Fluorescent metal organic framework material based on metal cadmium, preparation method of fluorescent metal organic framework material, fluorescent sensor array and application of fluorescent sensor array

Abstract

The invention relates to the technical field of fluorescence detection, in particular to a cadmium-metal-based fluorescent metal organic framework material, a preparation method of the cadmium-metal-based fluorescent metal organic framework material, a fluorescent sensor array and application of the cadmium-metal-based fluorescent metal organic framework material. Fluorescent probe molecules with different proportions can be obtained by changing the doping concentration of rhodamine B, the RhB (at) MOF has an emission peak of Cd-MOF at 430nm and an emission peak of rhodamine B at 570nm, and when the material is in contact with different benzene series solvents, the relative emission intensity of host-guest emission peaks is almost constant, and the material is unique for each RhB (at) MOF, so that the fluorescent probe can be used for detecting the fluorescence of the RhB (at) MOF. Benzene, toluene, xylene and ethylbenzene are specifically distinguished by using different relative emission ratios of host and guest emission peaks, a fluorescent sensing array is constructed to identify benzene series, and fluorescent probe molecules can be prepared into a fluorescent film to realize portable detection.

Description

Technical Field

[0001] The present invention relates to the field of fluorescence detection technology, and in particular to a fluorescent metal organic framework material based on metal cadmium, a preparation method thereof, a fluorescent sensor array and applications thereof. Background Art

[0002] Aromatic hydrocarbons are the main representatives of volatile organic compounds (VOCs), among which benzene, toluene, ethylbenzene and xylene (BTEX) are more likely to cause harm to human health and environmental safety due to their strong volatility and toxicity. For the detection of BTEX, the most commonly used technology is gas chromatography (GC) with various detectors, such as flame ionization detector (FID), ultraviolet / infrared detection and mass spectrometry (MS, etc.). These commonly used instrumental detection methods have the advantages of low detection limit, high selectivity and good reliability, but due to the large size, slow detection speed and complex operation of these detection instruments, it is difficult to perform real-time detection and effective differentiation on site. Therefore, various portable and simple-to-operate sensors have been developed, but most of these sensors are based on electrochemical technology. Electrochemical sensors are low-cost, portable and simple to operate, but have problems of poor sensitivity and poor selectivity. However, optical sensors based on fluorescence detection have been proven to be more practical in detecting and distinguishing aromatic hydrocarbons with subtle structural differences.

[0003] Fluorescence detection has the advantages of high sensitivity, strong selectivity and the ability to perform on-site in-situ detection, so it is also widely used in the detection of benzene series. For example, the disclosed microporous zinc-based metal organic framework (Zn-MOF) material can effectively identify and detect nitrobenzene (NB). The results of fluorescence quenching experiments show that Zn-MOF can selectively and sensitively perform fluorescence sensing on nitrobenzene. Also using fluorescence detection, the disclosed organic small molecule fluorescent probe TPMCN for selective detection of benzaldehyde and nitrobenzene has obvious fluorescence response to benzaldehyde and gaseous and liquid nitrobenzene. However, this fluorescence detection technology for benzene series is designed based on the one-to-one correspondence strategy of "lock and key". It has the advantages of high selectivity and strong specificity for detecting specific analytes, but these advantages are not suitable for the simultaneous detection of multiple analytes. Fluorescence sensor array is an analytical detection method developed by the olfactory or taste system that can quickly identify multiple targets in complex samples. Therefore, the construction of fluorescence sensor array can solve this problem. With the help of pattern recognition technology, the sensor array can distinguish multiple target analytes with similar structures in complex systems.

[0004] Fluorescent sensor arrays are also often used for detection and differentiation in the detection of benzene series. In the prior art, CdSe quantum dots (QDs) are combined with five different organic polymers to form five fluorescent probe molecules to construct a fluorescent sensor array to detect and differentiate substituted benzene compounds and explosives such as nitrobenzene. However, this method requires changing different polymers to synthesize a variety of fluorescent probe molecules. In the prior art, two fluorescent probe molecules, Eu@UiO-66 and Tb@UiO-66, are synthesized, and a 4-channel fluorescent sensor array is constructed to detect a variety of VOCs dissolved in water. Although this method detects low concentrations, the use of fluorescent probe molecule powder for detection may cause errors due to objective reasons such as weighing and other operations. Therefore, a fluorescent probe that is simple to synthesize and a fluorescent sensor array that is easy to carry with the probe molecule are needed.

