CN107749483A - A kind of catalyst for hydrogen-air fuel cell cathode material and preparation method thereof - Google Patents
A kind of catalyst for hydrogen-air fuel cell cathode material and preparation method thereof Download PDFInfo
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- CN107749483A CN107749483A CN201710440601.8A CN201710440601A CN107749483A CN 107749483 A CN107749483 A CN 107749483A CN 201710440601 A CN201710440601 A CN 201710440601A CN 107749483 A CN107749483 A CN 107749483A
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- H—ELECTRICITY
- H01—ELECTRIC ELEMENTS
- H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
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- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
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- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
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Abstract
The invention discloses a kind of catalyst for hydrogen-air fuel cell cathode material and preparation method thereof.In the present invention, the catalyst is by the way that VIII atom and Zn atoms are formed into metal organic frame with organoligand coordination jointly, then the absorption of at least one VIII atom in addition is carried out using Double solvent method, pass through the high temperature pyrolysis reaction under atmosphere of inert gases again, organoligand coordination forms the carbon carrier of nonmetallic heteroatoms doping, VIII atom interacts with nonmetallic heteroatoms, and is coated on inside carbon-coating and exists in the form of polyatomic.The present invention be using metal organic frame as presoma, only need to can be so that required catalyst be made by the method for high temperature pyrolysis, and preparation method is simple and easy and is the general method of synthesis polyatom.The scattered catalyst of VIII polyatom provided by the invention has good heat endurance and reflects excellent catalytic activity in the catalysis of hydrogen-air fuel cell cathodic oxygen reduction.
Description
Technical field
The invention belongs to hydrogen-air fuel cell technological invention field, and in particular to one kind is used for hydrogen-air fuel cell negative electrode material
The preparation method of the scattered catalyst of the VIII polyatom of material.
Background technology
The extensive pass of people is all caused with the development of human society, the problems such as the consumption and climate change of global energy
Note, therefore it is extremely urgent to find alternative clean energy resource.At present, the new energy developed include solar energy, wind energy,
Fuel cell etc..Wherein, hydrogen-air fuel cell be it is a kind of by the electrode reaction of hydrogen and air generate water directly by chemical energy
It is converted into the device of electric energy, it is not necessary to charge, waste gas will not be produced, because of energy conversion efficiency high (reaching 60%-80%) and environment
The superiority such as close friend are concerned by people, it is considered to be the clean energy resource generation technology of 21 century first choice.But hydrogen air-fuel material
The cathodic oxygen reduction dynamics of battery is slow, and expensive catalyst is the big factor for restricting commercializing fuel cells process.Now,
Platinum carbon is commercial most widely used catalyst, and the negative electrode of hydrogen-air fuel cell is oxygen reduction reaction, and anode is that hydroxide is anti-
Should, and the reaction rate of negative electrode seriously governs the efficiency of hydrogen-air fuel cell, so the carrying capacity of platinum carbon is anode in negative electrode
10 times of (0.4mg/cm2To 0.04mg/cm2).But because Pt resources are very limited on the Pt expensive and earth, these are all
It is to realize one of hydrogen-air fuel cell large-scale commercial urgent problem.Develop cheap, high performance non-platinum catalyst
To substitute the effective way that platinum carbon noble metal catalyst is these problems of solution.
Platinum carbon is as most widely used hydrogen-air fuel cell catalyst, not only expensive but also catalyst stabilization
Property it is poor, it is to substitute platinum carbon catalyst using platinum base alloy or non-platinum catalyst to solve method so far, so reduce into
Originally and stability is improved, what it is now for non-platinum catalyst most study is exactly new c-based nanomaterial.It is many non-expensive
The carbon of the doping such as the carbon material of metal such as nitrogen, sulphur, phosphorus is studied for the oxygen reduction catalyst of hydrogen-air fuel cell, but carbon
The cathodic oxygen reduction catalyst that the polyatomic non-noble metal nano material of base is used for acidic fuel cell is not reported also.Such as
The carbon-based non-platinum nano material of this polyatom of fruit can be used successfully to the cathode systems of hydrogen-air fuel cell, and with than platinum carbon also
Excellent catalytic activity and stability, this will greatly promote the commercialized development process of fuel cell.
The content of the invention
Catalyst disperseed it is an object of the invention to provide a kind of VIII polyatom and preparation method thereof, present invention system
The catalyst obtained shows superior catalytic performance and stability in the Cathodic oxygen reduction of hydrogen-air fuel cell, and prepares
Method is simple and easy, and heat endurance is good, and yield is high, cheap.
To achieve the above object, the present invention relates to following aspects：
<1>A kind of catalyst for hydrogen-air fuel cell negative electrode, it is monodispersed that the catalyst includes at least two
VIII and the methylimidazole as organic ligand, wherein, the organic ligand methylimidazole coordination type turns into nonmetallic
The carbon carrier of Heteroatom doping, the VIII atom and nonmetallic heteroatoms N atomic interactions, and be coated on the carbon and carry
Exist inside the carbon-coating of body and in the form of polyatomic.
