CN117039030A - Preparation method and application of N, S-doped porous carbon-loaded platinum alloy nano particles - Google Patents
Preparation method and application of N, S-doped porous carbon-loaded platinum alloy nano particles Download PDFInfo
- Publication number
- CN117039030A CN117039030A CN202311160218.9A CN202311160218A CN117039030A CN 117039030 A CN117039030 A CN 117039030A CN 202311160218 A CN202311160218 A CN 202311160218A CN 117039030 A CN117039030 A CN 117039030A
- Authority
- CN
- China
- Prior art keywords
- porous carbon
- doped porous
- platinum alloy
- mercaptobenzimidazole
- amino
- 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.)
- Pending
Links
- 229910052757 nitrogen Inorganic materials 0.000 title claims abstract description 37
- 239000002105 nanoparticle Substances 0.000 title claims abstract description 26
- 229910001260 Pt alloy Inorganic materials 0.000 title claims abstract description 22
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 20
- 229910052799 carbon Inorganic materials 0.000 title claims abstract description 18
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 19
- BXDMTLVCACMNJO-UHFFFAOYSA-N 5-amino-1,3-dihydrobenzimidazole-2-thione Chemical compound NC1=CC=C2NC(S)=NC2=C1 BXDMTLVCACMNJO-UHFFFAOYSA-N 0.000 claims abstract description 17
- 238000000034 method Methods 0.000 claims abstract description 16
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000002131 composite material Substances 0.000 claims abstract description 14
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 12
- 239000007864 aqueous solution Substances 0.000 claims abstract description 10
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000001301 oxygen Substances 0.000 claims abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 claims abstract description 9
- 238000000197 pyrolysis Methods 0.000 claims abstract description 9
- 238000001354 calcination Methods 0.000 claims abstract description 8
- 239000012298 atmosphere Substances 0.000 claims abstract description 7
- 239000007800 oxidant agent Substances 0.000 claims abstract description 7
- 230000001590 oxidative effect Effects 0.000 claims abstract description 7
- 238000003756 stirring Methods 0.000 claims abstract description 6
- 150000003057 platinum Chemical class 0.000 claims abstract description 5
- 239000002243 precursor Substances 0.000 claims abstract description 5
- 229910052723 transition metal Inorganic materials 0.000 claims abstract description 5
- -1 transition metal salt Chemical class 0.000 claims abstract description 5
- 238000001035 drying Methods 0.000 claims abstract description 3
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 3
- 238000001132 ultrasonic dispersion Methods 0.000 claims abstract description 3
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical group [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 12
- 239000000203 mixture Substances 0.000 claims description 10
- 238000006722 reduction reaction Methods 0.000 claims description 9
- 229910052739 hydrogen Inorganic materials 0.000 claims description 8
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 6
- 239000007789 gas Substances 0.000 claims description 6
- 239000001257 hydrogen Substances 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 239000000243 solution Substances 0.000 claims description 5
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical group 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 4
- 229910052708 sodium Inorganic materials 0.000 claims description 4
- 239000011734 sodium Substances 0.000 claims description 4
- 229910052786 argon Inorganic materials 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 3
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 3
- 229910021578 Iron(III) chloride Inorganic materials 0.000 claims description 2
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 2
- 238000010438 heat treatment Methods 0.000 claims description 2
- 238000003837 high-temperature calcination Methods 0.000 claims description 2
- RBTARNINKXHZNM-UHFFFAOYSA-K iron trichloride Chemical compound Cl[Fe](Cl)Cl RBTARNINKXHZNM-UHFFFAOYSA-K 0.000 claims description 2
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 abstract description 50
- 229910052697 platinum Inorganic materials 0.000 abstract description 20
- 230000003197 catalytic effect Effects 0.000 abstract description 9
- 230000009467 reduction Effects 0.000 abstract description 6
- 239000002245 particle Substances 0.000 abstract description 5
- 239000000446 fuel Substances 0.000 abstract description 3
