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Dual-Emitting Dye@MOF Composite as a SelfCalibrating Sensor for 2,4,6-Trinitrophenol Di-Ming Chen, Nan-Nan Zhang, Chun-Sen Liu, and Miao Du ACS Appl. Mater. Interfaces, Just Accepted Manuscript • DOI: 10.1021/acsami.7b07901 • Publication Date (Web): 06 Jul 2017 Downloaded from http://pubs.acs.org on July 8, 2017

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ACS Applied Materials & Interfaces

Dual-Emitting Dye@MOF Composite as a Self-Calibrating Sensor for 2,4,6-Trinitrophenol Di-Ming Chen, Nan-Nan Zhang, Chun-Sen Liu* and Miao Du* Henan Provincial Key Laboratory of Surface & Interface Science, Zhengzhou University of Light Industry, Zhengzhou 450002, P. R. China

ABSTRACT:

An

anionic

metal–organic

framework

{(NH2Me2)[Zn3

3-

OH)(tpt)(TZB)3](DMF)12}n (1, tpt = 2,4,6-tri(4-pyridyl)-1,3,5-triazine, H2TZB = 4-(1H-tetrazol5-yl)benzoic acid and DMF = N,N-dimethylformamide), with both nano-sized cages and partitions has been solvothermally synthesized, which can serve as a crystalline vessel to encapsulate the fluorescent dye Rhodamine 6G (Rh6G) via a “bottle around ship” approach. As a result, the obtained dye@MOF composite system features a blue-emitting of the ligand at 373 nm and a red-emitting of Rh6G at 570 nm when dispersed in solution, which could be used for decoding trace amount of 2,4,6-trinitrophenol (TNP) by referring the peak height ratio of each emission, even in coexistence with other potentially competitive nitroaromatic analytes. Furthermore, the observed uorescence responses of the composite towards TNP are highly stable and reversible after recycling experiments. To the best of our knowledge, this is the first example of MOFimplicated self-calibrated sensor for TNP detection. KEYWORDS: metal–organic framework, composite, dual-emitting, self-calibrated sensor, TNP detection

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INTRODUCTION Metal–organic frameworks (MOFs), composed of organic ligands and metal centers via a selfassembly approach, can provide a fascinating platform for developing functional materials that can be applied in various fields for their high porosity, adjustable compositions and postmodifiable structures.1-6 As an important subclass of MOF materials, luminescent MOFs are gaining interest as they can be used to rapid and selective detection of chemical explosives at a trace level, which is pioneered by Li’ group and then developed by Ghosh, Su, Zheng and other researchers.7-14 As a toxic pollutant and highly explosive molecule, 2,4,6-trinitrophenol (TNP) has been widely used in industrial processes such as dyes, fireworks, matches, and glass, which has also brought serious environmental and health issues for its discharge into our living surroundings.15 Hence, the facile and selective detection of TNP from other explosives is in high demand for environmental remediation, civilian safety, and military operations. In this context, the conventional TNP sensors based on MOFs mainly rely on the concentration-dependent fluorescence quenching of their maximum emissions. However, the accuracy of this approach is normally susceptible to errors introduced by interference of other similar nitro explosives, e.g. nitrobenzene (NB), p-nitrotoluene (PNT), 2,6-dinitrotoluene (2,6-DNT), and m-dinitrobenzene (m-DNB), because these compounds could also quench the fluorescent intensity of MOF sensors in various degrees.17-19 In addition, the absolute fluorescent intensity of MOF sensors varies depending on many uncontrollable factors such as optical occlusion, voltage, and concentration inhomogeneity. Hence, the introduction of additional referring emission should be a feasible approach to solve these problems mentioned above because this type of signal transduction can omit environmental interference such as drift of light resource or detector, concentration change of probe, and more importantly, create sensitivity to the targeted guests.20,21 Recently, some MOF-based self-calibrating sensors have been constructed for sensing temperature, solvents, pH


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conditions, and formaldehyde.22-28 For instance, Shi and co-workers have successfully synthesized a bimetallic lanthanide MOF material, which could behave as a self-calibrating luminescent sensor for glycol and 1,4-dioxane mixture.22 Yan’s group has succeeded in the fabrication of a bimetallic nanocrystalline MOF for self-calibrating detection of formaldehyde by monitoring the dual-emissive characters of this material.24 Nevertheless, there is no report for MOF-based self-calibrating probe that can selectively detect trace amount of TNP molecule.

