Preparation method of metal-doped hyperbranched silicon oxide material as well as product and application of metal-doped hyperbranched silicon oxide material

Abstract

The invention relates to a preparation method of a metal-doped hyperbranched silicon oxide material and a product and application thereof, and the preparation method comprises the following steps: mixing cetyltrimethylammonium bromide, sodium salicylate and tetraethyl orthosilicate with an aqueous solution of triethanolamine for reaction, adding a metal precursor solution for stirring reaction, then carrying out hydrothermal reaction, filtering, washing and drying to obtain the metal-doped hyperbranched silicon oxide material. And after the reaction is finished, washing to be neutral, drying and roasting to obtain the metal-doped hyperbranched silicon oxide material. According to the method, metal is creatively adopted to dope hyperbranched silicon oxide, the effect of reducing tar and harm can be achieved while the original style of the cigarette is kept unchanged, particularly, the effect of reducing polycyclic aromatic hydrocarbon is most obvious, the irritation of the cigarette is reduced, and the smoking comfort of the cigarette is effectively improved. The metal-doped hyperbranched silicon oxide material prepared by the invention is low in cost, easy to prepare on a large scale, free from changing the existing cigarette production process, and suitable for industrial production.

Description

Technical Field

[0001] The invention belongs to the technical field of tobacco processing, and relates to a preparation method of a metal-doped hyperbranched silicon oxide material, a product thereof and an application thereof. Background Art

[0002] Cigarette smoke is an extremely complex mixture of ingredients produced by high-temperature combustion, cracking, distillation and other processes during the smoking process. In the development history of the tobacco industry, reducing tar and reducing harm of cigarettes has always been a key research area. With the continuous improvement of public health awareness and in-depth understanding of the harm of smoking, reducing the tar content of cigarettes and reducing the release of harmful substances have become important directions for improving tobacco products. At present, the world's recognized major harmful substances nicotine, polycyclic aromatic hydrocarbons, hydrogen cyanide, ammonia, crotonaldehyde, phenol, and CO have a great impact on human health, especially polycyclic aromatic hydrocarbons such as benzo[a]pyrene, which have been reported to be highly carcinogenic. Therefore, reducing the intake of these harmful substances has important practical significance for protecting human health.

[0003] In the structure of cigarettes, the filter is an important line of defense to intercept and reduce harmful substances from entering the human body. Adding adsorbents to cigarette filter rods is the main way to reduce harmful substances in smoke. A variety of materials have been used in cigarette filters, such as cellulose acetate, activated carbon, and graphene. However, the harmful components in smoke are relatively complex, and the adsorption capacity and adsorption effect of the above materials are limited. With the improvement of consumers' demand for health, it is difficult to meet the market's expectations for low-harm cigarettes by relying solely on traditional technologies.

[0004] At present, although there have been some attempts to improve cigarette filters, there are still many shortcomings. On the one hand, some technologies rely too much on complex filter structure modifications in the process of harm reduction, resulting in a significant increase in production costs and difficulty in large-scale application in actual production. On the other hand, some methods of adding substances to filters may affect the taste and flavor of cigarettes, resulting in low consumer acceptance. Some additives may have poor stability during long-term storage, or poor compatibility with filter materials during processing, affecting the normal production and performance of filters.

[0005] Therefore, there is an urgent need for a new technology that can effectively reduce the various harmful substances produced by cigarette burning while ensuring the basic quality of cigarettes and the feasibility of the production process. Summary of the invention

[0006] In view of the deficiencies in the prior art, the object of the present invention is to provide a method for preparing a metal-doped hyperbranched silicon oxide material and its product and application.

[0007] In order to achieve the purpose of the invention, the present invention adopts the following technical solutions:

[0008] In a first aspect, the present invention provides a method for preparing a metal-doped hyperbranched silicon oxide material, the preparation method comprising the following steps:

[0009] (1) mixing hexadecyltrimethylammonium bromide, sodium salicylate and tetraethyl orthosilicate with an aqueous solution of triethanolamine to react;

[0010] (2) adding the metal precursor to the mixed solution of step (1), first stirring the mixture for reaction, and then performing a hydrothermal reaction;

[0011] (3) After the reaction is completed, the mixture is washed to neutrality, dried, and calcined to obtain the metal-doped hyperbranched silicon oxide material.

