CN112349918A - Method for preparing nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan and application thereof - Google Patents
Method for preparing nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan and application thereof Download PDFInfo
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- 229920001661 Chitosan Polymers 0.000 title claims abstract description 168
- 239000003054 catalyst Substances 0.000 title claims abstract description 115
- DSVGQVZAZSZEEX-UHFFFAOYSA-N [C].[Pt] Chemical compound [C].[Pt] DSVGQVZAZSZEEX-UHFFFAOYSA-N 0.000 title claims abstract description 94
- 238000000034 method Methods 0.000 title claims abstract description 26
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- 229910052697 platinum Inorganic materials 0.000 claims abstract description 67
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- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 11
- 230000007935 neutral effect Effects 0.000 claims abstract description 11
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 11
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- 239000002253 acid Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 18
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 17
- 229910052700 potassium Inorganic materials 0.000 claims description 17
- 239000011591 potassium Substances 0.000 claims description 17
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- 238000003756 stirring Methods 0.000 claims description 10
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 8
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- 238000001132 ultrasonic dispersion Methods 0.000 claims description 7
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 6
- 229920005552 sodium lignosulfonate Polymers 0.000 claims description 6
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- 239000002202 Polyethylene glycol Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- 235000019353 potassium silicate Nutrition 0.000 claims description 4
- 229960004063 propylene glycol Drugs 0.000 claims description 4
- GCLGEJMYGQKIIW-UHFFFAOYSA-H sodium hexametaphosphate Chemical compound [Na]OP1(=O)OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])OP(=O)(O[Na])O1 GCLGEJMYGQKIIW-UHFFFAOYSA-H 0.000 claims description 4
- 235000019982 sodium hexametaphosphate Nutrition 0.000 claims description 4
- NTHWMYGWWRZVTN-UHFFFAOYSA-N sodium silicate Chemical compound [Na+].[Na+].[O-][Si]([O-])=O NTHWMYGWWRZVTN-UHFFFAOYSA-N 0.000 claims description 4
- 239000001577 tetrasodium phosphonato phosphate Substances 0.000 claims description 4
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims description 2
- 229910052708 sodium Inorganic materials 0.000 claims description 2
- 239000011734 sodium Substances 0.000 claims description 2
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- 238000000197 pyrolysis Methods 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 30
- 229910052757 nitrogen Inorganic materials 0.000 description 24
- 238000002484 cyclic voltammetry Methods 0.000 description 17
- 229910052799 carbon Inorganic materials 0.000 description 12
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- YDEXUEFDPVHGHE-GGMCWBHBSA-L disodium;(2r)-3-(2-hydroxy-3-methoxyphenyl)-2-[2-methoxy-4-(3-sulfonatopropyl)phenoxy]propane-1-sulfonate Chemical compound [Na+].[Na+].COC1=CC=CC(C[C@H](CS([O-])(=O)=O)OC=2C(=CC(CCCS([O-])(=O)=O)=CC=2)OC)=C1O YDEXUEFDPVHGHE-GGMCWBHBSA-L 0.000 description 2
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- 229920005862 polyol Polymers 0.000 description 2
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- 125000003277 amino group Chemical group 0.000 description 1
- AAMATCKFMHVIDO-UHFFFAOYSA-N azane;1h-pyrrole Chemical compound N.C=1C=CNC=1 AAMATCKFMHVIDO-UHFFFAOYSA-N 0.000 description 1
- DLGYNVMUCSTYDQ-UHFFFAOYSA-N azane;pyridine Chemical compound N.C1=CC=NC=C1 DLGYNVMUCSTYDQ-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910052796 boron Inorganic materials 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
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- 238000001420 photoelectron spectroscopy Methods 0.000 description 1
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- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
- H01M4/92—Metals of platinum group
- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
- H01M4/926—Metals of platinum group supported on carriers, e.g. powder carriers on carbon or graphite
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Abstract
The invention relates to a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan and application thereof, belonging to the technical field of catalyst preparation. The invention prepares chitosan carbon powder by pyrolyzing chitosan; adding chitosan carbon powder into an ethanol solution containing polyalcohol and a dispersing agent, ultrasonically dispersing uniformly, adding a platinum precursor solution, carrying out a constant-temperature reduction reaction at 70-150 ℃ for 100-240min, washing the solid with deionized water at 70-80 ℃ until the washing liquid is neutral, drying, grinding and sieving to obtain the nitrogen-doped platinum-carbon catalyst. The highly dispersed PtNPs-loaded oxygen reduction cathode platinum-based catalyst with the average particle size of 3.5nm is prepared by controlling the pyrolysis temperature and time and the reduction reaction temperature and time, and has ultrahigh electrocatalytic stability and higher electrochemical activity.
Description
Technical Field
The invention relates to a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan and application thereof, belonging to the technical field of catalyst preparation.