- 238000006555 catalytic reaction Methods 0.000 abstract description 2
- 239000003054 catalyst Substances 0.000 description 32
- 229910045601 alloy Inorganic materials 0.000 description 12
- 239000000956 alloy Substances 0.000 description 12
- 230000000694 effects Effects 0.000 description 11
- 229910002837 PtCo Inorganic materials 0.000 description 9
- 229910052593 corundum Inorganic materials 0.000 description 6
- 239000010431 corundum Substances 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 229910052573 porcelain Inorganic materials 0.000 description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 6
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000008367 deionised water Substances 0.000 description 4
- 229910021641 deionized water Inorganic materials 0.000 description 4
- 239000003792 electrolyte Substances 0.000 description 4
- QWPPOHNGKGFGJK-UHFFFAOYSA-N hypochlorous acid Chemical compound ClO QWPPOHNGKGFGJK-UHFFFAOYSA-N 0.000 description 4
- 230000000670 limiting effect Effects 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000002441 X-ray diffraction Methods 0.000 description 3
- 230000002776 aggregation Effects 0.000 description 3
- 230000009286 beneficial effect Effects 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000011068 loading method Methods 0.000 description 3
- 239000002923 metal particle Substances 0.000 description 3
- 238000002336 sorption--desorption measurement Methods 0.000 description 3
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000005054 agglomeration Methods 0.000 description 2
- 150000001721 carbon Chemical class 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 125000005842 heteroatom Chemical group 0.000 description 2
- 239000012299 nitrogen atmosphere Substances 0.000 description 2
- 230000010287 polarization Effects 0.000 description 2
- 239000011148 porous material Substances 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 239000011833 salt mixture Substances 0.000 description 2
- 239000000725 suspension Substances 0.000 description 2
- 238000012546 transfer Methods 0.000 description 2
- 238000003917 TEM image Methods 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000004873 anchoring Methods 0.000 description 1
- 238000000137 annealing Methods 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000012512 characterization method Methods 0.000 description 1
- 239000007809 chemical reaction catalyst Substances 0.000 description 1
- XYVDNBKDAAXMPG-UHFFFAOYSA-M decyl 2-(1-heptylazepan-1-ium-1-yl)acetate;hydroxide Chemical compound [OH-].CCCCCCCCCCOC(=O)C[N+]1(CCCCCCC)CCCCCC1 XYVDNBKDAAXMPG-UHFFFAOYSA-M 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 239000012621 metal-organic framework Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000003980 solgel method Methods 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000009827 uniform distribution Methods 0.000 description 1
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
- H01M4/925—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
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- 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
-
- 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 N, S-doped porous carbon-loaded platinum alloy nano particles, and relates to the technical field of fuel cell catalysis. The method comprises the following steps: step 1, dissolving 5-amino-2-mercaptobenzimidazole in a hydrochloric acid aqueous solution, vigorously stirring, dropwise adding an oxidant, and performing oxidative polymerization reaction to obtain poly-5-amino-2-mercaptobenzimidazole; step 2, placing poly-5-amino-2-mercaptobenzimidazole in a tubular furnace, and performing pyrolysis under the condition of inert atmosphere to obtain an N, S co-doped porous carbon material NSPC; step 3, adding the N, S co-doped porous carbon material NSPC into the aqueous solution, and performing ultrasonic dispersion; and then adding platinum salt and a transition metal salt precursor, stirring, distilling under reduced pressure, drying, transferring to a tube furnace, and calcining at high temperature to obtain the N, S co-doped porous carbon-loaded platinum alloy nanoparticle composite material. The composite material prepared by the method is easy to prepare in large scale, platinum particles are not easy to agglomerate, and the composite material has high oxygen reduction catalytic activity.
Description
Technical Field
The invention relates to the technical field of fuel cell catalysis, in particular to a preparation method and application of N, S-doped porous carbon-loaded platinum alloy nano particles.
