CN115448301A - Large-size graphene oxide and preparation method thereof - Google Patents
Large-size graphene oxide and preparation method thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 27
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- 238000005286 illumination Methods 0.000 claims description 37
- YBCAZPLXEGKKFM-UHFFFAOYSA-K ruthenium(iii) chloride Chemical compound [Cl-].[Cl-].[Cl-].[Ru+3] YBCAZPLXEGKKFM-UHFFFAOYSA-K 0.000 claims description 23
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 12
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 12
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 10
- DKNJHLHLMWHWOI-UHFFFAOYSA-L ruthenium(2+);sulfate Chemical compound [Ru+2].[O-]S([O-])(=O)=O DKNJHLHLMWHWOI-UHFFFAOYSA-L 0.000 claims description 9
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- OJLCQGGSMYKWEK-UHFFFAOYSA-K ruthenium(3+);triacetate Chemical compound [Ru+3].CC([O-])=O.CC([O-])=O.CC([O-])=O OJLCQGGSMYKWEK-UHFFFAOYSA-K 0.000 claims description 5
- 239000012445 acidic reagent Substances 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 3
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- C01B32/15—Nano-sized carbon materials
- C01B32/182—Graphene
- C01B32/198—Graphene oxide
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Abstract
The invention discloses a large-size graphene oxide and a preparation method thereof, wherein the preparation method comprises the following steps: respectively adding graphene oxide and a catalyst into water, and uniformly stirring to obtain a solution; adding a pH regulator into the solution to regulate the pH value; illuminating the solution after the pH value is adjusted to generate precipitates; filtering the precipitate from the solution; and washing and drying the filtered filter residue to obtain the large-size graphene oxide. The graphene oxide-like prepared by the method is large in size, and the method has the advantages of easiness in industrialization, environmental friendliness, low cost and single surface group.
Description
Technical Field
The invention belongs to the technical field of graphene oxide preparation, and relates to large-size graphene oxide and a preparation method thereof.
Background
Graphene oxide has been widely used in the electronics, laser, catalyst, pharmaceutical, and other industries. As the function of graphene oxide is continuously being explored, graphene oxide has been mass produced and applied. The designed capacity of the graphene oxide of the built and under-built production enterprises in China is nearly 1 million tons, the Hummers method or the improved Hummers method is mostly adopted to produce the graphene oxide, and the size of the graphene oxide is within the range of 0.1 to 0.8 mu m. The photoelectric device needs a large-size graphene oxide material to improve the electrical conductivity and the thermal conductivity of the device.
Several methods for obtaining large-size graphene oxide-like sheets have been reported in succession. Aleksenkii et al prepare a large-size single-layer graphene oxide film on the surface of a silicon wafer by dropping graphene oxide suspension liquid; voiry et al prepared large-size graphene sheets using a microwave reduction process; wei et al separate graphene oxide sheets of different sizes by using different centrifugal speeds to separate out large-size graphene oxide-like sheets; takaoka et al separate large-size graphene oxide-like sheets by a chromatographic column chromatography method. To date, the preparation method of large-size graphene oxide-like sheets is basically in the laboratory research stage, and the factors such as production cost, production efficiency and environmental protection need to be considered in the industrial production of large-size graphene oxide-like sheets, so that the laboratory techniques are difficult to be used in industrial production.
Disclosure of Invention
The invention aims to overcome the defects in the prior art and provide large-size graphene oxide and a preparation method thereof.
In order to achieve the purpose, the invention is realized by adopting the following technical scheme:
a preparation method of large-size graphene oxide comprises the following steps:
respectively adding graphene oxide and a catalyst into water, and uniformly stirring to obtain a solution;
adding a pH regulator into the solution to regulate the pH value;
illuminating the solution after the pH value is adjusted to generate precipitates;
filtering the precipitate from the solution;
and washing and drying the filtered filter residue to obtain the large-size graphene oxide.
Optionally, the catalyst comprises ruthenium chloride, ruthenium sulfate, ruthenium acetate, manganese chloride, manganese sulfate, manganese acetate, manganese nitrate and hydrates thereof.
Optionally, the mass ratio of the graphene oxide to the catalyst is 1: 0.004-0.2, and the mass of the catalyst is Mn 2+ 、Ru 3+ And Ru 4+ Mass of the compound.
Optionally, the PH adjuster comprises an acidic reagent and an alkaline reagent;
the acidic reagent comprises hydrochloric acid, sulfuric acid, nitric acid and acetic acid;
the alkaline agent comprises sodium hydroxide or potassium hydroxide.
