Cadmium (II)-based metal organic framework crystalline material and its preparation method and application

Abstract

The present invention belongs to the technical field of fluorescent active material development, and particularly relates to a cadmium (II)-based metal organic framework crystalline material, its preparation method, and application. The molecular formula of the cadmium (II)-based metal organic framework crystalline material is {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n， The three-dimensional structure is formed using cadmium (II) ions as connecting nodes, BMIP and H2 (Br-BDC) ligands as bridging ligands. The structure contains Cd-O secondary structural units, with three Cd atoms forming a trinuclear Cd-O cluster structure through the Cd-O secondary structural units. The Cd1 and Cd1# atoms exhibit mirror-image symmetry. The present invention utilizes a one-pot solvothermal reaction to prepare a divalent cadmium ion fluorescent sensing material. This preparation method has the advantages of a simple process, easy operation, high yield, and good reproducibility. The cadmium (II) fluorescent sensing material exhibits a strong fluorescence emission spectrum and can be applied in molecular fluorescent probes, metal ion detection, and other fields.

Description

Technical Field

[0001] The present invention relates to the technical field of fluorescent active substance development, and in particular to a cadmium (II)-based metal organic framework crystalline material, a preparation method and an application thereof. Background Art

[0002] In recent years, environmental pollution remains a global challenge. Water pollution, for example, remains a serious problem due to industrial wastewater, domestic sewage, and agricultural non-point source pollution. Some rivers, lakes, and coastal waters are polluted to varying degrees, impacting aquatic ecosystems and human health. Industrial wastewater: Large amounts of wastewater containing heavy metals, organic matter, and other pollutants generated during industrial production are discharged directly into water bodies without effective treatment, causing serious pollution of surface and groundwater. Agricultural pollution: Excessive use of fertilizers and pesticides, as well as the discharge of livestock and poultry waste, lead to large amounts of nutrients such as nitrogen and phosphorus entering water bodies, causing eutrophication. Domestic sewage: With the acceleration of urbanization, the discharge of domestic sewage continues to increase. Pollutants such as organic matter and detergents in domestic sewage have a significant impact on the aquatic environment. Atmospheric deposition: Chemicals released from chimneys sometimes enter the atmosphere and then fall back to Earth as rainwater, entering oceans, rivers, and lakes, also causing water pollution.

[0003] In addition, there is soil pollution, where pollutants such as heavy metals, pesticide residues and plastic particles accumulate in the soil, posing a threat to crop growth and human health.

[0004] At present, there are different means of detecting environmental pollutants. High-performance gas-liquid chromatography, mass spectrometry, Raman spectroscopy and other detection methods are mainly based on expensive instruments. These analytical techniques have certain disadvantages, such as the need for well-trained professionals, high costs and complex equipment. MOFs as fluorescent sensing materials have been widely favored by scientific researchers due to their advantages such as simple operation, high selectivity and fast detection speed. There are three factors that cause MOFs to emit light: the conjugation effect produced by organic ligands, the central metal ions and the d 10 All MOFs formed by metals with valence electrons will cause them to emit light. Because MOFs materials have the characteristics of high specific surface area and pore structure, they show high adsorption capacity and better selectivity. Therefore, they have excellent performance in the adsorption of heavy metal ions and the detection of organic pollutants and pesticides. 3+ 、Cd 2+ Cr 3+ 、Ag + , K + 、Mn 2 + 、Al 3+It has a detection function. Therefore, by detecting the fluorescence changes before and after contact with organic pollutants, heavy metal ions and pesticides, it can be used to qualitatively or even quantitatively detect excessive organic pollutants, heavy metal ions and pesticides discharged into the environment. Summary of the Invention

[0005] The technical problem to be solved by the present invention is to address the deficiencies of the above-mentioned prior art and provide a cadmium (II)-based metal organic framework crystalline material and its preparation method and application. The molecular formula of the cadmium (II)-based metal organic framework crystalline material is {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n Using cadmium (II) ions as connecting nodes, BMIP and H2 (Br-BDC) ligands as bridging ligands to bridge each other to form a three-dimensional spatial structure, which was prepared by one-pot solvent thermal preparation and can be used in fluorescent sensors to detect ionic pollutants, and can also be used as a detector for Al 3+ fluorescent probes.