Background
In order to facilitate large-scale application of fuel cell technology, it is necessary to develop a highly active oxygen reduction reaction catalyst. At present, the catalyst with highest catalytic activity is still a platinum-based catalyst, and development of a catalyst with low platinum loading and high activity is the focus of research in the field. In platinum-based catalysts, the crystal form and particle size of the platinum have a crucial influence on the catalytic activity. Through reasonable design and method regulation, a platinum-based catalyst with rich active crystal faces is developed, the platinum loading is reduced on the premise of ensuring high activity, and the method has very important significance for promoting the commercial application of the platinum-based catalyst.
Porous carbon is a material with high surface area, light weight and chemical stability, and is a good carrier for platinum nanoparticles. Compared with other carbon carriers, the mesoporous carbon-supported platinum alloy has the following advantages: (1) The abundant pore structures can form a limiting effect on the nano particles, so that the aggregation of the particles is reduced; (2) The large specific surface area is beneficial to exposing more active sites, promotes mass transfer and has good promotion effect on improving the activity of the catalyst. And (3) the carbon material is cheap and easy to obtain, and the preparation cost is low. At present, a plurality of preparation methods are reported to be used for preparing the carbon-supported platinum-based composite catalyst, such as a sol-gel method, a solvothermal method, a KCl auxiliary annealing method, a metal-organic framework limiting co-reduction method and the like. However, these preparation methods still have the following problems in the preparation process:
(1) Platinum metal particles are easy to agglomerate in the preparation process, and the catalytic activity is influenced;
(2) The macro preparation difficulty is high, the preparation cost is high, and the practical application is limited;
(3) The Pt mass specific activity in the catalyst is low.
Accordingly, those skilled in the art have been working to develop a platinum-based composite catalyst which is easy to mass-produce, in which platinum metal particles are not easily agglomerated, and which has high oxygen reduction catalytic activity.
Disclosure of Invention
In view of the above-mentioned drawbacks of the prior art, the present invention aims to develop a platinum-based composite catalyst which is easy for mass preparation, has a uniform distribution of platinum metal particles, and has a high catalytic activity.
In order to achieve the above purpose, the invention provides a preparation method of N, S-doped porous carbon-loaded platinum alloy nano particles, which comprises the following steps:
step 1, dissolving 5-amino-2-mercaptobenzimidazole in a hydrochloric acid aqueous solution, vigorously stirring, dropwise adding an oxidant, and performing oxidative polymerization reaction to obtain poly-5-amino-2-mercaptobenzimidazole;
step 2, placing the poly 5-amino-2-mercaptobenzimidazole prepared in the step 1 into a tubular furnace, and performing pyrolysis under the condition of inert atmosphere to prepare an N, S co-doped porous carbon material NSPC;
step 3, adding the N, S co-doped porous carbon material NSPC prepared in the step 2 into an aqueous solution, and performing ultrasonic dispersion; and then adding platinum salt and a transition metal salt precursor, stirring, distilling under reduced pressure, drying, transferring to a tube furnace, and calcining at high temperature to obtain the N, S co-doped porous carbon-loaded platinum alloy nanoparticle composite material.
In a preferred embodiment of the present invention, in step 1, the oxidizing agent is ammonium persulfate.
In a preferred embodiment of the present invention, the mass ratio of the 5-amino-2-mercaptobenzimidazole to the ammonium persulfate is 1:3.
in a preferred embodiment of the present invention, in step 1, the concentration of the aqueous hydrochloric acid solution is 0.1mol/L, the reaction temperature is room temperature, the reaction time is 4-10 hours, and the reaction time is preferably 8 hours.
In another preferred embodiment of the present invention, in step 2, the pyrolysis temperature is 800-1000 ℃, the pyrolysis time is more than 1h, preferably the pyrolysis temperature is 900 ℃, and the pyrolysis time is 2h.
Further, in the step 2, the heating rate of the tube furnace is 2 ℃/min.
In another preferred embodiment of the present invention, in step 3, the mass-to-volume ratio of the N, S co-doped porous carbon material NSPC to the aqueous solution is 1:3.
In step 3, the platinum salt is sodium chloroplatinate, and the transition metal salt precursor is any one of cobalt chloride, copper chloride, ferric chloride and nickel chloride.
