CN115818650A - Carbon-coated silicon dioxide composite microsphere and preparation method and application thereof - Google Patents
Carbon-coated silicon dioxide composite microsphere and preparation method and application thereof Download PDFInfo
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- CN115818650A CN115818650A CN202211390220.0A CN202211390220A CN115818650A CN 115818650 A CN115818650 A CN 115818650A CN 202211390220 A CN202211390220 A CN 202211390220A CN 115818650 A CN115818650 A CN 115818650A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 130
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 123
- 239000004005 microsphere Substances 0.000 title claims abstract description 110
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 104
- 239000002131 composite material Substances 0.000 title claims abstract description 64
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 16
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 15
- 229910004298 SiO 2 Inorganic materials 0.000 claims abstract description 31
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 29
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- 229910052710 silicon Inorganic materials 0.000 claims abstract description 11
- 239000010703 silicon Substances 0.000 claims abstract description 11
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- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
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- ZMANZCXQSJIPKH-UHFFFAOYSA-N Triethylamine Chemical compound CCN(CC)CC ZMANZCXQSJIPKH-UHFFFAOYSA-N 0.000 description 3
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- GQHTUMJGOHRCHB-UHFFFAOYSA-N 2,3,4,6,7,8,9,10-octahydropyrimido[1,2-a]azepine Chemical compound C1CCCCN2CCCN=C21 GQHTUMJGOHRCHB-UHFFFAOYSA-N 0.000 description 2
- VHYFNPMBLIVWCW-UHFFFAOYSA-N 4-Dimethylaminopyridine Chemical compound CN(C)C1=CC=NC=C1 VHYFNPMBLIVWCW-UHFFFAOYSA-N 0.000 description 2
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 description 2
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 2
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 2
- 230000002378 acidificating effect Effects 0.000 description 2
- 239000003513 alkali Substances 0.000 description 2
- 229910021529 ammonia Inorganic materials 0.000 description 2
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- 238000002604 ultrasonography Methods 0.000 description 2
- OHVLMTFVQDZYHP-UHFFFAOYSA-N 1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-2-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound N1N=NC=2CN(CCC=21)C(CN1CCN(CC1)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)=O OHVLMTFVQDZYHP-UHFFFAOYSA-N 0.000 description 1
- LDXJRKWFNNFDSA-UHFFFAOYSA-N 2-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)-1-[4-[2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidin-5-yl]piperazin-1-yl]ethanone Chemical compound C1CN(CC2=NNN=C21)CC(=O)N3CCN(CC3)C4=CN=C(N=C4)NCC5=CC(=CC=C5)OC(F)(F)F LDXJRKWFNNFDSA-UHFFFAOYSA-N 0.000 description 1
- LWFUFLREGJMOIZ-UHFFFAOYSA-N 3,5-dinitrosalicylic acid Chemical compound OC(=O)C1=CC([N+]([O-])=O)=CC([N+]([O-])=O)=C1O LWFUFLREGJMOIZ-UHFFFAOYSA-N 0.000 description 1
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- NBSCHQHZLSJFNQ-GASJEMHNSA-N D-Glucose 6-phosphate Chemical compound OC1O[C@H](COP(O)(O)=O)[C@@H](O)[C@H](O)[C@H]1O NBSCHQHZLSJFNQ-GASJEMHNSA-N 0.000 description 1
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- RSIHJDGMBDPTIM-UHFFFAOYSA-N ethoxy(trimethyl)silane Chemical compound CCO[Si](C)(C)C RSIHJDGMBDPTIM-UHFFFAOYSA-N 0.000 description 1
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Images
Abstract
The invention discloses a carbon-coated silicon dioxide composite microsphere and a preparation method and application thereof, belonging to the field of composite materials 2 The composite microsphere comprises a modified silicon dioxide microsphere inner core and a hydrothermal carbon layer shell; the preparation method comprises the following steps: (1) Modifying the silicon dioxide microspheres with the surface provided with the silicon hydroxyl groups by using a modifier solution to obtain the modified silicon dioxide microspheres; (2) Carrying out hydrothermal reaction on modified silicon dioxide microspheres and a carbon source serving as raw materials, and coating a hydrothermal carbon layer on the surfaces of the modified silicon dioxide microspheres to obtain the carbon-coated SiO 2 And (3) compounding the microspheres. The method has the advantages of easily available raw materials, simple method, greenness and no pollution, and the prepared carbon-coated SiO 2 The composite microspheres have adjustable particle size, carbon layer morphology and shell carbon content, can efficiently catalyze and accelerate cellulose hydrolysis into sugar, and have good recycling effect.
