CN115872392A - Carbon quantum dot, preparation method and application thereof, proton exchange membrane and preparation method thereof - Google Patents
Carbon quantum dot, preparation method and application thereof, proton exchange membrane and preparation method thereof Download PDFInfo
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/50—Fuel cells
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Abstract
The invention relates to the technical field of proton exchange membranes, in particular to a carbon quantum dot, a preparation method and application thereof, a proton exchange membrane and a preparation method thereof. The preparation method provided by the invention comprises the following steps: p-phenylenediamine, ethylenediamine and ethanol are mixed and subjected to solvothermal reaction to obtain the carbon quantum dots. The carbon quantum dots prepared by the preparation method can improve the oxidation resistance of the proton exchange membrane.
Description
Technical Field
The invention relates to the technical field of proton exchange membranes, in particular to a carbon quantum dot, a preparation method and application thereof, a proton exchange membrane and a preparation method thereof.
Background
The hydrogen fuel cell is a device for directly converting the chemical energy of hydrogen into electric energy through electrochemical reaction, and has the advantages of cleanness, no pollution and high energy conversion efficiency. The hydrogen fuel cell stack is the core of the fuel cell; fuel cell stacks include various components such as catalysts, proton exchange membranes, gas diffusion layers, bipolar plates, and other structural members such as collector plates, seals, and end plates. The proton exchange membrane is one of the important components of a fuel cell stack, plays a role in blocking raw materials and transferring protons in the fuel cell, and can be classified into a perfluorosulfonic acid membrane, a partially fluorinated polymer proton exchange membrane and a composite proton exchange membrane according to the fluorine-containing condition. Currently, a commonly used commercial ion exchange membrane is a perfluorosulfonic acid membrane. The principle of the membrane is that the hydrophobic property of the main chain of the fluorocarbon and the hydrophilic property of the side chain are utilized to achieve the purpose of high-efficiency work, and the membrane has the excellent characteristics of high proton conductivity, strong acid resistance, strong alkali resistance and the like.
The power of the fuel cell is closely affected by the proton exchange membrane. Degradation of proton membranes can lead to loss of electrolyte and serious fuel cell failure, and the membrane degradation modes are mainly divided into three modes of chemical, mechanical and thermal degradation. Among them, chemical degradation is carried out by radical reaction, and radicals (such as. OH and. OOH) attack the structure of the membrane, causing loss of proton conductivity and mechanical properties of the membrane, which is generally considered to be a direct cause of chemical degradation of the membrane. Hydrogen peroxide is formed during the fuel cell reaction and readily decomposes to produce free radicals, particularly in the presence of metal ions, such as ferrous ions. In order to improve the service life of the proton exchange membrane, it is necessary to improve the oxidation resistance of the proton exchange membrane.
Disclosure of Invention
The invention aims to provide a carbon quantum dot, a preparation method and application thereof, a proton exchange membrane and a preparation method thereof.
In order to achieve the above object, the present invention provides the following technical solutions:
the invention provides a preparation method of a carbon quantum dot with antioxidant enzyme activity, which comprises the following steps:
and mixing p-phenylenediamine, ethylenediamine and ethanol, and carrying out solvothermal reaction to obtain the carbon quantum dots.
Preferably, the dosage ratio of the p-phenylenediamine, the ethylenediamine and the ethanol is (0.1-0.5) g: (0.2-1) mL: (10-30) mL.
Preferably, the temperature of the solvothermal reaction is 140-240 ℃ and the time is 6-12 h.
Preferably, the method further comprises modifying the carbon quantum dots obtained by the solvothermal reaction after the solvothermal reaction;
the modification process is to mix the carbon quantum dots obtained by the solvothermal reaction, phosphate buffer solution and N-hydroxysuccinimide for modification.
The invention also provides the carbon quantum dot with antioxidant enzyme activity prepared by the preparation method in the technical scheme.
The invention also provides application of the carbon quantum dots with the antioxidase activity in the proton exchange membrane.
The invention also provides a preparation method of the proton exchange membrane with oxidation resistance, which comprises the following steps:
soaking the proton exchange membrane in a carbon quantum dot solution to obtain the proton exchange membrane with oxidation resistance;
or mixing the high-molecular ionomer and the organic solvent, and then sequentially carrying out ultrasonic treatment and shearing to obtain a slurry dispersion liquid;
mixing the carbon quantum dots and the slurry dispersion liquid, and forming a film to obtain the proton exchange membrane with oxidation resistance;
the carbon quantum dots are the carbon quantum dots with the antioxidant enzyme activity in the technical scheme;
the carbon quantum dot solution is a solution containing the carbon quantum dots with the antioxidant enzyme activity.