In step 3, the high-temperature calcination atmosphere is argon-hydrogen mixture gas, wherein the argon-hydrogen mixture gas contains 5% of H by volume 2 And 95% by volume of Ar, the calcination temperature is 600 ℃, the calcination time is more than 1h, and the calcination time is preferably 2h.
In addition, the invention also discloses application of the N, S-doped porous carbon-loaded platinum alloy nano particles prepared by the method in electrocatalytic oxygen reduction reaction.
Compared with the prior art, the invention has the following beneficial effects:
(1) The hetero atoms N, S are introduced into the carbon material, N, S co-doped porous carbon is constructed, and the carbon-supported platinum-based catalyst is prepared by taking the hetero atoms N, S co-doped porous carbon as a carrier, so that not only can the electron cloud density of a carbon skeleton be regulated and controlled, but also the lower electronegativity of the carbon skeleton can be used for anchoring platinum nano particles, enhancing the interaction between the carrier and the platinum nano particles, reducing the agglomeration of platinum and improving the catalytic activity, and the particle size of the prepared platinum alloy nano particles is mainly concentrated at 3-5nm, is uniformly distributed, and has a good promoting effect on improving the performance of the catalyst;
(2) The preparation method is simple, low in preparation cost and easy to realize macro preparation;
(3) The invention can improve the intrinsic activity and effective active area of platinum by regulating the crystal form and the size of the platinum alloy nano particles, so that the activity of the catalyst with low platinum loading exceeds that of a commercial 70% Pt/C catalyst.
The conception, specific structure, and technical effects of the present invention will be further described with reference to the accompanying drawings to fully understand the objects, features, and effects of the present invention.
Drawings
FIG. 1 is an X-ray diffraction pattern of a PtCo alloy catalyst according to a preferred embodiment 1 of the present invention;
FIG. 2 is a graph showing the physical adsorption/desorption of nitrogen by PtCo alloy catalyst according to a preferred embodiment 1 of the present invention;
FIG. 3 is a transmission electron micrograph of a PtCo alloy catalyst according to a preferred embodiment 1 of the present invention;
FIG. 4 shows a PtCo alloy catalyst according to a preferred embodiment 1 of the invention with a commercial 70wt% Pt/C catalyst at 0.1M HClO 4 Oxygen reduction polarization curve in the electrolyte;
FIG. 5 shows PtCu in a preferred embodiment 2 of the invention 3 Alloy catalyst and commercial 70wt% Pt/C catalyst in 0.1M HClO 4 Oxygen reduction polarization curve in the electrolyte.
Detailed Description
The following description of the preferred embodiments of the present invention refers to the accompanying drawings, which make the technical contents thereof more clear and easy to understand. The present invention may be embodied in many different forms of embodiments and the scope of the present invention is not limited to only the embodiments described herein.
In the drawings, like structural elements are referred to by like reference numerals and components having similar structure or function are referred to by like reference numerals. The dimensions and thickness of each component shown in the drawings are arbitrarily shown, and the present invention is not limited to the dimensions and thickness of each component. The thickness of the components is exaggerated in some places in the drawings for clarity of illustration.
Example 1
(a) 1g of 5-amino-2-mercaptobenzimidazole was weighed out and dissolved in 250ml of 0.1M aqueous hydrochloric acid. Subsequently, an aqueous solution containing 3g of ammonium persulfate oxidizer was added dropwise, and stirred vigorously. The solution gradually changed from colorless to brown. After 8h of reaction, the brown suspension obtained was filtered off with suction and washed three times with deionized water and ethanol, and dried in vacuo to give poly-5-amino-2-mercaptobenzimidazole.
(b) 300mg of poly-5-amino-2-mercaptobenzimidazole is placed in a corundum porcelain boat, placed in a tube furnace, heated to 900 ℃ at a speed of 2 ℃/min under nitrogen atmosphere, and pyrolyzed for 2 hours to obtain the N, S co-doped porous carbon material (NSPC).
