1. Hierarchical pore SiO₂The preparation method of the microsphere material is characterized in that a silicon source precursor is used as a raw material, collagen extracted from tanning solid waste is used as a biomass template, a surfactant is used as a structure directing agent, and the hierarchical porous SiO is synthesized by a one-pot method under the condition of no need of high-temperature hydrothermal reaction₂A microsphere material.

2. The hierarchical porous SiO of claim 1₂The preparation method of the microsphere material is characterized by comprising the following steps:

dissolving collagen extracted from tanning solid waste in water to obtain a solution A containing the collagen, dissolving a surfactant in water to obtain a solution B containing the surfactant, and fully stirring the solution A and the solution B to obtain a mixed solution A;

preparing a solution C from a catalyst, water and an alcohol solvent; adding the solution C into the mixed solution A, and stirring to hydrolyze the catalyst to obtain a mixed solution B;

uniformly dispersing a silicon source precursor and a pore-expanding agent in an alcohol solvent to prepare a solution D, adding the solution D into the obtained mixed solution B, and stirring to prepare SiO₂Sol; mixing SiO₂Cleaning and drying the sol to obtain SiO₂Solid, mixing the obtained SiO₂Calcining the solid to obtain hierarchical porous SiO₂A microsphere material.

3. The hierarchical porous SiO of claim 2₂The preparation method of the microsphere material is characterized in that the reaction dosage ratio of collagen, surfactant and silicon source precursor extracted from tanning solid waste is 0.0005-0.0030 mol: 0.005-0.019 mol: 1.0-8.0 mL;

pore-expanding agent: the mass ratio of the surfactant is 0-2: 1.

4. the hierarchical porous SiO of claim 2₂The preparation method of the microsphere material is characterized in that the calcining temperature is 450-650 ℃.

5. The hierarchical porous SiO of claim 1₂The preparation method of the microsphere material is characterized in that the catalyst is one of ammonia water or acetic acid;

the alcohol solvent is one of methanol, ethanol or n-butanol.

6. The hierarchical porous SiO of claim 1₂The preparation method of the microsphere material is characterized in that the pore-enlarging agent is one of mesitylene, sodium chloride or n-hexane; the surfactant is one of CTAB, SDS, SDBS or P123.

7. The hierarchical porous SiO of claim 1₂The preparation method of the microsphere material is characterized in thatAnd when the solution C is prepared, the dosage ratio of the catalyst, water and the alcohol solvent is 1-3 mL:5mL:10 mL.

8. The hierarchical porous SiO of claim 1₂The preparation method of the microsphere material is characterized in that the precursor of the silicon source is one of methyl orthosilicate or ethyl orthosilicate.

9. Hierarchical pore SiO prepared by the preparation method of any one of claims 1 to 8₂A microsphere material.

10. A hierarchical porous SiO as claimed in claim 9₂The application of the microsphere material in adsorption.

Background

The porous microsphere material has a unique pore channel structure, and the adjustable pore size can not only interact with atoms, ions and molecules on the surface of the porous microsphere material, but also realize material transmission in the pore channel structure inside the porous microsphere material, so that the porous microsphere material has extensive research in the traditional application fields of ion exchange, adsorption, catalysis and the like. In practical applications, a single-pore (microporous, mesoporous, or macroporous) material has certain limitations, for example, the pore diameter of the microporous material is too small to facilitate the transmission of substances, the pore wall of the mesoporous material is an amorphous structure and has poor thermal stability, and the pore structure of the macroporous material is easily damaged. The hierarchical pore microsphere material has two or more than two unique pore channel structures. Compared with the traditional porous microsphere material, the microsphere material with the multilevel structure organically combines several single pore channel structures, comprehensively exerts the excellent characteristics of each level of pore structure, such as higher permeability, larger specific surface area and porosity, and is more suitable for the fields of separation, catalysis, heat preservation, energy storage and the like.