Description
Technical Field
The invention belongs to the field of composite materials, and particularly relates to a carbon-coated silicon dioxide composite microsphere as well as a preparation method and application thereof.
Background
The preparation and application of carbon materials have been through human history. Since the development of classical carbon materials (coal, activated carbon, etc.) to new carbon materials (graphene, carbon nanotubes, etc.) since 1960, carbon materials have been widely studied and applied due to their excellent thermodynamic properties, chemical stability, high specific surface area, high developability, and good biocompatibility. Hydrothermal carbonization (HTC) processes can form functional carbon materials rich in hydroxyl, carbonyl, and other reactive oxygen-containing functional groups directly in the pure water phase without the need for complex post-processing. The formation method can be carried out under mild reaction conditions (below 280 ℃), and the formed oxygen-enriched carbon material has uniform and stable distribution of oxygen-containing functional groups and is not easy to fall off, so that the oxygen-enriched carbon material is suitable for being widely applied to the fields of energy storage, new energy circulation, sensing, catalysis and environmental protection. The nano-scale hydrothermal carbon material with a large amount of hydroxyl on the surface is also used as a catalytic accelerator for cellulose hydrolysis, and the cellulose structure is broken through strong physical acting force, so that the reaction area of the cellulose is increased, and the cellulose is efficiently hydrolyzed into sugar under the conditions of full water phase and dilute acid.
However, during the formation of hydrothermal carbon, its spontaneously formed morphology is spherical, and its size and surface state are difficult to control, limiting its further application. In the Chinese patent publication No. CN114975957A, znCl is used 2 The surface of the hydrothermal carbon sphere is etched to control the surface morphology of the hydrothermal carbon sphere, but high-energy-consumption processes such as grinding and heating are needed in the process, and the preparation process of the two-step method is complex. Functional groups can also be introduced onto the surface of the hydrothermal carbon by a one-step method to provide the hydrothermal carbon with a special application function, for example, in chinese patent publication No. CN114762818A, disodium glucose-6-phosphate is used as a raw material to form a hydrothermal carbon structure with a surface rich in phosphate groups, but the introduction of phosphate groups significantly increases the morphological size of the hydrothermal carbon (10 μm), and although acidic functional groups are introduced, the surface area is limited. Therefore, it is of great significance to develop a hydrothermal carbon material with controllable structure and controllable size and further explore the application of the hydrothermal carbon material.
Disclosure of Invention
The invention provides a carbon-coated SiO 2 CompoundingThe microspheres comprise modified silicon dioxide microsphere cores and hydrothermal carbon layer shells; the carbon-coated SiO 2 The composite microspheres have adjustable particle size, carbon layer morphology and shell carbon content, can efficiently catalyze and accelerate cellulose hydrolysis into sugar, and have good recycling effect.
The technical scheme is as follows:
carbon cladding SiO 2 The composite microsphere comprises a modified silicon dioxide microsphere inner core and a hydrothermal carbon layer shell; the surface of the modified silicon dioxide microsphere is positively charged groups, and the particle size is 1nm-10 mu m; the thickness of the hydrothermal carbon layer is 1nm-10 mu m, and the hydrothermal carbon layer is obtained by taking modified silicon dioxide microspheres and a carbon source as raw materials through hydrothermal reaction.
When the hydrothermal reaction times is one time, the prepared carbon-coated SiO layer 2 The thickness of the hydrothermal carbon layer of the composite microsphere is 1-100nm; when the hydrothermal reaction times are at least two, the prepared carbon-coated SiO 2 The thickness of the hydrothermal carbon layer of the composite microsphere is 1nm-10 mu m.
The invention also provides the carbon-coated SiO 2 The preparation method of the composite microsphere comprises the following steps:
(1) Modifying the silicon dioxide microspheres with the surface provided with the silicon hydroxyl groups by using a modifier solution to obtain the modified silicon dioxide microspheres;
(2) Carrying out hydrothermal reaction on modified silicon dioxide microspheres and a carbon source serving as raw materials, and coating a hydrothermal carbon layer on the surfaces of the modified silicon dioxide microspheres to obtain the carbon-coated SiO 2 And (3) compounding the microspheres.
