CN103456969A - Preparation method of Pt-Co/C-single-layer graphene for fuel cell - Google Patents
Preparation method of Pt-Co/C-single-layer graphene for fuel cell Download PDFInfo
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 112
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 52
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- 239000000243 solution Substances 0.000 claims description 13
- 238000005406 washing Methods 0.000 claims description 11
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- 229910052697 platinum Inorganic materials 0.000 claims description 5
- 230000015572 biosynthetic process Effects 0.000 claims description 4
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- 239000000047 product Substances 0.000 claims description 4
- DLYUQMMRRRQYAE-UHFFFAOYSA-N tetraphosphorus decaoxide Chemical compound O1P(O2)(=O)OP3(=O)OP1(=O)OP2(=O)O3 DLYUQMMRRRQYAE-UHFFFAOYSA-N 0.000 claims description 4
- FFRBMBIXVSCUFS-UHFFFAOYSA-N 2,4-dinitro-1-naphthol Chemical compound C1=CC=C2C(O)=C([N+]([O-])=O)C=C([N+]([O-])=O)C2=C1 FFRBMBIXVSCUFS-UHFFFAOYSA-N 0.000 claims description 3
- 206010013786 Dry skin Diseases 0.000 claims description 3
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- 238000007254 oxidation reaction Methods 0.000 claims description 3
- 230000020477 pH reduction Effects 0.000 claims description 3
- USHAGKDGDHPEEY-UHFFFAOYSA-L potassium persulfate Chemical compound [K+].[K+].[O-]S(=O)(=O)OOS([O-])(=O)=O USHAGKDGDHPEEY-UHFFFAOYSA-L 0.000 claims description 3
- 235000019394 potassium persulphate Nutrition 0.000 claims description 3
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Substances [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 29
- 230000000694 effects Effects 0.000 description 7
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- 229910000510 noble metal Inorganic materials 0.000 description 5
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- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 2
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- 238000005260 corrosion Methods 0.000 description 2
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- YWEUIGNSBFLMFL-UHFFFAOYSA-N diphosphonate Chemical compound O=P(=O)OP(=O)=O YWEUIGNSBFLMFL-UHFFFAOYSA-N 0.000 description 2
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- 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
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Abstract
The invention discloses a preparation method of Pt-Co/C-single-layer graphene for a fuel cell, belongs to the chemical synthesis field, and relates to a preparation method of graphene. The Pt-Co/C-single-layer graphene for the fuel cell is prepared by the following steps: (1), preparation of graphite oxide; (2), pre-treatment of active carbon XC-72; and (3), preparation of an rGO-XC-72 composite carrier-loaded Pt-Co alloy nano particle. The metal alloy nano particle-graphene and XC-72 active carbon composite catalyst prepared by utilizing a microwave ethylene glycol auxiliary reduction method is simple and easy to implement, and is high in efficiency. Moreover, the obtained graphene has a single-layer structure and the alloy particle has uniform particle diameter distribution and an average particle diameter of 1.5 nm. The catalytic activity of the nano particle can be improved by interaction with the XC-72 active carbon as well as electronic modification to the metal nano particle. And obtained catalyst has excellent oxygen-reduction electro-catalysis performances.
Description
Technical field
The invention belongs to the field of chemical synthesis, relate to a kind of preparation method of Graphene.
Background technology
Graphene (Graphene), be a kind of two-dimensional structure new material that graphite material has the single or multiple lift atomic structure of carbon that is derived from, and it is comprised of the atomic structure of carbon that is arranged in the regular hexagon structure.Graphene is as a kind of special material of 21 century, and the Graphene thickness of single layer structure only has 0.335nm, is to find in the world at present the thinnest material.With respect to other carbon-based supports, the single-layer graphene of perfect structure has larger theoretical specific area and (is about 2630m
2g
-1) and better electronic conduction ability (be about 2 * 105cm
2v
-1s
-1), can be widely used in the fields such as electronics, chemistry, machinery.Nearest progress shows that graphene-based material has very far-reaching influence (Virendra S to the storage of electronics and photoelectronic device, chemical sensor, nano composite material and energy, Daeha J, Lei Z, et al. Graphene based materials:Past, present and future[J]. Progress in Materials Science, 2011,56 (8): 1178-1271.).
