Chemiluminescence detection material of triphenyl phosphate as well as preparation method and application of chemiluminescence detection material
By using chemiluminescence detection materials prepared by using phenylatic acid and iron salt assembled in triphenyl phosphate detection, ultraviolet light activation to generate reactive oxygen, the problems of high cost of oxidant and environmental pollution in the prior art are solved, and the problem of high cost of oxidant and environmental pollution in the prior art is realized. Fast and accurate TPHP detection with high selectivity and sensitivity.
Patent Information
- Application Number
- CN202411009842.3
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2024-07-26
- Publication Date
- 2024-12-17
AI Technical Summary
The methods used in the prior art for detection of triphenyl phosphate (TPHP) require high-cost oxidants, produce harmful environmental products, and are complex in equipment and have a long analysis time, making it difficult to achieve fast, accurate and economical testing.
Using triphenyl phosphate chemiluminescence detection material prepared from phenylatic acid and soluble iron salt, it is assembled through supramolecular interactions such as metal-ligand coordination, hydrogen bonding and π-π stacking to form low density and high proportions. Amorphous structural material with surface area uses ultraviolet light to generate reactive oxygen species (ROS), which can induce chemiluminescence without the need for additional oxidizing agents, and compete to consume TPHP for detection.
It realizes fast, accurate and economical TPHP detection without oxidants, with simple operation, high selectivity and sensitivity, and can detect TPHP in real water bodies, providing an environmentally friendly detection method.
Smart Images
Figure CN119147519A_ABST
Abstract
Description
Technical Field
[0001] The invention relates to the technical field of triphenyl phosphate detection, and in particular to a chemiluminescent detection material for triphenyl phosphate and a preparation method and application thereof. Background Art
[0002] Since brominated flame retardants were banned worldwide, organophosphorus flame retardants (OPFRs) have become an alternative to polybrominated diphenyl ethers due to their more cost-effectiveness and superior flame retardant properties. As a typical aromatic OPFR, triphenyl phosphate (TPHP) is increasingly being discharged into the environment as its production and use continue to expand. TPHP is toxic to the reproductive, neurodevelopmental, and genetic systems of humans and animals, and may cause malformations, carcinogenicity, and mutagenicity. In addition, TPHP has a strong resistance to pollutant removal processes, resulting in its long-term presence in the environment. Therefore, there is an urgent need to develop an accurate, environmentally friendly, and cost-effective TPHP detection method to determine the source of TPHP and lay the foundation for alleviating pollution problems.
[0003] At present, the methods for detecting TPHP mainly include gas chromatography (GC), gas chromatography-mass spectrometry (GC-MS), liquid chromatography-mass spectrometry (LC-MS), thin film diffusion gradient technology and fluorescence method. Although these methods have high accuracy and extremely low detection limits, expensive equipment, long analysis time and complex sample pretreatment are also limitations of these methods.
[0004] Chemiluminescence (CL) analysis technology has the characteristics of high sensitivity, simple instrumentation, easy operation, short analysis time, wide linear range, and easy automation, and has the potential to be used for TPHP sensing. Most OPFRs show high stability, and direct detection is challenging. In the prior art, ultraviolet light is used to activate oxidants (such as persulfate (PS) and peroxydisulfate (PMS)) to produce reactive oxygen species (ROS). ROS can decompose OPFRs and react with chemiluminescent reagents to produce chemiluminescent signals. Therefore, according to the changes in chemiluminescent signals before and after the addition of OPFRs, OPFRs can be indirectly detected. However, the oxidants used are expensive, produce environmentally harmful byproducts, and affect the stability of CL. Summary of the invention
[0005] The technical problem to be solved by the present invention is to provide a chemiluminescent detection material of triphenyl phosphate which can quickly detect TPHP without the need for an oxidant, and a preparation method and application thereof.
