A cation-doped lanthanide MOF material and its preparation method and application

Abstract

The present invention provides a cation-doped lanthanide MOF material and a preparation method and application thereof, which belongs to the technical field of metal organic framework. The preparation method comprises: 3+ , Yb 3+ and Sr 2+ The hexahydrate salt of the metal ion and 0.42 g of BTC were added to a 100 mL beaker, and 80 mL of DMF and 40 mL of deionized water were added. After ultrasonic treatment for 60 min, a mixed solution was obtained. The mixed solution was transferred to a 200 ml sealed container and stirred at room temperature for 2 h, then transferred to a polytetrafluoroethylene-lined autoclave, the autoclave was sealed, and gradually heated to 140 °C at a rate of 5 °C / min, and kept in an oven at 140 °C for 8 h. After the heating was completed, the mixture was allowed to cool naturally to room temperature. The obtained product was separated by centrifugation and washed three times with DMF and ethanol respectively. The obtained product was placed in a vacuum oven and dried at 100 °C to obtain lanthanide Tb 0.05 Yb 0.95‑y Sr y ‑BTC MOFs. The lanthanide MOF material prepared by the present invention has improved emission intensity and can be applied to sensing, fingerprint recognition, photon barcodes, and anti-counterfeiting, and has great potential.

Description

Technical Field

[0001] The present invention belongs to the technical field of metal organic frameworks, and in particular relates to a cation-doped lanthanide MOF material and a preparation method and application thereof. Background Art

[0002] A large number of studies have shown that lanthanide metal-organic frameworks (Ln-MOFs) with long-life luminescence can avoid the interference of excitation light and background fluorescence, and have great potential in the fields of bioimaging, optoelectronic devices, information encryption and advanced anti-counterfeiting. Compared with traditional luminescent materials such as fluorides, oxides, quantum dots and organic complexes, trivalent lanthanum ions (Ln 3+ ) are mainly related to the ff transition, for example, narrow line emission peaks, large energy offset between absorption and emission (significant Stokes shift), no photobleaching, long lifetime, and flexible topological structure supporting multiple emission centers to produce various photoluminescence. However, due to the forbidden ff transition, MOFs made with trivalent lanthanide ions generally have weak light absorption, which makes the direct excitation of lanthanide ions inefficient, or their metal luminescence is easily suppressed or quenched when in contact with analytes. Therefore, researchers have focused on tuning the energy transfer efficiency through host-analyte interactions to utilize Ln 3+ The luminescent response is mainly aimed at the "sensitized antenna effect" of the ligand-metal energy transfer (LMET) enhancement technology of Ln-MOFs. The ligands of Ln-MOF can effectively absorb light and then focus the light to the lanthanide metal emission center. However, since the distance between metal elements in lanthanide MOFs may be short, the energy transfer efficiency is low, which will lead to cross relaxation and may reduce the emission yield through concentration quenching. 3+ Luminescence conduction is more complicated than luminescence quenching because the luminescence behavior is affected by the antenna cutoff effect.

[0003] The researchers found that in Ln-MOFs (lanthanide metal organic frameworks), there are high-energy oscillators such as OH bonds in the solvent (such as hydroxyl groups in water molecules) or NH bonds (such as amino groups in amine groups). These bonds have high vibration frequencies and can be combined with the excited Ln through non-radiative vibrational relaxation pathways. 3+ The luminescence center of the ion is coupled, resulting in energy dissipation in the form of heat, thereby quenching (i.e., weakening or eliminating) Ln 3+In response to this situation, researchers mainly solve this problem by functionalizing the organic ligand structure of Ln-MOF, but this method is very time-consuming; Chen Jiabo and others found in the journal ADVANCEDFUNCTIONAL MATERIALS that a slight difference in the local crystal field symmetry of the lanthanide metal ion site will cause Ln 3+ The electronic energy levels and excited-state dynamics of the ions change dramatically. Summary of the invention

[0004] The purpose of the present invention is to provide a cation-doped lanthanide MOF material and a preparation method and application thereof, optimize the ligand size and arrangement to enhance the intermolecular interaction, and achieve stable luminescence of lanthanide element MOF, so as to solve the technical problems in the prior art that MOFs made of trivalent lanthanide ions have weak light absorption and the direct excitation efficiency of lanthanide ions is not high.

[0005] In order to solve the above technical problems, the specific technical solutions of the present invention are as follows:

[0006] A method for preparing a cation-doped lanthanide MOF material comprises the following steps:

[0007] Step S31: Tb 3+ , Yb 3+ and Sr 2+ The hexahydrate salt of the metal ion and 0.42 g of BTC were added to a 100 mL beaker, and 80 mL of DMF and 40 mL of deionized water were added. After ultrasonic treatment for 60 min, a mixed solution was obtained;

[0008] Step S32: the mixed solution obtained in step S31 was transferred to a 200 ml sealed container and stirred at room temperature for 2 h, then transferred to a polytetrafluoroethylene-lined autoclave, the polytetrafluoroethylene-lined autoclave was sealed, gradually heated to 140° C. at a rate of 5° C. / min, and maintained in an oven at 140° C. for 8 h;

[0009] Step S33: After the heating process in step S32 is completed, the mixture is allowed to cool naturally to room temperature. The obtained product is separated by centrifugation and washed three times with DMF and ethanol respectively;

[0010] Step S34: Place the product obtained in step S33 in a vacuum oven and dry at 100°C to obtain lanthanide Tb 0.05 Yb 0.95-y Sr y -BTC MOFs, white powdery probe powder.

