阅读说明：本技术 一种形貌可调控kit-6型有序介孔二氧化硅的制备方法 (Preparation method of shape-adjustable KIT-6 type ordered mesoporous silica ) 是由 王伟 孙蕊 喻凌峰 高颖 杨维领 于 2021-08-16 设计创作，主要内容包括：本发明的一种形貌可调控KIT-6型有序介孔二氧化硅的制备方法,属于介孔材料技术领域。步骤如下：按质量比,模板剂：硅源：结构导向剂：催化剂：水＝1:(1.49-2.5):(0.35-0.4):(4.5-6.5):(41.85-43.35),将模板剂、去离子水和酸性催化剂混合均匀,水浴条件下加入结构导向剂搅拌均匀,得到均一反应系统,加入硅源搅拌反应,获得终混物,硅源加入方式为一次性加入或分两次分批加入；将终混物进行水热反应后,经分离、洗涤、干燥和煅烧工艺,制得形貌可调控KIT-6型有序介孔二氧化硅粉末产物。该法制备工艺简单,实现了球形、棒状不同尺寸KIT-6制备,能够对介孔结构有序性、孔径和孔结构参数有效控制,最终获得具有明显性能优势的介孔二氧化硅。(The invention discloses a preparation method of KIT-6 type ordered mesoporous silica with adjustable morphology, and belongs to the technical field of mesoporous materials. The method comprises the following steps: according to the mass ratio, the template agent: silicon source: structure directing agent: catalyst: 1, 1.49-2.5 parts of water, (0.35-0.4 parts of water), (4.5-6.5 parts of water) (41.85-43.35), uniformly mixing a template agent, deionized water and an acid catalyst, adding a structure directing agent under the condition of water bath, uniformly stirring to obtain a uniform reaction system, adding a silicon source, and stirring to react to obtain a final mixture, wherein the silicon source is added in one step or added in two times in batches; and (3) carrying out hydrothermal reaction on the final mixture, and then carrying out separation, washing, drying and calcining processes to obtain a KIT-6 type ordered mesoporous silica powder product with adjustable morphology. The method has simple preparation process, realizes the preparation of KIT-6 with spherical and rod-like different sizes, can effectively control the order, the aperture and the pore structure parameters of the mesoporous structure, and finally obtains the mesoporous silicon dioxide with obvious performance advantages.)

1. A preparation method of KIT-6 type ordered mesoporous silica with adjustable morphology is characterized by comprising the following steps:

(1) according to the mass ratio, the template agent: silicon source: structure directing agent: catalyst: 1, 1.49-2.5, 0.35-0.4, 4.5-6.5 and 41.85-43.35, uniformly mixing a template agent, deionized water and an acid catalyst, adding a structure directing agent under the condition of water bath, uniformly stirring to obtain a uniform reaction system, adding a silicon source, and stirring to react to obtain a final mixture, wherein the silicon source is added in a one-time manner or added in batches in two times;

(2) transferring the final mixture to a high-pressure kettle, and carrying out hydrothermal reaction to obtain a final product;

(3) separating, washing, drying and calcining the hydrothermal product to obtain a KIT-6 type ordered mesoporous silicon dioxide powder product with adjustable morphology.

2. The method for preparing the morphology-controllable KIT-6 type ordered mesoporous silica according to claim 1, wherein the step (1) comprises the following steps:

when the silicon source is added at one time, the mass ratio of the added raw materials is that the template agent: silicon source: structure directing agent: catalyst: 1 part of water (1.49-1.71), 0.35-0.4, 4.5-6.5, 41.85-43.35); the silicon source adding process comprises the following steps:

directly adding a silicon source into the homogeneous reaction system, and stirring for reaction to obtain a final mixture;

when the silicon source is added in batches twice, the proportion relation of the addition amount of the raw materials is that the template agent: silicon source: structure directing agent: catalyst: water 1 (2-2.5): (0.35-0.4): 4.5-6.5): (41.85-43.35); wherein, the silicon source comprises a silicon source 1 and a silicon source 2, and the adding process of the silicon source is as follows:

adding a silicon source 1 into the homogeneous reaction system, and stirring for reaction; adding a silicon source 2, and continuously stirring for reaction to obtain a final mixture.

3. The method for preparing the shape-controllable KIT-6 type ordered mesoporous silica according to claim 1, wherein in the step (1), the template agent is a nonionic surfactant, the acidic catalyst is concentrated hydrochloric acid, the structure directing agent is benzyl alcohol, and the silicon source is Tetraethoxysilane (TEOS).

