Preparation method and application of CuI-MCOF sensitive material based on dia topological structure

Abstract

The invention discloses a preparation method and application of a Cu4I4-MCOF sensitive material based on a dia topological structure. The preparation method comprises the following steps: adding copper iodide powder and pyridine to an organic solvent to obtain Cu4I4(py)4 powder after reaction; dispersing the Cu4I4(py)4 powder in the organic solvent, then adding tri(m-tolyl)phosphine to obtain Cu4I4(P-(m-Tol)3)4 powder after reaction; dispersing the Cu4I4(P-(m-Tol)3)4 powder in water, then adding 4-formylpyridine, stirring at room temperature, and obtaining Cu4I4(py-CHO)4 powder after reaction; mixing the Cu4I4(py-CHO)4 powder and p-phenylenediamine in a mixed solution, emulsifying to obtain a uniform dispersion, and subjecting the mixture to multiple vacuum freeze-thaw degassing cycles, vacuum sealing, heating, centrifuging, washing, and drying to obtain the Cu4I4-MCOF sensitive material. The CuI-MCOF sensitive material obtained in the present invention was prepared into a chemiresistive HF gas sensor, which exhibited ppb-level ultra-sensitive HF gas capability at room temperature and showed excellent cross-response anti-interference ability in 13 mixed gases including HF.

Description

Technical Field

[0001] The present invention relates to the field of gas detection technology, and in particular to a preparation method and application of a CuI-MCOF sensitive material based on a dia topological structure. Background Art

[0002] Hydrofluoric acid (HF), an essential etchant and key chemical raw material, is widely used in industries such as semiconductor processing, lens surface processing, chemical raw materials, and biopharmaceuticals. However, HF is highly volatile and rapidly escapes from solvents at temperatures as low as 19°C. It can cause severe irritation and corrosion to human skin, eyes, respiratory tract, and digestive tract mucosa, potentially causing permanent damage. The permissible exposure limit for HF is only 3 ppm, with a short-term exposure limit of 6 ppm.

[0003] The analytical methods currently used to measure hydrofluoric acid in industrial environments mainly include spectrometry, potentiometry, and electrochemistry. However, these methods often require expensive and bulky instruments and equipment. In addition, the hydrofluoric acid gas sensors that have been reported so far generally have problems such as slow response speed, low sensitivity, and insufficient minimum detection line.

[0004] Chemiresistive gas sensors are ideal for detecting hydrogen fluoride (HF) due to their simple structure, wide availability of materials, ease of integration, miniaturization, and convenient online monitoring. However, there are currently few reports on semiconductor chemiresistive gas sensors for HF detection, and no highly responsive materials with excellent hydrofluoric acid selectivity and cross-sensitivity have been found.

[0005] Therefore, there is an urgent need for a sensitive material with high sensitivity and selectivity to hydrofluoric acid that can be used in a chemiresistive gas sensor. Summary of the Invention

[0006] The present invention aims to provide a method for preparing and applying a CuI-MCOF sensitive material based on a dia topology to address the aforementioned lack of corresponding sensitive materials for detecting hydrogen fluoride using chemiresistive gas sensors. Using tetraaldehyde-modified Cu4I4(py-CHO)4 clusters and p-phenylenediamine as precursors, the present invention successfully prepared a three-dimensional five-fold cluster-based COF material with a dia topology via a Schiff base reaction. This material, named CuI-MCOF, addresses the issues of selectivity, cross-sensitivity, and high response in HF sensors.

[0007] To achieve the above objectives, the first aspect of the present invention provides a method for preparing a CuI-MCOF sensitive material based on a dia topological structure, comprising the following steps:

[0008] (1) adding copper iodide powder and pyridine to an organic solvent, heating under reflux, then cooling to room temperature, washing and drying to obtain Cu4I4(py)4 powder;

[0009] (2) dispersing Cu4I4(py)4 powder in an organic solvent, then adding tri(m-tolyl)phosphine, heating under reflux, then cooling to room temperature, washing and drying to obtain Cu4I4(P-(m-Tol)3)4 powder;

[0010] (3) Dispersing Cu4I4(P-(m-Tol)3)4 powder in water, then adding 4-formylpyridine, stirring at room temperature, and then centrifuging, washing and drying to obtain Cu4I4(py-CHO)4 powder;

[0011] (4) Cu4I4(py-CHO)4 powder and p-phenylenediamine were mixed in a mixed solution and emulsified to obtain a uniform dispersion. After multiple vacuum freeze-thaw degassing cycles, the mixture was vacuum sealed, heated, and then centrifuged, washed, and dried to obtain the CuI-MCOF sensitive material.

