CN115676811A - Method for preparing graphene from lignin - Google Patents
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- CN115676811A CN115676811A CN202211385201.9A CN202211385201A CN115676811A CN 115676811 A CN115676811 A CN 115676811A CN 202211385201 A CN202211385201 A CN 202211385201A CN 115676811 A CN115676811 A CN 115676811A
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 89
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 88
- 229920005610 lignin Polymers 0.000 title claims abstract description 67
- 238000000034 method Methods 0.000 title claims abstract description 49
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 38
- 239000006185 dispersion Substances 0.000 claims abstract description 34
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000000502 dialysis Methods 0.000 claims abstract description 25
- 238000010335 hydrothermal treatment Methods 0.000 claims abstract description 19
- 238000001914 filtration Methods 0.000 claims abstract description 18
- 238000002360 preparation method Methods 0.000 claims abstract description 18
- 239000007790 solid phase Substances 0.000 claims abstract description 17
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 16
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 16
- 238000001035 drying Methods 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000003513 alkali Substances 0.000 claims description 14
- 230000014759 maintenance of location Effects 0.000 claims description 10
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 3
- 229920001732 Lignosulfonate Polymers 0.000 claims description 2
- 229920005611 kraft lignin Polymers 0.000 claims description 2
- 230000035484 reaction time Effects 0.000 claims description 2
- 230000000717 retained effect Effects 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 description 27
- 229910021641 deionized water Inorganic materials 0.000 description 27
- 239000002245 particle Substances 0.000 description 26
- 239000012982 microporous membrane Substances 0.000 description 21
- 239000007864 aqueous solution Substances 0.000 description 18
- 239000002244 precipitate Substances 0.000 description 18
- 230000000052 comparative effect Effects 0.000 description 16
- 238000006243 chemical reaction Methods 0.000 description 15
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 12
- 238000003828 vacuum filtration Methods 0.000 description 12
- 238000010790 dilution Methods 0.000 description 9
- 239000012895 dilution Substances 0.000 description 9
- 239000000706 filtrate Substances 0.000 description 9
- 238000007689 inspection Methods 0.000 description 9
- -1 polytetrafluoroethylene Polymers 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 238000003756 stirring Methods 0.000 description 9
- 238000009210 therapy by ultrasound Methods 0.000 description 9
- 239000000463 material Substances 0.000 description 5
- 230000009286 beneficial effect Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000011031 large-scale manufacturing process Methods 0.000 description 3
- 125000003118 aryl group Chemical group 0.000 description 2
- 238000005229 chemical vapour deposition Methods 0.000 description 2
- 239000002028 Biomass Substances 0.000 description 1
- 239000004117 Lignosulphonate Substances 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 125000001931 aliphatic group Chemical group 0.000 description 1
- 150000001491 aromatic compounds Chemical class 0.000 description 1
- 229920001222 biopolymer Polymers 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 125000004432 carbon atom Chemical group C* 0.000 description 1
- 239000011203 carbon fibre reinforced carbon Substances 0.000 description 1
- 238000003763 carbonization Methods 0.000 description 1
- 229920002678 cellulose Polymers 0.000 description 1
- 239000001913 cellulose Substances 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 235000019357 lignosulphonate Nutrition 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 239000000047 product Substances 0.000 description 1
- ODLMAHJVESYWTB-UHFFFAOYSA-N propylbenzene Chemical group CCCC1=CC=CC=C1 ODLMAHJVESYWTB-UHFFFAOYSA-N 0.000 description 1
- 239000002096 quantum dot Substances 0.000 description 1
- 125000004151 quinonyl group Chemical group 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000002699 waste material Substances 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/184—Preparation
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Nanotechnology (AREA)
- Inorganic Chemistry (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses a method for preparing graphene from lignin. The method for preparing graphene from lignin comprises the following preparation steps: step S1, mixing lignin and water, adding nitric acid with the mass fraction of 60-70%, reacting, filtering, and taking a black solid phase; s2, dispersing the black solid phase in water to obtain a dispersion liquid, then placing the dispersion liquid at 170-200 ℃ for hydrothermal treatment, filtering, and taking a liquid phase to obtain water-soluble graphene; and S3, carrying out dialysis treatment on the water-soluble graphene, and drying to obtain the graphene. The graphene preparation method is simple, high in yield and wide in application prospect.
