Use of hydroxyapatite in detecting isobutyraldehyde

Abstract

The application relates to the technical field of isobutyraldehyde detection, in particular to application of hydroxyapatite in detection of isobutyraldehyde. The application provides application of hydroxyapatite in detection of isobutyraldehyde, and also provides a preparation method of the hydroxyapatite. It is found that the hydroxyapatite has good responsiveness, specificity, stability and reproducibility in detection of isobutyraldehyde, and the application of the hydroxyapatite is expanded.

Description

TECHNICAL FIELD

[0001] The application relates to the technical field of isobutyraldehyde detection, in particular to application of hydroxyapatite in isobutyraldehyde detection. BACKGROUND

[0002] Currently, materials for selectively detecting isobutyraldehyde mainly include the following: mesoporous SiO2 nanospheres, nano Sm2O3 particles, nano barium titanate and SiO2 / MIL-53(Al) composite materials. The above-mentioned materials have respective advantages and characteristics in the selective detection of isobutyraldehyde, and provide effective detection means for the environmental monitoring and safety field of isobutyraldehyde. Currently, there is no related report on the use of hydroxyapatite for selectively detecting isobutyraldehyde. SUMMARY

[0003] The application aims to provide application of hydroxyapatite in isobutyraldehyde detection.

[0004] To achieve the above-mentioned purpose, the application provides the following scheme.

[0005] The application provides application of hydroxyapatite in isobutyraldehyde detection.

[0006] In a preferred embodiment of the application, the preparation method of the hydroxyapatite comprises the following steps:

[0007] CaCl2, Na2HPO4, urea and hexadecyl trimethyl ammonium are added into water, uniformly mixed and then subjected to hydrothermal reaction, and the obtained precipitate is calcined after being washed, so that the hydroxyapatite is obtained.

[0008] In a preferred embodiment of the application, the molar ratio of CaCl2, Na2HPO4, urea and hexadecyl trimethyl ammonium is 0.3:0.18:1:0.01.

[0009] In the application, CaCl2 and Na2HPO4 are used as raw materials for synthesizing hydroxyapatite; urea is used for adjusting pH and as a precipitating agent; and hexadecyl trimethyl ammonium is used as a surfactant. If the above-mentioned raw materials are replaced by other raw materials, the morphology, particle size and crystal form of the hydroxyapatite will be affected, thereby affecting the performance of the hydroxyapatite.

[0010] The application limits the molar ratio of CaCl2, Na2HPO4, urea and hexadecyl trimethyl ammonium to 0.3:0.18:1:0.01, because adjusting the ratio of the above-mentioned raw materials will affect the particle size, morphology and / or crystal form of the prepared material, and further affect the detection performance of the material on isobutyraldehyde.

[0011] The application does not particularly limit the amount of water, and the water can be used to fully mix the raw materials and fully perform the hydrothermal reaction.

[0012] In some embodiments of the present application, the concentration of urea in the mixed solution is 1M.

[0013] In a preferred embodiment of the present application, the temperature of the hydrothermal reaction is 180℃.

[0014] In a preferred embodiment of the present application, the time of the hydrothermal reaction is 6-48 hours.

[0015] In a further preferred embodiment of the present application, the time of the hydrothermal reaction is 24 hours.

[0016] In a preferred embodiment of the present application, the temperature of the calcination is 800℃.

[0017] In a preferred embodiment of the present application, the time of the calcination is 6 hours.

[0018] The method for preparing hydroxyapatite of the present application is simple, and the hydroxyapatite prepared by the method of the present application has sensitive response to isobutyraldehyde.

[0019] The present application discloses the following technical effects:

[0020] The present application finds that hydroxyapatite has good response, specificity, stability and reproducibility in detecting isobutyraldehyde, which expands the new application of hydroxyapatite. BRIEF DESCRIPTION OF DRAWINGS

[0021] In order to more clearly illustrate the technical solutions of the embodiments of the present application or the prior art, the drawings needed in the embodiments will be briefly introduced below. Obviously, the drawings in the following description are only some embodiments of the present application, and other drawings can also be obtained by those skilled in the art without creative labor.