<2>Basis<1>Described catalyst, wherein, wherein, at least two VIII included in the catalyst
The atomic ratio of race's atom sum and nonmetallic heteroatoms be in the range of 1: 30 to 1: 40, preferably 1: 4 to 1: 3 scope it
It is interior, most preferably within the scope of 1: 2 to 1: 3.
<3>According in the catalyst described in preceding any one, wherein, two or three of VIII is included in the catalyst
Atomic time, the mol ratio between them is in the range of 1: 1 to 1: 10 or 1: 1: 1-1: 10: 10, preferably 1: 2 to 1: 7 or 1: 1
: in the range of 1-1: 8: 8, most preferably in the range of 1: 4 to 1: 6 or 1: 1: 1-1: 6: 6.
<4>According in the catalyst described in preceding any one, wherein, the VIII atom in the catalyst be selected from Fe,
At least two metallic elements in Co, Ni, Pt, Pd and Ru.
<5>According in the catalyst described in preceding any one, wherein, the catalyst is further mixed by P atoms or S atom
It is miscellaneous.
<6>A kind of method prepared in the catalyst described in preceding any one, the described method comprises the following steps：
Step 1, the methanol solution of the methanol solution of the first VIII atomic compound and Zn compounds has been added to
In the methanol solution of machine part, or only the methanol solution of Zn compounds is added in the methanol solution of organic ligand, Bian Chao
Sound side is dissolved, and is then again stirred overnight mixed solution；
Step 2, by the mixed solution that step 1 obtains methanol centrifuge washing, dried in 60 DEG C of -90 DEG C of baking ovens overnight,
The solid powder containing the first VIII atom and Zn atoms is obtained, or obtains comprising only the solid powder of Zn atoms；
Step 3, the solid powder ultrasonic disperse containing the first VIII atom and Zn atoms step 2 obtained is insoluble
In the nonpoisonous organic solvent of water, under agitation by another selected or the water of a variety of VIII atomic compounds
Solution is added thereto for adulterating, and is stirred 1-3 hours, centrifugation, is dried overnight in 60 DEG C of -90 DEG C of baking ovens, obtain solid powder；
Or
The solid powder ultrasonic disperse for comprising only Zn atoms that step 2 is obtained is in nonpoisonous organic solvent not soluble in water
In, the aqueous solution of at least two selected VIII atomic compounds is added thereto for adulterating under agitation, stirred
Mix 1-3 hours, centrifuge, dried overnight in 60 DEG C of -90 DEG C of baking ovens, obtain solid powder；
Step 4, solid powder step 3 obtained is passed through inert gas in sealed states, heats up under an inert atmosphere
To 800-1000 DEG C, 1-3h is calcined, is then cooled to room temperature, 20min-40min is ground, produces required catalyst.
<7>According in the preparation method described in preceding any one, wherein, the first described VIII atom in step 1
Compound and Zn compounds are respective nitrate, in step 3 another for being used to adulterate and adding or a variety of
VIII atomic compound is chlorate.
<8>According in the preparation method described in preceding any one, wherein, the methanol solution of the VIII atomic compound
Molar concentration be 0.01-0.2mol/L, the molar concentration of the methanol solution of the Zn compounds is 0.01-0.2mol/L, institute
The molar concentration for stating the methanol solution of organic ligand is 0.1-1mol/L；Methanol solution, the Zn of the VIII atomic compound
Volume ratio between the methanol solution of compound, the methanol solution three of organic ligand is 1: 1: 2-1: 1: 10, and adulterates and add
The concentration of the aqueous solution of the other at least one VIII atomic compound entered is 10-200mg/ml, and the volume being doped and added to is
10-100ul。
<9>According in the preparation method described in preceding any one, wherein, the catalyst utilizes during high temperature pyrolysis
The volatilization property of atom containing P or S atom specific compound and further adulterated by P atoms or S atom, ultimately form VIII
The P compounds and S compounds of polyatom metal.
<10>According in the preparation method described in preceding any one, wherein, in step 4, described Zn atoms are in 800-
Volatilize during 1000 DEG C of high-temperature calcinations and leave unsaturated N empty sites.
Brief description of the drawings
Fig. 1 is the Pt, Co diatomics, Fe prepared, and Ni diatomics, Pd, Co diatomics and Ru, Co diatomic are in high angle
Image under annular dark field scanning transmission electron microscope；
Fig. 2 is the Fe prepared according to embodiments of the invention 1, and Co diatomics are in low power Electronic Speculum and high angle annular dark field
Image under scanning transmission electron microscope；
Fig. 3 is according to the Fe of the preparation of embodiments of the invention 1, the diatomic X-ray powder diffraction figures of Co；
Fig. 4 is according to the Fe of the preparation of embodiments of the invention 1, the double diatomic nitrogen-adsorption desorption isothermal curves of Co；
Fig. 5 is the Fe prepared according to embodiments of the invention 1, the double diatomic X ray near side (ns) absorbing structure collection of illustrative plates of Co with
And the extension side X-ray absorption fine structure collection of illustrative plates after Fourier transformation；
Fig. 6 is the Fe prepared according to embodiments of the invention 1, and Co diatomics are in 0.1M HClO4In linear scan circulation
Volt-ampere curve；
Fig. 7 is that atom and optimal Fe, Co be in pairs in pairs by two kinds of atomic ratios Fe, Co being prepared according to embodiments of the invention 1
The performance comparision of atom is in 0.1M HClO4In linear scan cyclic voltammetry curve；And
Fig. 8 be according to embodiments of the invention 1 prepare Fe, polarization curve of the Co diatomics in hydrogen-air fuel cell,
Power output, and stability.