Scheme 1. Fabrication of dye@MOF composite via the “bottle around ship” approach.

In this work, we report a unique self-calibrating MOF-based sensor fabricated by embedding a fluorescent dye Rhodamine 6G (Rh6G) into the pores of a pre-designed Zn(II)-MOF {(NH2Me2)- [Zn3

3-OH)(tpt)(TZB)3](DMF)12}n

(1), which affords a dual-emitting dye@MOF

composite (see Scheme 1). As expected, the composite features a blue-emitting of the ligand at 373 nm and a red-emitting of Rh6G at 570 nm when dispersed in solution. Notably, the ratio of luminescent intensity between the dye and ligand will be highly dependent on the concentration of TNP, while other nitro explosives show little effect on it. Thus, this dye@MOF composite can be readily applied as a promising self-calibrating sensor for TNP sensing. To our knowledge, the



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Rh6G@1 composite represents the first example of MOF-implicated self-calibrated sensor for TNP detection. EXPERIMENTAL SECTION Materials and Methods. All the reagents were commercially available and used as received. IR spectra were taken on a Bruker Tensor 27 OPUS FT-IR spectrometer. The C, H and N analyses were taken on a Vario EL III Elementar analyzer. Powder X-ray diffraction (PXRD) patterns were recorded on a Rigaku (model Ultima IV) diffractometer. Fluorescent emission spectra were performed using an F-7000 spectrophotometer (Hitachi). The Hitachi U-3010 spectrophotometer was applied to collect the UV-Vis spectra. The Belsorp MAX volumetric sorption equipment was used to achieve the N2 sorption behaviors for the targeted materials. Thermogravimetric analysis (TGA) curves were performed on a Labsys NETZSCH TG 209 Setaram apparatus with a heating rate of 10 °C/min in nitrogen atmosphere. Synthesis of {(NH2Me2)[Zn3


(1). A mixture of tpt (16 mg,

0.05 mmol), Zn(NO3)2·6H2O (24 mg, 0.1 mmol), H2TZB (9.5 mg, 0.05 mmol), DMF (2 mL) and HBF4 (1 mL, 40% aq) was sealed in a screw-capped vial (20 mL) and heated at 120 °C for 24 h. Colorless crystals of 1 were obtained in 58% yield (based on H2TZB ligand). Elemental analysis (%) found (calcd) for C80H117N31O19Zn3: C, 47.39 (47.73); H, 5.77 (5.86); N, 21.23 (21.57). Synthesis of {(NH2Me2)0.9(Rh6G)0.1[Zn3


(Rh6G@1). A

mixture of tpt (16 mg, 0.05 mmol), Zn(NO3)2·6H2O (24 mg, 0.1 mmol), H2TZB (9.5 mg, 0.05 mmol), DMF (4 mL), Rh6G (23.95 mg) and HBF4 (50 L, 40% aq) was sealed in a 20 mL screw-capped vial and heated at 120 °C for 24 h. Red crystals were obtained, washed with DMF thoroughly until no Rh6G could be detected in the filtrate (monitored by UV-Vis spectra). Ele-


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mental analysis (%) found (calcd) for C81.6H120.3N31.1O18.3Zn3: C, 48.79 (48.37); H, 5.95 (5.98); N, 21.22 (21.50). Single Crystal X-Ray Crystallography. The crystal data of 1 were obtained using an Agilent Technologies SuperNova single crystal diffractometer with graphite-monochromated Curadiation ( = 1.5418 Å). The structure was solved by SHELXT and refined by SHELXL embedded in the Olex2 software package.29 All non-hydrogen atoms were treated anisotropically and the H-atoms were placed geometrically. For the highly disordered nature of the lattice guests, they could not be finely made out in the Fourier map. Thus, the SQUEEZE program embedded in PLATON was used to remove the diffraction contributed from these highly disorder guests.30 The chemical formula was derived from the results of elemental analysis, thermogravimetric analysis and crystal data. RESULTS AND DISCUSSION Crystal Structure Analysis. Colorless crystals of MOF 1 were harvested by a solvothermal treatment of Zn(NO3)2·6H2O with tpt and H2TZB in DMF at 120 °C for 24 h (Figure S1). The Xray study shows that compound 1 belongs to the hexagonal P63/mmc space group, with trimeric [Zn3(OH)(COO)3(TZB)3] clusters as the secondary building units (Figure 1a). Notably, although the [M3(OH)(X)6] cluster is common for tri-valent V, Cr, Fe, and In or bi-valent Co and Ni, such a pure Zn(II)-based motif is quite scarce.31-35 These trimeric clusters are further connected by the TZB2– ligands to construct a MIL-88-type framework with hexagonal 1D infinite channels, which are spaced by the triangular tpt ligands along the c axis to result in the finite segments (Figure 1b). In addition to the finite segments, there also exist trigonal bipyrimidal cages, shaped by six TZB2– linkers and four trimeric clusters with an inner free space of ca. 6 Å in diameter for each (Figure 1c). Thus, the porous structure of 1 can also be viewed as the combination of trigo-



