Boron nitride catalytic luminescent material as well as preparation method and application thereof
By introducing nitrogen vacancy defects into boron nitride catalytic luminescent materials through vacuum calcination, the problems of insufficient sensitivity and selectivity in the detection of 3-chloro-2-butanone in the prior art have been solved, and a detection effect with high sensitivity and high selectivity has been achieved.
Patent Information
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-12-24
- Publication Date
- 2026-03-27
AI Technical Summary
Existing technologies lack highly sensitive and selective boron nitride catalysts for the detection of 3-chloro-2-butanone, which presents detection difficulties and safety hazards.
By introducing controllable nitrogen vacancy defects through vacuum calcination, boron nitride catalytic luminescent materials were prepared, optimizing their electronic structure and surface activity, and improving detection sensitivity and selectivity.
The detection sensitivity and selectivity of boron nitride catalytic luminescent material for 3-chloro-2-butanone are significantly improved. It has a wide linear range and low detection limit, low sensor signal interference, is suitable for trace detection, and has good process repeatability.
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Figure CN121732210A_ABST
Abstract
Description
Technical Field
[0001] This invention relates to the field of catalytic luminescent gas sensing technology, and in particular to a boron nitride catalytic luminescent material, its preparation method, and its application. Background Technology
[0002] 3-Chloro-2-Butanone is an important chemical raw material for the synthesis of fragrances such as pyrazine and acetoin, and also a crucial intermediate in the synthesis of bactericides and fuels such as thiazoles and their derivatives. However, 3-Chloro-2-Butanone is a lachrymatory agent, with slightly higher toxicity than chloroacetone. It irritates the eyes, mucous membranes, upper respiratory tract, and skin, and its decomposition under high heat releases corrosive and irritating fumes, posing a risk of combustion and explosion upon contact with open flames or oxidizers. Rapid and sensitive monitoring of 3-chloro-2-butanone vapor is crucial for protecting human health and safety and preventing environmental pollution in relevant industrial production and usage environments.
[0003] Cataluminescence (CTL) gas sensing technology is a detection method based on the chemiluminescence generated by gas-solid phase catalytic oxidation reactions. Compared with traditional methods such as chromatography and mass spectrometry, CTL sensors have advantages such as rapid response, ease of operation, lower cost, and the ability to achieve real-time online monitoring. The core of a CTL sensor is a high-performance catalytic material. Therefore, developing novel nanocatalytic materials with high sensitivity and selectivity for specific target gases (such as 3-chloro-2-butanone) is key to improving the performance of CTL sensors.
[0004] Boron nitride (BN) is a high-performance wide-bandgap semiconductor material with excellent thermal stability and chemical inertness. Previous studies have shown that its electronic structure and surface activity can be tuned by introducing defects (such as nitrogen vacancies), thereby endowing it with unique catalytic properties. However, there is currently a lack of boron nitride with specific defect structures that can be used as a catalytic luminescent material for the highly selective and sensitive detection of 3-chloro-2-butanone. Summary of the Invention
[0005] The purpose of this invention is to provide a boron nitride catalytic luminescent material, its preparation method, and its application. In the preparation of the boron nitride catalytic luminescent material, controllable nitrogen vacancy defects are introduced by vacuum calcination, which significantly improves the detection sensitivity and selectivity of the boron nitride catalytic luminescent material for 3-chloro-2-butanone.
[0006] To achieve the above objectives, the present invention provides a method for preparing a boron nitride catalytic luminescent material, comprising the following steps: Boron nitride was subjected to vacuum calcination to obtain boron nitride catalytic luminescent material; the vacuum calcination temperature was 250℃-350℃ and the time was 2h-5h.
[0007] Preferably, the vacuum calcination temperature is 300°C and the time is 3 hours.
[0008] Preferably, the method for preparing boron nitride includes the following steps: S1. Dissolve boric acid and melamine in deionized water at a mass ratio of 6-8:1-2 and stir to obtain a precursor solution; S2. Dry the precursor solution to obtain the precursor solid; S3. Under a nitrogen atmosphere, the precursor solid is calcined at 900℃-1100℃ for 1h-5h, then washed with deionized water and dried to obtain boron nitride.
[0009] Preferably, the mass ratio of boric acid to melamine in S1 is 4:1.
[0010] Preferably, the calcination temperature in S3 is 1000℃ and the time is 3h.
[0011] Preferably, the flow rate of nitrogen gas in S3 is 200 mL / min.
[0012] Preferably, the drying temperature in S2 and S3 is 60℃-100℃, and the drying time is 10h-14h.