As everyone knows, the Pt base nano-catalyst is modal fuel-cell catalyst, and wherein platinum particles normally loads on the carriers such as carbon black, gnf, carbon nano-tube.In recent years, the uniqueness showed as catalyst carrier due to Graphene and remarkable physical and chemical performance, thus caused the great interest of people.
But, due to the expensive and scarcity of resources of precious metals pt, hindered the industrial production of fuel cell.At present, the research of fuel-cell catalyst mainly concentrates on the carrier and composite catalyst of catalyst.In order to reduce the consumption of precious metals pt, it is a kind of method that effectively reduces noble metal dosage, improves catalyst activity that people attempt Pt and other transition metal (as: Fe, Co, Ni, Cr, Cu etc.) formation alloy.Wherein, because the Pt-Co alloy easily makes, make it become the most frequently used Pt-M alloy.In carried noble metal is catalyst based, carrier plays vital effect.The carrier that generally is applicable to fuel-cell catalyst should possess the condition of following several aspects: (l) have good electric conductivity, the electronics of timely iontophoresis electrode reaction needed, the electronics that the leadout electrode reaction produces; (2) rational in infrastructure, stable; (3) there is larger specific area, with the use amount that reduces noble metal and the decentralization that increases catalyst; (4) resistance to corrosion is good, can sustain electrolyte to its produce corrosion failure effect (Jiang Quantong. the preparation of graphene-based fuel-cell catalyst, sign and performance study [D]. Qingdao: Qingdao University of Science and Technology, 2011.).Carbon-based supports, as carbon black, acetylene black, carbon nano-tube etc., wherein carbon nano-tube has because of it ideal chose that good transmission electronic ability and structural stability become fuel-cell catalyst carrier, but the Graphene production cost is lower, and performance is more excellent, become the focus of current research.
Summary of the invention
For improving the catalytic activity of catalyst, often be difficult to the Graphene that preparation has single layer structure in the load alloy on Graphene.Complex carrier can increase more adsorption site with respect to single carrier in theory, increases specific area.XC-72 is combined with two-dimentional Graphene, can increases more absorption duct.The present invention is by selecting active carbon XC-72 to assist to prepare the single-layer graphene catalyst carrier, reach the purpose that improves catalyst activity, and then provide a kind of single-layer graphene catalyst that can prepare support type, and technique simple, benefit batch production, the method based on the standby fuel cell of chemical stripping legal system with the Pt-Co/C-single-layer graphene.
The present invention prepares fuel cell Pt-Co/C-single-layer graphene in accordance with the following steps:
(1) preparation of graphite oxide.Take natural flake graphite as raw material, by the Hummers method, its oxidation is obtained to graphite oxide.This method has been done following improvement based on the Hummers method: potassium peroxydisulfate and each 2.5g of phosphorus pentoxide are joined in 25mL concentrated sulfuric acid flask, oil bath 40-180 ℃ of lower stirring and refluxing is after it dissolves, slowly add the 1.0-5g graphite powder, stirring reaction heating 2-10h, natural flake graphite is carried out to preliminary treatment, and filtered water is washed till the graphite that obtains processing after neutrality; By the graphite of processing, put into the 50-200g concentrated sulfuric acid and stir at ice bath, slowly add 8-30gKMnO
4after stir 1-10h in ice bath; Proceed in the oil bath pan of 35 ± 3 ℃, stir 20-120min, then slowly be added drop-wise in said mixture by 100-300mL distilled water; Thing to be mixed is cool to room temperature, takes out and puts into the 2-5L large beaker, adds 500-1500mL distilled water and 5-60mLH
2o
2, continuing to be stirred to does not have Bubble formation, and mixed liquor becomes golden yellow by atropurpureus; Standing 5-48h, abandoning supernatant, the HCl that mixture is 0.1-2:10 by volume ratio and water is centrifuge washing repeatedly, obtains the colloid substance of brown; Colloid substance, 30-80 ℃ of lower vacuumize, grinds and obtains pitchy solid, i.e. graphite oxide.
(2) preliminary treatment of active carbon XC-72: adopt red fuming nitric acid (RFNA) acidifying and H
2o
2the processing method combined is carried out preliminary treatment to active carbon XC-72, that is: acidification 10-24h after washing is to neutral in 80-120 ℃ of red fuming nitric acid (RFNA) to take 100-200mgXC-72, and 40-60 ℃ of vacuumize, obtain the XC-72 of acidifying; Then by acidifying good XC-72 at H
2o
2middle ice-bath ultrasonic 20-40min, washing filtering, vacuumize 4-12h.