Description
Technical Field
The invention relates to the technical field of graphene preparation, in particular to a method for preparing graphene from lignin.
Background
Graphene is a new material with a single-layer sheet structure formed by carbon atoms, has excellent optical, electrical and mechanical properties, and has wide application prospects in the aspects of materials science, micro-nano processing, energy, biomedicine, drug delivery and the like. The existing preparation method of graphene mainly comprises a mechanical stripping method, a liquid phase stripping method, a SiC epitaxial growth method, a chemical vapor deposition method, graphene oxide reduction and the like, wherein the mechanical stripping method and the liquid phase stripping method have the advantages of low cost and the like, but the yield is low, and the method is not suitable for large-scale production; the graphene obtained by the SiC epitaxial growth method has good quality but high cost; although the chemical vapor deposition method can obtain a large-size continuous graphene film, the requirement of large-scale production is difficult to meet; the graphene material powder prepared by the oxidation-reduction method is low in cost and easy to implement, but a large amount of waste liquid is generated, and serious pollution is caused to the environment. Therefore, the current graphene preparation method still has certain limitations.
The lignin is a biopolymer with a three-dimensional network structure formed by mutually connecting 3 phenylpropane units through ether bonds and carbon-carbon bonds, and contains abundant active groups such as aromatic ring structures, aliphatic and aromatic hydroxyl groups, quinonyl groups and the like. Lignin, one of the few renewable resources in aromatic compounds, is the second largest biomass resource with the next reserve to cellulose in the plant world, and has the advantages of wide source, low cost, huge yield and the like. In the related art, although the production cost can be reduced to a certain extent by using lignin to prepare graphene, the method has the defects of high equipment requirement, complex preparation process, low yield and the like, so that the large-scale production of the lignin-prepared graphene is limited to a certain extent.
Based on the above, a method for preparing graphene from lignin is still needed, which is simple in preparation method, low in requirement on equipment, and high in yield of the prepared graphene.
Disclosure of Invention
The present invention is directed to solving at least one of the problems of the prior art. Therefore, the method for preparing the graphene from the lignin is simple, high in yield and capable of effectively improving the particle size uniformity of the graphene.
In a first aspect of the present invention, there is provided a method for preparing graphene from lignin, comprising the following preparation steps:
step S1, mixing lignin and water, adding nitric acid with the mass fraction of 60-70%, reacting, filtering, and taking a black solid phase;
s2, dispersing the black solid phase in water to obtain a dispersion liquid, then placing the dispersion liquid at 170-200 ℃ for hydro-thermal treatment, filtering, and taking a liquid phase to obtain water-soluble graphene;
and S3, dialyzing the water-soluble graphene, and drying to obtain the graphene.
The method for preparing graphene from lignin provided by the embodiment of the invention has at least the following beneficial effects: the method for preparing graphene by using lignin is simple, complex equipment is not needed, and the prepared graphene is high in yield and good in particle size uniformity.
According to some embodiments of the invention, in step S1, the lignin is selected from at least one of alkali lignin, lignosulphonate, kraft lignin.
According to some embodiments of the invention, the lignin is an alkali lignin.
According to some embodiments of the invention, in step S1, the solid-liquid volume ratio of lignin to water is 1:2 to 4 (g/mL).
According to some embodiments of the invention, in step S1, the solid-liquid volume ratio of lignin, water and nitric acid is 1:2 to 4:1 to 2 (g/mL).
According to some embodiments of the invention, in step S1, the reaction time is 10 to 12 hours.