Silicon dioxide (SiO)₂) The nanometer titanium dioxide is an acidic oxide, has low toxicity, good biocompatibility, easy functionalized surface, adjustable particle size and ordered and porous pore channel structure, and is widely applied to the fields of catalytic carriers, adsorption and separation, drug sustained and controlled release, biosensors and the like. Due to mesoporous SiO₂The pore size of (a) is small, which causes problems that the adsorption capacity is not high, effective separation of biomolecules cannot be achieved, and the like. So that SiO is mixed with₂Imparting a hierarchical pore structure, on the one hand due to the hierarchical pores SiO₂The inner part of the porous SiO film is provided with a larger pore passage to provide a warehouse and a transmission channel for protein molecules, so that the structure of the porous SiO film is prevented from being damaged by the external environment, and on the other hand, the porous SiO film is provided with multilevel pores₂Contains a large amount of silicon hydroxyl (-OH) groups, so that the silicon hydroxyl (-OH) groups can be effectively bonded with protein molecules, thereby greatly improving the adsorption and separation efficiency, and having great advantages compared with the traditional carrier.

The hierarchical pore SiO is currently concerned₂The preparation method has the advantages of high raw material price and heavy pollution on one hand, strict experimental conditions (high temperature or high pressure) on the other hand, complex synthetic steps and improvement on the SiO of the hierarchical pore₂The production cost of (2) greatly limits the SiO of the hierarchical pore₂Development of materials. Therefore, how to design a route with mild synthesis conditions, simple operation and contribution to industrial production to prepare the hierarchical pore SiO with larger pore volume, larger specific surface area and higher thermal stability₂Microsphere materials still present certain challenges.

Disclosure of Invention

In order to overcome the disadvantages of the prior art, the invention aims to provide a hierarchical porous SiO₂The invention prepares the hierarchical pore SiO with larger pore volume, larger specific surface area and excellent thermal stability by the preparation method which has mild conditions, simple operation and is beneficial to industrial production₂A microsphere material.

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

the invention discloses a hierarchical pore SiO₂A preparation method of a microsphere material comprises the steps of taking a silicon source precursor as a raw material, taking collagen extracted from tanning solid waste as a biomass template, taking a surfactant as a structure directing agent, and synthesizing hierarchical porous SiO by a one-pot method under the condition of no need of high-temperature hydrothermal process₂A microsphere material.

Preferably, the method comprises the following steps:

dissolving collagen extracted from tanning solid waste in water to obtain a solution A containing the collagen, dissolving a surfactant in water to obtain a solution B containing the surfactant, and fully stirring the solution A and the solution B to obtain a mixed solution A;

preparing a solution C from a catalyst, water and an alcohol solvent; adding the solution C into the mixed solution A, and stirring to hydrolyze the catalyst to obtain a mixed solution B;

uniformly dispersing a silicon source precursor and a pore-expanding agent in an alcohol solvent to prepare a solution D, adding the solution D into the obtained mixed solution B, and stirring to prepare SiO₂Sol; mixing SiO₂Cleaning and drying the sol to obtain SiO₂Solid, mixing the obtained SiO₂Calcining the solid to obtain hierarchical porous SiO₂A microsphere material.

Further preferably, the reaction dosage ratio of the collagen extracted from the tanning solid waste, the surfactant and the silicon source precursor is 0.0005-0.0030 mol: 0.005-0.019 mol: 1.0-8.0 mL;

pore-expanding agent: the mass ratio of the surfactant is 0-2: 1.

further preferably, the temperature of the calcination treatment is 450 to 650 ℃.

Further preferably, the stirring time of the solution A and the solution B at room temperature is 20-30 min;

adding the solution C into the mixed solution A, and stirring for 30-50 min;

and adding the solution D into the obtained mixed solution B, and stirring for 2-6 h.

Preferably, the catalyst is one of ammonia water or acetic acid;

the alcohol solvent is one of methanol, ethanol or n-butanol.

Preferably, the pore-expanding agent is one of mesitylene, sodium chloride or n-hexane; the surfactant is one of CTAB, SDS, SDBS or P123.

Preferably, when the solution C is prepared, the dosage ratio of the catalyst, the water and the alcohol solvent is 1-3 mL:5mL:10 mL.

Preferably, the silicon source precursor is one of methyl orthosilicate or ethyl orthosilicate.