[0012] The present invention makes full use of the three-dimensional porous properties of hyperbranched silica, the large specific surface area and the easy modification characteristics, and creatively uses metal to dope hyperbranched silica, thereby increasing the contact area and interaction between the material and the smoke, improving the adsorption of harmful substances in the smoke, and achieving a better tar reduction and harm reduction effect. The metal-doped hyperbranched silica material involved in the present invention can achieve the tar reduction and harm reduction effect while maintaining the original style of the cigarette, especially the reduction effect on polycyclic aromatic hydrocarbons is more obvious, which can be reduced by 40.32%, reducing the irritation of the cigarette, and effectively improving the smoking comfort of the cigarette. The metal-doped hyperbranched silica material involved in the present invention is low in cost, easy to prepare on a large scale, and can be suitable for industrial production without changing the existing cigarette production process.

[0013] Preferably, the mass ratio of triethanolamine, hexadecyltrimethylammonium bromide, sodium salicylate and tetraethyl orthosilicate is (0.2-0.8):(1-5):(0.2-3):(10-20), wherein (0.2-0.8) can be selected from 0.2, 0.3, 0.4, 0.5, 0.6, 0.7, 0.8, etc., and (1-5) can be selected from 1, 1.5, 2, 2.5, 3, 3.5, 4, 4.5, 5, etc., (0.2-3) can be selected as 0.2, 0.3, 0.5, 0.7, 1, 1.3, 1.6, 1.9, 2, 2.3, 2.6, 2.9, 3, etc., (10-20) can be selected as 10, 11, 12, 13, 14, 15, 16, 17, 18, 19, 20, etc., and any other point value within the above numerical range can be selected, so I will not go into details here.

[0014] The present invention creatively finds that changing the ratio of reactants, especially the addition ratio of sodium salicylate, will affect the microstructure of the hyperbranched silicon oxide material. When a specific mass ratio of sodium salicylate is used, the average pore size of the hyperbranched silicon oxide material can be further regulated, the specific surface area and pore volume can be increased, and thus the adsorption capacity thereof can be improved.

[0015] Preferably, the concentration of triethanolamine in the triethanolamine aqueous solution in step (1) is 0.2-1wt%, for example, 0.2wt%, 0.3wt%, 0.4wt%, 0.5wt%, 0.6wt%, 0.7wt%, 0.8wt%, 0.9wt%, 1wt%, etc. Any other point value within this numerical range can be selected, which will not be described in detail here.

[0016] Preferably, the reaction temperature in step (1) is 70-90°C (for example, 70°C, 72°C, 74°C, 76°C, 78°C, 80°C, 82°C, 84°C, 86°C, 88°C, 90°C, etc.), and the reaction time is 1.5-7h (for example, 1.5h, 2h, 3h, 3.5h, 4h, 4.5h, 5h, 5.5h, 6h, 6.5h, 7h, etc.). Any other point value within the above numerical range can be selected, and they will not be described one by one here.

[0017] Preferably, the metal precursor in step (2) comprises cerium nitrate hexahydrate, tin tetrachloride, zinc chloride or aluminum chloride.

[0018] Preferably, the metal precursor is cerium nitrate hexahydrate.

[0019] The present invention also creatively finds that metal doping can further enhance the adsorption effect of the hyperbranched silicon oxide material on harmful flue gas.

[0020] Preferably, when the metal precursor is cerium nitrate hexahydrate, before stirring the reaction, the pH of the solution is adjusted to 10-10.5, for example, 10, 10.1, 10.2, 10.3, 10.4, 10.5, etc. Any other point value within this numerical range can be selected, which will not be described here one by one.

[0021] Preferably, the stirring reaction temperature is 20-30°C (for example, 20°C, 21°C, 22°C, 23°C, 24°C, 25°C, 26°C, 27°C, 28°C, 29°C, 30°C, etc.), and the time is 0.5-1h (for example, 0.5h, 0.6h, 0.7h, 0.8h, 0.9h, 1h, etc.). Any other point value within the above numerical range can be selected, and they will not be described one by one here.