[0005] Metal organic frameworks (MOFs) are a class of inorganic, porous and coordinated polymer materials formed by a central metal component and a rigid ligand. MOFs are also often used to detect benzene series. In the prior art, a series of nano-lanthanide metal-organic frameworks (Ln-MOFs) isostructural with the parent MOF-76 (Ln) (Ln = Eu, Tb, Sm, Dy) have been synthesized, among which MOF-76Eu and MOF-76Tb can be used for fluorescent sensing of monoaromatic hydrocarbons (BTEX). Also using MOF molecules, a rare fluorescent nano-scale titanium-based metal organic framework material Ti6 (μ3-O) 6 (μ2-OH) 6 (BTB) 2 (DMF) 2 (ZSTU-2) was synthesized in the prior art, achieving highly sensitive detection of nitroaromatic compounds. However, this method of using absolute single fluorescence emission intensity for detection and judgment will change with many uncontrollable factors. Introducing dye molecules into MOFs can not only improve their fluorescence properties, but also enable them to be used as a luminescent platform for detecting target substances. In addition, the results of detection using the relative emission ratio of the dual fluorescence luminescence intensity of fluorescent dye@MOF are more reliable.

[0006] Therefore, in order to sensitively, selectively and quickly detect and distinguish multiple benzene derivatives in the actual complex components where multiple benzene derivatives coexist, the present application aims to provide a fluorescent metal organic framework material based on metallic cadmium and its preparation method, fluorescent sensor array and application, by constructing a fluorescent sensor array for the identification of benzene derivatives, and at the same time making the fluorescent probe molecules into fluorescent films to achieve portable detection. Summary of the invention

[0007] In order to solve the above problems, the present invention provides a fluorescent metal organic framework material based on metal cadmium, a preparation method thereof, a fluorescent sensor array and application thereof. The fluorescent metal organic framework material RhB@MOF based on metal cadmium doped with different concentrations of rhodamine B is synthesized in one step by a hydrothermal method. Fluorescent probe molecules with different ratios can be obtained by changing the doping concentration of rhodamine B. The RhB@MOF has an emission peak of Cd-MOF at 430nm and an emission peak of rhodamine B at 570nm. When the fluorescent material contacts different benzene series solvents, the relative emission intensity of the host and guest emission peaks is almost constant and unique for each RhB@MOF. The different relative emission ratios of the host and guest emission peaks are used to specifically distinguish benzene, toluene, xylene and ethylbenzene. A fluorescent sensor array is constructed for the identification of benzene series. At the same time, the fluorescent probe molecules are made into fluorescent films to achieve portable detection.

[0008] The technical solution adopted by the present invention is:

[0009] A method for preparing a fluorescent metal organic framework material based on metal cadmium comprises the following preparation steps:

[0010] S1. H2L and Cd(NO3)2·4H2O are dissolved in a mixed solution of DMF and HNO3, and then the mixed solution is sealed in a reaction container and heated at 75-85°C for 6-8 days, after which the reaction container is taken out and filtered to obtain colorless crystals, and the filtered solid is washed with DMF and acetone, and the washed solid is dried at room temperature to obtain a metal organic framework MOF;

[0011] S2. Add Rhodamine B solid to the metal organic framework MOF, mix thoroughly, and then heat and react at 75-85°C for 6-8 days to generate RhB@MOF solid doped with Rhodamine B, which is a fluorescent metal organic framework material based on metal cadmium.

[0012] Furthermore, in step S1, the molar ratio of H2L to Cd(NO3)2·4H2O is 1:2.

[0013] Further, in step S1, the concentration of HNO3 is 1M.

[0014] Based on the same inventive concept, the present application also provides a fluorescent metal organic framework material RhB@MOF based on metal cadmium prepared using the above-mentioned preparation method.

[0015] Furthermore, the RhB@MOF has the emission peak of Cd-MOF at 430 nm and the emission peak of rhodamine B at 570 nm.

[0016] Furthermore, when the RhB@MOF is exposed to different benzene-based solvents, the relative emission intensity of the host and guest emission peaks remains constant.

[0017] Based on the same inventive concept, the present application also provides a fluorescence sensor array, which is constructed by using the above-mentioned metal cadmium-based fluorescent metal organic framework material RhB@MOF as a benzene series sensing unit.

