CN112079347A - Method for preparing nano carbon spheres by cooperation of pressure and dispersing agent - Google Patents
Method for preparing nano carbon spheres by cooperation of pressure and dispersing agent Download PDFInfo
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- CN112079347A CN112079347A CN202010997321.9A CN202010997321A CN112079347A CN 112079347 A CN112079347 A CN 112079347A CN 202010997321 A CN202010997321 A CN 202010997321A CN 112079347 A CN112079347 A CN 112079347A
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Abstract
The invention relates to a nano carbon sphere preparation technology, in particular to a method for preparing nano carbon spheres by the cooperation of pressure and a dispersing agent, and solves the problems of easy adhesion and low yield of carbon spheres in the existing nano carbon sphere synthesis method. The method comprises the following steps: s1, preparing a mixed solution of glucose and a dispersing agent; the dispersing agent is a sodium polyacrylate, and the mass ratio of the glucose to the sodium polyacrylate is 1: 0.003-1: 0.01; s2, placing the mixed solution prepared in the step S1 into an autoclave, sealing the autoclave, introducing inert gas through a gas inlet, and pressurizing to enable the initial pressure in the autoclave to be 0.5-4.0 MPa; s3, heating the autoclave of the step S2 to carry out hydrothermal synthesis reaction to obtain a solution of nano carbon spheres; and S4, washing and drying the nano carbon sphere solution obtained in the step S3 to obtain the nano carbon spheres. According to the method, the nano carbon spheres with adjustable particle size of 75-96 nm, good dispersibility, uniform size and high yield can be obtained by changing the pressure and the using amount of the dispersing agent, and theoretical and technical support is provided for large-scale industrial production.
Description
Technical Field
The invention relates to a nano carbon sphere preparation technology, in particular to a method for preparing nano carbon spheres by the cooperation of pressure and a dispersing agent.
Background
The carbon nanospheres have small particle size (<100nm), regular spherical morphology and abundant surface functional groups, so that the carbon nanospheres are widely applied to the fields of catalysis or catalyst carriers, adsorption, electrochemistry, biomedicine and the like. Compared with micro-nano carbon spheres, the nano carbon spheres have higher specific surface area and richer surface functional groups, and show more excellent performance when being used as catalyst carriers, electrode materials and adsorbing materials.
The preparation of high quality nanocarbon spheres still faces a great challenge due to the synthetic mechanism of carbon spheres: firstly, glucose is decomposed to generate 5-hydroxymethyl furfural, various organic acids and other compounds. 5-hydroxymethylfurfural forms aromatic clusters through dehydration, condensation and polymerization, nucleation can occur when the aromatic clusters in the aqueous solution reach a critical over-saturation point, and carbon nuclei grow into carbon nanospheres by enriching various water-soluble small molecules. The surface energy of the carbon nanospheres is large, water-soluble small molecules are required to be continuously enriched to generate the carbon nanospheres in order to maintain the stability of a system, and the phenomenon is particularly remarkable when the glucose concentration is high and the carbonization time is long.
So far, there are only a few examples of successful synthesis of nanocarbon spheres. For example, in 2016, in English literature entitled Glucose-derived Carbonaceous nanoparticles for Photoacetic Imaging and Photothermal Therapy, published in ACS applied materials & interfaces, journal, Vol.8, 25, Miao et al synthesized nanocarbon spheres with an average particle size of 60nm using a lower Glucose concentration (0.28M); in 2009, in English literature entitled "A Two-Step Hydrothermal Synthesis Approach to Monodisspersed Colloidal Carbon Spheres", published in journal, Nanoscale Research Letters, volume 4, volume 9, Chen et al synthesized nanocarbon Spheres with an average particle size of 93nm using a lower carbonization temperature (160 ℃) and an extremely low glucose concentration (0.1M). Although the carbon sphere size can be reduced by reducing the glucose concentration and the carbonization temperature, the yield of the nano carbon spheres obtained by the method is extremely low (< 1%), raw materials are easily wasted, and the method is not suitable for large-scale industrial application. In 2014, in English literature entitled Design and Design of Scientific ports Carbon with a Template-free Method, Wang et al used sodium polystyrene sulfonate as additive to synthesize nano Carbon spheres with particle size of 70nm at high glucose concentration (0.9M), which is published in journal, Scientific Reports, volume 4, No. 1, but the application of the nano Carbon spheres prepared by the Method is limited due to adhesion.
Disclosure of Invention
The invention provides a method for preparing nano carbon spheres by the cooperation of pressure and a dispersing agent, aiming at solving the technical problems that carbon spheres are difficult to be small, easy to be adhered and low in yield in the existing nano carbon sphere synthesis method.
