PFCAs detection material as well as preparation method and application thereof

Abstract

The invention discloses a PFCAs detection material with double emission characteristics, high response speed and low detection limit as well as a preparation method and application thereof, and solves the technical problems that the method is complex and low in efficiency, fluorescence sensing depends on a single emission strategy and the detection stability is insufficient during PFCAs detection. The fluorescence spectrum of the PFCAs detection material has double emission peaks which are respectively located at 440nm and 592nm. The preparation method of the PFCAs detection material comprises the following steps: dissolving soluble Eu salt in ultrapure water to obtain a first solution; dPA and BDC-NH2 are dissolved in absolute ethyl alcohol of triethylamine, and a second solution is obtained; mixing the first solution and the second solution, and stirring to obtain a solid-liquid mixture; and collecting, washing and drying solids in the solid-liquid mixture to obtain the PFCAs detection material.

Description

Technical Field

[0001] This invention relates to the technical field of PFCAs detection, and more specifically, to PFCAs detection materials, their preparation methods, and applications. Background Technology

[0002] Perfluorocarboxylic acids (PFCAs) are widely used in commercial and industrial production of various products, including coatings, fire-fighting foams, inks, varnishes, lubricants, waterproofing agents, paper, and textiles, due to their unique surface activity, high thermal and chemical stability, and excellent light transmittance. However, PFCAs exhibit strong resistance to degradation in the natural environment, remarkable persistence, and a tendency to bioaccumulate in organisms. Given the increasing public concern regarding their toxicity and environmental persistence, long-chain PFCAs (C... n F2 n+1 The use of COOH (n≥7) has been strictly restricted in many countries. Against this backdrop, short-chain PFCAs (C n F 2n+1 COOH (n<7) is gradually becoming a substitute. However, the solubility of short-chain PFCAs increases with the decrease in the number of carbon atoms, resulting in greater mobility in the environment and a corresponding increase in the risk of polluting groundwater and soil.

[0003] PFCAs exhibit weak responses in ultraviolet absorption and fluorescence spectrophotometry. Gas chromatography-mass spectrometry (GC-MS) is difficult to apply efficiently to the detection of PFCAs due to the complex derivatization steps involved in sample pretreatment. Liquid chromatography-mass spectrometry (LC-MS) is currently the most widely used technique for detecting PFCAs, but it suffers from limitations such as complex sample preparation procedures, high instrument costs, and high requirements for skilled operators. Given these limitations, developing a simple, rapid, and economical molecular recognition technique to achieve efficient detection of PFCAs is particularly urgent.

[0004] In recent years, fluorescence-based sensing technology has been considered a highly promising detection strategy due to its high sensitivity and portability. However, most existing fluorescence detection methods rely on a single-emission strategy, which to some extent limits their feasibility and accuracy in practical applications. Summary of the Invention

[0005] The technical problem this invention aims to solve is the complexity and inefficiency of PFCAs detection methods, the reliance on single-emission strategies for fluorescence sensing, and insufficient detection stability. This invention provides a PFCAs detection material exhibiting dual-emission characteristics, fast response speed, and low detection limit, along with its preparation method and applications. The technical solution is as follows:

[0006] The PFCAs detection material exhibits a fluorescence spectrum with two emission peaks, located at 440 nm and 592 nm, respectively.

[0007] As a further improvement to the PFCAs detection material mentioned above: the ultraviolet-visible absorption spectrum has absorption peaks at 370 nm and 270 nm.

[0008] As a further improvement to the PFCAs detection material mentioned above: the XPS full spectrum has characteristic peaks of Eu 3d, O 1s, N 1s, C1s, and Eu 4d.

[0009] As a further improvement to the above-mentioned PFCAs detection material, it includes a metal-organic framework, a first ligand, and a second ligand, wherein the metal-organic framework is Eu-MOF, the first ligand is DPA, and the second ligand is BDC-NH2.