The invention takes spherical silicon dioxide with silicon hydroxyl groups on the surface as a substrate, and the surface of the silicon dioxide microsphere is modified to obtain a modified silicon dioxide microsphere, wherein the surface of the modified silicon dioxide microsphere is positively charged; then, hydrothermal carbon grows on the surface of the silicon dioxide by a hydrothermal method and depending on electrostatic interaction, and a hydrothermal carbon layer is coated on the surface of the modified silicon dioxide microspheres to form a carbon-coated SiO layer with a core-shell structure 2 And (3) compounding the microspheres. The particle size of the composite microsphere, the shape of the hydrothermal carbon layer and the carbon content of the shell are adjustable, and the composite microsphere can be applied to cellulose hydrolysis under the conditions of full water phase and low acid.
Preferably, the modifier is preferably a silane coupling agent, including but not limited to KH-550, KH-560, KH-792, and the like; by the action of the modifier, the hydroxyl negative electric groups on the surface of the silica microsphere can be partially or completely replaced by positive electric groups.
Further preferably, in the modification system, the concentration of the modifier solution is 0.1-1mol/L, and the concentration of the silicon dioxide microspheres is 0.05-20g/L; the modification temperature is 0-150 ℃ and the modification time is 0.5-8h.
The silica microspheres with the surface provided with the silicon hydroxyl groups can be directly purchased or synthesized in a laboratory by a gas phase method, a precipitation method and a sol-gel method; taking the sol-gel method as an example, the synthesis method comprises the following steps: adding a silicon source into a mixed solvent containing the alkali catalyst, stirring for 0.5-10h at 0-60 ℃, then centrifugally separating, and washing with water and ethanol for multiple times to obtain the silicon dioxide microspheres with silicon hydroxyl groups on the surfaces.
The mixed solvent comprises at least one of methanol, ethanol, water, tetrahydrofuran, glycol, n-amyl alcohol, propanol and cyclohexane; the alkali catalyst is selected from ammonia, sodium hydroxide, potassium hydroxide, triethylamine, 1, 8-diazabicyclo [5.4.0] undec-7-ene or 4-dimethylamino pyridine; the silicon source is selected from tetraethyl silicate, trimethylethoxysilane, methyltrimethoxysilane and trichlorosilane.
The carbon source can be any one or a combination of several of glucose, fructose, xylose, sucrose, cellobiose, 5-hydroxymethylfurfural, liquefied starch and the like, but is not limited thereto.
Preferably, in the hydrothermal reaction system of the step (2), the concentration of the carbon source is 0.01-10mol/L, the hydrothermal reaction temperature is 160-220 ℃, and the reaction time is 6-12 hours.
Specifically, the hydrothermal reaction times are at least one, and the modified silicon dioxide microspheres and/or carbon-coated SiO 2 The mass ratio of the composite microspheres to the carbon source is 1:0.05-5.
When only one hydrothermal reaction is carried out, the prepared carbon-coated SiO 2 The surface of the hydrothermal carbon layer of the composite microsphere is uneven and not smooth,has a raspberry-like structure; when the hydrothermal reaction is carried out for two or more times, the thickness of the hydrothermal carbon layer is increased, and the surface is smooth or not; that is, the hydrothermal carbon layer can be controllably formed on the surface of the inner core by supplying the carbon source step by step.
Specifically, in the step (2), modified silicon dioxide microspheres or carbon-coated SiO 2 The composite microspheres are added into carbon source liquid for full dispersion, and then placed in a high-pressure reaction kettle for hydrothermal reaction, wherein the dispersion process can adopt one or a combination of several methods such as a cell crushing instrument, microwave ultrasound, magnetic stirring, table dispersion and the like, but is not limited to the above.
The carbon coating SiO 2 The composite microspheres need to be fully washed by at least two of methanol, ethanol, water, tetrahydrofuran, ethylene glycol, n-amyl alcohol, propanol or cyclohexane.
The invention also provides the carbon-coated SiO 2 The application of the composite microspheres in catalyzing cellulose to be hydrolyzed into sugar.
The application mode is as follows: under the high-temperature closed condition, the carbon cladding SiO 2 The composite microspheres catalyze cellulose hydrolysis reaction in dilute acid solution to form sugar; the high-temperature sealing conditions are as follows: performing hydrolysis reaction in a hydrothermal reaction kettle at 50-200 deg.C for 60-360min.