[0022] Figure 1 XRD spectrum of hydroxyapatite prepared for Examples 1-3.

[0023] Figure 2 Response sensitivity of hydroxyapatite prepared for Examples 1-3 and dysprosium oxide, zirconium oxide, silicon carbide, zinc ferrite and nickel oxide to isobutyraldehyde.

[0024] Figure 3 Selective test results of hydroxyapatite prepared for Example 1 to isobutyraldehyde.

[0025] Figure 4 Selective test results of hydroxyapatite prepared for Example 2 to isobutyraldehyde.

[0026] Figure 5 Selective test results of hydroxyapatite prepared for Example 3 to isobutyraldehyde.

[0027] Figure 6 Results of the detection stability test of isobutyraldehyde by the hydroxyapatite prepared for Example 1.

[0028] Figure 7 Results of the detection stability test of isobutyraldehyde by the hydroxyapatite prepared for Example 2.

[0029] Figure 8 Results of the detection stability test of isobutyraldehyde by the hydroxyapatite prepared for Example 3.

[0030] Figure 9 Results of the reproducibility test of isobutyraldehyde by the hydroxyapatite prepared for Example 1.

[0031] Figure 10 Results of the reproducibility test of isobutyraldehyde by the hydroxyapatite prepared for Example 2.

[0032] Figure 11 Results of the reproducibility test of isobutyraldehyde by the hydroxyapatite prepared for Example 3.

[0033] Figure 12 Linear regression standard curve of isobutyraldehyde by the hydroxyapatite prepared for Example 1.

[0034] Figure 13 Linear regression standard curve of isobutyraldehyde by the hydroxyapatite prepared for Example 2.

[0035] Figure 14 Linear regression standard curve of isobutyraldehyde by the hydroxyapatite prepared for Example 3.

[0036] Figure 15 Results of the anti-interference test of isobutyraldehyde by the hydroxyapatite prepared for Example 1.

[0037] Figure 16 Results of the anti-interference test of isobutyraldehyde by the hydroxyapatite prepared for Example 2.

[0038] Figure 17 Results of the anti-interference test of isobutyraldehyde by the hydroxyapatite prepared for Example 3. DETAILED DESCRIPTION

[0039] Various example embodiments of the present application will now be described in detail with reference to the accompanying drawings. The detailed description provided herein is not intended in a limiting sense. Rather, well-known processes, well-known structures, and well-known technologies have been described only in a general sense and are not described with particularity since such processes, structures, and technologies are widely known to persons of ordinary skill in the art.

[0040] It is to be understood that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of the present application. Additionally, for a range of values of, for example, concentrations, amounts, and other

[0041] Unless otherwise defined, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs. Although methods and materials similar or equivalent to those described herein can be used in the practice or testing of the present application, preferred methods and materials are described. All publications mentioned herein are incorporated by reference to disclose and describe the methods and / or materials in connection with which the publications are cited. In case of conflict, the content of the present specification will control.

[0042] Various modifications and changes can be made to the specific embodiments described herein without departing from the scope or spirit of the application. Other embodiments will be apparent to those of ordinary skill in the art from the description and examples provided herein. The description and examples are illustrative only.

[0043] As used herein, the terms "comprises", "comprising", "includes", "including", "has", "having", "contains", "containing", or variations thereof, are intended to be open-ended terms that mean including, but not limited to.

[0044] The technical solutions described in the present application are all conventional solutions in the art unless specifically stated, and the reagents or raw materials used are purchased from commercial channels or are already disclosed.

[0045] The technical solutions provided by the present application will be described in detail below in conjunction with the examples, but they should not be understood as limiting the scope of protection of the present application.

[0046] Example 1: Preparation of hydroxyapatite

[0047] A mixed aqueous solution of 0.30 M CaCl2and 0.18 M Na2HPO4, urea (1 mol / L) and cetyltrimethylammonium (1.0 x 10 -2 mol / L) was prepared and stirred for 30 min before being transferred to a Teflon-lined autoclave and reacted at 180 °C for 6 h. The obtained precipitate was washed by centrifugation with ethanol and deionized water to remove residual organic matter and ions. Finally, the obtained powder was calcined at 800 °C for 6 h. The obtained hydroxyapatite was named HAp-6.