[0010] The above-mentioned method for preparing PFCAs detection materials includes the following steps:

[0011] The soluble Eu salt was dissolved in ultrapure water to obtain the first solution;

[0012] DPA and BDC-NH2 were dissolved in anhydrous ethanol of triethylamine to obtain a second solution;

[0013] The first and second solutions are mixed and stirred to obtain a solid-liquid mixture.

[0014] The solids in the solid-liquid mixture are collected, washed, and dried to obtain the PFCAs detection material.

[0015] As a further improvement to the preparation method of the above-mentioned PFCAs detection material: the total molar ratio of DPA and BDC-NH2 to Eu ions is 2:1; the molar ratio of DPA and BDC-NH2 is 3:2; and the volume ratio of the second solution to the first solution is 3:1.

[0016] As a further improvement to the preparation method of the above-mentioned PFCAs detection material: a solid-liquid mixture is obtained by stirring at 30-50°C for 2 hours.

[0017] As a further improvement to the preparation method of the above-mentioned PFCAs detection material: the PFCAs detection material is obtained after vacuum drying at 30-50℃.

[0018] The method for detecting trifluoroacetic acid involves using the PFCAs detection material described in any one of claims 1-4 to perform fluorescence detection of trifluoroacetic acid.

[0019] A method for detecting heptafluorobutyric acid, wherein the PFCAs detection material described in any one of claims 1-4 is used to perform fluorescence detection of heptafluorobutyric acid.

[0020] The advantages of the PFCAs detection material, its preparation method, and its application of the present invention are as follows: (1) Compared with the single emission strategy, the dual emission strategy has significant advantages. Through its built-in correction mechanism, it can effectively reduce the interference of external factors. The PFCAs detection material of the present invention has dual emission characteristics, which provides a basis for proportional fluorescence detection and improves the stability and accuracy of detection. (2) The hydrogen bond interaction between the carboxyl group of short-chain PFCAs and the amino group in the PFCAs detection material restricts the rotation of the benzene ring, thereby promoting the activation of the ligand fluorescence signal. This is the key mechanism for achieving rapid response and specific recognition of short-chain PFCAs. (3) As the concentration of short-chain PFCAs increases, the system exhibits a significant color change from red to blue, providing a clear signal for visual detection.

[0021] Verification showed that the PFCAs detection material of this invention exhibits a detection limit as low as 1.54 μM for trifluoroacetic acid (TFA) and 1.84 μM for heptafluorobutyric acid (PFBA) when using proportional fluorescence detection. This demonstrates that the PFCAs detection material, its preparation method, and its application of this invention successfully construct dual-emission characteristics through a dual-ligand strategy. This not only achieves proportional fluorescence detection but also enables rapid identification through visual color changes, offering advantages of economy and efficiency. It provides an intuitive and portable method for the rapid detection of PFCAs in the field of environmental and health monitoring, demonstrating strong practicality.

[0022] The present invention will be further described below with reference to the accompanying drawings and specific embodiments. Additional aspects and advantages of the invention will be set forth in part in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention. Attached Figure Description

[0023] The accompanying drawings, which form part of this invention, are used to aid in understanding the invention. The content provided in the drawings and their related descriptions can be used to explain the invention, but do not constitute an undue limitation of the invention. In the drawings:

[0024] Figure 1 Powder X-ray diffraction patterns of Eu-BDC-NH2, Eu-DPA, and Eu-DPA-BDC-NH2 with different molar ratios.

[0025] Figure 2 SEM images (ae) and TEM images (f) of Eu-DPA-BDC-NH2 with different molar ratios, and corresponding EDX elemental distribution maps.

[0026] Figure 3 Low- and high-magnification TEM images of Eu-DPA-BDC-NH2 with a molar ratio of 3:2.

[0027] Figure 4 XPS full spectrum (a), high-resolution XPS spectrum (be), and FT-IR spectrum (f) of Eu-DPA-BDC-NH2 with a molar ratio of 3:2.

[0028] Figure 5 The TGA curves and N2 adsorption-desorption isotherms (with built-in average pore size distribution map) for Eu-DPA-BDC-NH2 with a molar ratio of 3:2.