According to some embodiments of the invention, in step S1, ultrasonic waves are used for dispersion treatment during the reaction;
preferably, the power of the ultrasonic wave is 200 to 400W.
Ultrasonic wave is adopted for processing, which is beneficial to dispersion and improves the reaction rate; on the other hand, the method is favorable for permeating nitric acid and ensuring the reaction to be more sufficient.
According to some embodiments of the invention, the filtration is vacuum filtration using a 0.20 to 0.22 μm microporous membrane.
According to some embodiments of the invention, in step S2, a solid-liquid volume ratio of the black solid phase to water in the dispersion is 1:2 to 5.
According to some embodiments of the invention, the hydrothermal treatment time in step S2 is 10 to 12 hours.
According to some embodiments of the invention, the hydrothermal treatment time is 12h.
According to some embodiments of the invention, in step S2, the pressure of the hydrothermal treatment is 20 to 40MPa.
According to some embodiments of the invention, the pressure of the hydrothermal treatment in step S2 is 30MPa.
According to some embodiments of the invention, in step S2, the dispersion is ultrasonic dispersion, and the dispersion time is 20 to 30min.
According to some embodiments of the invention, in step S2, the dispersion is ultrasonic dispersion, and the dispersion time is 30min.
According to some embodiments of the invention, in step S2, the filtration is vacuum filtration using a 0.20 to 0.22 μm microporous membrane.
In step S2, a microporous membrane with the diameter of 0.20-0.22 μm is adopted for vacuum filtration, mainly for filtering insoluble carbon.
According to some embodiments of the invention, the dialysis treatment has a retention molecular weight of 2800 to 3200Da in step S3.
According to some embodiments of the invention, the dialysis treatment has a retained molecular weight of 3000Da.
The dialysis treatment with the retention molecular weight of 3000Da is beneficial to removing residual acid and other metal ion impurities in the water-soluble graphene.
According to some embodiments of the invention, the temperature of the drying in step S3 is 55 to 65 ℃.
According to some embodiments of the invention, in step S3, the graphene is a graphene quantum dot.
Additional features and advantages of the invention will be set forth in the description which follows, and in part will be obvious from the description, or may be learned by practice of the invention.
Detailed Description
The concept and technical effects of the present invention will be clearly and completely described below in conjunction with the embodiments to fully understand the objects, features and effects of the present invention. It is obvious that the described embodiments are only a part of the embodiments of the present invention, and not all embodiments, and those skilled in the art can obtain other embodiments without inventive effort based on the embodiments of the present invention, and all embodiments are within the protection scope of the present invention.
In the description of the present invention, reference to the description of "one embodiment", "some embodiments", "illustrative embodiments", "examples", "specific examples", or "some examples", etc., means that a particular feature, structure, material, or characteristic described in connection with the embodiment or example is included in at least one embodiment or example of the present invention. In this specification, the schematic representations of the terms used above do not necessarily refer to the same embodiment or example. Furthermore, the particular features, structures, materials, or characteristics described may be combined in any suitable manner in any one or more embodiments or examples.
In the present example, the CAS number for alkali lignin is 9005-53-2.
The examples, in which specific conditions are not specified, were conducted under conventional conditions or conditions recommended by the manufacturer. The reagents or instruments used are conventional products which are not indicated by manufacturers and are commercially available.
Example 1
The embodiment is a method for preparing graphene from lignin, which comprises the following preparation steps:
s1, dispersing 10g of alkali lignin in 20mL of deionized water to obtain a lignin aqueous solution;
s2, under the stirring condition of 80rpm, adding 10mL of concentrated nitric acid with the mass fraction of 65% into the lignin aqueous solution, dispersing for 12 hours by using ultrasonic waves (with the power of 200W), adding deionized water for dilution, performing vacuum filtration by using a 0.22-micrometer microporous membrane, and taking a solid phase to obtain a black precipitate sample;
s3, further dispersing the black precipitate sample into 20mL of deionized water, carrying out ultrasonic treatment for 30min to obtain a dispersion liquid, transferring the dispersion liquid into a polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal treatment for 12h under the conditions of 35MPa and 180 ℃, filtering by using a 0.22 mu m microporous membrane, and collecting filtrate to obtain water-soluble graphene;
and S4, putting the water-soluble graphene into a dialysis bag (with the retention molecular weight of 3000 Da) for dialysis for one week, and drying in an oven at 60 ℃ to obtain the graphene.
