Nanometer flower-shaped sulfur-doped cobalt-molybdenum hydroxide wave-absorbing material and preparation method thereof
Through the preparation method of nanoflower-like sulfur-doped cobalt-molybdenum hydroxide, the problems of low dielectric constant and weak magnetic loss of cobalt-molybdenum hydroxide absorption materials are solved, and more efficient electromagnetic wave loss capability and larger specific surface area are achieved.
Patent Information
- Application Number
- CN202510596596.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-05-09
- Publication Date
- 2025-08-12
AI Technical Summary
The existing cobalt-molybdenum hydroxide absorbing materials have low dielectric constant and weak magnetic loss ability, making it difficult to meet the requirements of "thin, light, wide and strong" absorbing materials.
Using the nanoflower-like sulfur-doped method, by preparing nanoflower-like sulfur-doped cobalt-molybdenum hydroxide, more non-uniform heterogeneous interfaces and defects are introduced to enhance the dielectric loss and magnetic loss capability of the material.
The material's loss ability to electromagnetic waves is significantly improved, a larger specific surface area and a smaller density are achieved, and the wave absorption performance is greatly improved.
Smart Images
Figure CN120463249A_ABST
Abstract
Description
Technical Field
[0001] The present invention relates to the technical field of novel absorbing materials, and in particular to a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material and a preparation method thereof. Background Art
[0002] With the continuous development of the information age, the application of electromagnetic waves in daily life has become more and more extensive, bringing great convenience to people's production and life. However, the ubiquitous electromagnetic waves have also brought a series of problems. Not only will they cause mutual interference between electronic devices, but they will also cause harm to human health. High-performance absorbing materials are one of the effective ways to solve the problems brought by electromagnetic waves. With the continuous development of absorbing materials and their increasingly widespread application in the field of absorbing waves, people have put forward higher requirements for them, and they need to meet the new requirements of "thin, light, wide and strong". Layered hydroxides are a traditional two-dimensional material. Their unique lamellar structure gives them the characteristics of high specific surface area, rich heterogeneous interfaces and a large number of defects, making them have the potential to become excellent absorbing materials. However, due to its low dielectric constant and weak magnetic loss capacity, the absorbing performance of pure cobalt molybdenum hydroxide is poor.
[0003] In existing technologies, element doping is an effective way to improve a material's microwave absorption properties. Doping can create lattice defects and vacancies, introduce more heterojunctions, and generate more dipole polarization and interface polarization, thereby enhancing absorption. It can also improve impedance matching and reduce electromagnetic wave reflections from the material surface. Summary of the Invention
[0004] The purpose of the present invention is to provide a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material and a preparation method thereof. The preparation method is simple, safe and reliable. The obtained nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material has a larger specific surface area and a smaller density, thereby significantly improving the material's loss capacity for incident electromagnetic waves.
[0005] To achieve the above object, the present invention provides a method for preparing a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material, comprising the following steps:
[0006] S1. Weigh cobalt chloride and cetyltrimethylammonium bromide in proportion and dissolve them in deionized water, stirring to obtain a clear and transparent solution A;
[0007] S2. Weigh 2-methylimidazole and dissolve it in deionized water, stirring to obtain a clear and transparent solution B. Add the clear and transparent solution B to the clear and transparent solution A obtained in S1, stirring to obtain a mixed solution A.
[0008] S3, centrifuging and washing the mixed solution A obtained in S2 several times, and then drying it to obtain a nano-cubic block of ZIF-67 absorbing material;
[0009] S4. Weigh ammonium molybdate in proportion and dissolve it in anhydrous ethanol. Stir and add the ZIF-67 absorbing material obtained in S3. Stir and then sonicate to obtain a mixed solution B. Centrifuge and wash the mixed solution B several times to obtain powder A.
[0010] S5. Dissolve the powder A obtained in S4 in deionized water, stir, and obtain a mixed solution C;
[0011] S6, keeping the mixed solution C obtained in S5 warm and allowing it to stand to obtain powder B;
[0012] S7, centrifuging and washing the powder B obtained in S6 several times, and then drying it to obtain a cobalt molybdenum hydroxide absorbing material having a hollow cubic shape;
[0013] S8, dissolving the cobalt molybdenum hydroxide absorbing material obtained in S7 in deionized water, adding sulfur powder, and stirring to obtain a mixed solution D;
[0014] S9. Transfer the mixed solution D obtained in S8 to a reactor for hydrothermal reaction, and then centrifuge and wash several times, and dry to obtain a nanoflower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material.
