CN113600139B - Preparation method and application of cellulose biomass-based in-situ mesoporous composite material - Google Patents
Preparation method and application of cellulose biomass-based in-situ mesoporous composite material Download PDFInfo
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Abstract
The invention discloses a preparation method of a cellulose biomass-based in-situ mesoporous composite material, which comprises the following steps: immersing cellulose biomass into alkali solution for treatment, preparing the functional mesoporous silica composite material on a biomass material matrix by adopting a copolycondensation-induced in-situ generation strategy, and carrying out functional enhancement modification on the composite material by adopting a hydroxyl-terminated hyperbranched polymer. The mesoporous composite material provided by the invention has the advantages of mild preparation conditions, simple process, short period, low cost, easiness in realization of large-scale industrial production and wide application prospect; the mesoporous material on the surface of the product has high dispersion density, stable physical and chemical structure, strong adsorption performance and good mechanical recoverability, and can be applied to the fields of heavy metal and organic wastewater adsorption treatment, heavy metal recovery and the like.
Description
Technical Field
The invention relates to a preparation method and application of a mesoporous composite material, in particular to a preparation method and application of a cellulose biomass-based in-situ mesoporous composite material.
Background
Mesoporous silicon is a silicon-based porous material with the aperture of 2-50 nm, has the advantages of large specific surface area, good hydrothermal stability, high plasticity, strong modifiable property and the like, and has great application potential in the fields of adsorption, catalysis, sensing, separation and the like. On the basis, the micro-nano mesoporous silicon spheres have high surface energy, high mass transfer rate, high-density functional sites and obvious interface effect, and have high-efficiency adsorption performance on organic wastewater and heavy metals. However, mesoporous silicon is singly adopted to adsorb heavy metal wastewater, and is not easy to recover when dispersed in water, so that secondary pollution can be caused, and the adsorption effect can be influenced.
Disclosure of Invention
Aiming at the defects in the prior art, the invention aims to provide a preparation method of a cellulose biomass-based in-situ mesoporous composite material, which aims to solve the problem of recycling of a mesoporous silicon composite material, so that the mesoporous silicon composite material can be recycled. The invention also aims to provide an application of the cellulose biomass-based in-situ mesoporous composite material.
The technical scheme of the invention is as follows: the preparation method of the cellulose biomass-based in-situ mesoporous composite material comprises the following steps:
s1, immersing a cellulose biomass material in an alkali solution with the concentration of 1-30wt% for heating treatment, filtering and fully washing a product, and drying to constant weight to obtain an activated biomass material;
s2, dissolving a template agent, an organic solvent and an alkaline regulator in water, heating to 30-100 ℃, mixing and stirring for 10-120 min, and controlling the component molar ratio to be the template agent, the alkaline regulator, the organic solvent, the water to be 0.05-5:0.05-5:0.5-60:100;
s3, adding a functional silane coupling agent and orthosilicate into the mixed system of the step S2, continuously stirring for 10-120 min at 30-100 ℃, and controlling the mass volume ratio of the functional silane coupling agent to the orthosilicate to be 0.01-5:1, wherein the mass volume ratio of the orthosilicate to the mixed system of the step S2 is 2-10%;
s4, adding the activated biomass material into the mixed system obtained in the step S3, wherein the bath ratio is 1:20-200, and standing for 6-48 h at 30-100 ℃;
s5, filtering, taking out, washing and drying the biomass material from the mixed system, refluxing the biomass material for 2-24 hours by adopting an organic solvent at the temperature of 40-120 ℃ under protective gas, filtering, washing and vacuum drying to obtain a primary biomass-based mesoporous composite material;
s6, dispersing the primary biomass-based mesoporous composite material in an organic solvent solution of 1-20wt% of hydroxyl-terminated hyperbranched polymer, reacting for 0.5-6 h at 30-100 ℃ under stirring, filtering and taking out the material, washing, and vacuum drying to obtain the cellulose biomass-based in-situ mesoporous composite material.