(3) preparation of rGO-XC-72 composite carrier load Pt-Co alloy nano particle: take 20-50mg graphite oxide powder, add in the mixed solution of 50-100mL ethylene glycol and 10-30mL isopropyl alcohol, ice-bath ultrasonic 15-30min disperses to form the ethylene glycol suspension-turbid liquid of even graphene oxide.The XC-72 active carbon 5-30mg handled well is added in above-mentioned graphite oxide ethylene glycol solution, after mixing magnetic agitation 20-60min, ice-bath ultrasonic is processed 10-20min again; To the H that splashes into 1.7-3.4mL, 0.0386mol/L in scattered mixture
2ptCl
6with 1.33-2.66mL, 0.1mol/L Co (CH
3cOO)
2solution, magnetic agitation 30-60min, add the NaOH solution of 0.2mol/L to regulate the pH value for 8-11, stirs 10-20min.Put into microwave reactor (power 800W), adopt microwave 1-2min, suspend 0.5-2min, then the program microwave reaction of microwave 0.5-2min.The question response system is cooled to room temperature, with acetone and ethanol repeatedly washing and filtering to the product after filtering no longer occur thickly, 60 ℃ of dryings, be ground to Powdered.By above-mentioned gained sample, put into tube furnace, under argon atmospher, 300 ℃ of calcination 30min, collect sample and put into drier.
The present invention utilizes standby metal alloy nano particle-Graphene and the XC-72 active carbon composite catalyst obtained of microwave ethylene glycol assisted Reduction legal system, simple, efficiency is high, and the Graphene obtained has single layer structure, the particle diameter of alloy particle is evenly distributed, and average grain diameter is about 1.5nm.By the interaction with the XC-72 active carbon and the catalytic activity that can improve nano particle to the electronics modification of metal nanoparticle.Resulting catalyst has excellent hydrogen reduction electrocatalysis characteristic.
Compared with prior art, the present invention has the following advantages: other carbon carriers relatively, it has excellent physical property the single-layer graphene of perfect structure, as larger specific area, outstanding mechanical property and better electronic conduction ability.Because the sticky coefficient of ethylene glycol is large, when required ultrasonic time that graphite oxide is uniformly dispersed therein increases, but also can increase due to the lengthening of ultrasonic time the energy between oxidized graphite flake layer, thereby promote the reunion of graphite oxide simultaneously.Based on this point, add appropriate viscosity coefficient little in ethylene glycol, low-boiling dispersion aids-isopropyl alcohol, effectively improve the extent of exfoliation of graphite oxide.Add active carbon XC-72 and Graphene compound, can improve the extent of exfoliation of Graphene on the one hand, carrier as catalyst can provide more absorption duct for noble metal on the other hand, can effectively improve bimetallic catalyst being uniformly distributed on Graphene, effectively improve the utilance of noble metal, greatly improve the efficiency of battery.The resulting Pt-Co double metallic composite material of the present invention has less particle diameter, and the alloy effect of Pt and Co is more complete, and disperses at the Graphene surface uniform, thereby improves the electro catalytic activity of catalyst.
The accompanying drawing explanation
The Pt that Fig. 1 is different GO and XC-72 mass ratio
1-Co
1the XRD figure of/rGO-XC-72 alloy catalyst, Pt
1-Co
1/ rGO
1-XC-72
1(a), Pt
1-Co
1/ rGO
2-XC-72
1(b), Pt
1-Co
1/ rGO
4-XC-72
1(c), Pt
1-Co
1/ rGO (d);
Fig. 2 is Pt
1-Co
1/ rGO
4-XC-72
1transmission electron microscope picture;
Fig. 3 is supporting Pt
1-Co
1transmission electron microscope on single-layer graphene and diffraction pattern thereof;
The cyclic voltammetry curve figure that Fig. 4 is each catalyst;
The linear scan curve chart that Fig. 5 is each catalyst.
Embodiment
Below in conjunction with drawings and Examples, technical scheme of the present invention is further described; but do not limit to so; every technical solution of the present invention is modified or is equal to replacement, and not breaking away from the spirit and scope of technical solution of the present invention, all should be encompassed in protection scope of the present invention.