[0012] Preferably, in step (1), the molar ratio of copper iodide to pyridine is 1:(3-5).

[0013] Preferably, in step (1), the organic solvent is ethanol, copper iodide is dispersed in ethanol to form a first dispersion, and then pyridine is added dropwise to the first dispersion at 35-45° C., refluxed for 0.5-1.5 h, and then cooled to room temperature.

[0014] Preferably, in step (2), the molar ratio of Cu4I4(py)4 powder to tri(m-tolyl)phosphine is 1:(0.4-0.6).

[0015] Preferably, in step (2), the organic solvent is ethanol, and the Cu4I4(py)4 powder is dispersed in ethanol to form a second dispersion, and then tri(m-tolyl)phosphine is added to the second dispersion at 55-65°C, refluxed for 10-15 hours, and then cooled to room temperature.

[0016] Preferably, in step (3), the mass ratio of Cu4I4(P-(m-Tol)3)4 powder to 4-formylpyridine is 1:(1-1.5).

[0017] Preferably, in step (4), the mass ratio of Cu4I4(py-CHO)4 powder to p-phenylenediamine is 1:(1.1-1.5).

[0018] Preferably, in step (4), the mixed solution comprises 1,4-dioxane, mesitylene and acetic acid solution in a volume ratio of 8:2:1, and the concentration of the acetic acid solution is 5.5 to 6.5 mol / L;

[0019] Cu4I4(py-CHO)4 powder and p-phenylenediamine were added to a Schlenk tube, followed by the addition of the mixed solution, emulsification for 15 to 30 minutes to form a uniform dispersion, flash-frozen under liquid nitrogen vacuum conditions, and subjected to three vacuum freeze-thaw degassing cycles. The tube was vacuum-sealed and heated at 60 to 80°C for 2 to 8 days. The CuI-MCOF sensitive material was then obtained after centrifugation, washing, and drying.

[0020] A second aspect of the present invention provides an application of a CuI-MCOF sensitive material, and an application of the CuI-MCOF sensitive material in hydrogen fluoride detection.

[0021] Preferably, the CuI-MCOF sensitive material is dispersed in ethanol to obtain a third dispersion liquid, and the third dispersion liquid is dropwise applied to the interdigital electrodes using a pipette and then dried to obtain a chemiresistive gas sensor for hydrogen fluoride detection.

[0022] Therefore, the present invention adopts the above-mentioned structure, a preparation method and application of a CuI-MCOF sensitive material based on a dia topological structure, which has the following beneficial effects:

[0023] (1) The present invention introduces copper iodine clusters with the ability to adjust electronic structure into the sensitive material, thereby enhancing the dipole-dipole interaction between the framework and HF, promoting charge transfer, and improving the conversion and amplification capabilities of the sensing signal.

[0024] (2) The present invention constructs the first chemiresistive HF gas sensor using CuI-MCOF sensitive material. The CuI-MCOF sensitive material is similar to the olfactory nerve in the human nasal cavity. It achieves specificity for HF gas molecules through a selective amplification process, exhibits ppb-level ultra-sensitive HF gas detection capability at room temperature, and exhibits excellent cross-response anti-interference ability in 13 mixed gases including HF.

[0025] (3) The CuI-MCOF prepared in the present invention is used as a sensitive material for HF gas sensors, with a response value of 7188% at 100 ppm, showing excellent HF selectivity, cross-sensitivity, and high response capability, which is in line with the development concept of green environmental protection and comprehensively realizes the unity of economic benefits, social benefits, and environmental benefits.