[0015] Preferably, in S1, the mass ratio of the cobalt chloride, the cetyltrimethylammonium bromide and the deionized water is 0.238-0.714:0.005-0.015:20.
[0016] Preferably, in S2, the mass ratio of the 2-methylimidazole to the deionized water is 3 to 9:70.
[0017] Preferably, in S3, the drying temperature is 60° C. and the drying time is 12 h.
[0018] Preferably, in S3 and S7, the washing reagent used is anhydrous ethanol, and the washing is performed 3 to 5 times.
[0019] Preferably, in S4, the mass ratio of the ammonium molybdate to the anhydrous ethanol is 0.03-0.09:30.
[0020] Preferably, in S4, the washing reagents used are deionized water and anhydrous ethanol, and the sample is first washed with deionized water for 1 to 2 times, and then washed with anhydrous ethanol for 1 to 2 times.
[0021] Preferably, in S5, the volume of deionized water required to dissolve the powder A is 30 mL.
[0022] Preferably, in S6, the temperature of the heat preservation and standing is 90° C. and the time is 1 hour.
[0023] Preferably, in S7, the drying temperature is 70° C. and the drying time is 9 hours.
[0024] Preferably, in S8, the mass ratio of the sulfur powder to the deionized water is 0.05-0.15:50.
[0025] Preferably, in S9, the reaction temperature of the hydrothermal reaction is 120-180° C., and the reaction time is 5-8 h;
[0026] The drying temperature is 60° C. and the drying time is 8 hours.
[0027] Preferably, in S9, the washing reagents used are deionized water and anhydrous ethanol, and the sample is first washed with deionized water for 1 to 2 times, and then washed with anhydrous ethanol for 2 to 3 times.
[0028] Therefore, the present invention adopts the above-mentioned nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material and its preparation method, and the beneficial effects are as follows:
[0029] (1) The nano-flower-shaped sulfur-doped cobalt-molybdenum hydroxide absorbing material of the present invention first uses cubic ZIF-67 as a precursor, and then etches ZIF-67 by adding ammonium molybdate to derive hollow cubic cobalt-molybdenum hydroxide. The hollow structure of the absorbing material not only facilitates the entry of incident electromagnetic waves into the interior of the material, but also can perform multiple losses on the electromagnetic waves entering the interior of the material, thereby enhancing the material's loss capacity for electromagnetic waves.
[0030] (2) The nanoflower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material of the present invention is prepared by using a non-metallic sulfur element doping method after preparing hollow cubic cobalt molybdenum hydroxide to prepare nanoflower-shaped sulfur-doped cobalt molybdenum hydroxide. A nanoflower structure is introduced on the surface of the hollow cubic block. Its unique two-dimensional sheet structure can extend the transmission and loss path of the incident electromagnetic wave and perform multiple reflections on the incident electromagnetic wave.
[0031] (3) The nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material of the present invention uses non-metallic sulfur elements to dope cobalt molybdenum hydroxide, introducing more non-uniform heterogeneous interfaces. More interface polarization occurs when electromagnetic waves are incident, which can effectively enhance the nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material's ability to reduce electromagnetic waves.
[0032] (4) The nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material of the present invention uses non-metallic sulfur elements to dope cobalt molybdenum hydroxide, which increases the number of defects inside the material and can generate more dipole polarization when electromagnetic waves are incident, thereby increasing the absorbing performance of the nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material.
[0033] (5) The nano-flower-shaped sulfur-doped cobalt-molybdenum hydroxide absorbing material of the present invention uses non-metallic sulfur elements to dope cobalt-molybdenum hydroxide. Part of the cobalt element in the cobalt-molybdenum hydroxide will combine with the sulfur element to obtain cobalt sulfide, and the magnetic loss capacity of the composite material is enhanced. At the same time, the doping of sulfur elements can also adjust the dielectric properties of the cobalt-molybdenum hydroxide and enhance its dielectric loss, thereby forming a synergistic effect of multiple loss mechanisms and significantly improving the absorbing ability of the composite material.
[0034] (6) The nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material of the present invention, when the thickness is 4.2 mm, has a minimum reflection loss of -25.52 dB at 9.06 GHz, and the widest effective absorption band (reflection loss less than -10 dB) at this time reaches 2.7 GHz, and its loss capacity for incident electromagnetic waves is significantly better than that of pure cobalt molybdenum hydroxide.