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nal bipyrimidal cages and finite segments (Figure 1d), which accounts for 62% effective solventaccessible voids of the overall crystal volume without considering the lattice guests as calculated by the PLATON software (probe radius: 1.4 Å).36 The network topology of 1 can be regarded as a binodal (3,9)-connected 3D net with a point symbol of (43)(421.615), by considering each tpt ligand and trimeric cluster as a 3- and 9-connected node, respectively (Figure S2).

Figure 1. (a) The trinuclear Zn(II) unit. (b) View of the tpt ligands locating in the channels along c axis. (c) The finite segments and trigonal bipyrimidal cages. (d) The solvent-accessible voids. Dye Encapsulation. Encouraged by the structural analysis results of 1, the fluorescent Rh6G dye molecule was tried to be encapsulated into the pores by adding Rh6G to the solution of MOF growth and as a result, red crystals of Rh6G@1 composite were obtained (Figure S3). The products were washed thoroughly using DMF to remove the Rh6G molecules adsorbed on the surface of MOF. The successful dye introduction has been confirmed by the reduced N2 uptake capacity (Figure 2) and BET surface area (from 868 to 552 m2/g) for Rh6G@1 compared with those for 1. Accordingly, the pore size distribution analysis using the Horvath–Kawazoe method demon-


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strates a reduced pore diameter from 0.66 to 0.64 nm (Figure S4). Furthermore, the PXRD patterns indicate that the as-prepared composite is structurally identical to 1 for both single crystal and powder samples (Figure S5). The formula of Rh6G@1 was determined as {(NH2Me2)0.9(Rh6G)0.1[Zn3


based on TGA result (Figure S6),

elemental analyses, and charge balance consideration, corresponding to one out of a hundred and twenty of Rh6G dye molecule per asymmetric unit. Therefore, it is difficult to get the detailed location of Rh6G in the framework of 1 from the electron-density Fourier map of the crystal data due to its very low occupancy.

Figure 2. The N2 sorption isotherm for the activated 1 and Rh6G@1. Luminescent Detection. Initially, we collected the solid-state emission spectrum of 1 at room temperature, which displays the resemblant emission peak with that of the tpt ligand at the wavelength of about 373 nm, illustrating that the luminescence for 1 is based on the tpt ligand rather than H2TZB (Figure S7).37-39 It is noteworthy that the Rh6G@1 presents a weak emission at 363 nm and a strong emission peak at 580 nm, which implies the presence of an efficient MOF-to-dye energy-transfer process (Figure 3a).40 This can be explained by the fluorescence resonance energy transfer (FRET) mechanism, as evidenced by the spectral overlap between the