Further, in the step S1, the cellulose biomass material is sequentially immersed in 2-5 alkali solutions with the concentration of 1-30wt% according to the increasing concentration order for heating treatment, and the concentration difference of the alkali solutions treated in two adjacent times is more than 5wt%.
Further, the cellulosic biomass is cotton, hemp, wheat straw, straw or bagasse.
Further, the alkali solution is one or more of sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution.
Further, the template agent is one or more of cetyl trimethyl ammonium chloride or cetyl trimethyl ammonium bromide.
Further, the alkaline regulator is one or more of ethanolamine, diethanolamine, triethanolamine and ammonia water.
Further, the functional silane coupling agent is one or more of 3-aminopropyl trimethoxy silane, 3-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl diethoxy silane and 3-aminopropyl triethoxy silane.
Further, the orthosilicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate and butyl orthosilicate.
Further, the organic solvent is one or more of methanol, absolute ethanol, acetone, toluene, cyclohexane and isopropanol.
The application of the cellulose biomass-based in-situ mesoporous composite material is that the cellulose biomass-based in-situ mesoporous composite material is used for adsorbing organic pollutants and/or heavy metal ions polluting a water body.
The preparation method of the hydroxyl-terminated hyperbranched polymer is characterized by referring to documents Xu S, chen S, zhang F, et al preparation and controlled coating of hydroxyl-modified silver nanoparticles on silk fibers through intermolecular interaction-reduced self-assembled [ J ]. Materials & Design,2016:107-118, and is obtained by synthesizing one of monomers containing double bonds and carboxyl or fat groups with polyhydroxy monomers and organic acids. The monomer containing double bonds and carboxyl or fat groups is methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic acid or methacrylic acid; the polyhydroxy monomer is iminodiethanol, trimethylolethane or trimethylolpropane; the organic acid is dodecylbenzene sulfonic acid, m-toluene sulfonic acid, o-toluene sulfonic acid or p-toluene sulfonic acid.
Compared with the prior art, the invention has the advantages that:
by adopting a copolycondensation-induction in-situ generation strategy, the silicon source is induced to be directly polycondensed on the surface of the silicon source by utilizing the negatively charged cellulose biomass to generate amino-functionalized mesoporous silicon, so that the biomass-based mesoporous composite material with high dispersion density is obtained, the high-efficiency adsorption performance of the functional mesoporous silicon can be fully exerted, and the recyclable performance of the biomass carrier can be utilized. The biomass material is activated by adopting the multi-concentration alkali solution in sequence, so that hydrogen bonds in the macromolecular chains can be further opened, fiber bundles are fully swelled, the effective reaction space of biomass is improved, and the reaction activity is enhanced.
The hydroxyl-terminated hyperbranched polymer is introduced into the high specific surface structure of the in-situ mesoporous silicon, and is in a spherical network-like branched molecular structure, so that the rheological property is high, the viscosity is low, the active reaction sites are many, the hydroxyl-terminated hyperbranched polymer is favorable for being fully developed when the nano porous material is modified, and the nano pore canal is not easy to be blocked; the cavity structure containing a large number of active sites can effectively control the nano material, form electrostatic repulsion between particles and prevent agglomeration; the hyperbranched polymer can induce the nano material to assemble on the surface thereof through electrostatic effect, and a strong hydrogen bond acting force is easy to form between the terminal active functional group with high density of the hyperbranched polymer and the nano material, thereby being beneficial to constructing a stable structure.
The mesoporous composite material has the advantages of mild preparation conditions, simple process, short period, rich sources of the biomass material and the mesoporous silicon material, low cost, strong plasticity, easy realization of large-scale industrial production and wide application prospect; the mesoporous material on the surface of the product has high dispersion density, stable physical and chemical structure, strong adsorption performance and good mechanical recoverability, and can be applied to the fields of heavy metal and organic wastewater adsorption treatment, heavy metal recovery and the like.
Drawings
FIG. 1 is a molecular structural formula of a hyperbranched polymer used for the cellulose biomass-based in-situ mesoporous composite material prepared by the embodiment of the invention.