[0011] Furthermore, Tb 3+ , Yb 3+ and Sr 2+The total amount of ions is 4mmol; Tb 3+ The molar ratio is 5%, Yb 3+ and Sr 2+ The total molar ratio is 95%, of which Sr 2+ The molar ratio changes from 1% to 5%, then Yb 3+ The proportion changes between 90% and 95%.

[0012] The present invention also proposes that the cation-doped lanthanide MOF material is Tb 0.05 Yb 0.95-y Sr y -BTC MOFs have a one-dimensional rod-like microstructure with a length of hundreds of micrometers and a width of tens of micrometers and appear in the form of nanoflowers.

[0013] Furthermore, when y is 0.05, the luminescence effect is the best, that is, Tb 0.05 Yb 0.9 Sr 0.05 -BTC MOFs have the best luminescence effect.

[0014] The present invention also proposes a method for preparing a cation-doped lanthanide MOF material and the application of the cation-doped lanthanide MOF material prepared by the method or the application of the cation-doped lanthanide MOF material in sensing.

[0015] The present invention also proposes a method for preparing a cation-doped lanthanide MOF material and an application of the cation-doped lanthanide MOF material prepared by the method or the application of the cation-doped lanthanide MOF material in a photon barcode.

[0016] The present invention also proposes a method for preparing a cation-doped lanthanide MOF material and an application of the cation-doped lanthanide MOF material prepared by the method or the application of the cation-doped lanthanide MOF material in fingerprint identification.

[0017] The present invention also proposes a cation-doped lanthanum MOF material prepared by a preparation method of the cation-doped lanthanum MOF material or an anti-counterfeiting application of the cation-doped lanthanum MOF material.

[0018] Compared with the prior art, the present invention has the following beneficial technical effects:

[0019] The present invention adopts Yb doping 3+ and Sr 2+ , prepared Tb 3+ -BTC MOF has an 8-fold increase in emission intensity. 2 + replaced the metal ions in MOF, in high Yb 3 + doping remains unchanged. Emission enhancement and Tb 3 + is related to the change of local electric field. Calculations show that Yb 3+ and Sr 2 + doping significantly changed the HOMO and LUMO energy levels and regulated the 3 +Concentration quenching and energy transfer process. Under UV excitation, 5% Tb doping 3 +、95%Yb 3 + and 5% Sr 2 + MOFs achieved the largest emission enhancement. These doped MOFs show great potential in photonic barcoding, anti-counterfeiting, and information security while improving the photostability of fingerprint recognition and reducing material requirements. 0.05 Yb 0.95 Sr 0.05 -BTC can detect ultra-low concentrations of quinolone antibiotics in water with high selectivity (1.0×10 -9 M), can also be made into hydrogels with various morphologies and loaded on various substrates for commercial applications, and respond within 20 seconds. BRIEF DESCRIPTION OF THE DRAWINGS

[0020] In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the accompanying drawings required for use in the description of the embodiments of the present invention will be briefly introduced below. Obviously, the accompanying drawings in the following description are only some embodiments of the present invention. For ordinary technicians in this field, other accompanying drawings can be obtained based on these accompanying drawings without paying creative labor.

[0021] Figure 1 This is a schematic diagram of the preparation process of the lanthanide MOF material doped with two cations according to the present invention.

[0022] Figure 2 It is a schematic diagram of the microscopic morphology scanning of Tb1-BTC-MOF of the present invention.

[0023] Figure 3 (a) is Tb of the present invention x Yb (1-x) -BTC MOFs fluorescence spectrum diagram; (b) Tb 0.05 Yb 0.95 -Schematic diagram of the microscopic morphology scanning of BTC MOFs.

[0024] Figure 4 (a) is Tb of the present invention 0.05 Yb 0.95-y Sr y -BTC MOFs fluorescence spectrum diagram; (b) Tb 0.05 Yb 0.9 Sr 0.05 -Schematic diagram of the microscopic morphology scanning of BTC MOFs.

[0025] Figure 5 (a) is Tb of the present invention 0.05 Yb 0.9 Sr 0.05 -BTC@CRG composite film for NOR visualization detection; (b) Tb with different NOR concentrations 0.05 Yb 0.9 Sr 0.05 -BTC@CRG film test results in fish meat; (c) Tb with different NOR concentrations 0.05 Yb 0.9 Sr 0.05 -BTC@CRG film solid-state fluorescence spectra; (d) Tb with different NOR concentrations 0.05 Yb 0.9 Sr 0.05 -BT@ filter paper film test results.