Embodiment
It is an aspect of the invention to provide a kind of monodispersed catalyst of VIII polyatom, the catalyst be pass through by
A kind of VIII atom and Zn atoms form metal organic frame with organoligand coordination jointly, or will comprise only Zn atoms
Metal organic frame is formed with organoligand coordination, the suction of at least one VIII atom in addition is then carried out using Double solvent method
It is attached, then by the high temperature pyrolysis reaction under atmosphere of inert gases, the carbon that organoligand coordination forms nonmetallic heteroatoms doping carries
Body, VIII polyatom interact with nonmetallic heteroatoms, and are coated on inside the carbon-coating of the carbon carrier with polyatomic
Form is present.
In the present invention, the polyatom form refers to that single dispersing has at least two VIII atoms in catalyst, preferably
It is to be dispersed with two or three of VIII atom, it is monodispersed is most preferably dispersed with two kinds of VIII atoms (that is, diatomic)
Catalyst.Specifically, Fe, Co diatomics, Pt are comprised at least in polyatom single dispersing catalyst of the present invention, Co diatomics, Pt,
Ni diatomics, Pd, Co diatomics and Ru, Co diatomic etc..
In the present invention, the carbon carrier refers to the carbon carrier of hetero atom N doping.
The VIII atom used in the catalyst of the present invention is at least two in Fe, Co, Ni, Pt, Pd, Ru
Metallic element.Preferably, in the VIII polyatom catalyst of the present invention, including at least Co as a kind of metal raw therein
Son.Most preferably, including at least Co and Fe as described two VIII atoms.
In the present invention, described organic ligand is methylimidazole.
In the present invention, described nonmetallic heteroatoms are N, and wherein N derives from part methylimidazole.Additionally can be with
It is former using the volatility confrontation catalyst of atom containing P or S atom specific compound doping P atoms, S during high temperature pyrolysis
Son, ultimately form the P compounds and S compounds of VIII polyatom metal.
Another aspect of the present invention provides a kind of preparation method of the scattered catalyst of VIII polyatom.In an implementation
In scheme, preparation method of the invention comprises the following steps：
Step 1, by the methanol solution of the first VIII atomic compound and the methanol solution of Zn compounds (wherein first
The mol ratio of kind VIII atomic compound and Zn compounds is 1/1 to 1/10) it is added in organic ligand methanol solution, or
Only the methanol solution of Zn compounds is added in organic ligand methanol solution, dissolved in ultrasound, then again by mixed solution
It is stirred overnight；
Step 2, by the mixed solution that step 1 obtains methanol centrifuge washing 3-5 times, dried in 60 DEG C of -90 DEG C of baking ovens
Overnight, respectively obtain the solid powder containing the first VIII atom and Zn atoms and comprise only the solid powder of Zn atoms；
Step 3, step 2 is obtained into the solid powder ultrasonic disperse containing the first VIII atom in such as hexane, ring
, under agitation will other at least one VIII atomic compound in the nonpoisonous organic solvent not soluble in water of hexane etc
The aqueous solution be added thereto；It is or the solid powder ultrasonic disperse of only Zn atoms is not soluble in water in hexane, hexamethylene etc.
In nonpoisonous organic solvent, the aqueous solution of other at least two VIIIs atomic compound is added thereto under agitation.So
Afterwards, stir 1-3 hours, centrifugation, dried overnight in 60 DEG C of -90 DEG C of baking ovens, obtain solid powder.
For the polyatom material containing Co, there is sequencing in the addition of a variety of VIII atomic compounds, wherein, Co
Salt is the first VIII atomic compound, and second VIII atom (or other in addition a variety of VIII atom sums)
Mol ratio between Zn atoms is 1/1 to 1/2；Polyatom material for not containing Co, more than two or three VIII
Sequencing is not present in race's atomic compound, can add simultaneously, and between two or three of VIII atom and Zn atoms
Mol ratio be 1/1/1 to 1/1/2 or 1/1/1/1 to 1/1/1/2, and the mol ratio between two or three of VIII atom
For 1/1 to 1/10 or 1/1/1-1/10/10.
