A porous organic polymer material with electrochemiluminescence performance, preparation method and application

Abstract

The present invention provides a porous organic polymer material, preparation method and application with electrochemiluminescence performance, belonging to the field of electrochemiluminescence (ECL) materials and sensor technology. The present invention uses perylene 3,4,9,10 tetracarboxylic acid dianhydride and tetrakis (4-aminobenzene) ethylene as ligand raw materials, and uses solid phase synthesis to synthesize porous organic polymers with electrochemiluminescence performance, effectively quenching the induced aggregation quenching phenomenon carried by the perylene series itself. The use of solid phase synthesis avoids the use of a large amount of solvents, high pressure and other conditions in the previous solvothermal method, which is green and environmentally friendly. The porous organic polymer material prepared by the present invention has a low degree of agglomeration, which solves the problem of poor luminescence performance caused by induced aggregation quenching of the perylene series itself. Compared with perylene 3,4,9,10 tetracarboxylic acid dianhydride and tetrakis (4-aminobenzene) ethylene used alone, the luminescence performance is significantly improved, and the luminescence efficiency is 536% higher than that of ruthenium bipyridine.

Description

Technical Field

[0001] The present invention relates to the field of electrochemiluminescence (ECL) materials and sensing technologies, and particularly to a porous organic polymer material with electrochemiluminescence performance, a preparation method and applications thereof. Background Art

[0002] Electrochemiluminescence is that under certain voltage conditions, electroactive substances on the electrode surface or in the solution form excited states through electron transfer, and emit light while the excited states return to the ground state. Electrochemiluminescence includes an electrochemical reaction process and a chemiluminescence process, and can generate two signals, namely an electrical signal and a luminescence intensity, during the detection process. Compared with traditional electrochemical detection, electrochemiluminescence has advantages such as rich parameter adjustment and multiple amplification levels. Compared with photoluminescence, electrochemiluminescence does not require the participation of an external light source during the detection process, simplifies the equipment, effectively avoids errors caused by background signals, and has higher sensitivity and selectivity. Compared with traditional chemiluminescence, electrochemiluminescence obtains the energy required to reach the excited state by an external voltage, making it have a higher luminescence intensity. In addition, the reaction site of ECL is fixed on the electrode surface, the luminescence points are concentrated, and it has high sensitivity and precision. At the same time, along with the repetition of the voltage, the luminescence process can be cycled.

[0003] The Tang Benzhong research group officially proposed the concept of "aggregation-induced emission (AIE)" in 2001. Materials with AIE performance show no emission or weak emission in their good solvents, and aggregation-induced emission will occur when the amount of their poor solvents gradually increases. This performance is opposite to the phenomenon that most organic groups are quenched in aggregation, and it is also based on the aggregation luminescence performance of AIE materials that AIE materials are applied to various luminescence sensor fields.

[0004] Compared with small-molecular-weight materials with AIE properties, AIE polymers have great potential for practical applications in processability, functionalization, and thermal stability. Porous organic polymers (POPs) are a class of organic porous materials with micropores or mesopores, generally composed of elements such as C, H, O, N, and B. Porous organic polymers are applied to various scientific field explorations due to their high stability, high modularity, easy access to structural units, and fixed porosity.

[0005] Perylene-based compounds have high quantum yields and high chemical stabilities, but due to the self-induced aggregation quenching of perylene-based compounds, the luminescence performance of perylene-based compounds is poor. Therefore, how to quench the self-induced aggregation quenching phenomenon of perylene-based compounds is of great significance for improving the luminescence performance of perylene-based compounds. Summary of the Invention

[0006] The object of the present invention is to provide a porous organic polymer material with electrochemiluminescence performance, a preparation method and an application, which can solve the problem of poor luminescence performance caused by aggregation-induced quenching of perylene-based compounds themselves.

[0007] In order to achieve the above object of the invention, the present invention provides the following technical solutions:

[0008] The present invention provides a porous organic polymer material with electrochemiluminescence performance, and the porous organic polymer material with electrochemiluminescence performance is prepared from perylene-3,4,9,10-tetracarboxylic dianhydride and tetra-(4-aminophenyl)ethylene according to a mass ratio of 1-2:1-2.

