CN114957696A - Amino-functionalized metal organic framework MOFs long afterglow coordination compound SUST-WZ-1, preparation and application thereof - Google Patents
Amino-functionalized metal organic framework MOFs long afterglow coordination compound SUST-WZ-1, preparation and application thereof Download PDFInfo
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Abstract
An amino-functionalized metal-organic framework (MOFs) long-afterglow coordination compound SUST-WZ-1 is prepared from terephthalic acid as main ligand, 6-aminopurine as auxiliary ligand and cadmium chloride through solvothermal reaction and self-assembly. The coordination compound is a two-dimensional framework structure with amino active points retained in molecular channels, has adjustable luminescence depending on blue to green excitation, and generates green long afterglow luminescence after a light source is removed; in addition, the coordination compound can be prepared into nano particles, and is further compounded with high molecular materials to prepare a non-toxic, long-service life, low-cost and gas-response multicolor luminous film, and the field visual detection of formaldehyde gas can be realized.
Description
Technical Field
The invention relates to the technical field of metal-organic framework long afterglow materials, in particular to an amino functionalized metal-organic framework long afterglow coordination compound formed by self-assembling terephthalic acid serving as a main ligand, 6-aminopurine serving as an auxiliary ligand and cadmium chloride, a preparation method thereof and application thereof in formaldehyde gas detection.
Background
Metal-organic frameworks (MOFs) are used as a novel porous coordination polymer formed by self-assembly of organic ligands and Metal ions/clusters, and have the characteristics of porous structure, adjustable pore diameter, large surface area, good thermal stability and the like. Due to their advantages, MOFs have been used in a variety of fields such as gas adsorption and separation, heterogeneous catalysis, proton conduction, light emitting OLEDs, and biosensing.
Formaldehyde is used as a chemical raw material and widely applied to multiple fields of textile industry, building materials, antiseptic solutions and the like. However, formaldehyde is known to be a carcinogen, and long term exposure to formaldehyde gas can cause health problems such as leukemia risk, myeloid leukemia, and the like. Therefore, in recent years, the awareness of formaldehyde has been gradually enhanced. To date, two luminescent recognition mechanisms have been used for formaldehyde detection. Firstly, limiting the photoelectron transfer process to recover the inherent optical characteristics of the luminous MOFs; second, the regulation of luminescence is achieved by the condensation of active sites such as amines (primary/secondary) with formaldehyde. The formaldehyde response MOFs materials based on the above recognition mechanisms have been gradually explored, but basically, fluorescence responses are the main ones, and the responses of the materials basically utilize advanced instruments, the test is complex, and trained professionals are needed, so that novel materials capable of simplifying formaldehyde detection are urgent.
The long afterglow MOFs luminescent material is a material which can absorb energy and still emit light after the irradiation of an excitation light source is stopped. It is luminous in dark room, can be directly observed by naked eyes, and has good signal-to-noise ratio. As such, long persistence MOFs have become of interest to researchers in recent years. Currently, researchers are mainly cut in from two aspects: on one hand, the long afterglow luminescence of the material is realized by strategies such as triplet state-triplet state energy transfer, FRET, host and guest and the like; on the other hand, strategies such as heavy atom effect, heteroatom effect, H-aggregation, metal-organic framework and the like are utilized to improve the long-afterglow luminescence of the material. Although the research is matured gradually, the development and the expansion of the materials are mainly focused at present, so that the materials are greatly limited in practical application, and therefore, the functionalized long-afterglow MOFs are worthy of further exploration. The amino group as the active group can carry out condensation reaction with aldehyde, and an amino active site is introduced into the long afterglow MOFs, so that luminous visual response of aldehyde substances can be realized. Based on the method, the long-afterglow MOFs with reserved active sites and pores are obtained by mainly utilizing the assembly of the phosphorescence ligand containing amino and metal ions, and the long-afterglow MOFs are applied to the visual noctilucent response detection of formaldehyde.