The invention discloses a hierarchical pore SiO prepared by the preparation method₂A microsphere material.

Preferably, the hierarchical pore SiO₂The aperture range of the microsphere material is 1.9-110 nm, and the appearance of the microsphere material is hair follicle type sphere.

The invention discloses the hierarchical pore SiO₂The application of the microsphere material in adsorption.

Compared with the prior art, the invention has the following beneficial effects:

the invention discloses a hierarchical pore SiO₂The microsphere material is prepared by mixing a surfactant in the prepared mesoporous material with collagen, wherein the surfactant is used as a template for forming a mesoporous structure on one hand, the order of the pore structure is maintained on the other hand, and the collagen template contains a large number of amino, carboxyl, hydroxyl and other groups which can be coordinated with a silicon source precursor, so that the hydrolysis rate of the collagen is slowed down. Therefore, hierarchical pore SiO with regular pore channels and a micropore-mesopore structure can be synthesized₂MicrospheresA material.

The invention also discloses a hierarchical pore SiO₂The preparation method of the microsphere material comprises the step of synthesizing hierarchical porous SiO at room temperature under the air condition₂The microspheres avoid the harsh experimental conditions (high temperature or high pressure) and complex synthetic steps in the prior art, so the microspheres have the advantages of mild synthetic conditions and simple operation, and are beneficial to industrial expanded production.

The invention also discloses the hierarchical pore SiO₂The application of the microsphere material in adsorption. The hierarchical pore SiO prepared by the invention₂The pore diameter range of the microsphere material is 1.9-110 nm, so that the biomacromolecule material can be effectively adsorbed, and related adsorption tests show that the hierarchical pore SiO is porous₂The microsphere material has good adsorption performance on lysozyme biomacromolecules, and the adsorption rate on lysozyme is up to 98.8%.

Drawings

FIG. 1 is a diagram of example 1 for synthesizing hierarchical porous SiO₂SEM spectrogram of the microsphere material;

FIG. 2 is a diagram of example 1 for synthesizing hierarchical porous SiO₂Wide angle XRD spectrum of microsphere material;

FIG. 3 is a diagram of the synthesis of hierarchical porous SiO in example 1₂A small-angle XRD spectrum of the microsphere material;

FIG. 4 is a diagram of the synthesis of hierarchical porous SiO in example 1₂Performance test patterns of the microsphere material; wherein (A) is N₂Adsorption and desorption isotherms, and (B) is a pore size distribution diagram;

FIG. 5 is a diagram of hierarchical pore SiO synthesized with different collagen contents₂The adsorption effect of the microsphere material on lysozyme is shown.

Detailed Description

In order to make the technical solutions of the present invention better understood, the technical solutions in the embodiments of the present invention will be clearly and completely described below with reference to the drawings in the embodiments of the present invention, and it is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

It should be noted that the terms "first," "second," and the like in the description and claims of the present invention and in the drawings described above are used for distinguishing between similar elements and not necessarily for describing a particular sequential or chronological order. It is to be understood that the data so used is interchangeable under appropriate circumstances such that the embodiments of the invention described herein are capable of operation in sequences other than those illustrated or described herein. Furthermore, the terms "comprises," "comprising," and "having," and any variations thereof, are intended to cover a non-exclusive inclusion, such that a process, method, system, article, or apparatus that comprises a list of steps or elements is not necessarily limited to those steps or elements expressly listed, but may include other steps or elements not expressly listed or inherent to such process, method, article, or apparatus.

The invention discloses hierarchical porous SiO with mild synthesis conditions and simple operation₂The invention relates to a preparation method of a microsphere material, which takes a silicon source precursor as a raw material, collagen extracted from tanning solid waste as a biomass template, a surfactant as a structure directing agent, and synthesizes hierarchical porous SiO by a simple one-pot method under the condition of no need of high-temperature hydrothermal process₂A microsphere material.

Preferably, the biomass template is collagen extracted from tanning solid waste.

Preferably, the surfactant is one of CTAB (cetyl trimethyl ammonium bromide), SDS (sodium dodecyl sulfate), SDBS (sodium dodecyl benzene sulfonate) or P123 (polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer of the formula PEO-PPO-PEO).

