CN109686992B - Preparation method of Pt/oxygen-doped carbon electrocatalyst based on organic alcohol carbonization - Google Patents
Preparation method of Pt/oxygen-doped carbon electrocatalyst based on organic alcohol carbonization Download PDFInfo
- Publication number
- CN109686992B CN109686992B CN201910001330.5A CN201910001330A CN109686992B CN 109686992 B CN109686992 B CN 109686992B CN 201910001330 A CN201910001330 A CN 201910001330A CN 109686992 B CN109686992 B CN 109686992B
- Authority
- CN
- China
- Prior art keywords
- organic alcohol
- oxygen
- doped carbon
- carbonization
- solution
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 title claims abstract description 73
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 45
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 44
- 239000010411 electrocatalyst Substances 0.000 title claims abstract description 32
- 238000003763 carbonization Methods 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 47
- 238000010438 heat treatment Methods 0.000 claims abstract description 23
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims abstract description 22
- 239000012279 sodium borohydride Substances 0.000 claims abstract description 21
- 229910000033 sodium borohydride Inorganic materials 0.000 claims abstract description 21
- 238000003756 stirring Methods 0.000 claims abstract description 21
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 20
- 239000001301 oxygen Substances 0.000 claims abstract description 20
- 238000006243 chemical reaction Methods 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000011780 sodium chloride Substances 0.000 claims abstract description 11
- 238000005406 washing Methods 0.000 claims abstract description 11
- KLFRPGNCEJNEKU-FDGPNNRMSA-L (z)-4-oxopent-2-en-2-olate;platinum(2+) Chemical compound [Pt+2].C\C([O-])=C\C(C)=O.C\C([O-])=C\C(C)=O KLFRPGNCEJNEKU-FDGPNNRMSA-L 0.000 claims abstract description 6
- 238000001816 cooling Methods 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 5
- 238000000227 grinding Methods 0.000 claims abstract description 5
- 238000010992 reflux Methods 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 3
- 239000000047 product Substances 0.000 claims description 30
- SBZXBUIDTXKZTM-UHFFFAOYSA-N diglyme Chemical compound COCCOCCOC SBZXBUIDTXKZTM-UHFFFAOYSA-N 0.000 claims description 24
- 229940068918 polyethylene glycol 400 Drugs 0.000 claims description 22
- 239000007787 solid Substances 0.000 claims description 8
- 239000002904 solvent Substances 0.000 claims description 8
- 239000006227 byproduct Substances 0.000 claims description 5
- 239000005456 alcohol based solvent Substances 0.000 claims description 4
- 239000002243 precursor Substances 0.000 claims description 3
- 238000005303 weighing Methods 0.000 claims description 2
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 claims 2
- 238000009833 condensation Methods 0.000 claims 1
- 230000005494 condensation Effects 0.000 claims 1
- 229910017053 inorganic salt Inorganic materials 0.000 claims 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 18
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 abstract description 12
- 239000003054 catalyst Substances 0.000 abstract description 10
- 239000000203 mixture Substances 0.000 abstract description 7
- 231100000572 poisoning Toxicity 0.000 abstract description 3
- 230000000607 poisoning effect Effects 0.000 abstract description 3
- 230000003647 oxidation Effects 0.000 abstract description 2
- 238000007254 oxidation reaction Methods 0.000 abstract description 2
- 230000000694 effects Effects 0.000 abstract 1
- 235000019441 ethanol Nutrition 0.000 description 25
- 230000015572 biosynthetic process Effects 0.000 description 12
- 238000003786 synthesis reaction Methods 0.000 description 12
- 125000005842 heteroatom Chemical group 0.000 description 8
- 238000011068 loading method Methods 0.000 description 6
- 238000000034 method Methods 0.000 description 6
- 150000003839 salts Chemical class 0.000 description 5
- 238000011065 in-situ storage Methods 0.000 description 4
- 230000004048 modification Effects 0.000 description 4
- 238000012986 modification Methods 0.000 description 4
- 239000004570 mortar (masonry) Substances 0.000 description 4