Disclosure of Invention
In order to overcome the defects of the prior art, the invention aims to provide an amino-functionalized metal-organic framework (MOFs) long afterglow coordination compound SUST-WZ-1, a preparation method and application thereof, solves the problems of difficult modification, narrow application field and the like of the traditional long afterglow MOFs, and provides the amino-functionalized long afterglow coordination compound SUST-WZ-1. The coordination compound is prepared by self-assembly of main ligand terephthalic acid, auxiliary ligand 6-aminopurine and cadmium chloride through solvothermal reaction. The coordination compound is a two-dimensional framework structure with amino active points retained in molecular channels, has the adjustable luminescence depending on blue to green excitation, and generates green long afterglow luminescence after a light source is removed; in addition, the coordination compound can be prepared into nano particles, and is further compounded with high molecular materials to prepare a non-toxic, long-service life, low-cost and gas-response multicolor luminous film, and the field visual detection of formaldehyde gas can be realized.
In order to achieve the purpose, the invention adopts the technical scheme that:
an amino-functionalized MOFs long-afterglow coordination compound SUST-WZ-1 with the molecular formula of C 78 H 72 Cd 6 N 30 O 33 。
The amino-functionalized MOFs coordination compound SUST-WZ-1 is obtained by self-assembly by taking terephthalic acid and 6-aminopurine as ligands and cadmium chloride as metal salt, and is divided into two forms of single crystal and microcrystal.
A preparation method of an amino-functionalized MOFs long afterglow complex SUST-WZ-1 comprises the following steps:
(1) specifically, the preparation method of the single crystal of the amino-functionalized coordination compound SUST-WZ-1 comprises the following steps:
s1, adding terephthalic acid, 6-aminopurine and N, N-dimethylformamide into a liner of a reaction kettle, then carrying out ultrasonic dissolution, adding cadmium chloride and water when the materials are completely dissolved, carrying out ultrasonic dissolution again, and putting the liner of the reaction kettle into a high-pressure reaction kettle and screwing down the liner of the reaction kettle and putting the liner of the reaction kettle into an electric heating air blast drying box when the materials are completely dissolved;
s2, carrying out hydrothermal reaction in an electrothermal blowing drying oven, heating the electrothermal blowing drying oven for 1-4 hours at the temperature of 80-110 ℃, keeping the temperature for heating for 40-60 hours, and then cooling for 8-20 hours to room temperature;
and S3, cooling to room temperature to obtain white crystals, filtering, and washing with N, N-dimethylformamide to obtain pure crystals.
Further, in the step S1, the molar ratio of the cadmium chloride to the terephthalic acid to the 6-aminopurine is 1-3: 1-3: 1 to 3.
Further, in step S1, the molar ratio of the cadmium chloride to the terephthalic acid to the 6-aminopurine is 1: 1: 1.
further, in the step S1, the dosage ratio of the water to the terephthalic acid is 1-5 mL: 0.05 mmol.
Further, in step S1, the ratio of the water to the terephthalic acid is 2 mL: 0.05 mmol.
Further, in the step S1, the dosage ratio of the N, N-dimethylformamide to the terephthalic acid is 1 to 5 mL: 0.05 mmol.
Further, in step S1, the dosage ratio of N, N-dimethylformamide to terephthalic acid is 1 mL: 0.05 mmol.
Further, in the step S1, the volume ratio of the water to the N, N-dimethylformamide is 1-5: 1 to 5.
Further, in step S1, the volume ratio of the water to the N, N-dimethylformamide is 2: 1.
further, in step S2, the temperature is raised from room temperature to 90 ℃ for 2 hours, and after heating at this temperature for 48 hours, the temperature is then cooled to room temperature for 10 hours.