[0026] (4) The excellent HF sensing performance of the CuI-MCOF sensitive material of the present invention not only provides a new idea for the development of a new generation of HF sensors, but also provides an important reference for the study of the structure-performance relationship of three-dimensional cluster-based COFs.

[0027] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS

[0028] Figure 1 Schematic diagram of the preparation process of CuI-MCOF sensitive materials;

[0029] Figure 2 IR spectra of CuI-MCOF, PDA and Cu4I4(py-CHO)4;

[0030] Figure 3 XRD pattern of the 5-fold interpenetrating topology model of CuI-MCOF;

[0031] Figure 4 PXRD spectra of five interpenetrating topological models of CuI-MCOF;

[0032] Figure 5 PXRD patterns of CuI-MCOF and 4-6 interpenetrating layers topology model;

[0033] Figure 6 The response of CuI-MCOF sensitive material to various 100ppm gases;

[0034] Figure 7 The responses of CuI-MCOF sensitive material to 4ppm HF and other different 100ppm acid gases;

[0035] Figure 8 Response and recovery curves of CuI-MCOF sensitive material to different concentrations of HF at room temperature (RT);

[0036] Figure 9 The response-concentration logarithmic linear fitting diagram of CuI-MCOF sensitive material;

[0037] Figure 10 Normalized response and recovery time curves of CuI-MCOF sensitive material to 2ppm HF;

[0038] Figure 11 The sensing response of CuI-MCOF sensitive material to 4ppm HF and 100ppm of 12 interfering gases;

[0039] Figure 12 The stability test of CuI-MCOF sensitive material to 4ppm HF within 90 days;

[0040] Figure 13 Comparison chart of the response time, recovery time, temperature and LOD value of CuI-MCOF sensitive material with the existing technology;

[0041] Figure 14 This is the appearance of the sensor box;

[0042] Figure 15 is the circuit diagram of the wireless HF sensor system;

[0043] Figure 16 A circuit board for a wireless HF sensor system;

[0044] Figure 17 It is a real-time HF detection chart in the air;

[0045] Figure 18 This is a real-time HF detection diagram in hydrogen fluoride gas;

[0046] Figure 19 This is the real-time HF detection diagram after removing hydrogen fluoride gas. DETAILED DESCRIPTION

[0047] The present invention will be further described below. It should be noted that this embodiment is based on the technical solution and provides a detailed implementation method and specific operation process, but the present invention is not limited to this embodiment.

[0048] Example 1

[0049] like Figure 1 As shown, a method for preparing a CuI-MCOF sensitive material based on a dia topological structure comprises the following steps:

[0050] (1) Synthesis of Cu4I4(py)4 powder

[0051] 0.19 g, 1 mmol CuI powder was dispersed in 20 ml of ethanol to obtain a first dispersion. 0.3 g of pyridine was added dropwise to the first dispersion at 40°C while stirring. The mixture was refluxed for 1 hour. After cooling to room temperature, the mixture was washed three times with ethanol by centrifugation. The white precipitate was vacuum dried at 60°C for 12 hours to obtain Cu4I4(py)4 powder.

[0052] (2) Synthesis of Cu4I4(P-(m-Tol)3)4 powder

[0053] Disperse 0.11 g, 0.1 mmol Cu4I4(py)4 powder in 20 ml of ethanol to obtain a second dispersion. Add 0.15 g of tri(m-tolyl)phosphine to the second dispersion at 60°C while stirring. Reflux for 24 hours. After cooling to room temperature, wash three times with ethanol and toluene by centrifugation. Dry the white precipitate in vacuum at 60°C for 12 hours to obtain Cu4I4(P-(m-Tol)3)4 powder.

[0054] (3) Synthesis of Cu4I4(py-CHO)4 powder

[0055] 0.04 g of Cu4I4(P-(m-Tol)3)4 nanoparticles was added to 40 ml of water to form an aqueous dispersion. Then, 0.25 mmol of 4-formylpyridine was added to the aqueous dispersion and stirred at room temperature for 24 h. The ligand-exchanged nanoparticles were collected by centrifugation, washed three times with water, and vacuum-dried at 60 °C for 12 h to obtain an orange-red powder, namely Cu4I4(py-CHO)4 powder.