[0018] Furthermore, the fluorescence sensor array was constructed by combining the binding properties of RhB@MOF doped with different rhodamine B concentrations with different benzene series.

[0019] Based on the same inventive concept, the present application also provides an application of a fluorescent film made of a fluorescent probe molecule in the detection of benzene series substances, wherein the fluorescent probe molecule is the above-mentioned fluorescent metal organic framework material RhB@MOF based on metal cadmium.

[0020] The beneficial effects of the present invention are as follows:

[0021] The invention utilizes a hydrothermal method to synthesize a fluorescent metal organic framework material RhB@MOF based on metal cadmium doped with different concentrations of rhodamine B in one step, and fluorescent probe molecules with different ratios can be obtained by changing the doping concentration of rhodamine B. The RhB@MOF has an emission peak of Cd-MOF at 430 nm and an emission peak of rhodamine B at 570 nm, and when the material contacts different benzene series solvents, the relative emission intensity of the host and guest emission peaks is almost constant and unique for each RhB@MOF, and the different relative emission ratios of the host and guest emission peaks are utilized to specifically distinguish benzene, toluene, xylene and ethylbenzene, and a fluorescent sensor array is constructed for the identification of benzene series, and the fluorescent probe molecules can be made into fluorescent films to realize portable detection. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] Figure 1 X-ray diffraction patterns of MOF, RhB@MOF1, RhB@MOF2, and RhB@MOF3 in the embodiments of the present invention;

[0023] Figure 2 The fluorescence response spectra of RhB@MOF1, RhB@MOF2, and RhB@MOF3 to benzene, toluene, ethylbenzene, and xylene in the embodiments of the present invention are shown;

[0024] Figure 3 (A) is the ratio of the peak fluorescence emission intensities at 430 nm and 570 nm for benzene, toluene, ethylbenzene and m-xylene of RhB@MOF1, RhB@MOF2, and RhB@MOF3 in the examples of the present invention, Figure 3(B) is a diagram showing the principal component analysis results of benzene, toluene, ethylbenzene and m-xylene of RhB@MOF1, RhB@MOF2, and RhB@MOF3 prepared in the embodiments of the present invention;

[0025] Figure 4 The LDA discriminant analysis results of RhB@MOF1, RhB@MOF2, and RhB@MOF3 for benzene, toluene, ethylbenzene, and m-xylene in the examples of the present invention are shown in FIG. Figure 4 (A) is a binary system, benzene / ethylbenzene (yellow five-pointed star), toluene / benzene (green five-pointed star), toluene / ethylbenzene (purple five-pointed star), ethylbenzene / m-xylene (blue five-pointed star), toluene / m-xylene (brown five-pointed star), benzene / m-xylene (red five-pointed star), Figure 4 (B) Single component (red five-pointed star), binary mixture (yellow five-pointed star), ternary mixture (yellow five-pointed star), and ternary mixture (orange five-pointed star);

[0026] Figure 5 This is a principal component analysis result diagram of benzene, toluene, ethylbenzene and m-xylene of RhB@MOF1, RhB@MOF2, and RhB@MOF3 in the examples of the present invention, where the circle, triangle and square represent concentrations of 0.1, 0.5 and 2.0 M, respectively. DETAILED DESCRIPTION

[0027] In order to facilitate the understanding of the present invention, the present invention will be described more comprehensively by way of examples, and preferred embodiments of the present invention are given below. However, the present invention can be implemented in a variety of different forms and is not limited to the embodiments described herein. Any other implementation schemes obtained by modifying or equivalently replacing the technical scheme of the present invention without creative results are within the protection scope of the present invention.

[0028] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as those commonly understood by those skilled in the art of the present invention. The terms used in the specification of the present invention are only for describing specific embodiments and are not intended to limit the present invention.

[0029] The numerical values ​​disclosed in the embodiments of the present invention are approximate values, not definite values. When the error or experimental conditions permit, all values ​​within the error range may be included without being limited to the specific numerical values ​​disclosed in the embodiments of the present invention.

[0030] Unless otherwise specified, various raw materials, reagents, instruments and equipment used in the present invention can be purchased from the market or prepared by existing methods.