Background
In the face of increasing energy consumption and the continuous decrease of other energy reserves, fuel cells are receiving attention due to their ultra-high energy conversion efficiency and environmental friendliness. However, the slow cathode kinetics and the high overpotential requirements severely limit their practical applications. Platinum-based materials are the most excellent ORR catalysts because of their effective promotion of the ORR reaction and the lower overpotential associated with the 4-electron reaction pathway. However, conventional Pt/C catalysts tend to increase activity at the expense of higher loading, where only a small fraction of the platinum atoms on the surface of each platinum nanoparticle participate in the reaction, resulting in lower platinum utilization and slow kinetics. Therefore, it is important to develop catalysts that reduce the required overpotential and platinum consumption and improve the cathode kinetic reaction performance.
Disclosure of Invention
The invention provides a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan, aiming at the problems of high cost, poor activity and stability and low dispersion degree of platinum nano particles (PtNPs) in the prior art and an application thereof2/gPtHalf-wave potential of 0.85VvsRHE)。
Heteroatom doping (N, P, B and the like) can improve the dispersity of platinum nanoparticles (PtNPs) and the activity and stability of the catalyst, the pyrolyzed chitosan carbon is used as a carbon source and a nitrogen source, more active sites can be introduced in a self-doping mode, the complicated synthesis process is avoided, and the pyrolyzed chitosan carbon contains amino groups and other nitrogen-containing groups and can anchor the PtNPs, so that the catalyst has excellent electrochemical performance and extremely high stability.
A method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan comprises the following specific steps:
(1) dissolving chitosan in dilute acid, adding a dispersing agent, and uniformly stirring to obtain chitosan gel;
(2) drying the chitosan gel obtained in the step (1) in vacuum until the chitosan gel is anhydrous, and grinding the chitosan gel into powder to obtain chitosan gel powder;
(3) under the protection of nitrogen atmosphere, uniformly heating the chitosan gel powder in the step (2) to 200-; the organic dispersant can be removed by the constant temperature treatment at the temperature of 200 ℃ and 600 ℃, and a hole structure is formed at the same time; the chitosan gel powder can be carbonized by the constant temperature treatment at the temperature of 700 ℃ and 1000 ℃;
(4) adding the chitosan carbon powder in the step (3) into an ethanol solution containing polyalcohol and a dispersing agent, adding a platinum precursor solution after ultrasonic dispersion is uniform, reacting at the constant temperature of 70-150 ℃ for 100-240min, washing the solid with deionized water at the temperature of 70-80 ℃ until the washing liquid is neutral, drying, grinding and sieving to obtain the nitrogen-doped platinum-carbon catalyst.
The diluted acid in the step (1) is hydrochloric acid, sulfuric acid, acetic acid or nitric acid, and the pH value of the diluted acid is 2-5.
The solid-to-liquid ratio g/mL of the chitosan to the dilute acid in the step (1) is 1: 50-300.
The dispersing agent in the step (1) and the step (1) is one or more of water glass, sodium hexametaphosphate, sodium lignosulfonate and polyoxyethylene polyoxypropylene ether block copolymer.
The mass ratio of the chitosan to the dispersant in the step (1) is 1: 0.5-3.
The constant temperature rise rate in the step (3) is 2-15 ℃/min.
The mass ratio of the chitosan carbon powder to the dispersing agent in the step (4) is 1: 0.1-5.
The polyhydric alcohol in the step (4) is one or more of ethylene glycol, polyethylene glycol, 1, 2-propylene glycol and glycerol, and the mass ratio of the chitosan carbon powder to the polyhydric alcohol is 1: 10-80.
The platinum precursor in the step (4) is one or more of sodium chloroplatinate, potassium chloroplatinate and chloroplatinic acid, the concentration of the platinum precursor solution is 0.01-1mol/L, and the solid-to-liquid ratio g: mL of the chitosan carbon powder to the platinum precursor solution is 1: 2-30.
The nitrogen-doped platinum-carbon catalyst is applied as an oxygen reduction cathode catalyst.
The invention has the beneficial effects that:
(1) according to the invention, chitosan is used as a carbon precursor as a carbon source and a nitrogen source, rich active sites are introduced in a self-doping manner, and a polyol is used as a reducing agent to load the high-dispersion platinum-based catalyst with the PtNPs particle size of 3.5nm on the premise of nitrogen doping, so that the high-dispersion platinum-based catalyst has the advantages of low reaction temperature and low platinum consumption;
(2) the electrochemical performance of common commercial platinum carbon can be achieved under the loading of 5 wt% of Pt, and the platinum carbon has higher stability than the commercial platinum carbon;
(3) the method has the advantages of simple preparation process, wide carbon precursor source, low price and excellent environmental friendliness.