Through inspection, the graphene prepared by the embodiment has good particle size uniformity, the average particle size of the graphene quantum dots is 3.65nm, and the yield is 8.52%.
Example 2
The embodiment is a method for preparing graphene from lignin, which comprises the following preparation steps:
s1, dispersing 10g of alkali lignin in 20mL of deionized water to obtain a lignin aqueous solution;
s2, under the stirring condition of 80rpm, adding 10mL of concentrated nitric acid with the mass fraction of 67% into the lignin aqueous solution, dispersing for 12 hours by using ultrasonic waves (with the power of 200W), adding deionized water for dilution, performing vacuum filtration by using a 0.22-micrometer microporous membrane, and taking a solid phase to obtain a black precipitate sample;
s3, further dispersing the black precipitate sample into 20mL of deionized water, carrying out ultrasonic treatment for 30min to obtain a dispersion liquid, transferring the dispersion liquid into a polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal treatment for 12h under the conditions of 35MPa and 180 ℃, filtering by using a 0.22 mu m microporous membrane, and collecting filtrate to obtain water-soluble graphene;
and S4, putting the water-soluble graphene into a dialysis bag (with the retention molecular weight of 3000 Da) for dialysis for one week, and drying in an oven at 60 ℃ to obtain the graphene.
Through inspection, the graphene prepared by the embodiment has good particle size uniformity, the average particle size of the graphene quantum dots is 3.14nm, and the yield is 8.63%.
Example 3
The embodiment is a method for preparing graphene from lignin, which comprises the following preparation steps:
s1, dispersing 10g of alkali lignin in 20mL of deionized water to obtain a lignin aqueous solution;
s2, under the stirring condition of 80rpm, adding 10mL of concentrated nitric acid with the mass fraction of 70% into the lignin aqueous solution, dispersing for 12 hours by ultrasonic waves (with the power of 200W), adding deionized water for dilution, performing vacuum filtration by using a 0.22-micron microporous membrane, and taking a solid phase to obtain a black precipitate sample;
s3, further dispersing the black precipitate sample into 20mL of deionized water, carrying out ultrasonic treatment for 30min to obtain a dispersion liquid, transferring the dispersion liquid into a polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal treatment for 12h under the conditions of 35MPa and 180 ℃, filtering by using a 0.22 mu m microporous membrane, and collecting filtrate to obtain water-soluble graphene;
and S4, putting the water-soluble graphene into a dialysis bag (with the retention molecular weight of 3000 Da) for dialysis for one week, and drying in an oven at 60 ℃ to obtain the graphene.
Through inspection, the graphene prepared by the embodiment has good particle size uniformity, the average particle size of the graphene quantum dots is 3.57nm, and the yield is 8.27%.
Example 4
The embodiment is a method for preparing graphene from lignin, which comprises the following preparation steps:
s1, dispersing 10g of alkali lignin in 20mL of deionized water to obtain a lignin aqueous solution;
s2, under the stirring condition of 80rpm, adding 10mL of concentrated nitric acid with the mass fraction of 67% into the lignin aqueous solution, dispersing for 12 hours by using ultrasonic waves (with the power of 200W), adding deionized water for dilution, performing vacuum filtration by using a 0.22-micrometer microporous membrane, and taking a solid phase to obtain a black precipitate sample;
s3, further dispersing the black precipitate sample into 20mL of deionized water, carrying out ultrasonic treatment for 30min to obtain a dispersion liquid, transferring the dispersion liquid into a polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal treatment for 12h under the conditions of 35MPa and 170 ℃, filtering by using a 0.22 mu m microporous membrane, and collecting filtrate to obtain water-soluble graphene;
and S4, putting the water-soluble graphene into a dialysis bag (with the reserved molecular weight of 3000 Da) for dialysis for one week, and drying in an oven at the temperature of 60 ℃ to obtain the graphene.
Through inspection, the graphene prepared by the embodiment has good particle size uniformity, the average particle size of the graphene quantum dots is 3.89nm, and the yield is 8.07%.
Example 5
The embodiment is a method for preparing graphene from lignin, which comprises the following preparation steps:
s1, dispersing 10g of alkali lignin in 20mL of deionized water to obtain a lignin aqueous solution;
s2, under the stirring condition of 80rpm, adding 10mL of concentrated nitric acid with the mass fraction of 67% into the lignin aqueous solution, dispersing for 12 hours by using ultrasonic waves (with the power of 200W), adding deionized water for dilution, performing vacuum filtration by using a 0.22-micrometer microporous membrane, and taking a solid phase to obtain a black precipitate sample;
s3, further dispersing the black precipitate sample into 20mL of deionized water, carrying out ultrasonic treatment for 30min to obtain a dispersion liquid, transferring the dispersion liquid into a polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal treatment for 12h under the conditions of 35MPa and 200 ℃, filtering by using a 0.22 mu m microporous membrane, and collecting filtrate to obtain water-soluble graphene;
and S4, putting the water-soluble graphene into a dialysis bag (with the retention molecular weight of 3000 Da) for dialysis for one week, and drying in an oven at 60 ℃ to obtain the graphene.
Through inspection, the graphene prepared by the embodiment has good particle size uniformity, the average particle size of the graphene quantum dots is 3.27nm, and the yield is 8.48%.
Comparative example 1
The comparative example is a method for preparing graphene from lignin, and the method comprises the following preparation steps:
s1, dispersing 10g of alkali lignin in 20mL of deionized water to obtain a lignin aqueous solution;
s2, under the stirring condition of 80rpm, adding 10mL of concentrated nitric acid with the mass fraction of 55% into the lignin aqueous solution, dispersing for 12 hours by using ultrasonic waves (with the power of 200W), adding deionized water for dilution, performing vacuum filtration by using a 0.22-micrometer microporous membrane, and taking a solid phase to obtain a black precipitate sample;
s3, further dispersing the black precipitate sample into 20mL of deionized water, carrying out ultrasonic treatment for 30min to obtain a dispersion liquid, transferring the dispersion liquid into a polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal treatment for 12h under the conditions of 35MPa and 180 ℃, filtering by using a 0.22 mu m microporous membrane, and collecting filtrate to obtain water-soluble graphene;
and S4, putting the water-soluble graphene into a dialysis bag (with the retention molecular weight of 3000 Da) for dialysis for one week, and drying in an oven at 60 ℃ to obtain the graphene.
Through inspection, the graphene prepared by the comparative example has poor particle size uniformity, the average particle size of the graphene quantum dots is 4.17nm, and the yield is 7.21%.
Comparative example 2
The comparative example is a method for preparing graphene from lignin, and the method comprises the following preparation steps:
s1, dispersing 10g of alkali lignin in 20mL of deionized water to obtain a lignin aqueous solution;
s2, under the stirring condition of 80rpm, adding 10mL of concentrated nitric acid with the mass fraction of 75% into the lignin aqueous solution, dispersing for 12 hours by ultrasonic waves (with the power of 200W), adding deionized water for dilution, performing vacuum filtration by using a 0.22-micron microporous membrane, and taking a solid phase to obtain a black precipitate sample;
s3, further dispersing the black precipitate sample into 20mL of deionized water, carrying out ultrasonic treatment for 30min to obtain a dispersion liquid, transferring the dispersion liquid into a polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal treatment for 12h under the conditions of 35MPa and 180 ℃, filtering by using a 0.22 mu m microporous membrane, and collecting filtrate to obtain water-soluble graphene;
and S4, putting the water-soluble graphene into a dialysis bag (with the reserved molecular weight of 3000 Da) for dialysis for one week, and drying in an oven at the temperature of 60 ℃ to obtain the graphene.