[0006] The present invention provides a cadmium (II)-based metal organic framework crystalline material, wherein the molecular formula of the cadmium (II)-based metal organic framework crystalline material is {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n The cadmium (II)-based metal organic framework crystalline material uses cadmium (II) ions as connecting nodes, and 1,3-bis(dimethylimidazolylpropane) and 2,5-dibromoterephthalic acid ligands as bridging ligands to bridge each other to form a three-dimensional spatial structure; the structure contains Cd-O secondary structural units, and three Cd atoms form a trinuclear Cd-O cluster structure through the Cd-O secondary structural units, and the Cd1 atom and the Cd1# atom are mirror-symmetrical.

[0007] The present invention provides a method for preparing the above-mentioned cadmium (II)-based metal organic framework crystalline material, comprising the following steps:

[0008] S1. Adding a cadmium salt, 1,3-bis(dimethylimidazolylpropane) and 2,5-dibromoterephthalic acid to a solvent DMA to obtain a mixture, adding glacial acetic acid to the mixture to adjust the pH value of the mixture to 4.5 to 6.5, and then performing a solvothermal reaction in a closed environment to obtain a reaction product;

[0009] S2. Allow the reaction product prepared in S1 to cool naturally and crystallize, then wash and filter under reduced pressure to obtain colorless needle-shaped crystals, and dry to obtain a cadmium (II)-based metal organic framework crystalline material.

[0010] According to the preparation method provided by the present invention, the molar volume ratio of the cadmium salt, 1,3-bis(dimethylimidazolylpropane), 2,5-dibromoterephthalic acid and DMA in S1 is (0.5-1.5) mmol: (0.05-0.15) mmol: (0.1-0.5) mmol: (2-10) mL, the amount of glacial acetic acid used is 50 µL, the concentration of the glacial acetic acid is 17 mol / L, the temperature of the solvothermal reaction is 90 ° C, and the time of the solvothermal reaction is (36-72) h.

[0011] According to the preparation method provided by the present invention, the molar volume ratio of the cadmium salt, 1,3-bis(dimethylimidazolylpentane), 2,5-dibromoterephthalic acid and DMA in S1 is 1.5 mmol:0.05 mmol:0.5 mmol:4 mL, the amount of glacial acetic acid used is 50 µL, the temperature of the solvent thermal reaction is 90 ° C, and the time of the solvent thermal reaction is 48 h.

[0012] According to the preparation method provided by the present invention, the drying temperature in S2 is 60° C., and the drying time is 2 to 4 h.

[0013] The present invention also provides an application of the above-mentioned cadmium (II)-based metal organic framework crystalline material. The cadmium (II)-based metal organic framework crystalline material can be used in fluorescent sensors to detect ionic pollutants, and can also be used as a detector for Al 3+ fluorescent probes.

[0014] Compared with the prior art, the present invention has the following advantages:

[0015] The present invention adopts a one-pot solvent thermal reaction to prepare a cadmium (II)-based metal organic framework crystalline material {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n , n is a positive integer. The preparation method has the advantages of simple process, convenient operation, high yield, good reproducibility, etc. The fluorescence emission spectrum intensity of the cadmium (II)-based metal organic framework crystalline material is strong and can be applied to the fields of molecular fluorescence enhancement or quenching effect, metal ion detection, etc. The detection method of the cadmium (II)-based metal organic framework crystalline material has the advantages of simple operation, low cost, high selectivity, and fast detection speed. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] In order to more clearly illustrate the technical solutions in the present invention or the prior art, a brief introduction will be given below to the drawings required for use in the embodiments or the description of the prior art. Obviously, the drawings described below are some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0017] Figure 1 This is a single molecule image of a cadmium (II)-based metal-organic framework crystalline material;

[0018] Figure 2 It is a three-dimensional porous framework structure of cadmium (II)-based metal organic framework crystalline material;

[0019] Figure 3 This is a topological structural view of cadmium (II)-based metal organic framework crystalline materials;

[0020] Figure 4 This is the IR spectrum of cadmium (II)-based metal organic framework crystalline material;