Further preferably, the concentration of hydrogen ions in the dilute acid solution is 0.01-0.2mol/L, and the dilute acid is selected from HCl and H 2 SO 4 、H 3 PO 4 At least one of maleic acid, oxalic acid and formic acid; the carbon coating SiO 2 The mass ratio of the composite microspheres to the cellulose is 1:0.1-50.
Compared with the prior art, the invention has the beneficial effects that:
(1) According to the invention, the caramelized substance formed by a carbon source in the hydrothermal process is driven to be adsorbed on the surface of the modified silicon dioxide microspheres by changing the surface electrical property of the silicon dioxide microspheres, so that the hydrothermal carbonization process is selectively controlled to occur on the surface of the modified silicon dioxide microspheres, and the composite microspheres with the core-shell structure are formed.
(2) The invention is provided withControl of carbon source content, rather than high energy consumption treatment methods or difficult-to-recycle chemical reagents for carbon-coated SiO 2 Controlling the surface morphology of the composite microspheres; under the condition of single hydrothermal reaction of a low-concentration carbon source, the hydrothermal carbon layer is not sufficient to supplement and form a smooth surface, a raspberry-like carbon layer structure in the forming process is reserved, and meanwhile, the formation of a byproduct non-core-shell structure hydrothermal carbon material is avoided; two or more times of hydrothermal reaction can ensure that the carbonization process preferentially occurs on the surface of the core-shell structure rather than in the solution.
(3) The method can control the surface morphology of the hydrothermal carbon layer, the particle size of the composite microspheres and the like, has simple operation, is suitable for large-scale production, has common reaction raw materials, does not relate to the use of high-risk and toxic organic solvents, meets the requirement of green chemistry, and has the advantages of simple operation, easy operation, no pollution to environment and low cost 2 The composite microsphere has wide application prospect in the fields of environment, energy and catalysis.
(4) The carbon-coated SiO of the invention 2 The composite microspheres can be used for catalyzing cellulose to be hydrolyzed into sugar, the hydrothermal carbon layer structure rich in hydroxyl on the surface layer has a good structural damage effect on the cellulose, the cellulose can be efficiently catalyzed and accelerated to be hydrolyzed into sugar, the obtained cellulose hydrolysis product comprises water-soluble reducing sugar and glucose, the yield of the reducing sugar is over 80%, and the yield of the glucose is over 65%.
Drawings
FIG. 1 is a scanning electron microscope image of unmodified silica microspheres from example 1.
FIG. 2 shows zeta potentials before and after modification of the silica microspheres in example 1.
FIG. 3 shows a carbon-coated SiO film obtained in example 1 2 Transmission electron microscopy images of composite microspheres.
FIG. 4 shows a SiO coating layer of a carbon coating layer in example 2 2 Transmission electron microscopy pictures of composite microspheres.
FIG. 5 shows a carbon-coated SiO film obtained in example 3 2 Transmission electron microscopy pictures of composite microspheres.
FIG. 6 shows unmodified silica nanospheres and carbon-coated SiO solid of example 4 2 Transmission electron microscope picture of composite microsphere, wherein A is unmodifiedSilicon dioxide nanosphere, B is carbon-coated SiO 2 And (3) compounding the microspheres.
FIG. 7 shows SiO as a product of comparative example 1 2 Transmission electron microscopy pictures of the base material.
FIG. 8 shows a SiO coating layer of a carbon layer in example 1 2 Scanning electron microscope images of the composite microspheres applied to hydrolysis of regenerated cellulose.
Detailed Description
The invention will be further elucidated below with reference to the embodiments and the accompanying drawings. It should be understood that these examples are for illustrative purposes only and are not intended to limit the scope of the present invention.
Example 1
(1) Adding 8mL of tetraethoxysilane into a mixed solution of water and ethanol with the ammonia concentration of 0.4mol/L, wherein the mixing ratio of the water to the ethanol is 2:8; placing the mixed solution on a magnetic stirring table, stirring for 2 hours at room temperature (25 ℃), and changing the solution from clear and transparent to milky white; centrifuging the product, washing the product for at least three times by ethanol and water respectively, and drying to obtain the silicon dioxide microspheres with the surface provided with the silicon hydroxyl groups; the SEM image of the silica microspheres is shown in figure 1, and the particle size is within the range of 250-400 nm.