[0006] In order to achieve the above object, according to the first aspect of the present invention, a chemiluminescent detection material of triphenyl phosphate is provided, and the technical scheme is as follows:
[0007] The chemiluminescent detection material of triphenyl phosphate has characteristic peaks at 285.1eV, 532.1eV, 712.1eV, 267.1eV, 199.1eV and 57.1eV in the XRS spectrum; the FT-IR spectrum has characteristic peaks at 3450cm -1 、1627cm -1 、1582cm -1 、1447cm -1 、1383cm -1 、482cm -1 and 757cm -1 There is an absorption peak at.
[0008] As a further improvement of the above-mentioned chemiluminescent detection material of triphenyl phosphate: the XRD spectrum shows an amorphous structure.
[0009] As a further improvement of the above-mentioned chemiluminescent detection material of triphenyl phosphate: the XPS spectrum of Fe 2p has characteristic peaks at 711.0 eV and 724.6 eV; the XPS spectrum of C 1s has characteristic peaks at 284.80 eV, 288.85 eV and 286.39 eV; the XPS spectrum of O 1s has characteristic peaks at 531.76 eV, 529.82 eV and 533.33 eV.
[0010] In order to achieve the above object, according to the second aspect of the present invention, a method for preparing the chemiluminescent detection material of triphenyl phosphate described in the first aspect is provided, and the technical scheme is as follows:
[0011] The preparation method of the chemiluminescent detection material of triphenyl phosphate comprises the following steps:
[0012] dissolving trimesic acid and soluble iron salt in anhydrous ethanol to obtain a reaction solution;
[0013] The reaction solution is subjected to high pressure solvent thermal treatment to obtain a gel material;
[0014] The gel material is dried to obtain a chemiluminescent detection material of triphenyl phosphate.
[0015] As a further improvement of the preparation method of the above-mentioned chemiluminescent detection material of triphenyl phosphate: the reaction solution is prepared according to the ratio of adding 0.25-0.35g of trimesic acid and 0.5-0.6g of FeCl3·6H2O to every 10mL of anhydrous ethanol.
[0016] As a further improvement to the preparation method of the above-mentioned chemiluminescent detection material of triphenyl phosphate: the heat treatment is to keep the temperature at 100-140° C. for 0.5-2 hours.
[0017] In order to achieve the above object, according to the third aspect of the present invention, a method for detecting triphenyl phosphate is provided, and the technical scheme is as follows:
[0018] The detection method of triphenyl phosphate comprises the following steps:
[0019] Adding a test solution containing triphenyl phosphate and the chemiluminescent detection material solution of triphenyl phosphate described in the first aspect into a photoreactor, turning on ultraviolet light irradiation to obtain a first precursor solution; adding a chemiluminescent reagent to the first precursor solution, and testing the chemiluminescent intensity I of the obtained first mixed solution;
[0020] The test solution is replaced with an equal volume of water, and ultraviolet light is turned on to obtain a second precursor solution; a chemiluminescent reagent is added to the second precursor solution, and the chemiluminescent intensity I0 of the obtained second mixed solution is tested;
[0021] According to the linear relationship between the relative chemiluminescence intensity and the concentration of triphenyl phosphate, the concentration of triphenyl phosphate in the solution to be tested is calculated; the relative chemiluminescence intensity = I / I0.
[0022] As a further improvement of the above-mentioned detection method of triphenyl phosphate: the concentration of the chemiluminescent detection material in the first precursor solution and the second precursor solution is 4 mg / L.
[0023] As a further improvement of the above-mentioned detection method of triphenyl phosphate: the ultraviolet light irradiation time is 1 min.
[0024] As a further improvement of the above-mentioned detection method of triphenyl phosphate: the chemiluminescent reagent is a buffer solution containing luminol; the concentration of luminol in the first mixed solution and the second mixed solution is 1 μM, and the pH is 11.