Optionally, the pH value is adjusted to be between 2.5 and 5.0.
Optionally, the wavelength of the light source used for illumination is in the ultraviolet and visible light regions.
Optionally, the illumination time is 4-12 days.
The large-size graphene oxide is prepared by the preparation method.
Compared with the prior art, the invention has the following beneficial effects:
compared with the prior art which uses a chromatographic column for separation or uses a silicon material surface deposition method, the method has low production cost and is easy for industrialized production; by using a photocatalysis method, the filtrate containing the catalyst after filtration can be reused, and the method has the characteristic of environmental friendliness; the prepared large-size graphene oxide has single hydroxyl on the surface and excellent optical properties.
Drawings
FIG. 1 shows FT-IR spectra (a) and (b) of a Large-size photo-reduction graphene oxide (LPRGOL) prepared according to an embodiment of the present invention;
fig. 2 is a graph showing the distribution of the particle sizes of the large-sized graphene oxide-like particles and graphene oxide particles prepared by the DLS method according to the embodiment of the present invention;
fig. 3 shows a pulse laser signal output by a pulse laser, in which the large-size graphene oxide-like material prepared by the embodiment of the present invention is used as a saturable absorber.
Detailed Description
The invention is further described below with reference to the accompanying drawings. The following examples are only for illustrating the technical solutions of the present invention more clearly, and the protection scope of the present invention is not limited thereby.
The endpoints of the ranges and any values disclosed herein are not limited to the precise range or value and should be understood to encompass values close to these ranges or values. For numerical ranges, each range between its endpoints and individual point values, and each individual point value can be combined with each other to give one or more new numerical ranges, and such numerical ranges should be construed as specifically disclosed herein.
For the purposes of the present specification and appended claims, unless otherwise indicated, all numbers expressing quantities, percentages or proportions, and other numerical values used in the specification and appended claims, are to be understood as being modified in all instances by the term "about". Moreover, all ranges disclosed herein are inclusive of the endpoints and independently combinable.
Example one
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of ruthenium sulfate into 200mL of water, uniformly stirring to completely dissolve the ruthenium sulfate to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolutionary science and technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute sulfuric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 7 days to generate a black precipitate; the light source is a 100W ultraviolet lamp, and the wavelength lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of the washing is neutral, and finally drying the washed black precipitate to obtain 0.59g of large-size graphene oxide.
FT-IR (KBr): ν = cm -1 EA, 74.3 percent of C, 1.65 percent of H and 24.05 percent of O. The average particle Diameter (DLS) was 5.6. Mu.m.
The mass ratio of the graphene oxide to the catalyst is maintained at 1: 0.004-0.2, and the prepared large-size graphene oxide is large in size and moderate in reaction time; the catalyst consumption is small, the reaction time is long, and the size of the prepared large-size graphene oxide is small; when the amount of the catalyst is more than 0.2 times of the amount of the graphene oxide, the reaction time is not reduced, and the washing water is increased in the post-treatment process. The pH value exceeds 2.5 to 5.0, the reaction time is prolonged, and the prepared large-size graphene oxide is small in size. The illumination time is 4 to 12 days, the illumination time is less than 4 days, and the reaction is incomplete; the reaction time is longer than 12 days, and the cost is increased.
The large-size graphene oxide is prepared by the technical preparation method.
Example two
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.004g of ruthenium sulfate into 200mL of water, uniformly stirring to completely dissolve the ruthenium sulfate to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolutionary science and technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute sulfuric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 11 days to generate black precipitates; a light source 100W is an ultraviolet lamp, and the wavelength is lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of washing is neutral, and finally drying the washed black precipitate to obtain 0.60g of large-size graphene oxide.
FT-IR (KBr): ν = cm -1 EA, 72.9 percent of C, 1.70 percent of H and 25.40 percent of O. Average particle size (DLS): 6.5 μm.
The large-size graphene oxide is prepared by the preparation method.
EXAMPLE III
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.20g of ruthenium sulfate into 200mL of water, uniformly stirring to completely dissolve the ruthenium sulfate to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolutionary science and technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute sulfuric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 4 days to generate black precipitates; the light source 100W is an ultraviolet lamp with the wavelength of lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of the washing is neutral, and finally drying the washed black precipitate to obtain 0.57g of large-size graphene oxide.
FT-IR (KBr): ν = cm -1 EA, 74.8 percent of C, 1.58 percent of H and 23.62 percent of O. Average particle size (DLS): 4.1 μm.
The large-size graphene oxide is prepared by the preparation method.
