CN112713278A - Catalyst and preparation method and application thereof - Google Patents
Catalyst and preparation method and application thereof Download PDFInfo
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- CN112713278A CN112713278A CN201911018826.XA CN201911018826A CN112713278A CN 112713278 A CN112713278 A CN 112713278A CN 201911018826 A CN201911018826 A CN 201911018826A CN 112713278 A CN112713278 A CN 112713278A
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- 239000003054 catalyst Substances 0.000 title claims abstract description 87
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000001257 hydrogen Substances 0.000 claims abstract description 55
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 55
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 14
- 229910052751 metal Inorganic materials 0.000 claims abstract description 4
- 239000002184 metal Substances 0.000 claims abstract description 4
- 239000003575 carbonaceous material Substances 0.000 claims abstract description 3
- 229910044991 metal oxide Inorganic materials 0.000 claims abstract description 3
- 150000004706 metal oxides Chemical class 0.000 claims abstract description 3
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 61
- 229910021389 graphene Inorganic materials 0.000 claims description 61
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 56
- 239000000203 mixture Substances 0.000 claims description 46
- 238000002156 mixing Methods 0.000 claims description 36
- 239000002245 particle Substances 0.000 claims description 33
- UAEPNZWRGJTJPN-UHFFFAOYSA-N methylcyclohexane Chemical compound CC1CCCCC1 UAEPNZWRGJTJPN-UHFFFAOYSA-N 0.000 claims description 32
- 239000000446 fuel Substances 0.000 claims description 31
- 238000005406 washing Methods 0.000 claims description 26
- 239000002356 single layer Substances 0.000 claims description 24
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Chemical compound O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 claims description 18
- 239000003638 chemical reducing agent Substances 0.000 claims description 17
- 150000001875 compounds Chemical class 0.000 claims description 17
- GYNNXHKOJHMOHS-UHFFFAOYSA-N methyl-cycloheptane Natural products CC1CCCCCC1 GYNNXHKOJHMOHS-UHFFFAOYSA-N 0.000 claims description 16
- 238000003860 storage Methods 0.000 claims description 16
- 238000001035 drying Methods 0.000 claims description 15
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 14
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 14
- 238000001914 filtration Methods 0.000 claims description 13
- 239000010410 layer Substances 0.000 claims description 10
- ZKATWMILCYLAPD-UHFFFAOYSA-N niobium pentoxide Chemical compound O=[Nb](=O)O[Nb](=O)=O ZKATWMILCYLAPD-UHFFFAOYSA-N 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- QTBSBXVTEAMEQO-UHFFFAOYSA-N Acetic acid Chemical compound CC(O)=O QTBSBXVTEAMEQO-UHFFFAOYSA-N 0.000 claims description 6
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims description 6
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 6
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 6
- NNBZCPXTIHJBJL-UHFFFAOYSA-N decalin Chemical compound C1CCCC2CCCCC21 NNBZCPXTIHJBJL-UHFFFAOYSA-N 0.000 claims description 6
- 238000002604 ultrasonography Methods 0.000 claims description 6
- 239000000126 substance Substances 0.000 claims description 5
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 4
- 239000003960 organic solvent Substances 0.000 claims description 4
- XDTMQSROBMDMFD-UHFFFAOYSA-N Cyclohexane Chemical compound C1CCCCC1 XDTMQSROBMDMFD-UHFFFAOYSA-N 0.000 claims description 3
- NUJOXMJBOLGQSY-UHFFFAOYSA-N manganese dioxide Chemical compound O=[Mn]=O NUJOXMJBOLGQSY-UHFFFAOYSA-N 0.000 claims description 3
- 229910052763 palladium Inorganic materials 0.000 claims description 3
- 229910052697 platinum Inorganic materials 0.000 claims description 3
- SBVSDAFTZIVQEI-UHFFFAOYSA-N 2,3,4,4a,4b,5,6,7,8,8a,9,9a-dodecahydro-1h-carbazole Chemical compound C1CCCC2C3CCCCC3NC21 SBVSDAFTZIVQEI-UHFFFAOYSA-N 0.000 claims description 2
- UPWOEMHINGJHOB-UHFFFAOYSA-N cobalt(III) oxide Inorganic materials O=[Co]O[Co]=O UPWOEMHINGJHOB-UHFFFAOYSA-N 0.000 claims description 2
- 239000012266 salt solution Substances 0.000 claims description 2
- CXWXQJXEFPUFDZ-UHFFFAOYSA-N tetralin Chemical compound C1=CC=C2CCCCC2=C1 CXWXQJXEFPUFDZ-UHFFFAOYSA-N 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 2
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims 1
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims 1
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims 1
- GNRSAWUEBMWBQH-UHFFFAOYSA-N nickel(II) oxide Inorganic materials [Ni]=O GNRSAWUEBMWBQH-UHFFFAOYSA-N 0.000 claims 1
- 239000007788 liquid Substances 0.000 abstract description 44