[0031] Sources of materials used in the following examples:

[0032] Cd(NO3)2·4H2O, 4-(2-carboxyvinyl)benzoic acid (H2L), and polyvinyl alcohol (PVA) were purchased from Shanghai Aladdin Biochemical Technology Co., Ltd., benzene, toluene, ethylbenzene, and m-xylene were purchased from Shanghai MacLean Biochemical Technology Co., Ltd., and all other chemical reagents were of analytical grade.

[0033] The instrument models used in the following examples are:

[0034] Fourier transform infrared spectrometer, model Nicolet iS5 FTIR, Thermo;

[0035] UV-visible spectrophotometer, model specification UV-8000, Shimadzu;

[0036] Fluorescence spectrophotometer, model specification FR-6000, Shimadzu, Japan;

[0037] Contact angle measuring instrument, model JC2000C1S, produced by Shanghai Zhongchen Digital Technology Equipment Co., Ltd.;

[0038] UV instrument, model HC-TG030011-WH, produced by Jiangmen Pengke Lighting Co., Ltd.;

[0039] UV lamp, model SupcreG6R, produced by Hangzhou Xunshu Technology Co., Ltd.;

[0040] Drying oven, model ZETASIZERNANOZS, Malven.

[0041] The following are specific embodiments

[0042] This embodiment provides a method for preparing a fluorescent metal organic framework material based on metal cadmium, comprising the following preparation steps:

[0043] S1. Synthesis of Metal-Organic Framework (MOF):

[0044] H2L (2.0 mg, 0.01 mmol) and Cd(NO3)2·4H2O (6.2 mg, 0.02 mmol), with a 1:2 ratio of the amount of substance between the two, were dissolved in a mixed solution of DMF (2 mL) and dilute HNO3 (1 M, 0.05 mL), and then the mixed solution was sealed in a screw-capped vial and heated at 80°C for one week. After one week, the transparent vial was taken out and filtered to obtain colorless crystals. The filtered solid was washed with DMF and acetone, and the washed solid was dried at room temperature to obtain MOF;

[0045] S2. Synthesis of RhB@MOF:

[0046] 0.3832 g, 0.1916 g, and 0.0383 g of Rhodamine B solid were weighed and added to the MOF synthesized in step S1 for thorough mixing. The mixture was then placed in an oven at 80 °C for one week to directly generate RhB@MOF solid doped with Rhodamine B by a hydrothermal method. The concentrations were 2 × 10 -2 mol / L、1×10 -2 mol / L、2×10 -3 mol / L.

[0047] In this embodiment, they are named RhB@MOF1, RhB@MOF2, and RhB@MOF3 according to the concentration of doped Rhodamine B.

[0048] The MOF, RhB@MOF1, RhB@MOF2, and RhB@MOF3 prepared in the above examples were characterized by X-ray diffraction (PXRD), see Figure 1 As shown in Figure A, the XRD peaks of MOF and RhB@MOF have similar characteristic peaks near 2θ=7.8° and 10°, indicating that RhB encapsulation does not significantly change the position of the diffraction peak of MOF. Therefore, it can be considered that the crystal structure of MOF is retained during the synthesis of RhB@MOF. The FT-IR spectra of MOF and RhB@MOF are shown in Figure 1. Figure 1 As shown in B, the doping of rhodamine B did not significantly affect the functional groups of MOF, with the peaks at 1598 cm -1 and 1390cm -1 The symmetric and asymmetric stretching vibrations of carboxylic acid at 1000 nm are not shifted, indicating that RhB encapsulation does not affect the coordination between H2L and cadmium ions. It can be considered that the functional groups of MOF are retained during the synthesis of RhB@MOF, and a new peak appears at 1000 nm, which is the same as the peak of rhodamine B, indicating that the functional groups of RhB molecules also exist.

[0049] The fluorescence spectra of MOF, RhB@MOF1, RhB@MOF2, and RhB@MOF3 were measured, such as Figure 1 As shown in Figure C, compared with the fluorescence spectrum of a single MOF, the RhB@MOF doped with rhodamine B has a fluorescence emission peak at around 570nm, indicating that the doped rhodamine B also exhibits fluorescence properties. It can be seen from the fluorescence detection results in the figure that when increasing the doping concentration of rhodamine B, the obtained RhB@MOF1, RhB@MOF2, and RhB@MOF3 show adjustable emission light intensity at 430nm and 570nm. Although the relative emission intensity of each RhB@MOF host and guest is different, this relative emission intensity is constant and unique for each RhB@MOF. Therefore, different benzene series can be distinguished by observing the changes in the relative fluorescence intensity of the two emission peaks of the host and guest of different benzene series.