- 239000012265 solid product Substances 0.000 description 4
- 229910021642 ultra pure water Inorganic materials 0.000 description 4
- 239000012498 ultrapure water Substances 0.000 description 4
- 239000007810 chemical reaction solvent Substances 0.000 description 3
- 239000000463 material Substances 0.000 description 3
- 229910052697 platinum Inorganic materials 0.000 description 3
- 230000001360 synchronised effect Effects 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- 208000005374 Poisoning Diseases 0.000 description 2
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 2
- CUJRVFIICFDLGR-UHFFFAOYSA-N acetylacetonate Chemical compound CC(=O)[CH-]C(C)=O CUJRVFIICFDLGR-UHFFFAOYSA-N 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000010949 copper Substances 0.000 description 2
- 238000002484 cyclic voltammetry Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 239000012467 final product Substances 0.000 description 2
- 239000000446 fuel Substances 0.000 description 2
- 239000012456 homogeneous solution Substances 0.000 description 2
- 238000002329 infrared spectrum Methods 0.000 description 2
- 239000002245 particle Substances 0.000 description 2
- 229920005862 polyol Polymers 0.000 description 2
- 150000003077 polyols Chemical class 0.000 description 2
- 238000000634 powder X-ray diffraction Methods 0.000 description 2
- 239000002244 precipitate Substances 0.000 description 2
- 238000007789 sealing Methods 0.000 description 2
- 239000006228 supernatant Substances 0.000 description 2
- 238000012876 topography Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 208000001408 Carbon monoxide poisoning Diseases 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241000590428 Panacea Species 0.000 description 1
- OAICVXFJPJFONN-UHFFFAOYSA-N Phosphorus Chemical compound [P] OAICVXFJPJFONN-UHFFFAOYSA-N 0.000 description 1
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000003638 chemical reducing agent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000007791 liquid phase Substances 0.000 description 1
- 238000007040 multi-step synthesis reaction Methods 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 125000004430 oxygen atom Chemical group O* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 229910052698 phosphorus Inorganic materials 0.000 description 1
- 239000011574 phosphorus Substances 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 239000000843 powder Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
Images
Classifications
-
- H—ELECTRICITY
- 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
- H01M4/921—Alloys or mixtures with metallic elements
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/42—Platinum
-
- B01J35/33—
-
- H—ELECTRICITY
- 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
-
- 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
Abstract
The invention discloses a preparation method of a Pt/oxygen doped carbon electrocatalyst based on organic alcohol carbonization, which comprises the following steps: mixing and grinding 0.16g of platinum acetylacetonate and 2.0 g of sodium chloride uniformly, pouring the mixture into a 250mL three-neck round-bottom flask, adding 100mL of organic alcohol, stirring for 1-2 hours at room temperature, heating by using an oil bath, dropwise adding 1.0g of sodium borohydride dissolved in 50mL of organic alcohol solution when the temperature reaches 100 ℃, gradually turning yellow and blacking the solution along with the addition of the sodium borohydride, continuously heating to 150 ℃ after the addition is finished, refluxing for 10 hours at 150 ℃, naturally cooling to room temperature after the reaction is finished, washing the product for 3-5 times by using ethanol and water respectively, and drying in vacuum to obtain the Pt/oxygen doped carbon electrocatalyst based on organic alcohol carbonization. The catalyst obtained by the invention greatly improves the activity and the CO poisoning resistance of the catalyst in the electrocatalytic oxidation of methanol due to the doping of oxygen in carrier carbon.
Description
Technical Field
The invention belongs to the field of electrocatalytic materials, and particularly relates to a preparation method of a Pt/oxygen doped carbon electrocatalyst based on organic alcohol carbonization.