[0009] The present invention also provides a preparation method of a porous organic polymer material with electrochemiluminescence performance, including the following steps:

[0010] (1) After perylene-3,4,9,10-tetracarboxylic dianhydride and tetra-(4-aminophenyl)ethylene are ground and mixed sufficiently, they are dissolved in a solvent to obtain a mixed system;

[0011] (2) The mixed system is calcined at a high temperature to obtain a porous organic polymer material.

[0012] Preferably, in step (1), the grinding time is 20-60 min; the solvent is dichloromethane, acetone, methanol, carbon tetrachloride.

[0013] Preferably, in step (1), the grinding time is 30 min; the solvent is dichloromethane

[0014] Preferably, in step (1), the concentration of the mixed system is 0.75 mg / mL - 5.0 mg / mL.

[0015] Preferably, in step (1), the concentration of the mixed system is 1 mg / mL.

[0016] Preferably, in step (2), the high-temperature calcination temperature is 300-350 °C, and the high-temperature calcination time is 3-5 h.

[0017] Preferably, in step (2), the high-temperature calcination temperature is 325 °C, and the high-temperature calcination time is 4 h.

[0018] The present invention also provides an application of the porous organic polymer material with electrochemiluminescence performance described in claim 1 or the porous organic polymer material with electrochemiluminescence performance prepared by the preparation method of the porous organic polymer material with electrochemiluminescence performance in the preparation of an electrochemiluminescence sensor.

[0019] The porous organic polymer material with electrochemiluminescence performance described in the present invention has the following beneficial effects compared with the prior art:

[0020] (1) The present invention selects perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) which is low in price, has high quantum yield and high chemical stability, and tetrakis(4-aminophenyl)ethene (ETTA) with a "propeller" structure as ligand raw materials, and uses a solid phase synthesis method to synthesize a porous organic polymer with electrochemiluminescence properties. The introduction of tetrakis(4-aminophenyl)ethene effectively quenches the aggregation-induced quenching (ACQ) phenomenon of the perylene series itself. The use of the solid phase synthesis method avoids the use of a large amount of solvents, high pressure and other conditions in the previous solvothermal method, and provides a new environmentally friendly synthesis method for the synthesis of AIE-type porous organic polymers, which is simple to operate and green and environmentally friendly.

[0021] (2) The porous organic polymer material prepared by the present invention has a low degree of agglomeration, which solves the problem of poor luminescence performance caused by induced aggregation quenching of the perylene series. Compared with the use of perylene-3,4,9,10-tetracarboxylic dianhydride and tetrakis-(4-aminophenyl)ethylene alone, the luminescence performance is significantly improved, and the luminescence efficiency is 536% higher than that of bipyridine ruthenium. BRIEF DESCRIPTION OF THE DRAWINGS

[0022] In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings required for use in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying creative labor.

[0023] Figure 1 The synthesis route of porous organic polymer materials with electrochemiluminescence performance in this application;

[0024] Figure 2 : are SEM images of Examples 1-4; wherein A is a SEM image of Example 1 at 20 μm, B is a SEM image of Example 2 at 20 μm, C is a SEM image of Example 3 at 20 μm, and D is a SEM image of Example 4 at 20 μm; E is a SEM image of Example 1 at 300 nm; F is a SEM image of Example 2 at 300 nm; G is a SEM image of Example 3 at 300 nm; and H is a SEM image of Example 4 at 300 nm;

[0025] Figure 3TEM images of Examples 1-4; where A is Example 1, B is Example 2, C is Example 3, and D is Example 4;

[0026] Figure 4 XRD patterns of Examples 1-4;

[0027] Figure 5 Pore size distribution and N 2 adsorption-desorption isotherm of Example 1; where A is the pore size distribution of Example 1, and B is the N 2 adsorption-desorption isotherm of Example 1; C is the pore size distribution of Example 2, and D is the N 2 adsorption-desorption isotherm of Example 2; E is the pore size distribution of Example 3, and F is the N 2 adsorption-desorption isotherm of Example 3; G is the pore size distribution of Example 4, and H is the N 2 adsorption-desorption isotherm of Example 4;