[0013] Preferably, the drying temperature in S2 and S3 is 80°C and the drying time is 12 hours.
[0014] This invention provides a boron nitride catalytic luminescent material, which is prepared by the above-described method for preparing a boron nitride catalytic luminescent material.
[0015] The present invention also provides an application of a boron nitride catalytic luminescent material, wherein the aforementioned boron nitride catalytic luminescent material is used as a sensitive material to prepare a catalytic luminescent sensor for detecting 3-chloro-2-butanone.
[0016] In summary, the boron nitride catalytic luminescent material, its preparation method, and its application provided by this invention offer the following advantages compared to traditional technologies: (1) The boron nitride catalytic luminescent material prepared in this invention introduces controllable nitrogen vacancy defects through vacuum calcination, which significantly improves the detection sensitivity and selectivity of boron nitride catalytic luminescent material for 3-chloro-2-butanone; the catalytic luminescence response signal for 3-chloro-2-butanone is strong, the linear range is wide, and the detection limit is low, which meets the requirements for trace detection; in the presence of common volatile organic compounds (such as benzene, formaldehyde, methanol and acetone) and inorganic gases (such as CO, NO2, SO2 and H2S), the interference of the sensing signal is minimal, and the sensitivity is significantly better than that of common metal oxides and commercial boron nitride.
[0017] (2) When preparing boron nitride catalytic luminescent materials, the concentration of nitrogen vacancies in boron nitride can be precisely controlled by adjusting the time and temperature of vacuum calcination, thereby optimizing its sensing performance. The process has good repeatability and is easy to scale up.
[0018] (3) The results of the catalytic luminescence sensor prepared by the present invention using boron nitride catalytic luminescence material as the sensitive material to test ambient air samples have good consistency (relative error <5.89%) with no significant difference compared with the results of the ambient air samples tested by gas chromatography-mass spectrometry (GC-MS) method, which proves its reliability in practical applications.
[0019] The technical method of the present invention will be further described in detail below with reference to the accompanying drawings and embodiments. Attached Figure Description
[0020] Figure 1 X-ray diffraction (XRD) spectra of BN-0, BN-2, BN-3, BN-4 and BN-5 prepared for the examples; Figure 2 Scanning electron microscope (SEM) images of BN-0, BN-2, BN-3, BN-4 and BN-5 prepared for the examples; Figure 2 (a) is the SEM image of BN-0; Figure 2 (b) is the SEM image of BN-2; Figure 2 (c) is the SEM image of BN-3; Figure 2 (d) is the SEM image of BN-4; Figure 2 (e) is the SEM image of BN-5; Figure 3 Electron paramagnetic resonance (EPR) spectra of BN-0, BN-2, BN-3, BN-4, and BN-5 prepared for the examples; Figure 4 The graphs show the response of 3-chloro-2-butanone on different comparative materials (MgO, ZnO, Y2O3, BN-S1, BN-S2, BN-S3, and BN-S4) and the catalytic luminescence signals of different gases (3-chloro-2-butanone, 2,3-butanedione, acetaldehyde, 3-heptanone, propionyl chloride, cyclopentanone, acetone, formaldehyde, methanol, carbon monoxide, carbon dioxide, n-hexane, benzene, o-xylene, trichloroethylene, hydrogen sulfide, phenethyl ether, ethyl acetate, nitric oxide, nitrogen dioxide, sulfur dioxide, and ammonia) on the surfaces of BN-0, BN-2, BN-3, BN-4, and BN-5.Figure 4 (a) Comparison of catalytic luminescence response signals of 3-chloro-2-butanone on different comparative materials and on the surfaces of BN-0, BN-2, BN-3, BN-4 and BN-5; Figure 4 (b) is a graph showing the catalytic luminescence signal response of different gases on the BN-0 catalytic luminescence sensor; Figure 4 (c) is a graph showing the catalytic luminescence signal response of different gases on the BN-2 catalytic luminescence sensor; Figure 4 (d) shows the catalytic luminescence signal response of different gases on the BN-3 catalytic luminescence sensor; Figure 4 (e) shows the catalytic luminescence signal response of different gases on the BN-4 catalytic luminescence sensor; Figure 4 (f) shows the catalytic luminescence signal response of different gases on the BN-5 catalytic luminescence sensor. Detailed Implementation
[0021] The technical method of the present invention will be further described below with reference to the accompanying drawings and embodiments.
[0022] The following description of at least one exemplary embodiment is merely illustrative and is in no way intended to limit the scope of this application and its application or use.