In order to achieve the purpose, the technical scheme provided by the invention is as follows:
a method for preparing nano carbon spheres by the cooperation of pressure and a dispersing agent is characterized by comprising the following steps:
s1, preparing a mixed solution of glucose and a dispersing agent; the dispersing agent is a sodium polyacrylate, and the mass ratio of the glucose to the sodium polyacrylate is 1: 0.003-1: 0.01;
s2, putting the mixed solution prepared in the step S1 into an autoclave, sealing the autoclave, and introducing nitrogen or inert gas through a gas inlet to pressurize to enable the initial pressure in the autoclave to be 0.5-4.0 MPa;
s3, heating the autoclave of the step S2 to carry out hydrothermal synthesis reaction to obtain a solution of nano carbon spheres;
and S4, washing and drying the nano carbon sphere solution obtained in the step S3 to obtain the nano carbon spheres.
Further, in step S1, the glucose concentration is 0.4M to 1.0M.
Further, in step S1, the mass ratio of the glucose to the sodium polyacrylate is 1:0.005 to 1: 0.008.
Further, in step S1, the glucose concentration is 0.5M to 0.8M.
Further, in step S1, the sodium salt is poly (4-styrenesulfonic acid-co-maleic acid) sodium salt.
Further, in step S2, the volume of the mixed solution is 1/3-2/3 of the volume of the autoclave.
Further, in step S3, the temperature of the hydrothermal synthesis reaction is 160-200 ℃ and the time is 3-15 h.
Further, in step S4, the nano carbon spheres are washed by three times of deionized water centrifugation and ultrasonic dispersion washing, and then by three times of anhydrous ethanol centrifugation and ultrasonic dispersion washing;
the centrifugal speed is 15000-20000 r/min, and the centrifugal time is 20-50 min.
Further, in the step S4, the drying of the carbon nanospheres is to put the cleaned carbon nanospheres into a vacuum drying oven and dry them at 40-60 ℃ for 12-24 h.
Compared with the prior art, the invention has the advantages that:
1. before the hydrothermal synthesis reaction, the initial pressure in the kettle is changed by using inert gas pressurization, and the initial pressure is increased, so that more H is ionized from water in a high-temperature state+And OH-And (3) ions, the rate of converting glucose into 5-Hydroxymethylfurfural (HMF) is accelerated, and the yield of the 5-Hydroxymethylfurfural (HMF) is improved. 5-Hydroxymethylfurfural (HMF) is rapidly generated in a large amount in a short time, so that more carbon nuclei can be continuously generated in the generation stage, and the carbon nuclei are difficult to grow further due to the limitation of the initial raw materials. The dispersant may be attached to the surface of the carbon core, on the one hand, to inhibit the growth rate of the carbon spheres, allowing more 5-Hydroxymethylfurfural (HMF) to be used for nucleation, and on the other hand, to provide a negative charge to prevent the carbon spheres from sticking. The method of the invention is thus improvedThe yield of the carbon core and the growth rate of the carbon core are controlled to realize the control of the carbon sphere in the nanometer scale, the obtained carbon sphere in the nanometer scale has good dispersibility, the yield is improved by dozens of times compared with the traditional method, and the guarantee is provided for the industrial large-scale generation.
2. According to the invention, the nano carbon spheres with adjustable size of 75-96 nm and good dispersibility can be efficiently prepared only by changing the initial pressure in the kettle and the using amount of the dispersing agent, so that the high-quality preparation of the nano carbon spheres is realized.
3. The hydrothermal carbon spheres prepared by the method have the advantages of good dispersibility, uniform size and high yield (10.8-15.1%).
Drawings
FIG. 1 is a scanning electron microscope image of a nanocarbon sphere obtained in example 1 of the method for preparing a nanocarbon sphere by synergy of pressure and a dispersant according to the present invention;
fig. 2 is a scanning electron microscope image of the nanocarbon sphere obtained in example 2 of the method for preparing nanocarbon spheres by synergy of pressure and a dispersant according to the present invention.
Detailed Description
The invention is described in further detail below with reference to the figures and specific embodiments.
The invention provides an efficient preparation method of hydrothermal carbon nanospheres, which realizes the regulation and control of the carbon nanospheres in the nanometer scale by improving the yield of carbon nuclei and controlling the growth rate of the carbon nuclei. According to the method, the nano carbon spheres with the adjustable particle size of 75-96 nm, good dispersibility, uniform size and high yield (10.8-15.1%) can be obtained by changing the pressure and the using amount of the dispersing agent, and theoretical and technical support is provided for large-scale industrial production.