[0021] Figure 5 This is the XRD pattern of cadmium (II) based metal organic framework crystalline material;

[0022] Figure 6 This is the fluorescence spectrum of cadmium (II) based metal organic framework crystalline material;

[0023] Figure 7 The fluorescence emission intensity diagram of cadmium (II)-based metal organic framework crystalline materials dispersed in 7 organic solvents;

[0024] Figure 8 Coordination polymer for Al 3+ Schematic diagram of the specificity of ion detection;

[0025] Figure 9 This is a graph showing the relationship between the fluorescence spectrum of cadmium (II)-based metal organic framework crystalline materials in ethanol solvent and the change of metal ion concentration;

[0026] Figure 10 Cadmium (II) based metal organic framework crystalline material with Al 3+ Schematic diagram of fluorescence intensity changes and fitting with solution concentration. DETAILED DESCRIPTION

[0027] Example 1

[0028] This embodiment provides a method for preparing a cadmium (II)-based metal organic framework crystalline material, and the specific steps are as follows:

[0029] S1. Dissolve 1.5 mmol of cadmium nitrate hexahydrate, 0.05 mmol of 1,3-bis(dimethylimidazolylpropane) (BMIP), and 0.5 mmol of 2,5-dibromoterephthalic acid (H2(Br-BDC)) in 4 mL of N,N'-dimethylacetamide (DMA) to obtain a mixture. Add 50 µL of 17 mol / L glacial acetic acid to adjust the pH of the mixture to 5.5, making it weakly acidic. Place the mixture in a glass scintillation vial and perform a solvothermal reaction at 90°C for 48 h to obtain a reaction product.

[0030] The structural formula of the above-mentioned BMIP is shown in the following formula (I):

[0031]

[0032] Formula (I);

[0033] The structural formula of the above H2(Br-BDC) is shown in the following formula (II):

[0034]

[0035] Formula (II);

[0036] The structural formula of the above DMA is shown in the following formula (III):

[0037]

[0038] Formula (III);

[0039] S2. The reaction product is naturally cooled and crystallized, and the crystals are rinsed with deionized water. The crystals are filtered under reduced pressure to obtain colorless needle-shaped crystals, which are placed in an oven at a constant temperature of 60°C for 3 h to obtain a cadmium (II)-based metal organic framework crystalline material.

[0040] The main preparation method provided in this embodiment is intended to overcome the problems of low yield, very low repeatability and excessive influence of reaction conditions in existing methods for preparing cadmium (II)-based metal organic framework crystalline materials.

[0041] Example 2

[0042] This embodiment provides a method for preparing a cadmium (II)-based metal organic framework crystalline material, and the specific steps are as follows:

[0043] S1. Dissolve 0.5 mmol of cadmium chloride, 0.1 mmol of 1,3-bis(dimethylimidazolylpropane), and 0.3 mmol of 2,5-dibromoterephthalic acid in 2 mL of N,N'-dimethylacetamide to obtain a mixture. Add 50 µL of 17 mol / L glacial acetic acid to adjust the pH of the mixture to 4.5, making it weakly acidic. Place the mixture in a glass scintillation vial and perform a solvothermal reaction at 90°C for 36 h to obtain a reaction product.

[0044] S2. The reaction product is naturally cooled and crystallized, and the crystals are rinsed with deionized water. The crystals are filtered under reduced pressure to obtain colorless needle-shaped crystals, which are placed in an oven at a constant temperature of 60°C for 2 h to obtain a cadmium (II)-based metal organic framework crystalline material.

[0045] Example 3

[0046] This embodiment provides a method for preparing a cadmium (II)-based metal organic framework crystalline material, and the specific steps are as follows:

[0047] S1. Dissolve 1.0 mmol of cadmium acetate, 0.15 mmol of 1,3-bis(dimethylimidazolylpropane), and 0.1 mmol of 2,5-dibromoterephthalic acid in 10 mL of N,N'-dimethylacetamide to obtain a mixture. Add 50 µL of 17 mol / L glacial acetic acid to adjust the pH of the mixture to 6.5, making it weakly acidic. Place the mixture in a glass scintillation vial and perform a solvothermal reaction at 90°C for 72 h to obtain a reaction product.