[0026] Figure 6 These are the fluorescence images of the PVA / PEI@Ln-MOFs solution of the present invention generated by 254nm excitation at different temperatures.

[0027] Figure 7 Tb 0.05 Yb 0.9 Sr 0.05 - BTC MOFs fluorescence photo showing fingerprints on plastic tape.

[0028] Figure 8 For Tb 0.05 Yb 0.9 Sr 0.05 -“Chinese calligraphy” written with BTC MOFs / glycerol / ethanol solution as ink, and fluorescence images under sunlight and UV light with wavelengths of 365nm, 254nm, and 302nm, respectively; scale bar: 2 cm. DETAILED DESCRIPTION

[0029] The following will be combined with the drawings in the embodiments of the present invention to clearly and completely describe the technical solutions in the embodiments of the present invention. Obviously, the described embodiments are only part of the embodiments of the present invention, not all of the embodiments. Based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work are within the scope of protection of the present invention.

[0030] The present invention proposes a method for doping lanthanide MOF materials with cations, which changes the local crystal field of pure luminescent lanthanide MOF, thereby enhancing the luminescence. 1,3,5-benzenetricarboxylic acid (BTC) ligand is selected, and Tb 3+As a photoactive lanthanide ion, Tb-BTC MOF was prepared. Ln-BTC MOF has been studied and applied due to its inherent photon properties, but Ln-BTC MOF has the problem of weak emission. Therefore, the present invention utilizes the photochemically inactive Yb 3+ The results showed that this could maintain the framework structure of Ln-BTC MOF and enhance its functionality, resulting in a MOF named Tb-Yb-BTC.

[0031] There have been many inventive studies on doping MOFs with ions of the same valence. However, the atomic radii of ions of the same valence can vary greatly, which can disrupt the structure and cause local crystal field symmetry violations, thereby creating harmful defects in the critical process of MOF luminescence. To solve this problem, the present invention uses Tb 3+ The luminescence properties are changed by changing the local crystal field symmetry of the site, and Sr 2+ ions serve as the required charge compensation to promote further beneficial symmetry changes. 2 + With Tb 3+ size compatible and forms a 6-coordinated Sr 2+ MOFs, similar to Tb-BTC. These dual-doped materials are called Tb-Yb-Sr-BTC MOFs. 3+ and Sr 2+ Ions are used to enhance emission, which directly reduces production costs and broadens the scope of application.

[0032] The present invention designs a preparation process for lanthanide MOF materials doped with cations, which changes the local crystal field of pure luminescent lanthanide MOF, thereby enhancing luminescence and broadening its application range. Figure 1 As shown, the following steps are included:

[0033] Step S1: Synthesis of Tb1-BTC MOFs

[0034] 1.5g TbCl3·6H2O (terbium chloride hexahydrate) and 0.42g BTC were added to a 100mL beaker, 80mL DMF (N,N-dimethylformamide) and 40mL deionized water were added, and ultrasonic treatment was performed for 60min, followed by transfer to a 200ml polytetrafluoroethylene-lined autoclave. After stirring at room temperature for 2h, the polytetrafluoroethylene-lined autoclave was sealed, gradually heated to 140℃ at a rate of 5℃ / min, and kept in an oven at 140℃ for 8h. After the heating process was completed, the mixture was allowed to cool naturally to room temperature. The obtained product was separated by centrifugation and washed three times with DMF and ethanol respectively. Finally, the product was placed in a vacuum oven and dried at 100℃.

[0035] Step S2: Tb x Yb (1-x) Synthesis of Tb-BTC MOFs (x = 1.0, 0.75, 0.5, 0.25, 0.1, 0.05 and 0) x Yb (1-x) The synthesis process of -BTC MOFs (x = 1.0, 0.75, 0.5, 0.25, 0.1, 0.05 and 0) is similar to that of Tb1-BTC MOFs, except that the Yb 3+ and Tb 3+ The total amount of ions was 4 mmol.

[0036] Step S3: Tb 0.05 Yb 0.95-y Sr y - Synthesis of BTC MOFs (y = 0.01, 0.025, 0.05, 0.075, 0.1 and 0.125)

[0037] Tb 0.05 Yb 0.95-y Sr y The synthesis process of -BTC MOFs (y = 0.01, 0.025, 0.05, 0.075, 0.1 and 0.125) is similar to that of Tb1-BTC MOFs, except that the doped Yb 3+ , Tb 3+ and Sr 2+ The total amount of ions was 4 mmol.

[0038] Implementation Example 1

[0039] Step S11: 1.5 g TbCl3·6H2O and 0.42 g BTC were added into a 100 mL beaker, 80 mL DMF and 40 mL deionized water were added, and ultrasonic treatment was performed for 60 min to obtain a mixed solution;

[0040] Step S12: The mixed solution obtained in step S11 was transferred to a 200 ml sealed container and stirred at room temperature for 2 h, then transferred to a polytetrafluoroethylene-lined autoclave, the polytetrafluoroethylene-lined autoclave was sealed, gradually heated to 140°C at a rate of 5°C / min, and maintained in an oven at 140°C for 8 h.