Drawings
FIG. 1 is a high resolution transmission electron micrograph (magnification 1000000 times) of a nitrogen-doped platinum-carbon catalyst of example 1;
FIG. 2 is a high resolution TEM image (magnification 1000000 times) of the N-doped Pt-C catalyst of example 2;
FIG. 3 is an XRD pattern of a nitrogen doped platinum carbon catalyst of example 1;
FIG. 4 shows the results of the electrochemical test and the photoelectron spectroscopy results of example 1: FIG. a is a comparison of cyclic voltammetry curves of CSC-Pt and JM 20 wt% commercial platinum carbon, FIG. d is a comparison of linear sweep voltammetry curves of CSC-Pt and JM 20 wt% commercial platinum carbon, FIGS. b and e are a comparison of accelerated aging tests of 10000 cycles CV sweeps of CSC-Pt and JM 20 wt% commercial platinum carbon, and FIG. f is a XPS N1s fit plot of CSC-Pt, wherein P-N represents pyridine nitrogen, Py-N represents pyrrole nitrogen, G-N represents graphite nitrogen, O-N represents oxidized nitrogen, and Pt-N represents platinum nitrogen; and c is a histogram of the calculated contents of each type of nitrogen in fig. 4 f.
Detailed Description
The present invention will be described in further detail with reference to specific embodiments, but the scope of the present invention is not limited to the description.
Example 1: a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan comprises the following specific steps:
(1) dissolving chitosan in dilute acetic acid with the pH value of 2, adding a dispersing agent polyoxyethylene polyoxypropylene ether block copolymer, and uniformly stirring to obtain chitosan gel; wherein the solid-liquid ratio g: mL of the chitosan to the dilute acetic acid is 1:100, and the mass ratio of the chitosan to the dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer) is 1: 1;
(2) placing the chitosan gel obtained in the step (1) at the temperature of 80 ℃ for vacuum drying until the chitosan gel is anhydrous, and grinding the chitosan gel into powder to obtain chitosan gel powder;
(3) uniformly heating the chitosan gel powder in the step (2) to 350 ℃ at a speed of 5 ℃/min under the protection of nitrogen atmosphere, carrying out constant temperature treatment for 120min, then uniformly heating to 900 ℃ for constant temperature treatment for 180 ℃, carrying out furnace cooling to normal temperature, and grinding to obtain chitosan carbon powder;
(4) adding the chitosan carbon powder obtained in the step (3) into an ethanol solution containing polyalcohol (ethylene glycol) and a dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer), adding a platinum precursor solution (chloroplatinic acid solution) after uniform ultrasonic dispersion, reacting at constant temperature of 120 ℃ for 240min, washing the solid with deionized water at the temperature of 70-80 ℃ until the washing liquid is neutral, drying, grinding and sieving with a 800-mesh sieve to obtain the nitrogen-doped platinum-carbon catalyst; wherein the mass ratio of the chitosan carbon powder to the dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer) is 1:1, the mass ratio of the chitosan carbon powder to the polyhydric alcohol (ethylene glycol) is 1:10, the concentration of the platinum precursor solution (chloroplatinic acid solution) is 0.1mol/L, and the solid-to-liquid ratio g: mL of the chitosan carbon powder to the platinum precursor solution (chloroplatinic acid solution) is 1: 2.55;
the high-resolution transmission electron microscope image of the nitrogen-doped platinum-carbon catalyst of the embodiment is shown in fig. 1, and it can be known from fig. 1 that the average particle size of PtNPs is 3.5nm and the PtNPs are uniformly dispersed;
the XRD pattern of the nitrogen-doped platinum-carbon catalyst is shown in figure 3, and as can be seen from figure 3, the nitrogen-doped platinum-carbon catalyst only has a platinum simple substance phase and has no other impurity peaks;
the results of the contents of C, N and Pt elements in the nitrogen-doped platinum-carbon catalyst measured by ICP-OES and an element analyzer are shown in Table 1,
TABLE 1 partial element content in the catalyst
As can be seen from Table 1, the nitrogen content was as high as 5.8%, and the platinum content was close to the target loading;
the electrochemical test results of the nitrogen-doped platinum-carbon catalyst are shown in fig. 4, and from the cyclic voltammetry curve and the linear sweep voltammetry curve, the oxygen reduction half-wave potential and the mass specific current of the catalyst are both larger than those of commercial JM 20 wt% of commercial platinum carbon, and after 10000 cycles of cyclic voltammetry sweep accelerated aging tests, the catalyst shows smaller half-wave potential drop than that of the commercial platinum carbon.