Step 4, solid powder step 3 obtained is put into porcelain boat, then porcelain boat is put into tube furnace sealing and is passed through indifferent gas
Body, 800-1000 DEG C being warming up under an inert atmosphere, calcining 1-3h, in the high-temperature burning process, the boiling point of Zn simple substance is 907
DEG C, the boiling point of Zn simple substance is only less than with the boiling point of the Zn atoms of N coordinations, so the process causes Zn volatilization, is left as coordination
N empty sites, then natural cooling cool to room temperature, take out and 20-40min ground in agate mortar, produce required urge
Agent.VIII is polyatomic to be existed and can support to show jointly by spherical aberration Electronic Speculum and synchrotron radiation data, while can also
Supported by plasma mass spectrograph data.
In one embodiment of the invention, the first VIII needed for metal organic frame described above is synthesized
Atomic compound and Zn compounds are respective nitrate, and are chlorine as the other VIII atomic compound being doped and added to
Salt dissolving.
In one embodiment of the invention, the molar concentration of the VIII atomic compound methanol solution is
0.01-0.2mol/L, the molar concentration of the Zn compound methanols solution are 0.01-0.2mol/L, the organic ligand methanol
The molar concentration of solution is 0.1-1mol/L；It is the VIII atomic compound methanol solution, Zn compound methanols solution, organic
Volume ratio between part methanol solution three is 1: 1: 2-1: 1: 10.As another being doped and added to, two or three
The concentration of the aqueous solution of VIII atomic compound above is 10-200mg/ml, and the volume being doped and added to is 10-100ul.
In one embodiment of the invention, described inert gas can be N2Or Ar gases.
Fig. 1 shows Pt prepared according to the methods of the invention, Co diatomics (A), Fe, and Ni diatomics (B), Pd, Co are double
The image of atom (C) and Ru, Co diatomic (D) under high angle annular dark field scanning transmission electron microscope.Can be with from Fig. 1
It is all monodispersed on the carbon carrier to find out four kinds of diatomics of the above.
Fig. 2 shows the Fe prepared according to a kind of preparation method of the present invention, figure of the Co diatomics in low power transmission electron microscope
As (A), the image (B) under annular dark field scanning transmission electron microscope, the figure under annular light field scanning transmission electron microscope
As (C), the image (D) under high angle annular dark field scanning transmission electron microscope, wherein red circle mark for diatomic.
Fe as can be seen from Figure 2, Co diatomic material are hollow material, wherein have one on each face of granatohedron
Hole, and diatomic is monodispersed is present on the carbon carrier of N doping.
Fig. 3 shows the Fe prepared according to a kind of preparation method of the present invention, the diatomic X-ray powder diffraction figures of Co.
The diatomic crystallinity of the Fe it can be seen from the figure, Co is poor, the presence without specific crystal formation similar to amorphous material.
Fig. 4 shows the Fe prepared according to a kind of preparation method of the present invention, Co diatomic nitrogens-adsorption desorption curve (A)
And pore size distribution curve (B).From Fig. 4 (A) and 4 (B) and Fig. 2 is combined, Fe, Co diatomic catalyst is one while deposited
In the material of micropore-mesopore-macropore.
Fig. 5 shows the Fe prepared according to a kind of preparation method of the present invention, and the X ray near side (ns) on the diatomic Fe sides of Co is inhaled
Receive the extension side X-ray absorption fine structure collection of illustrative plates (B) after structure collection of illustrative plates (A) and Fourier transformation, the X ray near side (ns) on Co sides
Extension side X-ray absorption fine structure collection of illustrative plates (D) after absorbing structure collection of illustrative plates (C) and Fourier transformation.Wherein, (A) and (C)
X-axis represent ABSORPTION EDGE electron energy scope, Y-axis represent absorption intensity；(B) and (D) X-axis represent by Fourier transformation it
The bond distance in R spaces afterwards, Y-axis represent the absorption intensity after Fourier transformation.From fig. 5, it can be seen that the presence of Fe-Co keys, enters one
Step illustrates that material is the monodispersed catalyst of diatomic.
Fig. 6 shows the Fe prepared according to a kind of preparation method of the present invention, and Co diatomics (red line) are with Pt contents
20% business platinum carbon (black line), hydrogen reduction performance comparision, electrolyte are 0.1M HClO4, rotating speed 1600rpm, sweeping speed is
10mV/s.The diatomic take-off potential of wherein Fe, Co is 1.06V, and platinum carbon is 1.03V, and half wave potential is 0.863V and platinum carbon
For 0.858V.From fig. 6, it can be seen that Fe, Co diatomic catalytic performance are slightly better than business platinum carbon.
Fig. 7 shows the Fe of the different atomic ratios prepared according to a kind of preparation method of the present invention, the reduction of Co diatomic oxygens
Performance comparision, electrolyte are 0.1M HClO4, rotating speed 1600rpm, it is 10mV/s to sweep speed.From figure 7 it can be seen that Fe, Co are double
Relation be present with Fe in the material, Co atomic ratio in the catalytic performance of atom.