[0041] Step S13: After the heating process in step S12 is completed, the mixture is allowed to cool naturally to room temperature. The obtained product is separated by centrifugation and washed three times with DMF and ethanol respectively.

[0042] Step S14: The product obtained in step S13 is placed in a vacuum oven and dried at 100° C. The lanthanide Tb1-BTC-MOF is obtained as a white powdery probe powder.

[0043] The lanthanide Tb1-BTC-MOF product is prepared through the above steps. Figure 2 This is the scanning electron microscope image of the Tb1-BTC-MOF metal organic framework material. Figure 2 It can be seen that the prepared material maintains a one-dimensional rod-like microstructure with a length of hundreds of microns and a width of tens of microns.

[0044] Implementation Example 2

[0045] Step S21: Yb 3+ and Tb 3+ The hexahydrate salt of the metal ion and 0.42 g of BTC were added to a 100 mL beaker, and 80 mL of DMF and 40 mL of deionized water were added. After ultrasonic treatment for 60 min, a mixed solution was obtained.

[0046] Furthermore, Yb 3+ and Tb 3+ The total amount of ions is 4mmol; Yb 3+ and Tb 3+ The molar ratio of Tb x Yb (1-x) -BTC MOFs (x = 1.0, 0.75, 0.5, 0.25, 0.1, 0.05 and 0) to change the ratio.

[0047] Step S22: The mixed solution obtained in step S21 was transferred to a 200 ml sealed container and stirred at room temperature for 2 h, then transferred to a polytetrafluoroethylene-lined autoclave, sealed the polytetrafluoroethylene-lined autoclave, gradually heated to 140°C at a rate of 5°C / min, and maintained in an oven at 140°C for 8 h.

[0048] Step S23: After the heating process in step S22 is completed, the mixture is allowed to cool naturally to room temperature. The obtained product is separated by centrifugation and washed three times with DMF and ethanol respectively.

[0049] Step S24: Place the product obtained in step S23 in a vacuum oven and dry at 100°C. x Yb (1-x) -BTC MOFs, white powdery probe powder.

[0050] The lanthanide Tb is prepared by the above steps x Yb (1-x) -BTC MOFs products, the present invention is for lanthanide Tb x Yb (1-x) -BTCMOFs were subjected to traversal experiments to obtain different proportions of Tb x Yb(1-x) -BTC MOFs, and tested their luminescence effects, such as Figure 3 As shown in (a), it can be seen from the figure that when the value of x is 0.05, the intensity of its fluorescence emission spectrum is the strongest, indicating that the luminescence effect is the best, that is, Tb 0.05 Yb 0.95 -BTC MOFs have the best luminescence effect. The present invention has the best luminescence effect on Tb 0.05 Yb 0.95 -BTC MOFs metal organic framework materials were scanned, such as Figure 3 As shown in (b), it can be seen from the figure that the prepared material maintains the one-dimensional rod-like microstructure of Tb1-BTC MOFs with a length of hundreds of microns and a width of tens of microns, and appears in the form of nanoflowers.

[0051] Implementation Example 3

[0052] Step S31: Tb 3+ , Yb 3+ and Sr 2+ The hexahydrate salt of the metal ion and 0.42 g of BTC were added to a 100 mL beaker, and 80 mL of DMF and 40 mL of deionized water were added. After ultrasonic treatment for 60 min, a mixed solution was obtained;

[0053] Furthermore, Yb 3+ , Tb 3+ and Sr 2+ The total amount of ions is 4 mmol. As shown in Example 2, the lanthanide Tb x Yb (1-x) -BTC MOF When x is 0.05, the ratio of Tb to Yb is optimal and the luminescence effect is the best. The optimal ratio of Tb and Yb selected in Example 2 is Tb x Yb (1-x) -BTC MOFs for Tb 0.05 Yb 0.95 -BTC MOFs, therefore, when the ratio of Tb is fixed at 0.05, by changing the Sr 2+ The molar ratio of Tb is adjusted to the optimal ratio of the three 0.05 Yb 0.95-y Sr y -BTCMOFs (y = 0.01, 0.025, 0.05, 0.075, 0.1 and 0.125), by changing Tb 0.05 Yb 0.95-y Sr y -y in BTC MOFs to change the ratio.

[0054] Tb 3+The molar ratio is 5%, Yb 3+ and Sr 2+ The total molar ratio is 95%, of which Sr 2+ The molar ratio changes from 1% to 12.5%, then Yb 3+ The proportion changes between 82.5% and 94%

[0055] Step S32: The mixed solution obtained in step S31 was transferred to a 200 ml sealed container and stirred at room temperature for 2 h, then transferred to a polytetrafluoroethylene-lined autoclave, sealed the polytetrafluoroethylene-lined autoclave, gradually heated to 140°C at a rate of 5°C / min, and maintained in an oven at 140°C for 8 h.