Preferably, the catalyst is one of ammonia water or acetic acid.

Preferably, the silicon source precursor is one of methyl orthosilicate (TMOS) or tetraethyl orthosilicate (TEOS).

Preferably, the alcohol solvent is one of methanol, ethanol or n-butanol.

Preferably, the pore-expanding agent is one of mesitylene (TMB), sodium chloride or n-hexane.

Preferably, the hierarchical pore SiO of the invention₂The preparation method of the microsphere material comprises the following steps:

s1, respectively dissolving collagen and a surfactant extracted from the tanning solid waste (extracted according to the mature existing extraction method technology) in distilled water to obtain a solution A containing the collagen and a solution B containing the surfactant, and fully stirring the solution A and the solution B at room temperature to obtain a mixed solution A;

s2, preparing a solution C from the catalyst, the alcohol solvent and the distilled water, adding the solution C into the mixed solution obtained in the step S1, and stirring to fully hydrolyze the catalyst to obtain a mixed solution B; when the solution C is prepared, the dosage ratio of the catalyst, the alcohol solvent and the distilled water is 1-3 mL:5mL:10 mL.

S3, dropwise adding a solution D prepared from a silicon source precursor, a pore-expanding agent and an alcohol solvent into the mixed solution B obtained in the step S2, and stirring to obtain SiO₂Sol of SiO₂The sol is cleaned and then dried to obtain dry SiO₂Solid, drying the obtained SiO₂Calcining the solid to obtain the hierarchical pore SiO₂A microsphere material.

Preferably, the temperature of the calcination treatment is 450-650 ℃, and the calcination is carried out for 300 min.

Preferably, the collagen extracted from the tanning solid waste is: surfactant (b): the dosage ratio of the silicon source precursor to the distilled water or the alcohol solvent is 0.0005-0.0030 mol: 0.005-0.019 mol: 1.0-8.0 mL: 5-20 mL, pore-expanding agent: the mass ratio of the surfactant is 0-2: 1.

preferably, the stirring time in step S1-3 is 20-30 min, 30-50 min and 2-6 h, respectively.

The hierarchical pore SiO is prepared by the preparation method₂Microsphere material, the hierarchical porous SiO₂The aperture range of the microsphere material is 1.9-110 nm, and the appearance of the microsphere material is hair follicle type sphere.

Obtained hierarchical porous SiO₂The microsphere material has good adsorption property on lysozyme biomacromolecules, so that the microsphere materialHierarchical pore SiO₂The microsphere material can be applied to the aspect of protein adsorption. In a specific performance test, the hierarchical pore SiO is known₂The adsorption rate of the microsphere material to lysozyme is as high as 98.8%.

Detailed description of the preferred embodimentsthe following detailed description of the present invention will be made with reference to the accompanying drawings 1-5, although it should be understood that the scope of the present invention is not limited to the specific embodiments. All other examples, which can be obtained by a person skilled in the art without inventive step based on the examples of the present invention, are within the scope of the present invention, and the test methods without specifying the specific conditions in the following examples are generally performed according to the conventional conditions or according to the conditions suggested by the respective manufacturers.

Example 1

Hierarchical pore SiO₂The preparation method of the microsphere material comprises the following steps:

weighing 1.3667g (0.015mol) CTAB and dissolving in 20mL distilled water, weighing 0.5g (0.001mol) collagen and dissolving in 15mL distilled water, mixing the aqueous solution of CTAB and the aqueous solution of collagen, stirring for 20min under air, adding the mixed solution of 0.5mL ammonia water, 5mL distilled water and 10mL ethanol, stirring for 30min, adding the mixed solution of 2mL ethyl orthosilicate and 10mL ethanol, and continuously stirring for 6h to obtain SiO₂Sol, then containing SiO₂The sol is transferred to a culture dish after being washed by alcohol, and is aged for 24 hours in a drying oven at 40 ℃ until the sample is dried, so that the nonmetal SiO is promoted₂Evaporating the solution for self-assembly, and drying the SiO₂Transferring the solid microspheres into a corundum crucible, calcining the solid microspheres in a muffle furnace at high temperature, heating to 550 ℃, and calcining for 300min to obtain white powdery hierarchical porous SiO₂A microsphere material.

