu ; Eu 3d XPS spectrum of Eu Eu 4d XPS spectrum of Eu Figure S5 Emission spectrum of Zn-MOF. The inset is the corresponding luminescence picture under UV-light irradiation of 365 nm. Figure S6 Emission spectrum of Eu (λex=349nm). The inset is the corresponding luminescence picture under UV-light irradiation of 365 nm. Figure S7 Emission spectra of Zn-MOF at different Fe , Cr 2 O 7 and CrO 4 concentrations (excited at 296 nm). Figure S8 Changes of fluorescence intensity (at 371 nm) with the concentration of 400 μm different metal ions (I= the luminescence intensity with 400 µm metal ions, I 0 = the initial luminescence intensity without any metal ions) Figure S9 Stern Volmer plots of Zn-MOF for Fe 3+, Cr 2 O 7 concentration region and Stern Volmer plots for Fe 3+, Cr 2 O 7 concentration region, respectively. and CrO 4 (e) in low (d) and CrO 4 (f) in full Figure S10 Emission spectra of Eu at different Fe 3+, Cr 2 O 7 2 and CrO 4 2 concentrations (excited at 349 nm). S1

2 30 Figure S11 Stern Volmer plots of Eu for Fe 3+, Cr 2 O 7 and CrO 4 (e) in low concentration region and Stern Volmer plots for Fe 3+, Cr 2 O 7 concentration region, respectively. (d) and CrO 4 (f) in full Figure S12 The corresponding luminescence picture of Zn-MOF with various metal ions and anions under UV-light irradiation of 365 nm. Figure S13 The corresponding luminescence picture of Eu with various metal ions and anions under UV-light irradiation of 365 nm. Figure S14 PXRD patterns of Zn-MOF in different environments. Figure S15 The excitation spectrum for the Zn-MOF and UV adsorption spectra of Fe(III) and Cr(VI) ions in water. Figure S16 The excitation spectrum for the Eu and UV adsorption spectra of Fe(III) and Cr(VI) ions in water. Figure S17. The hole diameter of Zn-MOF Figure S18. Emission spectra of Zn-MOF at different Fe 3+ concentrations (excited at 349 nm)., Cr 2 O 7 2 and CrO Figure S19. The corresponding quenching efficiency of Fe 3+, Cr 2 O 7, CrO 4 of Zn-MOF 46 at the different Fe 3+, Cr 2 O 7, CrO 4 concentrations excited at 296nm and 349 nm Figure S20. Decay curves of Zn-MOF, treatment with 400µM Cr 2 O 7 and CrO 4 (λ ex = 296 nm; λ em = 371 nm). Figure S21. Decay curves of Eu treatment with 400µM Fe 3+ ion, Cr 2 O 7 and CrO 4 (d) (λ ex = 296 nm; λ em = 371 nm). Table S1 Crystal data and structure refinement for Zn-MOF. Table S2 Selected bond lengths (Å) and angles (deg) for Zn-MOF. Table S3 The detailed ICP studies of Eu Table S4 K sv and LOD comparison between Zn-MOF and Eu Table S5 The detailed ICP studies of Zn-MOF before and after the addition of Fe 3+ ion. Table S6 Performance comparison between various MOF fluorescent sensors for Fe(III). Table S7 Performance comparison between various MOF fluorescent sensors for Cr(VI). 58 S2

3 Supporting Information Materials and physical measurements The chemical reagents and solvents in this paper were purchased from commercial sources, and they were used without further purification except ligand TPOM, which was got by the reported procedure. 1 Powder X-ray diffraction (PXRD) curves were obtained by a Rigaku D/max-IIIA diffractometer (CuKa, λ= Å). Thermogravimetric analysis (TGA) was performed on a NETZSCH TG 209 analyzer in the temperature range of C with a heating rate of 10 C min 1 under nitrogen flow. Fourier-transform infrared spectra (FT-IR) were obtained using a Bio-Rad FTS6000 spectrophotometer in the wavelength range of cm -1 (KBr pellets). Elemental analyses for C, H and N were measured on a Model 2400 II, Perkin-Elmer elemental analyzer. X-ray photoelectron spectrometry (XPS) spectrum was performed on Axis Ultra DLD instrument. Inductively coupled plasma atomic emission spectroscopy (ICP-AES) was performed on IRIS Advantage instrument. All fluorescence measurements were performed on a MPF-4 fluorescence spectrofluorometer at room temperature. Fluorescence lifetimes were measured employing the time-correlated single-photon counting (TCSPC) method by the Edinburgh Instrument Life-Spec II spectrometer. The fluorescence decays were analysed by the reconvolution method using the FAST software provided by Edinburgh Instruments. The samples Zn-MOF were excited at 296 nm keeping the emission wavelength at 371 nm using a nf920 lamp. The samples Eu were excited at 349 nm keeping the emission wavelength at 617 nm using a µf920 lamp X-ray structural determination and refinement The single-crystal data of Zn-MOF were collected by using a Bruker SMARTAPEX CCD diffractometer with a MoKa radiation source (λ = Å). The crystal structure of Zn-MOF was obtained by the direct method and refined by full-matrix least-squares techni ques based on F 2 values with Shelxtl. 2 The non-hydrogen atoms were refined by anisotropi c thermal parameters. The crystallographic data of the Zn-MOF have been stored in the C ambridge Crystallographic Data Centre, and the CCDC number is As shown in Table S1 and Tables S2, the crystallographic data and the chosen bond lengths and angles of Zn-MOF are provided, respectively S3

