CN108187719B - C3N4-Mt-SO3H composite material and preparation and application thereof - Google Patents
C3N4-Mt-SO3H composite material and preparation and application thereof Download PDFInfo
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- CN108187719B CN108187719B CN201711495264.9A CN201711495264A CN108187719B CN 108187719 B CN108187719 B CN 108187719B CN 201711495264 A CN201711495264 A CN 201711495264A CN 108187719 B CN108187719 B CN 108187719B
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- C07C29/141—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by reduction of an oxygen containing functional group of >C=O containing groups, e.g. —COOH of a —CHO group with hydrogen or hydrogen-containing gases
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Abstract
The invention discloses a C3N4‑Mt‑SO3H composite material and preparation and application thereof. Said C is3N4‑Mt‑SO3The H composite material is formed by inserting carbon nitride layer between montmorillonite layers and grafting sulfonic acid groups on the surface of the montmorillonite. C provided by the invention3N4‑Mt‑SO3The preparation method of the H composite material has the advantages of low cost, simple operation and basically no pollution to the environment. The invention also provides the compound C3N4‑Mt‑SO3The H composite material is used as a catalyst in the reaction of preparing the sorbitol by hydrolyzing and hydrogenating cellulose by a one-pot method, the catalyst can simultaneously catalyze the hydrolysis of the cellulose to obtain glucose and the reaction of converting the glucose into the sorbitol by hydrogenation, and the catalyst can be recycled.
Description
(I) technical field
The invention relates to a C taking layered clay as a carrier, grafting sulfonic acid on the surface of the layered clay, and intercalating carbon nitride between layers3N4-Mt-SO3Preparation of H composite material and application thereof in reaction of preparing sorbitol by hydrolyzing and hydrogenating cellulose.
(II) background of the invention
At present, the energy and organic chemical raw materials needed in the world are mostly derived from coal, petroleum and natural gas, and are not ideal resources which can be relied on by human for a long time in the long term. As a future resource and energy source on which humans can depend for a long time, it must be abundant in reserves, renewable, and its utilization does not cause environmental pollution. Based on this principle, plant-based biomass resources would be an ideal choice for the future of humans. Cellulose is a polysaccharide biomass resource which is most widely distributed and contained in nature, and hydrolysis of cellulose is an important way for conversion and utilization of cellulose in recent years, and a hydrolysis product of the cellulose is reducing sugar mainly comprising glucose. Glucose, as an important precursor, needs to be further subjected to reactions such as dehydration, oxidation, hydrogenation and the like to be converted into chemical products with high added values such as furfural, sorbitol, fuel ethanol and the like.
Cellulose is a linear polymer compound in which D-glucose units are bonded by β -1,4 glycosidic bonds. Due to the abundance of hydroxyl groups in the cellulose structure, these hydroxyl groups readily form hydrogen bonds with oxygen-containing groups on the cellulose molecules within or adjacent to the molecule. The intramolecular hydrogen bonds harden the cellulose chains and limit the free rotation of glucose units, and the intermolecular hydrogen bonds promote many cellulose molecules to approach each other to form the crystal structure of cellulose, so that the crystal structure ensures that the cellulose has stable properties and is insoluble in water and common organic solvents. The route utilized for cellulose conversion is generally divided into two steps, the first step: cellulose breaks beta-1, 4 glycosidic bonds through catalysis of a catalyst to form soluble monosaccharides (such as glucose, fructose, and the like), and the second step: the hydrolysis product glucose is hydrogenated to generate the sorbitol through the catalytic hydrogenation of noble metal. Solid acid catalyzed cellulose hydrolysis has been a research focus in recent years regarding the reaction of first step cellulose hydrolysis to form soluble monosaccharides, and has recoverable properties compared to liquid acid catalyzed cellulose hydrolysis reactions, which is beneficial for environmental protection and subsequent product handling, and which also reduces corrosion of equipment. Regarding the second step reaction, the most efficient oxygen reduction catalyst used for obtaining other chemicals from glucose is noble metal Pt, etc., but Pt has disadvantages of high price and easy deactivation, greatly limiting its commercial application. Therefore, the development of Pt substitute materials is an important task for the research in the field of catalysis.