Background
The direct methanol fuel cell is widely recognized as a novel energy utilization mode due to the characteristics of high energy conversion efficiency, low pollutant emission, portability and the like. And Pt/C electrocatalysts have been the preferred catalyst material. But it shows poor CO poisoning resistance as an anode catalyst of a direct methanol fuel cell, thereby greatly decreasing its stability and durability, hindering its commercialization progress. At present, doping carrier carbon by utilizing heteroatoms (oxygen, nitrogen, sulfur, phosphorus and the like) is a very effective modification means, and the catalytic activity of the catalyst can be further improved while the CO poisoning resistance of the catalyst is improved. However, such modification often requires multiple steps: synthesis of a carbon carrier (such as graphene and the like which are commonly used at present), heteroatom doping of the carbon carrier, and loading of Pt on the carbon carrier. These steps not only increase the synthesis cost, but also cause easy loss of heteroatoms and Pt particles on the carbon support, reducing the stability of the catalyst. Therefore, the Pt/heteroatom doped carbon catalyst material is prepared by a simple one-step synthesis method, and the heteroatom doping and the platinum loading are synchronously synthesized in situ on the carbon carrier, so that the catalyst has more application potential, but the successful synthesis cases of in-situ synchronous loading and doping are rare, because the synthesis of the carbon carrier and the heteroatom doping generally need higher reaction temperature, and the Pt loading only needs room temperature or low temperature conditions, and the platinum can be agglomerated and grown at high temperature. The great difference of the synthesis conditions becomes the main brake for one-step synthesis of the Pt/doped carbon electrocatalyst, and the low-temperature synthesis modes of carbon carrier synthesis and heteroatom doping need to be explored urgently.
Disclosure of Invention
Aiming at the defects and shortcomings of the prior art, the invention mainly aims to provide a low-temperature one-step preparation method of a Pt/oxygen-doped carbon electrocatalyst based on organic alcohol carbonization. The key technology of the method lies in the use of the oxygen-rich organic polyol and the introduction of salt bath in an organism system, and utilizes lower temperature (150-oC) And a strong reduction system (sodium borohydride) enables the doping of oxygen atoms and the loading of platinum on a carbon carrier to realize synchronous in-situ synthesis. The invention not only can save the reaction time and reduce the reaction cost, but also can improve the methanol oxidation capability and the carbon monoxide poisoning resistance of the catalyst.
The invention provides a preparation method of a Pt/oxygen doped carbon electrocatalyst based on organic alcohol carbonization, which comprises the following steps:
A. weighing 0.16-0.32g of platinum acetylacetonate and 2.0-4.0 g of sodium chloride solid, mixing and grinding for 30 minutes, pouring into a 250mL three-neck round-bottom flask, adding 100mL of specified organic alcohol solvent, and stirring at room temperature for 1-2 hours;
B. the three-necked round-bottomed flask A was equipped with a condenser and a thermometer, and transferred to an oil bath heating apparatus at 5 DEGoHeating at a heating rate of C/min, stopping heating when the temperature reaches 100-110 ℃, dropwise adding 1.0g of sodium borohydride dissolved in 50ml of specified organic alcohol, and finishing the adding within 10-20 min;
C. continuing the B solution at 5oHeating to 150-160 ℃ at the speed of C/min, refluxing for 10 hours at the temperature of 150-160 ℃, and naturally cooling to room temperature after the reaction is finished to obtain a first primary product;
D. the first primary product obtained from the step CWashing the product with ethanol and water for 3-5 times respectively at 80 deg.CoAnd C, drying in a vacuum oven for 12 hours to obtain the Pt/oxygen doped carbon electrocatalyst based on organic alcohol carbonization.
Further, the organic alcohol solvent in the step A is diethylene glycol dimethyl ether or polyethylene glycol 400.