4 Figure S1 FT-IR spectra of Zn-MOF Figure S2 PXRD patterns of Zn-MOF and Eu upon the treatment with water. S4

5 Figure S3 TG curve of Zn-MOF in N 2 condition Figure S4 The XPS spectrum of Eu ; Eu 3d XPS spectrum of Eu Eu 4d XPS spectrum of Eu S5

6 Figure S5 Emission spectrum of Zn-MOF. The inset is the corresponding luminescence picture under UV-light irradiation of 365 nm Figure S6 Emission spectrum of Eu (λex=349nm). The inset is the corresponding luminescence picture under UV-light irradiation of 365 nm S6

7 Figure S7 Emission spectra of Zn-MOF at different Fe 3+, Cr 2 O 7 2 and CrO 4 2 concentrations (excited at 296 nm). S7

8 Figure S8 Changes of fluorescence intensity (at 371 nm) with the concentration of 400 μm different metal ions (I= the luminescence intensity with 400 µm metal ions, I 0 = the initial luminescence intensity without any metal ions) S8

9 (d) (e) (f) Figure S9 Stern Volmer plots of Zn-MOF for Fe 3+, Cr 2 O 7 and CrO 4 (e) in low concentration region and Stern Volmer plots for Fe 3+, Cr 2 O 7 (d) and CrO 4 (f) in full concentration region, respectively S9

10 (b ) Figure S10 Emission spectra of Eu at different Fe 3+, Cr 2 O 7 2 and CrO 4 2 concentrations (excited at 349 nm). S10

11 (d) (e) (f) Figure S11 Stern Volmer plots of Eu for Fe 3+, Cr 2 O 7 and CrO 4 (e) in low concentration region and Stern Volmer plots for Fe 3+, Cr 2 O 7 (d) and CrO 4 (f) in full concentration region, respectively. S11

12 black Na + K + Mg 2+ Ca 2+ Ba 2+ Sr 2+ Al 3+ Pb 2+ Ag + Zn 2+ Cd 2+ Mn 2+ Ni 2+ Cu 2+ Co 2+ Cr 3+ Fe 2+ Fe 3+ Black Cl - Br - I - OAc - NO3 - CO3 HCO3 - C2O4 CrO4 Cr2O7 Figure S12 The corresponding luminescence picture of Zn-MOF with various metal ions and anions under UV-light irradiation of 365 nm. black Na + K + Mg 2+ Ca 2+ Ba 2+ Sr 2+ Al 3+ Pb 2+ Ag + Zn 2+ Cd 2+ Mn 2+ Ni 2+ Cu 2+ Co 2+ Cr 3+ Fe 2+ Fe 3+ Black Cl - Br - I - OAc - NO3 - CO3 HCO3 - C2O4 CrO4 Cr2O7 Figure S13 The corresponding luminescence picture of Eu with various metal ions and anions under UV-light irradiation of 365 nm S12

13 Figure S14 PXRD patterns of Zn-MOF in different environments. Figure S15 The excitation spectrum for the Zn-MOF and UV adsorption spectra of Fe(III) and Cr(VI) ions in water S13

14 Figure S16 The excitation spectrum for the Eu and UV adsorption spectra of Fe(III) and Cr(VI) ions in water Figure S17. The hole diameter of Zn-MOF S14

15 Figure S18. Emission spectra of Zn-MOF at different Fe 3+ concentrations (excited at 349 nm). S15, Cr 2 O 7 2 and CrO 4 2

16 Figure S19. The corresponding quenching efficiency of Fe 3+, Cr 2 O 7, CrO 4 of Zn-MOF at the different Fe 3+, Cr 2 O 7, CrO 4 concentrations excited at 296nm and 349 nm Figure S20. Decay curves of Zn-MOF, treatment with 400µM Cr 2 O 7 and CrO 4 (λ ex = 296 nm; λ em = 371 nm) S16

17 (d) Figure S21. Decay curves of Eu treatment with 400µM Fe 3+ ion, Cr 2 O 7 and CrO 4 (d) (λ ex = 296 nm; λ em = 371 nm) Table S1 Crystal data and structure refinement for Zn-MOF. complex [Zn 2 (TPOM)(NDC) 2 ] 3.5H 2 O Empirical formula C 98 H 86 Zn 4 N 8 O 31 Formula weight Crystal system monoclinic Space group P2 1 /c a (Å) (4) b (Å) (3) c (Å) (3) α ( ) β ( ) (3) γ ( ) V (Å 3 ) (16) Z 4 D calc (g cm 3 ) Theta range ( ) 3.48 to R(int) Data/res/parameters 8243/12/653 GOF on F R 1, wr 2 [I > 2σ(I)] , R 1, wr 2 (all data) , S17