[0029] Figure 6 Luminescence images of Eu-DPA-BDC-NH2 with and without TFA at different molar ratios.

[0030] Figure 7 The UV-Vis absorption spectra of BDC-NH2, DPA, and Eu-DPA-BDC-NH2 are shown.

[0031] Figure 8 The excitation spectrum is for Eu-DPA-BDC-NH2.

[0032] Figure 9 The fluorescence spectra of Eu-DPA-BDC-NH2 under different excitation wavelengths are shown.

[0033] Figure 10 The fluorescence spectra of Eu-DPA-BDC-NH2 at different concentrations are shown in the presence and absence of TFA.

[0034] Figure 11 The fluorescence spectra of Eu-DPA-BDC-NH2 in the presence of different concentrations of TFA (with built-in luminescence images under ultraviolet light irradiation).

[0035] Figure 12 For I 440nm and I 592nm Graph showing the change with TFA concentration.

[0036] Figure 13 For I 440nm / I 592nm Curve showing the change in TFA concentration (built-in linear relationship graph).

[0037] Figure 14 The fluorescence spectra of Eu-DPA-BDC-NH2 in the presence of different concentrations of PFBA (with built-in luminescence images under ultraviolet light irradiation).

[0038] Figure 15 For I 440nm and I 592nm Graph showing the change with PFBA concentration.

[0039] Figure 16 For I440nm / I 592nm Curve showing the change in PFBA concentration (built-in linear relationship graph).

[0040] Figure 17 The graph shows the change in fluorescence intensity ratio of Eu-DPA-BDC-NH2 to TFA and other interfering substances.

[0041] Figure 18 The graph shows the change in fluorescence intensity ratio of Eu-DPA-BDC-NH2 to PFBA and other interfering substances. Detailed Implementation

[0042] The present invention will now be clearly and completely described in conjunction with the accompanying drawings. Those skilled in the art will be able to implement the present invention based on these descriptions. Before describing the present invention in conjunction with the accompanying drawings, it should be particularly noted that:

[0043] The technical solutions and features provided in the various parts of this invention, including the following description, can be combined with each other without conflict.

[0044] Furthermore, the embodiments of the present invention described below are generally only some, not all, of the embodiments of the present invention. Therefore, all other embodiments obtained by those skilled in the art based on the embodiments of the present invention without inventive effort should fall within the scope of protection of the present invention.

[0045] Regarding the terminology and units used in this invention: The terms "comprising," "having," and any variations thereof in the specification, claims, and related parts of this invention are intended to cover non-exclusive inclusion.

[0046] An embodiment of the preparation method of the PFCAs detection material of the present invention includes the following steps: dissolving 0.5 mmol EuCl3·6H2O in 10 mL of ultrapure water to obtain a first solution; dissolving DPA (pyridine dicarboxylic acid) and BDC-NH2 (2-aminoterephthalic acid) in anhydrous ethanol containing triethylamine to obtain a second solution, wherein the total molar amount of DPA and BDC-NH2 is 1 mmol; mixing the first and second solutions and stirring at 40°C for 2 hours to obtain a solid-liquid mixture; collecting, washing, and drying the solid in the solid-liquid mixture, wherein the solid is washed three times with ethanol and ultrapure water respectively and then vacuum dried overnight at 40°C to obtain the PFCAs detection material. To achieve the optimal molar ratio of DPA to BDC-NH2, a series of PFCAs detection materials with molar ratios of 1:1, 3:2, 2:1, 3:1, and 4:1 were prepared. All PFCAs detection materials are designated as Eu-DPA-BDC-NH2.

[0047] To illustrate the advantages of dual ligands, this invention prepared single ligand materials Eu-BDC-NH2 and Eu-DPA as a comparison. Eu-BDC-NH2 was prepared using 1 mmol BDC-NH2, and Eu-DPA was prepared using 1 mmol DPA. The remaining steps were the same as above.

[0048] The following is the characterization data.

[0049] Figure 1 Powder X-ray diffraction patterns of Eu-BDC-NH2, Eu-DPA, and Eu-DPA-BDC-NH2 with different molar ratios.