[0022] Preferably, the temperature of the hydrothermal reaction is 75-85°C (for example, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, 81°C, 82°C, 84°C, 85°C, etc.), and the time is 4-6h (for example, 4h, 4.5h, 5h, 5.5h, 6h, etc.). Any other point value within the above numerical range can be selected, and they will not be described here one by one.

[0023] Preferably, the molar ratio of tetraethyl orthosilicate to the metal precursor is (10-45):1, for example 10:1, 13:1, 16:1, 19:1, 20:1, 23:1, 26:1, 29:1, 30:1, 33:1, 36:1, 39:1, 40:1, 42:1, 45:1, etc. Any other point value within the above numerical range can be selected, which will not be described here one by one.

[0024] Preferably, the drying temperature in step (3) is 75-80°C, for example, 75°C, 76°C, 77°C, 78°C, 79°C, 80°C, etc. Any other point value within this numerical range can be selected, which will not be described here one by one.

[0025] Preferably, the calcination heating rate is 1-4°C / min (for example, 1°C / min, 2°C / min, 3°C / min, 4°C / min, etc.), the temperature is raised to 550-560°C (for example, 550°C, 551°C, 552°C, 553°C, 554°C, 555°C, 556°C, 557°C, 558°C, 559°C, 560°C, etc.), and the temperature is kept for 6-7h (for example, 6h, 6.1h, 6.2h, 6.3h, 6.4h, 6.5h, 6.6h, 6.7h, 6.8h, 6.9h, 7h, etc.). Any other point value within the above numerical range can be selected, which will not be described here one by one.

[0026] In a second aspect, the present invention provides a metal-doped hyperbranched silicon oxide material prepared according to the preparation method described in the first aspect.

[0027] In a third aspect, the present invention provides use of the metal-doped hyperbranched silicon oxide material described in the second aspect in cigarettes.

[0028] Preferably, the metal-doped hyperbranched silica material is added into a cigarette filter.

[0029] In a fourth aspect, the present invention provides a cigarette filter, comprising the metal-doped hyperbranched silica material according to the second aspect.

[0030] Preferably, the amount of the metal-doped hyperbranched silica material added to the cigarette filter is 5-15 mg / cigarette, for example, 5 mg / cigarette, 6 mg / cigarette, 7 mg / cigarette, 8 mg / cigarette, 9 mg / cigarette, 10 mg / cigarette, 11 mg / cigarette, 12 mg / cigarette, 13 mg / cigarette, 14 mg / cigarette, 15 mg / cigarette, etc. Any other point value within this numerical range can be selected, and they will not be described one by one here.

[0031] Compared with the prior art, the present invention has the following beneficial effects:

[0032] The present invention makes full use of the three-dimensional porous properties of hyperbranched silica, the large specific surface area and the easy modification characteristics, and creatively uses metal to dope hyperbranched silica, thereby increasing the contact area and interaction between the material and the smoke, improving the adsorption of harmful substances in the smoke, and achieving a better tar reduction and harm reduction effect. The metal-doped hyperbranched silica material involved in the present invention can achieve the tar reduction and harm reduction effect while maintaining the original style of the cigarette, especially the reduction effect on polycyclic aromatic hydrocarbons is more obvious, which can be reduced by 40.32%, reducing the irritation of the cigarette, and effectively improving the smoking comfort of the cigarette. The metal-doped hyperbranched silica material involved in the present invention is low in cost, easy to prepare on a large scale, and can be suitable for industrial production without changing the existing cigarette production process. BRIEF DESCRIPTION OF THE DRAWINGS

[0033] Figure 1 is a scanning electron microscope image of the material prepared in Example 1;

[0034] Figure 2 is a scanning electron microscope image of the material prepared in Comparative Example 1;

[0035] Figure 3 This is a scanning electron microscope image of the material prepared in Comparative Example 2;

[0036] Figure 4 This is a transmission electron microscope image of the material prepared in Example 1. DETAILED DESCRIPTION

[0037] The technical solution of the present invention is further described below by specific implementation methods. It should be understood by those skilled in the art that the embodiments are only to help understand the present invention and should not be regarded as specific limitations of the present invention.