[0048] S2. The reaction product is naturally cooled and crystallized, and the crystals are rinsed with deionized water. The crystals are filtered under reduced pressure to obtain colorless needle-shaped crystals, which are placed in an oven at a constant temperature of 60°C for 4 h to obtain a cadmium (II)-based metal organic framework crystalline material.

[0049] Comparative Example 1

[0050] This comparative example provides a method for performing a solvothermal reaction for adjusting pH compared to Example 1, and the specific steps are as follows:

[0051] (1) 1.5 mmol of cadmium nitrate hexahydrate, 0.05 mmol of BMIP, and 0.016 g of 2,5-dibromoterephthalic acid were dissolved in 4 mL of DMA solvent to obtain a mixture, and the mixture was subjected to solvothermal reaction at 90°C in a glass scintillation vial for 48 hours;

[0052] (2) The reactants were cooled naturally to obtain a clear and transparent solution. The reason for the lack of crystallization was that the pH of the reaction system did not match.

[0053] Example 4

[0054] This example characterizes the cadmium (II)-based metal organic framework crystalline material prepared in Example 1:

[0055] (1) Crystal structure determination of cadmium (II)-based metal-organic framework crystalline materials

[0056] Select the appropriate size of 0.15×0.13×0.11 mm under the microscope 3 X-ray diffraction experiments were performed on single crystals at room temperature. Diffraction data were collected on a Bruker P4 CCD single crystal diffractometer and monochromated with a graphite monochromator. Mo-Kα ray (λ = 0.71073 Å), with φ-ω The diffraction points are collected in a scanning manner.

[0057] In addition, absorption and factor corrections were performed for Lp using the SADABS program. Full-matrix least-squares corrections were performed for all non-hydrogen atoms and their anisotropic thermal parameters using the SHELX-97 program. Detailed crystallographic data are shown in Table 1, and important bond length and angle data are shown in Table 2.

[0058] Table 1 Main crystallographic data of cadmium (II)-based metal-organic framework crystalline materials

[0059]

[0060] Table 2 Important bond lengths (Å) and bond angles (°) of cadmium (II)-based metal-organic framework crystalline materials

[0061]

[0062] In Table 1, a, b, and c represent the edge lengths of the crystal in the directions of the three crystal axes, and α, β, and γ represent the angles between a and b, a and c, and b and c, respectively; Z is the number of molecules contained in the unit cell; the diffraction index range of the limiting factor is (h, k, l); F (000) is the number of electrons in the unit cell; Final R indices [ I >2σ( I )] is the residual factor R value for the observable diffraction point; R is the non-weighted consistency factor; R1 and wR2 are both weighted consistency factors;

[0063] In the first row of Table 2, Cd(1) refers to Cd atom 1 in the cadmium (II)-based metal organic framework crystalline material single crystal, O(3) refers to O atom 3 in the cadmium (II)-based metal organic framework crystalline material single crystal, and Cd(1)-O(3) represents the bond length between Cd atom 1 and O atom 3, which is 2.342±5, with 5 being the standard deviation;

[0064] O(3)-Cd(1)-O(6) represents the bond angle between O atom 3, Cd atom 1 and O atom 6, and its bond angle is 84.74±18;

[0065] Single molecules of cadmium (II)-based metal organic framework crystalline materials such as Figure 1 As shown, the three-dimensional porous framework structure is Figure 2 As shown, the topology structure view is as follows Figure 3 As shown, the cadmium (II)-based metal organic framework crystalline material contains three Cd (II) ions, two BMIP ligands, and three deprotonated Br-BDC 2- Ligand and two crystal water molecules. Among them, Cd1 ion and Cd1# ion are mirror-symmetrical and have the same coordination mode. The Cd1 center is connected to the Br-BDC2- The three O atoms of the ligands coordinate to form a distorted trigonal bipyramidal coordination model. The coordination mode of Cd2 is different from that of Cd1. The six coordinated O atoms in Cd2 come from the chelate coordination of the carboxyl and carbonyl groups of the two ligands, forming an octahedral coordination model. The above three Cd(II) ions are catalyzed by BDC. 2- The bridging connection of the carboxyl oxygen of the ligand forms a trinuclear Cd-O cluster secondary structural unit, and through BDC 2- The ligand bridging connection formed a two-dimensional double-layer structure, and on this basis, the BMIP ligand was further bridged and expanded to form a three-dimensional skeleton.