In conclusion, if a recyclable catalyst capable of catalyzing the hydrolysis of cellulose to obtain glucose and the hydrogenation of glucose to sorbitol can be developed, the one-step method for realizing the conversion from cellulose to high-value-added chemicals is of great significance for the effective utilization of cellulose.
Disclosure of the invention
The first purpose of the invention is to provide a C3N4-Mt-SO3The H composite material has good structural stability, and can simultaneously catalyze cellulose hydrolysis to obtain glucose and the reaction of glucose hydrogenation to sorbitol.
The second purpose of the invention is to provide C which has low cost, simple operation and basically no pollution to the environment3N4-Mt-SO3A preparation method of the H composite material.
It is a third object of the present invention to provide said C3N4-Mt-SO3The H composite material is used as a catalyst in the reaction of preparing the sorbitol by hydrolyzing and hydrogenating cellulose by a one-pot method, can simultaneously catalyze the reaction of hydrolyzing the cellulose to obtain glucose and hydrogenating the glucose to convert the glucose into the sorbitol, and can be recycled.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
the invention provides a compound C3N4-Mt-SO3H composite material of carbon nitride (g-C) intercalated between montmorillonite layers3N4) And grafting sulfonic acid groups on the surface of the montmorillonite.
The invention further provides a compound C3N4-Mt-SO3The preparation method of the H composite material comprises the following steps:
(1) adding montmorillonite into deionized water, and uniformly stirring to obtain a mixture for later use;
(2) adding a carbon nitride precursor into the mixture obtained in the step (1), and stirring for 0.5-12 h at 10-150 ℃ for exchange adsorption to obtain homogenate, wherein the carbon nitride precursor is one or a combination of more of cyanamide, dicyandiamide, melamine, urea, ethylenediamine, ammonium azide, cyanuric chloride and cyanuric acid;
(3) removing water from the homogenate prepared in the step (2) to obtain a solid;
(4) drying the solid obtained in the step (3) at the temperature of 20-150 ℃ for 5-24 h;
(5) grinding the dried solid into powderIn a tubular furnace, heating from room temperature to 300-800 ℃ at the speed of 1-10 ℃/min in nitrogen atmosphere, roasting at constant temperature for 1-10 h, naturally cooling after roasting, and naming the obtained product as C3N4-Mt composite material;
(6) c obtained in the step (5)3N4Adding the-Mt composite material into toluene, and uniformly stirring to obtain homogenate;
(7) adding a compound containing a mercapto functional group into the homogenate obtained in the step (6), stirring and refluxing for 1-24 hours at 50-150 ℃, and then cooling to room temperature to obtain a mixed solution; wherein the compound containing the mercapto functional group is selected from one or any combination of the following compounds: 3-mercaptopropyltrimethoxysilane (MPTMS), 2, 3-dimercaptopropanesulfonic acid sodium salt (DMPS), 3-mercaptopropionic acid, 3-mercapto-1-propanesulfonic acid sodium salt, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid and methyl thioglycolate;
(8) filtering the mixed solution obtained in the step (7), washing with toluene, and drying to obtain a product named as C3N4-Mt-SH composite;
(9) c is to be3N4Adding the-Mt-SH composite material into a mixed solution containing hydrogen peroxide, water and methanol or hydrogen peroxide, stirring for 1-48h at 10-100 ℃, then filtering, washing, drying for 5-24 h at 20-150 ℃, grinding into powder after drying, and naming the obtained product as C3N4-Mt-SO3H composite material.
In the step (1), the mass ratio of montmorillonite to deionized water is 1: 5-1: 50.
in step (2) of the present invention, dicyandiamide is preferably used as the carbon nitride precursor.