EXAMPLE 1 Synthesis of hierarchical porous SiO₂The SEM spectrum of the sample is shown in FIG. 1, and the synthesized SiO can be seen from FIG. 1₂The material has a mesoporous and microporous hierarchical pore microsphere structure, and the pores are uniformly distributed, so that the collagen template containing a large amount of amino, carboxyl, hydroxyl and other groups can be coordinated with a silicon source precursor, the hydrolysis rate of the precursor can be slowed down, and the synthesis of hierarchical pore SiO with a regular structure can be promoted₂The pair synthesizes moreHierarchical pore SiO₂Has important significance.

EXAMPLE 1 Synthesis of hierarchical porous SiO₂The wide-angle XRD spectrum of the sample is shown in fig. 2, and it can be seen from fig. 2 that the XRD spectrum of the synthesized sample has an obvious diffraction peak at 2 θ of 20 ° to 30 °, indicating that the sample is amorphous SiO₂Exist in the form of (1).

EXAMPLE 1 Synthesis of hierarchical porous SiO₂The small-angle XRD spectrum of the sample is shown in fig. 3, and it can be seen from fig. 3 that the XRD spectrum of the synthesized sample has a strong diffraction peak at 2 θ ═ 0.9 °, indicating that the synthesized material has one-dimensional ordered mesopores.

Example 2

The hierarchical pore SiO provided by the embodiment₂A microsphere material was prepared in the same manner as in example 1 except That Mesitylene (TMB) was used in an amount of 0.7g (TMB: CTAB mass ratio of 0.5) in example 1.

Example 2 Synthesis of hierarchical porous SiO₂N of the sample₂The adsorption-desorption isotherms and pore size distribution profiles are shown in FIG. 4, and it can be seen from FIG. 4 that the synthesized SiO₂Has a wide range (1.9-110 nm) of pore distribution, and the average pore size of the sample calculated by the BJH method is mainly concentrated at 4.6 nm. Synthesis of N of the samples according to IUPAC Classification₂The adsorption and desorption isotherms are type IV isotherms and have an H2 hysteresis loop, which represents the presence of a mesoporous structure in the sample.

Example 3

The hierarchical pore SiO provided by the embodiment₂The microsphere material was prepared in the same manner as in example 1 except that the amount of collagen used in example 1 was 0.25g (0.0005 mol).

Example 4

The hierarchical pore SiO provided by the embodiment₂The microsphere material was prepared in the same manner as in example 1 except that the amount of collagen used in example 1 was 0.75g (0.0015 mol).

Example 5

The hierarchical pore SiO provided by the embodiment₂The preparation method of the microsphere material is the same as that of example 1, and the difference is only thatThe amount of collagen used in example 1 was 1.0g (0.0020 mol).

Example 6

The hierarchical pore SiO provided by the embodiment₂The microsphere material was prepared in the same manner as in example 1 except that the amount of collagen used in example 1 was 1.25g (0.0025 mol).

Example 7

The hierarchical pore SiO provided by the embodiment₂The microsphere material was prepared in the same manner as in example 1 except that the amount of collagen used in example 1 was 1.5g (0.0030 mol).

Example 8

The hierarchical pore SiO provided by the embodiment₂The microsphere material was prepared in the same manner as in example 1 except that in example 1 CTAB was used in an amount of 0.4556g (0.005 mol).

Example 9

The hierarchical pore SiO provided by the embodiment₂The microsphere material was prepared in the same manner as in example 1, except that in example 1 CTAB was used in an amount of 1.7312g (0.019 mol).

Example 10

The hierarchical pore SiO provided by the embodiment₂The preparation method of the microsphere material is the same as that of the embodiment 1, and the difference is only that the precursor of the silicon source is methyl orthosilicate, and the using amount of the methyl orthosilicate is 1 mL.

Example 11

The hierarchical pore SiO provided by the embodiment₂The microsphere material was prepared in the same manner as in example 1, except that the amount of methyl orthosilicate used in example 1 was 8 mL.