The embodiment 1, 2 and 3 shows that the dosage of the catalyst is controlled in the mass ratio of the graphene oxide to the catalyst of 1: 0.004-0.2, and the graphene oxide can be reduced into large-size graphene oxide. Therefore, in the following examples, the photocatalytic reduction of graphene oxide to prepare large-size graphene oxide is continuously studied according to the mass ratio of graphene oxide to catalyst of 1: 0.05.
Example four
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of ruthenium acetate into 200mL of water, uniformly stirring to completely dissolve the ruthenium acetate to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolutionary technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding glacial acetic acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 7 days to generate a black precipitate; the light source is a 100W ultraviolet lamp, and the wavelength lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of washing is neutral, and finally drying the washed black precipitate to obtain 0.60g of large-size graphene oxide.
EA, C73.2%, H1.75%, O25.05%. Average particle size (DLS): 5.7 μm.
The large-size graphene oxide is prepared by the preparation method.
EXAMPLE five
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of ruthenium chloride into 200mL of water, uniformly stirring to completely dissolve the ruthenium chloride to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolutionary technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute hydrochloric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 7 days to generate a black precipitate; the light source is a 100W ultraviolet lamp, and the wavelength is lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of the washing is neutral, and finally drying the washed black precipitate to obtain 0.58g of large-size graphene oxide.
EA, C, 74.8%, H, 1.62%, O, 23.58%. Average particle size (DLS): 5.9 μm.
The large-size graphene oxide is prepared by the preparation method.
Example six
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of manganese nitrate into 200mL of water, uniformly stirring to completely dissolve the manganese nitrate to obtain a solution, wherein the manufacturer of the graphene oxide is Hongdahu evolution science and technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute nitric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 7 days to generate black precipitates; the light source is a 100W ultraviolet lamp, and the wavelength lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of the washing is neutral, and finally drying the washed black precipitate to obtain 0.60g of large-size graphene oxide.
EA, C73.2%, H1.75%, O25.05%. Average particle size (DLS): 5.7 μm.
The large-size graphene oxide is prepared by the preparation method.
EXAMPLE seven
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of manganese acetate into 200mL of water, uniformly stirring to completely dissolve the manganese acetate to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolutionary technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding glacial acetic acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 7 days to generate black precipitates; the light source is a 100W ultraviolet lamp, and the wavelength lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of washing is neutral, and finally drying the washed black precipitate to obtain 0.60g of large-size graphene oxide.
EA, C73.6%, H1.63%, O24.77%. Average particle size (DLS): 5.9 μm.
The large-size graphene oxide is prepared by the technical preparation method.
Example eight
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of manganese chloride into 200mL of water, uniformly stirring to completely dissolve the manganese chloride to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolutionary technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute hydrochloric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 7 days to generate a black precipitate; the light source is a 100W ultraviolet lamp, and the wavelength lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of washing is neutral, and finally drying the washed black precipitate to obtain 0.57g of large-size graphene oxide.
75.1 percent of EA, 1.56 percent of C, 23.34 percent of H. Average particle size (DLS): 5.8 μm.
The large-size graphene oxide is prepared by the technical preparation method.
Example nine
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of manganese sulfate into 200mL of water, uniformly stirring to completely dissolve the manganese sulfate to obtain a solution, wherein the graphene oxide is produced by Hongdahu evolutionary technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute sulfuric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 7 days to generate black precipitates; the light source is a 100W ultraviolet lamp, and the wavelength lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of washing is neutral, and finally drying the washed black precipitate to obtain 0.59g of large-size graphene oxide.
EA, C, 74.5%, H, 1.70%, O, 23.80%. Average particle size (DLS): 5.4 μm.
The large-size graphene oxide is prepared by the preparation method.
As can be seen from examples 1 to 9, ruthenium chloride, ruthenium sulfate, ruthenium acetate, manganese chloride, manganese sulfate, manganese acetate, manganese nitrate as catalysts, dissolved in water, were used as Mn 2+ 、Ru 3+ Or Ru 4+ And catalytically reducing and polycondensing the graphene oxide by the metal ions under the irradiation of light to generate large-size graphene oxide. Therefore, in the following examples, the photocatalytic reduction of graphene oxide to prepare large-size graphene oxide is continuously studied by using ruthenium chloride as a catalyst according to a mass ratio of graphene oxide to the catalyst of 1: 0.05.