[0066] (2) IR spectrum characterization of cadmium (II)-based metal organic framework crystalline materials

[0067] Figure 4 This is the IR spectrum of the cadmium (II)-based metal organic framework crystalline material. The sample infrared spectrum data was collected from 500 to 4000 cm -1 , using KBr pellets. Figure 5 It can be seen that the crystalline material of cadmium (II)-based metal organic framework has a -1 There is a strong broad absorption peak at 1608 cm, which is the stretching vibration peak of the OH group. -1 The asymmetric and symmetric stretching vibrations of the carbonyl group are shown.

[0068] The molecular formula of the material is {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n , n is a positive integer, recorded as {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n。

[0069] (3) Phase purity characterization of cadmium (II)-based metal-organic framework crystalline materials

[0070] Using a Bruker / D8Advance X-ray diffractometer, the powder XRD characterization results of cadmium (II)-based metal organic framework crystalline materials showed that they have reliable phase purity, which provides a guarantee for their use as fluorescent probes to detect excessive organic pollutants, pesticides, and heavy metal ions emitted in the environment. Figure 5 shown.

[0071] (4) Solid-state fluorescence characterization of cadmium (II)-based metal-organic framework crystalline materials

[0072] The solid fluorescence properties of cadmium (II)-based metal organic framework crystalline materials were tested using Edinburgh instruments / FLS 1000 fluorescence spectrometer. The cadmium (II)-based metal organic framework crystalline materials have a strong fluorescence emission peak at 450nm with an excitation wavelength of 385nm, such as Figure 6 shown.

[0073] Effect Example 1

[0074] 2.0 mg of the thoroughly ground crystalline powder of the cadmium (II)-based metal-organic framework material prepared in Example 1 was weighed and placed in 4 mL of seven organic solvents, respectively. After sonication for half an hour and stabilization for one hour, the supernatant was collected and placed in a cuvette. The fluorescence emission intensity of the suspension in N,N'-diethylformamide (DEA), N,N'-diethylformamide (DEF), ethanol (EtOH), acetonitrile (ACN), water (H2O), N,N'-dimethylacetamide (DMA), and N,N'-dimethylformamide (DMF) as solvents was measured at an excitation wavelength of 255 nm. Figure 7 shown.

[0075] Depend on Figure 7 It can be seen that the fluorescence intensity of the cadmium (II)-based metal organic framework fluorescent sensing material is the strongest in ethanol solvent.

[0076] Effect Example 2

[0077] 2 mg of the thoroughly ground crystalline powder of the cadmium (II)-based metal-organic framework (MOF) prepared in Example 1 was placed in 4 mL of ethanol. After sonication for half an hour and allowing to stand for one hour, 3 mL of the supernatant was placed in a cuvette. At an excitation wavelength of 255 nm, aqueous solutions of 15 different metal cations were sequentially added to the supernatant of the cadmium (II)-based MOF, and their corresponding fluorescence responses were measured. Figure 8 shown.

[0078] Depend on Figure 8 It can be seen that the coordination polymer has a great influence on Al 3+ There is a significant fluorescence quenching effect.

[0079] Effect Example 3

[0080] In order to further study the preparation of {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n Al 3+ The sensitivity and selectivity of ion detection were further studied by quantitative titration experiments. 3+ ion detection capabilities, such as Figure 9 As shown, it can be clearly found that {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n The fluorescence intensity of Al 3+ The ion concentration gradually increased and showed a trend of gradually weakening. When 30 μL Al 3+ions, the fluorescence intensity is about one-fifth of the original.