[0025] The chemiluminescent detection material of triphenyl phosphate of the present invention and its preparation method and application have the advantages that the chemiluminescent detection material of triphenyl phosphate is assembled by organic ligands and metal ions through supramolecular interactions such as metal-ligand coordination, hydrogen bonding, π-π stacking, etc., and not only has low density, extremely high specific surface area and a wide range of large pore sizes, but also shows excellent peroxidase catalytic activity, can convert dissolved oxygen in water into ROS, and can induce strong CL emission without the need for additional oxidants. By adding TPHP to competitively consume ROS, CL is significantly inhibited, thereby establishing an environmentally friendly and economically feasible TPHP detection method. The verification results show that the TPHP detection method has the advantages of simple operation, rapid detection, high selectivity and sensitivity, can detect TPHP in real water bodies, and provides a simple strategy for developing a high-performance TPHP detection platform.
[0026] The present invention is further described below in conjunction with the accompanying drawings and specific embodiments. Additional aspects and advantages of the present invention will be partially given in the following description, partially become apparent from the following description, or be learned through the practice of the present invention. BRIEF DESCRIPTION OF THE DRAWINGS
[0027] The drawings constituting a part of the present invention are used to assist in understanding the present invention. The contents provided in the drawings and their related descriptions in the present invention can be used to explain the present invention, but do not constitute improper limitations on the present invention. In the drawings:
[0028] Figure 1 This is the XRD spectrum of the chemiluminescence detection material.
[0029] Figure 2 This is the full XPS spectrum of the chemiluminescent detection material.
[0030] Figure 3 This is the XPS spectrum of Fe 2p of the chemiluminescent detection material.
[0031] Figure 4 This is the XPS spectrum of C1s of the chemiluminescent detection material.
[0032] Figure 5 This is the XPS spectrum of O1s of the chemiluminescent detection material.
[0033] Figure 6 FT-IR spectrum of chemiluminescent detection material.
[0034] Figure 7 This is the SEM photo of the chemiluminescent detection material.
[0035] Figure 8 This is a TEM photo of the chemiluminescent detection material.
[0036] Fig. 9 is the chemiluminescence intensity of different test systems.
[0037] Fig.10 CL spectra of the system with and without TPHP.
[0038] Fig.11 O2 ·- Generated EPR spectrum.
[0039] Fig.12 EPR spectrum generated for ·OH.
[0040] Fig.13 for 1 EPR spectrum of O2 generation.
[0041] Fig.14This is a graph showing the CL inhibition degree of TPHP detected by UV / gel-luminol at different pH values.
[0042] Fig.15 This is a graph showing the CL inhibition degree of TPHP detected by UV / gel-luminol at different gel concentrations.
[0043] Fig.16 This is a graph showing the CL inhibition degree of TPHP detected by UV / gel-luminol at different luminol concentrations.
[0044] Fig.17 This is a graph showing the CL inhibition degree of TPHP detected by UV / gel-luminol under different UV irradiation durations.
[0045] Fig.18 The chemiluminescence intensity diagram of different concentrations of TPHP detected by UV / gel-luminol.
[0046] Fig.19 This is a linear relationship diagram between the relative chemiluminescence intensity and TPHP concentration when UV / gel-luminol is used to detect TPHP.
[0047] Fig. 20 This is a graph showing the selectivity of TPHP detection using UV / gel-luminol.
[0048] Fig.21 This is a graph showing the anti-interference ability of UV / gel-luminol detection of TPHP. DETAILED DESCRIPTION
[0049] The present invention is described clearly and completely below in conjunction with the accompanying drawings. A person 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:
[0050] The technical solutions and technical features provided in each part of the present invention, including the following description, may be combined with each other if there is no conflict.
[0051] In addition, the embodiments of the present invention involved in the following description are generally only a part of the embodiments of the present invention, rather than all the embodiments. Therefore, based on the embodiments of the present invention, all other embodiments obtained by ordinary technicians in this field without creative work should fall within the scope of protection of the present invention.
[0052] About the terms and units in the present invention: The terms "include", "have" and any variations thereof in the description and claims of the present invention and related parts are intended to cover non-exclusive inclusions.