Fig. 8 shows the Fe prepared according to a kind of preparation method of the present invention, and Co diatomics catalyst is in hydrogen air-fuel material electricity
Polarization curve in pond, power output (A), and the stability (B) under different current densities, carrying capacity are less than 1mg/cm2.Wherein
The maximum power output of Fe, Co diatomic catalyst is 505mW/cm2, the 664mW/cm2 of business platinum carbon；And can be with stable operation
100h.From figure 8, it is seen that Fe, Co diatomic catalyst have extraordinary business development prospect in hydrogen-air fuel cell.
Beneficial effects of the present invention：
(1) polyatom dispersed catalyst provided by the invention is using metal organic frame as presoma, only need to pass through high temperature
The method of pyrolysis can be to be made, and the preparation method is simple and easy, is also used to prepare other various monatomic or polyatoms, this
VIII atom exists in the form of polyatomic and is evenly dispersed on carbon-based in catalyst prepared by invention；
(2) the scattered catalyst of VIII polyatom provided by the invention has at a relatively high hydrogen reduction under sour environment
Catalytic activity.It is slightly better than the noble metal catalyst platinum carbon of business that test obtains hydrogen reduction take-off potential and half wave potential.
0.1mol/L HClO4In electrolyte, its hydrogen reduction take-off potential 1.02V, half wave potential 0.852V, cycle performance is also compared with platinum
Carbon is more excellent.Therefore, the catalyst that the VIII polyatom that prepared by the present invention disperses is suitable for hydrogen-air fuel cell cathode reaction.
In addition, the present invention may have the catalyst prepared without using pt, this kind of non-platinum catalyst is cheap, and stability is good, can
Promote the development of hydrogen-air fuel cell.
(3) this polyatomic synthetic method of the invention is also to be suggested first, and this synthetic method will be for more former
The synthesis of son provides a kind of new strategy.The maximum power output density of the hydrogen-air fuel cell of existing non-precious metal catalyst
For 0.41w/cm2, carrying capacity 3.8-4.1mg/cm2；And the catalyst that the VIII polyatom disperses is less than 1mg/cm in carrying capacity2
Under conditions of maximum power output density be 0.51w/cm2For the 76% of business platinum carbon.
Embodiment
Below, for a further understanding of the present invention, the preferred embodiment of the invention is described with reference to embodiment,
It is understood that these descriptions are simply further explanation the features and advantages of the present invention, rather than limitation of the present invention.
Prepare embodiment 1
The preparation of the scattered catalyst of Fe, Co diatomic：
(1) zinc nitrate hexahydrate methanol solution and the 0.125mol/L cabaltous nitrate hexahydrate methanol for configuring 0.125mol/L are molten
Liquid, 0.5mol/L methylimidazole methanol solution；Then by 15 milliliters of 0.125mol/L zinc nitrate hexahydrate methanol solutions
With the methylimidazole methanol that 30 milliliters are added to after 15 milliliters of 0.125mol/L cabaltous nitrate hexahydrate methanol solution mixing
In solution, dissolve in ultrasound, be then again stirred overnight mixed solution；
(2) by obtained mixed solution methanol centrifuge washing 3-5 times, dried overnight in 70 DEG C of baking ovens, obtain solid
Powder；
(3) metal organic frame obtained above is dispersed in n-hexane, it is 50mg/ml's then to add 50ul concentration
Washing and drying after ferric chloride in aqueous solution stirring 1-3h；
(4) obtained solid powder is put into porcelain boat, then porcelain boat is put into tube furnace sealing and is passed through inert gas, in inertia
900 DEG C are warming up under atmosphere, calcines 3h, then natural cooling cools to room temperature, takes out and 30min is ground in agate mortar, obtain
The catalyst disperseed to required Fe-Co diatomics, as shown in Fig. 2 observing that Fe-Co diatomics equably singly divide under Electronic Speculum
Be dispersed in N doping it is carbon-based on.
Prepare embodiment 2
The preparation of the scattered catalyst of the Fe of different atomic ratios, Co diatomic
(1) zinc nitrate hexahydrate methanol solution and the 0.125mol/L cabaltous nitrate hexahydrate methanol for configuring 0.125mol/L are molten
Liquid, 0.5mol/L methylimidazole methanol solution；Then by 15 milliliters of 0.125mol/L zinc nitrate hexahydrate methanol solutions
With the methylimidazole methanol that 30 milliliters are added to after 15 milliliters of 0.125mol/L cabaltous nitrate hexahydrate methanol solution mixing
In solution, dissolve in ultrasound, be then again stirred overnight mixed solution；
(2) by obtained mixed solution methanol centrifuge washing 3-5 times, dried overnight in 70 DEG C of baking ovens, obtain solid
Powder；
(3) metal organic frame obtained above is dispersed in n-hexane, it is 10mg/ml's then to add 50ul concentration
Ferric chloride in aqueous solution or 50ul concentration are 100mg/ml ferric chloride in aqueous solution, stir washing and drying after 1-3h；
(4) obtained solid powder is put into porcelain boat, then porcelain boat is put into tube furnace sealing and is passed through inert gas, in inertia
900 DEG C are warming up under atmosphere, calcines 3h, then natural cooling cools to room temperature, takes out and 30min is ground in agate mortar, obtain
The catalyst disperseed to required different atomic ratio Fe-Co diatomics.