[0023] In all the examples shown and discussed herein, any specific values should be interpreted as merely exemplary and not as limitations. Therefore, other examples of exemplary embodiments may have different values.
[0024] Unless otherwise defined, the technical or scientific terms used in this invention shall have the ordinary meaning as understood by one of ordinary skill in the art to which this invention pertains.
[0025] The specific implementation examples are as follows: Example 1 A method for preparing a boron nitride catalytic luminescent material (BN-2) includes the following steps: (1) Preparation of boron nitride, denoted as BN-0, includes the following steps: a. Add 16g of boric acid and 4g of melamine to 400mL of deionized water and stir magnetically at room temperature until completely dissolved to obtain a precursor solution.
[0026] b. Place the precursor solution in an oven at 80°C for 12 hours to dry and obtain the precursor solid.
[0027] c. After grinding the precursor solid into powder, place it in a tube muffle furnace and calcine it at 1000℃ for 3 hours under the protection of a high-purity nitrogen atmosphere with a flow rate of 200 mL / min. Then wash it three times with deionized water to remove soluble impurities, and finally dry it in an oven at 80℃ to obtain boron nitride, i.e., BN-0.
[0028] (2) Weigh 0.5g-1.0g of BN-0 and place it in a clean ceramic crucible. Then place the ceramic crucible in a vacuum muffle furnace and calcine it at a constant temperature of 300℃ for 2 hours under vacuum pressure of -0.1MPa. After cooling naturally to room temperature under vacuum, the boron nitride catalytic luminescent material, namely BN-2, is obtained.
[0029] Example 2 A method for preparing a boron nitride catalytic luminescent material (BN-3) is to replace "constant temperature calcination for 2 hours" in step (2) of Example 1 with "constant temperature calcination for 3 hours", and the remaining steps are the same as in Example 1, and BN-3 is finally obtained.
[0030] Example 3 A method for preparing a boron nitride catalytic luminescent material (BN-4) is to replace "constant temperature calcination for 2 hours" in step (2) of Example 1 with "constant temperature calcination for 4 hours", and the remaining steps are the same as in Example 1, and finally BN-4 is obtained.
[0031] Example 4 A method for preparing a boron nitride catalytic luminescent material (BN-5) is to replace "constant temperature calcination for 2 hours" in step (2) of Example 1 with "constant temperature calcination for 5 hours", and the remaining steps are the same as in Example 1, and finally BN-5 is obtained.
[0032] Material characterization The structures, morphologies, and defects of BN-0, BN-2, BN-3, BN-4, and BN-5 prepared in the examples were characterized.
[0033] XRD characterization: BN-0, BN-2, BN-3, BN-4, and BN-5 were analyzed using X-ray diffraction. The results are as follows: Figure 1 As shown, BN-0, BN-2, BN-3, BN-4, and BN-5 all exhibit distinct diffraction peaks at 26.66°, 41.56°, and 43.78°, corresponding to the (002), (100), and (101) crystal planes of the standard card (card number 34-0421) for hexagonal boron nitride (h-BN), respectively. This indicates that the prepared BN-0, BN-2, BN-3, BN-4, and BN-5 are all well-crystallized hexagonal boron nitride. After vacuum calcination, the diffraction peak positions of BN-0 did not shift significantly, but the full width at half maximum (FWHM) changed slightly, indicating that the prepared BN-2, BN-3, BN-4, and BN-5 have good crystallinity and a well-preserved hexagonal crystal system.
[0034] SEM characterization: The morphology of BN-0, BN-2, BN-3, BN-4, and BN-5 was observed using scanning electron microscopy. The results are as follows: Figure 2 As shown.Figure 2 As shown in (a), BN-0 consists of loosely stacked, regularly distributed two-dimensional layers with numerous small cracks on its surface. This facilitates sufficient contact with the detection gas. Figure 2 (b) Figure 2 (c) Figure 2 (d) and Figure 2 As shown in (e), after vacuum calcination, the nanosheets of BN-2, BN-3, BN-4, and BN-5 showed reduced sizes and looser stacking. Among them, BN-3 had nanosheets with smaller average sizes of 28.66 nm to 155.55 nm compared to the BN-0 nanosheets with sizes of 31.80 nm to 194.31 nm.