Embodiment 1
(1) take natural flake graphite as raw material, by the Hummers method, its oxidation is obtained to graphite oxide, concrete steps are as follows:
Potassium peroxydisulfate and each 2.5g of phosphorus pentoxide are joined in 25mL concentrated sulfuric acid flask, oil bath 40-180 ℃ of lower stirring and refluxing is after it dissolves, slowly add the 1.0-5g graphite powder, stirring reaction heating 2-10h, natural flake graphite is carried out to preliminary treatment, and filtered water is washed till the graphite that obtains processing after neutrality; By the graphite of processing, put into the 50-200g concentrated sulfuric acid and stir at ice bath, slowly add 8-30gKMnO
4after stir 1-10h in ice bath; Proceed in the oil bath pan of 35 ± 3 ℃, stir 20-120min, then slowly be added drop-wise in said mixture by 100-300mL distilled water; Thing to be mixed is cool to room temperature, takes out and puts into the 2-5L large beaker, adds 500-1500mL distilled water and 5-60mLH
2o
2, continuing to be stirred to does not have Bubble formation, and mixed liquor becomes golden yellow by atropurpureus; Standing 5-48h, abandoning supernatant, the HCl that mixture is 0.1-2:10 by volume ratio and water is centrifuge washing repeatedly, obtains the colloid substance of brown; Colloid substance, 30-80 ℃ of lower vacuumize, grinds and obtains pitchy solid, i.e. graphite oxide.
(2) first XC-72 is carried out to preliminary treatment, dry after acidification 12h in 120 ℃ of red fuming nitric acid (RFNA)s; Then by acidifying good XC-72 at H
2o
2middle ice-bath ultrasonic 30min, washing filtering, vacuumize 4h.
(3) take 40mg graphite oxide powder, add in the mixed solution of 60mL ethylene glycol and 10mL isopropyl alcohol, ice-bath ultrasonic 15min disperses to form the ethylene glycol suspension-turbid liquid of even graphene oxide.The XC-72 active carbon 10mg handled well again adds in above-mentioned graphite oxide ethylene glycol solution, and after mixing magnetic agitation 30min, ice-bath ultrasonic is processed 20min.
(4) to the H that splashes into 1.7mL, 0.0386mol/L in scattered mixture
2ptCl
6with 1.33mL, 0.1mol/L Co (CH
3cOO)
2solution, magnetic agitation 60min, add the NaOH solution of 0.2mol/L to regulate pH value (the pH value is 8-11), stirs 10min.Put into microwave reactor (power 800W), adopt microwave 2min, suspend 1min, then the program microwave reaction of microwave 1min.The question response system is cooled to room temperature, with acetone and ethanol repeatedly washing and filtering to the product after filtering no longer occur thickly, 60 ℃ of dryings, be ground to Powdered.By above-mentioned gained sample, put into tube furnace, under argon atmospher, 300 ℃ of calcination 30min, collect sample and put into drier.
As different from Example 1, control GO and XC-72 mass ratio is 2:1 and 1:1 to the present embodiment, obtains respectively Pt
1-Co
1/ rGO
2-XC-72
1and Pt
1-Co
1/ rGO
1-XC-72
1catalyst.
Embodiment 3
In order to contrast the impact on catalyst performance that adds of active carbon XC-72, the spy is one group of contrast experiment.Under same reaction conditions, preparation is simple by graphene-supported catalyst.
(1) preparation of graphite oxide is with reference to the step (1) of embodiment 1;
(2) take 60mg graphite oxide powder, add in the mixed solution of 60mL ethylene glycol and 10mL isopropyl alcohol, ice-bath ultrasonic 35min disperses to form the ethylene glycol suspension-turbid liquid of even graphene oxide.
(3) with reference to the step (4) of embodiment 1, utilize the auxiliary ethylene glycol method of microwave to obtain Pt
1-Co
1/ rGO catalyst.
Dry catalyst pulverize by obtaining, carry out the XRD sign.Fig. 1 is Pt and Co atom mass rate while being 1:1, with different quality, than active carbon XC-72 and the graphite oxide of (being respectively 1:1 (a), 2:1 (b), 4:1 (c) and 1:0 (d)), obtains catalyst Pt
1-Co
1the XRD figure of/GO-XC-72.As shown in Figure 1,2 θ values are 39.8 °, and three peaks of 46.5 ° and 67.8 ° belong to the characteristic diffraction peak of the face-centered cube (fcc) of Pt (JCPDS-ICDD, Card No:04-802).Correspond respectively to Pt (111), (200) and (220) crystal face diffraction maximum.Prove that all alloy catalysts all mainly exist with single-phase disordered structure.Contrast the data (JCPDS-ICDD) of the diffraction maximum powder diffraction association of mutually isomorphous large volume Pt), the diffraction maximum of Pt-Co alloy is offset to wide-angle.The structure that the skew of Pt (111) diffraction maximum has disclosed alloy is to be incorporated in the middle of the Pt structure of face-centred cubic structure by Co.Due to XRD to mass-sensitive, even in sample, very small amount of macroparticle also will make peak shape narrow down.Therefore, the broadening of several characteristic peaks of Pt in Fig. 1, show that prepared several Pt-Co alloy catalysts exist with quite little particle diameter and a kind of ordered form.
Obtained catalyst Pt
1-Co
1/ rGO
4-XC-72
1transmission electron microscope and high-resolution transmission electron microscope photo thereof see Fig. 2, as can be seen from Figure, active carbon XC-72 is adsorbed on Graphene, Pt
1-Co
1particle diameter is 1 ~ 3nm, loads on equably active carbon XC-72 and Graphene surface.The high-resolution transmission electron microscope demonstrates the Pt that the method obtains
1-Co
1nano particle is face-centerd cubic structure, and this and XRD data match.From the high power transmission electron microscope picture of Fig. 3, can learn, the Graphene of load has the feature diffractional lattice of single-layer graphene, illustrates that the Graphene in catalyst exists with the single layer structure form.
Take in the middle of the solution that the 2mg catalyst is dispersed in the 2mL redistilled water and absolute ethyl alcohol mixes with 1:1, sonic oscillation 15min, then get 4 μ L with pipettor, drips to carefully (0.071cm on polished glass-carbon electrode
2), after natural air drying in its air, then with 4 μ L0.5wt.%Nafion ethanolic solution coated electrode surfaces, dry.Adopt three-electrode system, the H of saturated 0.5mol/L at nitrogen
2sO
4in take sweep speed as 0.5V/s, sweep limits is carried out cyclic voltammetry scan for-0.2 to 1.0V.And work electrode is carried out to the linear scan test, and test condition is: electrode potential scope 0.8-0V; Sweep speed 0.0005V/s; Be 5s quiescent time; Reference electrode is the Ag/AgCl electrode; The H that electrolyte is 0.5mol/L
2sO
4; To electrode, it is pure platinum electrode.In electro-chemical test forward direction electrolyte, logical oxygen 30min, keep oxygen saturation in test process.All tests are all carried out under 25 ℃.
The data that the comprehensive resulting cyclic voltammetric of each work electrode (Fig. 4) and linear scan curve chart (Fig. 5) obtain are as shown in table 1, and when GO and XC-72 mass ratio are 2:1, catalyst has maximum electrochemically active specific surface area (179.4 m
2g
-1) and half wave potential (0.56V), mean that its catalyst activity is the highest.And, when the amount of GO increases, the activity of catalyst reduces on the contrary.This is while measuring very little due to the XC-72 adulterated in catalyst, can provide the quantity of catalyst adsorption site to reduce, and corresponding electrochemically active specific surface area also reduces, and electron transfer rate is corresponding reduction also, thereby causes the reduction of catalytic activity.But with respect to preparing under the same conditions Pt
1-Co
1/ rGO, the add electrochemically active specific surface area and the hydrogen reduction half wave potential that make catalyst of active carbon XC-72 all are improved.