Example 1
A high-efficiency preparation method of hydrothermal carbon nanospheres comprises the following steps:
s1, preparing a glucose solution with the concentration of 1.0M, wherein the dosage of a dispersant poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (PSSMA) is 1% of the dosage of glucose, and uniformly stirring to obtain a mixed solution;
s2, taking 33mL of the mixed solution prepared in the step S1, putting the mixed solution into a 100mL high-pressure kettle, sealing the high-pressure kettle, and introducing nitrogen through a gas inlet to enable the initial pressure in the kettle to be 4.0 MPa;
s3, heating the autoclave in the step S2 to 200 ℃, keeping the temperature for 3 hours, and naturally cooling to room temperature after the reaction is finished to obtain a nano carbon sphere solution;
s4, separating the nano carbon sphere solution obtained in the S3 at a centrifugal rate of 18000r/min for 30min, centrifuging by using deionized water, dispersing and cleaning by using ultrasonic for three times, and then centrifuging by using absolute ethyl alcohol, and dispersing and cleaning by using ultrasonic for three times; and putting the cleaned carbon nanospheres into a vacuum drying oven at 60 ℃ for drying for 12 hours to obtain the carbon nanospheres.
FIG. 1 is a scanning electron microscope image of the nanocarbon sphere obtained in example 1, and it can be seen from the image that the nanocarbon sphere has good dispersibility, an average particle diameter of 89nm, and a yield of 11.3%.
Example 2
A high-efficiency preparation method of hydrothermal carbon nanospheres comprises the following steps:
s1, preparing a glucose solution with the concentration of 0.8M, and uniformly stirring the dispersant poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (PSSMA) with the dosage of 0.5 percent of the dosage of the glucose to obtain a mixed solution;
s2, taking 60mL of the mixed solution prepared in the step S1, putting the mixed solution into a 100mL high-pressure kettle, sealing the high-pressure kettle, and introducing nitrogen through an air inlet to enable the initial pressure in the kettle to be 3.0 MPa;
s3, heating the autoclave in the step S2 to 180 ℃, keeping the temperature for 6 hours, and naturally cooling to room temperature after the reaction is finished to obtain a nano carbon sphere solution;
and S4, separating the nano carbon sphere solution obtained in the S3 at a centrifugal rate of 15000r/min for 20min, centrifuging by using deionized water, dispersing and cleaning by using ultrasonic for three times, centrifuging by using absolute ethyl alcohol, dispersing and cleaning by using ultrasonic for three times, and drying the cleaned nano carbon spheres in a vacuum drying oven at 50 ℃ for 15h to obtain the nano carbon spheres.
FIG. 2 is a scanning electron microscope image of the nanocarbon sphere obtained in example 2, and it can be seen from the image that the nanocarbon sphere has good dispersibility, an average particle size of 96nm, and a yield of 15.3%.
Example 3
A high-efficiency preparation method of hydrothermal carbon nanospheres comprises the following steps:
s1, preparing a glucose solution with the concentration of 0.7M, wherein the dosage of a dispersant poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (PSSMA) is 0.8 percent of the dosage of glucose, and uniformly stirring to obtain a mixed solution;
s2, taking 50mL of the mixed solution prepared in the step S1, putting the mixed solution into a 100mL high-pressure kettle, sealing the high-pressure kettle, and introducing nitrogen through an air inlet to enable the initial pressure in the kettle to be 2.5 MPa;
s3, heating the autoclave in the step S2 to 200 ℃, keeping the temperature for 3 hours, and naturally cooling to room temperature after the reaction is finished to obtain a nano carbon sphere solution;
and S4, separating the nano carbon sphere solution obtained in the S3 at a centrifugal rate of 20000r/min for 50min, centrifuging by using deionized water and carrying out ultrasonic dispersion cleaning for three times, centrifuging by using absolute ethyl alcohol and carrying out ultrasonic dispersion cleaning for three times, and drying the cleaned nano carbon spheres in a vacuum drying oven at 50 ℃ for 15h to obtain the nano carbon spheres.
This example obtained nanocarbon spheres having an average particle diameter of 79nm and a yield of 12.2%.