Further, as an alternative embodiment, the single crystal of the amino-functionalized complex compound SUST-WZ-1 is prepared by a method comprising: adding a mixture of terephthalic acid (83mg, 0.5mmol), 6-aminopurine (71mg, 0.5mmol), and cadmium chloride (93mg, 0.5mmol) to a 20mL reactor polytetrafluoroethylene liner, adding 2mL of water and 1mL of N, N-dimethylformamide, ultrasonically dissolving, capping, and loading into a matched stainless steel reactor; then placing the reaction kettle into an electric heating air blast drying box, heating the reaction kettle for 2 hours to 90 ℃, keeping the temperature for heating for 48 hours, and cooling the reaction kettle to room temperature for 10 hours; finally, the resulting mixture was filtered to obtain a white compound single crystal.
(2) Specifically, the preparation method of the coordination compound SUST-WZ-1 microcrystal comprises the following steps:
s1, adding terephthalic acid and 6-aminopurine into a beaker, then adding N, N-dimethylformamide, then carrying out ultrasonic dissolution, adding cadmium chloride and water after complete dissolution, and carrying out ultrasonic dissolution again;
s2, transferring the dissolved mixed solution into a high-temperature high-pressure stirring reaction kettle, keeping magnetic stirring at 400-600 r/min, heating for 1-2 h to 100-140 ℃, heating for 2-12 h at the temperature, naturally cooling for 3-6 h to room temperature (keeping magnetic stirring in the whole process), and obtaining a coordination compound SUST-WZ-1 microcrystal;
further, in the step S1, the molar ratio of the cadmium chloride to the terephthalic acid to the 6-aminopurine is 1-3: 1-3: 1 to 3.
Further, in step S1, the molar ratio of the cadmium chloride to the terephthalic acid to the 6-aminopurine is 1: 1: 1.
further, in the step S1, the dosage ratio of the water to the terephthalic acid is 1-5 mL: 0.05 mmol.
Further, in step S1, the ratio of the water to the terephthalic acid is 2 mL: 0.05 mmol.
Further, in the step S1, the dosage ratio of the N, N-dimethylformamide to the terephthalic acid is 1 to 5 mL: 0.05 mmol.
Further, in step S1, the dosage ratio of N, N-dimethylformamide to terephthalic acid is 1 mL: 0.05 mmol.
Further, in the step S1, the volume ratio of the water to the N, N-dimethylformamide is 1-3: 1 to 3.
Further, in step S1, the volume ratio of the water to the N, N-dimethylformamide is 2: 1.
further, as an alternative embodiment, the method for preparing the microcrystal of the coordination compound SUST-WZ-1 comprises the following steps: terephthalic acid (83mg, 0.5mmol), 6-aminopurine (71mg, 0.5mmol), cadmium chloride (93mg, 0.5mmol) were added to a beaker, and N, N-dimethylformamide and water were added for ultrasonic dissolution; and then transferring the dissolved mixed solution to a high-temperature high-pressure reaction kettle, keeping magnetic stirring at 400r/min, heating for 2 hours to 90 ℃, heating for 8 hours at the temperature, cooling for 3 hours to room temperature (keeping magnetic stirring in the whole process), and obtaining the SUST-WZ-1 microcrystal serving as the complex.
The preparation method of the long afterglow film SUST-WZ-F1 comprises the following steps:
putting cellulose diacetate into a round-bottom flask, adding N, N-dimethylformamide for dissolving, adding SUST-WZ-1 microcrystal after complete dissolution, adding methanol, and stirring for dispersion to obtain a colloid with uniformly dispersed microcrystals; and (3) filling the jelly into a needle tube, installing the needle tube on a spinning machine, adjusting the flow rate of the jelly and the voltage of an instrument, and performing electrostatic spinning to obtain the noctilucent film SUST-WZ-F1.
Further, the mass ratio of the diacetate fibers to the microcrystals SUST-WZ-1 is 1-50: 1.
further, the mass ratio of the diacetate fibers to the microcrystals SUST-WZ-1 is 10: 1.
further, the volume ratio of the N, N-dimethylformamide to the methanol is (1-10: 1-10).
Further, the volume ratio of the N, N-dimethylformamide to the methanol is 3: 1.
further, the dosage ratio of the N, N-dimethylformamide to the cellulose diacetate is 1-20 mL: 1000 mg.