Further, in the step A, the platinum acetylacetonate, the sodium chloride and the organic alcohol are stirred for 1-2 hours at room temperature, and the stirring time is set to be 1 hour for the diethylene glycol dimethyl ether solution and 2 hours for the polyethylene glycol 400 solution aiming at different organic alcohol solvents with different viscosities and solubilities.
Further, the stirring in the step A is strong stirring, and the speed is more than 600 revolutions per minute.
Further, the organic alcohol in the step B is the alcohol type added in the step A.
Further, 1.0g of sodium borohydride dissolved in 50ml of specified organic alcohol is added dropwise in the step B, the addition is completed within 10-20 minutes, the viscosity and the volume of the liquid drop are different for different organic alcohol solvents, and the dropwise adding time is 10 minutes for the diethylene glycol dimethyl ether solution; polyethylene glycol 400 solution for 20 minutes.
Further, the first primary product is washed with ethanol and water respectively in step D, and the purpose of the washing with ethanol is to remove the polyol solvent and the excess organic precursor and possible organic byproducts; washing with water removes excess inorganic salts such as NaCl and possible inorganic by-products.
Further, in the step D, the first primary product is washed 3-5 times with ethanol and water respectively, the primary product obtained in the diethylene glycol dimethyl ether solution is washed 3 times with ethanol and water respectively, and the primary product obtained in the polyethylene glycol 400 solution is washed 5 times with ethanol and water respectively.
The method adopts oxygen-rich organic alcohol as a reaction solvent, which is a carbon carrier source and an oxygen-doped precursor; sodium chloride is used as a medium of the salt bath, so that the carbonization temperature of organic matters can be effectively reduced, and the dispersion degree of Pt can be greatly improved; sodium borohydride is used as a reducing agent, and the heating (150-oC) Salt bath/Strong reductionThe original system promotes the accelerated carbonization of organic matters, and simultaneously leads the doping of oxygen and the reduction of Pt to synchronously occur, namely realizing the synchronous in-situ synthesis of oxygen doping and Pt loading on a carbon carrier. The method is based on organic alcohol liquid phase heating (150-oC) The Pt/oxygen-doped carbon electrocatalyst is synthesized in one step by a salt bath/strong reduction system, three major disadvantages of the traditional multi-step synthesis method (high cost, small yield, easy shedding of doped heteroatom and Pt particles) are avoided, no physical medium or equipment is introduced in the synthesis process, and the synthesis cost is greatly reduced; the reaction byproducts are few, and simultaneously, the solvent (organic alcohol), excessive NaCl and the like can be easily removed by washing with ethanol and water for many times, so that the purity of the product is greatly improved; moreover, the yield of the reaction is up to more than 90 percent, and the method can be popularized in the industry.
Drawings
FIG. 1 shows a diagram of an experimental setup for a Pt/oxygen doped carbon electrocatalyst reaction based on organic alcohol carbonization;
FIG. 2 shows an X-ray powder diffraction pattern of the Pt/oxygen-doped carbon electrocatalyst of example 1;
FIG. 3 shows a transmission electron microscopy topography of the Pt/oxygen doped carbon electrocatalyst of example 1;
FIG. 4 shows an X-ray photoelectron spectrum of the Pt/oxygen-doped carbon electrocatalyst in example 1;
FIG. 5 shows an IR spectrum of a Pt/oxygen doped carbon electrocatalyst according to example 1;
FIG. 6 shows cyclic voltammograms of the Pt/oxygen doped carbon electrocatalyst of example 1;
FIG. 7 shows an X-ray powder diffraction pattern of a Pt/oxygen-doped carbon electrocatalyst according to example 2;
FIG. 8 shows a transmission electron microscopy topography of a Pt/oxygen doped carbon electrocatalyst according to example 2;
FIG. 9 shows an X-ray photoelectron spectrum of the Pt/oxygen-doped carbon electrocatalyst according to example 2;
FIG. 10 shows an IR spectrum of a Pt/oxygen doped carbon electrocatalyst according to example 2;