Through inspection, the graphene prepared by the comparative example has good particle size uniformity, the average particle size of the graphene quantum dots is 4.32nm, and the yield is 7.69%.
Comparative example 3
The comparative example is a method for preparing graphene from lignin, and the method comprises the following preparation steps:
s1, dispersing 10g of alkali lignin in 20mL of deionized water to obtain a lignin aqueous solution;
s2, under the stirring condition of 80rpm, adding 10mL of concentrated nitric acid with the mass fraction of 67% into the lignin aqueous solution, dispersing for 12 hours by using ultrasonic waves (with the power of 200W), adding deionized water for dilution, performing vacuum filtration by using a 0.22-micrometer microporous membrane, and taking a solid phase to obtain a black precipitate sample;
s3, further dispersing the black precipitate sample into 20mL of deionized water, carrying out ultrasonic treatment for 30min to obtain a dispersion liquid, transferring the dispersion liquid into a polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal treatment for 12h under the conditions of 35MPa and 150 ℃, filtering by using a 0.22-micron microporous membrane, and collecting filtrate to obtain water-soluble graphene;
and S4, putting the water-soluble graphene into a dialysis bag (with the retention molecular weight of 3000 Da) for dialysis for one week, and drying in an oven at 60 ℃ to obtain the graphene.
Through inspection, the graphene prepared by the comparative example has poor particle size uniformity, the average particle size of the graphene quantum dots is 4.63nm, and the yield is 6.74%.
Comparative example 4
The comparative example is a method for preparing graphene from lignin, and the method comprises the following preparation steps:
s1, dispersing 10g of alkali lignin in 20mL of deionized water to obtain a lignin aqueous solution;
s2, under the stirring condition of 80rpm, adding 10mL of concentrated nitric acid with the mass fraction of 67% into the lignin aqueous solution, dispersing for 12 hours by ultrasonic waves (with the power of 200W), adding deionized water for dilution, performing vacuum filtration by using a 0.22-micron microporous membrane, and taking a solid phase to obtain a black precipitate sample;
s3, further dispersing the black precipitate sample into 20mL of deionized water, carrying out ultrasonic treatment for 30min to obtain a dispersion liquid, transferring the dispersion liquid into a polytetrafluoroethylene high-pressure reaction kettle, carrying out hydrothermal treatment for 12h under the conditions of 35MPa and 250 ℃, filtering by using a 0.22 mu m microporous membrane, and collecting filtrate to obtain water-soluble graphene;
and S4, putting the water-soluble graphene into a dialysis bag (with the retention molecular weight of 3000 Da) for dialysis for one week, and drying in an oven at 60 ℃ to obtain the graphene.
Through inspection, the graphene prepared by the comparative example has poor particle size uniformity, the average particle size of the graphene quantum dots is 3.41nm, and the yield is 7.52%.
As can be seen from the above description of the examples, the graphene prepared by the method of the present invention has good uniformity of particle size, the average particle size of the graphene quantum dots is between 3.65nm and 3.89nm, and the yield is not less than 8.07%.
Compared with the example 2, the concentration of the nitric acid is lower in the comparative example 1, the uniformity of the particle size of the graphene obtained by adopting the method is poorer, and the yield is lower, which is mainly related to incomplete oxidation of lignin;
compared with example 2, the concentration of nitric acid is higher in comparative example 2, and the yield and the average particle size of the graphene quantum dots of the graphene prepared by the method are reduced compared with example 2.