[0050] The RhB@MOF prepared in the above example was subjected to fluorescence response spectra measurement of different benzene series, and the specific operation was as follows:

[0051] 0.3 mg of fluorescent probe molecules MOF, RhB@MOF1, RhB@MOF2, and RhB@MOF3 were weighed respectively, and 500 μL of anhydrous ethanol was added as a solvent. The mixed solution was ultrasonically treated at room temperature for 5 min to obtain a dispersion of the fluorescent probe molecules. After standing, the supernatant was taken as the probe mother solution for subsequent fluorescence spectrum measurement, and the fluorescence spectrum of the solution was measured by adding different concentrations of benzene series, and the excitation wavelength was set to 340 nm.

[0052] See Fluorescence Spectroscopy Figure 2 It can be seen that the intensity enhancement or quenching of the 430nm and 570nm emission peaks of three different materials, RhB@MOF1, RhB@MOF2 and RhB@MOF3, after reacting with benzene, toluene, ethylbenzene and m-xylene respectively, varies. RhB@MOF exhibits a phenomenon different from the original fluorescence of MOF alone at 430nm. The reason is that in the composite material, the rhodamine molecules are embedded in the framework, and this restriction enhances the interaction between the aromatic guest molecules and the H2L groups embedded in the framework support. This also leads to the fluorescence of the excited complex with charge transfer (CT) characteristics or phosphorescence stabilized by the heavy atom effect. The enhancement of fluorescence intensity at 570nm is mainly due to the exchange of benzene compounds with rhodamine guests. When the rhodamine content increases, such as RhB@MOF3, the fluorescence intensity decreases after adding the four benzene compounds, which is consistent with the reaction of free rhodamine to the benzene compounds. Due to the different structures of the benzene compounds and the interaction with the framework, the three RhB@MOFs have different fluorescence intensity on the four benzene compounds. 430 / I 570 Different ratios can be used to distinguish different benzene compounds. Fluorescence sensor array to distinguish benzene series test:

[0053] Referring to the above fluorescence test, since the ratio of the host-guest fluorescence intensity of each RhB@MOF is a constant, the fingerprint spectrum of each benzene series can be generated according to the change of the host-guest fluorescence intensity ratio. After determining the binding characteristics of RhB@MOF with the three benzene series, a sensor array with RhB@MOF as the benzene series sensing unit can be constructed.

[0054] The four different RhB@MOF1, RhB@MOF2, and RhB@MOF3 prepared in the above examples were mixed with benzene, toluene, ethylbenzene, and m-xylene, and the measurement was repeated 5 times. A multidimensional response pattern of 3 sensing units × 4 benzene series × 5 repetitions was obtained. The results were analyzed using principal component analysis. Figure 3As shown in A, the four benzene series are clearly distinguished, and the two typical factors generated by principal component analysis in this sensing system represent the coverage of all information. The variance contribution rates are 94.3% and 4.9%, respectively. The two factors can cover 99.2% of the total information.

[0055] In addition, a training model was established based on RhB@MOF1, RhB@MOF2, and RhB@MOF3 to distinguish between benzene, toluene, ethylbenzene, and m-xylene mixed in pairs. First, through linear discriminant analysis (LDA). Six binary mixtures of benzene / toluene, benzene / xylene, benzene / ethylbenzene, toluene / xylene, toluene / ethylbenzene, and xylene / ethylbenzene were tested. The concentration ratio of each ion was 1:9, 1:4, 2:3, 3:2, 4:1, and 9:1. The score scatter plot obtained by LDA is shown in Figure 2. Figure 4 As shown in A, the first three principal components (PCs) explain about 100% of the variance. The four metal ions are clearly clustered into four groups. When the concentration ratio changes from 1:9 to 9:1, the data points are properly arranged between the two groups. The data points of the binary mixture are close to each group according to their mass ratio. Therefore, the sensing array based on RhB@MOF1, RhB@MOF2, and RhB@MOF3 can achieve clear identification of binary mixtures of benzene, toluene, ethylbenzene, and xylene.