(2) Putting the silica microspheres obtained in the step (1) and a silane coupling agent KH-792 into a methanol solution (the concentration of the silica microspheres is 20g/L, the concentration of the silane coupling agent KH-792 is 0.1 mol/L), heating to 50 ℃, reacting for 2 hours, centrifuging the product, washing with ethanol and water for at least three times, drying to obtain modified silica microspheres with the particle size of 250-400nm, and obtaining the modified silica microspheres (SiO) 2 -NH 2 ) The surface zeta potential changes from negative to positive in an acidic environment (fig. 2).
(3) Fully dispersing 0.1g of modified silicon dioxide microspheres in 160mL of water with fructose concentration of 0.01mol/L under the action of ultrasound, and placing the mixture in a high-pressure reaction kettle for hydrothermal reaction at the temperature of 160 ℃ for 12 hours; taking out the reaction product, fully washing the reaction product by using methanol, water and the like, and drying the reaction product to obtain the carbon-coated SiO 2 Composite microspheres, i.e. raspberry-like carbon-coated SiO 2 And (3) compounding the microspheres.
This exampleThe obtained 'raspberry-like' carbon coating SiO 2 The TEM image of the composite microsphere is shown in FIG. 3, the particle size is 250-400nm, the hydrothermal carbon layer is shown to be raspberry-like, and the layer thickness is about 1-5nm.
Example 2
0.5g of the "raspberry-like" carbon coating SiO obtained in example 1 2 After being fully washed, the composite microspheres are dispersed in 60mL of glycol with the concentration of 0.05mol/L of pentamethyl furfural, and are placed in a high-pressure reaction kettle for hydrothermal reaction at the reaction temperature of 180 ℃ for 6 hours. The reaction product was taken out and sufficiently washed with methanol, water, etc., and dried to obtain the carbon-coated SiO layer having an increased thickness as compared with the carbon layer of example 1 2 And (3) compounding the microspheres.
Carbon-coated SiO layer produced in this example 2 The TEM image of the composite microsphere is shown in FIG. 4, the particle size is 250-450nm, the hydrothermal carbon layer is similar to raspberry, and the layer thickness is about 5-20nm.
Example 3
5g of the "raspberry-like" carbon coating SiO obtained in example 1 2 After being fully washed, the composite microspheres are dispersed in 140mL of water with the glucose concentration of 0.4mol/L, and are placed in a high-pressure reaction kettle for hydrothermal reaction at the reaction temperature of 190 ℃ for 8 hours. Taking out the reaction product, fully washing the reaction product by using methanol, water and the like, and drying the reaction product to obtain the carbon-coated SiO with the smooth hydrothermal carbon layer 2 And (3) compounding the microspheres.
The carbon-coated SiO prepared in this example 2 The TEM image of the composite microsphere is shown in FIG. 5, the particle size is 350-550nm, the surface of the hydrothermal carbon layer is smooth, and the layer thickness is about 50-70nm.
Example 4
(1) The preparation method comprises the steps of adopting commercial silica microspheres (purchased from new materials science and technology limited of bond, and SEM is shown as A in figure 6) with the size of about 80nm and silicon hydroxyl groups on the surfaces, putting the silica microspheres and a silane coupling agent KH-550 into an ethylene glycol solution (the concentration of the silica microspheres is 3g/L, and the concentration of the silane coupling agent KH-550 is 0.5 mol/L), reacting for 3h at room temperature, centrifuging the product, washing the product for at least three times by using ethanol and water respectively, and drying to obtain the modified silica microspheres with the smooth surfaces and the particle sizes of 50-150 nm.
(2) Fully dispersing 3g of modified silicon dioxide microspheres in 60mL of water with 2mol/L cyclodextrin concentration under the ultrasonic action, and placing the mixture in a high-pressure reaction kettle for hydrothermal reaction at 220 ℃ for 6 hours. Taking out the reaction product, fully washing the reaction product by using methanol, water and the like, and drying the reaction product to obtain the carbon-coated SiO 2 And (3) compounding the microspheres.
The carbon-coated SiO prepared in this example 2 The TEM image of the composite microsphere is shown as B in FIG. 6, the particle size is 60-200nm, the surface of the hydrothermal carbon layer is not smooth, and the layer thickness is about 10-30nm.