Further, the dosage ratio of the N, N-dimethylformamide to the cellulose diacetate is 10 mL: 1000 mg.
Further, stirring the mixture for 8-24 h.
Further, the mixture was stirred for 24 h.
Further, as an alternative embodiment, the jelly is prepared by putting 1000mg of cellulose diacetate into a round-bottom flask, adding N, N-dimethylformamide to dissolve 10mL, adding 100mg of SUST-WZ-1 microcrystal after complete dissolution, adding 3.3mL of methanol, and stirring for dispersion to obtain a jelly with uniformly dispersed microcrystals; and (3) filling the jelly into a needle tube, installing the needle tube on a spinning machine, adjusting the flow rate of the jelly and the voltage of an instrument, and performing electrostatic spinning to obtain the noctilucent film SUST-WZ-F1.
In addition, the application of the SUST-WZ-1 and SUST-WZ-F1 noctilucent film of the coordination compound in the aspect of formaldehyde sensing is within the protection scope of the invention.
In particular, the application of the coordination compound SUST-WZ-1 and SUST-WZ-F1 noctilucent film in formaldehyde sensing is within the protection scope of the invention.
More specifically, as a referential embodiment, the method of application may be as follows:
formaldehyde gas with different concentrations is used for fumigating and dyeing the SUST-WZ-1 crystal or thin film SUST-WZ-F1 of the coordination compound, then a light source with the wavelength of 365nm is used for respectively exciting the SUST-WZ-1 single crystal or thin film SUST-WZ-F1 after fumigating and dyeing with different concentrations, and the noctilucence change conditions of the SUST-WZ-1 single crystal or thin film SUST-WZ-F1 are recorded by photographing.
Compared with the prior art, the invention comprises the following steps:
the invention prepares an amino-functionalized MOFs coordination compound through a large amount of research and exploration. The invention uses the organic ligand terephthalic acid (H) 2 L) and 6-aminopurine, metal salt cadmium chloride, and synthesizing a coordination compound SUST-WZ-1 by a hydrothermal reaction method, wherein the molecular formula is as follows: c 78 H 72 Cd 6 N 30 O 33 . The single crystal of appropriate size was selected for single crystal diffraction and the results showed that SUST-WZ-1 crystallized in the upper rhombohedral system and belonged to the P-1 space group. The asymmetric unit is composed of 3L 2- Ligand, 3 Cd 2+ 3, 6-aminopurineAnd 5 free water molecules. In SUST-WZ-1, Cd1 and Cd3 are both hepta-coordinated, while Cd2 is hexa-coordinated. Wherein the coordination atoms of Cd1 and Cd3 are respectively from three carboxyl ligands L 2- 5 coordinated oxygen atoms (Cd1 is O1, O2, O3, O4 and O3A, Cd3 is O5, O6, O8, O11 and O12) and two nitrogen atoms of the 6-aminopurine auxiliary ligand (Cd1 is N1 and N5, Cd3 is N10 and N15); and the coordinating atoms of Cd2 come from three ligands L 2- And four oxygen atoms (O6, O7, O9 and O10) and two nitrogen atoms (N6 and N11) of the 6-aminopurine ancillary ligand. Of these coordinating oxygen atoms, O3 passes through 2 Bridging Cd1 and Cd1A ions to form a stable binuclear cadmium cluster with a pentahedral bipyramidal geometry with O6 passing through 2 Bridging Cd2 and Cd3 formed a bi-nuclear cadmium cluster of a four-face bi-conical and five-face bi-conical geometry, and the multi-nuclear clusters were clustered by pairing L 2- The ligands are linked to form a 2D structure, and further the 2D structure forms a 3D framework structure through intermolecular and intramolecular non-covalent interactions. From the figure we can see that the amino active sites are intact and all exist in the gaps of the structure, which will probably interact with some toxic substances for the purpose of detection (figure 2).