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fluorescence emission of 1and the absorption of Rh6G (Figure S8), which leads to an efficient energy transfer from MOF to Rh6G.41 Additionally, the fluorescence emission of Rh6G@1 is also sensitive to the size of the MOF crystals, which is evidenced by the red-shift of the emission peak for its ground sample. It should be pointed out that the Rh6G molecule does not display any emission in the solid state for the aggregation-caused quenching, and the mechanically ground mixture of 1 and Rh6G only reveals the emission peak of 1 (Figure S9). These results indicate that the Rh6G molecule might be uniformly encapsulated in the voids of 1 as the free isolated guest, which thus can prevent the formation of solid-state aggregate.23 The Rh6G@1 sample dispersed in DMF exhibits two emission maxima at 373 and 570 nm, respectively, upon excitation at 320 nm (Figure 3b). The former strong emission could be due to the ligand-based charge transfer and the weak emission at 570 nm presumably originates from Rh6G. This also indicates that the energy transfer efficiency from MOF to dye could be turned in solution, as further probed by dispersing Rh6G@1 in different solvents such as CH2Cl2, CH3OH, EtOH and CH3CN. As shown in Figure S10, the emission peak-height ratios of ligand to dye are dependent on the solvents used and this also illuminate that the energy transfer efficiency from ligand to dye is solvent-dependent.21 Moreover, Rh6G@1 is stable in DMF and the included dye molecules could not leak into the solution after immersed in DMF for one day for the smaller pore size of 1 (6 Å) compared with the larger molecular size of the Rh6G (10.89 15.72 15.79 Å3), demonstrating that the Rh6G molecules have been confined within the cages of this MOF material (Figure S11).


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Figure 3. (a) Solid-state emission spectra for 1, Rh6G@1 and the ground Rh6G@1 samples. (b) Emission spectra for 1, Rh6G and Rh6G@1 in DMF solution. Inset: photos for the samples under a UV lamp.

Actually, the emission intensities of ligand-based and dye-based luminescence of Rh6G@1 dispersed in DMF solution are comparable. Therefore, we have further studied the detection capacity of Rh6G@1 toward various aromatic compounds with different substituent groups, by monitoring the emission peak heights of the dye and ligand in the luminescence spectra of Rh6G@1. The experiments for uorescent detection were carried out on Rh6G@1 in the presence of 200 ppm analyte. It could be noticed that the emission intensities of the dye and ligandbased fluorescence of Rh6G@1 show completely different response behaviors to various analytes (Figure 4a). For example, the non-nitroaromatic compounds exhibit little effect on the luminescent intensity, whereas most nitroaromatic compounds can simultaneously quench both the ligand and dye emissions. The most notable analyte is the TNP molecule, which mainly quenches the emission from MOF, but shows only a little effect on the emission of dye. The relative ratio of the uorescent intensities at 570 and 373 nm exhibits a 42-fold increase in the presence of only 200 ppm TNP molecule. Thus, a visible change in the luminescent intensity ratios between dye and ligand could be observed (Figure 4b). Moreover, the concentration-dependent fluores-



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cence spectra of Rh6G@1 toward different nitroaromatic compounds have also been collected (Figures S12~S16). As expected, the incremental addition of TNP results in fast and high fluorescence quenching of the ligand-based emission at 373 nm for Rh6G@1. The relative ratio (Idye/IMOF)

of the fluorescence intensities at 570 nm and 373 nm exhibits a 4, 10, and 42-fold in-

crease upon adding 50, 100, and 200 ppm of TNP, respectively. In comparison, the emission intensity ratios of Rh6G@1 after exposure to all the other nitro analytes are almost unchanged, regardless of the change of analyte concentrations during the detection process, which confirms that this composite system can serve as a self-calibrating luminescent sensor for TNP (Figure S17). Significantly, the variable quenching effects also make Rh6G@1 emit concentrationdependent colors from pink to orange with the addition of TNP under a UV lamp (Figure 4c). The observed emission colors of Rh6G@1 in the presence of different concentrations of TNP also correspond well with the CIE chromaticity diagram, which can be clearly observed with the naked eye (Figure 4d). The results illuminate that, in the fluorescence spectra of Rh6G@1, the emission height ratio of dye and ligand moieties is highly sensitive to the concentration of TNP in the system. Such a character could be used for sensing the TNP molecule at different concentrations with high selectivity and sensitivity. The high selectivity of Rh6G@1 toward TNP in the coexistence of other nitro analytes was further probed by carrying out a competitive fluorescence titration. To this end, we monitored the concentration-dependent fluorescent changes of Rh6G@1 toward TNP by adding equal amount of other nitro analytes to the system, and the experimental results are shown in Figure S18. It could be clearly observed that the addition of other nitro analytes will not influence the variation trend of the two emissions, confirming the exceptional selectivity of Rh6G@1 toward TNP. The high selectivity and sensitivity of Rh6G@1 toward TNP can make it a reliable and high-e cient self-calibrating sensor. To the best of our knowledge, Rh6G@1 represents the first paradigm for


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MOF-based sensor for decoding the TNP explosive via a self-calibrating approach. The recyclability of the detection process of Rh6G@1 towards TNP (100 ppm) was studied, which suggests that this composite could be regenerated and reused for at least three cycles by centrifugation and washed thoroughly with DMF, highlighting its practical use in TNP detection (Figure S19).