[0056] (4) Synthesis of CuI-MCOF

[0057] 0.1g Cu4I4(py-CHO)4 powder and 0.12g p-phenylenediamine (PDA) were added to a 65mm long Schlenk tube, and then 2ml of a mixed solution was added. The mixed solution included 1,4-dioxane, mesitylene and 6M acetic acid in a volume ratio of 8:2:1. It was then emulsified for 20 minutes to form a uniform dispersion. The dispersion was flash-frozen under liquid nitrogen (77K) vacuum conditions, and subjected to three vacuum freeze-thaw degassing cycles. The tube was vacuum-sealed and then heated at 70°C for 4 days. The solid material was collected by centrifugation, washed with DMF, acetone and cyclohexane for more than three times, and dried naturally to obtain the product CuI-MCOF sensitive material.

[0058] Test example

[0059] (1) The sensitive materials prepared in the examples were characterized by infrared spectroscopy and XRD.

[0060] from Figure 2 It can be seen that the CuI-MCOF sensitive material has a high sensitivity in the range of 3000-3400 cm-1 relative to the reaction monomers (PDA and Cu4I4(py-CHO)4). -1 The -NH2 vibration peak in the range and at 1712cm -1 The -C=O vibration peak at 1603cm -1 A new -C=N vibration peak appeared at , indicating that an imine bond was generated in the CuI-MCOF sensitive material, confirming that the CuI-MCOF sensitive material was successfully prepared.

[0061] The model of CuI-MCOF sensitive material was simulated, optimized and refined using powder X-ray diffraction (XRD) combined with theoretical calculation structure simulation (Materials Studio and first-principles simulation package (vasp)), and the crystal structure of the material was further characterized.

[0062] from Figure 3It can be seen that the position and intensity of the diffraction peaks in the experimental PXRD pattern are consistent with the calculation results based on the five-fold independent unit interpenetrating (dia) topological structure model, where the peaks at 6.85° and 9.8° represent the (220) and (211) crystal plane structures, respectively. The unit cell parameters (I41 / AMD space group, α=β=γ=90°) matches well with the model structure (Rwp(w / obck)=7.01%, Rp=8.33%).

[0063] Since there is a possibility of geometric intercommunication between independent units, the 1-fold to 8-fold interpenetrating model of CuI-MCOF was also analyzed through theoretical structural simulation. Figure 4 and Figure 5 It can be seen that according to the matching degree between the experimental PXRD pattern and the simulation pattern, it is found that the CuI-MCOF sensitive material prepared by the present invention is indeed a five-fold interpenetrating structure, which further proves that the crystal structure of the CuI-MCOF sensitive material is a five-fold interpenetrating model, and excludes other possible interpenetrating models.

[0064] (2) Testing the hydrogen fluoride detection performance of sensitive materials

[0065] The testing process is as follows:

[0066] 10 mg of the CuI-MCOF sensitive material was dispersed in 1 ml of anhydrous ethanol solution and sonicated for 30 minutes to obtain a CuI-MCOF ethanol solution. 20 μL of the CuI-MCOF ethanol solution was then drop-coated onto the interdigitated electrodes using a pipette. The resulting electrodes were vacuum-dried at 60°C for 6 hours to obtain a sample. The sample was then tested for its sensing performance using a static testing system.

[0067] First, the above sample was placed in a 1L sealed quartz glass bottle as a sensor device (referred to as gas cylinder No. 1, and the internal environment was air). The current value of the device was monitored by CHI660e. After the current signal of the device in gas cylinder No. 1 stabilized, it was quickly transferred to a 1L plastic bottle containing a certain concentration of HF (referred to as gas cylinder No. 2, and the liquid volume of HF with a certain concentration was calculated according to the liquid gas distribution formula, added to bottle No. 2, heated to completely evaporate HF into a gaseous state, and the test was started after cooling to room temperature). After the current of the device in gas cylinder No. 2 also reached a sufficiently high and stable value, the sensor was quickly transferred back to gas cylinder No. 1. In addition, during the gas test, the two bottles were cleaned by continuously vacuuming the gas cylinders for 2 minutes. The sensor bias was 3V, and the current was recorded using the CHI660e electrochemical workstation. Responsivity (R) is used to evaluate the effect of HF on the response, and the calculation formula is:

[0068] R=ΔI / I0,

[0069] Where I0 is the current in air and ΔI represents the change in current in the circuit after exposure to the analyte gas.