In the step (2) of the invention, the amount of the substance of the carbon nitride precursor added is 0.5-20 times, preferably 1-10 times, and most preferably 6 times of the Cation Exchange Capacity (CEC) of montmorillonite.
In the step (2), the exchange adsorption temperature is preferably 60-100 ℃, and most preferably 100 ℃; the exchange adsorption time is preferably 2-6 h, and most preferably 4 h.
In step (3) of the present invention, it is recommended to remove water by spin-steaming or centrifugation.
In the step (5), the heating rate is preferably 1-5 ℃/min, and most preferably 2.5 ℃/min; the roasting temperature is preferably 400-600 ℃, and most preferably 550 ℃; the calcination time is preferably 3 to 5 hours, most preferably 4 hours.
In step (7) of the present invention, the mercapto functional group-containing compound is preferably 3-mercaptopropyltrimethoxysilane.
In step (7) of the present invention, the mercapto-functional compound is added in an amount of C3N4The mass of-Mt is 1 to 4mL/g, preferably 1.5 to 2.5mL/g, and most preferably 2.25 mL/g.
In the step (7), the stirring reflux temperature is preferably 100-120 ℃ and the time is 2-6 h.
In the step (9), the volume ratio of the mixed solution containing hydrogen peroxide, water and methanol (hydrogen peroxide: water: methanol) is 8:1: 1-1: 1: 1.
In the step (9) of the invention, the stirring temperature is preferably room temperature, and the stirring time is preferably 12-24 h.
The preparation method of the invention is preferably carried out according to the following steps:
(1) adding montmorillonite into deionized water, wherein the mass ratio of the montmorillonite to the deionized water is 1: 5-1: 50, uniformly stirring to obtain a mixture for later use;
(2) adding dicyandiamide into the mixture obtained in the step (1), stirring for 2-6 h at 60-100 ℃ for exchange adsorption to obtain homogenate; the amount of dicyandiamide substance added is 6 times the cation exchange capacity of montmorillonite.
(3) Removing water from the homogenate prepared in the step (2) to obtain a solid;
(4) drying the solid obtained in the step (3) at the temperature of 20-150 ℃ for 5-24 h;
(5) grinding the dried solid into powder, placing the powder into a tubular furnace, heating the powder from room temperature to 400-600 ℃ at the speed of 1-5 ℃/min in a nitrogen atmosphere, roasting the powder at a constant temperature for 3-5h, naturally cooling the roasted powder after roasting is finished, and naming the obtained product as C3N4-Mt composite material;
(6) subjecting the product obtained in step (5)C of (A)3N4Adding the-Mt composite material into toluene, and uniformly stirring to obtain homogenate;
(7) adding 3-mercaptopropyltrimethoxysilane into the homogenate obtained in the step (6), stirring and refluxing for 2-6 h at 100-120 ℃, and then cooling to room temperature to obtain a mixed solution; 3-mercaptopropyltrimethoxysilane is added in an amount of C3N4Mass of-Mt is 2.25mL/g on a basis;
(8) filtering the mixed solution obtained in the step (7), washing with toluene, and drying to obtain a product named as C3N4-Mt-SH composite;
(9) c is to be3N4Adding the-Mt-SH composite material into hydrogen peroxide, stirring for 12-24h at room temperature, filtering, washing, drying for 5-24 h at 20-150 ℃, grinding into powder after drying, and naming the obtained product as C3N4-Mt-SO3H composite material.
The hydrogen peroxide used in the invention can be a commercial product, such as 30 percent hydrogen peroxide by mass of reagent grade.