- 238000006356 dehydrogenation reaction Methods 0.000 abstract description 7
- 150000002431 hydrogen Chemical class 0.000 abstract description 4
- 239000000956 alloy Substances 0.000 abstract 1
- 229910045601 alloy Inorganic materials 0.000 abstract 1
- 150000002739 metals Chemical class 0.000 abstract 1
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 52
- 239000000243 solution Substances 0.000 description 43
- 125000004435 hydrogen atom Chemical group [H]* 0.000 description 34
- 238000006243 chemical reaction Methods 0.000 description 33
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 28
- 229910052757 nitrogen Inorganic materials 0.000 description 26
- 239000012065 filter cake Substances 0.000 description 22
- 239000007789 gas Substances 0.000 description 15
- 238000012546 transfer Methods 0.000 description 15
- 239000008367 deionised water Substances 0.000 description 14
- 229910021641 deionized water Inorganic materials 0.000 description 14
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 description 14
- 238000003756 stirring Methods 0.000 description 13
- 238000012360 testing method Methods 0.000 description 13
- 239000002253 acid Substances 0.000 description 12
- 238000001132 ultrasonic dispersion Methods 0.000 description 10
- VCJMYUPGQJHHFU-UHFFFAOYSA-N iron(3+);trinitrate Chemical compound [Fe+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O VCJMYUPGQJHHFU-UHFFFAOYSA-N 0.000 description 8
- 229910001961 silver nitrate Inorganic materials 0.000 description 7
- 230000000052 comparative effect Effects 0.000 description 6
- 238000005984 hydrogenation reaction Methods 0.000 description 5
- 239000000463 material Substances 0.000 description 5
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 5
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 229910000831 Steel Inorganic materials 0.000 description 3
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 description 3
- 150000004945 aromatic hydrocarbons Chemical class 0.000 description 3
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 3
- 239000001301 oxygen Substances 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- ZNNZYHKDIALBAK-UHFFFAOYSA-M potassium thiocyanate Chemical compound [K+].[S-]C#N ZNNZYHKDIALBAK-UHFFFAOYSA-M 0.000 description 3
- 239000010959 steel Substances 0.000 description 3
- UFWIBTONFRDIAS-UHFFFAOYSA-N Naphthalene Chemical compound C1=CC=CC2=CC=CC=C21 UFWIBTONFRDIAS-UHFFFAOYSA-N 0.000 description 2
- 239000003792 electrolyte Substances 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000005839 oxidative dehydrogenation reaction Methods 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 1
- QCDFRRQWKKLIKV-UHFFFAOYSA-M chloroplatinum Chemical compound [Pt]Cl QCDFRRQWKKLIKV-UHFFFAOYSA-M 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 239000006185 dispersion Substances 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000295 fuel oil Substances 0.000 description 1
- 235000015220 hamburgers Nutrition 0.000 description 1
- 239000002198 insoluble material Substances 0.000 description 1
- QZRHHEURPZONJU-UHFFFAOYSA-N iron(2+) dinitrate nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Fe+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O QZRHHEURPZONJU-UHFFFAOYSA-N 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- PIBWKRNGBLPSSY-UHFFFAOYSA-L palladium(II) chloride Chemical compound Cl[Pd]Cl PIBWKRNGBLPSSY-UHFFFAOYSA-L 0.000 description 1
- 229940116357 potassium thiocyanate Drugs 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000002441 reversible effect Effects 0.000 description 1
- 238000007493 shaping process Methods 0.000 description 1
- 230000003068 static effect Effects 0.000 description 1
- 239000011232 storage material Substances 0.000 description 1
- 238000004448 titration Methods 0.000 description 1
- PXXNTAGJWPJAGM-UHFFFAOYSA-N vertaline Natural products C1C2C=3C=C(OC)C(OC)=CC=3OC(C=C3)=CC=C3CCC(=O)OC1CC1N2CCCC1 PXXNTAGJWPJAGM-UHFFFAOYSA-N 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
-
- 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
- H01M4/88—Processes of manufacture
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Manufacturing & Machinery (AREA)
- Catalysts (AREA)
Abstract
The present invention provides a catalyst comprising: and (2) component A: at least one group VIII metal and/or an alloy of at least two group VIII metals; and (B) component: at least one carbon material; and a component C: at least one variable valence metal oxide. The catalyst provided by the invention can directly convert hydrogen energy stored in organic liquid molecules into electric energy without a process of releasing hydrogen, so that the arrangement of devices such as a dehydrogenation reactor, a heat exchanger and the like can be avoided, the space can be greatly saved, and the cost can be reduced.
Description
Technical Field
The invention relates to the field of hydrogen energy, in particular to a catalyst and a preparation method and application thereof.
Background
On the german hamburger G20 peak in 7 months in 2017, some developed countries in europe and america have proposed a plan to ban fuel vehicles, which stipulates that fuel vehicles will be banned in full before the deadline comes. This measure indicates that the development of a conventional fuel-oil vehicle as a substitute for a vehicle is imminent.
One of the vehicles that are replaced by conventional fuel-powered vehicles is a fuel cell vehicle, which is a vehicle powered by the electrochemical reaction of hydrogen and oxygen. The hydrogen is obtained in the form of vehicle-mounted hydrogen, and the vehicle-mounted hydrogen can be obtained in two ways, wherein one way is to directly carry a hydrogen storage bottle, such as high-pressure hydrogen or liquid hydrogen, and the other way is to assemble a hydrogen generator and produce hydrogen through compound dehydrogenation on the vehicle.
The portable hydrogen storage cylinder is generally a 35MPa steel cylinder, and the method has the advantages of convenient operation, poor safety, large hydrogen storage energy consumption, large volume of the hydrogen storage steel cylinder, low hydrogen storage density and the like. For example, when 6.6Kg of hydrogen is stored in 140L cylinders, the weight of the cylinders (excluding the valve) is as high as 81Kg, and the frame specification is 1990mm × 510mm × 1720 mm.
When assembled, hydrogen generators are typically shipped with compounds that are convenient for storage and transport, and that produce hydrogen gas in the hydrogen generator through a dehydrogenation reaction. The method is characterized in that hydrogen is stored in a hydrogen-rich manner through chemical bond hydrogenation of unsaturated aromatic hydrocarbons by virtue of a hydrogenation-dehydrogenation reversible reaction between the unsaturated aromatic hydrocarbons (such as benzene, toluene, naphthalene and the like) and corresponding organic liquids (such as cyclohexane, methylcyclohexane and decalin), and then the hydrogen is conveyed to a hydrogenation station or a gas station by utilizing the existing oil pipelines, tank cars and other transportation modes at normal temperature and normal pressure and then is added to a vehicle needing hydrogenation. When hydrogen is required, the desired hydrogen can be obtained by dehydrogenation. The dehydrogenated compound is unloaded at a hydrogenation station or a gas station, transported back to a hydrogen-rich place, and hydrogen can be stored again after hydrogenation, and the steps are repeated in such a way, so that the storage and transportation of the hydrogen on the vehicle are realized, and the compound can be recycled. The method has the advantages of convenient hydrogen storage and transportation, safety and high efficiency, greatly solves the problem of steel cylinder hydrogen storage, and compounds are hydrogenated into hydrogen storage materials after dehydrogenation. However, the disadvantage of this technology is that the hydrogen generator and heat exchanger are bulky and costly, and the cost of the reaction system is as high as 50 ten thousand yuan, so that the research on this technology is limited to the bus at present.
At present, a new mode needs to be developed to solve the problems of large system volume, high cost and the like caused by carrying a hydrogen generator and a heat exchanger on a vehicle in the prior art.
Disclosure of Invention
In view of the problems in the prior art, the present invention aims to provide a catalyst, a preparation method and an application thereof. When the catalyst provided by the invention is applied to a fuel cell, particularly a direct fuel cell based on compound hydrogen storage, the compound can directly generate incomplete oxidative dehydrogenation discharge reaction at the anode of the fuel cell to generate a dehydrogenated compound and hydrogen atoms, wherein protons in the hydrogen atoms diffuse to the cathode through an electrolyte and react with oxygen on the cathode to generate water. Through the mode, hydrogen energy stored in organic liquid molecules can be directly converted into electric energy without the process of releasing hydrogen, so that devices such as a dehydrogenation reactor and a heat exchanger can be avoided, the space can be greatly saved, and the cost is reduced.
In one aspect, the present invention provides a catalyst comprising:
and (2) component A: at least one group VIII metal;
and (B) component: at least one carbon material; and
and (3) component C: at least one variable valence metal oxide.
According to the invention, component A is selected from Pd and/or Pt.
According to the invention, component A is Pd and Pt.
According to the invention, the atomic ratio of Pd and Pt in component a is 1: (0.1-2).
According to the invention, component B is selected from at least one of single-layer graphene, double-layer graphene and graphene oxide.
According to the invention, component B is a mixture of single-layer graphene and/or double-layer graphene and graphene oxide.
According to the invention, when the component B is a mixture of single-layer graphene and/or double-layer graphene and graphene oxide, the mass ratio of the single-layer graphene and/or double-layer graphene to the graphene oxide is (0.03-1): 1.
according to the invention, component C is selected from MoO3、V2O5、WO2、Nb2O5NiO and Co2O3At least one of (1).
According to the invention, component C is selected from MoO3、V2O5、WO2And Nb2O5At least one of (1).
Through a great deal of experiments and researches, the inventor of the application finds that when the component A, the component B and the component C are combined for use, the prepared catalyst can efficiently catalyze unsaturated aromatic hydrocarbon and organic liquid to directly carry out incomplete oxidative dehydrogenation discharge reaction on an anode of a fuel cell to generate a dehydrogenated compound and hydrogen atoms, wherein protons in the hydrogen atoms diffuse to a cathode through an electrolyte and react with oxygen on the cathode to generate water.
In some preferred embodiments of the present invention, the catalyst comprises, in parts by weight,
the content of the component A is 1-10 parts;
the content of the component B is 65-84 parts;
the content of the component C is 15-25 parts.
According to the invention, the content of the component A is 2-8 parts.
According to the invention, the content of the component B is 70-80 parts.
According to the invention, the content of the component C is 18-23 parts.
According to the present invention, when the content of each component is within the above range, it is advantageous to provide a catalyst having high catalytic performance.
In some preferred embodiments of the present invention, the particle size of the component a is 0.5nm to 5.0 nm.
In some preferred embodiments of the present invention, the particle size of the component a is 0.5nm to 3.0 nm.
According to the present invention, when the particle diameter of component A is within the above-specified range, the direct proton generation reaction proceeds favorably.
In another aspect of the present invention, a preparation method of the catalyst is provided, which includes:
the method comprises the following steps: dispersing the component B in an organic solvent to prepare a first suspension containing the component B;
step two: adding the salt solution of the component A into the first suspension, and then adding a reducing agent to obtain a second suspension containing insoluble substances; and
step three: mixing the insoluble substances with the component C and forming to obtain the catalyst.
According to the invention, mixing in step three refers to mechanical mixing, more specifically to mixing by means of a kneader or ball mill.
According to the invention, the shaping in step three means that the mixture of insoluble matter and component C is made into a thin layer.
In some preferred embodiments of the present invention, the dispersion in step one is accomplished by means of ultrasound or microwaves.
In some preferred embodiments of the present invention, the power of the ultrasound is 40kW to 100 kW.
In some preferred embodiments of the present invention, the power of the microwave is 10kW to 40 kW.
In some preferred embodiments of the present invention, the time of the ultrasound or the microwave is 1 to 6 hours.
In some preferred embodiments of the present invention, the organic solvent is selected from C2～C5Alcohol or C2～C5The ketone of (3) is preferably at least one of ethanol, isopropanol, glycerol or acetone.
In some preferred embodiments of the present invention, the reducing agent is selected from at least one of ethylene glycol, hydrazine hydrate, acetic acid and acetonitrile.
According to the invention, the second suspension containing insoluble material is obtained after 4-12 h of addition of the reducing agent.
In some preferred embodiments of the present invention, the method further comprises the steps of filtering the second suspension to obtain the insolubles, and washing and drying the insolubles.
In still another aspect, the present invention provides a use of the catalyst or the catalyst prepared by the above preparation method in a fuel cell.
In still another aspect, the present invention provides a use of the above catalyst or the catalyst prepared by the above preparation method in a direct fuel cell based on hydrogen storage of a compound.
In still another aspect, the present invention provides a use of the catalyst or the catalyst prepared by the above preparation method as an anode catalyst for a fuel cell or a direct fuel cell based on hydrogen storage of a compound.
In some preferred embodiments of the present invention, the compound in the compound hydrogen storage based direct fuel cell is selected from at least one of methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole, and perhydrocarbazole
In a fuel cell, the catalyst provided by the invention or the catalyst prepared by the preparation method can enable the transfer amount of hydrogen atoms to reach more than 5.0 wt%.
Detailed Description
The present invention will be described in detail below with reference to examples, but the scope of the present invention is not limited to the following description.
In an embodiment of the present invention, the hydrogen atom transferring ability is tested by the following method:
0.02g of silver nitrate and 0.3g of iron nitrate nonahydrate (ferric nitrate is used as an indicator) were added to 50mL of deionized water to prepare a silver nitrate/ferric nitrate solution.
0.1g of the reacted catalyst was taken and placed in a silver nitrate/ferric nitrate solution. Taking a certain amount of potassium thiocyanate (KSCN) solution with the concentration of 0.01mol/L by using a basic burette, and dripping back the silver nitrate/ferric nitrate solution until the solution becomes brownish red and then reaches the titration end point. And calculating the amount of the residual silver nitrate after the reaction with the catalyst according to the consumed KSCN solution, wherein the difference value of the amount of the silver nitrate added and the amount of the residual silver nitrate after the reaction with the catalyst is the amount of the hydrogen atoms.
In an embodiment of the present invention, the particle size of Pt and the particle size of Pd in the catalyst are measured by a static chemisorption method.
The particle size of the noble metal in each example is 0.5-3 nm.
Example 1
Mechanically mixing single-layer graphene and graphene oxide according to a mass ratio of 1:4, dispersing 80 parts of the single-layer graphene and the graphene oxide in an ethanol solution, adding a chloroplatinic acid solution with a Pt content of 5 parts, performing ultrasonic dispersion treatment for 3 hours with a power of 60kW, adding a reducing agent hydrazine hydrate, reducing for 8 hours, washing the solution with clear water, and filtering to obtain a filter cake. Adding MoO3And V2O5Mixing according to the mass ratio of 4:1, and mechanically mixing 15 parts of the mixture with a filter cake to obtain the fuel cell catalyst.
1g of catalyst is loaded into a 100mL high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, the mixture is kept for 4h for reduction, then 3 times of replacement is carried out by high-purity nitrogen, 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Example 2
Mechanically mixing single-layer graphene and graphene oxide according to a mass ratio of 1:4, dispersing 80 parts of the single-layer graphene and the graphene oxide in an ethanol solution, adding 1 part of chloroplatinic acid solution with Pt content, performing ultrasonic dispersion treatment for 3 hours with the power of 60kW, adding a reducing agent hydrazine hydrate, reducing for 8 hours, washing the solution with clear water, and filtering to obtain a filter cake. Adding MoO3With WO2Mixing the components according to the mass ratio of 4:1, and mechanically mixing 19 parts of the components with a filter cake to obtain the fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Example 3
Mechanically mixing single-layer graphene and graphene oxide according to a mass ratio of 1:4, dispersing 70 parts of the single-layer graphene and the graphene oxide in an ethanol solution, adding a chloroplatinic acid solution with a Pt content of 5 parts, performing ultrasonic dispersion treatment for 3 hours by adopting a power of 60kW, adding a reducing agent hydrazine hydrate, reducing for 8 hours, washing the solution with clear water, and filtering to obtain a filter cake. Adding MoO3And Nb2O5Mixing the components according to the mass ratio of 4:1, and mechanically mixing 25 parts of the components with a filter cake to obtain the fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Example 4
Mechanically mixing double-layer graphene and graphene oxide according to a mass ratio of 1:4, taking 70 parts of the mixture to disperse in an ethanol solution, adding a chloroplatinic acid solution with a Pt content of 10 parts, performing ultrasonic dispersion treatment for 3 hours by adopting a power of 60kW, adding a reducing agent hydrazine hydrate, reducing for 8 hours, washing the solution with clear water, and filtering to obtain a filter cake. Adding MoO3And V2O5Mixing according to the mass ratio of 4:1, taking 20 parts and filteringThe cake was mechanically mixed to obtain a fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Example 5
Mechanically mixing single-layer graphene and graphene oxide according to the mass ratio of 1:1, dispersing 70 parts of the single-layer graphene and the graphene oxide in an ethanol solution, adding a chloroplatinic acid solution with the Pt content of 5 parts, performing ultrasonic dispersion treatment for 3 hours by adopting the power of 60kW, adding a reducing agent hydrazine hydrate, reducing for 8 hours, washing the solution with clear water, and filtering to obtain a filter cake. Adding MoO3And V2O5Mixing the components according to the mass ratio of 4:1, and mechanically mixing 25 parts of the components with a filter cake to obtain the fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Example 6
Mechanically mixing double-layer graphene and graphene oxide according to a mass ratio of 1:4, taking 70 parts of the mixture to disperse in an ethanol solution, adding a chloroplatinic acid solution with a Pt content of 5 parts, adopting a microwave with a power of 30kW to disperse for 3 hours, adding a reducing agent hydrazine hydrate, and addingAnd washing the solution with clear water for 8h, and filtering to obtain a filter cake. Adding MoO3And V2O5Mixing the components according to the mass ratio of 1:1, and mechanically mixing 25 parts of the components with a filter cake to obtain the fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Example 7
Mechanically mixing single-layer graphene and graphene oxide according to a mass ratio of 1:4, dispersing 70 parts of the single-layer graphene and the graphene oxide in an ethanol solution, adding a chloroplatinic acid solution with a Pt content of 5 parts, performing ultrasonic dispersion treatment for 3 hours by adopting a power of 60kW, adding a reducing agent hydrazine hydrate, reducing for 8 hours, washing the solution with clear water, and filtering to obtain a filter cake. 25 parts of MoO3And mechanically mixing with a filter cake to obtain the fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Example 8
Mechanically mixing single-layer graphene and graphene oxide according to the mass ratio of 1:4, taking 70 parts of the mixture to disperse in an ethanol solution, and adding 5 parts of chloroplatinum with the Pt contentAnd (3) dispersing the acid solution for 3 hours by adopting ultrasonic waves with the power of 60kW, adding a reducing agent hydrazine hydrate, reducing for 8 hours, washing the solution by using clear water, and filtering to obtain a filter cake. Taking 25 parts of Nb2O5Mixing the materials according to the mass ratio of 4:1, and mechanically mixing the materials with a filter cake to obtain the fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Example 9
Mechanically mixing single-layer graphene and graphene oxide according to a mass ratio of 1:4, dispersing 70 parts of the single-layer graphene and the graphene oxide in an ethanol solution, adding a chloroplatinic acid solution with a Pt content of 5 parts, performing ultrasonic dispersion treatment for 3 hours by adopting a power of 60kW, adding a reducing agent hydrazine hydrate, reducing for 8 hours, washing the solution with clear water, and filtering to obtain a filter cake. Taking 25 parts of MnO2And mechanically mixing with a filter cake to obtain the fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Example 10
Mechanically mixing graphene and graphene oxide according to the mass ratio of 1:4,70 parts of the raw materials are dispersed in an ethanol solution, a chloroplatinic acid solution with the Pt content of 2.5 parts and a palladium chloride solution with the Pd content of 2.5 parts are added, ultrasonic dispersion treatment with the power of 60kW is adopted for 3 hours, a reducing agent hydrazine hydrate is added, reduction is carried out for 8 hours, and the solution is washed by clear water and filtered to obtain a filter cake. Adding MoO3And V2O5Mixing the components according to the mass ratio of 4:1, and mechanically mixing 25 parts of the components with a filter cake to obtain the fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Comparative example 1
Mechanically mixing single-layer graphene and graphene oxide according to a mass ratio of 1:4, dispersing 70 parts of the single-layer graphene and the graphene oxide in an ethanol solution, performing ultrasonic dispersion treatment for 3 hours by adopting 60kW power, adding a reducing agent hydrazine hydrate, reducing for 8 hours, washing the solution with clear water, and filtering to obtain a filter cake. Adding MoO3And Nb2O5Mixing the materials according to the mass ratio of 4:1, and mechanically mixing the materials with a filter cake to obtain the fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Comparative example 2
Loading a chloroplatinic acid solution with the Pt content of 5 parts on MoO3And Nb2O5Mixed according to the mass ratio of 4:1, and used as a fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
Comparative example 3
Mechanically mixing single-layer graphene and graphene oxide according to a mass ratio of 1:4, dispersing 70 parts of the single-layer graphene and the graphene oxide in an ethanol solution, adding a chloroplatinic acid solution with a Pt content of 5 parts, performing ultrasonic dispersion treatment for 3 hours by adopting a power of 60kW, adding a reducing agent hydrazine hydrate, reducing for 8 hours, washing the solution with clear water, and filtering to obtain a filter cake serving as a fuel cell catalyst.
1g of catalyst is loaded into a 100ml high-pressure reaction kettle, 10g of methylcyclohexane is simultaneously loaded, 1MPa high-purity hydrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, then the mixture is kept for 4h for reduction, then the mixture is replaced by high-purity nitrogen for 3 times, then 3MPa high-purity nitrogen is introduced, the temperature is raised to 250 ℃ by a program of 5 ℃/min, and then the mixture is kept for 6 h. And (3) exhausting the gas in the high-pressure reaction kettle, collecting the liquid, pouring ethanol into the liquid, stirring for 10min, putting the mixed liquid into a 50ml centrifugal tube, centrifuging at 9500r/min for 60min, washing with deionized water again, repeating for 3 times, putting the obtained catalyst particles into an oven, drying, and testing the amount of hydrogen atoms in the catalyst particles. The hydrogen atom transfer ability is shown in table 1.
TABLE 1
| Examples | Hydrogen content wt% |
| Example 1 | 12.7 |
| Example 2 | 11.4 |
| Example 3 | 20 |
| Example 4 | 5.6 |
| Example 5 | 6.4 |
| Example 6 | 8.3 |
| Example 7 | 6.0 |
| Example 8 | 6.8 |
| Example 9 | 7.0 |
| Example 10 | 7.1 |
| Comparative example 1 | 3.1 |
| Comparative example 2 | 2.4 |
| Comparative example 3 | 3.0 |
From the data in table 1, it can be seen that the catalyst of the present invention has a higher hydrogen atom transfer ability.
It should be noted that the above-mentioned embodiments are only for explaining the present invention, and do not constitute any limitation to the present invention. The present invention has been described with reference to exemplary embodiments, but the words which have been used herein are words of description and illustration, rather than words of limitation. The invention can be modified, as prescribed, within the scope of the claims and without departing from the scope and spirit of the invention. Although the invention has been described herein with reference to particular means, materials and embodiments, the invention is not intended to be limited to the particulars disclosed herein, but rather extends to all other methods and applications having the same functionality.
Claims (10)
1. A catalyst, comprising:
and (2) component A: at least one group VIII metal, preferably Pd and/or Pt, more preferably Pd and Pt, more preferably the atomic ratio of Pd to Pt is 1: (0.1-2);
and (B) component: at least one carbon material, preferably at least one of single-layer graphene, double-layer graphene and graphene oxide, more preferably a mixture of single-layer graphene and/or double-layer graphene and graphene oxide, more preferably the mass ratio of single-layer graphene and/or double-layer graphene to graphene oxide is (0.03-1): 1; and
and (3) component C: at least one variable valence metal oxide, preferably MoO3、V2O5、WO2、Nb2O5、NiO、MnO2、Fe2O3、Cu2O and Co2O3More preferably MoO3、V2O5、WO2And Nb2O5At least one of (1).
2. The catalyst according to claim 1, characterized in that, in parts by weight,
the content of the component A is 1-10 parts, preferably 2-8 parts;
the content of the component B is 65-84 parts, preferably 70-80 parts;
the content of the component C is 15-25 parts, and preferably 18-23 parts.
3. Catalyst according to claim 1 or 2, characterized in that the particle size of component a is between 0.5nm and 5.0nm, preferably between 0.5nm and 3.0 nm.
4. A method of preparing the catalyst of any one of claims 1-3, comprising:
the method comprises the following steps: dispersing the component B in an organic solvent to prepare a first suspension containing the component B;
step two: adding the salt solution of the component A into the first suspension, and then adding a reducing agent to obtain a second suspension containing insoluble substances; and
step three: mixing the insoluble substances with the component C and forming to obtain the catalyst.
5. The method according to claim 4, wherein the dispersing in step one is performed by means of ultrasound or microwave, preferably the power of the ultrasound is 40kW to 100kW, the power of the microwave is 10kW to 40kW, and/or the time of the ultrasound or microwave is 1h to 6 h.
6. The method according to claim 4 or 5, wherein the organic solvent is selected from C2～C5Alcohol or C2～C5Ketone of (2), preferablyIs selected from at least one of ethanol, isopropanol, glycerol or acetone.
7. The production method according to any one of claims 4 to 6, characterized in that the reducing agent is selected from at least one of ethylene glycol, hydrazine hydrate, acetic acid, and acetonitrile.
8. The production method according to any one of claims 4 to 7, further comprising the steps of filtering the second suspension to obtain the insolubles, and washing and drying the insolubles.
9. Use of the catalyst according to any one of claims 1-3 or the catalyst prepared by the preparation method according to any one of claims 4-8 in a fuel cell, preferably in a direct fuel cell based on storage of hydrogen in a compound, more preferably as anode catalyst for a fuel cell or a direct fuel cell based on storage of hydrogen in a compound.
10. Use according to claim 9, wherein the compound in the direct fuel cell based on compound hydrogen storage is selected from at least one of methylcyclohexane, cyclohexane, tetrahydronaphthalene, decahydronaphthalene, perhydroazeethylcarbazole and perhydrocarbazole.
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| CN103515620A (en) * | 2012-06-20 | 2014-01-15 | 中国地质大学（武汉） | Electrode material, its application, direct fuel cell and electrochemical hydrogenation electrolytic tank |
| CN104437467A (en) * | 2014-10-27 | 2015-03-25 | 杭州聚力氢能科技有限公司 | Hydrogenation catalyst, application of hydrogenation catalyst, dehydrogenation catalyst and application of dehydrogenation catalyst |
| CN105964274A (en) * | 2016-06-07 | 2016-09-28 | 东南大学 | Precious metal platinum nanometer catalyst and preparation method and application thereof |
| CN106513013A (en) * | 2016-11-14 | 2017-03-22 | 江汉大学 | Preparation method of Pt/graphene oxide/ferric oxide catalyst used for enhancing room temperature catalytic oxidation activity of formaldehyde |
| CN107970920A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | High dispersion metal material and purposes |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103515620A (en) * | 2012-06-20 | 2014-01-15 | 中国地质大学（武汉） | Electrode material, its application, direct fuel cell and electrochemical hydrogenation electrolytic tank |
| CN104437467A (en) * | 2014-10-27 | 2015-03-25 | 杭州聚力氢能科技有限公司 | Hydrogenation catalyst, application of hydrogenation catalyst, dehydrogenation catalyst and application of dehydrogenation catalyst |
| CN105964274A (en) * | 2016-06-07 | 2016-09-28 | 东南大学 | Precious metal platinum nanometer catalyst and preparation method and application thereof |
| CN107970920A (en) * | 2016-10-21 | 2018-05-01 | 中国石油化工股份有限公司 | High dispersion metal material and purposes |
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