[0035] EPR Characterization: EPR is an effective method for sensitively detecting single-electron trapped vacancy defects in semiconductor photocatalysts. To further confirm the vacancy structure, electron paramagnetic resonance spectroscopy was used to analyze BN-0, BN-2, BN-3, BN-4, and BN-5 and identify the relative abundance of unpaired electrons. The results are as follows: Figure 3 As shown. By Figure 3 Based on the peak height of the EPR signal, the nitrogen vacancy content follows the order: EPR BN-3 > BN-2 > BN-4 > BN-5 > BN-0. Unpaired electrons are used to characterize the nitrogen vacancy defect concentration. The results are as follows: Figure 3 As shown, BN-0, BN-2, BN-3, BN-4, and BN-5 all exhibit a symmetrical single-peak signal at g (Lande factor) = 2.004, which is attributed to nitrogen vacancy defects in boron nitride. Comparison of peak intensities reveals that the nitrogen vacancy concentration order is: BN-3 > BN-2 > BN-4 > BN-5 > BN-0. This indicates that vacuum calcination at 300℃ for 3 hours is the optimal condition for introducing nitrogen vacancies.
[0036] Catalytic luminescence sensor performance test The BN-0, BN-2, BN-3, BN-4 and BN-5 prepared in the examples were used to assemble catalytic luminescence sensors.
[0037] Comparison of responses to different materials: at a concentration of 50 mg / m³ 3 The signal response of 3-chloro-2-butanone standard gas in sensors using different sensitive materials BN-0, BN-2, BN-3, BN-4, BN-5, MgO, ZnO, Y2O3, and four commercial boron nitrides (BN-S1, BN-S2, BN-S3, and BN-S4) is shown in the figure. Figure 4As shown in (a), MgO, ZnO, and Y2O3 produce weak signals for 3-chloro-2-butanone, while among the four commercial boron nitrides (BN-S1, BN-S2, BN-S3, and BN-S4), only BN-S1 produces a weak signal for 3-chloro-2-butanone, while BN-S2, BN-S3, and BN-S4 produce no signal. The BN-0, BN-2, BN-3, BN-4, and BN-5 prepared in this invention all produce strong signals for 3-chloro-2-butanone, with BN-3 showing the strongest signal. The order of signal strength among BN-0, BN-2, BN-3, BN-4, and BN-5 corresponds to the order of nitrogen vacancy content in the materials, i.e., BN-3 > BN-2 > BN-4 > BN-5 > BN-0. The content of nitrogen vacancies on the surface can affect the response of the sensor, confirming that nitrogen vacancies are the key to improving catalytic activity and sensitivity.
[0038] Selectivity Testing: Furthermore, selectivity testing was conducted by comparing the response signals of 3-chloro-2-butanone (1), 2,3-butanedione (2), acetaldehyde (3), 3-heptanone (4), propionyl chloride (5), cyclopentanone (6), acetone (7), formaldehyde (8), methanol (9), carbon monoxide (10), carbon dioxide (11), n-hexane (12), benzene (13), o-xylene (14), trichloroethylene (15), hydrogen sulfide (16), phenethyl ether (17), ethyl acetate (18), nitric oxide (19), nitrogen dioxide (20), sulfur dioxide (21), and ammonia (22) on BN-0, BN-2, BN-3, BN-4, and BN-5 catalytic luminescence sensors. The results are as follows: Figure 4 (b) Figure 4 (c) Figure 4 (d) Figure 4 (e) and Figure 4 As shown in (f), except for a few structurally similar ketones and acyl chlorides (such as acetaldehyde, 2,3-butanedione, 3-heptanone, propionyl chloride, and cyclopentanone) that produce weak responses, the other gases do not generate signals. This indicates that the BN-0, BN-2, BN-3, BN-4, and BN-5 catalytic luminescence sensors prepared in this invention have high specificity for 3-chloro-2-butanone.
[0039] Analytical Characteristic Tests: Under optimal test conditions, different concentrations (0.1 mg / m³) were tested. 3 -400mg / m 3 The standard gas of 3-chloro-2-butanone was passed into BN-0, BN-2, BN-3, BN-4, and BN-5 catalytic luminescence sensors, and standard operating curves were plotted. The linear range, regression equation (where S is the catalytic luminescence signal and C is the concentration of 3-chloro-2-butanone), and correlation coefficient (R0) were also analyzed. 2 The detection limits and their corresponding limits are shown in Table 1. As can be seen from Table 1, the BN-3 catalytic luminescence sensor has a detection limit of 0.5 mg / m³.3 -300mg / m 3 It exhibits good linearity across the concentration range, with the widest linear range and the lowest detection limit of 0.01 mg / m³. 3 The linear range and detection limit of the BN-0, BN-2, BN-4, and BN-5 catalytic luminescence sensors confirm the excellent performance of these sensors. Furthermore, these results also demonstrate the significant impact of nitrogen vacancy content on sensitivity and detection limit.