The invention further provides the compound C3N4-Mt-SO3The H composite material is used as a catalyst in the reaction of preparing sorbitol by hydrolyzing and hydrogenating cellulose by a one-pot method. The application specifically comprises the following steps:
adding cellulose and C into a stainless steel automatic high-pressure reaction kettle with a polytetrafluoroethylene lining3N4-Mt-SO3H composite and deionized water, wherein the cellulose is mixed with C3N4-Mt-SO3The mass ratio of the H composite material is 0.5: 1-8: 1, and uniformly stirring; sealing the reaction kettle, and then using high-purity H2(the purity is more than or equal to 99.999 percent) replacing the air in the reaction kettle, and filling high-purity H2To a set pressure value (0.1-5 MPa); stirring and heating the reaction kettle, timing after the reaction kettle reaches a set temperature (100-400 ℃), cooling the reaction kettle in an ice water bath to stop the reaction after the set reaction time (1-12 h), slowly reducing the pressure to release gas, and centrifugally separating the product. The liquid product is qualitatively analyzed by gas chromatography-mass spectrometer (GC-MS), then quantitatively analyzed by High Performance Liquid Chromatography (HPLC), and the solid residue is poured into a flaskAfter being dried fully in a cup, the solid residue after drying can be used as an adsorbent for adsorbing organic dye by weighing to calculate the conversion rate.
In the application of the invention, the cellulose is mainly microcrystalline cellulose.
In the application of the invention, cellulose and C3N4-Mt-SO3The mass ratio of the H composite is preferably 4: 1.
In the use according to the invention, H2The pressure is preferably 4MPa, the reaction temperature is preferably 200 ℃ and the reaction time is preferably 4 hours.
Compared with the prior art, the invention has the beneficial effects that:
(1) said C3N4-Mt-SO3The H composite material retains the structural characteristics of the carbon nitride and the montmorillonite, and the structures of the carbon nitride and the montmorillonite are not changed after the carbon nitride and the montmorillonite are roasted at the high temperature of 600 ℃, so the C3N4-Mt-SO3The H composite material has good structural stability;
(2) said C3N4-Mt-SO3The raw materials used in the preparation of the H composite material are cheap and easy to obtain, the preparation method has the advantages of easy control of reaction conditions, simple and safe operation and the like, and the prepared sample is large in amount and suitable for large-scale production;
(3) said C3N4-Mt-SO3The H composite material integrates the traditional two-step cellulose hydrolysis hydrogenation process into a one-step method, and realizes the effective conversion from cellulose to sorbitol.
(IV) description of the drawings
FIG. 1 is C3N4-Mt-SO3A preparation process schematic diagram of the H composite material;
FIG. 2 shows Mt, C3N4,C3N4-Mt,C3N4-Mt-SO3XRD spectrum of H;
FIG. 3 shows Mt, C3N4,C3N4-Mt,C3N4-Mt-SO3And H, an infrared spectrum.
(V) detailed description of the preferred embodiments
The present invention is described in more detail by the following examples, which are merely illustrative of the best mode of carrying out the invention and are not intended to limit the scope of the invention in any way.
Example 1
Weighing 5g of montmorillonite (the cation exchange capacity of the montmorillonite is 50mmol/100g CEC), placing the montmorillonite in a round bottom flask, pouring 50mL of deionized water, stirring for 20min, adding 0.42g of dicyandiamide (2CEC), stirring for 4h at 100 ℃ for exchange adsorption, then performing rotary evaporation on the product until the water is completely removed, then placing the solid in an evaporation dish, drying at 100 ℃ in a constant temperature drying oven, grinding the dried solid into powder, pouring the powder into a quartz tank, then placing the quartz tank in a quartz sleeve of a single-tube furnace, and enabling the sample to be in a constant temperature area. And introducing nitrogen for 1h after sealing, and removing air in the quartz sleeve. Raising the temperature of the tubular furnace from room temperature to 550 ℃ at the speed of 2.5 ℃/min, keeping the temperature for 4 hours, and naturally cooling after roasting to obtain a product C3N4-Mt composite material. Then weighing 2gC3N4Putting the-Mt into a round-bottom flask, adding 40mL of toluene and 3mL of 3-mercaptopropyltrimethoxysilane (MPTMS), stirring and refluxing for 4h at 110 ℃, naturally cooling to room temperature, filtering, washing with toluene and filtering for multiple times, removing the excess MPTMS on the surface of the sample, and drying in an oven at 80 ℃ for 12 h. Weighing 1g of dried C3N4Adding the-Mt-SH sample into 20mL of 30% (mass percent concentration) hydrogen peroxide, stirring for 12h at room temperature, and adding C3N4Oxidation of-Mt-SH to C3N4-Mt-SO3H, then filtering, washing with water, drying at 100 ℃ for 12H, drying and grinding into powder. The catalyst prepared under this synthesis condition is designated as sample 1. The XRD spectrum (FIG. 2) and IR spectrum (FIG. 3) of sample 1 are shown below.