[0028] Figure 6 Fluorescence lifetime characterization of Examples 1-4; where A is Example 1, B is Example 2, C is Example 3, and D is Example 4;

[0029] Figure 7 Solid UV and diffuse reflectance spectroscopy characterization of Examples 1-4; where A is Example 1, B is Example 2, C is Example 3, and D is Example 4;

[0030] Figure 8 Infrared spectroscopy characterization of Example 2;

[0031] Figure 9 XPS characterization of Example 2;

[0032] Figure 10 ECL intensity characterization in Test Example 1;

[0033] Figure 11 CV curve characterization of Example 2, PTCDA, ETTA, and bare electrode (Bare GCE) in Test Example 2;

[0034] Figure 12 ECL intensity characterization of Example 2, PTCDA, ETTA, and bare electrode in Test Example 2;

[0035] Figure 13 ECL comparison between Example 2 and ruthenium bipyridine in Test Example 3. Detailed implementation manners

[0036] Embodiments of the present invention will be described in detail below. These embodiments are intended to explain the present invention and should not be construed as limiting the present invention. For those without specific technical or conditions noted in the embodiments, the techniques or conditions described in the literature in this field or according to the product specifications are followed. For reagents or instruments without the manufacturer noted, they are all conventional products that can be obtained through commercial purchases.

[0037] The present invention uses perylene-3,4,9,10-tetracarboxylic dianhydride (PTCDA) and tetra-(4-aminophenyl)ethylene (ETTA) to synthesize a porous organic polymer material (PTC-ETTA-POP) with electrochemiluminescence performance through a solid-phase synthesis method. The synthesis route is as Figure 1 shown.

[0038] Example 1

[0039] In Example 1 of the present invention, a porous organic polymer material with electrochemiluminescence performance was prepared. The specific preparation method is as follows:

[0040] (1) Weigh equal masses of perylene-3,4,9,10-tetracarboxylic dianhydride and tetra-(4-aminophenyl)ethylene respectively. After mixing evenly, grind for 30 min, and then ultrasonically dissolve in a certain volume of dichloromethane to obtain a mixed system with a concentration of 0.75 mg / mL for each ligand.

[0041] (2) Take the mixed system in step (1), drop it onto a glass slide to form a liquid film about 1 mm thick, and calcine at 325 °C in air for 4 h to obtain a porous organic polymer material with electrochemiluminescence performance.

[0042] The porous organic polymer material with electrochemiluminescence performance was characterized by SEM, TEM, XRD, solid-state UV and diffuse reflection spectroscopy; its pore size and specific surface area were further detected by nitrogen adsorption-desorption tests; then its fluorescence lifetime and quantum yield were detected. The results are shown in Figure 2-7 .

[0043] From Figure 2 A and E in, it can be seen from the SEM characterization that the aggregation degree of the porous organic polymer material in Example 1 is relatively low.

[0044] From Figure 3 A in, it can be obtained from the TEM characterization that the lattice spacing of the porous organic polymer material in Example 1 is 0.34 nm.

[0045] From Figure 4 A in, it can be obtained from the XRD characterization that the peak positions of the porous organic polymer material in Example 1 are 8.9°, 12.4°, 24.89°, and 27.47°.

[0046] From Figure 5As can be seen from A and B, through nitrogen adsorption-desorption tests, the pore size of the porous organic polymer material of Example 1 is mainly distributed in the range of 25-40 nm, and its specific surface area is 15.8 m 2 g -1 .

[0047] From Figure 6 A, through fluorescence lifetime tests, the fluorescence lifetime of the porous organic polymer material of Example 1 is 4.98 ns. The quantum yield of the porous organic polymer material in aqueous solution is 1.3%.

[0048] From Figure 7 A, through solid-state UV and diffuse reflectance spectroscopy characterization, the band gap energy of the porous organic polymer material of Example 1 is 1.32 eV.

