CN111992212A - Preparation method of lignin carbon-based flexible composite material and application of lignin carbon-based flexible composite material in photocatalytic synthesis of xylonic acid - Google Patents
Preparation method of lignin carbon-based flexible composite material and application of lignin carbon-based flexible composite material in photocatalytic synthesis of xylonic acid Download PDFInfo
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- 229920005610 lignin Polymers 0.000 title claims abstract description 78
- 239000002131 composite material Substances 0.000 title claims abstract description 48
- 230000001699 photocatalysis Effects 0.000 title claims abstract description 47
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 35
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 32
- QXKAIJAYHKCRRA-UHFFFAOYSA-N D-lyxonic acid Natural products OCC(O)C(O)C(O)C(O)=O QXKAIJAYHKCRRA-UHFFFAOYSA-N 0.000 title claims abstract description 17
- QXKAIJAYHKCRRA-FLRLBIABSA-N D-xylonic acid Chemical compound OC[C@@H](O)[C@H](O)[C@@H](O)C(O)=O QXKAIJAYHKCRRA-FLRLBIABSA-N 0.000 title claims abstract description 17
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 230000015572 biosynthetic process Effects 0.000 title claims abstract description 12
- 238000003786 synthesis reaction Methods 0.000 title claims abstract description 12
- 239000000463 material Substances 0.000 claims abstract description 43
- 238000003756 stirring Methods 0.000 claims abstract description 31
- QPLDLSVMHZLSFG-UHFFFAOYSA-N Copper oxide Chemical compound [Cu]=O QPLDLSVMHZLSFG-UHFFFAOYSA-N 0.000 claims abstract description 29
- 239000005751 Copper oxide Substances 0.000 claims abstract description 29
- 229910000431 copper oxide Inorganic materials 0.000 claims abstract description 29
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 27
- 239000002127 nanobelt Substances 0.000 claims abstract description 25
- 238000000034 method Methods 0.000 claims abstract description 17
- 238000001354 calcination Methods 0.000 claims abstract description 16
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims abstract description 16
- 229920002134 Carboxymethyl cellulose Polymers 0.000 claims abstract description 14
- 239000001768 carboxy methyl cellulose Substances 0.000 claims abstract description 14
- 235000010948 carboxy methyl cellulose Nutrition 0.000 claims abstract description 14
- 239000008112 carboxymethyl-cellulose Substances 0.000 claims abstract description 14
- 239000000243 solution Substances 0.000 claims description 27
- 238000004108 freeze drying Methods 0.000 claims description 18
- SRBFZHDQGSBBOR-IOVATXLUSA-N D-xylopyranose Chemical compound O[C@@H]1COC(O)[C@H](O)[C@H]1O SRBFZHDQGSBBOR-IOVATXLUSA-N 0.000 claims description 14
- 239000002243 precursor Substances 0.000 claims description 12
- 239000012670 alkaline solution Substances 0.000 claims description 10
- 238000006243 chemical reaction Methods 0.000 claims description 8
- 239000000203 mixture Substances 0.000 claims description 8
- PYMYPHUHKUWMLA-UHFFFAOYSA-N arabinose Natural products OCC(O)C(O)C(O)C=O PYMYPHUHKUWMLA-UHFFFAOYSA-N 0.000 claims description 7
- SRBFZHDQGSBBOR-UHFFFAOYSA-N beta-D-Pyranose-Lyxose Natural products OC1COC(O)C(O)C1O SRBFZHDQGSBBOR-UHFFFAOYSA-N 0.000 claims description 7
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 4
- 239000012298 atmosphere Substances 0.000 claims description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N nitrogen Substances N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 2
- 238000005286 illumination Methods 0.000 claims description 2
- 229910052757 nitrogen Inorganic materials 0.000 claims description 2
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 claims 1
- 230000000694 effects Effects 0.000 abstract description 2
- 238000009776 industrial production Methods 0.000 abstract description 2
- 238000002156 mixing Methods 0.000 abstract description 2
- 239000000047 product Substances 0.000 description 31
- 238000007906 compression Methods 0.000 description 12
- 239000008367 deionised water Substances 0.000 description 12