FIG. 11 shows the cyclic voltammogram of the Pt/oxygen doped carbon electrocatalyst of example 2;
the specific implementation mode is as follows:
the invention is described in further detail below by way of specific examples in conjunction with the following figures:
example 1
Step 101, weigh 0.16g of platinum acetylacetonate (Pt (acac))2) 2.0 g of sodium chloride (NaCl) is poured into a mortar and ground for 30 minutes, so that the two solids are fully and uniformly mixed;
102, pouring the ground solid in the last step into a 250ml three-necked bottle, adding 100ml of diethylene glycol dimethyl ether, putting a magneton, putting the three-necked bottle on a magnetic stirrer, and stirring for 60 minutes at a stirring speed of 600 revolutions per minute to ensure that the solid in the three-necked bottle is uniformly dispersed in the diethylene glycol dimethyl ether;
103, putting a three-mouth bottle into an oil bath, placing a spherical condenser pipe at the middle port of the three-mouth bottle, sealing the left port by using a plug, placing a thermometer (shown in figure 1) with the measuring range of 300 ℃ at the right port, heating the oil bath kettle at the heating rate of 5 ℃ per minute, controlling the stirring speed at 600 revolutions per minute, and heating the solution to 100-;
step 104, weigh 1.0g sodium borohydride (NaBH)4) Pouring the mixture into a mortar, grinding for five minutes, adding the mixture into a beaker filled with 50ml of diethylene glycol dimethyl ether solution, placing the beaker on a magnetic stirrer and stirring for 10 minutes to completely dissolve sodium borohydride in the diethylene glycol dimethyl ether to form homogeneous solution;
105, dropwise adding sodium borohydride dissolved in diethylene glycol dimethyl ether into the reaction solution at the temperature of 110 ℃ in the step 103 by using a dropper (0.05 mL/drop), wherein the dropwise addition is completed within 10 minutes, and the color of the solution turns yellow and then turns grey;
in other embodiments, sodium borohydride dissolved in polyethylene glycol 400 can be used to replace sodium borohydride dissolved in diethylene glycol dimethyl ether, but the addition of sodium borohydride in polyethylene glycol 400 is slow due to its high viscosity, which requires 20 minutes to complete.
Step 106, continuously heating the solution obtained in the step 105 to 150-160 ℃ at a temperature rising speed of 5 ℃, keeping the temperature constant, refluxing for 10 hours, and gradually changing the color of the solution into black to obtain a black precipitate (a first initial product);
step 107: cooling the solution reacted in the step 106 to room temperature, then pouring the solution after the reaction into a centrifuge tube, centrifuging at the speed of 9000 r/min for 10 min, and after the centrifugation is finished, pouring out the supernatant to leave the residual solid product (second primary product);
step 108: alternately washing the second product with ultrapure water and absolute ethyl alcohol respectively, washing the second product for 3 times respectively, and centrifuging the second product at a speed of 9000 revolutions per minute to obtain a washed solid product (a third initial product);
in other embodiments, if polyethylene glycol 400 is used as the reaction solvent, the sample is washed 5 times with ultrapure water and ethanol, to ensure that the sample is washed clean.
Step 109: and (3) placing the third primary product in a vacuum oven at 80 ℃ and drying for 12 hours to obtain a final product Pt/oxygen-doped carbon electrocatalyst.
Next, the composition, structure and performance of the resulting Pt/oxygen-doped carbon electrocatalyst were characterized:
characterization of the product phase was performed using a Panalytical Empyream (Cu copper target, 40 kV, 40 mA) powder diffractometer from the family panacea, as shown in fig. 2 and 7;
the product morphology was analyzed using a high resolution transmission electron microscope, FEITecnai F20 (200 kV), USA, as shown in FIGS. 3 and 8.
The product composition and surface chemistry analysis was performed using a Japan Shimadzu AXIS-ULTRADLD multifunctional photoelectron spectrometer and a PerkinElmer Fourier Infrared spectrometer, such as FIG. 4, FIG. 5, FIG. 9 and FIG. 10.