[0048] Example 2: Preparation of hydroxyapatite

[0049] A mixed aqueous solution of 0.30 M CaCl2and 0.18 M Na2HPO4, urea (1 mol / L) and hexadecyltrimethylammonium (1.0 x 10 -2 mol / L) was prepared and stirred for 30 minutes before being transferred to a Teflon-lined autoclave and reacted at 180°C for 24 hours. The obtained precipitate was washed by centrifugation with ethanol and deionized water to remove residual organic matter and ions. The final powder was calcined at 800°C for 6 hours. The obtained hydroxyapatite was named HAp-24. (i.e., the only difference from Example 1 is that the hydrothermal reaction time is 24 hours, and the rest of the steps and parameters are the same as in Example 1)

[0050] Example 3: Preparation of hydroxyapatite

[0051] A mixed aqueous solution of 0.30 M CaCl2and 0.18 M Na2HPO4, urea (1 mol / L) and hexadecyltrimethylammonium (1.0 x 10 -2 mol / L) was prepared and stirred for 30 minutes before being transferred to a Teflon-lined autoclave and reacted at 180°C for 48 hours. The obtained precipitate was washed by centrifugation with ethanol and deionized water to remove residual organic matter and ions. The final powder was calcined at 800°C for 6 hours. The obtained hydroxyapatite was named HAp-48. (i.e., the only difference from Example 1 is that the hydrothermal reaction time is 48 hours, and the rest of the steps and parameters are the same as in Example 1)

[0052] Effect verification example: effect verification of hydroxyapatite (HAp-6, HAp-24, HAp-48) prepared in Examples 1-3

[0053] The test device used in this effect verification example is the peroxide ketone detection device disclosed in ZL202010814034.X, and the catalytic layer attached to the surface of the substrate is replaced by the test material (hydroxyapatite, dysprosium oxide, zirconium oxide, silicon carbide, zinc ferrite, nickel oxide) in this effect example.

[0054] 1. XRD analysis

[0055] To determine the crystal form of the prepared hydroxyapatite, HAp-6, HAp-24, and HAp-48 were subjected to X-ray diffraction measurement, and the results are shown in Figure 1 Compared with the standard XRD pattern, HAp-6, HAp-24, and HAp-48 are all hexagonal hydroxyapatite.

[0056] 2. Sensitivity material screening

[0057] The detection device detected the isobutyraldehyde gas with a concentration of 20 ppm under the conditions of a detection wavelength of 425 nm, a reaction temperature of 237°C, and a carrier gas flow rate of 800 mL / min, to obtain the cataluminescence signals of isobutyraldehyde on the surfaces of different materials, and the results are shown in Figure 2 It can be seen that the three kinds of hydroxyapatites all have a relatively sensitive response to isobutyraldehyde, but HAp-24 has the strongest response. The purchased dysprosium oxide (particle size 30 nm, purity 99.5%), zirconium oxide (80 nm, 99.9%), silicon carbide (150 nm, 99.9%), zinc ferrite (50 nm, 99.5%), and nickel oxide (100 nm, 99.5%) have almost no response to isobutyraldehyde.

[0058] 3. Specificity

[0059] The detection device detected fourteen kinds of gases under the conditions of a detection wavelength of 425 nm, a reaction temperature of 237°C, and a carrier gas flow rate of 800 mL / min, using HAp-6, HAp-24, and HAp-48 respectively, and the fourteen kinds of gases were: 1: isobutyraldehyde, 2: isobutyl alcohol, 3: n-butyraldehyde, 4: n-propyl aldehyde, 5: acetone, 6: dimethylamine, 7: benzene, 8: trichloroethylene, 9: m-xylene, 10: a-methyl acrylic acid, 11: ethyl acetate, 12: 4-iodophenol, 13: phenyl ether, and 14: o-xylene. The concentrations of the gases 1-4 were 20.0 ppm, and the concentrations of the other gases were all 2600 ppm. The results are shown in Figures 3-5 It can be seen that HAp-6, HAp-24, and HAp-48 all have good selectivity to isobutyraldehyde.