[0038] In the following examples, unless otherwise specified, the reagents and consumables used were purchased from conventional reagent manufacturers in the field; unless otherwise specified, the experimental methods and technical means used were conventional methods and means in the field.

[0039] Example 1

[0040] This embodiment provides a metal-doped hyperbranched silicon oxide material, and the preparation method is as follows:

[0041] (1) Dissolve 0.205 g of triethanolamine in 75 mL of 80°C hot water and stir until completely dissolved.

[0042] (2) 1.14 g of hexadecyltrimethylammonium bromide and 0.50 g of sodium salicylate were added in sequence, and 11.22 g of tetraethyl orthosilicate was added dropwise to the above solution to react for 2 h;

[0043] (3) 0.584 g of cerium nitrate hexahydrate was dissolved in 2 mL of deionized water, and then added dropwise to the above reaction solution. The pH of the reaction solution was adjusted to 10 with 0.5 mol / L of sodium hydroxide. The reaction was stirred at 25° C. for 0.7 h and then a hydrothermal reaction was performed. The hydrothermal reaction temperature was 80° C. and the reaction time was 5 h.

[0044] (4) After the reaction is completed, the sample is taken out, cooled, washed with deionized water and ethanol until neutral, and dried at 80° C. The dried sample is heated to 550° C. at a rate of 2° C. / min in a muffle furnace and calcined for 7 h to obtain a cerium-doped hyperbranched silica material.

[0045] Example 2

[0046] This embodiment provides a metal-doped hyperbranched silicon oxide material, and the preparation method is as follows:

[0047] (1) Dissolve 0.2 g of triethanolamine in 70 mL of 70°C hot water and stir until completely dissolved.

[0048] (2) 1 g of hexadecyltrimethylammonium bromide and 0.3 g of sodium salicylate were added in sequence, and 10 g of tetraethyl orthosilicate was added dropwise to the above solution to react for 2.5 h;

[0049] (3) 0.695 g of cerium nitrate hexahydrate was dissolved in 2 mL of deionized water, and then added dropwise to the above reaction solution. The pH of the reaction solution was adjusted to 10.3 with 0.5 mol / L of sodium hydroxide. The reaction was stirred at 22° C. for 0.5 h and then a hydrothermal reaction was performed. The hydrothermal reaction temperature was 75° C. and the reaction time was 6 h.

[0050] (4) After the reaction is completed, the sample is taken out, cooled, washed with deionized water and ethanol until neutral, and dried at 77°C; the dried sample is heated to 550°C in a muffle furnace at a rate of 1°C / min and calcined for 6 hours to obtain a cerium-doped hyperbranched silica material.

[0051] Example 3

[0052] This embodiment provides a metal-doped hyperbranched silicon oxide material, and the preparation method is as follows:

[0053] (1) Dissolve 0.5 g of triethanolamine in 100 mL of 80°C hot water and stir until completely dissolved;

[0054] (2) 2 g of hexadecyltrimethylammonium bromide and 1 g of sodium salicylate were added in sequence, and 15 g of tetraethyl orthosilicate was added dropwise to the above solution to react for 3 h;

[0055] (3) 1.5 g of cerium nitrate hexahydrate was dissolved in 2 mL of deionized water, and then added dropwise to the above reaction solution. The pH of the reaction solution was adjusted to 10.5 with 0.5 mol / L of sodium hydroxide. The mixture was stirred at 27° C. for 1 h and then subjected to a hydrothermal reaction at a temperature of 90° C. for 4 h.

[0056] (4) After the reaction is completed, the sample is taken out, cooled, washed with deionized water and ethanol until neutral, and dried at 75° C. The dried sample is heated to 560° C. at a rate of 4° C. / min in a muffle furnace and calcined for 6 h to obtain a cerium-doped hyperbranched silica material.

[0057] Example 4

[0058] This embodiment provides a metal-doped hyperbranched silicon oxide material, which differs from Embodiment 1 only in that in step (3), cerium nitrate hexahydrate is replaced by tin tetrachloride in an equimolar amount, and there is no need to adjust the pH, while other conditions remain unchanged.