[0070] This study investigated the sensing performance of the CuI-MCOF sensitive material by depositing sensitive material samples onto interdigitated electrodes using a drop coating method. Gas selectivity is a key metric for evaluating gas sensors, and the device's gas sensitivity was screened using eight representative gases (NH3, NO2, CO2, toluene, ethanol, acetone, and HF) at 100 ppm.

[0071] like Figure 6 As shown in Figure 2, the CuI-MCOF sensitive material has a response value of 7188% in a 100ppm HF atmosphere at room temperature, while there is almost no response value to other gases. In order to further verify the specific response of the CuI-MCOF sensitive material to HF, gas sensing tests were carried out on other different types of organic acids and inorganic acids. Figure 7 It can be seen that when tested under different acidic atmospheres, the response value of the CuI-MCOF sensitive material to HF is significantly higher than that of other acidic atmospheres. Even at 4 ppm, its HF response value is still 6 times that of 100 ppm HCl and 290 times that of HCOOH.

[0072] from Figure 8 As can be seen from the figure, the CuI-MCOF sensitive material exhibits concentration-dependent characteristics and high response / recovery properties in a wide HF atmosphere concentration range (100 ppb-100 ppm). In particular, even in a low HF concentration atmosphere (100 ppb), a 5% response value is still achieved, far below the detection limit of HF leaks for environmental monitoring (3 ppm). This demonstrates the good sensitivity and potential application prospects of the CuI-MCOF sensitive material in low-concentration HF detection.

[0073] from Figure 9 It can be seen that the response-concentration logarithmic linear fitting diagram of CuI-MCOF sensitive material shows a good linear relationship (R 2 =0.99831), and the calculated LOD was 11 ppb, which is the lowest among the reported HF-sensitive materials.

[0074] CuI-MCOF sensitive materials exhibit high response / recovery performance in a wide range of HF concentrations. Figure 10 It can be seen that the response and recovery times in 2ppm HF atmosphere are 4s and 2s respectively. This fast response and recovery time is very beneficial to improving the real-time response of the sensor.

[0075] Under working conditions, the target gas to be detected coexists with other interfering gases in the air, and the ambient humidity also changes in real time. Therefore, anti-interference ability is an important indicator for evaluating the performance of sensing materials. In order to evaluate the reliable selective sensing of HF gas by CuI-MCOF sensitive materials in an interfering environment, 12 interfering gases (NO2, CO2, etc.) were mixed with HF to form a mixed atmosphere. The concentration of the interfering gas was 25 times that of HF. The gas sensing test of CuI-MCOF sensitive materials was carried out at room temperature. Figure 11 It can be seen that after 12 common cross-sensitive gases such as acetic acid were mixed with HF, no significant change in response was observed, indicating that the CuI-MCOF sensitive material prepared by the present invention has good resistance to interference from other gases after being prepared into a sensor. Figure 11 It can also be seen that after mixing 13 gases including HF, the response values ​​detected in four consecutive cycles are all 290%, indicating that even if multiple gases are mixed with hydrogen fluoride at the same time, there is basically no effect on the response of hydrogen fluoride, and the results do not change significantly, which shows that the CuI-MCOF sensitive material has excellent anti-interference ability.

[0076] from Figure 12 It can be seen that in the long-term cycling stability test (measured every 10 days), the CuI-MCOF sensitive material exhibited excellent long-term cycling stability within 90 days, which may be attributed to the stable covalent bond connection in the CuI-MCOF sensitive material framework.