(c) 100mg of NSPC is added into 300ml of deionized water, and the mixture is dispersed by ultrasonic; subsequently, 87mg of sodium chloroplatinate and 52mg of cobalt chloride were added, stirred for 10 hours, and further dispersed by ultrasonic waves for 1 hour. The water was removed by rotary evaporator to give a porous carbon/metal salt mixture.
(d) Transferring the mixture into a corundum porcelain boat, and putting the corundum porcelain boat into a tube furnace. In 5% hydrogen/argon (i.e. containing 5% H by volume) 2 And Ar with the volume of 95 percent) in the atmosphere of the mixed gas, the temperature is raised to 900 ℃ at the temperature raising rate of 2 ℃/min, the heat is preserved for 2 hours, and the mixture is naturally cooled to the room temperature. And obtaining the N, S co-doped porous carbon supported PtCo alloy composite material.
Example 2
(a) 1g of 5-amino-2-mercaptobenzimidazole was weighed out and dissolved in 250ml of 0.1M aqueous hydrochloric acid. Subsequently, an aqueous solution containing 3g of ammonium persulfate oxidizer was added dropwise, and stirred vigorously. The solution gradually changed from colorless to brown. After 8h of reaction, the brown suspension obtained was filtered off with suction and washed three times with deionized water and ethanol, and dried in vacuo to give poly-5-amino-2-mercaptobenzimidazole.
(b) 300mg of poly-5-amino-2-mercaptobenzimidazole is placed in a corundum porcelain boat, placed in a tube furnace, heated to 900 ℃ at a speed of 2 ℃/min under nitrogen atmosphere, and pyrolyzed for 2 hours to obtain the N, S co-doped porous carbon material (NSPC).
(c) 100mg of NSPC is added into 300ml of deionized water, and the mixture is dispersed by ultrasonic; subsequently, 87mg of sodium chloroplatinate and 150mg of copper chloride were added, stirred for 10 hours, and further dispersed by ultrasonic waves for 1 hour. The water was removed by rotary evaporator to give a porous carbon/metal salt mixture.
(d) Transferring the mixture into a corundum porcelain boat, and putting the corundum porcelain boat into a tube furnace. In 5% hydrogen/argon (i.e. containing 5% H by volume) 2 And Ar with the volume of 95 percent) in the atmosphere of the mixed gas, the temperature is raised to 900 ℃ at the temperature raising rate of 2 ℃/min, the heat is preserved for 2 hours, and the mixture is naturally cooled to the room temperature. Obtaining N, S co-doped porous carbon loaded PtCu 3 An alloy composite material.
Characterization of the structure of example 1.
X-ray diffraction (XRD) measurements were performed on the composite material prepared in example 1The test is carried out, the generator voltage is 40kV, the generator current is 40mA, and the scanning speed is 6 DEG min -1 。
As shown in XRD spectrum lines of FIG. 1, the material has obvious diffraction peaks at 24 degrees, 34.7 degrees, 42.1 degrees and 48.3 degrees, and the diffraction peaks are matched with signal peaks of PtCo alloy standard cards, so that the PtCo alloy composite material is successfully prepared.
The composite material prepared in example 1 was subjected to nitrogen physical adsorption/desorption test, and the pore structure of the material was studied.
Results from the adsorption/desorption curves of FIG. 2, the specific surface area of the material was calculated to reach 214m 2 The high specific surface area is beneficial to exposing more active sites and reaction mass transfer, and has good promotion effect on improving the catalytic activity of the catalyst.
The composite material prepared in example 1 was subjected to Transmission Electron Microscope (TEM) testing, and a small amount of the sample of example 1 was dispersed on a conductive tape for TEM testing.
As shown in FIG. 3, the particle size of PtCo alloy nano particles in the material is about 5nm, which indicates that N, S co-doping and the porous structure of the material can avoid agglomeration of platinum to a certain extent, and the effective activity site number of the catalyst and the utilization rate of platinum are improved.