[0059] Example 5

[0060] This embodiment provides a metal-doped hyperbranched silicon oxide material, which differs from Embodiment 1 only in that in step (3), cerium nitrate hexahydrate is replaced by zinc chloride in an equimolar amount, and there is no need to adjust the pH, while other conditions remain unchanged.

[0061] Example 6

[0062] This embodiment provides a metal-doped hyperbranched silicon oxide material, which differs from Embodiment 1 only in that in step (3), cerium nitrate hexahydrate is replaced by aluminum chloride in an equimolar amount, and there is no need to adjust the pH, while other conditions remain unchanged.

[0063] Example 7

[0064] This embodiment provides a metal-doped hyperbranched silicon oxide material, which differs from Embodiment 1 only in that in step (2), the amount of sodium salicylate added is 0.15 g, and other conditions remain unchanged.

[0065] Example 8

[0066] This embodiment provides a metal-doped hyperbranched silicon oxide material, which differs from Embodiment 1 only in that in step (2), the amount of sodium salicylate added is 3.3 g, and other conditions remain unchanged.

[0067] Example 9

[0068] This embodiment provides a metal-doped hyperbranched silicon oxide material, which differs from Embodiment 1 only in that the amount of cerium nitrate hexahydrate added in step (3) is 0.4 g, and other conditions remain unchanged.

[0069] Example 10

[0070] This embodiment provides a metal-doped hyperbranched silicon oxide material, which differs from Embodiment 1 only in that the amount of cerium nitrate hexahydrate added in step (3) is 2.65 g, and other conditions remain unchanged.

[0071] Comparative Example 1

[0072] This comparative example provides a hyperbranched silicon oxide material, and the preparation method is as follows:

[0073] (1) Dissolve 0.205 g of triethanolamine in 75 mL of 80°C hot water and stir until completely dissolved.

[0074] (2) 1.14 g of hexadecyltrimethylammonium bromide and 0.50 g of sodium salicylate were added in sequence, and 11.22 g of tetraethyl orthosilicate was added dropwise to the above solution for 2 h, followed by a hydrothermal reaction at 80 °C for 5 h;

[0075] (3) After the reaction is completed, the sample is taken out, cooled, washed with deionized water and ethanol until neutral, and dried at 80° C. The dried sample is heated to 550° C. at a rate of 2° C. / min in a muffle furnace and calcined for 7 h to obtain a hyperbranched silica material.

[0076] Comparative Example 2

[0077] This comparative example provides a hyperbranched silicon oxide material, and the preparation method is as follows:

[0078] (1) Dissolve 0.205 g of triethanolamine in 75 mL of 80°C hot water and stir until completely dissolved.

[0079] (2) 1.14 g of hexadecyltrimethylammonium bromide and 0.25 g of sodium salicylate were added in sequence, and 11.22 g of tetraethyl orthosilicate was added dropwise to the above solution for 2 h, and then a hydrothermal reaction was carried out at 80 ° C for 5 h;

[0080] (3) After the reaction is completed, the sample is taken out, cooled, washed with deionized water and ethanol until neutral, and dried at 80° C. The dried sample is heated to 550° C. at a rate of 2° C. / min in a muffle furnace and calcined for 7 h to obtain a hyperbranched silica material.

[0081] Test Example 1

[0082] In this test example, scanning electron microscope (SEM) scans were performed on Example 1 and Comparative Examples 1-2, and transmission electron microscope (TEM) scans were performed on Example 1. The results are as follows: Figure 1-4 As shown, it can be seen that the hyperbranched silicon oxide material prepared in the present invention has a typical three-dimensional central radial radiation structure.

[0083] The nitrogen adsorption-desorption curve and BJH adsorption-desorption pore volume distribution curve of the sample were measured by the static adsorption method using Quadrasorb Evo analyzer under liquid nitrogen constant temperature conditions (-196°C) to obtain the specific surface area, pore volume and average pore size of the sample. Before the test, all samples were vacuum pretreated at 200°C for 4 hours. The microstructure information is shown in Table 1.