[0081] According to the above experimental data, the supernatant of ethanol of cadmium (II)-based metal organic framework crystalline material was further analyzed. I / I 0 value( I represents the fluorescence intensity of Cd(II)-based metal-organic framework crystalline materials in ethanol solvent after adding organic solvent; I 0 represents the fluorescence intensity of the cadmium (II) based metal organic framework crystalline material in ethanol solvent when no organic solvent is added) and the metal ion Al 3+ The linear regression equation of the ion aqueous solution was further calculated based on 3σ / slope (σ is the standard deviation of the fluorescence emission intensity of 11 groups of blank experiments, and the slope value is obtained from the linear calibration curve of fluorescence intensity and target ion concentration). n Al 3+ The limit of detection (LOD) was 1.86643×10 -6 mol / L.

[0082] according to Figure 10 It can be seen that {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n The fluorescence emission spectrum intensity increases with the 3+ The concentration of Al 3+ The concentration reached 300 μmol·L -1 When the fluorescence intensity of the coordination polymer no longer decreases, it gradually levels off. {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n The fluorescence intensity of Al 3+ The concentration showed a good linear relationship (R 2 =0.99341), which can be explained by {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n Can sensitively detect Al in aqueous solution 3+ ions. According to the prepared coordination polymer {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n Al 3+ The fluorescence quenching effect is obvious, so {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n Can be used as a new type of detection Al 3+ fluorescent probes.

[0083] The above description is only a preferred embodiment of the present invention and does not limit the present invention in any way. Any simple modification, change and equivalent variation made to the above embodiment based on the essence of the invention technology shall still fall within the scope of protection of the technical solution of the present invention.

Claims

1. A cadmium (II)-based metal organic framework crystalline material, characterized in that: The molecular formula of the cadmium (II)-based metal organic framework crystalline material is {[Cd3(Br-BDC)3(BMIP)2]·2H2O} n The cadmium (II)-based metal organic framework crystalline material uses cadmium (II) ions as connecting nodes, and 1,3-bis(dimethylimidazolylpropane) and 2,5-dibromoterephthalic acid ligands as bridging ligands to bridge each other to form a three-dimensional spatial structure; the structure contains Cd-O secondary structural units, and three Cd atoms form a trinuclear Cd-O cluster structure through the Cd-O secondary structural units, and the Cd1 atom and Cd1# atom show mirror symmetry. The space group of the cadmium (II)-based metal organic framework crystalline material is C2 / c, and the unit cell parameters of the cadmium (II)-based metal organic framework crystalline material are a=26.5639(7)Å, b=13.0736(4)Å, c=15.8749(5)Å, α=90°, β=93.5260(10)° and γ=90°.

2. A method for preparing the cadmium (II)-based metal organic framework crystalline material as claimed in claim 1, characterized in that: The following steps are involved: S1. Adding a cadmium salt, 1,3-bis(dimethylimidazolylpropane) and 2,5-dibromoterephthalic acid to a solvent DMA to obtain a mixture, adding glacial acetic acid to the mixture to adjust the pH value of the mixture to 4.5 to 6.5, and then performing a solvothermal reaction in a closed environment to obtain a reaction product; S2. Allow the reaction product prepared in S1 to cool naturally and crystallize, then wash and filter under reduced pressure to obtain colorless needle-shaped crystals, and dry to obtain a cadmium (II)-based metal organic framework crystalline material.

3. The preparation method according to claim 2, characterized in that: The cadmium salt described in S1 is any one of cadmium chloride, cadmium nitrate and cadmium acetate.

4. The preparation method according to claim 2, characterized in that The molar volume ratio of the cadmium salt, 1,3-bis(dimethylimidazolylpropane), 2,5-dibromoterephthalic acid and DMA in S1 is (0.5-1.5) mmol: (0.05-0.15) mmol: (0.1-0.5) mmol: (2-10) mL, the amount of glacial acetic acid used is 50 µL, the concentration of glacial acetic acid is 17 mol / L, the temperature of the solvothermal reaction is 90 °C, and the time of the solvothermal reaction is (36-72) h.

5. The preparation method according to claim 2, characterized in that: The drying temperature in S2 is 60° C., and the drying time is 2 to 4 hours.

6. A use of the cadmium (II)-based metal organic framework crystalline material as claimed in claim 1, characterized in that: The cadmium (II)-based metal organic framework crystalline material can be used in fluorescent sensors to detect ionic pollutants, and can also be used as a detector for Al 3+ fluorescent probes.

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