[0056] Step S33: After the heating process in step S32 is completed, the mixture is allowed to cool naturally to room temperature. The obtained product is separated by centrifugation and washed three times with DMF and ethanol respectively.

[0057] Step S34: Place the product obtained in step S33 in a vacuum oven and dry at 100°C. 0.05 Yb 0.95-y Sr y -BTC MOFs, white powdery probe powder.

[0058] The lanthanide Tb prepared by the above steps 0.05 Yb 0.95-y Sr y -BTC MOFs products, the present invention is for lanthanide Tb 0.05 Yb 0.95-y Sr y -BTC MOFs were subjected to proportional selection experiments to obtain different proportions of Tb 0.05 Yb 0.95-y Sr y -BTC MOFs, and tested their luminescence effects, such as Figure 4 As shown in (a), it can be seen from the figure that when the value of y is 0.05, the intensity of its fluorescence emission spectrum is the strongest, indicating that the luminescence effect is the best, that is, Tb 0.05 Yb 0.9 Sr 0.05 -BTC MOFs have the best luminescence effect. The present invention has the best luminescence effect on Tb 0.05 Yb 0.9 Sr 0.05 -BTC MOFs metal organic framework materials were scanned, such as Figure 4 As shown in (b), it can be seen from the figure that the prepared material maintains the one-dimensional rod-like microstructure of Tb1-BTC MOFs with a length of hundreds of microns and a width of tens of microns, and also maintains the xYb (1-x) -Morphology of nanoflowers of BTC MOFs.

[0059] Optionally, the luminescent metal ion Tb 3+ Replace with Eu 3+ ion.

[0060] Optionally, the trivalent doping ion Yb 3+ Replace with Sc 3+ .

[0061] Optionally, the divalent doping ion Sr may be used during preparation. 2+ Replaced with Ca 2+ .

[0062] Implementation Example 4Tb 0.05 Yb 0.9 Sr 0.05 -Application of BTC in sensing

[0063] Step S41: prepare ciprofloxacin (CIP) ethanol solution, norfloxacin (NOR) ethanol solution, ofloxacin (OFX) ethanol solution, gallic acid (GA) ethanol solution, sulfadiazine (SDZ) ethanol solution, sulfamethoxazole (SMX) ethanol solution, tetracycline hydrochloride antibiotic ethanol solution, the concentration of each ethanol solution is 10 -3 M.

[0064] Step S42: Prepare Tb with a concentration of 0.2 mg / mL 0.05 Yb 0.9 Sr 0.05 -BTC suspension, take 2mlTb 0.05 Yb 0.9 Sr 0.05 -BTC suspension was placed in 300 μL of various antibiotic ethanol solutions prepared in step S41 to perform quenching experiments.

[0065] Step S43: Record the fluorescence spectra of the mixed solution obtained in step S42 at excitation wavelengths of 302 nm and 254 nm. The experimental results show that NOR antibiotics have a strong effect on Tb 0.05 Yb 0.9 Sr 0.05 -BTC suspension had the greatest degree of quenching.

[0066] Example 5 Determination of Antibiotic Detection Limit

[0067] Step S51: configure the concentration to 10 -3 M Norfloxacin (NOR) ethanol solution.

[0068] Step S52: diluting the norfloxacin (NOR) ethanol solution in step S51 in a series of concentrations to obtain a series of norfloxacin solutions with different concentrations.

[0069] Step S53: Prepare Tb with a concentration of 0.2 mg / mL 0.05 Yb 0.9 Sr 0.05 -BTC suspension, take 2mlTb 0.05 Yb 0.9 Sr 0.05 -BTC suspension was placed in 300 μL NOR aqueous solution of different concentrations in step S52, and the luminescence spectrum of the suspension was recorded at excitation wavelengths of 302 nm and 254 nm to determine the antibiotic detection limit. From the test results, it was concluded that Tb 0.05 Yb 0.9 Sr 0.05 -BTC’s detection limit for NOR can reach 1.0×10 -9 mol / L, indicating Tb 0.05 Yb 0.9 Sr 0.05 -BTC is highly selective for NOR quinolone antibiotics.

[0070] Determination of quenching response time of Example 6

[0071] Step S61: Configure the concentration to 10 -3 M Norfloxacin (NOR) ethanol solution.

[0072] Step S62: Prepare Tb with a concentration of 0.2 mg / mL 0.05 Yb 0.9 Sr 0.05 -BTC suspension.

[0073] Step S63: Take 2 mL of Tb prepared in step S62 0.05 Yb 0.9 Sr 0.05 -BTC suspension was placed in 300 μL of NOR aqueous solution in step S61, and the fluorescence emission spectrum of the suspension at 380-670 nm was repeatedly recorded at 302 nm and 254 nm every 20 s at the excitation wavelength to measure the response time of antibiotic detection. It was found that Tb could be detected within 20 s. 0.05 Yb 0.95 Sr 0.05 -BTC completes the fluorescence quenching reaction with high efficiency.