Comparative example 1
In the comparative example, the preparation method of the silica microspheres with silicon hydroxyl groups on the surfaces is the same as that in example 1, except that the unmodified silica microspheres are directly and fully dispersed in 160mL of water with fructose concentration of 2mol/L by a cell crushing method without modification by a modifier, and the mixture is placed in a high-pressure reaction kettle for hydrothermal reaction at the temperature of 160 ℃ for 12 hours. Taking out the reaction product, and fully washing the reaction product by using methanol, water and the like to prepare the product SiO 2 A base material;
FIG. 7 shows the SiO content of the product obtained after hydrothermal treatment 2 The appearance of the base material shows that the surface of the silica microspheres is kept smooth, and the hydrothermal carbon and the silica microspheres independently exist without coating behavior, which indicates that the electrical property change after the surface modification of the silica microspheres is necessary for the hydrothermal coating process.
Application example
Coating the carbon with SiO 2 The composite microspheres as catalytic accelerating auxiliary agent are uniformly mixed with regenerated cellulose, and the mixture is added into a full aqueous diluted acid system under hydrothermal condition to hydrolyze the regenerated cellulose into sugar; in the hydrolysis process, the SiO layer is coated with carbon 2 The mass ratio of the composite microspheres to the regenerated cellulose can be 1:0.1-50, the concentration of hydrogen ions in the dilute acid water solution is 0.01-0.2 mol/L; the hydrothermal condition is 50-220 deg.C, 60-360min. The obtained hydrolysate was tested to include water-soluble reducing sugar and glucose, reducing sugarThe yield is more than 80%, and the yield of glucose is more than 65%.
Specifically, 0.1g of the carbon-coated SiO prepared in example 1 and example 3 was added 2 The composite microspheres are used as a catalytic acceleration auxiliary agent, and are mixed with 1g of regenerated cellulose in a mass ratio of 1:10 was thoroughly dispersed in 160mL of a 0.01mol/L dilute sulfuric acid solution by a cell disruptor, and then the above mixed solution was placed in an autoclave. Setting the rotating speed of a high-pressure reaction kettle in the homogeneous reactor as 1r/s, the hydrolysis temperature as 160 ℃, and reacting for 60min. The reaction product hydrolyzed in example 1 was filtered, neutralized, and analyzed to calculate the cellulose conversion rate, the reducing sugar yield, and the glucose yield to be 96%, 83%, and 75%, respectively. Example 3 the hydrolysate was filtered and neutralized under the same hydrolysis conditions, and the cellulose conversion, reducing sugar yield and glucose yield were 90%, 75% and 62%, respectively.
The method for measuring the yield (TRS yield%) of reducing sugar adopts a 3, 5-dinitrosalicylic acid (DNS) method to obtain the mass of the reducing sugar, and the calculation method is as follows:
the glucose yield (glucose yield%) was calculated as follows:
wherein m is TRS Represents the mass of reducing sugars in the product, m RC Representing the mass of cellulose before hydrolysis, C glucose The glucose concentration measured by liquid chromatography was represented by n as a dilution factor and V as the total volume of the hydrolysis mixture solution.
The carbon-coated SiO 2 The composite microspheres can be reused, coated with "raspberry-like" carbon SiO as in example 1 2 The composite microspheres are taken as an example, and the hydrolysis effect of the regenerated cellulose into sugar after the composite microspheres are repeatedly subjected to accelerated hydrolysis for three times under the same hydrolysis condition is shown in table 1.
TABLE 1 example 1 carbon coating SiO in the form of "raspberry-like" carbon 2 Reuse performance of composite microspheres
While SiO, a product obtained by using the unmodified silica microspheres in comparative example 1 2 The base material is hydrolyzed by regenerated cellulose under the same conditions, the conversion rate of the cellulose is 70 percent, the yield of reducing sugar is 60 percent, the yield of glucose is 45 percent, the difference is not large compared with a pure acid blank group, and the obvious effect of accelerating the hydrolysis of the regenerated cellulose does not appear.
From the above data, it can be seen that the carbon-coated SiO layer 2 The composite microsphere catalytic accelerating assistant breaks the cellulose structure through the strong interaction between the shell hydrothermal carbon layer and the cellulose, so that the contact area of cellulose fragments and the ultra-dilute acid proton catalyst is increased, the hydrolysis process of the regenerated cellulose into sugar is accelerated, and fig. 8 shows that the carbon-coated SiO is 2 The composite microspheres catalyze and accelerate the process of breaking the cellulose structure of the auxiliary agent in the hydrolysis process. By coating the carbon with SiO 2 The surface morphology and the size of the composite microsphere catalytic acceleration auxiliary agent are controlled to improve the contact efficiency and the catalytic effect of cellulose, the construction method is simple, green, environment-friendly and low in energy consumption, and the prepared carbon-coated SiO is 2 The composite microsphere catalytic acceleration auxiliary agent has good repeated use effect.