XRD spectrum shows C3N4-Mt-SO3H substantially retained the characteristic peak of montmorillonite, but the intensity of the characteristic peak was weakened, indicating that C3N4-Mt-SO3H has a layered structure of montmorillonite. Compared with carbon nitride, C3N4-Mt-SO3H has a weak peak at 27.35 degrees, and does not have a peak characteristic to the 100 crystal plane of carbon nitride at about 13 degrees, which is thatThis is not because no carbon nitride is formed, but because the amount of carbon nitride formed is relatively small. The yield of carbon nitride is reduced because melamine is formed during the polymerization of the precursor of carbon nitride and sublimes at about 335 ℃. C3N4-Mt-SO3Whether carbon nitride is formed in the H composite we will continue to verify by means of infrared characterization. The infrared spectrum shows C3N4-Mt-SO3H at 806cm-1,1100cm-1,1240cm-1In the presence of-SO3The characteristic absorption peak of H shows that sulfonic acid groups are grafted to the surface of montmorillonite, 1240-1640cm-1The characteristic absorption peak corresponds to the skeleton vibration of the 3-S-triazine ring in the carbon nitride structural unit, and indicates that the carbon nitride is intercalated between montmorillonite layers.
Example 2
The mass of dicyandiamide in example 1 was changed to 0.84g (4CEC), the other steps were as in example 1, and the catalyst prepared under this synthesis condition was designated as sample 2.
Example 3
The mass of dicyandiamide in example 1 was changed to 1.26g (6CEC), the other steps were as in example 1, and the catalyst prepared under this synthesis condition was designated as sample 3.
Example 4
The mass of dicyandiamide in example 1 was changed to 1.68g (8CEC), the other steps were as in example 1, and the catalyst prepared under this synthesis condition was designated as sample 4.
Example 5
The mass of dicyandiamide in example 1 was changed to 2.10g (10CEC), the other steps were as in example 1, and the catalyst prepared under this synthesis condition was designated as sample 5.
Example 6
The amount of 3-mercaptopropyltrimethoxysilane (MPTMS) in example 1 was changed to 1.5mL and the other steps were as in example 1, and the catalyst prepared under this synthesis condition was designated as sample 6.
Example 7
The amount of 3-mercaptopropyltrimethoxysilane (MPTMS) in example 1 was changed to 4.5mL and the other steps were as in example 1, and the catalyst prepared under this synthesis condition was designated as sample 7.
Example 8
The amount of 3-mercaptopropyltrimethoxysilane (MPTMS) in example 1 was changed to 6.0mL and the other steps were as in example 1, and the catalyst prepared under this synthesis condition was designated as sample 8.
Example 9
The catalyst prepared under the synthesis conditions was designated as sample 9, except that in example 1, the volume ratio of 20mL of 30% hydrogen peroxide in example 1 was changed to 20mL of a mixed solution of 30% hydrogen peroxide, water and methanol (30% hydrogen peroxide: water: methanol: 8:1: 1).
Example 10
The catalysts prepared in the above examples 1 to 9 were applied to cellulose hydrolysis reaction, and the hydrolysis performance thereof is shown in table 1.