Prepare embodiment 3
(the diatomic material containing Co) Pt, the preparation of the scattered catalyst of Co diatomics
(1) zinc nitrate hexahydrate methanol solution and the 0.125mol/L cabaltous nitrate hexahydrate methanol for configuring 0.125mol/L are molten
Liquid, 0.5mol/L methylimidazole methanol solution；Then by 15 milliliters of 0.125mol/L zinc nitrate hexahydrate methanol solutions
With the methylimidazole methanol that 30 milliliters are added to after 15 milliliters of 0.125mol/L cabaltous nitrate hexahydrate methanol solution mixing
In solution, dissolve in ultrasound, be then again stirred overnight mixed solution；
(2) by obtained mixed solution methanol centrifuge washing 3-5 times, dried overnight in 70 DEG C of baking ovens, obtain solid
Powder；
(3) metal organic frame obtained above is dispersed in n-hexane, it is 20mg/ml's then to add 40ul concentration
The platinic sodium chloride aqueous solution, stir washing and drying after 1-3h；
(4) obtained solid powder is put into porcelain boat, then porcelain boat is put into tube furnace sealing and is passed through inert gas, in inertia
900 DEG C are warming up under atmosphere, calcines 3h, then natural cooling cools to room temperature, takes out and 30min is ground in agate mortar, obtain
The catalyst disperseed to required Pt-Co diatomics.
Prepare embodiment 4
(the diatomic material for being free of Co) Fe, the preparation of the scattered catalyst of Ni diatomics
(1) 0.125mol/L zinc nitrate hexahydrate methanol solution, 0.5mol/L methylimidazole methanol solution are configured；
Then 15 milliliters of 0.125mol/L zinc nitrate hexahydrate methanol solutions are added to 30 milliliters of methylimidazole methanol solution
In, dissolve in ultrasound, be then again stirred overnight mixed solution；
(2) by obtained mixed solution methanol centrifuge washing 3-5 times, dried overnight in 70 DEG C of baking ovens, obtain solid
Powder；
(3) metal organic frame obtained above is dispersed in n-hexane, then adds the mixed of iron chloride and nickel chloride
Washing and drying after Heshui solution 40ul (concentration 20mg/ml) stirrings 1-3h；
(4) obtained solid powder is put into porcelain boat, then porcelain boat is put into tube furnace sealing and is passed through inert gas, in inertia
900 DEG C are warming up under atmosphere, calcines 3h, then natural cooling cools to room temperature, takes out and 30min is ground in agate mortar, obtain
The catalyst disperseed to required Fe-Ni diatomics.
Prepare embodiment 5
(three atom materials containing Co) Fe, Ni, the wherein preparation of the scattered catalyst of the atoms of Co tri-, Fe, Co, Ni three are former
Sub- ratio is 1/1/10-1/10/10.
(1) zinc nitrate hexahydrate methanol solution and the 0.125mol/L cabaltous nitrate hexahydrate methanol for configuring 0.125mol/L are molten
Liquid, 0.5mol/L methylimidazole methanol solution；Then by 15 milliliters of 0.125mol/L zinc nitrate hexahydrate methanol solutions
With the methylimidazole methanol that 30 milliliters are added to after 15 milliliters of 0.125mol/L cabaltous nitrate hexahydrate methanol solution mixing
In solution, dissolve in ultrasound, be then again stirred overnight mixed solution；
(2) by obtained mixed solution methanol centrifuge washing 3-5 times, dried overnight in 70 DEG C of baking ovens, obtain solid
Powder；
(3) metal organic frame obtained above is dispersed in n-hexane, then adds the mixed of iron chloride and nickel chloride
Washing and drying after Heshui solution 40ul (concentration 20mg/ml) stirrings 1-3h；
(4) obtained solid powder is put into porcelain boat, then porcelain boat is put into tube furnace sealing and is passed through inert gas, in inertia
900 DEG C are warming up under atmosphere, calcines 3h, then natural cooling cools to room temperature, takes out and 30min is ground in agate mortar, obtain
The catalyst disperseed to the required atoms of Fe-Ni-Co tri-.
Prepare embodiment 6
(three atom materials for being free of Co) Fe, Ni, the preparation of the scattered catalyst of the atoms of Pt tri-
(1) 0.125mol/L zinc nitrate hexahydrate methanol solution, 0.5mol/L methylimidazole methanol solution are configured；
Then 15 milliliters of 0.125mol/L zinc nitrate hexahydrate methanol solutions are added to 30 milliliters of methylimidazole methanol solution
In, dissolve in ultrasound, be then again stirred overnight mixed solution；
(2) by obtained mixed solution methanol centrifuge washing 3-5 times, dried overnight in 70 DEG C of baking ovens, obtain solid
Powder；
(3) metal organic frame obtained above is dispersed in n-hexane, then adds iron chloride, nickel chloride and chlorine platinum
Mixed aqueous solution 40ul (concentration 20mg/ml) stirrings of sour (wherein Fe, Ni, Pt three atomic ratio are 1/1/10-1/10/10)
Washing and drying after 1-3h；
(4) obtained solid powder is put into porcelain boat, then porcelain boat is put into tube furnace sealing and is passed through inert gas, in inertia
900 DEG C are warming up under atmosphere, calcines 3h, then natural cooling cools to room temperature, takes out and 30min is ground in agate mortar, obtain
The catalyst disperseed to the required atoms of Fe-Ni-Pt tri-.