The invention aims to solve the technical problems of difficult modification, narrow application field and the like of the traditional long afterglow MOFs and provides an amino functionalized long afterglow coordination compound SUST-WZ-1. The coordination compound is a two-dimensional framework structure with amino active points retained in molecular channels, has adjustable luminescence depending on blue to green excitation, and generates green long afterglow luminescence after a light source is removed; in addition, the coordination compound can be prepared into nano particles, and is further compounded with high molecular materials to prepare a non-toxic, long-service life, low-cost and gas-response multicolor luminous film, and the field visual detection of formaldehyde gas can be realized.
The invention has the following beneficial effects:
(1) the invention provides a long afterglow coordination compound adopting amino functionalized MOFs;
(2) the coordination compound SUST-WZ-1 has stable luminous performance, no toxicity, no harm and environmental friendliness;
(3) the noctilucent film prepared based on the coordination compound SUST-WZ-1 is easy to process, low in cost, simple and convenient in use method, non-toxic and non-volatile.
(4) The noctilucent film prepared based on the coordination compound SUST-WZ-1 can respond to formaldehyde gas, and realizes on-site, simple and convenient noctilucent visual sensing.
Drawings
FIG. 1 shows the molecular structure of terephthalic acid, 6-aminopurine and the preparation of SUST-WZ-1, a metal-organic framework long-afterglow compound.
FIG. 2 shows the crystal structure of SUST-WZ-1. a) An asymmetric unit; b, c, D) 2D structures along different directions; e, f) non-covalent interactions form the original and simplified 3D framework structure.
FIG. 3 is a PXRD spectrum of simulated and synthesized SUST-WZ-4.
FIG. 4 shows the excitation spectrum, emission spectrum and decay curve of each emission peak of SUST-WZ-1 at 300K.
FIG. 5 shows the long persistence emission spectrum and CIE coordinates for SUST-WZ-1300K.
FIG. 6 is the CIE coordinates of the gate spectrum, time resolved emission spectrum, the varied excitation emission spectrum and the varied excitation emission of SUST-WZ-1 at air and 300K.
FIG. 7 is a temperature-varying spectrum of SUST-WZ-1 under vacuum and the temperature-varying attenuation curves of the corresponding CIE coordinates and different emission peaks.
FIG. 8 is a crystal diagram of SUST-WZ-1 under natural light and ultraviolet light and with the ultraviolet light removed.
FIG. 9 is a night light picture of SUST-WZ-1 after UV light removal at different formaldehyde concentrations.
Detailed Description
The invention is further described with reference to the following figures and examples. The examples are not intended to limit the invention in any way. Reagents, methods and apparatus used in the present invention are conventional in the art unless otherwise indicated.
Unless otherwise indicated, reagents and materials used in the following examples are commercially available.
The applied instrument is: single crystal data in the presence of a molybdenum target
The single crystal X-ray diffractometer on the Rigaku-Oxford supernova X-ray diffractometer system; powder X-ray diffraction (PXRD) was measured using a Rigaku SmartLab diffractometer (Bragg-Brentano geometry, Cu k α 1 radiation, λ ═ 1.54056 a); fluorescence spectra were measured by Edinburgh FLS 980 spectrometer. Long-lasting luminescence is obtained by testing with a Q65 Pro instrument; the FA sensing picture is obtained by taking a picture of the mobile phone.
EXAMPLE 1 preparation of a functionalized Metal-organic framework Long persistence Complex SUST-WZ-1
Preparation of the amino-functionalized complex SUST-WZ-1 (divided into two forms, single crystal and microcrystalline):
(1) preparation of a Single Crystal of Complex SUST-WZ-1:
adding a mixture of terephthalic acid (8.3mg, 0.05mmol), 6-aminopurine (7.1mg, 0.05mmol) and cadmium chloride (9.3mg, 0.05mmol) into a polytetrafluoroethylene lining of a 20mL reaction kettle in a liner of the reaction kettle, adding 2mL of water and 1mL of N, N-dimethylformamide, ultrasonically dissolving, covering and filling the mixture into a matched stainless steel reaction kettle; then placing the reaction kettle into an electric heating air blast drying box, heating the reaction kettle for 2 hours to 90 ℃, keeping the temperature for heating for 48 hours, and cooling the reaction kettle to room temperature for 10 hours; finally, the resulting mixture was filtered to obtain a white compound single crystal.