[0049] Example 2

[0050] In Example 2 of the present invention, the method of Example 1 was adopted to prepare a porous organic polymer material with electrochemiluminescence performance. The difference from Example 1 is that the concentration of a single ligand in Example 2 is 1 mg / mL. Infrared spectroscopy characterization and XPS characterization were also carried out on the porous organic polymer material with electrochemiluminescence performance of Example 2, and the results are shown in Figure 2-9 .

[0051] From Figure 2 B and F, through SEM characterization, it can be seen that the degree of agglomeration of the porous organic polymer material of Example 2 is moderate.

[0052] From Figure 3 B, through TEM characterization, the lattice spacing of the porous organic polymer material of Example 2 is 0.35 nm.

[0053] From Figure 4 B, through XRD characterization, the peak positions of the porous organic polymer material of Example 2 are 8.9°, 12.4°, 24.89°, and 27.47°.

[0054] From Figure 5 C and D, through nitrogen adsorption-desorption tests, the pore size of the porous organic polymer material of Example 2 is mainly distributed in the range of 25-40 nm, and its specific surface area is 28.5 m 2 g -1 .

[0055] From Figure 6 B, through fluorescence lifetime tests, the fluorescence lifetime of the porous organic polymer material of Example 1 is 5.07 ns. The quantum yield of the porous organic polymer material in aqueous solution is 38%.

[0056] From Figure 7As can be seen from B in the figure, through solid ultraviolet and diffuse reflection spectroscopy characterization, the band gap energy of the porous organic polymer material in Example 1 is 1.29 eV.

[0057] From Figure 8 it can be seen that through infrared spectroscopy characterization, the absorption peaks of perylene-3,4,9,10-tetracarboxylic dianhydride at 1773 cm -1 and 1580 cm -1 are the symmetric and asymmetric vibration peaks of the carbonyl group and the peaks generated when the carbonyl group is conjugated with the benzene ring. The absorption peak of tetra-(4-aminophenyl)ethylene at 3360 cm -1 appears and belongs to -NH 2 in its structure. On the absorption curve of the porous organic polymer, the retention of the characteristic peaks at 3360 cm -1 , 1775 cm -1 and the appearance of the stretching vibration peak of the -C-N-C- bond at 1300 cm -1 indicate the appearance of the imide bond, proving that -NH 2 reacts with the carbonyl group.

[0058] From Figure 9 it can be seen that through X-ray photoelectron spectroscopy (XPS) characterization, a C-N-C peak at 399.58 eV and an N-H peak at 403.68 eV are obtained. A C=O peak at 531.53 eV and an -OH peak at 533.38 eV are obtained. A C-C / C=C peak at 283.68, a C-N peak at 285.38, and a C=O peak at 287.48 eV are obtained.

[0059] Example 3

[0060] In Example 3 of the present invention, the method of Example 1 was adopted to prepare a porous organic polymer material with electrochemiluminescence performance. The difference from Example 1 is that the concentration of a single ligand in Example 3 is 2 mg / mL. The porous organic polymer material with electrochemiluminescence performance prepared in Example 3 was characterized, and the results are as Figure 2-7 shown.

[0061] From Figure 2 C and G in the figure, it can be seen through SEM characterization that the aggregation degree of the porous organic polymer material in Example 3 is relatively high.

[0062] From Figure 3 C in the figure, it can be seen through TEM characterization that the lattice spacing of the porous organic polymer material in Example 3 is 0.25 nm.

[0063] From Figure 4 C in the figure, it can be seen through XRD characterization that the peak positions of the porous organic polymer material in Example 3 are 8.9°, 12.4°, 24.89°, and 27.47°.

[0064] From Figure 5 E and F in [reference], it can be seen that through nitrogen adsorption - desorption test, the pore size distribution range of the porous organic polymer material in Example 3 is relatively large and not concentrated, and its specific surface area is 8.37 m 2 g -1 .

[0065] From Figure 6 C in [reference], it can be seen that through fluorescence lifetime test, the fluorescence lifetime of the porous organic polymer material in Example 3 is 4.47 ns. The quantum yield of the porous organic polymer material in aqueous solution is 35%.