Compared with example 2, the temperature of the high-pressure reaction is obviously reduced in comparative example 3, and the result shows that the effect of the hydrothermal carbonization treatment is reduced due to the reduction of the temperature of the high-pressure reaction, the yield of the graphene is reduced, and the average particle size of the graphene quantum dots is increased.
In comparative example 4, the temperature of the high-pressure reaction was higher than that of example 2, and was 250 ℃.
In conclusion, the method for preparing graphene by using lignin is simple, complex equipment is not needed, and the prepared graphene is high in yield, good in particle size uniformity and wide in application value.
The embodiments of the present invention have been described in detail, but the present invention is not limited to the embodiments, and various changes can be made without departing from the gist of the present invention within the knowledge of those skilled in the art. Furthermore, the embodiments of the present invention and the features of the embodiments may be combined with each other without conflict.
Claims (10)
1. The method for preparing graphene from lignin is characterized by comprising the following preparation steps:
step S1, mixing lignin and water, adding nitric acid with the mass fraction of 60-70%, reacting, filtering, and taking a black solid phase;
s2, dispersing the black solid phase in water to obtain a dispersion liquid, then placing the dispersion liquid at 170-200 ℃ for hydrothermal treatment, filtering, and taking a liquid phase to obtain water-soluble graphene;
and S3, carrying out dialysis treatment on the water-soluble graphene, and drying to obtain the graphene.
2. The method according to claim 1, wherein in step S1, the lignin is selected from at least one of alkali lignin, lignosulfonate, kraft lignin;
preferably, the lignin is alkali lignin.
3. The method according to claim 1, wherein in step S1, the solid-liquid volume ratio of lignin to water is 1:2 to 4.
4. The method according to claim 1, wherein the reaction time in step S1 is 10 to 12 hours.
5. The method according to claim 1, wherein in step S2, the solid-liquid volume ratio of the black solid phase to the water in the dispersion is 1:2 to 5.
6. The method according to claim 1, wherein in step S2, the hydrothermal treatment is carried out for 10 to 12 hours;
preferably, the hydrothermal treatment time is 12h.
7. The method according to claim 1, wherein the pressure of the hydrothermal treatment in step S2 is 20 to 40MPa.
8. The method according to claim 1, wherein in step S2, the dispersion is ultrasonic dispersion;
preferably, the time for dispersion is 20 to 30min.
9. The method according to any one of claims 1 to 8, wherein in step S3, the dialysis treatment has a retained molecular weight of 2800 to 3200Da;
preferably, the dialysis treatment has a retention molecular weight of 3000Da.
10. The method of claim 9, wherein the temperature of the drying in step S3 is 55-65 ℃.
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| CN202211385201.9A CN115676811A (en) | 2022-11-07 | 2022-11-07 | Method for preparing graphene from lignin |
| NL2034209A NL2034209B1 (en) | 2022-11-07 | 2023-02-23 | Method for preparing graphene by using lignin |
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| CN202211385201.9A CN115676811A (en) | 2022-11-07 | 2022-11-07 | Method for preparing graphene from lignin |
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Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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| CN111039280A (en) * | 2019-12-16 | 2020-04-21 | 华南理工大学 | Lignin-based graphene quantum dot and preparation method and application thereof |
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| US20150307356A1 (en) * | 2013-06-05 | 2015-10-29 | The United States Of America As Represented By The Secretary Of Agriculture | Methods for Synthesizing Graphene from a Lignin Source |
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| CN108977198A (en) * | 2018-07-12 | 2018-12-11 | 北京林业大学 | A kind of method that lignin prepares single crystal graphene quantum dot |
| CN110589811A (en) * | 2019-09-04 | 2019-12-20 | 广东工业大学 | Lignin-based graphene quantum dot material and preparation method and application thereof |
| CN111039280A (en) * | 2019-12-16 | 2020-04-21 | 华南理工大学 | Lignin-based graphene quantum dot and preparation method and application thereof |
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| NL2034209B1 (en) | 2024-07-02 |
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