The electrochemical properties of the products were tested using the rotolab PGSTAT302N electrochemical workstation, wangtong, switzerland, as shown in fig. 6 and 11;
example 2
Step 201, weigh 0.32g of platinum acetylacetonate (Pt (acac))2) 4.0 g of sodium chloride (NaCl) is poured into a mortar and ground for 30 minutes, and the two solids are fully and uniformly mixed;
step 202, pouring the ground solid in the last step into a 250ml three-necked bottle, adding 100ml of diethylene glycol dimethyl ether, adding magnetons, placing the three-necked bottle on a magnetic stirrer, and stirring for 60 minutes at a stirring speed of 600 revolutions per minute to ensure that the solid in the three-necked bottle is uniformly dispersed in the diethylene glycol dimethyl ether;
Step 203, putting the three-mouth bottle into an oil bath, placing a spherical condenser pipe at the middle port of the three-mouth bottle, sealing the left port by using a plug, placing a thermometer (shown in figure 1) with the measuring range of 300 ℃ at the right port, heating the oil bath kettle at the heating rate of 5 ℃ per minute, controlling the stirring speed at 600 revolutions per minute, and heating the solution to 110 ℃ at 100-;
step 204, weigh 1.0g sodium borohydride (NaBH)4) Pouring the mixture into a mortar, grinding for five minutes, adding the mixture into a beaker filled with 50ml of diethylene glycol dimethyl ether solution, placing the beaker on a magnetic stirrer and stirring for 10 minutes to completely dissolve sodium borohydride in the diethylene glycol dimethyl ether to form homogeneous solution;
Step 205, dropwise adding sodium borohydride dissolved in diethylene glycol dimethyl ether into the reaction solution at the temperature of 100 ℃ and 110 ℃ in the step 203 by using a dropper (0.05 mL/drop), completing dropwise adding within 10 minutes, wherein the color of the solution turns yellow and then turns grey;
in other embodiments, sodium borohydride dissolved in polyethylene glycol 400 can be used to replace sodium borohydride dissolved in diethylene glycol dimethyl ether, but the addition of sodium borohydride in polyethylene glycol 400 is slow due to its high viscosity, which requires 20 minutes to complete.
Step 206, heating the solution obtained in step 205 to 150-160 ℃ at a heating rate of 5 ℃, keeping the temperature constant, refluxing for 10 hours, and gradually changing the color of the solution to black to obtain a black precipitate (a first initial product);
step 207: cooling the solution reacted in the step 206 to room temperature, then pouring the solution after the reaction into a centrifuge tube, centrifuging at the speed of 9000 r/min for 10 min, and after the centrifugation is finished, pouring out the supernatant to leave the residual solid product (second primary product);
step 208: alternately washing the second product with ultrapure water and absolute ethyl alcohol respectively, washing the second product for 3 times respectively, and centrifuging the second product at a speed of 9000 revolutions per minute to obtain a washed solid product (a third initial product);
in other embodiments, if polyethylene glycol 400 is used as the reaction solvent, the sample is washed 5 times with ultrapure water and ethanol, to ensure that the sample is washed clean.