Example 4
A high-efficiency preparation method of hydrothermal carbon nanospheres comprises the following steps:
s1, preparing a glucose solution with the concentration of 0.4M, uniformly stirring the solution and the dispersant poly (4-styrenesulfonic acid-co-maleic acid) sodium salt (PSSMA) with the dosage of 0.3 percent of the dosage of the glucose to obtain a mixed solution;
s2, taking 66mL of the mixed solution prepared in the step S1, putting the mixed solution into a 100mL high-pressure kettle, sealing the high-pressure kettle, and introducing nitrogen through an air inlet to enable the initial pressure in the kettle to be 1.5 MPa;
s3, heating the autoclave in the step S2 to 160 ℃, keeping the temperature for 15 hours, and naturally cooling to room temperature after the reaction is finished to obtain a nano carbon sphere solution;
and S4, separating the nano carbon sphere solution obtained in the S3 at a centrifugal rate of 20000r/min for 50min, centrifuging by using deionized water and carrying out ultrasonic dispersion cleaning for three times, centrifuging by using absolute ethyl alcohol and carrying out ultrasonic dispersion cleaning for three times, and drying the cleaned nano carbon spheres in a vacuum drying oven at 40 ℃ for 24h to obtain the nano carbon spheres.
This example obtained nanocarbon spheres having an average particle diameter of 75nm and a yield of 10.8%.
The above description is only for the purpose of describing the preferred embodiments of the present invention and does not limit the technical solutions of the present invention, and any known modifications made by those skilled in the art based on the main technical concepts of the present invention fall within the technical scope of the present invention.
Claims (9)
1. A method for preparing nano carbon spheres by the cooperation of pressure and a dispersing agent is characterized by comprising the following steps:
s1, preparing a mixed solution of glucose and a dispersing agent; the dispersing agent is a sodium polyacrylate, and the mass ratio of the glucose to the sodium polyacrylate is 1: 0.003-1: 0.01;
s2, putting the mixed solution prepared in the step S1 into an autoclave, sealing the autoclave, and introducing nitrogen or inert gas through a gas inlet to pressurize to enable the initial pressure in the autoclave to be 0.5-4.0 MPa;
s3, heating the autoclave of the step S2 to carry out hydrothermal synthesis reaction to obtain a solution of nano carbon spheres;
and S4, washing and drying the nano carbon sphere solution obtained in the step S3 to obtain the nano carbon spheres.
2. The method for preparing nano carbon spheres by the cooperation of the pressure and the dispersing agent as claimed in claim 1, wherein the pressure and the dispersing agent are as follows: in step S1, the glucose concentration is 0.4M to 1.0M.
3. The method for preparing nano carbon spheres by the cooperation of the pressure and the dispersing agent as claimed in claim 2, wherein: in step S1, the mass ratio of the glucose to the sodium polyacrylate is 1: 0.005-1: 0.008.
4. The method for preparing nano carbon spheres by the cooperation of the pressure and the dispersing agent according to claim 3, wherein the pressure and the dispersing agent are as follows: in step S1, the glucose concentration is 0.7M to 0.8M.
5. The method for preparing nano carbon spheres by the cooperation of the pressure and the dispersing agent according to any one of claims 1 to 4, wherein: in step S1, the sodium salt is poly (4-styrenesulfonic acid-co-maleic acid) sodium salt.
6. The method for preparing nano carbon spheres by the cooperation of the pressure and the dispersing agent as claimed in claim 1, wherein the pressure and the dispersing agent are as follows: in step S2, the volume of the mixed solution is 1/3-2/3 of the volume of the autoclave.
7. The method for preparing nano carbon spheres by the cooperation of the pressure and the dispersing agent as claimed in claim 1, wherein the pressure and the dispersing agent are as follows: in step S3, the temperature of the hydrothermal synthesis reaction is 160-200 ℃ and the time is 3-15 h.
8. The method for preparing nano carbon spheres by the cooperation of the pressure and the dispersing agent as claimed in claim 1, wherein the pressure and the dispersing agent are as follows: in the step S4, the nano carbon ball washing is to adopt three times of centrifugal and ultrasonic dispersion washing of deionized water, and then adopt three times of centrifugal and ultrasonic dispersion washing of absolute ethyl alcohol;
the centrifugal speed is 15000-20000 r/min, and the centrifugal time is 20-50 min.
9. The method for preparing nano carbon spheres by the cooperation of the pressure and the dispersing agent according to claim 8, wherein the pressure and the dispersing agent are as follows: in the step S4, the drying of the carbon nanospheres is to put the cleaned carbon nanospheres into a vacuum drying oven and dry the carbon nanospheres for 12-24 hours at the temperature of 40-60 ℃.
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| CN115215322A (en) * | 2022-07-29 | 2022-10-21 | 东北林业大学 | Preparation method and application of cellulose carbon nanospheres |
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Application publication date: 20201215 |