[0040] Table 1 Performance Analysis of BN-0, BN-2, BN-3, BN-4 and BN-5 Catalytic Emission Sensors
[0041] Actual sample testing To verify the practicality of the catalytic luminescence sensor of this invention, three ambient air samples that may contain 3-chloro-2-butanone contamination were collected. The BN-3 catalytic luminescence sensor of this invention was used to detect the three ambient air samples using both the CTL method and GC-MS method. The results are shown in Table 2. The detection results of the CTL method and GC-MS method showed good agreement. Taking the result obtained by the GC-MS method as the true value, the relative error of the detection results of the BN-3 catalytic luminescence sensor was less than 5.89%. Furthermore, statistical t-tests showed no significant difference between the results obtained by the two methods, demonstrating the promising future of the boron nitride gas sensor in practical applications.
[0042] Table 2 Comparison of Detection and Analysis Results of Ambient Air Samples
[0043] Note: (1) The degrees of freedom for both sets of data for each ambient air sample are 2. F value( F Test statistic table, F 0.05,2,2 =19.00, three ambient air samples F < F 0.05,2,2 This indicates that there is no significant difference in the precision of the results obtained by the two methods. (2) p Value (probability value) f =n1+n2-2=4, where, f n represents the degrees of freedom, n1 is the sample size detected by GC-MS, and n2 is the sample size detected by CTL. p =95%, check t value( t The test statistic table is used to obtain the results. t 0.05,4 =2.776. t <t 0.05,4 There was no significant difference between the results obtained by the two methods. (3) A GC-MS A represents the mean ± standard deviation of the GC-MS detection results; CTL This represents the mean ± standard deviation of the CTL method detection results.
[0044] Finally, it should be noted that the above embodiments are only used to illustrate the technical methods of the present invention and not to limit them. Although the present invention has been described in detail with reference to preferred embodiments, those skilled in the art should understand that modifications or equivalent substitutions can still be made to the technical methods of the present invention, and these modifications or equivalent substitutions cannot cause the modified technical methods to deviate from the spirit and scope of the technical methods of the present invention.
Claims
1. A method for preparing a boron nitride catalytic luminescent material, characterized in that, Includes the following steps: Boron nitride was subjected to vacuum calcination to obtain boron nitride catalytic luminescent material; the vacuum calcination temperature was 250℃-350℃ and the time was 2h-5h.
2. The method for preparing a boron nitride catalytic luminescent material according to claim 1, characterized in that, The vacuum calcination treatment was carried out at a temperature of 300°C for 3 hours.
3. The method for preparing a boron nitride catalytic luminescent material according to claim 1, characterized in that, The method for preparing boron nitride includes the following steps: S1. Dissolve boric acid and melamine in deionized water at a mass ratio of 6-8:1-2 and stir to obtain a precursor solution; S2. Dry the precursor solution to obtain the precursor solid; S3. Under a nitrogen atmosphere, the precursor solid is calcined at 900℃-1100℃ for 1h-5h, then washed with deionized water and dried to obtain boron nitride.
4. The method for preparing a boron nitride catalytic luminescent material according to claim 3, characterized in that, The mass ratio of boric acid to melamine in S1 is 4:
1.
5. The method for preparing a boron nitride catalytic luminescent material according to claim 3, characterized in that, The calcination temperature described in S3 is 1000℃, and the time is 3 hours.
6. The method for preparing a boron nitride catalytic luminescent material according to claim 3, characterized in that, The nitrogen flow rate described in S3 is 200 mL / min.
7. The method for preparing a boron nitride catalytic luminescent material according to claim 3, characterized in that, The drying temperature described in S2 and S3 is 60℃-100℃, and the drying time is 10h-14h.
8. The method for preparing a boron nitride catalytic luminescent material according to claim 7, characterized in that, The drying temperature described in S2 and S3 is 80°C, and the drying time is 12 hours.
9. A boron nitride catalytic luminescent material, characterized in that, The boron nitride catalytic luminescent material is prepared by the preparation method of the boron nitride catalytic luminescent material according to any one of claims 1-8.
10. An application of a boron nitride catalytic luminescent material, characterized in that, A catalytic luminescent material as described in claim 9 is used as a sensitive material to prepare a catalytic luminescent sensor for detecting 3-chloro-2-butanone.