Example 2: a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan comprises the following specific steps:
(1) dissolving chitosan in dilute acetic acid with pH value of 5, adding sodium hexametaphosphate serving as a dispersing agent, and uniformly stirring to obtain chitosan gel; wherein the solid-liquid ratio g: mL of the chitosan to the dilute acetic acid is 1:50, and the mass ratio of the chitosan to the dispersing agent (sodium hexametaphosphate) is 1: 2;
(2) placing the chitosan gel obtained in the step (1) at the temperature of 80 ℃ for vacuum drying until the chitosan gel is anhydrous, and grinding the chitosan gel into powder to obtain chitosan gel powder;
(3) uniformly heating the chitosan gel powder in the step (2) to 200 ℃ at a speed of 2 ℃/min under the protection of nitrogen atmosphere, carrying out constant temperature treatment for 120min, then uniformly heating to 800 ℃ for 180 ℃, carrying out furnace cooling to normal temperature, and grinding to obtain chitosan carbon powder;
(4) adding the chitosan carbon powder obtained in the step (3) into an ethanol solution containing polyalcohol (polyethylene glycol) and a dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer), ultrasonically dispersing uniformly, adding a platinum precursor solution (chloroplatinic acid solution), reacting at a constant temperature of 80 ℃ for 180min, washing the solid with deionized water at a temperature of 70-80 ℃ until the washing liquid is neutral, drying, grinding, and sieving with a 800-mesh sieve to obtain a nitrogen-doped platinum carbon catalyst CSC-Pt; wherein the mass ratio of the chitosan carbon powder to the dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer) is 1:0.5, the mass ratio of the chitosan carbon powder to the polyhydric alcohol (polyethylene glycol) is 1:20, the concentration of the platinum precursor solution (chloroplatinic acid solution) is 0.1mol/L, and the solid-to-liquid ratio g: mL of the chitosan carbon powder to the platinum precursor solution (chloroplatinic acid solution) is 1: 2.55;
the high-resolution transmission electron microscope image of the nitrogen-doped platinum-carbon catalyst of the embodiment is shown in fig. 2, and it can be seen from fig. 2 that the average particle size of PtNPs is 3.7nm, and the PtNPs are uniformly dispersed;
the XRD pattern of the nitrogen-doped platinum-carbon catalyst shows that the nitrogen-doped platinum-carbon catalyst only has a platinum simple substance phase and has no other impurity peaks;
the results of the contents of C, N and Pt elements in the nitrogen-doped platinum-carbon catalyst measured by ICP-OES and an element analyzer are shown in Table 2,
TABLE 2 partial element content in the catalyst
As can be seen from Table 2, the nitrogen content was as high as 5.7%, and the platinum content was close to the target loading;
the nitrogen-doped platinum-carbon catalyst is subjected to electrochemical test, the oxygen reduction half-wave potential and the mass specific current of the catalyst are respectively larger than commercial JM 20 wt% platinum carbon from a cyclic voltammetry curve and a linear sweep voltammetry curve, and after 10000 cycles of cyclic voltammetry sweep accelerated aging test, the catalyst shows smaller half-wave potential drop than the commercial platinum carbon.
Example 3: a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan comprises the following specific steps:
(1) dissolving chitosan in dilute acetic acid with the pH value of 4, adding a dispersing agent polyoxyethylene polyoxypropylene ether block copolymer, and uniformly stirring to obtain chitosan gel; wherein the solid-liquid ratio g: mL of the chitosan to the dilute acetic acid is 1:100, and the mass ratio of the chitosan to the dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer) is 1: 0.5;
(2) placing the chitosan gel obtained in the step (1) at the temperature of 90 ℃ for vacuum drying until the chitosan gel is anhydrous, and grinding the chitosan gel into powder to obtain chitosan gel powder;
(3) uniformly heating the chitosan gel powder in the step (2) to 300 ℃ at a speed of 15 ℃/min under the protection of nitrogen atmosphere, carrying out constant temperature treatment for 120min, then uniformly heating to 800 ℃ for 120 ℃ at constant temperature treatment, cooling to normal temperature along with a furnace, and grinding to obtain chitosan carbon powder;
(4) adding the chitosan carbon powder obtained in the step (3) into an ethanol solution containing polyalcohol (1, 2-propylene glycol) and a dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer), ultrasonically dispersing uniformly, adding a platinum precursor solution (potassium chloroplatinate solution), reacting at a constant temperature of 150 ℃ for 180min, washing the solid with deionized water at a temperature of 70-80 ℃ until the washing liquid is neutral, drying, grinding and sieving with a 800-mesh sieve to obtain the nitrogen-doped platinum-carbon catalyst; wherein the mass ratio of the chitosan carbon powder to the dispersing agent (polyoxyethylene polyoxypropylene ether segmented copolymer) is 1:0.5, the mass ratio of the chitosan carbon powder to the polyalcohol (1, 2-propylene glycol) is 1:15, the concentration of the platinum precursor solution (potassium chloroplatinate solution) is 0.1mol/L, and the solid-to-liquid ratio g: mL of the chitosan carbon powder to the platinum precursor solution (potassium chloroplatinate solution) is 1: 2.55;
as shown in a high-resolution transmission electron microscope picture of the nitrogen-doped platinum-carbon catalyst, the average particle size of PtNPs is 3.9nm, and the PtNPs are uniformly dispersed;
the XRD pattern of the nitrogen-doped platinum-carbon catalyst shows that the nitrogen-doped platinum-carbon catalyst only has a platinum simple substance phase and has no other impurity peaks; the results of the contents of C, N and Pt elements in the nitrogen-doped Pt-C catalyst measured by ICP-OES and an element analyzer are shown in Table 3,
TABLE 3 partial element content in catalyst
As can be seen from Table 3, the nitrogen content was as high as 5.1% and the platinum content was close to the target loading;
the nitrogen-doped platinum-carbon catalyst is subjected to electrochemical test, the oxygen reduction half-wave potential and the mass specific current of the catalyst are respectively larger than commercial JM 20 wt% platinum carbon from a cyclic voltammetry curve and a linear sweep voltammetry curve, and after 10000 cycles of cyclic voltammetry sweep accelerated aging test, the catalyst shows smaller half-wave potential drop than the commercial platinum carbon.