Application Example 1
Oxygen reduction activity evaluation is carried out to preparing the catalyst that Fe-Co diatomics are scattered made from embodiment 1：
5mg above-described embodiments are added in containing Nafion the and 950ul ethanol solutions that 50ul mass concentrations are 5%
The scattered catalyst of the 3 Fe-Co diatomics prepared, ultrasonic disperse 30min, obtains scattered catalyst solution.Then in 0.1M
HClO4Tested in solution.Reaction condition is：In 0.1M HClO4In solution, lead to oxygen saturation, take obtained point of fraction
Scattered catalyst solution is dripped in being dried on glass-carbon electrode, is 1600r in electrode rotating speed at room temperature, and it is to be obtained under 10mV/s to sweep speed
Linear sweep voltammetry curve.The performance test results are referring to accompanying drawing 6.
Comparative example 1
5mg business Pt/C is added into Nafion the and 950ul ethanol solutions that the mass concentration containing 50ul is 5%
(Pt contents are 20%) catalyst, ultrasonic disperse 30min, obtains solution；Then business Pt/C catalyst is 0.1mol/L's
HClO4Electro-chemical test is carried out in electrolyte.
Solution drop coating described in 5ul is taken after room temperature is dried, to obtain membrane electrode in rotating disk electrode (r.d.e)；With Ag/AgCl electricity
Pole is as reference electrode, Pt silks as the three-electrode system to electrode.In oxygen-saturated 0.1mol/L HClO4Utilized in solution
Rotating disk electrode (r.d.e) carries out linear volt-ampere test, sweep speed 10mV/s.
Application Example 2
Fe- to preparing different atomic ratios (being respectively that Fe/Co ratios are respectively 5/1 and 20/1) made from Examples 1 and 2
The scattered catalyst of Co diatomics carries out oxygen reduction activity evaluation：
5mg above-described embodiments are added in containing Nafion the and 950ul ethanol solutions that 50ul mass concentrations are 5%
The catalyst that the Fe-Co diatomics of the 1 different atomic ratios prepared disperse, ultrasonic disperse 30min, it is molten to obtain scattered catalyst
Liquid.Then in 0.1M HClO4Tested in solution.Reaction condition is：In 0.1M HClO4In solution, lead to oxygen saturation, take
The catalyst solution disperseed made from fraction is dripped in being dried on glass-carbon electrode, at room temperature, is 1600r in electrode rotating speed, is swept speed
To obtain linear sweep voltammetry curve under 10mV/s.The performance test results are referring to accompanying drawing 7.
Comparative example 2
5mg business Pt/C is added into Nafion the and 950ul ethanol solutions that the mass concentration containing 50ul is 5%
(Pt contents are 20%) catalyst, ultrasonic disperse 30min, obtains solution；Then business Pt/C catalyst is 0.1mol/L's
HClO4Electro-chemical test is carried out in electrolyte.
Solution drop coating described in 5ul is taken after room temperature is dried, to obtain membrane electrode in rotating disk electrode (r.d.e)；With Ag/AgCl electricity
Pole is as reference electrode, Pt silks as the three-electrode system to electrode.In oxygen-saturated 0.1mol/L HClO4Utilized in solution
Rotating disk electrode (r.d.e) carries out linear volt-ampere test, sweep speed 10mV/s.
Application Example 3
To preparing the catalyst hydrogen-air fuel cell activity rating that Fe-Co diatomics are scattered made from embodiment 1：
The above-mentioned implementations of 20mg are added in containing Nafion the and 950ul ethanol solutions that 50ul mass concentrations are 5%
The catalyst that Fe-Co diatomics prepared by example 1 disperse, ultrasonic disperse 30min, obtains scattered catalyst solution.Then should
Catalyst solution is sprayed on 5cm*5cm carbon paper, then with PEM hot pressing, so as to obtain the moon of hydrogen-air fuel cell
Pole.It is 0.05mg/cm that platinum carbon (content is 20% business platinum carbon) carrying capacity, which is similarly made,2Hydrogen-air fuel cell anode.Sun
Extremely logical hydrogen, negative electrode blowing air, total air pressure is 0.2MPa, and wherein the air pressure ratio of hydrogen and oxygen is 1.5 to 2.5, and
Tested under the conditions of 90 DEG C.The performance test results are referring to accompanying drawing 8.