18 Table S2 Selected bond lengths (Å) and angles (deg) for Zn-MOF. Zn-MOF Zn(1)-O(1) 1.952(4) Zn(1)-O(3) 1.954(4) Zn(1)-N(2)# (5) Zn(1)-N(1) 2.042(4) Zn(2)-O(5) 1.946(4) Zn(2)-O(7) 1.948(4) Zn(2)-N(3)# (5) Zn(2)-N(4) 2.023(4) O(1)-Zn(1)-O(3) (17) O(1)-Zn(1)-N(2)# (18) O(1)-Zn(1)-N(1) (18) O(3)-Zn(1)-N(2)# (18) O(3)-Zn(1)-N(1) (17) N(1)-Zn(1)-N(2)# (18) O(5)-Zn(2)-O(7) 93.5(2) O(5)-Zn(2)-N(3)# (2) O(5)-Zn(2)-N(4) (18) O(7)-Zn(2)-N(3)# (18) O(7)-Zn(2)-N(4) (19) N(4)-Zn(2)-N(3)# (18) Table S3 The detailed ICP studies of Eu Sample Zn 2+ (ppm) Eu 3+ (ppm) Eu Table S4 K sv and LOD comparison between Zn-MOF and Eu MOF Fe 3+ Cr 2 O 7 CrO 4 K sv (M -1 ) / LOD(µM) Zn-MOF / / / 2.50 Eu / / / S18

19 Table S5 The detailed ICP studies of Zn-MOF before and after the addition of Fe 3+ ion. Sample Zn 2+ (ppm) Zn-MOF Fe Table S6 Performance comparison between various MOF fluorescent sensors for Fe(III). Fluorescent Materials Quenching constant Detection Ref. (K SV, M -1 ) Limits (µm) [Eu(Hpzbc) 2 (NO 3 )] H 2 O 26 3 {[Cd(5-asba)(bimb)]} n [Tb 3 (TCA) 2 (DMA) 0.5 (OH) 3 (H 2 O) ] 3H 2 O {[Eu 2 L 1.5 (H 2 O) 2 EtOH] DMF} n {[Eu(L)(BPDC) 1/2 (NO 3 )] H 2 O} n {[Tb(L)(BPDC) 1/2 (NO 3 )] H 2 O} n {[Cd(L)(BPDC)] 2H 2 O} n {[Cd(L)(SDBA)(H 2 O)] 0.5H 2 O} n Zn-MOF This work S19

20 Table S7 Performance comparison between various MOF fluorescent sensors for Cr(VI). Fluorescent Materials analyte Quenching [Zn(btz)] n Cr 2 O 7 /CrO 4 2 [Zn 2 (ttz)h 2 O] n Cr 2 O 7 /CrO 4 2 Eu Cr 2 O constant (K SV, M -1 ) Detection Limits (µm) Ref / 2/ / 20/ [Eu(Hpzbc) 2 (NO 3 )] H 2 O Cr 2 O [Cd(TPTZ)(H 2 O) 2 (HCOO H) (IPA) 2 ] n {[Zn 2.5 (cpbda)(oh) 2 ] solv ent 2 } n Cr 2 O 7 Cr 2 O 7 /CrO [Cd 6 (L) 2 (bib) 2 (DMA) 4 ] Cr 2 O 7 /CrO [Cd 3 (L)(tib)(DMF) 2 ] Cr 2 O 7 /CrO Zn-MOF Cr 2 O 7 /CrO / 2.35/2.50 This work References (1) Baldrighi, M.; Metrangolo, P.; Meyer, F.; Pilati, T.; Proserpio, D.; Resnati, G.; Terraneo, G. Halogen-bonded and interpenetrated networks through the self-assembly of diiodoperfluoroarene and tetrapyridyl tectons. J. Fluorine Chem. 2010, 131, (2) Sheldrick, G. A short history of SHELX. Acta Crystallogr. Sect. A: Found. Crystallogr. 2008, 64, 112. (3) Li, G.-P.; Liu, G.; Li, Y.-Z.; Hou, L.; Wang, Y.-Y.; Zhu, Z.-H. Uncommon Pyrazoyl-Carboxyl Bifunctional Ligand-Based Microporous Lanthanide Systems: Sorption and Luminescent Sensing Properties. Inorg. Chem. 2016, 55, (4) Yang, Y.-J.; Wang, M.-J.; Zhang, K.-L. A novel photoluminescent Cd(II)-organic framework exhibiting rapid and efficient multi-responsive fluorescence sensing for trace amounts of Fe 3+ ions and some NACs, especially for 4-nitroaniline and methyl-4-nitroaniline. J. Mater. Chem. C 2016, S20

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