Step 209: and (3) placing the third primary product in a vacuum oven at 80 ℃ and drying for 12 hours to obtain a final product Pt/oxygen-doped carbon electrocatalyst.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (6)
1. The preparation method of the Pt/oxygen doped carbon electrocatalyst based on organic alcohol carbonization is characterized by comprising the following steps:
A. weighing 0.16-0.32g of platinum acetylacetonate and 2.0-4.0 g of sodium chloride solid, mixing and grinding for 30 minutes, pouring into a 250mL three-neck round-bottom flask, adding 100mL of specified organic alcohol solvent, and stirring at room temperature for 1-2 hours;
B. b, configuring a condensation tube and a thermometer on the three-neck round-bottom flask in the step A, transferring the flask into an oil bath heating device, heating at the heating speed of 5 ℃/min, stopping heating when the temperature reaches 100-;
C. continuously heating the solution obtained in the step B to 150-160 ℃ at the speed of 5 ℃/min, refluxing for 10 hours at the temperature of 150-160 ℃, and naturally cooling to room temperature after the reaction is finished to obtain a first initial product;
D. washing the first primary product obtained in the step C with ethanol and water for 3-5 times respectively at 80 deg.CoC, drying in a vacuum oven for 12 hours to obtain a Pt/oxygen doped carbon electrocatalyst based on organic alcohol carbonization;
the organic alcohol solvent in the step A is diethylene glycol dimethyl ether or polyethylene glycol 400, and the organic alcohol in the step B is the organic alcohol solvent added in the step A.
2. The organic alcohol carbonization-based Pt/oxygen-doped carbon electrocatalyst preparation method according to claim 1, wherein:
the stirring time set for different organic alcohol solvents in step a is: diethylene glycol dimethyl ether solution for 1 hour, polyethylene glycol 400 solution for 2 hours.
3. The organic alcohol carbonization-based Pt/oxygen-doped carbon electrocatalyst preparation method according to claim 2, wherein:
the stirring is strong stirring, and the speed is more than 600 revolutions per minute.
4. The organic alcohol carbonization-based Pt/oxygen-doped carbon electrocatalyst preparation method according to claim 1, wherein:
and step B, dropwise adding 1.0g of sodium borohydride dissolved in 50ml of specified organic alcohol, and finishing the addition within 10-20 minutes, wherein the dropwise adding time set for different organic alcohol solvents is as follows: diethylene glycol dimethyl ether solution for 10 minutes; polyethylene glycol 400 solution for 20 minutes.
5. The organic alcohol carbonization-based Pt/oxygen-doped carbon electrocatalyst preparation method according to claim 1, wherein:
and D, washing by using ethanol to remove the organic alcohol solvent, the excessive organic precursor and the organic byproduct, and washing by using water to remove the excessive inorganic salt and the inorganic byproduct.
6. The organic alcohol carbonization-based Pt/oxygen-doped carbon electrocatalyst preparation method according to claim 1, wherein:
in the step D, the primary product obtained in the diethylene glycol dimethyl ether solution is washed with ethanol and water for 3 times respectively, and the primary product obtained in the polyethylene glycol 400 solution is washed with ethanol and water for 5 times respectively.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910001330.5A CN109686992B (en) | 2019-01-02 | 2019-01-02 | Preparation method of Pt/oxygen-doped carbon electrocatalyst based on organic alcohol carbonization |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910001330.5A CN109686992B (en) | 2019-01-02 | 2019-01-02 | Preparation method of Pt/oxygen-doped carbon electrocatalyst based on organic alcohol carbonization |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN109686992A CN109686992A (en) | 2019-04-26 |
| CN109686992B true CN109686992B (en) | 2021-09-24 |
Family
ID=66190393
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910001330.5A Expired - Fee Related CN109686992B (en) | 2019-01-02 | 2019-01-02 | Preparation method of Pt/oxygen-doped carbon electrocatalyst based on organic alcohol carbonization |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN109686992B (en) |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101288849A (en) * | 2008-05-09 | 2008-10-22 | 南京大学 | Carbon nitrogen nano fiber loaded platinum ruthenium nano particle electrode catalyst and preparation method |