Example 4: a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan comprises the following specific steps:
(1) dissolving chitosan in dilute acetic acid with the pH value of 2, adding a dispersing agent polyoxyethylene polyoxypropylene ether block copolymer, and uniformly stirring to obtain chitosan gel; wherein the solid-liquid ratio g: mL of the chitosan to the dilute acetic acid is 1:150, and the mass ratio of the chitosan to the dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer) is 1: 1;
(2) placing the chitosan gel obtained in the step (1) at the temperature of 80 ℃ for vacuum drying until the chitosan gel is anhydrous, and grinding the chitosan gel into powder to obtain chitosan gel powder;
(3) uniformly heating the chitosan gel powder in the step (2) to 400 ℃ at a speed of 5 ℃/min under the protection of nitrogen atmosphere, carrying out constant temperature treatment for 120min, then uniformly heating to 900 ℃ for 180 ℃, carrying out furnace cooling to normal temperature, and grinding to obtain chitosan carbon powder;
(4) adding the chitosan carbon powder obtained in the step (3) into an ethanol solution containing polyol (glycerol) and a dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer), uniformly dispersing by ultrasonic waves, adding a platinum precursor solution (chloroplatinic acid solution), reacting at a constant temperature of 150 ℃ for 180min, washing the solid by deionized water at a temperature of 70-80 ℃ until the washing liquid is neutral, drying, grinding and sieving to obtain the nitrogen-doped platinum-carbon catalyst; wherein the mass ratio of the chitosan carbon powder to the dispersing agent (polyoxyethylene polyoxypropylene ether segmented copolymer) is 1:1, the mass ratio of the chitosan carbon powder to the polyalcohol (glycerol) is 1:10, the concentration of the platinum precursor solution (chloroplatinic acid solution) is 0.1mol/L, and the solid-to-liquid ratio g: mL of the chitosan carbon powder to the platinum precursor solution (chloroplatinic acid solution) is 1: 10.21;
as shown in a high-resolution transmission electron microscope picture of the nitrogen-doped platinum-carbon catalyst, the average particle size of PtNPs is 3.5nm, and the PtNPs are uniformly dispersed;
the XRD pattern of the nitrogen-doped platinum-carbon catalyst shows that the nitrogen-doped platinum-carbon catalyst only has a platinum simple substance phase and has no other impurity peaks; the results of the contents of C, N and Pt elements in the nitrogen-doped Pt-C catalyst measured by ICP-OES and an element analyzer are shown in Table 4,
TABLE 4 partial element content in catalyst
As can be seen from Table 4, the nitrogen content was as high as 5.8%, and the platinum content was close to the target loading;
the nitrogen-doped platinum-carbon catalyst is subjected to electrochemical test, the oxygen reduction half-wave potential and the mass specific current of the catalyst are respectively larger than commercial JM 20 wt% platinum carbon from a cyclic voltammetry curve and a linear sweep voltammetry curve, and after 10000 cycles of cyclic voltammetry sweep accelerated aging test, the catalyst shows smaller half-wave potential drop than the commercial platinum carbon.
