CN103227336A - Band-shaped carbon-carrier metal catalyst, preparation method and application thereof - Google Patents
Band-shaped carbon-carrier metal catalyst, preparation method and application thereof Download PDFInfo
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- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims abstract description 60
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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 carbon-carrier precious metal catalyst for fuel cell, a preparation method thereof and an application thereof. The catalyst uses band-shaped nanometer carbon as the carrier, sodium borohydride, methanol or glycol as a reducing agent, and co-reduces the band-shaped nanometer carbon and the precious metal acid or the precious metal salts to obtain the precious metal/band-shaped nanometer carbon catalyst for the fuel cell, preferably a platinum loading amount being 10-60 wt %. The catalyst is high in initial electrochemical active surface area, relatively small in current density attenuation during a chronoamperometry test, and relatively high in current density during an electrochemical timing current test compared with that of present catalysts, and shows relatively high electrochemical activity, relatively high current density and relatively excellent electrochemical stability.
Description
Technical field
The present invention relates to a kind of banded carbon-supported metal catalyst and its production and application, particularly a kind of fuel cell nano strip carbon supported platinum catalyst and preparation method thereof.
Background technology
Catalyst carrier is one of critical material of polymer-membrane fuel battery Catalytic Layer.As the carrier of catalyst, it must possess bigger specific area, suitable pore-size distribution, fabulous electrochemical stability and high conductivity etc., and high conductive capability, good gas passage, enough appearance outlet capacities can be provided.Catalyst carrier not only directly influences particle diameter, decentralization and the activity of catalyst, and influences conductivity, mass transfer and the electrochemistry specific area etc. of Catalytic Layer.Catalyst carrier is mainly based on material with carbon element at present.Wherein activated carbon, ketjenblack EC, carbon nano-fiber, carbon nano-tube (CNTs) etc. all have certain application.At present, the carbon carrier that extensively adopts is the Vulcan XC-72 carbon black of Cabot company etc.But under the condition of DMFCs peracidity, high potential and higher temperature, carbon carrier can corrode under the effect of hydrone, and the surface is oxidized to CO or CO
2For the polymer-membrane fuel battery in operation below 100 ℃, only 100,000/several CO will cause the catalyst based serious poisoning of Pt; The Pt that the corrosion of carbon carrier also can be quickened high degree of dispersion assembles.When battery brought into operation and be out of service, the electrode local voltage can reach 1.2 V; The corrosion rate of carbon carrier obviously increases, thereby causes the electrochemical surface of precious metals pt to amass loss or the reunion that reduces with Pt.This is the active one of the main reasons that reduces with electrode life of eelctro-catalyst.One of method of slowing down the reduction of electrode performance variation and useful life is exactly to adopt more stable carbon carrier.Therefore, people begun one's study carbon nano-tube, mesoporous carbon, carbon fiber, carbon nano-fiber, corrosion-resistant carrier such as carbon nanohorn, however these carbon carrier surfaces are stronger inertia, dispersion (the Jiang Yulin that is unfavorable for catalyst metal particles, He Daping, in the wood soil spring, carbon nano-tube supports the method for nano-noble metal catalyst, battery, 2012,42, (5); Halder A, Sharma S, Hegde M, et al. An timicrobial activity of single walled carbon nanotubes. J Phys Chem C, 2009,113 (4): 1466-1473).
Mesoporous carbon is the novel non-silicon-based mesoporous material of a class of recent findings, because it has huge specific area and (can reach 2500 m
2/ g) and pore volume (can reach 2.25 cm
3/ g), be expected to very much be applied in aspects such as catalyst carrier, hydrogen storage material, electrode material, therefore be subjected to people and pay much attention to.Synthetic method commonly used is a hard template method, utilizes mesopore molecular sieves such as MCM-48, SBA-15 to be template, selects suitable predecessor, makes the predecessor carbonization under acid catalysis, is deposited in the duct of mesoporous material, dissolves away mesoporous SiO with NaOH or HF etc. then
2, promptly get mesoporous carbon.But the cell catalyst carrier that acts as a fuel is said and is not suitable for from the cost angle, and complicated preparation technology also makes its application be restricted.