[0050] like Figure 1 As shown, when the molar ratio of DPA to BDC-NH2 is high (especially 3:1 and 4:1), the diffraction peak of Eu-DPA-BDC-NH2 is more prominent and consistent with the diffraction peak height of Eu-DPA. Conversely, when the molar ratio of DPA to BDC-NH2 is low (from 2:1 to 1:1), the diffraction peak intensity of Eu-DPA-BDC-NH2 gradually weakens. This is because the first ligand DPA affects Eu... 3 + The ions exhibit strong affinity and high coordination ability, while the second ligand, BDC-NH2, has a relatively weak impact on the structure of Eu-DPA-BDC-NH2. When the molar ratio of DPA to BDC-NH2 is 1:1, the main diffraction peak of Eu-DPA-BDC-NH2 disappears at 6.9°, indicating that the crystallinity of the material is poor at this molar ratio.

[0051] Figure 2 SEM images (ae) and TEM images (f) of Eu-DPA-BDC-NH2 with different molar ratios, and corresponding EDX elemental distribution maps. Figure 3 Low- and high-magnification TEM images of Eu-DPA-BDC-NH2 with a molar ratio of 3:2.

[0052] SEM images show that the crystallinity of Eu-DPA-BDC-NH2 decreases and its morphology becomes more irregular with increasing BDC-NH2 content. At a molar ratio of 1:1, it exhibits irregular particles; at 3:2, it displays a micron-sized flower-like structure with attached nanoparticles; and in the range of 2:1 to 4:1, a more regular nanostructure is formed. This demonstrates that introducing the second ligand, BDC-NH2, can effectively regulate the morphology and crystallinity of Eu-DPA-BDC-NH2.

[0053] TEM images revealed a micron-scale flower-like structure with nanoparticles attached to its surface at a molar ratio of 3:2. This micron-scale flower-like structure typically possesses a porous or layered surface, which can significantly increase the effective surface area for interaction with the analyte.

[0054] As can be seen from the EDX elemental distribution diagram, C, N, O and Eu elements are uniformly distributed in Eu-DPA-BDC-NH2.

[0055] Figure 4 XPS full spectrum (a), high-resolution XPS spectrum (be), and FT-IR spectrum (f) of Eu-DPA-BDC-NH2 with a molar ratio of 3:2.

[0056] The full X-ray photoelectron spectroscopy (XPS) spectrum showed characteristic peaks for Eu3d, O1s, N1s, C1s, and Eu4d, revealing the presence of Eu, N, O, and C elements. A high-resolution spectrum of Eu3d was also provided. Figure 4 b) Characteristic peaks are observed at 1165.3 eV and 1135.8 eV, which are attributed to Eu. 3+ The electron binding energy. The additional peaks at 1155.3 eV and 1125.9 eV indicate the presence of a small amount of Eu. 2+ This may originate from the surface layer of the material. (High-resolution spectrum of N1s) Figure 4 c) Peaks are observed at 400.3 eV and 399.7 eV, attributed to the NH and CN bonds on BDC-NH2, respectively. High-resolution spectrum of C1s ( Figure 4 Three peaks were observed in d), located at 288.9 eV, 285.8 eV, and 284.8 eV, corresponding to the carboxyl carbon, the CN bond, and the aliphatic carbon in the benzene ring, respectively. High-resolution O1s spectrum ( Figure 4 e) Peaks are observed at 533.0 eV, 532.3 eV, and 531.5 eV, corresponding to the CO bond, oxygen in the carboxyl group, and Eu-O bond, respectively.

[0057] The 3300-3600 cm⁻¹ region was not observed in the Fourier transform infrared (FT-IR) spectrum. -1 The broad absorption band at 1695 cm⁻¹ is characteristic of aromatic amine groups, indicating that both DPA and BDC-NH₂ are completely deprotonated in Eu-DPA-BDC-NH₂. Furthermore, the C=O stretching vibration peak of the carboxyl group in DPA is located at 1695 cm⁻¹. -1 The C=O stretching vibration peak of the carboxyl group in BDC-NH2 is located at 1689 cm⁻¹. -1 In contrast, a location at 1612 cm⁻¹ was observed in Eu-DPA-BDC-NH₂. -1 The peak indicates that the carboxylate group reacts with Eu. 3+Ion coordination resulted in a stable structure. These spectral results collectively confirm the successful synthesis of Eu-DPA-BDC-NH2.