[0084] Table 1

[0085] Group <![CDATA[Specific surface area (m 2 / g)]]> <![CDATA[Total pore volume (cm 3 / g)]]> Average pore size (nm) Example 1 690.24 1.39 11.57 Comparative Example 1 684.39 1.37 11.87 Comparative Example 2 423.45 1.28 14.67

[0086] Comparing the microstructures of Comparative Example 1 and Comparative Example 2, it can be seen that when a specific amount of sodium salicylate is used, the specific surface area and total pore capacity of the hyperbranched silica material can be significantly increased, the average pore size can be effectively reduced, and the adsorption capacity thereof can be enhanced.

[0087] Comparing the microstructures of Example 1 with those of Comparative Example 1, it can be seen that cerium doping has little effect on the microstructure of the sample, with a slight increase in the specific surface area and total pore volume and a slight decrease in the average pore diameter.

[0088] Test Example 2

[0089] In this test example, 5 mg of the hyperbranched silicon oxide materials prepared in Examples 1-10 and Comparative Examples 1-2 were added to the filter of the cigarette, and then 7 smoking evaluation experts conducted sensory evaluation of the cigarettes according to the standard of "GB 5606.4-2005 Cigarette Part 4: Sensory Technical Requirements". The results are averaged, and the blank group is a normal cigarette without adding hyperbranched silicon material. The evaluation results are shown in Table 2.

[0090] Table 2

[0091] Group luster aroma Harmony Miscellaneous gas Irritant Aftertaste total Example 1 5 28.57 5.07 10.21 18.36 21.79 89.00 Example 2 5 28.21 5.07 10.07 18.29 21.79 88.43 Example 3 5 28.57 5.07 10.07 17.93 21.57 88.21 Example 4 5 27.36 4.07 9.43 16.86 21.14 83.86 Example 5 5 27.43 4.71 9.64 17.86 20.86 85.36 Example 6 5 28.29 4.71 9.64 17.86 21.36 86.64 Example 7 5 28.21 5 10 18.07 21.79 88.07 Example 8 5 27.79 5 9.79 18.07 21.36 87.00 Example 9 5 28.14 5 9.57 17.93 21.29 86.93 Example 10 5 27.43 5 10 17.93 20.86 86.22 Comparative Example 1 5 28.14 5 9.57 17.93 21.29 86.93 Comparative Example 2 5 27.5 4.36 9.57 17.00 21.43 84.86 Blank Group 5 27.07 4.14 9.29 16.71 20.93 83.14

[0092] It can be seen from the smoking evaluation results in Table 2 that the cerium-doped hyperbranched silica material prepared by the invention can reduce irritation, soften smoke, and has no negative impact on the sensory quality of cigarettes.

[0093] Comparing Example 1 with Examples 4-6, it can be seen that the cerium-doped hyperbranched silica material can effectively reduce irritation and soften smoke compared to other metal-doped hyperbranched silica materials.

[0094] Comparing Example 1 with Examples 7-10, it can be seen that when a specific amount of sodium salicylate, a metal precursor and a molar ratio of tetraethyl orthosilicate are used, the obtained metal-doped hyperbranched silica material can further reduce irritation and soften smoke.

[0095] Comparing Example 1 with Comparative Examples 1-2, it can be seen that the cerium-doped hyperbranched silica material can more effectively reduce the irritation and impurities of cigarettes, and the smoke is more harmonious, compared with the hyperbranched silica material without metal doping.

[0096] Test Example 3

[0097] According to the method in the literature (Carbohydrate Polymers 241 (2020) 116308), the mainstream smoke of the cigarette prepared in Test Example 2 was analyzed using a fluorescence photometer to calculate the PAH removal rate. The result was the average value after three measurements, as shown in Table 3.

[0098] Table 3

[0099]

[0100]

[0101] It can be seen from the data in Table 3 that the cerium-doped hyperbranched silica material prepared in the present invention can effectively adsorb harmful flue gas, and the removal rate of polycyclic aromatic hydrocarbons is as high as over 38.48%.

[0102] Comparing Example 1 with Examples 4-6, it can be seen that the cerium-doped hyperbranched silica material can more effectively adsorb harmful flue gas and remove polycyclic aromatic hydrocarbons than other metal-doped hyperbranched silica materials.