Preferably, the polymeric ionomer comprises one or more of PTFE, perfluorosulfonic acid resin, meta-fluorosulfonic acid resin, and non-fluorosulfonic acid resin;
the organic solvent comprises one or more of methanol, ethanol, isopropanol, n-propanol, butanol, nitrogen-nitrogen dimethylformamide and toluene.
Preferably, the mass ratio of the carbon quantum dots to the polymer ionomer is (0.05 to 0.2): 1.
the invention also provides the proton exchange membrane with oxidation resistance prepared by the preparation method of the technical scheme.
The invention provides a preparation method of a carbon quantum dot with antioxidant enzyme activity, which comprises the following steps: p-phenylenediamine, ethylenediamine and ethanol are mixed and subjected to solvothermal reaction to obtain the carbon quantum dots. According to the invention, the preparation raw materials of the carbon quantum dots are adjusted (p-phenylenediamine and ethylenediamine are used as precursors), so that the prepared carbon quantum dots have excellent performances such as low toxicity, easy functionalization and stable photoelectric properties, and simultaneously have activities such as Peroxidase (POD) resistance, catalase (CAT) resistance and superoxide dismutase (SOD) resistance, and active substances such as hydrogen peroxide and hydroxyl radicals can be effectively eliminated; meanwhile, the preparation method is simple, and the product is easy to modify; after the carbon quantum dots prepared by the preparation method are applied to the proton exchange membrane, the influence of active substances such as hydroxyl radicals on membrane degradation can be effectively reduced, and the service life of the proton exchange membrane is prolonged; meanwhile, the prepared carbon quantum dots do not contain metal ions, so that the oxidation resistance of the proton exchange membrane is improved, other negative effects on the membrane are avoided, the mechanical property of the proton exchange membrane can be obviously improved, and the service life of the proton exchange membrane can be obviously prolonged.
Drawings
FIG. 1 is a graph of output voltage versus current density for fuel cells prepared with proton exchange membranes as described in example 1 and comparative example 1;
FIG. 2 is a graph of open circuit voltage curves for fuel cells prepared from the proton exchange membranes described in example 1 and comparative example 1;
fig. 3 is a graph showing fluoride release rate curves of middle proton exchange membranes of fuel cells prepared by the proton exchange membranes described in example 1 and comparative example 1.
Detailed Description
The invention provides a preparation method of a carbon quantum dot with antioxidant enzyme activity, which comprises the following steps:
and mixing p-phenylenediamine, ethylenediamine and ethanol, and carrying out solvothermal reaction to obtain the carbon quantum dots.
In the present invention, all the starting materials for the preparation are commercially available products well known to those skilled in the art, unless otherwise specified.
In the present invention, the amount ratio of p-phenylenediamine, ethylenediamine, and ethanol is preferably (0.1 to 0.5) g: (0.2-1) mL: (10-30) mL, more preferably (0.2-0.4) g: (0.3-0.8) mL: (15-25) mL, most preferably (0.25-0.35) g: (0.4-0.6) mL: (18-22) mL.
The mixing process is not limited in any way, and the mixing process can be carried out by adopting a process known by a person skilled in the art and ensuring uniform mixing.
In the present invention, the temperature of the solvothermal reaction is preferably 140 to 240 ℃, more preferably 150 to 230 ℃, and most preferably 180 to 210 ℃; the time is preferably 6 to 12 hours, more preferably 8 to 10 hours.
In the present invention, the solvothermal reaction is preferably carried out in a teflon lined stainless steel autoclave.
In the present invention, the effect of controlling the condition parameters of the solvothermal reaction within the above ranges is: under the condition parameters, the obtained carbon quantum dots are most uniform in size and have the strongest oxidation resistance.
After the solvothermal reaction is finished, the method also preferably comprises dialysis and drying which are sequentially carried out; the dialysis and drying process of the present invention is not particularly limited, and may be performed by a process known to those skilled in the art.
After the dialysis and drying are completed, the present invention preferably further comprises modifying the obtained carbon quantum dots. In the present invention, the modification is preferably an amino modification. In the present invention, the amino group modification process is preferably performed by mixing a carbon quantum dot obtained by the solvothermal reaction, a phosphate buffer solution, and N-hydroxysuccinimide.
In the present invention, the pH of the phosphate buffer solution is preferably 6.8.
In the present invention, the mixing is preferably performed by adding the N-hydroxysuccinimide after dissolving the carbon quantum dots in the phosphate buffer solution.
In the invention, the dosage ratio of the carbon quantum dots, the phosphate buffer solution and the N-hydroxysuccinimide is preferably 1-10; 1 to 10, more preferably 3 to 7; 3 to 7, most preferably 5 to 6, 150 to 160;5 to 6.
In the present invention, the temperature of the modification is preferably room temperature, and the time is preferably 2 hours.
In the invention, the carbon quantum dots modified by the amino groups can be more favorable for the carboxylation reaction of the amino groups and the carboxyl groups and are more closely connected with a proton exchange membrane.
The invention also provides the carbon quantum dots with antioxidant enzyme activity prepared by the preparation method in the technical scheme.
The invention also provides application of the carbon quantum dot with the antioxidase activity in the proton exchange membrane.
The invention also provides a preparation method of the proton exchange membrane with oxidation resistance, which comprises the following steps:
soaking the proton exchange membrane in a carbon quantum dot solution to obtain the proton exchange membrane with oxidation resistance;
or mixing the high-molecular ionomer and the organic solvent, and then sequentially carrying out ultrasonic treatment and shearing to obtain a slurry dispersion liquid;
mixing the carbon quantum dots and the slurry dispersion liquid, and then forming a film to obtain the proton exchange membrane with oxidation resistance;
the carbon quantum dot is the carbon quantum dot with the antioxidant enzyme activity in the technical scheme;
the carbon quantum dot solution is a solution containing the carbon quantum dots with the antioxidant enzyme activity.
The proton exchange membrane is soaked in the carbon quantum dot solution to obtain the proton exchange membrane with oxidation resistance.
In the present invention, the proton exchange membrane is preferably a perfluorosulfonic acid resin membrane or a Nafion membrane.
Before the soaking, the invention preferably carries out swelling treatment on the proton exchange membrane; the swelling treatment process is preferably to swell the proton exchange membrane in a methanol-water solution. The volume ratio of methanol to water in the methanol-water solution is preferably 1 to 10; the dosage ratio of the proton exchange membrane to the methanol-water solution is preferably 1-10; the swelling condition is preferably 12 to 24 hours, more preferably 14 to 20 hours, and most preferably 16 to 18 hours.
In the present invention, the concentration of the carbon quantum dot solution is preferably 1. Mu. Mol/L.
In the present invention, the ratio of the amount of the proton exchange membrane to the amount of the carbon quantum dot solution is preferably 1 to 15.
In the present invention, the soaking temperature is preferably 80 ℃, and the soaking time is preferably 12 to 18 hours, more preferably 13 to 16 hours, and most preferably 14 to 15 hours.
After the soaking, the invention also preferably comprises the steps of soaking the soaked proton exchange membrane in phosphoric acid and drying. In the present invention, the mass concentration of the phosphoric acid is preferably 85%; the soaking temperature is preferably 60-80 ℃, more preferably 65-75 ℃, and most preferably 68-72 ℃; the time is preferably 24 to 36 hours, more preferably 28 to 33 hours. After the soaking, the invention also preferably comprises wiping the soaked proton exchange membrane to remove the phosphoric acid on the surface of the proton exchange membrane. In the invention, the drying is preferably vacuum drying, and the temperature of the vacuum drying is preferably 110-120 ℃, more preferably 112-118 ℃, and most preferably 114-116 ℃; the time is preferably 24 to 36 hours, more preferably 26 to 32 hours, and most preferably 28 to 30 hours.
Or the preparation method comprises the steps of mixing the high-molecular ionomer and the organic solvent, and then sequentially carrying out ultrasonic treatment and shearing to obtain the slurry dispersion liquid.
In the present invention, the polymeric ionomer preferably comprises one or more of PTFE, perfluorosulfonic acid resin, meta-fluorosulfonic acid resin, and non-fluorosulfonic acid resin; when the polymer ionomer is two or more of the above specific choices, the present invention does not have any particular limitation on the ratio of the above specific substances, and the specific substances may be mixed in any ratio. In the present invention, the organic solvent preferably includes one or more of methanol, ethanol, isopropanol, n-propanol, butanol, nitrogen-nitrogen dimethylformamide, and toluene; when the organic solvent is more than two of the above specific choices, the invention does not have any special limitation on the proportion of the specific substances, and the specific substances can be mixed according to any proportion.
In the present invention, the ratio of the amount of the polymer ionomer to the organic solvent is preferably 1 to 10, more preferably 3 to 8.