[0035] (7) The preparation method of the present invention is simple, safe and reliable, and is suitable for industrial promotion.
[0036] The technical solution of the present invention is further described in detail below through the accompanying drawings and embodiments. BRIEF DESCRIPTION OF THE DRAWINGS
[0037] Figure 1 This is an SEM image of a blank example of a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material and its preparation method of the present invention;
[0038] Figure 2 This is a graph showing the wave absorption performance of a blank example of a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide wave absorbing material and its preparation method according to the present invention;
[0039] Figure 3 This is a SEM image of Example 1 of a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material and a preparation method thereof of the present invention;
[0040] Figure 4 This is a graph showing the wave absorption performance of Example 1 of a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide wave absorbing material and a preparation method thereof according to the present invention;
[0041] Figure 5 This is a SEM image of Example 2 of a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material and a preparation method thereof of the present invention;
[0042] Figure 6 This is a graph showing the wave absorption performance of Example 2 of a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide wave absorbing material and a preparation method thereof according to the present invention;
[0043] Figure 7 This is an SEM image of Example 3 of a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material and a preparation method thereof of the present invention;
[0044] Figure 8 This is a graph showing the wave absorption performance of Example 3 of a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide wave absorbing material and a preparation method thereof according to the present invention. DETAILED DESCRIPTION
[0045] The technical solution of the present invention is further described below with reference to the accompanying drawings and embodiments.
[0046] Unless otherwise defined, technical or scientific terms used in the present invention shall have the same meaning as commonly understood by one of ordinary skill in the art to which the present invention belongs.
[0047] Blank example
[0048] A coaxial ring sample is prepared as follows:
[0049] S1. Weigh 0.238 g of cobalt chloride and 0.005 g of hexadecyltrimethylammonium bromide respectively and dissolve them in 20 mL of deionized water. Stir magnetically for 20 min to obtain a clear and transparent solution A.
[0050] S2. The obtained clear and transparent solution A was injected into deionized water containing 3 g of 2-methylimidazole, and the mixture was magnetically stirred for 1 h to obtain a mixed solution A.
[0051] S3. The mixed solution A was centrifuged and washed with anhydrous ethanol three times. The powder after centrifugation was then dried in a forced air drying oven at 60° C. for 12 h to obtain a nano-cubic ZIF-67 absorbing material.
[0052] S4. Weigh 0.09 g of ammonium molybdate and dissolve it in 30 mL of anhydrous ethanol. Magnetically stir for 20 min. Then add nanocubic ZIF-67 absorbing material. After magnetic stirring for 30 min, ultrasonic treatment is performed for 20 min to obtain a mixed solution B. The mixed solution B is centrifuged and washed twice with deionized water to obtain powder A.
[0053] S5. Dissolve powder A in 30 mL of deionized water and stir magnetically for 30 min to obtain a mixed solution C.
[0054] S6. Maintain the mixed solution C at 90° C. for 1 hour to obtain powder B.
[0055] S7. The powder B is centrifuged and washed with ethanol 5 times. The powder B after centrifugation is then dried in a forced air drying oven at 70° C. for 9 h to obtain a cobalt molybdenum hydroxide absorbing material having a hollow cubic shape.
[0056] S8. According to the ratio of 30% doping of cobalt molybdenum hydroxide absorbing material in paraffin, a coaxial ring sample with an inner diameter of 3 mm and an outer diameter of 7 mm was prepared.
[0057] Example 1
[0058] A nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material, the preparation method of which is as follows:
[0059] S1. Weigh 0.238 g of cobalt chloride and 0.005 g of hexadecyltrimethylammonium bromide respectively and dissolve them in 20 mL of deionized water. Stir magnetically for 20 min to obtain a clear and transparent solution A.
[0060] S2. The obtained clear and transparent solution A was injected into deionized water containing 3 g of 2-methylimidazole, and the mixture was magnetically stirred for 1 h to obtain a mixed solution A.
[0061] S3. The mixed solution A was centrifuged and washed with anhydrous ethanol three times. The powder after centrifugation was then dried in a forced air drying oven at 60° C. for 12 h to obtain a nano-cubic ZIF-67 absorbing material.