[0077] Taking into account the test temperature, response time, recovery time and LOD value, Figure 13 It can be seen that compared with the prior art, the CuI-MCOF sensitive material prepared in the present invention is the best HF gas sensor, far surpassing other types of HF sensors reported.

[0078] Other prior arts reported in the literature are as follows:

[0079] [1] Devadhasan, JP; Kim, D.; Lee, DY; Kim, S. Smartphone coupled handheld array reader for real-time toxic gas detection. Analytica Chimica Acta, 2017, 984, 168-176.

[0080] [2]Lu,Y.S.;Vijayakumar,S.;Chaix,A.;Pimentel,B,P.;Bentz,K.C.;Li,S.;Chan,A.;Wahl,C.;Ha,J.S.;Hunka,D.E.;Boss,G.R.;Cohen,S.M.;Sailor,M.J.RemoteDetection of HCN,HF,and Nerve Agent Vapors Based onSelf-Referencing,Dye-Impregnated Porous Silicon Photonic Crystals.ACSSensors,2021,6,418-428.

[0081] [3]Hoke,S.H.Hydrogen fluoride analyzer for gases andaerosols.AnalyticaChimicaActa,2002,460,219-225.

[0082] [4]Meulendyk,B.J.;Wheeler,M.C.;Cunha,M.P.D.Hydrogen FluorideGasDetection Mechanism on Quartz Using SAW Sensors.IEEE Sensors Journal,2011,11,1768-1775.

[0083] [5]Wu,M.;Ma,Z.;Fan,Y.;Wu,Y.;An,Z.;Zhao,H.;Liu,Y.;Xu,J.MaterialsDesign,Sensing Performance and Mechanism of Anhydrous Hydrogen Fluoride GasSensor Based on Amino-Functionalized MIL-101(Cr)for New EnergyVehicles.Coatings 2022,12,260-273.

[0084] [6] S.;Zelinger,Z.; V.; Dorogan, A.; Ferus, M.; Iakovlev, V.; Sirbu A.; Mereuta, A.; Caliman, A.; Suruceanu, G.; Kapon, E.

[0085] [7] Appelhans, LN; Finnegan, PS; Massey, LT; Luk, TS; Rodriguez, MA; Brumbach, MT; McKenzie, B.; Craven, J. Transformation of amorphous TiO2

[0086] to a hydronium oxofluorotitanate and applications as an HFsensor.SensorsandActuatorsB Chemical,2016,228,117-123.

[0087] In order to demonstrate the effectiveness of CuI-MCOF-based HF sensors in practical applications, a portable wireless HF sensor system was designed on a printed circuit board. The detailed circuit board design is shown in the figure. Figure 15-16 As shown. Figure 14-16 As shown, the sensor box (8*6*8cm) consists of a power module, a sensor module, a microcontroller stm32c8t6, ​​and a wireless data transmission module (low-power Bluetooth unit). The Bluetooth unit supports wireless connection between the sensor module and the computer, and displays the concentration and safety level of HF. For practical applications, a static test method is used to simulate the real environment of the sensor equipment test, and the voltage threshold for the first alarm light to light up is set to 0.1V, corresponding to an HF concentration of 1ppm, and the voltage threshold for the alarm buzzer to sound is 0.1V. The second light is 0.2V, corresponding to an HF concentration of 3ppm, and the third light is 0.3V, corresponding to an HF concentration of 5ppm. A syringe is used to create a certain concentration of HF environment, and the response / recovery time of the sensor is only 1 second and 1.4 seconds. The sensor system is used for real-time HF detection ( Figure 17-19) and transmitted it to the computer in real time via wireless Bluetooth protocol, showing the dynamic response and recovery of HF sensing. All these results indicate that the designed sensor can effectively perform the task of environmental monitoring, especially HF selective detection.

[0088] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention rather than to limit the same. Although the present invention has been described in detail with reference to the preferred embodiments, those skilled in the art should understand that they can still modify or replace the technical solutions of the present invention with equivalents, and these modifications or equivalent replacements cannot cause the modified technical solutions to deviate from the spirit and scope of the technical solutions of the present invention.