[0074] Example 6 Detection of different water qualities

[0075] Step S61: taking water from West Lake, East Lake, pure water and tap water from the Qingshuihe Campus of University of Electronic Science and Technology of China as water sources.

[0076] Step S62: Use the different water qualities in step S61 to configure a concentration of 10 -3 M Norfloxacin (NOR) ethanol solution.

[0077] Step S63: Prepare Tb with a concentration of 0.2 mg / mL 0.05 Yb 0.9 Sr 0.05 -BTC suspension.

[0078] Step S64: Take 2 mL of Tb prepared in step S63 0.05 Yb 0.9 Sr 0.05 -BTC suspension was placed in 300 μL of NOR aqueous solution in step S62, and the fluorescence emission spectrum of the suspension at 380-670 nm was measured at excitation wavelengths of 302 nm and 254 nm to determine the water quality interference with antibiotic detection. The results showed that although different water qualities had an effect on Tb 0.05 Yb 0.9 Sr 0.05 -BTC has a certain fluorescence quenching effect, but it does not affect the detection effect of NOR.

[0079] Example 7 Recovery Test

[0080] Step S71: Configure the concentration to 10 -3 M Norfloxacin (NOR) ethanol solution.

[0081] Step S72: Prepare Tb with a concentration of 0.2 mg / mL 0.05 Yb 0.9 Sr 0.05 -BTC suspension.

[0082] Step S73: Take 2 mL of Tb prepared in step S72 0.05 Yb 0.9 Sr 0.05 -BTC suspension was placed in 300 μL of NOR aqueous solution in step S71, and the fluorescence emission spectrum of the suspension at 380-670 nm was measured at excitation wavelengths of 302 nm and 254 nm and recorded in detail.

[0083] Step S74: Take the Tb after centrifugal drying in step S73 0.05 Yb 0.9 Sr 0.05 -BTC powder, reconstituted into 0.2mg / mL Tb 0.05 Yb 0.9 Sr0.05 -BTC suspension, then take 2 mL of the suspension and add 300 μL NOR (10 -3 M) aqueous solution, mixed evenly, took out 2 mL, and recorded the fluorescence emission spectrum of the suspension at 380-670 nm under excitation wavelengths of 302 nm and 254 nm. The above operation was repeated 5 times. It was found that after 5 cycles of detection, the detection limit could still be maintained at 1.0×10 -9 mol / L, further illustrating Tb 0.05 Yb 0.9 Sr 0.05 -The stability of BTC luminescent materials.

[0084] Example 8 Simulated plasma and urine interference test

[0085] Step S81: The concentration is 10 -3 M and contains NaHCO3, Na2CO3, Na2SO4, MgSO4, KCl, NaCl, CaCl2, glucose and protein model human plasma.

[0086] Step S82: The concentration is 10 -3 M and contains NH4Cl, Na2SO4, KCl, NaCl, urea, glucose, and protein model human urine species.

[0087] Step S83: Prepare Tb with a concentration of 0.2 mg / mL 0.05 Yb 0.9 Sr 0.05 -BTC suspension.

[0088] Step S84: Prepare a NOR ethanol solution with a concentration of 1 mM.

[0089] Step S85: 1 mL of each of the solutions in step S81, step S82, and step S83 was taken, and 40 μL of the NOR ethanol solution in step S84 was added thereto to obtain a mixed solution.

[0090] Step S86: The fluorescence emission spectrum of the suspension in step S85 at 380-670 nm was measured at excitation wavelengths of 302 nm and 254 nm and recorded in detail. The results showed that although Tb 0.05 Yb 0.9 Sr 0.05 The fluorescence intensity of -BTC will be reduced, but the presence of plasma and urine stock solutions does not interfere with the detection of the antibiotic NOR.

[0091] Example 9 Preparation of Tb for NOR detection of minced fish 0.05 Yb 0.9 Sr 0.05-BTC@CRG membrane

[0092] Step S91: Prepare 6 equal amounts of minced fish and place them in a large centrifuge tube containing 20 ml of deionized water.

[0093] Step S92: adding different masses of NOR into the centrifuge tube of step S91 to prepare NOR solutions with concentrations of 1500 ppm, 150 ppm, 15 ppm, 1.25 ppm, 0.15 ppm and 0 ppm, respectively.

[0094] Step S93: The mixture in the centrifuge tube in step S92 is fully dispersed by ultrasound and then centrifuged to take 10 mL of the supernatant.

[0095] Step S94: Add 250 mg of carrageenan to 10 mL of the supernatant of step S93, and stir thoroughly in a 90° C. water bath to dissolve.

[0096] Step S95: Tb 0.05 Yb 0.9 Sr 0.05 -5 mg of the BTC powder sample was ground into carrageenan and stirred to mix them thoroughly.

[0097] Step S96: 0.8 mL of the mixed Tb 0.05 Yb 0.9 Sr 0.05 -BTC@CRG is evenly applied in the plastic test box and cooled to form a film at room temperature. After being left to stand naturally at room temperature for one day, the dehydrated Tb 0.05 Yb 0.9 Sr 0.05 -BTC@CRG transparent film, such as Figure 5 As shown in (a) in .