Example 5: a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan comprises the following specific steps:
(1) dissolving chitosan in dilute acetic acid with the pH value of 3, adding sodium lignin sulfonate serving as a dispersing agent, and uniformly stirring to obtain chitosan gel; wherein the solid-liquid ratio g: mL of the chitosan to the dilute acetic acid is 1:100, and the mass ratio of the chitosan to the dispersing agent (sodium lignin sulfonate) is 1: 1;
(2) placing the chitosan gel obtained in the step (1) at the temperature of 80 ℃ for vacuum drying until the chitosan gel is anhydrous, and grinding the chitosan gel into powder to obtain chitosan gel powder;
(3) uniformly heating the chitosan gel powder in the step (2) to 350 ℃ at a speed of 10 ℃/min under the protection of nitrogen atmosphere, carrying out constant temperature treatment for 180min, then uniformly heating to 1000 ℃ for 120 ℃ at a constant temperature, carrying out furnace cooling to normal temperature, and grinding to obtain chitosan carbon powder;
(4) adding the chitosan carbon powder obtained in the step (3) into an ethanol solution containing polyalcohol (ethylene glycol) and a dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer), adding a platinum precursor solution (potassium chloroplatinate solution) after uniform ultrasonic dispersion, reacting at constant temperature of 120 ℃ for 240min, washing the solid with deionized water at the temperature of 70-80 ℃ until the washing liquid is neutral, drying, grinding and sieving to obtain a nitrogen-doped platinum-carbon catalyst; wherein the mass ratio of the chitosan carbon powder to the dispersing agent (polyoxyethylene polyoxypropylene ether segmented copolymer) is 1:2, the mass ratio of the chitosan carbon powder to the polyhydric alcohol (ethylene glycol) is 1:10, the concentration of the platinum precursor solution (potassium chloroplatinate solution) is 0.1mol/L, and the solid-to-liquid ratio g: mL of the chitosan carbon powder to the platinum precursor solution (potassium chloroplatinate solution) is 1: 2.55;
as shown in a high-resolution transmission electron microscope picture of the nitrogen-doped platinum-carbon catalyst, the average particle size of PtNPs is 4.0nm, and the PtNPs are uniformly dispersed;
the XRD pattern of the nitrogen-doped platinum-carbon catalyst shows that the nitrogen-doped platinum-carbon catalyst only has a platinum simple substance phase and has no other impurity peaks; the results of the contents of C, N and Pt elements in the nitrogen-doped Pt-C catalyst measured by ICP-OES and an element analyzer are shown in Table 5,
TABLE 5 partial element content in catalyst
As can be seen from Table 5, the nitrogen content was as high as 5.0% and the platinum content was close to the target loading;
the nitrogen-doped platinum-carbon catalyst is subjected to electrochemical test, the oxygen reduction half-wave potential and the mass specific current of the catalyst are respectively larger than commercial JM 20 wt% platinum carbon from a cyclic voltammetry curve and a linear sweep voltammetry curve, and after 10000 cycles of cyclic voltammetry sweep accelerated aging test, the catalyst shows smaller half-wave potential drop than the commercial platinum carbon.
Example 6: a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan comprises the following specific steps:
(1) dissolving chitosan in dilute hydrochloric acid with the pH value of 5, adding a dispersing agent polyoxyethylene polyoxypropylene ether segmented copolymer, and uniformly stirring to obtain chitosan gel; wherein the solid-to-liquid ratio g: mL of the chitosan to the dilute hydrochloric acid is 1:200, and the mass ratio of the chitosan to the dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer) is 1: 1.5;
(2) placing the chitosan gel obtained in the step (1) at the temperature of 80 ℃ for vacuum drying until the chitosan gel is anhydrous, and grinding the chitosan gel into powder to obtain chitosan gel powder;
(3) uniformly heating the chitosan gel powder in the step (2) to 200 ℃ at a speed of 2 ℃/min under the protection of nitrogen atmosphere, carrying out constant temperature treatment for 120min, then uniformly heating to 800 ℃ for 180 ℃, carrying out furnace cooling to normal temperature, and grinding to obtain chitosan carbon powder;
(4) adding the chitosan carbon powder obtained in the step (3) into an ethanol solution containing polyalcohol (ethylene glycol) and a dispersing agent (sodium lignosulfonate), adding a platinum precursor solution (potassium chloroplatinate solution) after ultrasonic dispersion is uniform, reacting for 180min at a constant temperature of 90 ℃, washing the solid with deionized water at a temperature of 70-80 ℃ until the washing liquid is neutral, drying, grinding and sieving to obtain a nitrogen-doped platinum-carbon catalyst; wherein the mass ratio of the chitosan carbon powder to the dispersing agent (sodium lignosulfonate) is 1:0.5, the mass ratio of the chitosan carbon powder to the polyhydric alcohol (ethylene glycol) is 1:10, the concentration of the platinum precursor solution (potassium chloroplatinate solution) is 0.1mol/L, and the solid-to-liquid ratio g: mL of the chitosan carbon powder to the platinum precursor solution (potassium chloroplatinate solution) is 1: 2.55;
as shown in a high-resolution transmission electron microscope picture of the nitrogen-doped platinum-carbon catalyst, the average particle size of PtNPs is 3.4nm, and the PtNPs are uniformly dispersed;
the XRD pattern of the nitrogen-doped platinum-carbon catalyst shows that the nitrogen-doped platinum-carbon catalyst only has a platinum simple substance phase and has no other impurity peaks; the results of the contents of C, N and Pt elements in the nitrogen-doped Pt-C catalyst measured by ICP-OES and an element analyzer are shown in Table 6,
TABLE 6 partial element content in catalyst
As can be seen from Table 6, the nitrogen content was as high as 5.3%, and the platinum content was close to the target loading;
the nitrogen-doped platinum-carbon catalyst is subjected to electrochemical test, the oxygen reduction half-wave potential and the mass specific current of the catalyst are respectively larger than commercial JM 20 wt% platinum carbon from a cyclic voltammetry curve and a linear sweep voltammetry curve, and after 10000 cycles of cyclic voltammetry sweep accelerated aging test, the catalyst shows smaller half-wave potential drop than the commercial platinum carbon.