[0058] Figure 5 The TGA curves and N2 adsorption-desorption isotherms (with built-in average pore size distribution map) for Eu-DPA-BDC-NH2 with a molar ratio of 3:2.

[0059] Thermogravimetric analysis (TGA) curves show that Eu-DPA-BDC-NH2 possesses thermal stability up to 400°C. The specific surface area of ​​Eu-DPA-BDC-NH2, measured using the BET (Brunauer-Emmett-Teller) method, is 108.31 m². 2 The relative pressure (P / P0) was 0.199. Pore size analysis showed that the pore size of Eu-DPA-BDC-NH2 was approximately 17.82 nm. These results indicate that Eu-DPA-BDC-NH2 possesses good thermal stability and a high specific surface area, making it suitable for sensing applications.

[0060] The following are the performance test data.

[0061] For fluorescence detection, Eu-DPA-BDC-NH2 was first dispersed in anhydrous ethanol to prepare a 2 mg / mL stock solution. Then, an appropriate amount of the stock solution was placed in a 5 mL quartz cuvette and diluted to the desired concentration. Short-chain PFCAs (concentration and type selected as needed) were then added, and the final solution volume was adjusted to 2 mL. Simultaneously, the fluorescence color of the solution was photographed using a 265 nm portable UV lamp to visually observe the changes in fluorescence color.

[0062] Figure 6 Luminescence images of Eu-DPA-BDC-NH2 with and without TFA at different molar ratios.

[0063] like Figure 6 As shown, a significant color change was observed when the molar ratio was 3:2 (already converted to grayscale), making it suitable for visual inspection. Therefore, Eu-DPA-BDC-NH2 with a molar ratio of 3:2 was ultimately selected for the detection of short-chain PFCAs.

[0064] Figure 7 The UV-Vis absorption spectra of BDC-NH2, DPA, and Eu-DPA-BDC-NH2 are shown.

[0065] like Figure 7As shown, BDC-NH2 has absorption peaks at 230 nm and 365 nm, DPA has absorption peaks at 225 nm and 270 nm, while Eu-DPA-BDC-NH2 has absorption peaks at 370 nm and 270 nm, respectively, indicating that it successfully integrates the characteristics of DPA and BDC-NH2.

[0066] Figure 8 The excitation spectrum is for Eu-DPA-BDC-NH2. Figure 9 The fluorescence spectra of Eu-DPA-BDC-NH2 under different excitation wavelengths are shown.

[0067] like Figure 8-9 As shown, Eu-DPA-BDC-NH2 exhibits significant dual emission under excitation at 250 nm and 260 nm, with the metal center showing higher emission intensity at 260 nm, resulting in a more pronounced red-blue color transition. Therefore, the optimal excitation wavelength for achieving dual emission of Eu-DPA-BDC-NH2 was determined to be 260 nm, and subsequent fluorescence spectra in the range of 400 nm to 650 nm were recorded at this excitation wavelength.

[0068] Figure 10 The fluorescence spectra of Eu-DPA-BDC-NH2 at different concentrations are shown in the presence and absence of TFA.

[0069] like Figure 10 As shown, at an excitation wavelength of 260 nm, the fluorescence spectrum of Eu-DPA-BDC-NH2 exhibits three emission peaks at 440 nm, 592 nm, and 618 nm. The emission peaks at 592 nm and 618 nm are both Eu emission peaks. 3+ The characteristic peaks originate from Eu 3+ Ionic 5 D0→ 7 F1 and 5 D0→ 7 The F2 electronic transition. Significant intensity fluctuations in the emission peak at 618 nm may mask the fluorescence peak of the ligand, thus reducing the sensitivity of proportional fluorescence sensing. In contrast, the emission intensity of the emission peak at 592 nm remains stable, effectively avoiding this problem and significantly enhancing signal contrast. Therefore, the fluorescence intensity ratio of the emission peaks at 440 nm and 592 nm is used for sensing applications of short-chain PFCAs. The emission intensity of the 440 nm emission peak is represented by I0. 440nm The emission intensity at the emission peak at 592 nm is represented by I. 592nm This indicates that the fluorescence intensity is higher than that expressed by I. 440nm / I 592nm express.