[0098] Figure 5 (b) shows the Tb with different NOR concentrations. 0.05 Yb 0.9 Sr 0.05 -BTC@CRG film test results in fish meat. It can be seen from the figure that as the concentration of NOR increases, Tb 0.05 Yb 0.9 Sr 0.05 -The green luminescence of BTC@CRG film gradually weakens, which can qualitatively indicate that Tb 0.05 Yb 0.9 Sr 0.05 -BTC@CRG film can visually detect the concentration of NOR in fish meat. Figure 5 (c) Tb with different NOR concentrations 0.05 Yb 0.9 Sr 0.05-BTC@CRG film solid-state fluorescence spectrum. It can be seen from the figure that as the concentration of NOR increases, Tb 0.05 Yb 0.9 Sr 0.05 The fluorescence emission spectrum intensity of the -BTC@CRG film gradually decreases, and its characteristic peak of NOR also increases, which can quantitatively explain that Tb 0.05 Yb 0.9 Sr 0.05 -BTC@CRG film can detect the concentration of NOR in fish meat. Figure 5 (d) shows the Tb with different NOR concentrations. 0.05 Yb 0.9 Sr 0.05 -BT@filter paper film test results. It can be seen from the figure that with the increase of NOR concentration, its fluorescence luminescence will weaken and increase, indicating that Tb 0.05 Yb 0.9 Sr 0.05 -BT@filter paper film can be used to visually detect the concentration of NOR antibiotics.

[0099] Example 10 PVA / PEI@Tb 0.05 Yb 0.9 Sr 0.05 Preparation of -BTC hydrogel

[0100] Step S101: Weigh 0.5 g of polyethyleneimine (PEI) (Mw. 600) into a 20 mL glass bottle, and add 9 mL of pure water.

[0101] Step S102: Place the glass bottle containing the solution in step S101 on a 90° C. heating table and stir thoroughly to dissolve all components.

[0102] Step S103: 1 g of polyvinyl alcohol (PVA) was added to the solution in which each component was dissolved in step S102, and stirring was continued at 90° C. for 2 h to make it into a uniform hydrogel precursor liquid.

[0103] Step S104: Use a pipette to measure 2 mL of the hydrogel precursor liquid prepared in step S103 and transfer it to the desired mold.

[0104] Step S105: The hydrogel precursor liquid measured in step S104 is placed in a -20°C refrigerator and frozen overnight, and then placed in the upper layer of a 4°C refrigerator to thaw; after three freeze-thaw cycles, a hydrogel is formed.

[0105] Implementation Example 11 Design of Photonic Barcode

[0106] The definition rule of the photon barcode is to place the black parallel lines in the barcode at the emission peak position, and the line width is proportional to the relative integrated intensity of the peak. The line width corresponding to the strongest emission is standardized to "1", and the other line widths are determined according to the relative intensity ratio. Based on this principle, manufacturers can embed different combinations of Ln-BTC MOF modules into goods and detect them at specific wavelengths as anti-counterfeiting labels, such as Figure 6 As shown in Figure 1, a high-capacity photonic barcode design strategy is used, which uses the emission peaks at 490 nm and 545 nm, which are adjusted by the excitation wavelength (such as 254 nm or 302 nm) and the MOF composition (such as the ratio of Tb, Yb and Sr). As a verification, we selected Tb1-BTC, Tb 0.05 Yb 0.9 and Tb 0.05 Yb 0.9 Sr 0.05 -BTC modules form an anti-counterfeiting label, generating 6 sub-barcodes under 254nm and 302nm light sources, such as Figure 6 (a) to (f) are shown, and they are combined into a photonic barcode for information storage and anti-counterfeiting. By adjusting the type and number of Ln-BTC MOF modules, a large amount of spectral information can be generated. And through the combination of sub-barcodes, a large-capacity photonic barcode can be realized, which significantly improves the anti-counterfeiting ability and is suitable for the anti-counterfeiting field of valuable items such as currency and archives.

[0107] Implementation Example 12 Fingerprint Identification

[0108] Step S121: We place fingerprints on the smooth surfaces of glass, plastic and cutlery respectively.

[0109] Step S122: The carefully ground Tb 0.05 Yb 0.9 Sr 0.05 -Sprinkle BTC crystals on the fingerprints and blow off the excess powder.

[0110] Step S123: Under 254nm ultraviolet irradiation, Tb 0.05 Yb 0.9 Sr 0.05 -BTC crystals emit strong green light with high contrast against the background provided by different substrates, which is beneficial for the detection of latent fingerprints (LFPs).