The cellulose hydrolysis hydrogenation reaction is carried out in a stainless steel automatic high-pressure reaction kettle with a polytetrafluoroethylene lining, and 1.00g of cellulose and C are added in each reaction3N4-Mt-SO30.25g of H catalyst and 7mL of deionized water are uniformly stirred; sealing the reaction kettle, and then using high-purity H2(the purity is more than or equal to 99.999 percent) replacing air in the reaction kettle for 3 times, and filling high-purity H2To a set pressure value of 4 MPa. Stirring and heating the reaction kettle, timing after the reaction kettle is heated to the set temperature of 200 ℃, cooling in ice water bath to stop the reaction after the set reaction time is reached (4h), slowly reducing the pressure to release gas, centrifuging the liquid product, then putting the liquid product into a reagent bottle, qualitatively analyzing the product by using a gas chromatography-mass spectrometer (GC-MS), quantitatively analyzing the product by using a High Performance Liquid Chromatography (HPLC), and pouring the solid residue into a beaker, fully drying and weighing to calculate the conversion rate.
The specific data are as follows:
TABLE 1.C3N4-Mt-SO3Cellulose conversion rate of H-catalyzed cellulose hydrolysis hydrogenation reactionaAnd yield of each productb
a: cellulose conversion ═ (mass of unreacted cellulose-mass of starting cellulose)/mass of starting cellulose
b: the yield is calculated according to the standard curve of the external standard method of each product by the peak area value in the high performance liquid chromatography
Example 10
The amount of 3-mercaptopropyltrimethoxysilane (MPTMS) in example 3 was changed to 4.5mL, the procedure was the same as in example 3, and the catalyst prepared under the synthesis conditions was designated as sample 9. Sample 9 was used to explore cellulose hydrolysis hydrogenation process conditions. The cellulose conversion and the yield of each product of sample 9 under different hydrolysis hydrogenation conditions were discussed.
Condition 1: the mass ratio of the catalyst to the cellulose is 0.25:1, and the hydrothermal reaction condition is 200 ℃ and 2 hours.
Condition 2: the mass ratio of the catalyst to the cellulose is 0.50:1, and the hydrothermal reaction condition is 200 ℃ and 2 h.
Condition 3: the mass ratio of the catalyst to the cellulose is 0.75:1, and the hydrothermal reaction condition is 200 ℃ and 2 h.
Condition 4: the mass ratio of the catalyst to the cellulose is 1:1, and the hydrothermal reaction condition is 200 ℃ and 2 h.
Condition 5: the mass ratio of the catalyst to the cellulose is 0.25:1, the hydrothermal reaction condition is 160 ℃, and the time is 2 hours.
Condition 6: the mass ratio of the catalyst to the cellulose is 0.25:1, and the hydrothermal reaction condition is 180 ℃ and 2 hours.
Condition 7: the mass ratio of the catalyst to the cellulose is 0.25:1, and the hydrothermal reaction condition is 220 ℃ and 2 hours.
Condition 8: the mass ratio of the catalyst to the cellulose is 0.25:1, and the hydrothermal reaction condition is 240 ℃ for 2 h.
Condition 9: the mass ratio of the catalyst to the cellulose is 0.25:1, the hydrothermal reaction condition is 200 ℃, and the time is 1 h.
Condition 10: the mass ratio of the catalyst to the cellulose is 0.25:1, and the hydrothermal reaction condition is 200 ℃ and 4 hours.
Condition 11: the mass ratio of the catalyst to the cellulose is 0.25:1, and the hydrothermal reaction condition is 200 ℃ and 6 hours.