[0070] When the concentrations of Eu-DPA-BDC-NH2 were 10 μg / mL and 20 μg / mL without the addition of TFA, the intensities of both the ligand peak and the metal center peak were weak, which was unfavorable for fluorescence detection. When the concentration of Eu-DPA-BDC-NH2 was increased to 30-60 μg / mL, the fluorescence intensity increased, and the Ig ratio before and after the addition of TFA also improved. 440nm / I 592nm Significant changes were observed. Specifically, when the Eu-DPA-BDC-NH2 concentration was 40 μg / mL, the I before and after the addition of TFA showed… 440nm / I 592nm The difference was the greatest, with a ratio of 1.38. Therefore, a concentration of 40 μg / mL was subsequently selected for sensing applications of short-chain PFCAs.

[0071] Figure 11 The fluorescence spectra of Eu-DPA-BDC-NH2 in the presence of different concentrations of TFA (with built-in luminescence images under ultraviolet light irradiation). Figure 12 For I 440nm and I 592nm Graph showing the change with TFA concentration. Figure 13 For I 440nm / I 592nm Curve showing the change in TFA concentration (built-in linear relationship graph).

[0072] like Figure 11-12 As shown, with increasing TFA concentration, the fluorescence intensity of Eu-DPA-BDC-NH2 at 440 nm gradually increases, while the emission intensity at 592 nm remains stable. Therefore, I 440nm / I 592nm It also increases with increasing TFA concentration. From Figure 11 The built-in graph shows a significant color change from red to bright blue (already converted to grayscale) as the TFA concentration increases; this change is easily visible to the naked eye. Figure 13 As shown, I 440nm / I 592nm The TFA concentration showed an excellent linear relationship in the range of 0 to 6 μg / mL, and the linear regression equation obtained by fitting was y = 0.72x + 0.52, R0. 2 =0.9980, detection limit is 1.54 μM.

[0073] Figure 14 The fluorescence spectra of Eu-DPA-BDC-NH2 in the presence of different concentrations of PFBA (with built-in luminescence images under ultraviolet light irradiation). Figure 15 For I 440nm and I 592nm Graph showing the change with PFBA concentration. Figure 16 For I 440nm / I592nm Curve showing the change in PFBA concentration (built-in linear relationship graph).

[0074] like Figure 14-15 As shown, with increasing PFBA concentration, the fluorescence intensity of Eu-DPA-BDC-NH2 at 440 nm gradually increases, while the emission intensity at 592 nm remains stable. Therefore, I 440nm / I 592nm It also increases with increasing PFBA concentration. From Figure 14 The built-in graph shows a significant color change from red to bright blue as the PFBA concentration increases (already converted to grayscale), a change easily visible to the naked eye. For example... Figure 16 As shown, I 440nm / I 592nm The PFBA concentration showed an excellent linear relationship in the range of 0 to 8 μg / mL, and the linear regression equation obtained by fitting was y = 0.47x + 0.38, R0. 2 =0.9926, detection limit is 1.84 μM.

[0075] Figure 17 The graph shows the change in fluorescence intensity ratio of Eu-DPA-BDC-NH2 to TFA and other interfering substances. Figure 18 The graph shows the fluorescence intensity ratio changes of Eu-DPA-BDC-NH2 against PFBA and other interfering substances. In the graph, PFOA represents perfluorooctanoic acid, PFNA represents perfluorononanoic acid, PFBS-K represents potassium perfluorobutyl sulfonate, and PFOS-K represents potassium perfluorooctane sulfonate.