Example ten
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of ruthenium chloride into 200mL of water, uniformly stirring to completely dissolve the ruthenium chloride to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolution science and technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute hydrochloric acid into the solution to adjust the pH value to 2.5;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 8 days to generate a black precipitate; the light source is a 100W ultraviolet lamp, and the wavelength lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of washing is neutral, and finally drying the washed black precipitate to obtain 0.57g of large-size graphene oxide.
75.5 percent of EA, 1.52 percent of C, 22.98 percent of H. Average particle size (DLS): 4.8 μm.
The large-size graphene oxide is prepared by the preparation method.
EXAMPLE eleven
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of ruthenium chloride into 200mL of water, uniformly stirring to completely dissolve the ruthenium chloride to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolution science and technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute hydrochloric acid into the solution to adjust the pH value to 5.0;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 7 days to generate a black precipitate; the light source is a 100W ultraviolet lamp, and the wavelength lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of the washing is neutral, and finally drying the washed black precipitate to obtain 0.62g of large-size graphene oxide.
70.8 percent of EA, 1.84 percent of C, and 27.36 percent of O. Average particle size (DLS): 6.1 μm.
The large-size graphene oxide is prepared by the technical preparation method.
In examples 5, 10, and 11, it can be seen that when ruthenium chloride is used as a catalyst, and the mass ratio of graphene oxide to the catalyst is 1: 0.05, the pH is controlled within a range of 2.5 to 5.0, and graphene oxide is catalytically reduced and polycondensed under light irradiation to form large-size graphene oxide. Therefore, in the following examples, the photocatalytic reduction of graphene oxide to prepare large-size graphene oxide was continuously studied, with a mass ratio of graphene oxide to catalyst of 1: 0.05, using ruthenium chloride as a catalyst, and a pH of 3.
Example twelve
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of ruthenium chloride into 200mL of water, uniformly stirring to completely dissolve the ruthenium chloride to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolutionary technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute hydrochloric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 4 days to generate black precipitates; the light source is a 100W ultraviolet lamp, and the wavelength is lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of washing is neutral, and finally drying the washed black precipitate to obtain 0.69g of large-size graphene oxide.
EA, C, 68.9%, H, 1.81%, O, 29.29%. Average particle size (DLS): 4.5 μm.
The large-size graphene oxide is prepared by the preparation method.
EXAMPLE thirteen
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of ruthenium chloride into 200mL of water, uniformly stirring to completely dissolve the ruthenium chloride to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolutionary technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute hydrochloric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 12 days to generate black precipitates; the light source is a 100W ultraviolet lamp, and the wavelength is lambda = 185 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of washing is neutral, and finally drying the washed black precipitate to obtain 0.58g of large-size graphene oxide.
EA, C, 74.9%, H, 1.56%, O, 23.54%. Average particle size (DLS): 5.6 μm.
The large-size graphene oxide is prepared by the technical preparation method.
In examples 5, 12, and 13, it can be seen that when ruthenium chloride is used as a catalyst and the mass ratio of graphene oxide to the catalyst is 1: 0.05, the pH is 3, and the illumination time is 4 to 12 days, graphene oxide is catalytically reduced and polycondensed to produce large-size graphene oxide. Therefore, in the following examples, the photocatalytic reduction of graphene oxide to prepare large-size graphene oxide was continuously studied according to a mass ratio of graphene oxide to catalyst of 1: 0.05, using ruthenium chloride as a catalyst, a pH of 3, and a light irradiation time of 7 days.
Example fourteen
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of ruthenium chloride into 200mL of water, uniformly stirring to completely dissolve the ruthenium chloride to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolutionary technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute hydrochloric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 7 days to generate a black precipitate; the light source is a 100W xenon lamp, the wavelength is lambda = 280-980 nm, and the median value is 630 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of washing is neutral, and finally drying the washed black precipitate to obtain 0.62g of large-size graphene oxide.
EA, C73.7%, H1.59%, O24.71%. Average particle size (DLS): 5.4 μm.
The large-size graphene oxide is prepared by the preparation method.
Example fifteen
As shown in fig. 1 to 3, a method for preparing large-sized graphene oxide includes the following steps:
s1, respectively adding 1g of graphene oxide and 0.05g of ruthenium chloride into 200mL of water, uniformly stirring to completely dissolve the ruthenium chloride to obtain a solution, wherein the production manufacturer of the graphene oxide is Hongdahu evolution science and technology Limited company in Shenzhen, and the carbon content is about 42.7%;
s2, dropwise adding dilute hydrochloric acid into the solution to adjust the pH value to 3;
s3, placing the solution with the adjusted pH value into an illumination incubator for illumination for 7 days to generate black precipitates; the light source is a 100W mercury lamp, and the wavelength lambda = 365 nm;
s4, filtering the black precipitate from the solution;
and S5, washing the filtered black precipitate until the filtrate of the washing is neutral, and finally drying the washed black precipitate to obtain 0.59g of large-size graphene oxide.