The specific data are as follows:
TABLE 2 cellulose conversion under different hydrolysis hydrogenation conditionsaAnd yield of each productb
a: cellulose conversion ═ (mass of unreacted cellulose-mass of starting cellulose)/mass of starting cellulose
b: the yield is calculated according to the standard curve of the external standard method of each product by the peak area value in the high performance liquid chromatography
The conditions 1-4 can be used for obtaining that: as the amount of catalyst is increased, the yield of glucose as the main product is not increased, but rather the yield of glucose is decreased. This is because on the one hand the glucose is dissociated in the acidic sites of the catalyst and in the hot water H+The further isomerization is carried out under the action of the catalyst, 5-hydroxymethyl furfural is generated by dehydration, and the 5-hydroxymethyl furfural can be hydrolyzed to generate levulinic acid. On the other hand, the cellulose hydrolysate glucose is hydrogenated under the action of the hydrogenation site to generate sorbitol, and the two reactions have a competitive relationship. The conditions 5-8 and 9-11 can be used for obtaining that: as the hydrolysis hydrogenation temperature is increased and the hydrolysis hydrogenation time is prolonged, the cellulose conversion rate is increased and the yield of the hydrolysis main product glucose is increased. The hydrolysis temperature is increased, the time is prolonged, and H is dissociated from liquid water+Will increase H+And a strong acid B site is provided, so that the hydrolysis product glucose is continuously dehydrated to generate byproducts such as 5-hydroxymethylfurfural and levulinic acid. Considering comprehensively, in order to reduce the amount of by-products and facilitate the product separation, the optimal hydrolysis conditions are as follows: the mass ratio of the catalyst to the cellulose is 0.5:1, and hydrothermal reaction is carried outThe temperature was 200 ℃ and the time was 4 h.
Claims (12)
1. The application of the C3N4-Mt-SO3H composite material as a catalyst in the reaction of preparing sorbitol by hydrolyzing and hydrogenating cellulose by a one-pot method is characterized in that: the C3N4-Mt-SO3H composite material is formed by inserting carbon nitride between montmorillonite layers and grafting sulfonic acid groups on the surfaces of the montmorillonite;
the application specifically comprises the following steps: adding cellulose, a C3N4-Mt-SO3H composite material and deionized water into a stainless steel automatic high-pressure reaction kettle with a polytetrafluoroethylene lining, wherein the mass ratio of the cellulose to the C3N4-Mt-SO3H composite material is 0.5: 1-8: 1, and uniformly stirring; after the reaction kettle is sealed, replacing air in the reaction kettle with high-purity H2, and filling high-purity H2 to a set pressure value of 0.1-5 MPa; stirring and heating the reaction kettle, timing after the temperature is 100-400 ℃, reacting for 1-12 h, cooling in ice water bath to stop the reaction, slowly decompressing to release gas, and centrifugally separating the product to obtain the product.
2. The use of claim 1, wherein: the preparation method of the C3N4-Mt-SO3H composite material comprises the following steps:
(1) adding montmorillonite into deionized water, and uniformly stirring to obtain a mixture for later use;
(2) adding a carbon nitride precursor into the mixture obtained in the step (1), and stirring for 0.5-12 h at 10-150 ℃ for exchange adsorption to obtain homogenate, wherein the carbon nitride precursor is one or a combination of more of cyanamide, dicyandiamide, melamine, urea, ethylenediamine, cyanuric chloride and cyanuric acid;
(3) removing water from the homogenate prepared in the step (2) to obtain a solid;
(4) drying the solid obtained in the step (3) at the temperature of 20-150 ℃ for 5-24 h;
(5) grinding the dried solid into powder, placing the powder in a tubular furnace, heating the powder from room temperature to 300-800 ℃ at the speed of 1-10 ℃/min in a nitrogen atmosphere, roasting the powder at a constant temperature for 1-10 hours, and naturally cooling the roasted powder after roasting is finished to obtain a product named as a C3N4-Mt composite material;
(6) adding the C3N4-Mt composite material obtained in the step (5) into toluene, and uniformly stirring to obtain a homogenate;
(7) adding a compound containing a mercapto functional group into the homogenate obtained in the step (6), stirring and refluxing for 1-24 hours at 50-150 ℃, and then cooling to room temperature to obtain a mixed solution; wherein the compound containing the mercapto functional group is selected from one or any combination of the following compounds: 3-mercaptopropyltrimethoxysilane, 2, 3-dimercaptopropanesulfonic acid sodium salt, 3-mercaptopropionic acid, 3-mercapto-1-propanesulfonic acid sodium salt, 3-mercaptobenzoic acid, 4-mercaptobenzoic acid and methyl thioglycolate;
(8) filtering the mixed solution obtained in the step (7), washing with toluene, and drying to obtain a product named as a C3N4-Mt-SH composite material;
(9) adding the C3N4-Mt-SH composite material into a mixed solution containing hydrogen peroxide, water and methanol or hydrogen peroxide, stirring for 1-48h at 10-100 ℃, then filtering, washing, drying for 5-24 h at 20-150 ℃, drying and grinding into powder, and obtaining the product named C3N4-Mt-SO3H composite material.