Example 12

The hierarchical pore SiO provided by the embodiment₂The microsphere material was prepared in the same manner as in example 1, except that the pore-enlarging agent was n-hexane, and the amount of n-hexane used was 2.8g (mass ratio of n-hexane: CTAB: 2: 1); adding 5mL of ethanol into the mixed solution B; the calcination temperature was 450 ℃.

Example 13

The embodiment providesHierarchical porous SiO₂The microsphere material was prepared in the same manner as in example 1, except that the surfactant was SDS in an amount of 2.8838g (0.01 mol); adding 8mL of ethanol into the mixed solution B; the calcination temperature was 650 ℃.

Example 14

The hierarchical pore SiO provided by the embodiment₂The microsphere material was prepared in the same manner as in example 1, except that the amount of the catalyst, distilled water and alcohol solvent in mL was 3mL, 5mL and 10mL, respectively, when preparing the solution C.

Example 15

The hierarchical pore SiO provided by the embodiment₂The preparation method of the microsphere material is the same as that of example 1, except that the volume ratio of the catalyst, the distilled water and the alcohol solvent is 1.5mL, 5mL and 10mL when the solution C is prepared; wherein the catalyst is acetic acid.

It should be noted that examples 1 to 7 described above are all directed to the synthesized hierarchical porous SiO₂The sample of the microsphere material is subjected to SEM spectrogram, wide-angle XRD spectrogram and small-angle XRD spectrogram, and the result shows that the SiO synthesized in each example is₂The samples have regular mesoscopic structures, and the existence of the mesoscopic structures can effectively maintain the stability of the skeleton structure and is beneficial to material transmission; furthermore, the SiO synthesized₂The material also has a microporous structure, and has important significance for adsorbing protein molecules with different sizes. A series of structural characterization means prove that the method can successfully prepare SiO with a hierarchical pore structure₂A material.

In addition, the hierarchical pore SiO prepared by the invention₂The microsphere material was subjected to a lysozyme adsorption experiment:

1) for the hierarchical porous SiO synthesized in the above-mentioned examples 1-2 of the present invention₂The microsphere material was subjected to lysozyme adsorption experiments, and the results were as follows:

weighing the hierarchical porous SiO synthesized in example 1₂The microsphere material is 0.1g, 10mL of lysozyme with the concentration of 500 mu g/mL is adsorbed for 4h, and the adsorption rate of the lysozyme is 61.6 percent.

Weighing the hierarchical porous SiO synthesized in example 2₂Microsphere material 0.1g, suction10mL of lysozyme with the concentration of 500 mu g/mL is added for 4h, and the adsorption capacity of the lysozyme is 98.8 percent.

2) The invention also synthesizes hierarchical porous SiO with different collagen contents₂The sample was subjected to lysozyme adsorption experiments as follows:

the collagen dosage in the embodiments 1, 3, 4, 5, 6 and 7 of the present invention is specifically as follows: the amount of collagen used in example 1 was 0.0010mol (0.5 g); the collagen amount in example 3 was 0.0005mol (0.25g), the collagen amount in example 4 was 0.0015mol (0.75g), the collagen amount in example 5 was 0.0020mol (1.0g), the collagen amount in example 6 was 0.0025mol (1.25g), and the collagen amount in example 7 was 0.0030mol (1.5 g).

The hierarchical pore SiO synthesized by the above embodiment is weighed respectively₂Sample 0.1g, hierarchical pore SiO synthesized from different collagen contents₂The sample adsorbs 10mL of 500 mu g/mL lysozyme, the mixed solution is respectively taken at 4h, the mixed solution is centrifuged for 5min at 5000r/min, and the supernatant is taken to measure the absorbance of the supernatant at 278 nm. Hierarchical pore SiO synthesized by different collagen contents₂The adsorption effect of lysozyme is shown in FIG. 5. from FIG. 5, it can be seen that the synthesized hierarchical pore SiO increases with the amount of collagen₂The adsorption capacity of the material to lysozyme shows a tendency of increasing and then reducing, and when the dosage of the collagen is 0.0010mol (0.5g), the synthesized hierarchical pore SiO is₂The adsorption performance to lysozyme is optimal.