[0103] Comparing Example 1 with Examples 7-8, it can be seen that when a specific amount of sodium salicylate is used to prepare a metal-doped hyperbranched silica material, harmful flue gas can be more effectively adsorbed and polycyclic aromatic hydrocarbons can be removed.

[0104] Comparing Example 1 with Examples 9-10, it can be seen that the molar ratio of the metal precursor to tetraethyl orthosilicate will also affect the effect of preparing the metal-doped hyperbranched silica material for adsorbing harmful flue gas.

[0105] By comparing Example 1 with Comparative Examples 1-2, it can be seen that the scavenging rate of polycyclic aromatic hydrocarbons of the cerium-doped hyperbranched silicon oxide material is significantly improved compared with the hyperbranched silicon oxide material without metal doping.

[0106] The applicant declares that the present invention illustrates the technical solution of the present invention through the above-mentioned embodiments, but the present invention is not limited to the above-mentioned embodiments, that is, it does not mean that the present invention must rely on the above-mentioned embodiments to be implemented. Those skilled in the art should understand that any improvement of the present invention, equivalent replacement of various raw materials of the product of the present invention, addition of auxiliary components, selection of specific methods, etc., all fall within the protection scope and disclosure scope of the present invention.

[0107] The preferred embodiments of the present invention are described in detail above. However, the present invention is not limited to the specific details in the above embodiments. Within the technical concept of the present invention, a variety of simple modifications can be made to the technical solution of the present invention, and these simple modifications all belong to the protection scope of the present invention.

[0108] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, the present invention will not further describe various possible combinations.

Claims

1. A method for preparing a metal-doped hyperbranched silicon oxide material, characterized in that: The preparation method comprises the following steps: (1) mixing hexadecyltrimethylammonium bromide, sodium salicylate and tetraethyl orthosilicate with an aqueous solution of triethanolamine to react; (2) adding the metal precursor to the mixed solution of step (1), first stirring the mixture for reaction, and then performing a hydrothermal reaction; (3) After the reaction is completed, the mixture is washed to neutrality, dried, and calcined to obtain the metal-doped hyperbranched silicon oxide material.

2. The preparation method according to claim 1, characterized in that: The mass ratio of triethanolamine, hexadecyltrimethylammonium bromide, sodium salicylate and tetraethyl orthosilicate is (0.2-0.8):(1-5):(0.2-3):(10-20).

3. The preparation method according to claim 1 or 2, characterized in that: The concentration of triethanolamine in the aqueous solution of triethanolamine in step (1) is 0.2-1wt%.

4. The preparation method according to any one of claims 1 to 3, characterized in that The reaction temperature of step (1) is 70-90°C and the reaction time is 1.5-7h.

5. The preparation method according to any one of claims 1 to 4, characterized in that: The metal precursor in step (2) includes cerium nitrate hexahydrate, tin tetrachloride, zinc chloride or aluminum chloride; Preferably, the metal precursor is cerium nitrate hexahydrate; Preferably, when the metal precursor is cerium nitrate hexahydrate, the pH of the solution is adjusted to 10-10.5 before stirring the reaction; Preferably, the stirring reaction temperature is 20-30°C and the time is 0.5-1h; Preferably, the temperature of the hydrothermal reaction is 75-85°C and the time is 4-6h.

6. The preparation method according to any one of claims 1 to 5, characterized in that: The molar ratio of tetraethyl orthosilicate to the metal precursor is (10-45):

1.

7. The preparation method according to any one of claims 1 to 6, characterized in that: The drying temperature in step (3) is 75-80° C. Preferably, the calcination temperature is increased at a rate of 1-4°C / min, the temperature is increased to 550-560°C, and the temperature is kept for 6-7h.

8. The metal-doped hyperbranched silicon oxide material obtained according to the preparation method according to any one of claims 1 to 7.

9. Use of the metal-doped hyperbranched silicon oxide material according to claim 8 in cigarettes; Preferably, the metal-doped hyperbranched silica material is added into a cigarette filter.

10. A cigarette filter, characterized in that: The cigarette filter comprises the metal-doped hyperbranched silicon oxide material according to claim 8; Preferably, the amount of metal-doped hyperbranched silica material added to the cigarette filter is 5-15 mg / cigarette.

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