- 229910021641 deionized water Inorganic materials 0.000 description 12
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 11
- 230000006835 compression Effects 0.000 description 8
- 238000010586 diagram Methods 0.000 description 6
- 239000012299 nitrogen atmosphere Substances 0.000 description 6
- 238000005516 engineering process Methods 0.000 description 4
- 210000003811 finger Anatomy 0.000 description 4
- 238000004811 liquid chromatography Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 210000003813 thumb Anatomy 0.000 description 4
- 239000002028 Biomass Substances 0.000 description 3
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000011084 recovery Methods 0.000 description 3
- CDBYLPFSWZWCQE-UHFFFAOYSA-L Sodium Carbonate Chemical compound [Na+].[Na+].[O-]C([O-])=O CDBYLPFSWZWCQE-UHFFFAOYSA-L 0.000 description 2
- UIIMBOGNXHQVGW-UHFFFAOYSA-M Sodium bicarbonate Chemical compound [Na+].OC([O-])=O UIIMBOGNXHQVGW-UHFFFAOYSA-M 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000003575 carbonaceous material Substances 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 238000005215 recombination Methods 0.000 description 2
- 230000006798 recombination Effects 0.000 description 2
- 239000004065 semiconductor Substances 0.000 description 2
- -1 BiOX Chemical class 0.000 description 1
- RQPZNWPYLFFXCP-UHFFFAOYSA-L barium dihydroxide Chemical compound [OH-].[OH-].[Ba+2] RQPZNWPYLFFXCP-UHFFFAOYSA-L 0.000 description 1
- 229910001863 barium hydroxide Inorganic materials 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 238000010907 mechanical stirring Methods 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 229910052976 metal sulfide Inorganic materials 0.000 description 1
- 150000004767 nitrides Chemical class 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- TYJJADVDDVDEDZ-UHFFFAOYSA-M potassium hydrogencarbonate Chemical compound [K+].OC([O-])=O TYJJADVDDVDEDZ-UHFFFAOYSA-M 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 229910000030 sodium bicarbonate Inorganic materials 0.000 description 1
- 235000017557 sodium bicarbonate Nutrition 0.000 description 1
- 229910000029 sodium carbonate Inorganic materials 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 150000003568 thioethers Chemical class 0.000 description 1
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
- B01J23/74—Iron group metals
- B01J23/75—Cobalt
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
- C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
- C07C51/21—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen
- C07C51/23—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups
- C07C51/235—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation with molecular oxygen of oxygen-containing groups to carboxyl groups of —CHO groups or primary alcohol groups
Abstract
The invention discloses a preparation method of a lignin carbon-based flexible composite material and application of the lignin carbon-based flexible composite material in photocatalytic synthesis of xylonic acid, and belongs to the field of flexible photocatalytic materials. The preparation method of the lignin carbon-based flexible composite material comprises the following steps: mixing industrial lignin, a copper oxide nanobelt and a cobalt chloride solution, stirring fully, then performing ultrasonic defoaming, adding carboxymethyl cellulose and water, stirring uniformly, preparing a lignin-carbon-based flexible composite photocatalytic material by adopting a guide freeze drying-calcining method, and applying the lignin-carbon-based flexible composite photocatalytic material to photocatalytic synthesis of xylonic acid. The flexible composite photocatalytic material synthesized by the method has excellent performances of good flexibility, high activity, recyclability and the like, and is easy to realize industrial production.
Description
Technical Field
The invention relates to preparation of a lignin carbon-based flexible composite material and application thereof in photocatalytic synthesis of xylonic acid, belonging to the field of flexible photocatalytic materials.