[0066] From Figure 7 C in [reference], it can be seen that through solid - state UV and diffuse reflectance spectroscopy characterization, the band - gap energy of the porous organic polymer material in Example 3 is 1.39 eV.

[0067] Example 4

[0068] In Example 4 of the present invention, the method of Example 1 was adopted to prepare a porous organic polymer material with electrochemiluminescence performance. The difference from Example 1 is that the concentration of a single ligand in Example 4 is 5 mg / mL. And the porous organic polymer material with electrochemiluminescence performance prepared in Example 4 was characterized, and the results are as Figure 2-7 shown.

[0069] From Figure 2 D and H in [reference], it can be seen that through SEM characterization, the agglomeration degree of the porous organic polymer material in Example 4 is relatively serious.

[0070] From Figure 3 D in [reference], it can be seen that through TEM characterization, the lattice spacing of the porous organic polymer material in Example 4 is 0.37 nm.

[0071] From Figure 4 D in [reference], it can be seen that through XRD characterization, the peak positions of the porous organic polymer material in Example 4 are 8.9°, 12.4°, 24.89°, 27.47°.

[0072] From Figure 5 G and H in [reference], it can be seen that through nitrogen adsorption - desorption test, the pore size distribution range of the porous organic polymer material in Example 4 is relatively large and not concentrated, and its specific surface area is 11.7 m 2 g -1 .

[0073] From Figure 6 D in [reference], it can be seen that through fluorescence lifetime test, the fluorescence lifetime of the porous organic polymer material in Example 4 is 4.47 ns. The quantum yield of the porous organic polymer material in aqueous solution is 35%.

[0074] From Figure 7As can be seen from the solid-state UV and diffuse reflectance spectra, the band gap energy of the porous organic polymer material of Example 4 is 1.39 eV.

[0075] Test Example 1

[0076] In Test Example 1 of the present invention, the electrochemiluminescence intensities of the porous organic polymer materials prepared in Examples 1 to 4 were measured. The specific operation steps are as follows:

[0077] (1) Take a bare glassy carbon electrode, polish it with aluminum powder, then ultrasonically clean it with distilled water and ethanol, and dry it with nitrogen.

[0078] (2) Respectively take 1 mg of the porous organic polymer materials prepared in Examples 1 to 4 and disperse them in 6 mL of Nafion solution to obtain a dispersion. Take 10 μL of the dispersion and drop it onto the surface of the glassy carbon electrode, and let it stand to dry to serve as the working electrode. Another 0.1 M PBS (pH 7.4) containing 0.1 M 2 S 2 O 8 is used as the co-reaction solvent. A saturated Ag / AgCl electrode is used as the reference electrode, and a platinum wire electrode is used as the counter electrode to construct a three-electrode system with the working electrode prepared above. Place the three-electrode system in the co-reaction solvent, and use cyclic voltammetry to test the electrochemiluminescence signal ECL to detect the electrochemiluminescence intensity. The results are as Figure 10 shown.

[0079] Figure 10 It shows that the porous organic polymer materials prepared in Examples 1 to 4 all have good electrochemiluminescence properties, and among them, the porous organic polymer material with a concentration of 1 mg / mL in Example 2 has the most excellent electrochemiluminescence properties.

[0080] Test Example 2

[0081] In Test Example 2 of the present invention, working electrodes respectively carrying perylene-3,4,9,10-tetracarboxylic dianhydride and tetra-(4-aminophenyl)ethylene prepared by the method of Test Example 1 were used. Taking the above two electrodes as controls, the CV curves of the working electrode prepared using the porous organic polymer material of Example 2 in Test Example 1 were detected by the same method as in Test Example 1, and the electrochemiluminescence signal was tested. The results are as Figure 11 、 12 shown.

[0082] Figure 11 It shows that through CV detection, it is found that there are similar peak potentials between the perylene-3,4,9,10-tetracarboxylic dianhydride and tetra-(4-aminophenyl)ethylene polymers and the two ligands.

[0083] Figure 12It is shown that through ECL tests, it is found that the working electrodes modified with different materials have significantly different ECL signal response intensities. Among them, the ECL emission intensity of the porous organic polymer material in Example 2 is significantly higher than that of a single ligand.