[0053] An embodiment of the method for preparing the chemiluminescent detection material of triphenyl phosphate of the present invention comprises the following steps:
[0054] (1) Dissolve trimesic acid and FeCl3·6H2O in anhydrous ethanol to obtain a reaction solution; the reaction solution is prepared by adding 0.29 g trimesic acid and 0.57 g FeCl3·6H2O to every 10 mL of anhydrous ethanol.
[0055] (2) The reaction solution was placed in a polytetrafluoroethylene-lined reactor and kept at 120° C. for 1 hour to obtain a gel material.
[0056] (3) Drying the gel material to obtain the chemiluminescent detection material of TPHP (expressed as gel).
[0057] An embodiment of the detection method of triphenyl phosphate of the present invention comprises the following steps:
[0058] Adding a test solution containing TPHP and the above-mentioned chemiluminescent detection material solution into a photoreactor, turning on ultraviolet light irradiation to obtain a first precursor solution; adding a chemiluminescent reagent to the first precursor solution, and testing the chemiluminescent intensity I of the obtained first mixed solution; the chemiluminescent reagent is a buffer solution containing luminol;
[0059] Replace the test solution with an equal volume of water, turn on ultraviolet light irradiation, and obtain a second precursor solution; add a chemiluminescent reagent to the second precursor solution, and test the chemiluminescent intensity I0 of the obtained second mixed solution; I0 can obtain an on-site test value during implementation, or directly use an existing test value;
[0060] According to the linear relationship between the relative chemiluminescence intensity and the concentration of triphenyl phosphate, the concentration of triphenyl phosphate in the solution to be tested is calculated; the relative chemiluminescence intensity = I / I0.
[0061] The beneficial effects of the present invention are illustrated below by characterization data and test data.
[0062] Figure 1 This is the XRD spectrum of the chemiluminescence detection material.
[0063] like Figure 1 As shown, the chemiluminescent detection material has an amorphous structure.
[0064] Figure 2 This is the full XPS spectrum of the chemiluminescent detection material. Figure 3 This is the XPS spectrum of Fe 2p of the chemiluminescent detection material. Figure 4 This is the XPS spectrum of C1s of the chemiluminescent detection material. Figure 5 This is the XPS spectrum of O1s of the chemiluminescent detection material.
[0065] like Figure 2 As shown in the figure, the binding energies of the XPS full spectrum at 285.1eV, 532.1eV, 712.1eV, 267.1eV, 199.1eV and 57.1eV are the characteristic peaks of C1s, O 1s, Fe 2p, Cl 2s, Cl 2p and Cl 3s, respectively. Figure 3 As shown in the XPS spectrum of Fe 2p, two typical characteristic peaks were observed at 711.0eV and 724.6eV, corresponding to Fe 2p3 / 2 and Fe2p1 / 2, respectively, indicating that Fe 3+ and trimesic acid. Figure 4 As shown in Figure 1, the XPS spectrum of C 1s can be decomposed into three different characteristic peaks, located at 284.80 eV, 288.85 eV and 286.39 eV, corresponding to the phenyl signal, carboxyl signal and carbon on the sample surface. Figure 5 As shown, the characteristic peaks of the XPS spectrum of O 1s are located at 531.76 eV, 529.82 eV, and 533.33 eV, corresponding to the Fe-OC group, Fe-O group, and CO group, respectively.
[0066] Figure 6 FT-IR spectrum of chemiluminescent detection material.
[0067] like Figure 6 As shown, at 3450cm -1 The broad absorption peak at 1627 cm -1 、1582cm -1 The absorption peak at 1447 cm -1 and 1383cm -1 The absorption peak at can be attributed to the asymmetric stretching vibration of the carboxyl group Ar-(OCO) (expressed as vas(-COO)), and the difference between vas(-COO) and vs(-COO) is 180 cm -1 (1627cm -1 -1447cm -1 ) and 199cm -1 (1582cm -1 -1383cm -1 ), indicating a coordination pattern between the metal ion center and the carboxyl group; at 482 cm -1 and 757cm -1 The absorption peaks at correspond to the existence of Fe-O bonds and the stretching vibration of Ar-CH bonds, respectively.