Carbon aerogels is the product that obtains by the high temperature cabonization organic aerogel, it is a kind of light weight, specific area is big, mesopore is flourishing, conductivity is good, the network-like amorphous carbon material of the nanoporous of stable electrochemical property, its porosity is up to 80～98%, and specific area is 400～1000 m
2/ g, conductivity is 10～25 S/cm.But nanometer carbon aerogels preparation difficulty, and as amorphous carbon aerogels material, chemical corrosion takes place in the PEMFC bad working environment easily, cause the durability of catalyst to reduce.
Graphene is a kind of by the tightly packed bi-dimensional cellular shape lattice structure carbonaceous material that forms of monolayer carbon atom, the present outstanding material of electric conductivity has huge specific area, very high carrier mobility speed and than characteristics such as high Young's modulus, ferromagnetism.Nanostructure that it is special and performance impel grapheme material to demonstrate huge application potential at numerous areas such as electronics, optics, magnetics, biomedicine, catalysis, electrochemistry, transducer, energy storage.
Summary of the invention
The objective of the invention is to prepare metal/banded nanocarbon catalyst that a kind of fuel cell is used, its preferred platinum carrying capacity is 10～60wt%.This catalyst uses cutting single armed multi-arm carbon nanotube and the banded nano-sized carbon of other material with carbon element gained to be carrier, utilize the ductility and the remaining unreacted oxygen-containing functional group of distinctive quantization effect of banded nano-sized carbon and two dimension, to improve the catalytic activity of catalyst, the anti-carbon monoxide toxicity of noble metal platinum and the stability in use of catalyst.By with banded nano-sized carbon and metal acid or hybrid metal acid and slaine blend, with sodium borohydride, methyl alcohol or ethylene glycol are reducing agent, obtain a kind of fuel cell metal/banded nanocarbon catalyst, by regulating the cutting agent consumption of carbon pipe or other material with carbon element, cleavage reaction time and recovery time are controlled catalytic activity and stability, and then prepare high activity, high stability, catalyst cheaply.
A kind of banded carbon-supported metal catalyst, described banded carbon be bonding oxygen-containing functional group and carbon-to-oxygen ratio are arranged is the nanometer carbon ribbon of 1000:5～100:50, the surface deposition of described nanometer carbon ribbon has the nano metal that is of a size of 0.1～100nm; Described nano metal is one or more the mixture in transition metal, lanthanide series metal, the actinide metals.Wherein, carbon-to-oxygen ratio is preferably 100:5～100:20, and nano metal is preferably dimensioned to be 0.5～10nm.
Described nanometer carbon ribbon is made of the banded Graphene of single or multiple lift, and the thickness of described single or multiple lift Graphene is 1～10nm, and banded area is 0.05～0.2 μ m
2
Described transition metal is platinum, palladium, rhodium, manganese, chromium, nickel, gold or molybdenum.
The mass ratio of described nano metal and described banded carbon is 1:100～100:1, preferred 1:10～9:10.
Above-mentioned Preparation of catalysts method comprises following steps: carbon nano-tube is placed sulfuric acid solution, and 30～120 ℃ are stirred 0.5～6h down, add KMnO
4, continue to stir 0.5～8h, the solid H that obtains after the reaction
2O
2Washing, add metal acid or slaine (as chloroplatinic acid or other metal acid or slaine) again, regulating the pH value with alkaline aqueous solution is 9～13, after the stirred for several minute, add reducing agent and deionized water at 20～180 ℃ of following reduction reaction 3～24h, filter, 60～100 ℃ of following vacuumize sediments promptly obtain described catalyst after the cooling; Described carbon nano-tube: sulfuric acid solution: KMnO
4: metal acid or slaine: reducing agent: the mass ratio of deionized water is 1:5～500:0.5～20:2.66～15.93:160～640:5000～10000; The mass percentage concentration of described sulfuric acid solution is 20～100%.
Described carbon nano-tube is single armed or multi-arm carbon pipe, preferred multi-arm carbon pipe.
Described sulfuric acid solution is the aqueous solution of sulfuric acid, and mass percentage concentration is 20～98%.
Described KMnO
4With the mass ratio of described carbon nano-tube be 1:1～8:1.
Described alkaline aqueous solution is 0.5～4M potassium hydroxide aqueous solution.