Background
With the increasing exhaustion of fossil fuels in the world, the problem of energy sources is highlighted, and the demand of people for energy sources is continuously increased along with the progress of science and technology, so the development of new energy sources and the concept of high efficiency and energy conservation become the subjects of sustainable economic development. Based on this, the utilization of biomass energy and solar energy is receiving much attention. The biomass is used as a unique sustainable source of organic carbon, can be converted into various fuels and high-value chemicals, can be used for preparing various functional carbon materials, and has important significance for the sustainable development of the society by efficient utilization. Also, solar energy is an inexhaustible clean energy, and the application field thereof is increasing year by year. The photocatalysis technology is an important means for efficiently utilizing solar energy, and the photocatalysis technology is combined with high-value utilization of biomass resources, so that the photocatalysis technology has important significance for sustainable development of the global society. In recent years, semiconductors such as metal oxides, sulfides, and nitrides, and materials such as BiOX, which have been widely used in photocatalytic processes, all exhibit high photocatalytic activity, but some photocatalytic materials also have problems such as poor stability and difficulty in recovery. Therefore, the development of a high-efficiency and stable photocatalytic material is of great significance.
In recent years, flexible carbon materials have attracted much attention because of their advantages such as low cost, large specific surface area, large aspect ratio, strong conductivity, simple and controllable preparation conditions, and the like. Industrial lignin is a by-product of the paper making process with annual production of several million tons, but its utilization is less than 20%. Therefore, it is important to develop high-value utilization of industrial lignin.
Disclosure of Invention
The invention aims to provide a novel, simple and convenient preparation method of a lignin carbon-based flexible composite material and application thereof in photocatalytic synthesis of xylonic acid aiming at the problems of poor stability of a photocatalytic material, difficulty in recovery, limited absorption range of visible light, easiness in recombination of surface photon-generated carriers, low yield in a xylonic acid synthesis process, harsh reaction conditions and the like. The invention takes industrial lignin (carbon source) and copper oxide nanobelts (semiconductor material) as raw materials, prepares the lignin-based flexible composite photocatalytic material by a simple method (through a controllable freeze drying-calcining process), and applies the lignin-based flexible composite photocatalytic material to photocatalytic oxidation synthesis of xylonic acid. The industrial lignin used as the raw material has wide sources, low price and easy obtainment, and has good biocompatibility, safety and biodegradability, thus being an ideal raw material for preparing flexible materials. The synthesis method is simple and easy to control, and is 'green' and pollution-free.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of a lignin carbon-based flexible composite material comprises the following steps:
(1) dispersing industrial lignin and copper oxide nanobelts in water, and uniformly dispersing the industrial lignin and the copper oxide nanobelts in the water in an ultrasonic stirring or mechanical stirring manner; wherein the ratio of the industrial lignin to the copper oxide nanobelts to the water is 0.5-3 g: 0.05-0.2 g: 40 mL;
(2) adding a cobalt chloride solution into the mixture obtained in the step (1), uniformly stirring, adding carboxymethyl cellulose and water, uniformly stirring, and performing ultrasonic defoaming; wherein the concentration of the cobalt chloride solution is 20-40 mol/L; the ratio of the copper oxide nanobelt to the cobalt chloride solution is 0.05-0.2 g: 1 mL; the ratio of the copper oxide to the carboxymethyl cellulose to the water is 0.05-0.2 g: 4-6 g: 20 mL;
(3) preparing a photocatalytic material precursor from the product obtained in the step (2) in a freeze drying mode;
(4) and (4) calcining the product (photocatalytic material precursor) obtained in the step (3) at a high temperature of 500-600 ℃ for 1.5-2.5 h under the protection of inert atmosphere to obtain the lignin carbon-based flexible composite material.
According to the technical scheme, in the step (1), the ratio of the industrial lignin, the copper oxide nanobelts and the water is preferably 1.0 g: 0.1 g: 40 mL.
According to the technical scheme, in the step (2), the concentration of the cobalt chloride solution is preferably 30 mol/L.
According to the above technical solution, in step (2), the ratio of the copper oxide to the carboxymethyl cellulose to the water is preferably 0.1 g: 5 g: 20 mL.
According to the technical scheme, preferably, in the step (3), the temperature of the freeze drying is-50 to-45 ℃, and the time of the freeze drying is 2 to 3 days.