[0062] S4. Weigh 0.06 g of ammonium molybdate and dissolve it in 30 mL of anhydrous ethanol. Magnetically stir for 20 min. Then add nanocubic ZIF-67 absorbing material. After magnetic stirring for 30 min, ultrasonic treatment is performed for 20 min to obtain a mixed solution B. The mixed solution B is centrifuged and washed twice with deionized water to obtain powder A.
[0063] S5. Dissolve powder A in 30 mL of deionized water and stir magnetically for 30 min to obtain a mixed solution C.
[0064] S6. Maintain the mixed solution C at 90° C. for 1 hour to obtain powder B.
[0065] S7. The powder B is centrifuged and washed with ethanol 5 times. The powder B after centrifugation is then dried in a forced air drying oven at 70° C. for 9 h to obtain a cobalt molybdenum hydroxide absorbing material having a hollow cubic shape.
[0066] S8. Dissolve the hollow cubic cobalt molybdenum hydroxide absorbing material in 50 mL of deionized water, add 0.1 g of sulfur powder, and stir magnetically for 30 minutes to obtain a mixed solution D.
[0067] S9. Transfer the mixed solution D to a hydrothermal reactor with a 100 mL polytetrafluoroethylene liner. The reaction temperature is 150° C. and the reaction time is 5 h. After the reaction is completed, the powder obtained is washed twice with deionized water and then twice with anhydrous ethanol. The powder is dried in a forced air drying oven at 60° C. for 8 h to obtain a nanoflower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material.
[0068] S10. According to the ratio of 30% of the cobalt-doped molybdenum hydroxide absorbing material doped in paraffin, a coaxial ring sample with an inner diameter of 3 mm and an outer diameter of 7 mm was prepared.
[0069] Example 2
[0070] A nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material, the preparation method of which is as follows:
[0071] S1. Weigh 0.238 g of cobalt chloride and 0.005 g of hexadecyltrimethylammonium bromide respectively and dissolve them in 20 mL of deionized water. Stir magnetically for 20 min to obtain a clear and transparent solution A.
[0072] S2. The obtained clear and transparent solution A was injected into deionized water containing 3 g of 2-methylimidazole, and the mixture was magnetically stirred for 1 h to obtain a mixed solution A.
[0073] S3. The mixed solution A was centrifuged and washed with anhydrous ethanol three times. The powder after centrifugation was then dried in a forced air drying oven at 60° C. for 12 h to obtain a nano-cubic ZIF-67 absorbing material.
[0074] S4. Weigh 0.06 g of ammonium molybdate and dissolve it in 30 mL of anhydrous ethanol. Magnetically stir for 20 min. Then add nanocubic ZIF-67 absorbing material. After magnetic stirring for 30 min, ultrasonic treatment is performed for 20 min to obtain a mixed solution B. The mixed solution B is centrifuged and washed twice with deionized water to obtain powder A.
[0075] S5. Dissolve powder A in 30 mL of deionized water and stir magnetically for 30 min to obtain a mixed solution C.
[0076] S6. Maintain the mixed solution C at 90° C. for 1 hour to obtain powder B.
[0077] S7. The powder B is centrifuged and washed with ethanol 5 times. The powder B after centrifugation is then dried in a forced air drying oven at 70° C. for 9 h to obtain a cobalt molybdenum hydroxide absorbing material having a hollow cubic shape.
[0078] S8. Dissolve the hollow cubic cobalt molybdenum hydroxide absorbing material in 50 mL of deionized water, add 0.05 g of sulfur powder, and stir magnetically for 30 minutes to obtain a mixed solution D.
[0079] S9. Transfer the mixed solution D to a hydrothermal reactor with a 100 mL polytetrafluoroethylene liner. The reaction temperature is 150° C. and the reaction time is 5 h. After the reaction is completed, the powder obtained is washed twice with deionized water and then twice with anhydrous ethanol. The powder is dried in a forced air drying oven at 60° C. for 8 h to obtain a nanoflower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material.
[0080] S10. According to the ratio of 30% of the cobalt-doped molybdenum hydroxide absorbing material doped in paraffin, a coaxial ring sample with an inner diameter of 3 mm and an outer diameter of 7 mm was prepared.
[0081] Example 3
[0082] A nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material, the preparation method of which is as follows:
[0083] S1. Weigh 0.238 g of cobalt chloride and 0.005 g of hexadecyltrimethylammonium bromide respectively and dissolve them in 20 mL of deionized water. Stir magnetically for 20 min to obtain a clear and transparent solution A.