The samples prepared in inventive examples 1 and 2 were tested for electrocatalytic oxygen reduction performance using a commercially available 70wt% pt/C catalyst as a control:
as shown in FIG. 4, the PtCo alloy catalyst was prepared at 0.1M HClO 4 The electrolyte shows excellent oxygen reduction catalytic performance, and the limiting current density reaches 6.0mA cm -2 The half-wave potential reached 0.938V, exceeding commercial 70wt.% Pt/C catalyst.
As shown in FIG. 5, ptCu was prepared 3 Alloy catalyst in 0.1M HClO 4 The limiting current density in the electrolyte reaches 5.9mA.cm -2 The half-wave potential reaches 0.940V, again exceeding commercial 70wt.% Pt/C catalyst. The catalyst developed by the invention has the prospect of replacing commercial Pt/C catalyst, and provides a new thought for the development of high-efficiency catalysts.
The foregoing describes in detail preferred embodiments of the present invention. It should be understood that numerous modifications and variations can be made in accordance with the concepts of the invention without requiring creative effort by one of ordinary skill in the art. Therefore, all technical solutions which can be obtained by logic analysis, reasoning or limited experiments based on the prior art by the person skilled in the art according to the inventive concept shall be within the scope of protection defined by the claims.
Claims (10)
1. The preparation method of the N, S-doped porous carbon-loaded platinum alloy nano-particles is characterized by comprising the following steps:
step 1, dissolving 5-amino-2-mercaptobenzimidazole in a hydrochloric acid aqueous solution, vigorously stirring, dropwise adding an oxidant, and performing oxidative polymerization reaction to obtain poly-5-amino-2-mercaptobenzimidazole;
step 2, placing the poly 5-amino-2-mercaptobenzimidazole prepared in the step 1 into a tubular furnace, and performing pyrolysis under the condition of inert atmosphere to prepare an N, S co-doped porous carbon material NSPC;
step 3, adding the N, S co-doped porous carbon material NSPC prepared in the step 2 into an aqueous solution, and performing ultrasonic dispersion; and then adding platinum salt and a transition metal salt precursor, stirring, distilling under reduced pressure, drying, transferring to a tube furnace, and calcining at high temperature to obtain the N, S co-doped porous carbon-loaded platinum alloy nanoparticle composite material.
2. The method for preparing N, S-doped porous carbon-supported platinum alloy nanoparticles according to claim 1, wherein in step 1, the oxidant is ammonium persulfate.
3. The method for preparing the N, S-doped porous carbon-supported platinum alloy nanoparticles according to claim 2, wherein the mass ratio of the 5-amino-2-mercaptobenzimidazole to the ammonium persulfate is 1:3.
4. the method for preparing N, S-doped porous carbon-supported platinum alloy nanoparticles according to claim 1, wherein in step 1, the concentration of the aqueous hydrochloric acid solution is 0.1mol/L, the reaction temperature is room temperature, and the reaction time is 4-10h.
5. The method for preparing N, S-doped porous carbon supported platinum alloy nanoparticles according to claim 1, wherein in step 2, the pyrolysis temperature is 800-1000 ℃ and the pyrolysis time is more than 1h.
6. The method for preparing N, S-doped porous carbon-supported platinum alloy nanoparticles according to claim 5, wherein in step 2, the heating rate of the tube furnace is 2 ℃/min.
7. The method for preparing N, S-doped porous carbon-supported platinum alloy nanoparticles according to claim 1, wherein in step 3, the mass-to-volume ratio of the N, S-doped porous carbon material NSPC to the aqueous solution is 1:3.
8. The method for preparing N, S doped porous carbon supported platinum alloy nanoparticles according to claim 1, wherein in step 3, the platinum salt is sodium chloroplatinate, and the transition metal salt precursor is any one of cobalt chloride, copper chloride, ferric chloride, and nickel chloride.
9. The method for preparing N, S-doped porous carbon-supported platinum alloy nanoparticles according to claim 1, wherein in step 3, the high-temperature calcination atmosphere is argon-hydrogen mixture gas, and the argon-hydrogen mixture gas contains 5% by volume of H 2 And 95% Ar by volume, the calcination temperature is 600 ℃, and the calcination time is more than 1h.