Fig. 2 is a scanning electron microscope image of the cellulose biomass-based in-situ mesoporous composite material prepared in example 2 of the present invention.
Fig. 3 is a graph showing the static adsorption kinetics of the cellulose biomass-based in-situ mesoporous composite material prepared in example 2 of the present invention for adsorbing organic dye and heavy metal ions.
Fig. 4 is a graph showing the regeneration adsorption performance of the cellulose biomass-based in-situ mesoporous composite material prepared in example 2 of the present invention on organic dye and heavy metal ions.
Detailed Description
The invention is further illustrated, but is not limited, by the following examples.
Example 1:
the cotton fiber was immersed in a 5wt% sodium hydroxide solution for heat treatment (100 ℃) and then the product was filtered and washed thoroughly and dried to constant weight to obtain an activated cotton fiber.
Cetyl trimethyl ammonium chloride, absolute ethyl alcohol and diethanolamine are dissolved in water, heated to 50 ℃, mixed and stirred for 30min. Controlling the component molar ratio of cetyltrimethylammonium chloride to diethanolamine to absolute ethanol to water to be 0.3 to 1 to 5 to 100.
Adding 3-aminopropyl trimethoxysilane and tetraethoxysilane into the mixed system, continuously stirring for 60min at 50 ℃, and controlling the component molar ratio of 3-aminopropyl trimethoxysilane: the mass volume ratio of the ethyl orthosilicate to the mixed system is 8.4 percent.
And adding 5g of activated cotton fiber into the mixed system, standing at 50deg.C for 12 hr at a bath ratio of 1:100.
And filtering, taking out, washing and drying cotton fibers from the mixed system, refluxing the cotton fibers for 6 hours at the temperature of 60 ℃ under nitrogen by adopting absolute ethyl alcohol, filtering, washing and drying the cotton fibers in vacuum to obtain the primary biomass-based mesoporous composite material.
Dispersing 5g of primary composite material in an organic solvent solution of 5wt% of hydroxyl-terminated hyperbranched polymer, wherein the bath ratio is 1:100, stirring and reacting for 2 hours at 60 ℃, filtering and taking out the material, washing, and vacuum drying to obtain the cellulose biomass-based in-situ mesoporous composite material. The molecular structure of the hydroxyl-terminated hyperbranched polymer is shown in figure 1, and the hydroxyl-terminated hyperbranched polymer has a highly branched cavity structure and abundant active groups such as carbonyl groups, hydroxyl groups and the like, and can obviously enhance the functional activity of the composite material.
The prepared cellulose biomass-based in-situ mesoporous composite material is put into an organic dye (methylene blue) and heavy metal ions (Cu) with certain concentration and pH value 2+ ) In the simulated wastewater of (2), an oscillation adsorption experiment and an adsorption-desorption cyclic utilization experiment are carried out, and the results are as follows:
after 4 adsorption-desorption cyclic utilization processes, the average adsorption capacity of the two pollutants can still be kept to be more than 73% of the first saturated adsorption capacity. Test results show that mesoporous silicon is introduced into the composite material by adopting a copolycondensation-induced in-situ generation strategy, so that the surface adsorption structure has strong stability and good regeneration adsorption performance, and the composite material can be used as a biomass adsorption material with strong sustainability.
Example 2:
the cotton fiber is firstly soaked in sodium hydroxide solution with the concentration of 2wt percent for heating treatment (100 ℃), the product is filtered and then soaked in sodium hydroxide solution with the concentration of 10wt percent for heating treatment (50 ℃), and then the product is filtered and fully washed and dried to constant weight, thus obtaining the activated cotton fiber.
Cetyl trimethyl ammonium chloride, absolute ethyl alcohol and diethanolamine are dissolved in water, heated to 50 ℃, mixed and stirred for 30min. Controlling the component molar ratio of cetyltrimethylammonium chloride to diethanolamine to absolute ethanol to water to be 0.3 to 1 to 5 to 100.