According to the technical scheme, in the step (4), the calcination temperature is preferably 600 ℃ and the calcination time is preferably 2 hours.
According to the above technical solution, in the step (4), the inert atmosphere is preferably nitrogen, argon, or the like.
The lignin carbon-based flexible composite material prepared by the method is applied to photocatalytic synthesis of xylonic acid, and the reaction process is as follows: uniformly mixing the lignin carbon-based flexible composite material (serving as a photocatalyst) with xylose and an alkaline solution, then carrying out an illumination reaction on the system at the temperature of 400-900 ℃ for 5-180 min, and finally detecting the obtained product by using a liquid chromatography to determine the yield of the xylonic acid.
According to the above technical solution, preferably, the light source for the light reaction is visible light.
According to the above technical solution, the alkaline solution is preferably a water-soluble alkaline solution, such as a potassium hydroxide solution, a sodium hydroxide solution, a barium hydroxide solution, a sodium carbonate solution, a potassium carbonate solution, a sodium bicarbonate solution, and the like, and preferably a potassium hydroxide solution.
According to the technical scheme, under the preferable condition, the ratio of the lignin carbon-based flexible composite photocatalytic material to the xylose to the alkaline solution is 5-100 mg: 200 mg: 10ml, preferably 40 mg: 200 mg: 10 ml.
According to the above technical solution, preferably, the concentration of the alkaline solution is 0 to 3mol/L, preferably 0.5 to 3mol/L, and more preferably 1 mol/L.
According to the technical scheme, preferably, the reaction temperature is 50 ℃, and the reaction time is 90 min.
The invention relates to preparation of a lignin carbon-based flexible composite material and application thereof in photocatalytic synthesis of xylonic acid, belongs to a green synthesis process easy to operate, and has the advantages of simplicity, convenience and high efficiency. The flexible composite photocatalytic material synthesized by the method has good flexibility and high activity, and is easy to realize industrial production.
The invention has the following advantages:
(1) the invention adopts cheap, nontoxic, renewable, biodegradable and biocompatible industrial lignin and copper oxide nanobelts as raw materials to prepare the flexible composite photocatalytic material, which is beneficial to environmental protection;
(2) the preparation method of the lignin carbon-based flexible composite photocatalytic material is simple to operate, and the reaction conditions are easy to control;
(3) the lignin carbon-based flexible composite photocatalytic material prepared by the invention has the advantages of high strength, light weight, durability and the like;
(4) the product of the invention provides an effective way for solving the problems of poor stability, difficult recovery, limited absorption range of visible light, easy recombination of surface photon-generated carriers, harsh reaction conditions and the like of the photocatalytic material.
Drawings
Fig. 1 is a schematic diagram of the flexible compression of a non-calcined lignin-based flexible composite photocatalytic material precursor when the amount of industrial lignin is 1.0g in example 1, where a to d are schematic diagrams of a flexible compression process of the material, and e to h are schematic diagrams of a rebound process of the material after the flexible compression.
Fig. 2 is a schematic diagram of flexible compression of the lignin-based flexible composite photocatalytic material prepared in example 1 with the amount of industrial lignin of 1.0g, where a to d are schematic diagrams of a flexible compression process of the material and e to h are schematic diagrams of a rebound process of the material after flexible compression.
FIG. 3 is a graph showing the yield of xylonic acid in example 9.
Detailed Description
The present invention will be further described below by way of examples for better understanding of the technical features of the present invention, but the scope of the present invention claimed is not limited thereto.