[0084] S2. The obtained clear and transparent solution A was injected into deionized water containing 3 g of 2-methylimidazole, and the mixture was magnetically stirred for 1 h to obtain a mixed solution A.
[0085] S3. The mixed solution A was centrifuged and washed with anhydrous ethanol three times. The powder after centrifugation was then dried in a forced air drying oven at 60° C. for 12 h to obtain a nano-cubic ZIF-67 absorbing material.
[0086] S4. Weigh 0.03 g of ammonium molybdate and dissolve it in 30 mL of anhydrous ethanol. Magnetically stir for 20 min. Then add nanocubic ZIF-67 absorbing material. After magnetic stirring for 30 min, ultrasonic treatment is performed for 20 min to obtain a mixed solution B. The mixed solution B is centrifuged and washed twice with deionized water to obtain powder A.
[0087] S5. Dissolve powder A in 30 mL of deionized water and stir magnetically for 30 min to obtain a mixed solution C.
[0088] S6. Maintain the mixed solution C at 90° C. for 1 hour to obtain powder B.
[0089] S7. The powder B is centrifuged and washed with ethanol 5 times. The powder B after centrifugation is then dried in a forced air drying oven at 70° C. for 9 h to obtain a cobalt molybdenum hydroxide absorbing material having a hollow cubic shape.
[0090] S8. Dissolve the hollow cubic cobalt molybdenum hydroxide absorbing material in 50 mL of deionized water, add 0.1 g of sulfur powder, and stir magnetically for 30 minutes to obtain a mixed solution D.
[0091] S9. Transfer the mixed solution D to a hydrothermal reactor with a 100 mL polytetrafluoroethylene liner. The reaction temperature is 150° C. and the reaction time is 5 h. After the reaction is completed, the powder obtained is washed twice with deionized water and then twice with anhydrous ethanol. The powder is dried in a forced air drying oven at 60° C. for 8 h to obtain a nanoflower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material.
[0092] S10. According to the ratio of 30% of the cobalt-doped molybdenum hydroxide absorbing material doped in paraffin, a coaxial ring sample with an inner diameter of 3 mm and an outer diameter of 7 mm was prepared.
[0093] Experimental testing
[0094] The electromagnetic parameters of the blank sample and the absorbing materials of Examples 1 to 3 were measured by a vector network analyzer, and then the absorbing performance was calculated using CST STUDIO SUITE software.
[0095] The SEM of the pure cobalt molybdenum hydroxide sample prepared in the blank example is as follows Figure 1 Its absorbing performance is as shown in Figure 2 The SEM image of the nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material prepared in Example 1 is shown in FIG. Figure 3 Its absorbing performance is as shown in Figure 4 The SEM image of the nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material prepared in Example 2 is shown in FIG. Figure 5 Its absorbing performance is as shown in Figure 6 The SEM image of the nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material prepared in Example 3 is shown in FIG. Figure 7 Its absorbing performance is as shown in Figure 8 shown.
[0096] Depend on Figure 1 It can be seen that the layered cobalt molybdenum hydroxide is in the shape of a hollow cubic block. Figure 2 It can be seen that the overall absorption performance in the range of 2-18GHz is poor, with the minimum reflection loss being only -2.99dB, which cannot meet actual application requirements.
[0097] Depend on Figure 3 It can be seen that after the non-metallic sulfur element is doped, the cobalt-molybdenum hydroxide, which was originally a hollow cubic block, has obvious nano-flowers on its surface. Doping with sulfur can introduce more non-uniform heterogeneous interfaces and generate a large number of defects inside the material. Figure 4 It can be seen that when the thickness of the composite material is 4.2mm, the minimum reflection loss at 9.06GHz reaches -25.52dB, and the widest effective absorption band at this time reaches 2.7GHz. Compared with pure cobalt molybdenum hydroxide powder, the composite material's ability to reduce electromagnetic waves has been significantly enhanced.
[0098] Depend on Figure 5 It can be seen that after sulfur doping, the surface of the hollow cubic cobalt-molybdenum hydroxide is covered with a layer of nanosheets, but because the doping amount of sulfur powder is too low, no regular nanoflowers appear on the surface of the cobalt-molybdenum hydroxide. Figure 6It can be seen that the doping of sulfur powder will improve the absorption performance of cobalt molybdenum hydroxide to a certain extent, but due to the low doping amount, the improvement in absorption performance is not high. When the thickness of the composite material is 3.8mm, the minimum reflection loss at 12.48GHz reaches -11.64dB, and the widest effective absorption band at this time is only 0.1GHz.