The process of the ultrasonic treatment and the shearing is not limited in any way, and the ultrasonic treatment and the shearing are well known to those skilled in the art, and after the ultrasonic treatment and the shearing are carried out once, the ultrasonic treatment and the shearing are repeated until the slurry is uniformly dispersed.
After the slurry dispersion liquid is obtained, the carbon quantum dots and the slurry dispersion liquid are mixed to form a film, and the proton exchange membrane with the oxidation resistance is obtained.
In the present invention, it is preferable that the carbon quantum dots are sufficiently dispersed in an organic solvent before being mixed with the slurry dispersion, and then mixed with the slurry dispersion. The kind of the organic solvent is preferably the same as that of the organic solvent in the slurry dispersion liquid. In the present invention, the ratio of the carbon quantum dot to the organic solvent is preferably 10 to 40, more preferably 20 to 35, 55 to 85, and most preferably 25 to 30.
In the present invention, the mass ratio of the carbon quantum dots to the polymer ionomer is preferably (0.05 to 0.2): 1, more preferably (0.08 to 0.16): 1, most preferably (0.12 to 0.15): 1.
in the present invention, the mixing is preferably performed by ultrasound, and the process of ultrasound is not limited in any way, and can be performed by a process known to those skilled in the art.
In the invention, the film forming mode is preferably casting film forming or casting film forming; the film forming temperature is preferably 80 to 100 ℃.
The invention also provides the proton exchange membrane with oxidation resistance prepared by the preparation method of the technical scheme.
In the invention, the proton exchange membrane with oxidation resistance comprises a proton exchange membrane and carbon quantum dots doped in the proton exchange membrane; the carbon quantum dot is the carbon quantum dot with the antioxidant enzyme activity in the technical scheme.
The carbon quantum dots, the preparation method and the application thereof, the proton exchange membrane and the preparation method thereof provided by the invention are described in detail with reference to the following examples, but the carbon quantum dots and the preparation method thereof are not to be construed as limiting the scope of the invention.
Example 1
Mixing 0.2g of p-phenylenediamine, 0.4mL of ethylenediamine and 20mL of ethanol, transferring the mixture into a 50mL teflon-lined stainless steel autoclave, reacting for 8 hours at 160 ℃, and then sequentially dialyzing and drying to obtain carbon quantum dots;
mixing 5g of perfluorosulfonic acid resin and 50mL of ethanol, sequentially placing the obtained mixed solution in an ultrasonic disperser for ultrasonic treatment, placing the mixed solution in a high-shear emulsifier for shearing, and repeating the ultrasonic treatment and shearing processes to obtain a uniformly mixed slurry dispersion liquid;
and mixing 0.5g of the carbon quantum dots with 25mL of ethanol, mixing with the slurry dispersion liquid, performing ultrasonic dispersion, casting the obtained mixed slurry into a flat mold, and forming a film at 80 ℃ to obtain the proton exchange membrane with the oxidation resistance.
Example 2
Mixing 0.3g of p-phenylenediamine, 0.5mL of ethylenediamine and 25mL of ethanol, transferring the mixture into a 50mL Teflon-lined stainless steel autoclave, reacting at 200 ℃ for 10 hours, and then sequentially dialyzing and drying to obtain carbon quantum dots;
mixing 5g of perfluorosulfonic acid resin and 50mL of isopropanol, sequentially placing the obtained mixed solution in an ultrasonic disperser for ultrasonic treatment, placing the mixed solution in a high-shear emulsifier for shearing, and repeating the ultrasonic treatment and shearing processes to obtain uniformly mixed slurry dispersion liquid;
and mixing 1.0g of the carbon quantum dots with 25mL of isopropanol, mixing with the slurry dispersion liquid, performing ultrasonic dispersion, casting the obtained mixed slurry into a flat mold, and forming a film at 100 ℃ to obtain the proton exchange membrane with oxidation resistance.
Example 3
Mixing 0.5g of p-phenylenediamine, 1.0mL of ethylenediamine and 25mL of ethanol, transferring the mixture into a 50mL Teflon-lined stainless steel autoclave, reacting at 220 ℃ for 12 hours, and then sequentially dialyzing and drying to obtain carbon quantum dots;
mixing 5g of perfluorosulfonic acid resin and 50mL of isopropanol, sequentially placing the obtained mixed solution in an ultrasonic disperser for ultrasonic treatment, placing the mixed solution in a high-shear emulsifier for shearing, and repeating the ultrasonic treatment and shearing processes to obtain uniformly mixed slurry dispersion liquid;
and mixing 1.0g of the carbon quantum dots with 25mL of isopropanol, mixing with the slurry dispersion liquid, performing ultrasonic dispersion, casting the obtained mixed slurry into a flat mold, and forming a film at 100 ℃ to obtain the proton exchange membrane with the oxidation resistance.