Example 7: a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan comprises the following specific steps:
(1) dissolving chitosan in dilute sulfuric acid with the pH value of 5, adding a dispersant polyoxyethylene polyoxypropylene ether block copolymer, and uniformly stirring to obtain chitosan gel; wherein the solid-to-liquid ratio g: mL of the chitosan to the dilute sulfuric acid is 1:100, and the mass ratio of the chitosan to the dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer) is 1: 1;
(2) placing the chitosan gel obtained in the step (1) at the temperature of 80 ℃ for vacuum drying until the chitosan gel is anhydrous, and grinding the chitosan gel into powder to obtain chitosan gel powder;
(3) uniformly heating the chitosan gel powder in the step (2) to 350 ℃ at a speed of 5 ℃/min under the protection of nitrogen atmosphere, carrying out constant temperature treatment for 120min, then uniformly heating to 800 ℃ for 180 ℃, carrying out furnace cooling to normal temperature, and grinding to obtain chitosan carbon powder;
(4) adding the chitosan carbon powder obtained in the step (3) into an ethanol solution containing polyalcohol (ethylene glycol) and a dispersing agent (sodium lignosulfonate), adding a platinum precursor solution (potassium chloroplatinate solution) after ultrasonic dispersion is uniform, reacting for 180min at a constant temperature of 140 ℃, washing the solid with deionized water at a temperature of 70-80 ℃ until the washing liquid is neutral, drying, grinding, and sieving with a 800-mesh sieve to obtain the nitrogen-doped platinum-carbon catalyst; wherein the mass ratio of the chitosan carbon powder to the dispersing agent (sodium lignosulfonate) is 1:0.5, the mass ratio of the chitosan carbon powder to the polyhydric alcohol (ethylene glycol) is 1:10, the concentration of the platinum precursor solution (potassium chloroplatinate solution) is 0.1mol/L, and the solid-liquid ratio g: mL of the chitosan carbon powder to the platinum precursor solution (potassium chloroplatinate solution) is 1: 5.1;
as shown in a high-resolution transmission electron microscope picture of the nitrogen-doped platinum-carbon catalyst, the average particle size of PtNPs is 3.9nm, and the PtNPs are uniformly dispersed;
the XRD pattern of the nitrogen-doped platinum-carbon catalyst shows that the nitrogen-doped platinum-carbon catalyst only has a platinum simple substance phase and has no other impurity peaks; the results of the contents of C, N and Pt elements in the nitrogen-doped Pt-C catalyst measured by ICP-OES and an element analyzer are shown in Table 7,
TABLE 7 partial element content in catalyst
As can be seen from Table 7, the nitrogen content was as high as 5.0%, and the platinum content was close to the target loading;
the nitrogen-doped platinum-carbon catalyst is subjected to electrochemical test, the oxygen reduction half-wave potential and the mass specific current of the catalyst are respectively larger than commercial JM 20 wt% platinum carbon from a cyclic voltammetry curve and a linear sweep voltammetry curve, and after 10000 cycles of cyclic voltammetry sweep accelerated aging test, the catalyst shows smaller half-wave potential drop than the commercial platinum carbon.