[0111] The above method can be used to put fingerprints on various papers, such as supermarket receipts, train tickets and subway invoices. The main chemicals that cause LFPs are biological exocrine substances and oily substances such as inorganic salts, amino acids, oils and fats. 0.05 Yb 0.9 Sr 0.05 -The porous structure of BTC allows the absorption of these substances and thus the identification of LFPs. Figure 7 In the magnified image of the plastic pattern shown, detailed information of the fingerprint can be clearly observed, including: cross bifurcation, termination, scar, sweat pores, etc.; the four marked areas (1-4) of the fingerprint on the tape are magnified and displayed. All fingerprints were excited in a 254nm UV light box. Therefore, using Tb 0.05 Yb 0.9 Sr 0.05 - BTC fingerprinting is effective and reliable.

[0112] Implementation Example 13 Anti-counterfeiting Application

[0113] Step S131: Get Tb 0.05 Yb 0.9 Sr 0.05 -BTC crystal powder 100 mg, dissolve the crystal powder in 5 ml of anhydrous ethanol, then add 2 ml of dichloromethane, 2 ml of glycerol and 1 ml of acetone, mix well to obtain a mixed solution.

[0114] Step S132: ultrasonically subjecting the mixed solution in step S131 to 45 minutes to obtain an anti-counterfeiting ink having green fluorescent properties.

[0115] Step S133: The prepared solution in step S132 is used as an oil-based ink to write a series of Chinese characters directly on non-fluorescent paper with a brush, and heated at 80° C. for 2 hours to evaporate the water.

[0116] Step S134: The Chinese characters written in step S133 all show green fluorescence color under the ultraviolet excitation of 340, 365 and 395nm, but the luminous intensity is inconsistent. 0.05 Yb 0.9 Sr 0.05 -The text obtained by BTC ink on rice paper is invisible in sunlight. Under the excitation of 254nm, 302nm and 365-395nm, the color is green. Figure 8 shown.

[0117] It is to be understood that the present invention is described by some embodiments, and it is known to those skilled in the art that various changes or equivalent substitutions may be made to these features and embodiments without departing from the spirit and scope of the present invention. In addition, under the teachings of the present invention, these features and embodiments may be modified to adapt to specific circumstances and materials without departing from the spirit and scope of the present invention. Therefore, the present invention is not limited by the specific embodiments disclosed herein, and all embodiments falling within the scope of the claims of this application are within the scope of protection of the present invention.

Claims

1. A method for preparing a cation-doped lanthanide MOF material, characterized in that: The steps include: Step S31: Tb 3+ , Yb 3+ and Sr 2+ The hexahydrate salt of the metal ion and 0.42 g of BTC were added to a 100 mL beaker, and 80 mL of DMF and 40 mL of deionized water were added. After ultrasonic treatment for 60 min, a mixed solution was obtained; Step S32: the mixed solution obtained in step S31 was transferred to a 200 ml sealed container and stirred at room temperature for 2 h, then transferred to a polytetrafluoroethylene-lined autoclave, the polytetrafluoroethylene-lined autoclave was sealed, gradually heated to 140° C. at a rate of 5° C. / min, and maintained in an oven at 140° C. for 8 h; Step S33: After the heating process in step S32 is completed, the mixture is allowed to cool naturally to room temperature; the obtained product is separated by centrifugation, and washed three times with DMF and ethanol respectively; Step S34: Place the product obtained in step S33 in a vacuum oven and dry at 100°C to obtain lanthanide Tb 0.05 Yb 0.95- y Sr y -BTC MOFs, white powdery probe powder; Tb 3+ , Yb 3+ and Sr 2+ The total amount of ions is 4mmol; Tb 3+ The molar ratio is 5%, Yb 3+ and Sr 2+ The total molar ratio is 95%, of which Sr 2+ The molar ratio changes from 1% to 12.5%, then Yb 3+ The proportion varies from 82.5% to 94%.

2. A cation-doped lanthanide MOF material, characterized in that: The cation-doped lanthanum MOF material is prepared by the preparation method according to claim 1, and the cation-doped lanthanum MOF material is Tb 0.05 Yb 0.95-y Sr y -BTC MOFs have a one-dimensional rod-like microstructure with a length of hundreds of micrometers and a width of tens of micrometers and appear in the form of nanoflowers.

3. The cation-doped lanthanide MOF material according to claim 2, characterized in that: When the value of y is 0.05, the luminous effect is the best, that is, Tb 0.05 Yb 0.9 Sr 0.05 -BTC MOFs have the best luminescence effect.

4. Application of the cation-doped lanthanide MOF material prepared by the preparation method of the cation-doped lanthanide MOF material according to claim 1 or the cation-doped lanthanide MOF material according to claim 2 in sensing.

5. Application of the cation-doped lanthanide MOF material prepared by the preparation method of the cation-doped lanthanide MOF material according to claim 1 or the cation-doped lanthanide MOF material according to claim 2 in photonic barcodes.

6. Use of the cation-doped lanthanide MOF material prepared by the preparation method of the cation-doped lanthanide MOF material according to claim 1 or the cation-doped lanthanide MOF material according to claim 2 in fingerprint identification.

7. Anti-counterfeiting application of the cation-doped lanthanide MOF material prepared by the preparation method of the cation-doped lanthanide MOF material according to claim 1 or the cation-doped lanthanide MOF material according to claim 2.

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