Comparative example
The proton exchange membrane was prepared by reference to example 1, except that no carbon quantum dots were added.
Test example
The proton exchange membranes described in example 1 and comparative example were assembled into a fuel cell: respectively sticking a cathode catalyst layer and an anode catalyst layer on two sides of the proton exchange membrane, performing hot pressing to obtain a membrane electrode assembly, and placing the membrane electrode assembly in the middle of a graphite end plate to obtain a single cell;
FIG. 1 is a graph of output voltage-current density of the fuel cell (wherein example 1 corresponds to example 1, and comparison corresponds to comparative example 1), and it can be seen from FIG. 1 that the output voltages of the two are substantially the same, demonstrating that the addition of carbon quantum dots does not cause loss of output voltage and power of the proton exchange membrane;
fig. 2 is a curve of open circuit voltage of the fuel cell (48 h is continuously measured, and open circuit voltage is measured every 4 h) (wherein example 1 corresponds to example 1, and comparison corresponds to comparative example 1), and it can be known from fig. 2 that the open circuit voltage of the fuel cell prepared by the proton exchange membrane described in example 1 does not drop significantly under continuous operation of the fuel cell, which proves that the proton exchange membrane of the present invention has better stability.
And (3) carrying out fluoride release rate test on the fuel cell, wherein the test process and conditions are as follows: placing the proton exchange membrane in a solution containing 1mol of H 2 O 2 With 1mol of Fe 2+ In the beaker, the solutions with different soaking times are analyzed through liquid chromatography, and the release rate of the fluoride is calculated; the test result is shown in fig. 3 (wherein example 1 corresponds to example 1, and comparison corresponds to comparative example 1), and as can be seen from fig. 3, the fluoride release rate of the proton exchange membrane described in example 1 is significantly lower than that of comparative example 1, which proves that the proton exchange membrane described in example 1 is significantly lower than that of comparative example 1 under the attack of free radicals, and thus the proton exchange membrane of the present invention has better oxidation resistance.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. A preparation method of a carbon quantum dot with antioxidant enzyme activity is characterized by comprising the following steps:
p-phenylenediamine, ethylenediamine and ethanol are mixed and subjected to solvothermal reaction to obtain the carbon quantum dots.
2. The method according to claim 1, wherein the p-phenylenediamine, the ethylenediamine and the ethanol are used in a ratio of (0.1 to 0.5) g: (0.2-1) mL: (10-30) mL.
3. The process according to claim 1, wherein the solvothermal reaction is carried out at a temperature of 140 to 240 ℃ for 6 to 12 hours.
4. The production method according to any one of claims 1 to 3, further comprising modifying the carbon quantum dots obtained by the solvothermal reaction after the solvothermal reaction;
the modification process is to mix the carbon quantum dots obtained by the solvothermal reaction, phosphate buffer solution and N-hydroxysuccinimide for modification.
5. A carbon quantum dot having antioxidase activity, which is produced by the production method according to any one of claims 1 to 4.
6. The use of the carbon quantum dots with antioxidant enzyme activity of claim 5 in proton exchange membranes.
7. A preparation method of a proton exchange membrane with oxidation resistance is characterized by comprising the following steps:
soaking the proton exchange membrane in a carbon quantum dot solution to obtain the proton exchange membrane with oxidation resistance;
or mixing the high-molecular ionomer and the organic solvent, and then sequentially carrying out ultrasonic treatment and shearing to obtain a slurry dispersion liquid;
mixing the carbon quantum dots and the slurry dispersion liquid, and forming a film to obtain the proton exchange membrane with oxidation resistance;
the carbon quantum dot is the carbon quantum dot with antioxidant enzyme activity of claim 5;
the carbon quantum dot solution is a solution containing the carbon quantum dots having an antioxidase activity according to claim 5.
8. The method of claim 7, wherein the polymeric ionomer comprises one or more of PTFE, perfluorosulfonic acid resin, meta-fluorosulfonic acid resin, and non-fluorosulfonic acid resin;
the organic solvent comprises one or more of methanol, ethanol, isopropanol, n-propanol, butanol, nitrogen-nitrogen dimethylformamide and toluene.
9. The method according to claim 7, wherein the mass ratio of the carbon quantum dot to the polymer ionomer is (0.05 to 0.2): 1.
10. the proton exchange membrane with oxidation resistance prepared by the preparation method of any one of claims 7 to 9.
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