[0068] Figure 7 This is the SEM photo of the chemiluminescent detection material. Figure 8 This is a TEM photo of the chemiluminescent detection material.
[0069] like Figure 7-8 As shown, the chemiluminescent detection material is in the form of flakes with a rough and irregular surface.
[0070] With ultraviolet light, solvent (water or acetonitrile) in the photoreactor, gel, and TPHP as variables, 8 test systems were established to preliminarily explore the effects of these variables on the chemiluminescence intensity. The test process is: gel (with or without) and TPHP (with or without) are added to the photoreactor with water or acetonitrile as the solvent and irradiated with ultraviolet light (with or without), and part of the solution in the photoreactor is taken into the quartz reaction dish of the BPCL-2 analyzer and then the luminol buffer solution is added to obtain the final chemiluminescence intensity.
[0071] Fig. 9 The chemiluminescence intensity of different test systems. Among them, (a) represents luminol-gel-water, that is, no ultraviolet light and TPHP are used, (b) represents luminol-gel-acetonitrile, that is, no ultraviolet light and TPHP are used; (c) represents luminol-gel-TPHP-water, that is, no ultraviolet light is used; (d) represents luminol-gel-UV-water, that is, no TPHP is used; (e) represents luminol-gel-UV-acetonitrile, that is, no TPHP is used; (f) represents luminol-gel-UV-TPHP-water; (g) represents luminol-water-UV, that is, no gel and TPHP are used; (h) represents luminol-acetonitrile-UV, that is, no gel and TPHP are used.
[0072] like Fig. 9As shown, (d) and (e) have obvious chemiluminescence, which indicates that the ROS generated by gel has good oxidizing properties and can oxidize luminol to produce chemiluminescence. By comparing (a), (b) and (c), it can be seen that the introduction of TPHP has little effect on the chemiluminescence signal without the use of ultraviolet light, indicating that TPHP is difficult to be catalytically oxidized under dark conditions. Compared with (a), when ultraviolet light is introduced, the chemiluminescence intensity of (d) is sharply enhanced by about 94 times, indicating that ultraviolet light can promote the generation of a large amount of ROS. Compared with (d), the chemiluminescence signal of (e) is reduced, indicating that organic solvents such as acetonitrile have a certain inhibitory effect on the chemiluminescence signal. Compared with (d), the chemiluminescence signal after the introduction of the target pollutant TPHP in (f) is reduced by 83%, indicating that the introduction of TPHP competitively consumes ROS. Curves (g) and (h) show that the presence of gel plays a vital role in the detection of TPHP. In the absence of gel, the effect of ultraviolet light alone on chemiluminescence is very limited.
[0073] Fig.10 CL spectra of the system with and without TPHP. (a) represents luminol-gel-UV-water, that is, without TPHP; (b) represents luminol-gel-UV-TPHP-water.
[0074] like Fig.10 As shown, the CL spectrum of (a) has a maximum emission wavelength at 425nm, which belongs to the emission wavelength of excited 3-aminophthalate (3-APA*), which is a typical emission of luminol reaction. After the introduction of TPHP, the CL wavelength of (b) did not change, but the intensity decreased, indicating that the luminophores of the two systems are the same, that is, 3-APA* excited by luminol oxidation.
[0075] In order to study the mechanism and types of ROS generated by TPHP photocatalysis, electron paramagnetic resonance (EPR) analysis was performed on the gel solution without UV irradiation, the gel solution irradiated with UV for 1 min (expressed as gel+UV), and the gel solution and TPHP solution irradiated with UV for 1 min (expressed as gel+TPHP+UV).
[0076] Fig.11 O2 ·- Generated EPR spectrum. Fig.12 EPR spectrum generated for ·OH. Fig.13 for 1 EPR spectrum of O2 generation.
[0077] Figure 11-13The signals showed similar trends of change. The gel solutions without UV irradiation did not generate ROS signals. After being irradiated with UV for 1 minute, gel+UV generated a strong ROS signal. However, after the introduction of TPHP, the ROS signal of gel+TPHP+UV was significantly weakened. It can be seen that gel is a catalyst in the photocatalytic process and can be activated by UV light to generate ROS as an oxidant to degrade TPHP.