10. Use of the N, S-doped porous carbon-supported platinum alloy nanoparticles prepared by the method of any one of claims 1-9 in an electrocatalytic oxygen reduction reaction.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311160218.9A CN117039030A (en) | 2023-09-08 | 2023-09-08 | Preparation method and application of N, S-doped porous carbon-loaded platinum alloy nano particles |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202311160218.9A CN117039030A (en) | 2023-09-08 | 2023-09-08 | Preparation method and application of N, S-doped porous carbon-loaded platinum alloy nano particles |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN117039030A true CN117039030A (en) | 2023-11-10 |
Family
ID=88639210
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202311160218.9A Pending CN117039030A (en) | 2023-09-08 | 2023-09-08 | Preparation method and application of N, S-doped porous carbon-loaded platinum alloy nano particles |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN117039030A (en) |
-
2023
- 2023-09-08 CN CN202311160218.9A patent/CN117039030A/en active Pending
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN109841854B (en) | Nitrogen-doped carbon-supported monatomic oxygen reduction catalyst and preparation method thereof | |
| KR100868756B1 (en) | Pt/Ru alloy supported catalyst, manufacturing method thereof, and fuel cell using the same | |
| CN109659570B (en) | Application of metal organic framework compound hollow microspheres loaded with iron cobalt sulfide | |
| CN109728311B (en) | Metal organic framework compound hollow microsphere loaded with iron cobalt sulfide | |
| CN111244484B (en) | Preparation method of sub-nano platinum-based ordered alloy | |
| CN106784900B (en) | Carbon nano tube covered by platinum-based nano particle coated tin dioxide and preparation method thereof | |
| CN112968185A (en) | Preparation method of plant polyphenol modified manganese-based nano composite electrocatalyst with supermolecular network framework structure | |
| CN113611881B (en) | Atomic-level dispersed Fe/nitrogen-doped mesoporous carbon spheres and preparation method and application thereof | |
| Su et al. | Palladium nanoparticles immobilized in B, N doped porous carbon as electrocatalyst for ethanol oxidation reaction | |
| CN107195914B (en) | Amorphous manganese oxide loaded nitrogen-doped carbon-based catalyst and preparation method thereof | |
| CN110277565B (en) | Platinum-indium catalyst for fuel cell and preparation method and application thereof | |
| CN113285079A (en) | Double-heteroatom-doped CoFe/SNC composite material and preparation and application thereof | |
| CN115570143B (en) | Low-platinum high-entropy alloy nano-particle and preparation method and application thereof | |
| CN112397732A (en) | ORR catalyst material and preparation method and application thereof | |
| CN114824319B (en) | N-doped TiO 2-x Preparation method and application of supported PtCu alloy nano catalyst | |
| CN113809341B (en) | Cu-N-C oxygen reduction catalyst and preparation method thereof | |
| CN112701307B (en) | Double MOF (metal organic framework) connection structure nano composite electrocatalyst for proton membrane fuel cell and preparation method thereof | |
| CN115133050A (en) | Platinum-cobalt alloy catalyst, preparation method and application thereof | |
| CN117039030A (en) | Preparation method and application of N, S-doped porous carbon-loaded platinum alloy nano particles | |
| CN114188550A (en) | Sulfur, nitrogen and monoatomic iron co-doped carbon-based catalyst prepared from methionine and method thereof | |
| Yang et al. | PdCu nanoalloys deposited on porous carbon as a highly efficient catalyst for ethanol oxidation | |
| CN108091890B (en) | Preparation method of silver-cobalt-guanine-based nano flaky material | |
| Li et al. | Carbothermal shock synthesis of CoO/N/C nanoparticles with superior durability for oxygen reduction reaction | |
| Wan et al. | Coordinated Co-NC/CoFe dual active centre embedded three-dimensional ordered macroporous framework as bifunctional catalyst for efficient and stable zinc–air batteries | |
| CN113224321B (en) | Vanadium-doped carbon-coated iron carbide multifunctional composite electrocatalyst and preparation method and application thereof |
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 |