4. The preparation method of the shape-controllable KIT-6 type ordered mesoporous silica as claimed in claim 1, wherein the water bath temperature in step (1) is 28-35 ℃, and the stirring time after the structure-directing agent is added is 10-25 min.

5. The method for preparing the shape-controllable KIT-6 type ordered mesoporous silica according to claim 2, wherein in the step (1), when the silicon source is added at one time, the stirring reaction time after the silicon source is added is 20-24 hours.

6. The method for preparing the shape-controllable KIT-6 type ordered mesoporous silica according to claim 2, wherein in the step (1), when the silicon source is added twice in batches, the mass ratio of the silicon source 1: the silicon source 2 is (6-8) and (2-4).

7. The method for preparing the shape-controllable KIT-6 type ordered mesoporous silica according to claim 6, wherein in the step (1), the silicon source is 1: and the silicon source 2 is 7: 3.

8. The preparation method of the shape-controllable KIT-6 type ordered mesoporous silica as claimed in claim 2, wherein in the step (1), when the silicon source is added in batches twice, the stirring reaction time after the silicon source 1 is added is 2-4h, and the stirring reaction time after the silicon source 2 is added is 20-24 h.

9. The preparation method of the shape-controllable KIT-6 type ordered mesoporous silica as claimed in claim 1, wherein in the step (2), the hydrothermal temperature is 80-110 ℃ and the hydrothermal time is 20-30 h.

10. The method for preparing the KIT-6 type ordered mesoporous silica with controllable morphology as claimed in claim 1, wherein the aperture of the KIT-6 type ordered mesoporous silica with controllable morphology prepared in the step (3) is 8.8-10.3nm, and the specific surface area is 786-837m²·g^-1Pore volume of 0.87-1.37cm³·g^-1Lattice constant a₀Is 24-27 nm.

The technical field is as follows:

the invention belongs to the technical field of mesoporous materials, and particularly relates to a preparation method of KIT-6 type ordered mesoporous silica with an adjustable morphology.

Background art:

since 1992, scientists in Mobil corporation (Mobil) used alkyl quaternary ammonium salt cationic surfactant as a template to successfully synthesize a novel M41S mesoporous molecular sieve [ C.T. Kresge, M.E. Leonowicz, W.J. Roth, J.C. Vartuli and J.S. Beck, Nature,1992,359,710], the research of mesoporous materials was vigorously developed. The mesoporous material has an ordered mesostructure, a high specific surface area and a large pore volume, and has huge application prospects in the aspects of adsorption, catalysis, separation and the like.

The principle of the preparation of ordered mesoporous materials is based on the self-assembly process between inorganic species and surfactants, among the many surfactants that have been used, non-ionic block copolymer surfactants (such as P123) are of interest because they allow the preparation of mesoporous materials with larger pore sizes and more flexible structural design [ d.zhao, q.huo, j.feng, b.f.chromelka and g.d.stucky, j.am.chem.soc.,1998,120,6024 ]. However, compared with other types of mesoporous silica (such as the famous SBA-15 with a two-dimensional hexagonal pore structure), the cubic phase (Ia3d) mesoporous silica KIT-6 with a three-dimensional pore structure has an important application potential in the fields of catalytic carriers, adsorption, hard template agents, reactors and the like because the cubic phase mesoporous silica KIT-6 has a three-dimensional pore structure and larger most probable pore diameter. KIT-6 was first discovered in 2002 by Zhao east Yuan of the university of Compound Dan [ Kleitz F, Choi S H, Ryoo R.chemical Communications,2003,9(17):2136-2137], and KIT-6 was prepared experimentally using 3-mercaptopropyltrimethoxysilane (benzene, methylbenzene, dimethylbenzene and trimethylbenzene) n-butanol as a cosolvent and using the principle of volatile self-assembly of a nonionic surfactant P123. Then, Ryoo et al n-butyl alcohol is used as a cosolvent, KIT-6 powder is prepared in a solution by utilizing a nonionic surfactant P123 based on a surfactant self-assembly principle, and the powder preparation of KIT-6 is further developed and perfected; liu X, Tian B, Dr C Y, et al, Angewandte Chemie International Edition,2002,41(20): 3876) -3878; kim T W, Freddy K, Blain P, et al, Journal of the American Chemical Society,2005,127(20): 7601-7610.). Thereafter, researchers [ Meka A K, Niu Y T, Karmakar S, et al, CHEMINAMANOMAT, 2016,2, 220-. However, the formation process limited to the bicontinuous cubic phase (Ia3d) structure is complicated, resulting in extremely harsh preparation conditions, so that the current research has limited progress, especially in terms of morphology and structure control.