[0078] In summary, under the action of UV light, gel can produce ROS, while luminol and TPHP can competitively consume ROS. Therefore, a CL-based and oxidant-free TPHP detection system can be established, named UV / gel-luminol.
[0079] In order to explore the best experimental conditions for detecting TPHP, multiple parallel tests were conducted and the CL inhibition degree was used as the evaluation index to optimize the gel concentration, pH value, luminol concentration, and UV irradiation time. The test process is as follows:
[0080] 800 μL of water is placed in a photoreactor, TPHP solution and gel solution (TPHP concentration is 10 mg / L, gel concentration is 1-10 mg / L) are added to the photoreactor, and ultraviolet light is turned on for 0.5-5 minutes to obtain a first precursor solution; 100 μL of the first precursor solution is put into the quartz reaction dish of the BPCL-2 analyzer, the light window is closed, 300 μL of luminol buffer solution (pH is 8-12, luminol concentration is 0.1-4 μM) is added to the first precursor solution, and the chemiluminescence intensity I of the obtained first mixed solution is tested. Then, the solution to be tested is replaced with an equal volume of water, and the other parameters remain unchanged, and ultraviolet light is turned on to obtain a second precursor solution; luminol buffer solution is added to the second precursor solution, and the chemiluminescence intensity I0 of the obtained second mixed solution is tested. The CL inhibition degree = (I0-I) / I0.
[0081] Fig.14 This is a graph showing the CL inhibition degree of TPHP detected by UV / gel-luminol at different pH values. Fig.15 This is a graph showing the CL inhibition degree of TPHP detected by UV / gel-luminol at different gel concentrations. Fig.16 This is a graph showing the CL inhibition degree of TPHP detected by UV / gel-luminol at different luminol concentrations. Fig.17 This is a graph showing the CL inhibition degree of TPHP detected by UV / gel-luminol under different UV irradiation durations.
[0082] like Fig.14 As shown in Figure 2, CL inhibition increases with increasing pH and reaches a maximum at pH = 11. Fig.15 As shown in Figure 2, CL inhibition increased with increasing gel concentration from 0 to 4 mg / L and then decreased at higher gel concentrations. Fig.16 As shown, the best degree of CL inhibition was obtained at a luminol concentration of 1 μM. Fig.17 As shown in the figure, when the UV irradiation time is 1 to 2 minutes, the CL inhibition effect is relatively stable, and when the UV irradiation time exceeds 1 minute, the inhibition effect gradually weakens. Therefore, the optimal pH value is 11, the gel concentration is 4 mg / L, the luminol concentration is 1 μM, and the UV irradiation time is 1 minute.
[0083] Then, under the optimal test conditions, a linear relationship between the relative intensity of chemiluminescence and the concentration of TPHP was established, and the process was as follows: 800 μL of water was placed in a photoreactor, TPHP solution and gel solution (gel concentration was 4 mg / L) were added to the photoreactor, and ultraviolet light was turned on for 1 minute to obtain a first precursor solution; 100 μL of the first precursor solution was taken to the quartz reaction dish of the BPCL-2 analyzer, the light window was closed, 300 μL of luminol buffer solution (pH was 11, luminol concentration was 1 μM) was added to the first precursor solution, and the chemiluminescence intensity I of the obtained first mixed solution was tested. Then, an equal volume of water was used to replace the solution to be tested, and the other parameters remained unchanged, and ultraviolet light was turned on to obtain a second precursor solution; luminol buffer solution was added to the second precursor solution, and the chemiluminescence intensity I0 of the obtained second mixed solution was tested.
[0084] Fig.18 The chemiluminescence intensity diagram of different concentrations of TPHP detected by UV / gel-luminol. Fig.19 This is a linear relationship diagram between the relative chemiluminescence intensity and TPHP concentration when UV / gel-luminol is used to detect TPHP.