Figure 4. (a) The analyte-dependent emission spectra for Rh6G@1. (b) The peak-height ratio of dye-to-ligand after addition of 200 ppm various analytes. (c) The emission spectra for Rh6G@1 at different concentrations of TNP (inset: the colour changes for Rh6G@1 dispersed in solution at different levels of TNP). (d) CIE chromaticity coordinates.

To better understand why Rh6G@1 could behave as a self-calibrating sensor for TNP, we monitored the emission spectra of 1 and Rh6G with various concentrations of TNP under the same excitation wavelength. As shown in Figure S20, the fluorescent intensity of 1 shows a rapid



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decrease upon the addition of TNP, where the quenching trend resembles that of the ligand-based emission of Rh6G@1. This result reveals that the exceptionally quick response ability of Rh6G@1 toward TNP might inherit from the parent framework of 1. Meanwhile, the Rh6G only has a little fluorescent intensity change with the increased concentration of TNP in DMF solution, and the decrease extent is far less than that of 1. Furthermore, a blue shift in the emission maxima of ligand-based emission upon the addition of TNP could be observed for both 1 and Rh6G@1, suggesting the existence of electrostatic interactions between the acidic TNP molecule and the N-rich MOF 1, while this is not observed for other nitro analytes and Rh6G dye embedded in 1. As depicted above, the pore size distribution analysis of Rh6G@1 shows a narrow pore size distribution around 6.4 Å, which is smaller than the molecular diameter of TNP (8.6 8.8 Å2), indicating the sensing is happening on the surface of the composite rather than within the pores. In this case, the TNP molecules could not interact with the Rh6G guest confined in the pores of 1 directly. In addition, it has been reported that the –OH group on TNP can form the strong intermolecular interactions with the Lewis basic –N sites on MOF surface.14 Thus, due to the occurrence of electrostatic interactions, the TNP molecule shows a highly quenching ability to ligand-based emission, but not to dye-based emission, resulting in the variation of intensity ratio between dye and ligand.

Conclusion In conclusion, a unique dual-emissive fluorescent dye@MOF composite has been successfully fabricated based on a “bottle around ship” approach. The implantation of dye can make the composite show the simultaneous luminescence of both ligand and dye to form a dual-emitting sensor. The selective and sensitive detection of TNP is firstly realized with a MOF-based selfcalibrating sensor relying on the ratio of emission-peak-height of dye to ligand as the detectable signal. Quick response and variable luminescent colors that are visible to naked eye have also


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been successfully achieved. This work will offer additional insights into the development of promising guest@MOF luminescent composites as the self-calibrating sensors for practical applications.

ASSOCIATED CONTENT Supporting Information Supplementary structural figures, crystal photos, PXRD patterns, TGA curves, luminescent spectra, and UV-Vis absorption spectra (PDF) CCDC 1540005

AUTHOR INFORMATION Corresponding Authors * E-mail: [email protected]; [email protected]. Notes The authors declare no competing nancial interest.

ACKNOWLEDGMENTS Financial supports from the National Natural Science Foundation of China (21471134, 21571158 and 21601160), Program for Science & Technology Innovative Research Team in University of Henan Province (15IRTSTHN-002), Plan for Scientific Innovation Talent of Henan Province (154200510011), Innovation Scientists and Technicians Troop Construction Projects of Henan Province (152101510003), and the Doctoral Fund of Zhengzhou University of Light Industry (2015BSJJ042) are greatly acknowledged.

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Dual-Emitting Dye@MOF Composite as a Self-Calibrating Sensor for 2,4,6-Trinitrophenol

Di-Ming Chen, Nan-Nan Zhang, Chun-Sen Liu* and Miao Du*

A dual-emissive dye@MOF composite system was fabricated and applied as a self-calibrating luminescent probe for detecting trace amount of 2,4,6-trinitrophenol in solution for the first time.


Dual-Emitting Dye@MOF Composite as a Self ... - ACS Publications

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