3. Use according to claim 2, characterized in that: the carbon nitride precursor is dicyandiamide.
4. Use according to claim 2 or 3, characterized in that: in the step (2), the amount of the carbon nitride precursor added is 0.5-20 times of the cation exchange capacity of the montmorillonite.
5. The use of claim 4, wherein: in the step (2), the amount of the carbon nitride precursor added is 1-10 times of the cation exchange capacity of the montmorillonite.
6. The use of claim 4, wherein: in the step (2), the amount of the substance of the carbon nitride precursor added is 6 times of the cation exchange capacity of the montmorillonite.
7. Use according to claim 2, characterized in that: in the step (7), the compound containing a mercapto functional group is 3-mercaptopropyltrimethoxysilane.
8. Use according to claim 2 or 7, characterized in that: in the step (7), the adding amount of the compound containing the mercapto functional group is 1-4 mL/g based on the mass of C3N 4-Mt.
9. The use of claim 8, wherein: in the step (7), the amount of the compound containing a mercapto functional group added is 1.5-2.5 mL/g based on the mass of C3N 4-Mt.
10. The use of claim 8, wherein: in step (7), the mercapto-functional compound was added in an amount of 2.25mL/g based on the mass of C3N 4-Mt.
11. The use according to claim 2, characterized in that the preparation process is carried out according to the following steps: (1) adding montmorillonite into deionized water, wherein the mass ratio of the montmorillonite to the deionized water is 1: 5-1: 50, uniformly stirring to obtain a mixture for later use;
(2) adding dicyandiamide into the mixture obtained in the step (1), stirring for 2-6 h at 60-100 ℃ for exchange adsorption to obtain homogenate; the amount of dicyandiamide substance added is 6 times of the cation exchange capacity of montmorillonite;
(3) removing water from the homogenate prepared in the step (2) to obtain a solid;
(4) drying the solid obtained in the step (3) at the temperature of 20-150 ℃ for 5-24 h;
(5) grinding the dried solid into powder, placing the powder in a tubular furnace, heating the powder from room temperature to 400-600 ℃ at the speed of 1-5 ℃/min in a nitrogen atmosphere, roasting at a constant temperature for 3-5h, and naturally cooling after roasting is finished to obtain a product named as a C3N4-Mt composite material;
(6) adding the C3N4-Mt composite material obtained in the step (5) into toluene, and uniformly stirring to obtain a homogenate;
(7) adding 3-mercaptopropyltrimethoxysilane into the homogenate obtained in the step (6), stirring and refluxing for 2-6 h at 100-120 ℃, and then cooling to room temperature to obtain a mixed solution; the adding amount of the 3-mercaptopropyltrimethoxysilane is 2.25mL/g based on the mass of C3N 4-Mt;
(8) filtering the mixed solution obtained in the step (7), washing with toluene, and drying to obtain a product named as a C3N4-Mt-SH composite material;
(9) adding the C3N4-Mt-SH composite material into hydrogen peroxide, stirring for 12-24h at room temperature, then filtering, washing with water, drying for 5-24 h at 20-150 ℃, grinding into powder after drying, and obtaining the product named C3N4-Mt-SO3H composite material.
12. The use of claim 1, wherein: the mass ratio of the cellulose to the C3N4-Mt-SO3H composite material is 4: 1; the pressure value of H2 was set to 4MPa, the reaction temperature was set to 200 ℃ and the reaction time was set to 4 hours.
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