[0084] The test parameters for ECL are a potential range of -1.6 to 0 V, a photomultiplier voltage of 600 V, and a voltage sweep rate of 100 mV / s.

[0085] Test Example 3

[0086] In Test Example 3 of the present invention, a 1 mM ruthenium tris(bipyridine) solution was used, and the method of Test Example 1 was adopted to prepare a working electrode as a control. Using the same method as in Test Example 1, the working electrode prepared from the porous organic polymer material of Example 2 in Test Example 1 was subjected to ELC detection, and the results are as Figure 13 shown.

[0087] Since the absolute ECL efficiency of the luminescent body is not easy to measure, the relative ECL efficiency is usually used instead.

[0088] The following formula is used for calculation:

[0089]

[0090] where is the ECL efficiency of Ru(bpy) 3 2+ (1 mM), with the value in 0.1 M K 2 S 2 O 8 of 0.1 M PBS (pH 7.4) as the standard, set at 100%, I is the ECL intensity, i is the current value, and x is the sample.

[0091] As Figure 13 shown, the luminescence intensity of the electrochemiluminescent material provided by the present invention is 7.6 times that of ruthenium bipyridine under the same experimental conditions, and the luminescence efficiency is 536% of that of ruthenium tris(bipyridine) under the same experimental conditions. The test potential range for ECL is -1.6 to 0 V, the photomultiplier voltage is 600 V, and the voltage sweep rate is 100 mV / s.

[0092] The above are only the preferred embodiments of the present invention. It should be noted that for those of ordinary skill in the art, without departing from the principle of the present invention, several improvements and refinements can be made, and these improvements and refinements should also be regarded as the protection scope of the present invention.

Claims

1. A porous organic polymer material having electrochemiluminescence properties, characterized in that: The porous organic polymer material with electrochemiluminescent properties is prepared from perylene-3,4,9,10-tetracarboxylic dianhydride and tetrakis-(4-aminophenyl)ethylene in a mass ratio of 1:

1. The structure of the porous organic polymer material with electrochemiluminescent properties is shown in Formula I:

2. A method for preparing a porous organic polymer material having electrochemiluminescence properties as claimed in claim 1, characterized in that: The steps include: (1) grinding and mixing perylene-3,4,9,10-tetracarboxylic dianhydride and tetrakis-(4-aminophenyl)ethylene sufficiently, and dissolving them in a solvent to obtain a mixed system; (2) The mixed system is calcined at high temperature to obtain a porous organic polymer material.

3. The method for preparing a porous organic polymer material having electrochemiluminescence properties according to claim 2, characterized in that: In step (1), the grinding time is 20 to 60 minutes; and the solvent is one of dichloromethane, acetone, methanol and carbon tetrachloride.

4. The method for preparing a porous organic polymer material having electrochemiluminescence properties according to claim 3, characterized in that: In step (1), the grinding time is 30 min; and the solvent is dichloromethane.

5. The method for preparing a porous organic polymer material having electrochemiluminescence properties according to claim 2, characterized in that: In step (1), the concentration of the mixed system is 0.75 mg / mL to 5.0 mg / mL.

6. The method for preparing a porous organic polymer material having electrochemiluminescence properties according to claim 5, characterized in that: In step (1), the concentration of the mixed system is 1 mg / mL.

7. The method for preparing a porous organic polymer material having electrochemiluminescence properties according to claim 2, characterized in that: In step (2), the high temperature calcination temperature is 300-350° C., and the high temperature calcination time is 3-5 hours.

8. The method for preparing a porous organic polymer material having electrochemiluminescence properties according to claim 7, characterized in that: In step (2), the high temperature calcination temperature is 325° C., and the high temperature calcination time is 4 hours.

9. Use of the porous organic polymer material with electrochemiluminescence performance according to claim 1 or the porous organic polymer material with electrochemiluminescence performance prepared by the preparation method of the porous organic polymer material with electrochemiluminescence performance according to any one of claims 2 to 8 in preparing an electrochemiluminescence sensor.

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