[0085] like Figure 18-19 As shown in the figure, with the increase of TPHP concentration, the chemiluminescence signal intensity gradually weakened, and there was a good linear relationship in the range of 10-1000 μg / L. The linear regression equation of the relative chemiluminescence intensity and TPHP concentration was fitted as follows: y=-0.0005x+0.89647, and the correlation coefficient R 2 =0.99053, y is the relative chemiluminescence intensity, y=I / I0, x is the TPHP concentration in the first precursor solution. Twelve parallel measurements were performed for a TPHP solution with a concentration of 10 μg / L, and the relative standard deviation (RSD) value was 1.87%. According to the detection limit calculation method specified by IUPAC, the detection limit (LOD, 3σ) of this method was calculated to be 210 ng / L (S / N=3).
[0086] Fig. 20 This is a graph showing the selectivity of TPHP detection using UV / gel-luminol. Fig.21 This is a graph showing the anti-interference ability of UV / gel-luminol detection of TPHP.
[0087] like Fig.18 As shown, common organophosphorus flame retardants and organophosphorus pesticides were selected, including tris(2-butoxyethyl) phosphate (abbreviated as TBEP), tris(2-chloroethyl) phosphate (abbreviated as TCEP), tris(1-chloro-2-propyl) phosphate (abbreviated as TCPP), tris(1,3-dichloropropyl) phosphate (abbreviated as TDCPP), tris(2-ethylhexyl) phosphate (abbreviated as TEHP), triethyl phosphate (abbreviated as TEP), triisobutyl phosphate (abbreviated as TIBP), trimethyl phosphate (abbreviated as TMP), tri-n-butyl phosphate (abbreviated as TNBP), chlorpyrifos, cypermethrin and phoxim. At the same concentration, only TPHP has a significant inhibitory effect on the chemiluminescence of the system, while other substances have little effect on the chemiluminescence signal of the system. As Fig.19 As shown, when TPHP coexists with interfering ions, 100 times the SO4 2- 、Na + , 50 times K + , Ca 2+ Mg 2+ , Cl - , 10 times the NO3 - and 1 times HCO3 - The influence on the intensity of chemiluminescent signal is small. It can be seen that the CL analysis method for detecting TPHP established by the present invention using chemiluminescent detection materials has excellent selectivity and anti-interference ability.
[0088] Then, the practicality of UV / gel-luminol for detecting TPHP was tested as follows: lake water, tap water and PM were tested by standard addition method. 2.5 TPHP level in the extract. 2.5 The extract was from an environmental monitoring station in Chengdu, and the PM 2.5 The sample filter membrane was placed in a beaker containing acetonitrile, subjected to ultrasonication in ice water for 30 minutes, and then filtered using an organic filter membrane with a pore size of 0.45 μm to obtain PM 2.5 Extract. After pre-treating the actual water sample with a 0.22 μm filter membrane, TPHP with accurate concentration was added to the water sample, and the TPHP concentration and recovery rate were calculated according to the above linear regression equation.
[0089] As shown in Table 1, the detected concentration of TPHP in the water sample is consistent with the added concentration, and the recovery rate is 97.86-108.35%. The results show that the UV / gel-luminol based on the CL analysis method of the present invention also has good accuracy in detecting the concentration of TPHP in actual water samples.
[0090] Table 1
[0091]
[0092] The equipment used for the above characterization is as follows: XRD spectrum is obtained by X-ray diffractometer (MiniFlex 600, Rigaku Co., Ltd.); XPS spectrum is obtained by X-ray photoelectron spectroscopy analyzer (Thermo Scientific K-Alpha, Thermo Fisher Scientific Inc.); FT-IR spectrum is obtained by infrared spectrometer (Specturm 2, PerkinElmer Instrument Co., Ltd.); SEM photos are obtained by field emission electron scanning microscope (JSM 7800F Prime, JEOL Ltd.); TEM photos are obtained by transmission electron microscope (JEOL JEM-F 200 (HR), JEOL Ltd.); EPR spectrum is obtained by Bruker EMX PLUS; chemiluminescence signal is collected by BPCL ultra-weak chemiluminescence instrument; the cross-sectional diameter of the photoreactor is 24 mm, the model of the ultraviolet lamp is GGZ (Shanghai Ji Guang Special Lighting Appliance Factory), and the distance between the ultraviolet light and the liquid surface in the photoreactor is 18 cm.