Adding 3-aminopropyl trimethoxysilane and tetraethoxysilane into the mixed system, continuously stirring for 60min at 50 ℃, and controlling the component molar ratio of 3-aminopropyl trimethoxysilane: the ratio of ethyl orthosilicate is 0.6:1. The mass volume ratio of the tetraethoxysilane to the mixed system is 6.4 percent.
And adding 5g of activated cotton fiber into the mixed system, standing at 50deg.C for 12 hr at a bath ratio of 1:100.
And filtering, taking out, washing and drying cotton fibers from the mixed system, refluxing the cotton fibers for 6 hours at the temperature of 60 ℃ under nitrogen by adopting absolute ethyl alcohol, filtering, washing and drying the cotton fibers in vacuum to obtain the primary biomass-based mesoporous composite material.
Dispersing 5g of primary composite material in an organic solvent solution of 5wt% of hydroxyl-terminated hyperbranched polymer, wherein the bath ratio is 1:100, stirring and reacting for 2 hours at 60 ℃, filtering and taking out the material, washing, and vacuum drying to obtain the cellulose biomass-based in-situ mesoporous composite material. FIG. 2 is a scanning electron microscope image of a composite material, a large number of mesoporous silicon microspheres with the particle diameters of about 100-1000 nm are generated on the surface of biomass in situ, hyperbranched polymers are coated on the surface, and the specific surface area and the functionality of the material are remarkably improved. FIG. 3 shows the adsorption of organic dye (methylene blue) and heavy metal ion (Cu) by the composite material 2+ ) Experimental results prove that the mesoporous silicon-hyperbranched adsorption structure of the composite material has high-efficiency adsorption performance on two pollutants, and the saturated adsorption amounts are 222mg/g and 124mg/g respectively. FIG. 4 is a graph showing the regenerated adsorption performance of the composite material to organic dye and heavy metal ions. After four times of suctionAfter the cyclic utilization process of the adsorption-desorption, the average adsorption capacity of the two pollutants can still be kept to be more than 80% of the first saturated adsorption capacity.
Experimental results prove that the method can further open hydrogen bonds in the macromolecular chains by sequentially adopting the alkali solution with increasing concentration for multiple activation treatments, so that the surfaces of the biomasses are fully swelled, the effective reaction space of the biomasses is improved, the reaction activity is enhanced, and the static saturated adsorption capacity and the circulating adsorption capacity of the composite material on pollutants are effectively improved.
Example 3:
the fibrilia is firstly immersed in a sodium carbonate solution with the concentration of 5 weight percent for heating treatment (120 ℃), the product is filtered and then immersed in a sodium carbonate solution with the concentration of 10 weight percent for heating treatment (40 ℃), the product is filtered and then immersed in a sodium carbonate solution with the concentration of 25 weight percent (40 ℃) for heating treatment, and then the product is filtered and fully washed and dried to constant weight, so that the activated fibrilia is obtained.
Cetyl trimethylammonium bromide, methanol and triethanolamine were dissolved in water, heated to 50 ℃, mixed and stirred for 30min. Controlling the component molar ratio of cetyltrimethylammonium bromide, triethanolamine, methanol and water to be 0.5:2:7:100.
Adding 3-aminopropyl triethoxysilane and methyl orthosilicate into the mixed system, continuously stirring for 120min at 60 ℃, and controlling the component molar ratio of 3-aminopropyl triethoxysilane: the weight-volume ratio of methyl orthosilicate to the mixed system is 5.2% and the ratio of methyl orthosilicate to the mixed system is 0.3:1.
Adding 10g of activated fibrilia into the mixed system, standing at 80deg.C for 24 hr at bath ratio of 1:80.
And filtering, taking out, washing and drying fibrilia from the mixed system, refluxing with methanol at 60 ℃ under nitrogen for 8 hours, filtering, washing and drying in vacuum to obtain the primary biomass-based mesoporous composite material.