In order to solve the problem, the applicant proposes a method for preparing KIT-6 type ordered mesoporous silica with different shapes by using benzyl alcohol as a novel cosolvent and a nonionic surfactant P123 as a template and adopting a spacing self-assembly method (PCSA) [ W.Wang, W.J.Shann, H.Ru, N.Wu, J.Mater.Chem.,2011,21,12059 ] reported by the applicant previously. This patent application has the following advantages over the current methods: (1) the preparation condition range is wide, so that the KIT-6 can be prepared more conveniently; (2) the control of different shapes and sizes of the powder, such as spherical shape, rod shape and the like, is realized; (3) allowing the preparation of the grade mesoporous KIT-6 type ordered mesoporous silica.

The invention content is as follows:

the invention aims to overcome the difficulties in the prior art for preparing the bicontinuous cubic phase (Ia3d) KIT-6 and controlling the morphology, and provides a preparation method of a shape-controllable KIT-6 type ordered mesoporous silica.

In order to achieve the purpose, the invention adopts the following technical scheme:

a preparation method of KIT-6 type ordered mesoporous silica with adjustable morphology comprises the following steps:

(1) according to the mass ratio, the template agent: silicon source: structure directing agent: catalyst: 1, (1.49-2.5), (0.35-0.4), (4.5-6.5), (41.85-43.35), uniformly mixing a template agent, deionized water and an acid catalyst, transferring to a temperature-controlled stirring water bath, adding a structure directing agent to stir uniformly when the temperature is constant to obtain a uniform reaction system, adding a silicon source to react under stirring to obtain a final mixture, wherein the silicon source is added in one step or added in batches at two times;

(2) transferring the final mixture to a high-pressure kettle, and carrying out hydrothermal reaction to obtain a final product;

(3) separating, washing, drying and calcining the hydrothermal product to obtain a KIT-6 type ordered mesoporous silicon dioxide powder product with adjustable morphology.

In the step (1):

when the silicon source is added at one time, the mass ratio of the added raw materials is that the template agent: silicon source: structure directing agent: catalyst: 1 part of water (1.49-1.71), 0.35-0.4, 4.5-6.5, 41.85-43.35); the silicon source adding process comprises the following steps:

directly adding a silicon source into the homogeneous reaction system, and stirring for reaction to obtain a final mixture;

when the silicon source is added in batches twice, the proportion relation of the addition amount of the raw materials is that the template agent: silicon source: structure directing agent: catalyst: water 1 (2-2.5): (0.35-0.4): 4.5-6.5): (41.85-43.35); wherein, the silicon source comprises a silicon source 1 and a silicon source 2, and the adding process of the silicon source is as follows:

adding a silicon source 1 into the homogeneous reaction system, and stirring for reaction; adding a silicon source 2, and continuously stirring for reaction to obtain a final mixture.

In the step (1), the template agent is a nonionic surfactant, the acidic catalyst is concentrated hydrochloric acid, the structure directing agent is benzyl alcohol, and the silicon source is Tetraethoxysilane (TEOS).

In the step (1), the nonionic surfactant is P123 surfactant, the P123 surfactant is commercial Pluronic polyoxyethylene glycol based front-end copolymer nonionic surfactant, and the molecular weight is 5800.

In the step (1), the mass ratio of the template to the catalyst in the raw material is calculated by the mass of the solute, and the water in the raw material comprises the water contained in the raw material added in the form of solution.

In the step (1), the mass fraction of the concentrated hydrochloric acid is 37%.

In the step (1), the water bath temperature is 28-35 ℃, and preferably 30 ℃.

In the step (1), the stirring time after the structure directing agent is added is 10-25 min.

In the step (1), when the silicon source is added once, the stirring reaction time after the silicon source is added is 20-24 h.

In the step (1), when the silicon source is added in batches twice, the mass ratio of the silicon source 1: the silicon source 2 is (6-8) and (2-4).

In the step (1), when the silicon source is added in batches twice, preferably, the mass ratio of the silicon source 1: the silicon source 2 is 7:3, and the mesostructure can be still ensured when the silicon source is 6:4 and 8:2, but the shape is irregular.