Example 1
(1) Slowly adding industrial lignin (Shandong Longli biological science and technology Co., Ltd.) into 40mL of deionized water, and stirring at room temperature until the industrial lignin is uniformly dispersed; wherein the use amounts of the industrial lignin are respectively set to be 0.5g, 1g, 1.5g and 3 g;
(2) adding 0.1g of copper oxide nanobelt into the product obtained in the step (1), and stirring to uniformly disperse the copper oxide nanobelt;
(3) adding 1mL of cobalt chloride (30mol/L) solution into the mixture obtained in the step (2) and uniformly stirring;
(4) continuously adding 5g of carboxymethyl cellulose and 20mL of deionized water into the product obtained in the step (3), uniformly stirring, and performing ultrasonic defoaming;
(5) preparing a photocatalytic material precursor from the product obtained in the step (4) in a freeze drying mode; wherein the freeze drying temperature is-47 deg.C, and the time is 3 days;
(6) and (4) calcining the product obtained in the step (5) at a high temperature of 600 ℃ for 2h under the protection of a nitrogen atmosphere to obtain the lignin carbon-based flexible composite material.
Example 2
(1) Slowly adding industrial lignin (Shandong Longli biological science and technology Co., Ltd.) into 40mL of deionized water, and stirring at room temperature until the industrial lignin is uniformly dispersed; wherein the use amounts of the industrial lignin are respectively set to be 1 g;
(2) adding a copper oxide nanobelt into the product obtained in the step (1), and stirring to uniformly disperse the copper oxide nanobelt; wherein the dosage of the copper oxide nanobelt is respectively set to be 0.05g, 0.15g and 0.2 g;
(3) adding 1mL of cobalt chloride (30mol/L) solution into the mixture obtained in the step (2) and uniformly stirring;
(4) continuously adding 5g of carboxymethyl cellulose and 20mL of deionized water into the product obtained in the step (3), uniformly stirring, and performing ultrasonic defoaming;
(5) preparing a photocatalytic material precursor from the product obtained in the step (4) in a freeze drying mode; wherein the freeze drying temperature is-47 deg.C, and the time is 3 days;
(6) and (4) calcining the product obtained in the step (5) at a high temperature of 600 ℃ for 2h under the protection of a nitrogen atmosphere to obtain the lignin carbon-based flexible composite material.
Example 3
(1) Slowly adding industrial lignin (Shandong Longli biological science and technology Co., Ltd.) into 40mL of deionized water, and stirring at room temperature until the industrial lignin is uniformly dispersed; wherein the use amounts of the industrial lignin are respectively set to be 1 g;
(2) adding 0.1g of copper oxide nanobelt into the product obtained in the step (1), and stirring to uniformly disperse the copper oxide nanobelt;
(3) adding 1mL of cobalt chloride solution into the mixture obtained in the step (2) and uniformly stirring; wherein the concentration of the cobalt chloride solution is 20mol/L and 40mol/L respectively;
(4) continuously adding 5g of carboxymethyl cellulose and 20mL of deionized water into the product obtained in the step (3), uniformly stirring, and performing ultrasonic defoaming;
(5) preparing a photocatalytic material precursor from the product obtained in the step (4) in a freeze drying mode; wherein the freeze drying temperature is-47 deg.C, and the time is 3 days;
(6) and (4) calcining the product obtained in the step (5) at a high temperature of 600 ℃ for 2h under the protection of a nitrogen atmosphere to obtain the lignin carbon-based flexible composite material.
Example 4
(1) Slowly adding industrial lignin (Shandong Longli biological science and technology Co., Ltd.) into 40mL of deionized water, and stirring at room temperature until the industrial lignin is uniformly dispersed; wherein the use amounts of the industrial lignin are respectively set to be 1 g;
(2) adding 0.1g of copper oxide nanobelt into the product obtained in the step (1), and stirring to uniformly disperse the copper oxide nanobelt;
(3) adding 1mL of cobalt chloride (30mol/L) solution into the mixture obtained in the step (2) and uniformly stirring;
(4) continuously adding carboxymethyl cellulose and 20mL of deionized water into the product obtained in the step (3), uniformly stirring, and performing ultrasonic defoaming; wherein the setting dosage of the carboxymethyl cellulose is respectively set to be 4g and 6 g;
(5) preparing a photocatalytic material precursor from the product obtained in the step (4) in a freeze drying mode; wherein the freeze drying temperature is-47 deg.C, and the time is 3 days;
(6) and (4) calcining the product obtained in the step (5) at a high temperature of 600 ℃ for 2h under the protection of a nitrogen atmosphere to obtain the lignin carbon-based flexible composite material.