Dispersing 10g primary composite material in 25wt% hydroxyl-terminated hyperbranched polymer organic solvent solution at a bath ratio of 1:80, stirring at 60deg.C for reaction for 5 hr, filtering, washing, and vacuum drying to obtain cellulose biomassA basic in-situ mesoporous composite material. The material is subjected to organic dye (methylene blue) and heavy metal ion (Cu) 2+ ) Static adsorption experiments show that the saturation adsorption quantity of methylene blue is 205mg/g, cu 2+ The saturated adsorption quantity of (C) is 116mg/g, the adsorption-desorption cycle is utilized for 4 times, the average adsorption quantity of methylene blue is 166mg/g, and Cu 2+ The average adsorption amount of (C) was 99mg/g.
Example 4:
the activated straw fiber is obtained by immersing the straw fiber in a sodium bicarbonate solution with the concentration of 5wt percent for heat treatment (100 ℃), filtering the product, immersing the product in a sodium bicarbonate solution with the concentration of 20wt percent for heat treatment (50 ℃), filtering the product, fully washing the product, and drying the product to constant weight.
Cetyl trimethylammonium bromide, absolute ethyl alcohol and triethanolamine are dissolved in water, heated to 60 ℃, mixed and stirred for 60min. Controlling the component molar ratio of cetyltrimethylammonium bromide, triethanolamine, absolute ethanol and water to be 0.5:3:5:100.
Adding 3-aminopropyl triethoxysilane and tetraethoxysilane into the mixed system, continuously stirring at 50 ℃ for 60min, and controlling the component molar ratio of 3-aminopropyl triethoxysilane: the mass volume ratio of the ethyl orthosilicate to the mixed system is 6.8% and is 0.4:1.
Adding 5g of activated straw fiber into the mixed system, standing at 50deg.C for 12 hr at a bath ratio of 1:100.
Filtering, taking out, washing and drying straw fibers from the mixed system, refluxing with absolute ethyl alcohol at 60 ℃ under nitrogen for 6 hours, filtering, washing and drying in vacuum to obtain the primary biomass-based mesoporous composite material.
Dispersing 5g of primary composite material in an organic solvent solution of 5wt% of hydroxyl-terminated hyperbranched polymer, wherein the bath ratio is 1:100, stirring and reacting for 2 hours at 60 ℃, filtering and taking out the material, washing, and vacuum drying to obtain the cellulose biomass-based in-situ mesoporous composite material. The material is subjected to organic dye (methylene blue) and heavy metal ion (Cu) 2+ ) Static adsorption experiments show that the saturation adsorption quantity of methylene blue is 217mg/g, cu 2+ The saturated adsorption amount of (C) is 109mg/g, the adsorption-desorption cycle is utilized for 4 times, the average adsorption amount of methylene blue is 153mg/g, and Cu 2+ The average adsorption amount of (C) was 85mg/g.
Example 5:
the wheat straw fiber is firstly immersed in a sodium carbonate solution with the concentration of 5wt percent for heating treatment (120 ℃), the product is filtered and then immersed in a sodium carbonate solution with the concentration of 10wt percent for heating treatment (60 ℃), the product is filtered and then immersed in a sodium carbonate solution with the concentration of 20wt percent for heating treatment (40 ℃), and finally the product is filtered and then immersed in a sodium carbonate solution with the concentration of 25wt percent for heating treatment (30 ℃), and then the product is filtered and fully washed and dried to constant weight, so that the activated wheat straw fiber is obtained.
Cetyl trimethyl ammonium chloride, absolute ethyl alcohol and ethanolamine are dissolved in water, heated to 65 ℃, mixed and stirred for 90min. Controlling the component molar ratio of cetyltrimethylammonium chloride to ethanolamine to absolute ethanol to water to be 0.3 to 3 to 6 to 100.
Adding 3-aminopropyl trimethoxysilane and methyl orthosilicate into the mixed system, continuously stirring for 90min at 65 ℃, and controlling the component molar ratio of 3-aminopropyl trimethoxysilane: methyl orthosilicate is 0.25:1, and the mass volume ratio of the methyl orthosilicate to the mixed system is 5.6%.