In the step (1), when the silicon source is added in batches twice, the stirring reaction time after the silicon source 1 is added is 2-4 h.

In the step (1), when the silicon source is added in batches twice, the stirring reaction time after the silicon source 2 is added is 20-24 hours.

In the step (2), the hydrothermal temperature is 80-110 ℃ and the time is 20-30 h.

In the step (2), the hydrothermal temperature is preferably 90-100 ℃ and the time is preferably 20-30 h.

In the step (2), the calcining temperature is 500-^-1。

In the step (3), the holes in the prepared KIT-6 type ordered mesoporous silica with the adjustable morphology are hierarchical holes, including micropores and mesopores.

In the step (3), the prepared morphology-controllable KIT-6 type ordered mesoporous silica has the aperture of 8.8-10.3nm and the specific surface area of 786-837m²·g^-1Pore volume of 0.87-1.37cm³·g^-1The lattice constant a0 is 24-27 nm.

In the step (3), preferably, the prepared morphology-controllable KIT-6 type ordered mesoporous silica has the aperture of 9.0-10.3nm and the specific surface area of 800-²·g^-1Pore volume of 0.93-1.37cm³·g^-1Lattice constant a₀Is 25-27 nm.

In the step (3), the prepared KIT-6 type ordered mesoporous silica with adjustable morphology is spherical, ellipsoidal or rod-shaped, and when the shape is spherical, the particle size is 3-6 μm.

In the preparation process of the method, the addition of the benzyl alcohol is matched with the interval selfThe assembly process reduces the ratio of the volume of the hydrophilic micelle to the volume of the hydrophobic micelle, is easy to form a la3d structure with lower curvature, and can obtain KIT-6 mesoporous silica with different shapes and pore structures by adjusting reaction parameters. Wherein path two results in a of KIT-6 material₀The value of the KIT-6 material is larger than that of the KIT-6 material obtained by the traditional method, the PCSA path is adopted, the TEOS is added step by step to reduce the volume of the hydrophilic micelle, and the addition of the organic structure directing agent also increases the volume of the hydrophobic micelle, so that the curvature of the P123 micelle is reduced, the formation of the final three-dimensional cubic phase is facilitated, and a larger lattice constant a can be obtained₀。

The invention has the beneficial effects that:

(l) The method has simple preparation process, wide condition range and convenient preparation and regulation;

(2) the method realizes the preparation of KIT-6 with different sizes of spherical and rod-like shapes;

(3) the method realizes the control of the order, the aperture and the pore structure parameters of the mesoporous structure by adjusting the preparation parameters, finally obtains the mesoporous silicon dioxide with obvious performance advantages, can provide more reaction sites by obtaining the three-dimensional mesoporous structure, and has good application in the fields of catalysis and adsorption.

Description of the drawings:

FIG. 1 is a small-angle XRD pattern of KIT-6 mesoporous silica prepared in example 1 of the present invention wherein FIG. 1(a) is a small-angle XRD curve;

fig. 2 is an SEM image and a nitrogen adsorption-desorption curve and a pore size distribution curve of KIT-6 mesoporous silica prepared in example 2 of the present invention, wherein fig. 2(a) is a small-angle XRD curve;

fig. 3 is SEM image and small-angle XRD image and nitrogen adsorption-desorption curve and pore size distribution curve of KIT-6 mesoporous silica prepared in example 3 of the present invention, wherein fig. 3(a) is SEM image, fig. 3(b) is small-angle XRD curve, fig. 3(c) is nitrogen adsorption-desorption curve, and fig. 3(d) is pore size distribution curve;

fig. 4 is an SEM image and a small-angle XRD image and a nitrogen adsorption-desorption curve and a pore size distribution curve of KIT-6 mesoporous silica prepared in example 6 of the present invention, wherein fig. 4(a) is the SEM image, fig. 4(b) is the small-angle XRD curve, fig. 4(c) is the nitrogen adsorption-desorption curve, and fig. 4(d) is the pore size distribution curve;

FIG. 5 is a small-angle XRD pattern, a nitrogen adsorption-desorption curve and a pore size distribution curve of KIT-6 mesoporous silica prepared in comparative examples 3-3 of the present invention, wherein FIG. 5(a) is a small-angle XRD curve, FIG. 5(b) is a nitrogen adsorption-desorption curve, and FIG. 5(c) is a pore size distribution curve;

fig. 6 is a small-angle XRD image and a nitrogen adsorption-desorption curve and a pore size distribution curve of KIT-6 mesoporous silica prepared in example 8 of the present invention, wherein fig. 6(a) is a small-angle XRD curve, fig. 6(b) is a nitrogen adsorption-desorption curve, and fig. 6(c) is a pore size distribution curve;

FIG. 7 is an SEM image and a small-angle XRD image of KIT-6 mesoporous silica prepared in example 9 of the present invention, wherein FIG. 7(a) is the SEM image and FIG. 7(b) is the small-angle XRD curve;

fig. 8 is an SEM image and a small-angle XRD image of the path of KIT-6 mesoporous silica prepared by the conventional path in comparative examples 3-4 of the present invention, in which fig. 8(a) is an SEM image and fig. 8(b) is a small-angle XRD curve.

The specific implementation mode is as follows:

the present invention will be described in further detail with reference to examples.

In the following examples:

triblock nonionic surfactant P123, analytical grade, Sigma-Aldrich;

the surfactant is added after being prepared into 10 wt% aqueous solution in advance;

benzyl alcohol assay pure, Sigma-Aldrich;

tetraethoxysilane (TEOS) relative density 0.93g cm^-3Analytically pure, chemical reagents of national drug group limited;

concentrated hydrochloric acid with the mass fraction of 36-38 percent, analytically pure, chemical reagent of national drug group limited;

deionized water, university school of northeast university;

the holes in the prepared KIT-6 type ordered mesoporous silica with the adjustable morphology are hierarchical holes, including micropores and mesopores.

A preparation method for preparing KIT-6 type ordered mesoporous silica with different shapes and sizes comprises the following steps:

path one: (1) according to the mass ratio, the nonionic surfactant: silicon source: structure directing agent: catalyst: 1, preparing (1.49-1.71), (0.35-0.5), (4.5-6.5), (41.85-43.35) and preparing materials; mixing deionized water, a catalyst and a nonionic surfactant according to a ratio to form a mixed solution, heating the mixed solution to 28-35 ℃ under stirring, adding a structure directing agent, stirring for 10min, adding a silicon source, stirring and reacting at a rotating speed of 500-700r/min for 24h, transferring to an autoclave, and carrying out hydrothermal reaction at 80-110 ℃ for 24 h. After the reaction is finished, cooling the autoclave to room temperature to obtain white precipitate, wherein the white precipitate is KIT-6 type ordered mesoporous silica; the silicon source is tetraethyl orthosilicate (TEOS), the nonionic surfactant is a polyoxypropylene polyoxyethylene copolymer (P123), the catalyst is hydrochloric acid, and the structure directing agent is benzyl alcohol.

The remaining steps are the same as those in path two.

And a second route: (1) according to the mass ratio, the silicon source: nonionic surfactant: structure directing agent: catalyst: 1:2.14 (0.35-0.5) and (4.5-6.5) and (41.85-43.35), and preparing materials; mixing deionized water, a catalyst and a nonionic surfactant according to a ratio to form a mixed solution, heating the mixed solution to 30-41 ℃ under stirring, adding a structure directing agent, stirring for 10min, adding a first part of silicon source, stirring and reacting for 2-4h at the rotating speed of 500-700r/min, adding a second part of silicon source, stirring for 24h, transferring to a high-pressure kettle, and carrying out hydrothermal reaction for 24h at the temperature of 90-110 ℃. After the reaction is finished, cooling the autoclave to room temperature to obtain white precipitate, wherein the white precipitate is KIT-6 type ordered mesoporous silica; the silicon source is tetraethyl orthosilicate (TEOS), the nonionic surfactant is a polyoxypropylene polyoxyethylene copolymer (P123), the catalyst is hydrochloric acid, and the structure directing agent is benzyl alcohol.

(2) And centrifuging, washing and drying the hydrothermal sample, and removing the surfactant to obtain the KIT-6 type ordered mesoporous silica. Wherein, the method for removing the surfactant comprises chemical extraction, calcination and the like, when the calcination is adopted, the calcination temperature is 450-600 ℃, the calcination time is 3-5h, and the heating rate is 1-2 ℃ min-1.