| CN105597827A (en) * | 2015-10-19 | 2016-05-25 | 华南理工大学 | Xylose hydrothermal carbonized microsphere supported palladium catalyst, and preparation method and application thereof |
| CN106299385A (en) * | 2016-08-26 | 2017-01-04 | 南京理工大学 | N doping carbonization bacterial cellulose loaded nanometer platinum electrode material and preparation method thereof |
-
2019
- 2019-01-02 CN CN201910001330.5A patent/CN109686992B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101288849A (en) * | 2008-05-09 | 2008-10-22 | 南京大学 | Carbon nitrogen nano fiber loaded platinum ruthenium nano particle electrode catalyst and preparation method |
| CN105597827A (en) * | 2015-10-19 | 2016-05-25 | 华南理工大学 | Xylose hydrothermal carbonized microsphere supported palladium catalyst, and preparation method and application thereof |
| CN106299385A (en) * | 2016-08-26 | 2017-01-04 | 南京理工大学 | N doping carbonization bacterial cellulose loaded nanometer platinum electrode material and preparation method thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN109686992A (en) | 2019-04-26 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Maleki et al. | Transesterification of canola oil and methanol by lithium impregnated CaO–La2O3 mixed oxide for biodiesel synthesis | |
| EP2786999B1 (en) | Sulphonate based compound, polymer electrolyte membrane comprising same and fuel cell comprising same | |
| Feng et al. | Production of γ-valerolactone from levulinic acid over a Ru/C catalyst using formic acid as the sole hydrogen source | |
| CN110947427B (en) | Metal-ligand co-catalysis by nitrogen-hydrogen arm deprotonation/pyridine dearomatization for efficient hydrogen generation from formic acid | |
| CN105047953A (en) | Non-noble metal-nitrogen-carbon oxygen reduction catalyst and preparation method thereof | |
| CN112877714B (en) | Double-defect ultrathin metal organic framework nanosheet catalyst and preparation method and application thereof | |
| CN110767911A (en) | Preparation method of novel CoZn bimetal MOF material and polyaniline composite electrode material | |
| CN103319379A (en) | Process for synthesizing anthraquinone compound | |
| CN114892187B (en) | Method for electrochemically synthesizing imidazole polycyclic aromatic compounds | |
| CN109686992B (en) | Preparation method of Pt/oxygen-doped carbon electrocatalyst based on organic alcohol carbonization | |
| CN110773202A (en) | Preparation method of yolk-shell structured nickel-molybdenum bimetallic sulfide applied to water cracking | |
| Liu et al. | Large particle spherical poly-ionic liquid–solid base catalyst for high-efficiency transesterification of ethylene carbonate to prepare dimethyl carbonate | |
| CN115536860B (en) | Biological MOF material for electrocatalysis and photocatalysis, and preparation method and application thereof | |
| CN109453757B (en) | CO (carbon monoxide)2Nano composite catalyst for high-efficiency conversion into cyclic carbonate and preparation method thereof | |
| CN110665525A (en) | Perovskite of composite carbon nitride photocatalytic material and preparation method and application thereof | |
| CN105552385B (en) | Boron doping carbon material and its preparation method and application | |
| CN108671962A (en) | A method of based on graphene-supported modified COFs bases elctro-catalyst catalytic performance | |
| CN111744553B (en) | Zirconium dodecylbenzene sulfonate catalyst and application thereof in furfuryl alcohol alcoholysis reaction | |
| CN110380005B (en) | Organic lithium-rich cathode material, preparation method and application thereof | |
| CN111203267B (en) | Solid acid catalyst for catalyzing decarboxylation of gamma-valerolactone to prepare butene, and preparation method and application thereof | |
| Fu et al. | Edge-engineering of donor-acceptor sp2-carbon-conjugated covalent organic frameworks for high-performance photocatalysts | |
| CN113957461A (en) | Electrochemical synthesis method of 1,1' -binaphthyl compound | |
| JP2021130062A (en) | Carbon catalyst carrying polyazine, and catalyst electrode therewith | |
| CN114573796B (en) | Tris (4-ethynylphenyl) amine conjugated microporous polymer, preparation method and application | |
| CN104327802A (en) | Novel high-molecular quasi-solid-solid phase transition material and chemical preparation method |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20210924 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |