CN113113624A - Nano platinum catalyst with carbon nano tube as carrier and preparation method thereof - Google Patents
Nano platinum catalyst with carbon nano tube as carrier and preparation method thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 title claims abstract description 124
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 66
- 229910052697 platinum Inorganic materials 0.000 title claims abstract description 54
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 53
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 52
- 239000003054 catalyst Substances 0.000 title claims abstract description 40
- 238000002360 preparation method Methods 0.000 title abstract description 10
- 238000000034 method Methods 0.000 claims abstract description 14
- 230000008569 process Effects 0.000 claims abstract description 5
- 238000006073 displacement reaction Methods 0.000 claims abstract description 4
- 239000002048 multi walled nanotube Substances 0.000 claims description 34
- 239000002245 particle Substances 0.000 claims description 16
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 15
- 239000007864 aqueous solution Substances 0.000 claims description 12
- 239000002253 acid Substances 0.000 claims description 11
- 229910017053 inorganic salt Inorganic materials 0.000 claims description 10
- 239000002109 single walled nanotube Substances 0.000 claims description 10
- 239000012286 potassium permanganate Substances 0.000 claims description 9
- 238000002791 soaking Methods 0.000 claims description 9
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 claims description 8
- 229910044991 metal oxide Inorganic materials 0.000 claims description 8
- 150000004706 metal oxides Chemical class 0.000 claims description 8
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- 229910052751 metal Inorganic materials 0.000 claims description 6
- 239000002184 metal Substances 0.000 claims description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims description 4
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 4
- 238000001354 calcination Methods 0.000 claims description 4
- 229910052802 copper Inorganic materials 0.000 claims description 4
- 239000010949 copper Substances 0.000 claims description 4
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 4
- 229910052742 iron Inorganic materials 0.000 claims description 4
- WPBNNNQJVZRUHP-UHFFFAOYSA-L manganese(2+);methyl n-[[2-(methoxycarbonylcarbamothioylamino)phenyl]carbamothioyl]carbamate;n-[2-(sulfidocarbothioylamino)ethyl]carbamodithioate Chemical compound [Mn+2].[S-]C(=S)NCCNC([S-])=S.COC(=O)NC(=S)NC1=CC=CC=C1NC(=S)NC(=O)OC WPBNNNQJVZRUHP-UHFFFAOYSA-L 0.000 claims description 4
- 239000011701 zinc Substances 0.000 claims description 4
- 229910052725 zinc Inorganic materials 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 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 claims description 3
- NWAHZABTSDUXMJ-UHFFFAOYSA-N platinum(2+);dinitrate Chemical compound [Pt+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O NWAHZABTSDUXMJ-UHFFFAOYSA-N 0.000 claims description 3
- 229910052700 potassium Inorganic materials 0.000 claims description 3
- 239000011591 potassium Substances 0.000 claims description 3
- 229910052708 sodium Inorganic materials 0.000 claims description 3
- 239000011734 sodium Substances 0.000 claims description 3
- 238000005649 metathesis reaction Methods 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims description 2
- 239000007787 solid Substances 0.000 claims description 2
- AMWRITDGCCNYAT-UHFFFAOYSA-L hydroxy(oxo)manganese;manganese Chemical compound [Mn].O[Mn]=O.O[Mn]=O AMWRITDGCCNYAT-UHFFFAOYSA-L 0.000 abstract description 58
- 239000011572 manganese Substances 0.000 abstract description 14
- 230000009467 reduction Effects 0.000 abstract description 14
- 239000000446 fuel Substances 0.000 abstract description 10
- PWHULOQIROXLJO-UHFFFAOYSA-N Manganese Chemical compound [Mn] PWHULOQIROXLJO-UHFFFAOYSA-N 0.000 abstract description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 5
- 229910052748 manganese Inorganic materials 0.000 abstract description 5
- 239000001301 oxygen Substances 0.000 abstract description 5
- 229910052760 oxygen Inorganic materials 0.000 abstract description 5
- 238000000151 deposition Methods 0.000 abstract description 3
- 239000010410 layer Substances 0.000 abstract description 3
- -1 platinum ions Chemical class 0.000 abstract description 3
- 239000007791 liquid phase Substances 0.000 abstract description 2
- 238000003487 electrochemical reaction Methods 0.000 abstract 1
- 239000002346 layers by function Substances 0.000 abstract 1
- 239000000843 powder Substances 0.000 description 17
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 13
- 239000001257 hydrogen Substances 0.000 description 13
- 229910052739 hydrogen Inorganic materials 0.000 description 13
- 239000000047 product Substances 0.000 description 13
- 229910052799 carbon Inorganic materials 0.000 description 11
- 239000011247 coating layer Substances 0.000 description 11
- 239000002131 composite material Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 11
- 238000011068 loading method Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 8
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- 239000011248 coating agent Substances 0.000 description 7
- 238000000576 coating method Methods 0.000 description 7
- 239000002994 raw material Substances 0.000 description 7
- 239000000203 mixture Substances 0.000 description 6
- 239000012071 phase Substances 0.000 description 6
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 5
- 238000006243 chemical reaction Methods 0.000 description 5
- 150000001875 compounds Chemical class 0.000 description 5
- 239000012528 membrane Substances 0.000 description 5
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012299 nitrogen atmosphere Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
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- 229910052757 nitrogen Inorganic materials 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910052786 argon Inorganic materials 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000000052 comparative effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 239000004744 fabric Substances 0.000 description 2
- 238000010304 firing Methods 0.000 description 2
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- 238000004519 manufacturing process Methods 0.000 description 2
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- 239000000243 solution Substances 0.000 description 2
- 238000003756 stirring Methods 0.000 description 2
- 238000000967 suction filtration Methods 0.000 description 2
- 230000010757 Reduction Activity Effects 0.000 description 1
- 239000012300 argon atmosphere Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 230000001627 detrimental effect Effects 0.000 description 1
- 238000011549 displacement method Methods 0.000 description 1
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- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
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- 238000006056 electrooxidation reaction Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- PPNAOCWZXJOHFK-UHFFFAOYSA-N manganese(2+);oxygen(2-) Chemical compound [O-2].[Mn+2] PPNAOCWZXJOHFK-UHFFFAOYSA-N 0.000 description 1
- VASIZKWUTCETSD-UHFFFAOYSA-N manganese(II) oxide Inorganic materials [Mn]=O VASIZKWUTCETSD-UHFFFAOYSA-N 0.000 description 1
- GEYXPJBPASPPLI-UHFFFAOYSA-N manganese(III) oxide Inorganic materials O=[Mn]O[Mn]=O GEYXPJBPASPPLI-UHFFFAOYSA-N 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000003541 multi-stage reaction Methods 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 150000003057 platinum Chemical class 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000004381 surface treatment Methods 0.000 description 1
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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
- H01M4/925—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
-
- 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
- H01M4/9016—Oxides, hydroxides or oxygenated metallic salts
-
- 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 relates to a nano platinum catalyst which is used for fuel cell oxygen reduction electrochemical reaction and takes a carbon nano tube as a carrier and a preparation method thereof. The preparation method is characterized in that a manganese oxide functional layer covered on the surface of the carbon nano tube is utilized to cause the platinum ions in the liquid phase and the manganese with lower valence state to generate displacement reaction, thereby uniformly depositing the nano platinum atomic layer on the manganese oxide for forming. The preparation method has simple process, and the synthesized catalyst has high oxygen reduction performance and good industrial application prospect.
Description
Technical Field
The invention relates to an oxygen reduction catalyst for a hydrogen fuel cell and a manufacturing method thereof, belonging to the technical field of fuel cell catalysts.
Background
The hydrogen fuel cell is an important energy conversion device of the future hydrogen energy society, can efficiently convert hydrogen energy into electric energy, and can achieve zero carbon emission in the process. In the development of hydrogen fuel cells, an important aspect is the development of fuel cell electrode catalysts having high oxygen reduction activity, low noble metal usage, and long service life.
The existing active carbon loaded by mainly applying Pt catalyst is XC-72R, which has good conductivity, but has the problems of reduced specific surface area and low loading capacity after surface treatment, and the like. In the non-patent literature (schurer, research on a platinum nanoparticle catalyst support based on nitrogen-doped porous carbon [ D ] mansion university, 2018.) is disclosed a fuel cell catalyst in which a nitrogen-doped porous carbon material is first prepared, and Pt is supported on a carbon support after being supported by a platinum source and subjected to reduction treatment.
Research shows that the active carbon carrier with high specific surface area widely used in the hydrogen fuel cell at present has the problems of poor chemical stability, low conductivity and strong surface hydrophobicity, which are not beneficial to forming a good three-phase reaction interface on the surface of the catalyst. To better solve the above problems, it is necessary to find more advanced novel carbon carriers, which have the corresponding functions and characteristics required.
In addition, Carbon Nanotubes (CNTs) have been extensively studied, and for example, a preparation process based on a CNT-supported Pt catalyst is also disclosed in non-patent literature (Chenweixiang, Korea, LEE Jim Yang, et al. microwave rapid synthesis of Pt/CNT nanocatalysts and electrocatalytic performance thereof for electrochemical oxidation of methanol [ J ] advanced chemical bulletin of higher schools, 2003,24(12): 2285-. However, due to the hydrophobicity of the surface of the CNT, the Pt catalyst has a low loading amount on the surface thereof, so that the catalytic activity of the material is not good.
Disclosure of Invention
The present invention is directed to solving the above-mentioned problems, and by using a one-dimensional carbon nanotube with high chemical stability and high conductivity as a new carrier and performing surface oxide coating modification functionalization on the one-dimensional carbon nanotube, the surface hydrophilicity of the one-dimensional carbon nanotube is effectively enhanced. Through the replacement reaction between the functionalized layer on the surface of the carbon nano tube and platinum ions, the carrier can efficiently disperse nano platinum particles on the surface to form a composite phase structure. When the catalyst prepared by the preparation method is used as a cathode of a fuel cell, better electrochemical characteristics are shown.
A nano platinum catalyst using carbon nano tube as carrier is prepared by loading metal oxide and Pt on carbon nano tube carrier.
Preferably, the carbon nanotube carrier refers to single-walled carbon nanotubes, multi-walled carbon nanotubes or a solid containing the single-walled carbon nanotubes and the multi-walled carbon nanotubes.
Preferably, the metal oxide has the formula: mxOyX and y are atomic numbers, M is a metal element, and the valence of M is less than + 4.
Preferably, said M is an element of group VIB, VIIB, IB or IIB.
Preferably, M is one of manganese, iron, copper or zinc.
Preferably, Pt is in a nano platinum particle state, and the particle size of the Pt is 1-50 nm; more preferably 1-10 nm; preferably 1-3 nm.
A method for preparing a nano platinum catalyst with a carbon nano tube as a carrier comprises the following steps:
and 3, soaking the carbon nano tube carrier obtained in the step 2 in an aqueous solution containing a platinum source to perform a displacement reaction on the platinum source and the metal oxide to obtain the nano platinum catalyst.
Preferably, in step 1, the soluble inorganic salt is selected from inorganic salts of metal M, wherein M is an element of group VIB, VIIB, IB or IIB.
Preferably, the soluble inorganic salt is an inorganic salt containing manganese, iron, copper or zinc.
Preferably, the soluble inorganic salt is potassium permanganate.
Preferably, in step 1, the hydrothermal synthesis conditions are 60-90 ℃ for 1-10 h.
Preferably, in step 2, the calcination temperature is 300-600 ℃.
Preferably, in step 2, the calcination process is carried out in an inert or reducing atmosphere.
Preferably, in step 3, the platinum source is selected from chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate or platinum nitrate.
Preferably, in step 3, the metathesis reaction is carried out at 50-90 ℃ for 1-5 h.
Advantageous effects
The catalyst is a preparation process for applying to a hydrogen fuel cell, wherein a manganese oxide coating layer grows in situ on a carbon nano tube carrier to form a functional compound, and then the nano platinum catalyst is loaded by a liquid phase reduction displacement method. The main component of the manganese oxide coating layer before heat treatment is hydrated manganese oxide (manganese is in a valence state of + 4), and the main component after heat treatment is trimanganese tetroxide (manganese is in a valence state of +2 and + 3).
The carbon nanotube carrier used in the invention can be single-wall carbon nanotube powder, multi-wall carbon nanotube powder, ordered array film composed of single-wall/multi-wall carbon nanotubes, disordered film, carbon paper, carbon cloth, silk and other various products with different macroscopic forms.
The invention has the advantages that: the carbon nano tube is used as a novel carbon carrier of the catalyst, so that the conductivity and chemical stability of the catalyst can be effectively improved. In addition, the invention provides a material functional design of growing an oxide coating layer on the surface of the carbon nano tube in situ, which can effectively make up for the defects caused by the strong hydrophobicity of the carbon nano tube. The surface of the carbon nano tube carrier coated with the surface is converted into hydrophilicity, which is more beneficial to the platinum displacement reaction in the next step of aqueous solution, thereby improving the dispersibility of the nano platinum catalyst and finally enhancing the overall performance of the composite catalyst.
Drawings
FIG. 1 is a schematic diagram of a manufacturing process used in the present invention.
FIG. 2 is a graph of Pt20/Mn as prepared in example 13O4Electron Microscopy (SEM) image of/VACNT sample.
Fig. 3 is an XRD pattern of the MWCNT sample with manganese oxide functionalized coating layer prepared in example 2 before and after heat treatment reduction roasting.
FIG. 4 is Pt10/Mn prepared in example 23O4TEM image of the/MWCNT product.
FIG. 5 is Pt10/Mn prepared in example 23O4XRD pattern of the/MWCNT product. FIG. 6 shows Pt20/Mn3O4Graph comparing the performance of the/MWCNT with Pt20// WCNT; FIG. 7 shows Pt20/Mn3O4/MWCNT（N2) And Pt20/Mn3O4/MWCNT（H2) Performance of (c) is compared with the graph.
Detailed Description
The preparation steps of the invention are detailed as follows:
And step 2, performing heat treatment on the carbon nano tube coated by the manganese oxide in the step 1, and roasting at the temperature of 300-600 ℃ in an inert/reducing atmosphere to obtain a trimanganese tetroxide coating layer with a lower valence state as a functionalized layer on the surface of the carbon nano tube.
And 3, soaking the surface functionalized carbon nano tube carrier obtained in the step 2 in a platinum-containing aqueous solution, stirring and reacting at a constant temperature of 50-90 ℃ for 1-5 hours to ensure that high-valence platinum ions are reduced into nano platinum particles by low-valence manganese and are firmly deposited in a trimanganese tetroxide coating layer on the surface of the carbon nano tube to form a composite phase, and finally obtaining the nano platinum catalyst product taking the carbon nano tube as the carrier through the processes of suction filtration, washing and drying.
The carbon nanotube carrier includes, but is not limited to, single-wall carbon nanotube powder, multi-wall carbon nanotube powder, ordered array film comprising single-wall/multi-wall carbon nanotubes, disordered film, carbon paper, carbon cloth, silk and other products in different macroscopic forms.
Inert/reducing atmospheres, including but not limited to nitrogen, argon, and various ratios of hydrogen to argon, and hydrogen to nitrogen. The platinum-containing aqueous solution described in step 3 includes, but is not limited to, various water-soluble platinum salts, such as chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, platinum nitrate, etc.
Example 1:
the preparation method of the invention is shown in a schematic diagram 1. 0.1g of the ordered carbon nanotube array membrane is soaked in 50mL of water, 0.1g of potassium permanganate is added to be fully dissolved, the mixture is heated in a water bath at 60 ℃ to react for 2.5h, and then the membrane is taken out, washed and dried. Roasting the dried precursor membrane at 400 ℃ for 2h in an argon atmosphere, then soaking the membrane in 25mL of chloroplatinic acid aqueous solution, setting the theoretical charge ratio of a platinum raw material to be 20wt%, reacting at 70 ℃ for 2h at constant temperature, replacing nano platinum particles with manganous oxide, depositing the nano platinum particles on the surface of a carbon nano tube coating layer, finally taking out the membrane, washing and drying to obtain Pt20/Mn3O4a/VACNT composite catalyst material. An electron microscope image of the material is shown in FIG. 2, from which it can be seen that the loading is Mn3O4The Pt nanoparticles on the/VACNT support are very uniformly distributed and the order of the carbon nanotube array is largely preserved intact.
Example 2:
1.0 g of commercial multi-walled carbon nanotube powder is soaked in 100 mL of water, 1.0 g of potassium permanganate is added to be fully dissolved, the mixture is heated in a water bath at 90 ℃ to react for 1 hour, and then the reaction product is filtered, washed and dried. And roasting the dried powder at 300 ℃ for 6h in a nitrogen atmosphere. The XRD crystal phase structure characteristic curve of the MWCNT sample with the manganese oxide functionalized coating before and after reduction firing is shown in fig. 3, for example, and it can be seen that the product after reduction firing shows a distinct crystal phase of Mn3O 4. Then, the Mn obtained by the thermal reduction is subjected to3O4the/MWCNT compound is soaked in 250mL of chloroplatinic acid water solutionIn the solution, the theoretical charge ratio of the platinum raw material is set to 10wt%, the reaction is carried out for 5 hours at the constant temperature of 50 ℃, so that the trimanganese tetroxide displaces the nano platinum particles, the nano platinum particles are deposited on the surface of the carbon nano tube coating, and finally the product is taken out, washed and dried to obtain the Pt10/Mn3O4A/MWCNT composite catalyst material. A TEM image of this material is shown in FIG. 4, from which it can be seen that Pt nanoparticles are in Mn3O4the/VACNT carrier is uniformly distributed and has small particle size. Mn3O4The XRD crystal phase structure of the/VACNT loaded Pt is shown in figure 5.
Example 3:
1.0 g of commercial single-walled carbon nanotube powder is soaked in 100 mL of water, 0.5 g of potassium permanganate is added, after full dissolution, the mixture is heated in a water bath at 60 ℃ for reaction for 10 hours, and then is filtered, washed and dried. Roasting the dried powder at 600 ℃ for 0.5h in the atmosphere of hydrogen-nitrogen mixed gas (hydrogen accounts for 5%), then soaking the powder in 250mL of aqueous solution of chloroplatinic acid, setting the theoretical charge ratio of the platinum raw material to be 5wt%, reacting at the constant temperature of 90 ℃ for 1h to replace the nano platinum particles by the manganic oxide, depositing the nano platinum particles on the surface of the carbon nano tube coating layer, finally taking out the product, washing and drying to obtain Pt 5/Mn3O4a/SWCNT composite catalyst material. The result of electrochemical test shows that the prepared Pt 5/Mn3O4the/SWCNT composite catalyst was 0.117A/mgPt, slightly less electrochemically active for oxygen reduction than the 20wt% platinum loading commercial Pt/C catalyst (0.131A/mgPt), while the actual platinum loading in the product was 5 wt%. The results show that the nano platinum catalyst which takes the carbon nano tube as the carrier and is produced by the technical method can effectively reduce the required platinum content in the catalyst.
Comparative example 1
The difference from example 3 is that: directly carrying out composite reaction on the carbon nano tube and chloroplatinic acid solution, and loading platinum on the carbon nano tube.
1.0 g of commercial multi-walled carbon nanotube powder is soaked in 100 mL of water, 1.0 g of potassium permanganate is added to be fully dissolved, the mixture is heated in a water bath at 90 ℃ to react for 1 hour, and then the reaction product is filtered, washed and dried. And roasting the dried powder at 300 ℃ for 6h in a nitrogen atmosphere.And reducing and roasting to obtain the MWCNT sample with the manganese oxide functionalized coating layer. Then, the Mn obtained by the thermal reduction is subjected to3O4Soaking the MWCNT compound in 250mL of chloroplatinic acid aqueous solution, setting the theoretical charge ratio of the platinum raw material to be 20wt%, reacting at the constant temperature of 50 ℃ for 5h to ensure that the trimanganese tetroxide displaces the nano platinum particles to be deposited on the surface of the carbon nano tube coating, finally taking out the product, washing and drying to obtain Pt20/Mn3O4A/MWCNT composite catalyst material. 1.0 g of commercial multi-walled carbon nanotube powder was calcined at 300 ℃ for 6h under nitrogen atmosphere. And then soaking the roasted sample in 250mL of chloroplatinic acid aqueous solution, setting the theoretical feeding ratio of a platinum raw material to be 20wt%, reacting at the constant temperature of 50 ℃ for 5 hours, finally taking out a product, washing and drying to obtain the Pt20// WCNT composite catalyst material. FIG. 6 shows Pt20/Mn3O4The comparison graph of the performance of the MWCNT and the Pt20// WCNT shows that the sample obtained by directly loading Pt on the commercialized multi-wall carbon nano tube powder without Mn treatment has basically no catalytic activity. The original WCNT without Mn treatment proved to be detrimental to Pt loading.
Comparative example 2
The difference from example 3 is that: the carbon nanotubes loaded with manganese oxide are not subjected to roasting treatment in an atmosphere containing hydrogen.
1.0 g of commercial multi-walled carbon nanotube powder is soaked in 100 mL of water, 1.0 g of potassium permanganate is added to be fully dissolved, the mixture is heated in a water bath at 90 ℃ to react for 1 hour, and then the reaction product is filtered, washed and dried. And roasting the dried powder at 300 ℃ for 6h in a nitrogen atmosphere. And roasting to obtain the MWCNT sample with the manganese oxide functionalized coating layer. Then, the Mn obtained by the thermal reduction is subjected to3O4Soaking the MWCNT compound in 250mL of chloroplatinic acid aqueous solution, setting the theoretical charge ratio of the platinum raw material to be 20wt%, reacting at the constant temperature of 50 ℃ for 5h to ensure that the trimanganese tetroxide displaces the nano platinum particles to be deposited on the surface of the carbon nano tube coating, finally taking out the product, washing and drying to obtain Pt20/Mn3O4/MWCNT（N2) A composite catalyst material. 1.0 g of commercial multi-walled carbon nanotube powder is soaked in 100 mL of water, 1.0 g of potassium permanganate is added to be fully dissolved, and then the mixture is heated in water bath at 90 ℃ for reactionAnd after 1h, carrying out suction filtration, washing and drying. And roasting the dried powder at 300 ℃ for 6h in a hydrogen atmosphere. And reducing and roasting to obtain the MWCNT sample with the manganese oxide functionalized coating layer. Then, the Mn obtained by the thermal reduction is subjected to3O4Soaking the MWCNT compound in 250mL of chloroplatinic acid aqueous solution, setting the theoretical charge ratio of the platinum raw material to be 20wt%, reacting at the constant temperature of 50 ℃ for 5h to ensure that the trimanganese tetroxide displaces the nano platinum particles to be deposited on the surface of the carbon nano tube coating, finally taking out the product, washing and drying to obtain Pt20/Mn3O4/MWCNT（H2) A composite catalyst material. FIG. 7 shows Pt20/Mn3O4/MWCNT（N2) And Pt20/Mn3O4/MWCNT（H2) The performance comparison graph shows that the valence state of the manganese oxide can be reduced after hydrogen reduction, the conversion reaction can be promoted, and Pt is better loaded on the WCNT.
Claims (10)
1. A nano platinum catalyst using carbon nano tubes as a carrier is characterized in that metal oxide and Pt are loaded on the carbon nano tube carrier.
2. The nano platinum catalyst using carbon nanotubes as a carrier according to claim 1, wherein the carbon nanotube carrier is a single-walled carbon nanotube, a multi-walled carbon nanotube or a solid containing the same.
3. The nano platinum catalyst using carbon nanotube as carrier according to claim 1, wherein the metal oxide has a general formula: mxOyX and y are atomic numbers, M is a metal element, and the valence of M is less than + 4;
m is an element in VIB group, VIIB group, IB group or IIB group;
m is one of manganese, iron, copper or zinc;
pt is in a nano platinum particle state, and the particle size of the Pt is 1-50 nm; more preferably 1-10 nm; preferably 1-3 nm.
4. The method for preparing nano platinum catalyst using carbon nano tube as carrier according to claim 1, characterized by comprising the steps of:
step 1, adding soluble inorganic salt of metal and a carbon nano tube carrier into water, carrying out hydrothermal synthesis, and forming metal oxide on the surface of the carbon nano tube carrier;
step 2, roasting the carbon nano tube carrier obtained in the step 1;
and 3, soaking the carbon nano tube carrier obtained in the step 2 in an aqueous solution containing a platinum source to perform a displacement reaction on the platinum source and the metal oxide to obtain the nano platinum catalyst.
5. The method according to claim 4, wherein in step 1, the soluble inorganic salt is selected from inorganic salts of metal M, wherein M is an element of group VIB, group VIIB, group IB or group IIB;
the soluble inorganic salt is an inorganic salt containing manganese, iron, copper or zinc.
6. The method of claim 4, wherein the soluble inorganic salt is potassium permanganate.
7. The method according to claim 4, wherein the hydrothermal synthesis conditions in step 1 are 60-90 ℃ for 1-10 h.
8. The method as claimed in claim 4, wherein the calcination temperature in step 2 is 300-600 ℃; the calcination process is carried out in an inert or reducing atmosphere.
9. The method according to claim 4, wherein the source of platinum is selected from chloroplatinic acid, sodium chloroplatinate, potassium chloroplatinate, or platinum nitrate.
10. The method according to claim 4, wherein the metathesis reaction is carried out at 50 to 90 ℃ for 1 to 5 hours.
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