[0099] Depend on Figure 7 It can be seen that the amount of ammonium molybdate added during the etching of ZIF-67 is reduced, resulting in a decrease in the amount of cobalt-molybdenum hydroxide produced. Therefore, when sulfur is doped, the nanoflowers generated on the surface are composed of tiny nanosheets. Figure 8 It can be seen that when the thickness of the composite material is 4.8 mm, the minimum reflection loss at 17.50 GHz reaches -40.86 dB, and the widest effective absorption band at this time reaches 1.2 GHz.
[0100] Therefore, the present invention adopts the above-mentioned nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material and its preparation method. The preparation method is simple, safe and reliable. The obtained nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material has a larger specific surface area and a smaller density, thereby greatly improving the material's loss capacity for incident electromagnetic waves.
[0101] Finally, it should be noted that the above embodiments are only used to illustrate the technical solutions of the present invention and not to limit it. 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 nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material, characterized in that: The following steps are involved: S1. Weigh cobalt chloride and cetyltrimethylammonium bromide in proportion and dissolve them in deionized water, stirring to obtain a clear and transparent solution A; S2. Weigh 2-methylimidazole and dissolve it in deionized water, stirring to obtain a clear and transparent solution B. Add the clear and transparent solution B to the clear and transparent solution A obtained in S1, stirring to obtain a mixed solution A. S3, centrifuging and washing the mixed solution A obtained in S2 several times, and then drying it to obtain a nano-cubic block of ZIF-67 absorbing material; S4. Weigh ammonium molybdate in proportion and dissolve it in anhydrous ethanol. Stir and add the ZIF-67 absorbing material obtained in S3. Stir and then sonicate to obtain a mixed solution B. Centrifuge and wash the mixed solution B several times to obtain powder A. S5. Dissolve the powder A obtained in S4 in deionized water, stir, and obtain a mixed solution C; S6, keeping the mixed solution C obtained in S5 warm and allowing it to stand to obtain powder B; S7, centrifuging and washing the powder B obtained in S6 several times, and then drying it to obtain a cobalt molybdenum hydroxide absorbing material having a hollow cubic shape; S8, dissolving the cobalt molybdenum hydroxide absorbing material obtained in S7 in deionized water, adding sulfur powder, and stirring to obtain a mixed solution D; S9. Transfer the mixed solution D obtained in S8 to a reactor for hydrothermal reaction, and then centrifuge and wash several times, and dry to obtain a nanoflower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material.
2. The method for preparing a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material according to claim 1, characterized in that: In S1, the mass ratio of the cobalt chloride, the cetyltrimethylammonium bromide, and the deionized water is 0.238-0.714:0.005-0.015:
20.
3. The method for preparing a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material according to claim 1, characterized in that: In S2, the mass ratio of the 2-methylimidazole to the deionized water is 3 to 9:
70.
4. The method for preparing a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material according to claim 1, characterized in that: In S3, the drying temperature is 60° C. and the drying time is 12 h.
5. The method for preparing a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material according to claim 1, characterized in that: In S4, the mass ratio of the ammonium molybdate to the anhydrous ethanol is 0.03-0.09:
30.
6. The method for preparing a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material according to claim 1, characterized in that: In S6, the temperature of the heat preservation and standing is 90° C. and the time is 1 hour.
7. The method for preparing a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material according to claim 1, characterized in that: In S7, the drying temperature is 70° C. and the drying time is 9 hours.
8. The method for preparing a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material according to claim 1, characterized in that: In S8, the mass ratio of the sulfur powder to the deionized water is 0.05-0.15:
50.
9. The method for preparing a nano-flower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material according to claim 1, characterized in that: In S9, the reaction temperature of the hydrothermal reaction is 120-180° C., and the reaction time is 5-8 hours; The drying temperature is 60° C. and the drying time is 8 hours.
10. A sulfur-doped cobalt molybdenum hydroxide absorbing material prepared by the method for preparing the nanoflower-shaped sulfur-doped cobalt molybdenum hydroxide absorbing material according to any one of claims 1 to 9.