(2) Preparation of microcrystalline SUST-WZ-3 Complex:
terephthalic acid (8.3mg, 0.05mmol), 6-aminopurine (7.1mg, 0.05mmol), cadmium chloride (9.3mg, 0.05mmol) were added to a beaker, and N, N-dimethylformamide and water were added for ultrasonic dissolution; and then transferring the dissolved mixed solution to a high-temperature high-pressure reaction kettle, keeping magnetic stirring at 400r/min, heating for 2 hours to 90 ℃, heating for 8 hours at the temperature, cooling for 3 hours to room temperature (keeping magnetic stirring in the whole process), and obtaining the SUST-WZ-1 microcrystal serving as the complex.
Example 2 Crystal Structure determination of amino-functionalized MOFs Complex SUST-WZ-1
Is provided with a molybdenum target
Single crystal X-ray diffraction data of SUST-WZ-1 were collected at 50kV and 0.80mA on a Rigaku-Oxford Ulnova X-ray diffractometer system.
The structure is solved by adopting a direct method, and is refined by utilizing a SHELXL-2014 program package and adopting a full matrix least square method. All hydrogen atoms are obtained by a theoretical hydrogenation method and refined along the anisotropic direction; the relevant crystallographic data for SUST-WZ-1 are shown in Table 1 below.
TABLE 1 is the crystallographic data of the metal organic framework complex SUST-WZ-1
EXAMPLE 3 optical Properties measurement of SUST-WZ-1
The diffraction peaks measured in the X-ray powder diffraction (PXRD) experiment for the SUST-WZ-1 complex were substantially consistent with those simulated by the single crystal data, indicating that SUST-WZ-1 has a relatively high phase purity (FIG. 3).
Under excitation at 340nm, SUST-WZ-1 shows blue fluorescence at room temperature, the maximum emission peak is around 430nm (figure 4), and the maximum emission peak lifetime is 5.16 ns. Meanwhile, when the sample is placed under vacuum, the emission spectrum of the sample is substantially consistent with that of the sample in the air, which indicates that the structure is not changed under vacuum. Interestingly, when the UV lamp was removed, the sample emitted a bright green long afterglow luminescence with a maximum emission wavelength around 530nm (FIG. 5). In order to understand the source of the long afterglow luminescence, the gated spectrum was further measured, and after delays of 1ms, 2ms, 5ms, 10ms and 30ms, strong emission peaks still exist between 500 and 540nm, which indicates that the wavelength band is a phosphorescence emission peak. Carefully we found that there were two emission peaks at 510 and 545nm and the transient spectra were further measured in order to distinguish their origin. The lifetimes at 510 and 545nm of the emission peaks were 382.86 and 369.03ms, respectively, indicating that the emission peaks belong to the same energy level, being the splitting peak of the lowest triplet level. Furthermore, we also measured time resolved emission spectra, which showed that the intensity of the emission peak retained a certain intensity over time, and several emission peaks appeared over time, consistent with gated spectra (fig. 6). Because of the existence of singlet and triplet state luminescence, the excitation-dependent emission spectrum of SUST-WZ-1 at room temperature is further measured, and the blue to green luminescence of the sample can be adjusted along with the change of the wavelength (in the range of 280 nm-400 nm), and the corresponding CIE gives the change of the color. Considering that temperature is an important factor affecting phosphorescence, we next studied the temperature dependent emission spectrum, as shown in fig. 9, the emission intensity and phosphorescence lifetime of the sample gradually increased with decreasing temperature under excitation at 340nm, further indicating the phosphorescence properties of the material, and the corresponding color change can be obtained from CIE.
The PXRD spectrum of SUST-WZ-1 simulation and synthesis of SUST-WZ-4 is shown in FIG. 3.
The transient spectrum of the excitation/emission and different emission peaks of SUST-WZ-1 (air, vacuum) at room temperature is shown in FIG. 4.