EA, 73.6 percent of C, 1.62 percent of H and 24.78 percent of O. Average particle size (DLS): 5.5 μm.
The large-size graphene oxide is prepared by the technical preparation method.
In examples 5, 14 and 15, it can be seen that when ruthenium chloride is used as a catalyst, the mass ratio of graphene oxide to the catalyst is 1: 0.05, the pH value is 3, and the graphene oxide is catalytically reduced and polycondensed by using ultraviolet visible light (wavelength: 185-630 nm) for 7 days to produce large-size graphene oxide.
In FIG. 1b, absorption peaks 3387, 1726, 1618, 1365 and 1058 cm-1 are the absorption peaks for hydroxyl, carbonyl, carbon-carbon double bond, C-O and C-O-C oscillations, respectively, and in FIG. 1a, absorption peaks 3375 and 1137 cm-1 are the absorption peaks for hydroxyl and C-O oscillations of alcohol, respectively. Thus, the carbonyl group has been reduced and the epoxide group is also converted to a hydroxyl group.
Actually measured particle size distribution range of graphene oxide particle size: 0.50 to 1.10 μm (average about 0.85 μm), and the particle size distribution range is marked on the commercial specification: 0.20 to 1.0 μm, which is basically consistent with the specification. The particle size distribution range of the large-size graphene oxide is as follows: the particle size of the graphene oxide particles is about 6.59 times of the particle size of the graphene oxide particles, and the particle size is about 2.75 to 6.45 [ mu ] m (about 5.6 [ mu ] m on average). The area is proportional to the square of the particle size, and thus the area of the average large-sized graphene oxide is 43.4 times the area of the average graphene oxide, i.e., about 43.4 graphene oxide sheets are condensed to form one large-sized graphene oxide-like sheet.
The large-size graphene oxide is applied to a pulse laser as a saturable absorber, and the pulse sequence of a continuous mode-locked (CWML) green laser is shown in FIG. 3. The pulse sequence output by the CWML green laser at 6W incident pump power is 87 MHz. In fig. 3, the half-wave width of the green laser output signal is 4.4ns. Therefore, the graphene oxide material is an ideal saturable absorber, and has the advantages of large modulation depth, strong saturation intensity, wide absorption range and quick recovery time.
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, it is possible to make various improvements and modifications without departing from the technical principle of the present invention, and those improvements and modifications should be considered as the protection scope of the present invention.
Claims (8)
1. A preparation method of large-size graphene oxide is characterized by comprising the following steps:
respectively adding graphene oxide and a catalyst into water, and uniformly stirring to obtain a solution;
adding a pH regulator into the solution to regulate the pH value;
illuminating the solution after the pH value is adjusted to generate precipitates;
filtering the precipitate from the solution;
and washing and drying the filtered filter residue to obtain the large-size graphene oxide.
2. The method for preparing large-size graphene oxide according to claim 1, wherein the method comprises the following steps: the catalyst comprises ruthenium chloride, ruthenium sulfate, ruthenium acetate, manganese chloride, manganese sulfate, manganese acetate, manganese nitrate and hydrate thereof.
3. The method for preparing large-size graphene oxide according to claim 2, wherein the method comprises the following steps: the mass ratio of the graphene oxide to the catalyst is 1: 0.004-0.2, and the mass of the catalyst is Mn 2+ 、Ru 3+ And Ru 4+ Mass of the compound.
4. The method for preparing large-size graphene oxide according to claim 1, wherein the method comprises the following steps: the pH regulator comprises an acidic reagent and an alkaline reagent;
the acidic reagent comprises hydrochloric acid, sulfuric acid, nitric acid and acetic acid;
the alkaline agent comprises sodium hydroxide or potassium hydroxide.
5. The method for preparing large-size graphene oxide according to claim 4, wherein the method comprises the following steps: the PH value is adjusted to be between 2.5 and 5.0.
6. The method for preparing large-size graphene oxide according to claim 1, wherein the method comprises the following steps: the wavelength of the light source used for illumination is in the ultraviolet and visible light regions.
7. The method for preparing large-size graphene oxide according to claim 6, wherein the method comprises the following steps: the illumination time is 4-12 days.
8. A large-size graphene oxide is characterized in that: prepared by the preparation method of any one of claims 1 to 7.
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