Example 5
(1) Slowly adding industrial lignin (Shandong Longli biological science and technology Co., Ltd.) into 40mL of deionized water, and stirring at room temperature until the industrial lignin is uniformly dispersed; wherein the use amounts of the industrial lignin are respectively set to be 1 g;
(2) adding 0.1g of copper oxide nanobelt into the product obtained in the step (1), and stirring to uniformly disperse the copper oxide nanobelt;
(3) adding 1mL of cobalt chloride (30mol/L) solution into the mixture obtained in the step (2) and uniformly stirring;
(4) continuously adding 5g of carboxymethyl cellulose and 20mL of deionized water into the product obtained in the step (3), uniformly stirring, and performing ultrasonic defoaming;
(5) preparing a photocatalytic material precursor from the product obtained in the step (4) in a freeze drying mode; wherein the freeze drying temperature is-47 deg.C, and the time is 3 days;
(6) calcining the product obtained in the step (5) at high temperature for 2 hours under the protection of nitrogen atmosphere to obtain a lignin carbon-based flexible composite material; wherein the calcining temperature is respectively set to 400 ℃, 500 ℃, 700 ℃, 800 ℃ and 900 ℃, and the lignin carbon-based flexible composite material is obtained.
Example 6
(1) Slowly adding industrial lignin (Shandong Longli biological science and technology Co., Ltd.) into 40mL of deionized water, and stirring at room temperature until the industrial lignin is uniformly dispersed; wherein the use amounts of the industrial lignin are respectively set to be 1 g;
(2) adding 0.1g of copper oxide nanobelt into the product obtained in the step (1), and stirring to uniformly disperse the copper oxide nanobelt;
(3) adding 1mL of cobalt chloride (30mol/L) solution into the mixture obtained in the step (2) and uniformly stirring;
(4) continuously adding 5g of carboxymethyl cellulose and 20mL of deionized water into the product obtained in the step (3), uniformly stirring, and performing ultrasonic defoaming;
(5) preparing a photocatalytic material precursor from the product obtained in the step (4) in a freeze drying mode; wherein the freeze drying temperature is-47 deg.C, and the time is 3 days;
(6) calcining the product obtained in the step (5) at high temperature of 600 ℃ under the protection of nitrogen atmosphere to obtain the lignin carbon-based flexible composite material; wherein, the calcining time is respectively set to be 3h, 4h, 5h and 6 h.
Example 7
(1) 40mg of the lignin-based flexible composite photocatalytic material prepared by using 1.0g of the industrial lignin in the embodiment 1 and 200mg of xylose are placed in a reactor, and then 20mL of KOH solution with different concentrations of 0mol/L, 1mol/L, 1.5mol/L and 3mol/L is added;
(2) and (2) reacting the system in the step (1) at 30 ℃ for 60min, and detecting the obtained product by using liquid chromatography to determine the yield of the xylonic acid.
Example 8
(1) 40mg of the lignin-based flexible composite material prepared by using 1.0g of the industrial lignin in the example 1 and 200mg of xylose are placed in a reactor, and then 20mL of KOH solution (3 mol/L) is added;
(2) and (2) reacting the system in the step (1) at 40 ℃, 50 ℃, 60 ℃, 70 ℃, 80 ℃ and 90 ℃ for 60min, and detecting the obtained product by using liquid chromatography to determine the yield of the xylonic acid.
Example 9
(1) 40mg of the lignin-based flexible composite material prepared by using 1.0g of the industrial lignin in the example 1 and 200mg of xylose are placed in a reactor, and then 20mL of KOH solution (3 mol/L) is added;
(2) then the system is respectively reacted for 5min, 10min, 15min, 20min, 25min, 30min, 45min, 120min, 150min and 180min at the temperature of 50 ℃, and finally the obtained product is detected by liquid chromatography to determine the yield of the xylonic acid.