The SUST-WZ-1 long persistence spectrum and CIE coordinates at room temperature are shown in FIG. 5.
The time-resolved emission and excitation dependent optical fluorescence spectra of SUST-WZ-1 are shown in FIG. 6.
The variable temperature transient spectrum and the variable temperature emission spectrum of SUST-WZ-1 at 77-300K and corresponding CIE coordinates are shown in FIG. 7.
EXAMPLE 4 preparation of gas sensing films
Putting 1000mg of cellulose diacetate into a round-bottom flask, then adding N, N-dimethylformamide to dissolve 10mL, adding 100mg of SUST-WZ-1 microcrystal after complete dissolution, then adding 3.3mL of methanol, stirring and dispersing to obtain a colloid with uniformly dispersed microcrystals; and (3) filling the jelly into a needle tube, installing the needle tube on a spinning machine, adjusting the flow rate of the jelly and the voltage of an instrument, and performing electrostatic spinning to obtain the noctilucent film SUST-WZ-F1.
EXAMPLE 5 use of the Complex SUST-WZ-1 and its thin film SUST-WZ-F1
Working examples of formaldehyde detection for the coordination compounds SUST-WZ-1 and SUST-WZ-F1:
the SUST-WZ-1 complex is white at room temperature under sunlight. Under the excitation of 365nm ultraviolet light source, the light-emitting color of the coordination compound SUST-WZ-1 can be observed to be blue at room temperature, and the SUST-WZ-1 shows green afterglow after the excitation of the ultraviolet light source is stopped.
Adding formaldehyde gas into a closed container, placing SUST-WZ-1 or SUST-WZ-F1 into a container with air inlet and closed container, and controlling formaldehyde at 0.01, 0.04, 0.08, 0.16, 0.32 and 0.64mg/m 3 And (3) smoking and dyeing the coordination compound SUST-WZ-110 min under the conditions of different concentrations, exciting the coordination compound SUST-WJ-1 smoked by formaldehyde by using a 365nm ultraviolet light source, observing the change of afterglow, and taking a picture for recording. It was found that the afterglow time of the complex SUST-WJ-1 decreased as the formaldehyde concentration increased.
The crystal pattern of the coordination compound SUST-WZ-1 after 365nm UV excitation and light source removal is shown in FIG. 8.
The luminous patterns of the complexes SUST-WZ-1 and SUST-WZ-F1 after being fumigated with formaldehyde at different concentrations after UV excitation at 365nm and removal of the light source are shown in FIG. 9.
Claims (9)
1. An amino-functionalized metal-organic framework (MOFs) long afterglow coordination compound SUST-WZ-1 is characterized in that the molecular formula is C 78 H 72 Cd 6 N 30 O 33 The space group of the triclinic system is P-1.
2. The process for preparing amino-functionalized MOFs long persistence coordination compound SUST-WZ-1 as claimed in claim 1, wherein said coordination compound SUST-WZ-1 is obtained by self-assembly using terephthalic acid and 6-aminopurine as organic ligands and cadmium ion as metal ion.
3. A preparation method of an amino-functionalized metal-organic frameworks (MOFs) long afterglow coordination compound SUST-WZ-1 is characterized by comprising the following steps:
s1, adding terephthalic acid, 6-aminopurine and N, N-dimethylformamide into a liner of a reaction kettle, then carrying out ultrasonic dissolution, adding cadmium chloride and water when the materials are completely dissolved, carrying out ultrasonic dissolution again, placing the liner of the reaction kettle into a high-pressure reaction kettle when the materials are completely dissolved, screwing and sealing the liner of the reaction kettle, and placing the liner of the reaction kettle into an electric heating air blast drying box; the method is characterized in that the terephthalic acid, the 6-aminopurine and the cadmium chloride are mixed according to a molar ratio (1-3: 1-3), the N, N-dimethylformamide and water (the volume ratio is 1-5: 1-5), and the consumption ratio of the water to the terephthalic acid is 1-5 mL: 0.05mmol, wherein the dosage ratio of the N, N-dimethylformamide to the terephthalic acid is 1-5 mL: 0.05 mmol;
s2, carrying out hydrothermal reaction in an electrothermal blowing drying oven, heating the electrothermal blowing drying oven for 1-4 hours to 80-110 ℃, keeping the temperature for heating for 40-80 hours, and then cooling for 8-20 hours to room temperature;
s3, cooling to room temperature to obtain white crystals, filtering and washing with N, N-dimethylformamide to obtain pure SUST-WZ-1 crystals.