[0093] The above is a description of the relevant contents of the present invention. A person skilled in the art will be able to implement the present invention based on these descriptions. Based on the above contents of the present invention, all other embodiments obtained by a person skilled in the art without creative work shall fall within the scope of protection of the present invention.
Claims
1. A chemiluminescent detection material of triphenyl phosphate, characterized in that: The XRS spectrum has characteristic peaks at 285.1eV, 532.1eV, 712.1eV, 267.1eV, 199.1eV and 57.1eV; the FT-IR spectrum has characteristic peaks at 3450cm -1 、1627cm -1 、1582cm -1 、1447cm -1 、1383cm -1 、482cm -1 and 757cm -1 There is an absorption peak at.
2. The chemiluminescent detection material of triphenyl phosphate as claimed in claim 1, characterized in that: XRD spectrum showed an amorphous structure.
3. The chemiluminescent detection material of triphenyl phosphate as claimed in claim 1, characterized in that: The XPS spectrum of Fe 2p has characteristic peaks at 711.0 eV and 724.6 eV; the XPS spectrum of C 1s has characteristic peaks at 284.80 eV, 288.85 eV and 286.39 eV; and the XPS spectrum of O 1s has characteristic peaks at 531.76 eV, 529.82 eV and 533.33 eV.
4. The method for preparing the chemiluminescent detection material of triphenyl phosphate according to any one of claims 1 to 3, characterized in that: The following steps are involved: dissolving trimesic acid and soluble iron salt in anhydrous ethanol to obtain a reaction solution; The reaction solution is subjected to high pressure solvent thermal treatment to obtain a gel material; The gel material is dried to obtain a chemiluminescent detection material of triphenyl phosphate.
5. The method for preparing the chemiluminescent detection material of triphenyl phosphate as claimed in claim 4, characterized in that: The reaction solution is prepared by adding 0.25-0.35 g of trimesic acid and 0.5-0.6 g of FeCl3·6H2O to every 10 mL of anhydrous ethanol.
6. The method for preparing the chemiluminescent detection material of triphenyl phosphate as claimed in claim 4, characterized in that: The heat treatment is carried out by keeping the temperature at 100-140° C. for 0.5-2 hours.
7. The detection method of triphenyl phosphate is characterized in that: The following steps are involved: Adding a test solution containing triphenyl phosphate and a chemiluminescent detection material solution of triphenyl phosphate according to any one of claims 1 to 3 into a photoreactor, turning on ultraviolet light irradiation to obtain a first precursor solution; adding a chemiluminescent reagent to the first precursor solution, and testing the chemiluminescent intensity I of the obtained first mixed solution; Replacing the test solution with an equal volume of water, turning on ultraviolet light irradiation, and obtaining a second precursor solution; Adding a chemiluminescent reagent to the second precursor solution, and testing the chemiluminescent intensity I0 of the resulting second mixed solution; According to the linear relationship between the relative chemiluminescence intensity and the concentration of triphenyl phosphate, the concentration of triphenyl phosphate in the solution to be tested is calculated; the relative chemiluminescence intensity = I / I0.
8. The detection method of triphenyl phosphate as claimed in claim 7, characterized in that: The concentration of the chemiluminescent detection material in the first precursor solution and the second precursor solution is 4 mg / L.
9. The detection method of triphenyl phosphate as claimed in claim 7, characterized in that: The UV irradiation time was 1 min.
10. The method for detecting triphenyl phosphate according to claim 7, wherein: The chemiluminescent reagent is a buffer solution containing luminol; the concentration of luminol in the first mixed solution and the second mixed solution is 1 μM, and the pH is 11.