Adding 10g of activated wheat straw fiber into the mixed system, standing at 65deg.C for 9 hr at a bath ratio of 1:50.
Filtering, taking out, washing and drying the wheat straw fibers from the mixed system, refluxing the wheat straw fibers for 6 hours at the temperature of 60 ℃ under nitrogen by adopting absolute ethyl alcohol, filtering, washing and drying the wheat straw fibers in vacuum to obtain the primary biomass-based mesoporous composite material.
Dispersing 10g of primary composite material in an organic solvent solution of 10wt% of hydroxyl-terminated hyperbranched polymer, stirring and reacting for 4 hours at 65 ℃ with a bath ratio of 1:50, filtering and taking out the material, washing, and vacuum drying to obtain the cellulose biomass-based in-situ mesoporous composite material. The material is subjected to organic dye (methylene blue) and heavy metal ion (Cu) 2+ ) Static adsorption experiments show that the saturated adsorption quantity of methylene blue is 219mg/g, cu 2+ Saturated adsorption capacity of (2)The adsorption-desorption cycle was carried out for 4 times at 118mg/g, the average adsorption amount of methylene blue was 179mg/g, cu 2+ The average adsorption amount of (C) was 90mg/g.
Example 6:
the fibrilia is firstly soaked in sodium hydroxide solution with the concentration of 5 weight percent for heat treatment (100 ℃), the product is filtered and then soaked in sodium hydroxide solution with the concentration of 20 weight percent for heat treatment (60 ℃), and then the product is filtered and fully washed and dried to constant weight, thus obtaining the activated fibrilia.
Cetyl trimethylammonium bromide, methanol and diethanolamine were dissolved in water, heated to 60 ℃, mixed and stirred for 60min. Controlling the component molar ratio of cetyltrimethylammonium bromide to diethanolamine to methanol to water to be 0.5:5:10:100.
Adding 3-aminopropyl triethoxysilane and propyl orthosilicate into the mixed system, continuously stirring at 60 ℃ for 60min, and controlling the component molar ratio of 3-aminopropyl triethoxysilane: the mass volume ratio of the propyl orthosilicate to the mixed system is 7.1% and the ratio of the propyl orthosilicate to the mixed system is 0.6:1.
Adding 15g of activated fibrilia into the mixed system, standing at 60deg.C for 12 hr at a bath ratio of 1:60.
And filtering, taking out, washing and drying fibrilia from the mixed system, refluxing with methanol at 60 ℃ under nitrogen for 12 hours, filtering, washing and drying in vacuum to obtain the primary biomass-based mesoporous composite material.
Dispersing 15g of the primary composite material in an organic solvent solution of 8wt% of hydroxyl-terminated hyperbranched polymer, stirring and reacting for 6 hours at 60 ℃ with a bath ratio of 1:60, filtering and taking out the material, washing, and vacuum drying to obtain the cellulose biomass-based in-situ mesoporous composite material. The material is subjected to organic dye (methylene blue) and heavy metal ion (Cu) 2+ ) Static adsorption experiments show that the saturated adsorption quantity of methylene blue is 204mg/g, cu 2+ The saturated adsorption amount of (C) is 102mg/g, the adsorption-desorption cycle is utilized for 4 times, the average adsorption amount of methylene blue is 152mg/g, and Cu 2+ The average adsorption amount of (C) was 74mg/g.