The technical solutions of the present invention have been described in detail with reference to the above embodiments, it should be understood that the above embodiments are only specific examples of the present invention and should not be construed as limiting the present invention, and any modifications, additions or similar substitutions made within the scope of the principles of the present invention should be included in the protection scope of the present invention.
Claims (10)
1. Carbon cladding SiO 2 The composite microsphere is characterized by comprising a modified silicon dioxide microsphere inner core and a hydrothermal carbon layer shell;
the surface of the modified silicon dioxide microsphere is positively charged groups, and the particle size is 1nm-10 mu m;
the thickness of the hydrothermal carbon layer is 1nm-10 mu m, and the modified silicon dioxide microspheres and a carbon source are used as raw materials and are obtained through hydrothermal reaction.
2. Carbon-coated SiO as claimed in claim 1 2 The composite microsphere is characterized in that when the hydrothermal reaction times are one time, the prepared carbon-coated SiO is 2 The thickness of the hydrothermal carbon layer of the composite microsphere is 1-100nm; when the hydrothermal reaction times are at least two, the prepared carbon-coated SiO 2 The thickness of the hydrothermal carbon layer of the composite microsphere is 1nm-10 mu m.
3. Carbon-coated SiO as claimed in claim 1 or 2 2 The preparation method of the composite microspheres is characterized by comprising the following steps:
(1) Modifying the silicon dioxide microspheres with the surface provided with the silicon hydroxyl groups by using a modifier solution to obtain the modified silicon dioxide microspheres;
(2) Carrying out hydrothermal reaction on modified silicon dioxide microspheres and a carbon source serving as raw materials, and coating a hydrothermal carbon layer on the surfaces of the modified silicon dioxide microspheres to obtain the carbon-coated SiO 2 And (3) compounding the microspheres.
4. Carbon-coated SiO as claimed in claim 3 2 The preparation method of the composite microspheres is characterized in that in the modification system in the step (1), the modifier is a silane coupling agent, and the concentration of a modifier solution is 0.1-1mol/L; the concentration of the silicon dioxide microspheres is 0.05-20g/L; the modification temperature is 0-150 ℃ and the modification time is 0.5-8h.
5. Carbon-coated SiO as claimed in claim 3 2 The preparation method of the composite microspheres is characterized in that the carbon source comprises at least one of glucose, fructose, xylose, sucrose, cellobiose, cyclodextrin, 5-hydroxymethylfurfural and liquefied starch.
6. Carbon-coated SiO as claimed in claim 3 2 CompoundingThe preparation method of the microspheres is characterized in that in the hydrothermal reaction system in the step (2), the concentration of the carbon source is 0.01-10mol/L, the hydrothermal reaction temperature is 160-220 ℃, and the reaction time is 6-12 hours.
7. The carbon-clad SiO of claim 3 or 6 2 The preparation method of the composite microsphere is characterized in that the hydrothermal reaction times are at least one time, and the modified silicon dioxide microsphere and/or carbon-coated SiO 2 The mass ratio of the composite microspheres to the carbon source is 1:0.05-5.
8. Carbon-coated SiO as claimed in claim 1 or 2 2 The application of the composite microspheres in catalyzing cellulose hydrolysis into sugar.
9. Carbon-coated SiO as claimed in claim 8 2 The application of the composite microspheres in catalyzing cellulose to be hydrolyzed into sugar is characterized in that the application mode is as follows: under the high-temperature closed condition, the carbon cladding SiO 2 The composite microspheres catalyze cellulose hydrolysis reaction in dilute acid solution to form sugar; the high-temperature sealing conditions are as follows: performing hydrolysis reaction in a hydrothermal reaction kettle at 50-200 deg.C for 60-360min.
10. Carbon-coated SiO according to claim 9 2 The application of the composite microspheres in catalyzing hydrolysis of cellulose into sugar is characterized in that the concentration of hydrogen ions in the dilute acid solution is 0.01-0.2mol/L, and the dilute acid is selected from HCl and H 2 SO 4 、H 3 PO 4 At least one of maleic acid, oxalic acid and formic acid; the carbon coating SiO 2 The mass ratio of the composite microspheres to the cellulose is 1:0.1-50.
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