Fig. 1 is a schematic view of compression of a lignin-based flexible composite photocatalytic material precursor (which is a cylinder with a diameter of about 1cm and a height of 1.5cm, and when a pressure test is performed, the upper end and the lower end of the cylinder are located between an index finger and a thumb, and the index finger and the thumb provide pressure) under no pressure, wherein a to d are schematic views of a flexible compression process of the material, and e to h are schematic views of a rebound process after the flexible compression of the material.
Fig. 2 is a schematic view of compression of a lignin-based flexible composite photocatalytic material (a cylinder with a diameter of about 1cm and a height of 1.5cm, and when a pressure test is performed, the upper end and the lower end of the cylinder are located between an index finger and a thumb, and the index finger and the thumb provide pressure) without pressure, where a to d are schematic views of a flexible compression process of the material, and e to h are schematic views of a rebound process of the material after the flexible compression.
FIG. 3 shows the yield of xylonic acid in example 9 over various time periods, which is seen to be maximal at 180 min.
The above embodiments are part of the implementation process of the present invention, but the implementation manner of the present invention is not limited by the above embodiments, and any other changes, substitutions, combinations, and simplifications which are made without departing from the spirit and principle of the present invention should be regarded as equivalent replacements within the protection scope of the present invention.
Claims (10)
1. A preparation method of a lignin carbon-based flexible composite material is characterized by comprising the following steps:
(1) dispersing industrial lignin and copper oxide nanobelts in water;
wherein the ratio of the industrial lignin to the copper oxide nanobelts to the water is 0.5-3 g: 0.05-0.2 g: 40 mL;
(2) adding a cobalt chloride solution into the mixture obtained in the step (1), uniformly stirring, adding carboxymethyl cellulose and water, uniformly stirring, and performing ultrasonic defoaming;
wherein the concentration of the cobalt chloride solution is 20-40 mol/L; the ratio of the copper oxide nanobelt to the cobalt chloride solution is 0.05-0.2 g: 1 mL; the ratio of the copper oxide to the carboxymethyl cellulose to the water is 0.05-0.2 g: 4-6 g: 20 mL;
(3) freeze-drying the product obtained in the step (2) to obtain a precursor of the photocatalytic material;
(4) and (4) calcining the photocatalytic material precursor obtained in the step (3) for 1.5-2.5 h at 500-600 ℃ under the protection of inert atmosphere to obtain the lignin carbon-based flexible composite material.
2. The preparation method of the lignin-based flexible composite material according to claim 1, wherein in the step (1), the ratio of the industrial lignin, the copper oxide nanobelts and the water is 1.0 g: 0.1 g: 40 mL.
3. The preparation method of the lignin-based flexible composite material according to claim 1, wherein in the step (2), the concentration of the cobalt chloride solution is 30 mol/L; the ratio of copper oxide, carboxymethyl cellulose and water is 0.1 g: 5 g: 20 mL.
4. The preparation method of the lignin-based flexible composite material according to claim 1, wherein in the step (3), the temperature of the freeze drying is-50 to-45 ℃, and the time of the freeze drying is 2 to 3 days.
5. The preparation method of the lignin-carbon-based flexible composite material according to claim 1, wherein in the step (4), the calcination temperature is 600 ℃ and the calcination time is 2 h.
6. The method for preparing the lignin carbon-based flexible composite material according to claim 1, wherein in the step (4), the inert atmosphere is nitrogen or argon.
7. Use of a lignin carbon-based flexible composite material prepared by the method of claims 1 to 6 for photocatalytic synthesis of xylonic acid.
8. The application of claim 7, wherein the lignin carbon-based flexible composite material, xylose and an alkaline solution are uniformly mixed, and then the system is subjected to an illumination reaction at a temperature of 400-900 ℃ for 5-180 min.
9. The use according to claim 7, wherein the alkaline solution is a water-soluble alkaline solution, and the concentration of the alkaline solution is 0-3 mol/L.
10. The application of claim 7, wherein the ratio of the lignin carbon-based flexible composite photocatalytic material to the xylose to the alkaline solution or water is 5-100 mg: 200 mg: 10 ml.
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