[0060] 4. Stability

[0061] In this experiment, the three kinds of hydroxyapatites were used to continuously determine the isobutyraldehyde gas with a concentration of 20.0 ppm for 7 days under the conditions of a detection wavelength of 425 nm, a reaction temperature of 237°C, and a carrier gas flow rate of 800 mL / min, and the signal change trends are shown in Figure 6 (HAp-6), Figure 7 (HAp-24), and Figure 8 (HAp-48), and the RSDs were 5%, 2%, and 5% respectively, indicating that HAp has good stability as a catalyst for detecting isobutyraldehyde.

[0062] 5. Reproducibility

[0063] In this experiment, under the conditions of a detection wavelength of 425 nm, a reaction temperature of 237 °C, and a carrier gas flow rate of 800 mL / min, isobutyraldehyde gas with a concentration of 20.0 ppm was detected by continuous automated injection using the HAp prepared in Examples 1, 2, and 3. Ten consecutive automated injections were performed in parallel, with a sampling time and interval of 15 s. The obtained signals remained stable, and the results are as follows: Figure 9 (HAp-6) Figure 10 (HAp-24) and Figure 11 As shown in (HAp-48), the RSDs were 0.6%, 0.6%, and 1.0%, respectively, indicating good reproducibility.

[0064] 6. Standard Curve

[0065] Under conditions of a wavelength of 425 nm, a reaction temperature of 237 °C, and a carrier gas flow rate of 800 mL / min, isobutyraldehyde standard gas samples with concentrations of 3, 5, 10, 15, 20, 40, 70, and 100 ppm were measured three times in parallel using HAp-6, HAp-24, and HAp-48. The measured catalytic luminescence signals were then subjected to linear regression, and the results are as follows: Figures 12-14 As shown. The linear regression equation for HAp-24 is S = 747.9c + 195.8, where S is the luminescence intensity, c is the isobutyraldehyde concentration, and the correlation coefficient R is... 2 =0.9946; the linear regression equation for HAp-6 is S = 442.4c - 792.2, and the correlation coefficient R is 0.9946. 2 =0.9984; the HAP-48 linear regression equation is S = 416.9c - 6.6, and the correlation coefficient R is 0.9984. 2 =0.9919.

[0066] 7. Anti-interference capability

[0067] To further verify the application value of the prepared hydroxyapatite material in the detection of isobutyraldehyde, 20 ppm of isobutyraldehyde was mixed with other gases in a certain proportion, and the isobutyraldehyde recovery rate was determined. The results obtained using HAp-6, HAp-24, and HAp-48 are as follows: Figures 15-17 As shown, the recoveries ranged from 94.4% to 109.1%, further demonstrating the potential of the prepared HAp-6, HAp-24, and HAp-48 in the detection of isobutyraldehyde.

[0068] The embodiments described above are merely preferred embodiments of the present invention and are not intended to limit the scope of the present invention. Various modifications and improvements made by those skilled in the art to the technical solutions of the present invention without departing from the spirit of the present invention should fall within the protection scope defined by the claims of the present invention.

Claims

1. The application of hydroxyapatite as a photocatalyst in the detection of isobutyraldehyde, characterized in that, The method for preparing the hydroxyapatite includes the following steps: CaCl2, Na2HPO4, urea and hexadecyltrimethylammonium were added to water and mixed, and then subjected to a hydrothermal reaction. The resulting precipitate was washed and then calcined to obtain the hydroxyapatite. The molar ratio of CaCl2, Na2HPO4, urea, and hexadecyltrimethylammonium is 0.3:0.18:1:0.01; The temperature of the hydrothermal reaction is 180°C; The hydrothermal reaction time is 6-48 hours; The calcination temperature is 800°C; The calcination time is 6 hours.

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