Claims

1. A method for preparing a CuI-MCOF sensitive material based on a dia topological structure, characterized by: The following steps are involved: (1) Copper iodide powder and pyridine are added to an organic solvent, heated to reflux, then cooled to room temperature, washed and dried to obtain Cu4I4(py)4 powder; (2) Dispersing Cu4I4(py)4 powder in an organic solvent, then adding tri(m-tolyl)phosphine, heating to reflux, then cooling to room temperature, washing and drying to obtain Cu4I4(P-(m-Tol)3)4 powder; (3) Dispersing Cu4I4(P-(m-Tol)3)4 powder in water, then adding 4-formylpyridine, stirring at room temperature, and then centrifuging, washing and drying to obtain Cu4I4(py-CHO)4 powder; (4) Cu4I4(py-CHO)4 powder and p-phenylenediamine were mixed in a mixed solution and emulsified to obtain a uniform dispersion. After multiple vacuum freeze-thaw degassing cycles, the mixture was vacuum sealed, heated, and then centrifuged, washed, and dried to obtain the CuI-MCOF sensitive material.

2. The method for preparing a CuI-MCOF sensitive material based on a dia topological structure according to claim 1, characterized in that: In step (1), the molar ratio of copper iodide to pyridine is 1:(3-5).

3. The method for preparing a CuI-MCOF sensitive material based on a dia topological structure according to claim 1, characterized in that: In step (1), the organic solvent is ethanol, copper iodide is dispersed in ethanol to form a first dispersion, and then pyridine is added dropwise to the first dispersion at 35-45° C., refluxed for 0.5-1.5 h, and then cooled to room temperature.

4. The method for preparing a CuI-MCOF sensitive material based on a dia topological structure according to claim 1, characterized in that: In step (2), the molar ratio of Cu4I4(py)4 powder to tri(m-tolyl)phosphine is 1:(0.4-0.6).

5. The method for preparing a CuI-MCOF sensitive material based on a dia topological structure according to claim 1, characterized in that: In step (2), the organic solvent is ethanol, and the Cu4I4(py)4 powder is dispersed in ethanol to form a second dispersion. Then, tri(m-tolyl)phosphine is added to the second dispersion at 55-65°C, refluxed for 10-15 hours, and then cooled to room temperature.

6. The method for preparing a CuI-MCOF sensitive material based on a dia topological structure according to claim 1, characterized in that: In step (3), the mass ratio of Cu4I4(P-(m-Tol)3)4 powder and 4-formylpyridine is 1:(1~1.5).

7. The method for preparing a CuI-MCOF sensitive material based on a dia topological structure according to claim 1, characterized in that: In step (4), the mass ratio of Cu4I4(py-CHO)4 powder to p-phenylenediamine is 1:(1.1~1.5).

8. The method for preparing a CuI-MCOF sensitive material based on a dia topological structure according to claim 1, characterized in that: In step (4), the mixed solution includes 1,4-dioxane, mesitylene and acetic acid solution in a volume ratio of 8:2:1, and the concentration of the acetic acid solution is 5.5-6.5 mol / L; Cu4I4(py-CHO)4 powder and p-phenylenediamine were added to a Schlenk tube, followed by the addition of the mixed solution and emulsification for 15-30 minutes to form a uniform dispersion. The dispersion was flash-frozen under liquid nitrogen vacuum conditions, and subjected to three vacuum freeze-thaw degassing cycles. The tube was vacuum-sealed and heated at 60-80°C for 2-8 days. The CuI-MCOF sensitive material was then obtained after centrifugation, washing, and drying.

9. Application of the CuI-MCOF sensitive material obtained by the preparation method according to any one of claims 1 to 8, characterized in that: Application of CuI-MCOF sensitive material in hydrogen fluoride detection.

10. The use of the CuI-MCOF sensitive material according to claim 9, characterized in that: The CuI-MCOF sensitive material is dispersed in ethanol to obtain a third dispersion liquid, and the third dispersion liquid is dropwise applied to the interdigital electrode using a pipette and then dried to obtain a chemical resistance type gas sensor for hydrogen fluoride detection.

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