Example 1:

nonionic surfactant: silicon source: structure directing agent: catalyst: water 1:1.50:0.35:5.25: 42.3; 20g (10 wt%) of P123 aqueous solution, 60g of deionized water and 10.5g of HCl (37%) are stirred uniformly in a water bath kettle at 33 ℃, 0.7g of benzyl alcohol is added, after stirring for 15min, 2.99g of TEOS is added, stirring is carried out for 24h, after the reaction is finished, the mixed solution is transferred to a high-pressure reaction kettle, and hydrothermal treatment is carried out for 24h at 100 ℃. And finally, centrifugally washing, drying and calcining by using deionized water. Calcining conditions are as follows: 550 ℃ and 4 h. The heating rate is 1.5 ℃ min^-1The obtained KIT-6 type ordered mesoporous silica is named as 7-24 h. Its small angle XRD pattern is shown in FIG. 1(a), a₀23nm, a pore diameter of 5.1nm and a specific surface area of 541m²·g^-1Pore volume of 0.5cm³·g^-1. And (4) irregular appearance.

Example 2

Nonionic surfactant: silicon source: structure directing agent: catalyst: water (1: 1.71:0.35:5.25: 42.3), 20g (10 wt%) of an aqueous solution of P123, 60g of deionized water and 10.5g of HCl (37%) are stirred uniformly in a 33 ℃ water bath, 0.7g of benzyl alcohol is added, after stirring for 15min, 3.42g of TEOS is added, stirring is carried out for 24h, after the reaction is finished, the mixed solution is transferred to a high-pressure reaction kettle, and hydrothermal treatment is carried out for 24h at 100 ℃. And finally, centrifugally washing, drying and calcining by using deionized water. Calcining conditions are as follows: 550 ℃ and 4 h. The heating rate is 1.5 ℃ min^-1The obtained KIT-6 type ordered mesoporous silica is named as 8-24 h. Its small angle XRD pattern is shown in FIG. 2(a), a₀23nm, a pore diameter of 5.2nm and a specific surface area of 581m²·g^-1Pore volume of 0.5cm³·g^-1. And (4) irregular appearance.

Example 3:

according to the mass ratio, the nonionic surfactant: silicon source: structure directing agent: catalyst: water 1:2.14:0.35:5.25:42.3, silicon source 1: the silicon source 2 is 7:3, P123, deionized water and hydrochloric acid are stirred evenly in a water bath kettle at the temperature of 30 ℃, benzyl alcohol is added,stirring for 15min, adding a silicon source 1, stirring for reacting for 4h, adding a silicon source 2, stirring for 24h at the same water bath temperature, transferring the mixed solution into a high-pressure reaction kettle after the reaction is finished, carrying out hydrothermal treatment at 100 ℃ for 24h, and finally, carrying out centrifugal washing, drying and calcining by using deionized water. Calcining conditions are as follows: 550 ℃ and 4 h. The heating rate is 1.5 ℃ min^-1The obtained KIT-6 type ordered mesoporous silica is named as 7-4h-3, and the SEM image is shown in figure 3(a), the small-angle XRD image is shown in figure 3(b), the nitrogen adsorption and desorption curve is shown in figure 3(c), and the pore size distribution curve is shown in figure 3 (d). As can be seen from the figure, the prepared KIT-6 type ordered mesoporous silica has better sphericity, the particle size is 4-5 mu m, the order is higher, the larger pore diameter is 10.3nm, and the specific surface area is 837m²·g^-1Pore volume of 1.37cm³·g^-1The morphology is spherical, a₀＝27nm。

Comparative example 3-1

The difference from example 3 is that the hydrothermal parameter is 120 ℃,20 h, and the detection shows that although the product with spherical appearance can be obtained, the specific surface area is obviously reduced and only reaches 661m²·g^-1。

Comparative examples 3 to 2

The difference from example 3 is that the time interval between the addition of the silicon source 2 and the addition of the silicon source 1 is 5 hours, and detection shows that the obtained product has a spherical shape but has an unordered structure and a specific surface area reduced to 600m due to too long interval time²·g^-1，a₀＝22nm。

Comparative examples 3 to 3:

the difference from example 3 is that, in mass ratio, the nonionic surfactant: silicon source: structure directing agent: catalyst: the obtained KIT-6 type ordered mesoporous silica is named as [email protected] with the water ratio of 1:2.14:0.5:5.25:42.3, and the small-angle XRD pattern, the nitrogen adsorption and desorption curve and the pore size distribution curve thereof are shown in fig. 5, fig. 5(a) is the small-angle XRD pattern, fig. 5(b) is the nitrogen adsorption and desorption curve and fig. 5(c) is the pore size distribution curve. As can be seen from the figure, the prepared KIT-6 type ordered mesoporous silica has higher degree of order, the appearance comprises a small amount of spherical particles, the rest is mostly irregular, and the aperture is 9.3nm694m specific surface area²G-1, pore volume 0.84cm³·g-1，a₀＝23nm。