[0056] Based on the sensor array, discriminant analysis was also performed on single, binary, ternary and quaternary mixtures. Figure 4 As shown in Figure B, single metal ions were accurately predicted to the corresponding groups with a prediction accuracy of 100%. Samples containing dimetallic ions, trimetallic ions, and tetrametallic ions were distributed in different regions according to their compositions. In summary, the results show that the fluorescence sensor array based on RhB@MOF1, RhB@MOF2, and RhB@MOF3 is able to distinguish between benzene, toluene, ethylbenzene, and xylene with different compositions.

[0057] In order to investigate the possible effects of different concentrations of benzene, toluene, ethylbenzene and m-xylene on the cluster analysis results, the sensor arrays were used to perform cluster analysis on the responses of benzene, toluene, ethylbenzene and m-xylene at three different concentrations. The results showed that despite the different concentrations, the principal component analysis results showed that the four benzene derivatives were clearly clustered in different groups. For details, see Figure 5 As shown, the experimental results confirmed the practicality and stability of the RhB@MOF-based fluorescence sensing array.

[0058] In summary, in this application, a series of cadmium metal ion coordinated metal organic framework materials RhB@MOF were synthesized by doping with rhodamine B. The relative intensity of the emission peak of the complex at 430nm and the emission peak of rhodamine B at 570nm was constant. Based on the host-guest recognition effect of RhB@MOF, the two emission peaks showed different responses to the four benzene series, and a fluorescence sensing array for benzene, toluene, xylene and ethylbenzene was constructed. The principal component analysis method showed that the four benzene series achieved clustering. The linear discriminant analysis method predicted the binary and ternary mixtures of benzene, toluene, xylene and ethylbenzene, and the discrimination accuracy rate reached 100%. At the same time, the study found that the sensor array based on RhB@MOF can distinguish between benzene, toluene, xylene and ethylbenzene of different concentrations.

[0059] The above-mentioned embodiments only express several implementation methods of the present invention, and the description thereof is relatively specific and detailed, but it cannot be understood as limiting the scope of the patent of the present invention. It should be pointed out that, for ordinary technicians in this field, several variations and improvements can be made without departing from the concept of the present invention, which all belong to the protection scope of the present invention. Therefore, the protection scope of the patent of the present invention shall be subject to the attached claims.

Claims

1. A method for preparing a fluorescent metal organic framework material based on metal cadmium, characterized in that: The method comprises the following preparation steps: S1. H2L and Cd(NO3)2·4H2O are dissolved in a mixed solution of DMF and HNO3, and then the mixed solution is sealed in a reaction container and heated at 75-85°C for 6-8 days, after which the reaction container is taken out and filtered to obtain colorless crystals, and the filtered solid is washed with DMF and acetone, and the washed solid is dried at room temperature to obtain a metal organic framework MOF; S2. Add Rhodamine B solid to the metal organic framework MOF, mix thoroughly, and then heat and react at 75-85°C for 6-8 days to generate RhB@MOF solid doped with Rhodamine B, which is a fluorescent metal organic framework material based on metal cadmium.

2. The method for preparing a fluorescent metal organic framework material based on metal cadmium according to claim 1, characterized in that: In step S1, the molar ratio of H2L to Cd(NO3)2·4H2O is 1:

2.

3. The method for preparing a fluorescent metal organic framework material based on metal cadmium according to claim 1, characterized in that: In step S1, the concentration of HNO3 is 1M.

4. A fluorescent metal organic framework material RhB@MOF based on metal cadmium prepared by the preparation method according to any one of claims 1 to 3.

5. The fluorescent metal organic framework material RhB@MOF based on metal cadmium according to claim 4, characterized in that: The RhB@MOF has the emission peak of Cd-MOF at 430 nm and the emission peak of rhodamine B at 570 nm.

6. The fluorescent metal organic framework material RhB@MOF based on metal cadmium according to claim 4, characterized in that: When the RhB@MOF is exposed to different benzene-based solvents, the relative emission intensity of the host and guest emission peaks remains constant.

7. A fluorescence sensor array, characterized in that: The fluorescent sensor array is constructed by using the fluorescent metal organic framework material RhB@MOF based on metal cadmium as the benzene series sensing unit described in claim 4.

8. The fluorescence sensor array according to claim 7, characterized in that: The fluorescent sensor array is constructed by combining the binding properties of RhB@MOF doped with different rhodamine B concentrations with different benzene series.

9. Application of a fluorescent film made of fluorescent probe molecules in the detection of benzene series, characterized in that: The fluorescent probe molecule is the fluorescent metal organic framework material RhB@MOF based on metal cadmium as described in claim 4.

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