4. The method for preparing amino-functionalized metal-organic frameworks (MOFs) long persistence complex SUST-WZ-1 according to claim 3, wherein the method for preparing the crystallites of the complex SUST-WZ-1 comprises the following steps:
s1, adding terephthalic acid and 6-aminopurine into a beaker, adding N, N-dimethylformamide, performing ultrasonic dissolution, adding cadmium chloride and water after the materials are completely dissolved, and performing ultrasonic dissolution again, wherein the molar ratio of the terephthalic acid to the 6-aminopurine to the cadmium chloride is (1-3: 1-3), the molar ratio of the N, N-dimethylformamide to the water is (1-5: 1-5), and the dosage ratio of the water to the terephthalic acid is 1-5 mL: 0.05mmol, wherein the dosage ratio of the N, N-dimethylformamide to the terephthalic acid is 1-5 mL: 0.05 mmol;
s2, transferring the dissolved mixed solution into a high-temperature high-pressure stirring reaction kettle, keeping magnetic stirring at 400-600 r/min, heating for 1-2 h to 100-140 ℃, heating for 2-12 h at the temperature, naturally cooling for 3-6 h to room temperature, and keeping magnetic stirring in the whole process to obtain the SUST-WZ-1 microcrystal serving as the coordination compound.
5. The process for preparing amino functionalized MOFs long afterglow complex SUST-WZ-1 according to claim 3 or 4, wherein said hydrothermal reaction is carried out in an electrothermal blowing dry box, and the obtained product is sealed and then placed at 90 ℃ for reaction for 48 hours.
6. The method for preparing amino-functionalized metal-organic frameworks (MOFs) long-afterglow coordination compounds SUST-WZ-1 as claimed in claim 4, wherein the long-afterglow thin film is prepared by compounding diacetic fiber and SUST-WZ-1 microcrystals serving as raw materials to obtain the SUST-WZ-F1.
7. The method for preparing amino-functionalized metal-organic frameworks (MOFs) long-afterglow coordination compounds SUST-WZ-1 according to claim 6, wherein the method for preparing said long-afterglow thin film SUST-WZ-F1 comprises the following steps:
s1, adding diacetate fibers into a round-bottom flask, adding N, N-dimethylformamide for dissolving, adding SUST-WZ-1 microcrystals after complete dissolution, adding methanol for stirring, and dispersing the microcrystals SUST-WZ-1 to obtain a jelly with uniformly dispersed microcrystals, wherein the volume ratio of the diacetate fibers to the microcrystals SUST-WZ-1 is 1-50: 1, the volume ratio of the N, N-dimethylformamide to the methanol is 1-10: 1-10, wherein the dosage ratio of N, N-dimethylformamide to diacetate fiber is 1-20 mL: 1000mg, the dosage ratio of the N, N-dimethylformamide to the microcrystalline SUST-WZ-1 is 1-20 mL: 1000 mg;
s2, filling the jelly into a needle tube, installing the needle tube on a spinning machine, adjusting the flow rate of the jelly and the voltage of an instrument, and spinning to obtain the SUST-WZ-F1 film.
8. The method for preparing SUST-WZ-F1 as claimed in claim 6, wherein the stirring time is 8-24 h.
9. The use of the amino functionalized MOFs long persistence complex SUST-WZ-1 and SUST-WZ-F1 as claimed in claim 3, 4 or 6, for the detection of formaldehyde gas by noctilucence visualization.
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