Example 8: a method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan comprises the following specific steps:
(1) dissolving chitosan in dilute nitric acid with the pH value of 5, adding a dispersing agent polyoxyethylene polyoxypropylene ether block copolymer, and uniformly stirring to obtain chitosan gel; wherein the solid-to-liquid ratio g: mL of the chitosan to the dilute nitric acid is 1:100, and the mass ratio of the chitosan to the dispersing agent (polyoxyethylene polyoxypropylene ether block copolymer) is 1: 1;
(2) placing the chitosan gel obtained in the step (1) at the temperature of 80 ℃ for vacuum drying until the chitosan gel is anhydrous, and grinding the chitosan gel into powder to obtain chitosan gel powder;
(3) uniformly heating the chitosan gel powder in the step (2) to 250 ℃ at a speed of 15 ℃/min under the protection of nitrogen atmosphere, carrying out constant temperature treatment for 120min, then uniformly heating to 900 ℃ for constant temperature treatment for 180 ℃, carrying out furnace cooling to normal temperature, and grinding to obtain chitosan carbon powder;
(4) adding the chitosan carbon powder obtained in the step (3) into an ethanol solution containing polyalcohol (ethylene glycol) and a dispersing agent (water glass), adding a platinum precursor solution (potassium chloroplatinate solution) after ultrasonic dispersion is uniform, reacting for 180min at a constant temperature of 130 ℃, washing the solid with deionized water at a temperature of 70-80 ℃ until the washing liquid is neutral, drying, grinding and sieving to obtain a nitrogen-doped platinum-carbon catalyst; wherein the mass ratio of the chitosan carbon powder to the dispersing agent (water glass) is 1:0.5, the mass ratio of the chitosan carbon powder to the polyhydric alcohol (ethylene glycol) is 1:10, the concentration of the platinum precursor solution (potassium chloroplatinate solution) is 0.1mol/L, and the solid-to-liquid ratio g: mL of the chitosan carbon powder to the platinum precursor solution (potassium chloroplatinate solution) is 1: 25.5;
as shown in a high-resolution transmission electron microscope picture of the nitrogen-doped platinum-carbon catalyst, the average particle size of PtNPs is 3.5nm, and the PtNPs are uniformly dispersed;
the XRD pattern of the nitrogen-doped platinum-carbon catalyst shows that the nitrogen-doped platinum-carbon catalyst only has a platinum simple substance phase and has no other impurity peaks; the results of the contents of C, N and Pt elements in the nitrogen-doped Pt-C catalyst measured by ICP-OES and an element analyzer are shown in Table 8,
TABLE 7 partial element content in catalyst
As can be seen from Table 8, the nitrogen content was as high as 5.6% and the platinum content was close to the target loading;
the nitrogen-doped platinum-carbon catalyst is subjected to electrochemical test, the oxygen reduction half-wave potential and the mass specific current of the catalyst are respectively larger than commercial JM 20 wt% platinum carbon from a cyclic voltammetry curve and a linear sweep voltammetry curve, and after 10000 cycles of cyclic voltammetry sweep accelerated aging test, the catalyst shows smaller half-wave potential drop than the commercial platinum carbon.
While the present invention has been described in detail with reference to the specific embodiments thereof, it will be apparent to one skilled in the art that various changes and modifications can be made therein without departing from the spirit and scope thereof.
Claims (10)
1. A method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan is characterized by comprising the following specific steps:
(1) dissolving chitosan in dilute acid, adding a dispersing agent, and uniformly stirring to obtain chitosan gel;
(2) drying the chitosan gel obtained in the step (1) in vacuum until the chitosan gel is anhydrous, and grinding the chitosan gel into powder to obtain chitosan gel powder;
(3) under the protection of nitrogen atmosphere, uniformly heating the chitosan gel powder in the step (2) to 200-;
(4) adding the chitosan carbon powder in the step (3) into an ethanol solution containing polyalcohol and a dispersing agent, adding a platinum precursor solution after ultrasonic dispersion is uniform, reacting at the constant temperature of 70-150 ℃ for 100-240min, washing the solid with deionized water at the temperature of 70-80 ℃ until the washing liquid is neutral, drying, grinding and sieving to obtain the nitrogen-doped platinum-carbon catalyst.
2. The method for preparing the nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan according to claim 1, wherein: the diluted acid in the step (1) is hydrochloric acid, sulfuric acid, acetic acid or nitric acid, and the pH value of the diluted acid is 2-5.
3. The method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan according to claim 1 or 2, wherein: the solid-to-liquid ratio g/mL of the chitosan to the dilute acid in the step (1) is 1: 50-300.
4. The method for preparing the nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan according to claim 1, wherein: the dispersing agent in the step (1) and the step (1) is one or more of water glass, sodium hexametaphosphate, sodium lignosulfonate and polyoxyethylene polyoxypropylene ether block copolymer.
5. The method for preparing a nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan according to claim 1 or 4, wherein: the mass ratio of the chitosan to the dispersing agent in the step (1) is 1: 0.5-3.
6. The method for preparing the nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan according to claim 1, wherein: the constant temperature rise rate of the step (3) is 2-15 ℃/min.
7. The method for preparing the nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan according to claim 1, wherein: the mass ratio of the chitosan carbon powder to the dispersing agent in the step (4) is 1: 0.1-5.
8. The method for preparing the nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan according to claim 1, wherein: the polyhydric alcohol in the step (4) is one or more of ethylene glycol, polyethylene glycol, 1, 2-propylene glycol and glycerol, and the mass ratio of the chitosan carbon powder to the polyhydric alcohol is 1: 10-80.
9. The method for preparing the nitrogen-doped platinum-carbon catalyst by pyrolyzing chitosan according to claim 1, wherein: and (4) the platinum precursor is one or more of sodium chloroplatinate, potassium chloroplatinate and chloroplatinic acid, the concentration of the platinum precursor solution is 0.01-1mol/L, and the solid-to-liquid ratio g: mL of the chitosan carbon powder to the platinum precursor solution is 1: 2-30.
10. Use of a nitrogen-doped platinum-carbon catalyst prepared by the method of claims 1-9 as an oxygen reduction cathode catalyst.
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