Claims (9)
1. the preparation method of Pt-Co/C-single-layer graphene for a fuel cell is characterized in that described method step is as follows:
(1) preparation of graphite oxide: take natural flake graphite as raw material, adopt the Hummers method that its oxidation is obtained to graphite oxide;
(2) preliminary treatment of active carbon XC-72: adopt red fuming nitric acid (RFNA) acidifying and H
2o
2the processing method combined is carried out preliminary treatment to active carbon XC-72;
(3) preparation of rGO-XC-72 composite carrier load Pt-Co alloy nano particle: take 20-50mg graphite oxide powder, add in the mixed solution of 50-100mL ethylene glycol and 10-30mL isopropyl alcohol, ice-bath ultrasonic 15-30min disperses to form the ethylene glycol suspension-turbid liquid of even graphene oxide; The XC-72 active carbon 5-30mg handled well is added in above-mentioned graphite oxide ethylene glycol solution, after mixing magnetic agitation 20-60min, ice-bath ultrasonic is processed 10-20min again; To the H that splashes into 1.7-3.4mL, 0.0386mol/L in scattered mixture
2ptCl
6with 1.33-2.66mL, 0.1mol/L Co (CH
3cOO)
2solution, magnetic agitation 30-60min, add the NaOH solution of 0.2mol/L to regulate the pH value for 8-11, stirs 10-20min; Put into microwave reactor, adopt microwave 1-2min, suspend 0.5-2min, then the program microwave reaction of microwave 0.5-2min, the question response system is cooled to room temperature, with acetone and ethanol repeatedly washing and filtering to the product after filtration no longer occur thick; Then drying, grinding, calcination, obtain fuel cell Pt-Co/C-single-layer graphene.
2. the preparation method of Pt-Co/C-single-layer graphene for fuel cell according to claim 1 is characterized in that, in described step (1), the concrete preparation method of graphite oxide is as follows:
Potassium peroxydisulfate and each 2.5g of phosphorus pentoxide are joined in 25mL concentrated sulfuric acid flask, oil bath 40-180 ℃ of lower stirring and refluxing is after it dissolves, slowly add 1.0-5g natural flake graphite powder, stirring reaction heating 2-10h, natural flake graphite is carried out to preliminary treatment, and filtered water is washed till the graphite that obtains processing after neutrality; The graphite of processing is put into to the 50-200g concentrated sulfuric acid and stir at ice bath, slowly add 8-30g KMnO
4after stir 1-10h in ice bath; Proceed in the oil bath pan of 35 ± 3 ℃, stir 20-120min, then slowly be added drop-wise in said mixture by 100-300mL distilled water; Thing to be mixed is cool to room temperature, takes out and puts into the 2-5L large beaker, adds 500-1500mL distilled water and 5-60mLH
2o
2, continuing to be stirred to does not have Bubble formation, and mixed liquor becomes golden yellow by atropurpureus; Standing 5-48h, abandoning supernatant, the HCl that mixture is 0.1-2:10 by volume ratio and water is centrifuge washing repeatedly, obtains the colloid substance of brown; Colloid substance, 30-80 ℃ of lower vacuumize, grinds and obtains pitchy solid, i.e. graphite oxide.
3. the preparation method of Pt-Co/C-single-layer graphene for fuel cell according to claim 1 is characterized in that, in described step (2), the preprocess method step of active carbon XC-72 is as follows:
Acidification 10-24h after washing is to neutral in 80-120 ℃ of red fuming nitric acid (RFNA) to take 100-200mgXC-72, and 40-60 ℃ of vacuumize, obtain the XC-72 of acidifying; Then by acidifying good XC-72 at H
2o
2middle ice-bath ultrasonic 20-40min, washing filtering, vacuumize 4-12h.
4. the preparation method of Pt-Co/C-single-layer graphene for fuel cell according to claim 1, is characterized in that, in described step (3), the power of microwave reactor is 800W.
5. the preparation method of Pt-Co/C-single-layer graphene for fuel cell according to claim 1, is characterized in that, in described step (3), filtration product, 60 ℃ of dryings, is ground to Powdered; Then put into tube furnace, under argon atmospher, 300 ℃ of calcination 30min.
6. the preparation method of Pt-Co/C-single-layer graphene for fuel cell according to claim 1, is characterized in that, in described step (3), the atom mass rate of Pt and Co is 1:1.
7. the preparation method of Pt-Co/C-single-layer graphene for fuel cell according to claim 1, is characterized in that, in described step (3), GO and XC-72 mass ratio are 4:1.
8. the preparation method of Pt-Co/C-single-layer graphene for fuel cell according to claim 1, is characterized in that, in described step (3), GO and XC-72 mass ratio are 2:1.
9. the preparation method of Pt-Co/C-single-layer graphene for fuel cell according to claim 1, is characterized in that, in described step (3), GO and XC-72 mass ratio are 1:1.
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