Comparative example 3
The negative electrode platinum carbon (content is 60% business platinum carbon) that hydrogen-air fuel cell is made in method same as Example 4 carries
Measure as 0.3mg/cm2, anode platinum carbon (content is 20% business platinum carbon) carrying capacity is 0.05mg/cm2.Anode leads to hydrogen, and negative electrode leads to
Air, total air pressure are 0.2MPa, and wherein the air pressure ratio of hydrogen and oxygen is 1.5 to 2.5, and is surveyed under the conditions of 90 DEG C
Examination.
Industrial applicability
For the catalyst that VIII polyatom prepared by the present invention disperses due to cheap, stability is good, it is contemplated that will be in work
There is good potential prospect in industry application.It can be suitable for hydrogen-air fuel cell cathode reaction, can promote hydrogen air-fuel material
The tremendous development of battery.
Claims (10)
1. a kind of catalyst for hydrogen-air fuel cell negative electrode, the catalyst include at least two monodispersed VIIIs and
As the methylimidazole of organic ligand, wherein, the organic ligand methylimidazole coordination type is mixed as nonmetallic heteroatoms
Miscellaneous carbon carrier, the VIII atom and nonmetallic heteroatoms N atomic interactions, and it is coated on the carbon-coating of the carbon carrier
The inside simultaneously exists in the form of polyatomic.
2. catalyst according to claim 1, wherein, at least two VIIIs atom included in the catalyst
The atomic ratio of sum and nonmetallic heteroatoms is in the range of 1: 30 to 1: 40.
3. catalyst according to claim 1, wherein, comprising between two or three of VIII atom in the catalyst
When, the mol ratio between them is in the range of 1: 1 to 1: 10 or 1: 1: 1-1: 10: 10.
4. catalyst according to claim 1, wherein, the VIII atom in the catalyst be selected from Fe, Co, Ni,
At least two metallic elements in Pt, Pd and Ru.
5. catalyst according to claim 1, wherein, the catalyst is further adulterated by P atoms or S atom.
6. a kind of method for preparing the catalyst according to claim any one of 1-5, the described method comprises the following steps：
Step 1, the methanol solution of the methanol solution of the first VIII atomic compound and Zn compounds is added to organic match somebody with somebody
In the methanol solution of body, or only the methanol solution of Zn compounds is added in the methanol solution of organic ligand, in ultrasound
Mixed solution, is then stirred overnight by dissolving again；
Step 2, by the mixed solution that step 1 obtains methanol centrifuge washing, dry overnight, obtain in 60 DEG C of -90 DEG C of baking ovens
Solid powder containing the first VIII atom and Zn atoms, or obtain comprising only the solid powder of Zn atoms；
Step 3, the solid powder ultrasonic disperse containing the first VIII atom and Zn atoms step 2 obtained is not soluble in water
Nonpoisonous organic solvent in, under agitation by another selected or the aqueous solution of a variety of VIII atomic compounds
It is added thereto for adulterating, stirs 1-3 hours, centrifugation, dried overnight in 60 DEG C of -90 DEG C of baking ovens, obtain solid powder；Or
The solid powder ultrasonic disperse for comprising only Zn atoms that step 2 is obtained in nonpoisonous organic solvent not soluble in water,
The aqueous solution of at least two selected VIII atomic compounds is added thereto for adulterating under stirring condition, stirs 1-3
Hour, centrifugation, dried overnight in 60 DEG C of -90 DEG C of baking ovens, obtain solid powder；
Step 4, solid powder step 3 obtained is passed through inert gas in sealed states, is warming up under an inert atmosphere
800-1000 DEG C, 1-3h is calcined, is then cooled to room temperature, 20min-40min is ground, produces required catalyst.
7. preparation method according to claim 6, wherein, the first described VIII atomic compound in step 1
It is respective nitrate with Zn compounds, another or a variety of VIIIs for being used to adulterate and adding in step 3
Atomic compound is chlorate.
8. preparation method according to claim 6, wherein, the methanol solution of the first VIII atomic compound
Molar concentration is 0.01-0.2mol/L, and the molar concentration of the methanol solution of the Zn compounds is 0.01-0.2mol/L, described
The molar concentration of the methanol solution of organic ligand is 0.1-1mol/L；The methanol of the first VIII atomic compound is molten
Liquid, the methanol solution of Zn compounds, organic ligand methanol solution three between volume ratio be 1: 1: 2-1: 1: 10, and mix
The concentration of the aqueous solution of other at least one VIII atomic compound of miscellaneous addition is 10-200mg/ml, the body being doped and added to
Product is 10-100ul.
9. preparation method according to claim 6, wherein, the catalyst utilizes atom containing P during high temperature pyrolysis
Or S atom specific compound volatilization property and further adulterated by P atoms or S atom, ultimately form VIII polyatom
The P compounds and S compounds of metal.
10. preparation method according to claim 6, wherein, in step 4, described Zn atoms are in 800-1000 DEG C of height
Volatilize during temperature calcining and leave unsaturated N empty sites.
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