3) For the hierarchical porous SiO synthesized in the above-mentioned examples 1, 8 and 9 of the present invention₂The microsphere material was subjected to lysozyme adsorption experiments, and the results were as follows:

weighing the hierarchical porous SiO synthesized in example 1₂The microsphere material is 0.1g, 10mL of lysozyme with the concentration of 500 mu g/mL is adsorbed for 4h, and the adsorption rate of the lysozyme is 61.6 percent.

Weighing the hierarchical porous SiO synthesized in example 8₂The microsphere material is 0.1g, 10mL of lysozyme with the concentration of 500 mu g/mL is adsorbed for 4h, and the adsorption rate of the lysozyme is 9.4 percent.

Weighing the hierarchical porous SiO synthesized in example 9₂Microsphere material0.1g of the material adsorbs 10mL of lysozyme with the concentration of 500 mu g/mL for 4h, and the adsorption rate of the lysozyme is 5.4 percent.

4) For the hierarchical porous SiO synthesized in the above-mentioned examples 1, 8 and 9 of the present invention₂The microsphere material was subjected to lysozyme adsorption experiments, and the results were as follows:

weighing the hierarchical porous SiO synthesized in example 1₂The microsphere material is 0.1g, 10mL of lysozyme with the concentration of 500 mu g/mL is adsorbed for 4h, and the adsorption rate of the lysozyme is 61.6 percent.

Weighing the hierarchical porous SiO synthesized in example 10₂The microsphere material is 0.1g, 10mL of lysozyme with the concentration of 500 mu g/mL is adsorbed for 4h, and the adsorption rate of the lysozyme is 19.8 percent.

Weighing the hierarchical porous SiO synthesized in example 11₂The microsphere material is 0.1g, 10mL of lysozyme with the concentration of 500 mu g/mL is adsorbed for 4h, and the adsorption rate of the lysozyme is 6.4%.

It should be noted that, the surfactant referred to in the claims of the present invention may be any one of CTAB, P123, SDS or SDBS, the silicon source precursor is any one of methyl orthosilicate or ethyl orthosilicate, the catalyst may be any one of ammonia water or acetic acid, the pore-expanding agent is any one of mesitylene, sodium chloride or n-hexane, and the alcohol solvent is any one of methanol, ethanol or n-butanol, it should be understood that any combination of the above-mentioned raw materials may be selected, and since the steps and methods adopted are the same as those in the embodiments, the present invention describes preferred embodiments and effects thereof in order to prevent redundancy.

When the claims of the present invention refer to numerical ranges, it should be understood that two endpoints of each numerical range and any value between the two endpoints can be selected, and since the steps and methods adopted are the same as those of the embodiment, the present invention describes a preferred embodiment and effects thereof in order to prevent redundancy. Additional variations and modifications in those embodiments may occur to those skilled in the art once they learn of the basic inventive concepts. Therefore, it is intended that the appended claims be interpreted as including preferred embodiments and all such alterations and modifications as fall within the scope of the invention.

Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that changes, modifications, substitutions and alterations can be made in these embodiments without departing from the principles and spirit of the invention, the scope of which is defined in the appended claims and their equivalents.

In conclusion, the invention discloses a hierarchical pore SiO synthesized by a biomass template₂A microsphere material and a preparation method and application thereof, belonging to the technical field of preparation of hierarchical porous non-metallic oxide microsphere materials. The preparation method comprises the steps of taking collagen as a biomass template, stirring and mixing the biomass template and a silicon source precursor to form sol, and then synthesizing the hierarchical pore SiO through a series of steps₂A microsphere material. The preparation method takes the biomass material as a template, and synthesizes the hierarchical pore SiO with the pore diameter range of 1.9-110 nm by a simple one-pot method under the condition of no need of high-temperature hydrothermal₂Microsphere material, hierarchical porous SiO prepared₂The microsphere material has good adsorption performance on lysozyme protein.

The above-mentioned contents are only for illustrating the technical idea of the present invention, and the protection scope of the present invention is not limited thereby, and any modification made on the basis of the technical idea of the present invention falls within the protection scope of the claims of the present invention.