[0076] like Figure 17-18 As shown, compared with other substances, I in the presence of TFA and PFBA 440nm / I 592nm The results show that Eu-DPA-BDC-NH2 can serve as a sensitive and selective ratiometric fluorescent probe for the detection of TFA and PFBA.

[0077] The equipment used for the above characterization and experiments is as follows:

[0078] The ultraviolet-visible absorption spectra were measured using a Shimadzu UV-2450 spectrophotometer.

[0079] Fluorescence spectra were recorded using an Edinburgh Instruments FLS1000 steady-state and transient fluorescence spectrometer.

[0080] Fourier transform infrared (FT-IR) spectra were obtained using a Nicolet / Nexus-670 FTIR spectrometer (KBr pellet).

[0081] Thermogravimetric analysis (TGA) was performed on a TGA / DSC3+ simultaneous thermal analyzer, heated in air at a heating rate of 15 °C min⁻¹, starting at 20 °C.

[0082] Powder X-ray diffraction (PXRD) was performed using a Panaco Empyrean X-ray diffractometer with CuKα as the radiation source.

[0083] Scanning electron microscope (SEM) images were obtained using a Zeiss Sigma 500 field emission scanning electron microscope.

[0084] Transmission electron microscopy (TEM) images and EDX elemental distribution maps were obtained using a JEM-2100F transmission electron microscope.

[0085] The N2 adsorption-desorption isotherm was performed at 274 K on an ASAP2460 surface area and porosity analyzer.

[0086] X-ray photoelectron spectroscopy (XPS) was obtained using a microprobe of the Thermo Fisher Scientific ESCALAB QXi X-ray photoelectron spectrometer.

[0087] The foregoing has described the relevant content of the present invention. Those skilled in the art will be able to implement the present invention based on these descriptions. All other embodiments obtained by those skilled in the art based on the above description of the present invention without inventive effort should fall within the scope of protection of the present invention.

Claims

1. A PFCAs detection material, characterized by: The fluorescence spectrum has double emission peaks at 440 nm and 592 nm.

2. The PFCAs detection material of claim 1, wherein: The ultraviolet-visible absorption spectrum has absorption peaks at 370 nm and 270 nm.

3. The PFCAs detection material of claim 1, wherein: The XPS full spectrum has characteristic peaks of Eu 3d, O 1s, N 1s, C 1s and Eu 4d.

4. The PFCAs detecting material according to any one of claims 1 to 3, characterized in that: The PFCAs detection material comprises a metal organic framework, a first ligand and a second ligand, the metal organic framework is Eu-MOF, the first ligand is DPA, and the second ligand is BDC-NH2.

5. A method for preparing a PFCAs detecting material according to any one of claims 1 to 4, characterized in that: The method comprises the following steps: dissolving a soluble Eu salt in ultrapure water to obtain a first solution; dissolving DPA and BDC-NH2 in triethylamine anhydrous ethanol to obtain a second solution; mixing the first solution and the second solution and stirring to obtain a solid-liquid mixture; collecting, washing and drying the solid in the solid-liquid mixture to obtain the PFCAs detection material.

6. The method for preparing the PFCAs detection material as described in claim 5, characterized in that: The total molar amount of DPA and BDC-NH2 and the molar ratio of Eu ions are 2:1; the molar ratio of DPA and BDC-NH2 is 3:2; and the volume ratio of the second solution to the first solution is 3:

1.

7. The method for preparing the PFCAs detection material as described in claim 5, characterized in that: The solid-liquid mixture is obtained after stirring at 30-50℃ for 2 hours.

8. The method for preparing the PFCAs detection material as described in claim 5, characterized in that: The PFCAs detection material is obtained after vacuum drying at 30-50℃.

9. A method for detecting trifluoroacetic acid, characterized in that: The PFCAs detection material of any one of claims 1-4 is used for fluorescence detection of trifluoroacetic acid.

10. A method for the detection of heptafluorobutyric acid characterized in that: The PFCAs detection material of any one of claims 1-4 is used for fluorescence detection of heptafluorobutyric acid.

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