Comparative examples 3 to 4:

the difference from example 3 is that the silicon source is added at one time, and the obtained KIT-6 type ordered mesoporous silica is named as 10-0, and the SEM image is shown in FIG. 8(a), and FIG. 8(b) is a small-angle XRD image. As can be seen from the figure, the prepared mesoporous silica belongs to a typical SBA-15 two-dimensional hexagonal structure, the curvature of the micelle cannot be reduced to the curvature required by the formation of a three-dimensional phase due to the addition of excessive silicon sources at one time, the formation of the three-dimensional phase cannot be promoted, the specific surface area is obviously reduced, and a₀＝21nm。

Comparative examples 3 to 5

The difference is that the same amount of n-butanol is used to replace benzyl alcohol to prepare the product, and the obtained product is KIT-6 type mesoporous silica product through detection, but the appearance is irregular, a₀23nm, a pore diameter of 6.2nm, a specific surface area of 605m²·g^-1Pore volume 0.78cm³·g^-1。

Example 4

The difference from example 3 is that the nonionic surfactant: silicon source: structure directing agent: catalyst: the obtained product has ordered KIT-6 three-dimensional structure, good sphericity, particle size of 5-6 μm, high order, large pore diameter of 10.2nm, and specific surface area of 810m²·g^-1Pore volume of 1.0cm³·g^-1，a₀＝25nm。

Example 5

The difference from the example 3 is that the time interval between the silicon source 2 and the silicon source 1 is 3h, and the detection shows that the structure is an ordered KIT-6 three-dimensional structure, the sphericity is better, the particle size is 4-6 mu m, the order is higher, the pore diameter is larger and is 9.6nm, and the specific surface area is 809m²·g^-1Pore volume of 1.07cm³·g^-1，a₀＝26nm。

Example 6:

same as example 3, zoneIn addition, the nonionic surfactant: silicon source: structure directing agent: catalyst: the obtained KIT-6 type ordered mesoporous silica is named as [email protected] with water being 1:2.14:0.4:5.25:42.3, and SEM image thereof is shown in fig. 4(a), fig. 4(b) is small angle XRD image, fig. 4(c) is nitrogen adsorption and desorption curve, and fig. 4(d) is pore size distribution curve. As can be seen from the figure, the prepared KIT-6 type ordered mesoporous silica has better ellipsoidal shape, higher degree of order, larger aperture of 10.0nm and specific surface area of 805m²·g^-1Pore volume of 1.02cm³·g^-1，a₀＝25nm。

Example 7

The difference from the example 3 is that the mass ratio of the TEOS of the first part to the TEOS of the second part is 6:4, the structure is a KIT-6 three-dimensional structure with higher order degree, the appearance is a certain amount of irregular appearance in a spherical shape, the pore diameter is 8.8nm, and the specific surface area is 788m²G-1, pore volume 0.89cm³·g^-1，a₀＝24nm。

Example 8:

the difference from example 3 is that the first part TEOS: the mass ratio of the second part of TEOS is 8:2, and the obtained KIT-6 type ordered mesoporous silica is named as 8-4 h-2. Fig. 6(a) is a small-angle XRD pattern, fig. 6(b) is a nitrogen adsorption/desorption curve, and fig. 6(c) is a pore size distribution curve. As can be seen from the figure, the prepared KIT-6 type ordered mesoporous silica has higher degree of order, a certain amount of irregular morphology is included in the spherical shape, the larger aperture is 8.9nm, and the specific surface area is 786m²·g^-1Pore volume of 0.87cm³·g^-1，a₀＝24nm。

Example 9:

the difference from example 3 is that the hydrothermal parameter is 90 ℃ and 26h, the obtained KIT-6 type ordered mesoporous silica is named as [email protected], the SEM image is shown in figure 7(a), the figure 7(b) is a small-angle XRD image, and the prepared KIT-6 type ordered mesoporous silica has a good long rod-like structure, high degree of order, 9.0nm of pore diameter and 800m of specific surface area²·g^-1Pore volume of 0.93cm³·g^-1，a₀＝25nm。