Claims (9)
1. The preparation method of the cellulose biomass-based in-situ mesoporous composite material is characterized by comprising the following steps of:
s1, immersing a cellulose biomass material in an alkali solution with the concentration of 1-30 wt% for heating treatment, filtering and fully washing a product, and drying to constant weight to obtain an activated biomass material;
s2, dissolving a template agent, an organic solvent and an alkaline regulator in water, heating to 30-100 ℃, mixing and stirring for 10-120 min, and controlling the component molar ratio to be the template agent, the alkaline regulator, the organic solvent, the water to be 0.05-5:0.05-5:0.5-60:100;
s3, adding a functional silane coupling agent and orthosilicate into the mixed system of the step S2, continuously stirring for 10-120 min at 30-100 ℃, and controlling the mass volume ratio of the orthosilicate to the mixed system of the step S2 to be 2-10% by controlling the molar ratio of the orthosilicate to the functional silane coupling agent to be 0.01-5:1; the functional silane coupling agent is one or more of 3-aminopropyl trimethoxy silane, 3-aminopropyl methyl dimethoxy silane, 3-aminopropyl methyl diethoxy silane and 3-aminopropyl triethoxy silane;
s4, adding the activated biomass material into the mixed system obtained in the step S3, wherein the bath ratio is 1:20-200, and standing for 6-48 h at 30-100 ℃;
s5, filtering, taking out, washing and drying the biomass material from the mixed system, refluxing the biomass material for 2-24 hours by adopting an organic solvent at the temperature of 40-120 ℃ under protective gas, filtering, washing and vacuum drying to obtain a primary biomass-based mesoporous composite material;
s6, dispersing the primary biomass-based mesoporous composite material in an organic solvent solution of 1-20 wt% of hydroxyl-terminated hyperbranched polymer, wherein the bath ratio is 1:20-200, stirring and reacting for 0.5-6 h at 30-100 ℃, filtering and taking out the material, washing, and vacuum drying to obtain the cellulose biomass-based in-situ mesoporous composite material, wherein the hydroxyl-terminated hyperbranched polymer is obtained by synthesizing one of monomers containing double bonds and carboxyl or ester groups with polyhydroxy monomers and organic acid, and the monomers containing double bonds and carboxyl or ester groups are methyl acrylate, ethyl acrylate, methyl methacrylate, acrylic acid or methacrylic acid; the polyhydroxy monomer is iminodiethanol, trimethylolethane or trimethylolpropane; the organic acid is dodecylbenzene sulfonic acid, m-toluene sulfonic acid, o-toluene sulfonic acid or p-toluene sulfonic acid.
2. The method for preparing the cellulose biomass based in-situ mesoporous composite material according to claim 1, wherein in the step S1, the cellulose biomass material is sequentially immersed in 2-5 alkali solutions with the concentration of 1-30 wt% according to the increasing concentration order for heating treatment, and the concentration difference of the alkali solutions treated by two adjacent treatments is more than 5wt%.
3. The method for preparing a cellulose biomass based in situ mesoporous composite according to claim 1, wherein the cellulose biomass is cotton, hemp, wheat straw, straw or bagasse.
4. The method for preparing a cellulose biomass based in situ mesoporous composite according to claim 1, wherein the alkaline solution is one or more of sodium hydroxide solution, sodium carbonate solution or sodium bicarbonate solution.
5. The method for preparing a cellulose biomass based in situ mesoporous composite according to claim 1, wherein the template agent is one or more of cetyltrimethylammonium chloride or cetyltrimethylammonium bromide.
6. The method for preparing a cellulose biomass based in situ mesoporous composite according to claim 1, wherein the alkaline regulator is one or more of ethanolamine, diethanolamine, triethanolamine, and ammonia water.
7. The method for preparing a cellulose biomass based in situ mesoporous composite according to claim 1, wherein the orthosilicate is one or more of methyl orthosilicate, ethyl orthosilicate, propyl orthosilicate, and butyl orthosilicate.
8. The method for preparing a cellulose biomass based in situ mesoporous composite according to claim 1, wherein the organic solvent is one or more of methanol, absolute ethanol, acetone, toluene, cyclohexane, and isopropanol.
9. The application of the cellulose biomass in-situ mesoporous composite material is characterized in that the cellulose biomass in-situ mesoporous composite material prepared by the preparation method of the cellulose biomass in-situ mesoporous composite material according to any one of claims 1 to 8 is used for adsorbing organic pollutants and/or heavy metal ions polluting water bodies.
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