Described reducing agent is sodium borohydride, ethylene glycol or methyl alcohol, 60～160 ℃ of the temperature of described reduction reaction.
In the method for the invention, H
2O
2Effect mainly be washing impurity-removing, and metal acid example hydrochloric acid solution is used for strengthening washing impurity-removing, alkaline aqueous solution such as potassium hydroxide aqueous solution are used for regulating pH value, so on consumption not special limit.
In concrete enforcement of the present invention, preferably that preliminary treatment is good carbon pipe is immersed in the salpeter solution, and 30～90 ℃ of reflux 0.5～6 hour are carried out pre-oxidation treatment.
A kind of fuel cell comprises the aforesaid banded carbon-supported metal catalyst of the present invention, and for example a kind of banded carbon carries platinum metal catalyst etc.
Preferably, the banded carbon-supported metal catalyst of fuel cell of the present invention comprises oxygen-containing functional group.
The banded carbon-supported metal catalyst that contains oxygen-containing functional group of the present invention have a following advantage:
(1) the banded nano-sized carbon that contains oxygen-containing functional group of the present invention's employing is as catalyst carrier, because the existence of its complanation structure, quantization, oxygen-containing functional group, graphene nanobelt is easier to form electric negative center on its surface, absorption nano metal particles such as platinum particles in catalyst preparation process, make nano metal particles more stably be adsorbed on carrier surface, be difficult for migration, its bigger specific area also can stop metallic particles to be reunited effectively, more help metal load, improved the catalytic activity and the stability of catalyst;
(2) the similar bimetallic alloy of the effect between oxygen-containing functional group and the nano metal improves the anti-carbon monoxide poisoning capability of nano metal, has prolonged life of catalyst, effectively reduces the catalyst cost, realizes that it is efficient, antitoxin, target cheaply.
Description of drawings
The electrochemistry cyclic voltammogram of the banded nanocarbon catalyst that contains oxygen-containing functional group in sulfuric acid solution that Fig. 1 embodiment 7 prepares; Wherein, a is the test result of embodiment 7, and b, c are respectively the test results of Comparative Examples 1 and Comparative Examples 2;
Fig. 2 is the electrochemistry cyclic voltammogram of the banded nanocarbon catalyst that contains oxygen-containing functional group in sulfuric acid methyl alcohol blend solution that embodiment 7 prepares; Wherein, a is the test result of embodiment 7, and b, c are respectively the test results of Comparative Examples 1 and Comparative Examples 2;
Fig. 3 is the banded nanocarbon catalyst timing current curve that contains oxygen-containing functional group that embodiment 7 prepares; Wherein, a is the test result of embodiment 7, and b, c are respectively the test results of Comparative Examples 1 and Comparative Examples 2.
Embodiment
Below, further specify content of the present invention with embodiment, but protection scope of the present invention is not limited in embodiment.Other variation and modification to those skilled in the art makes under the situation that does not deviate from the present invention's spirit and protection range still are included within the protection range of the present invention.
The raw material that uses in the embodiments of the invention is the commercially available prod except that specifying.
The fuel cell that the present invention obtains is finished by carry out electro-chemical test in the standard three-electrode system with the electro-chemical activity surface area of platinum/banded nano-sized carbon and the inspection method of methanol tolerance toxicity and stability.Adopt platinum filament to do electrode, silver/silver chlorate is done reference electrode, and the glass-carbon electrode of diameter 3mm is a work electrode, and electrolyte is sulfuric acid solution or 0.5 mol/L sulfuric acid and the 1mol/L methanol mixed solution of 0.5mol/L.Test is carried out in the AutoLab system of Switzerland Wan Tong company, and specific operation process is: accurately weigh the 5mg catalyst fines, add 50 μ L 5wt% Nafion (Eastern Mountain group) solution, ultrasonic being scattered in the 1ml deionized water.Pipetting 6 μ L drips in glass-carbon electrode surface, drying at room temperature.The cyclic voltammetric method of testing is surveyed the electro-chemical activity surface area: feed nitrogen before the test earlier more than half an hour in the sulfuric acid solution that immerses three-electrode system, carry out repeatedly cyclic voltammetry scan at-0.25V to the 1V interval with the sweep speed of 50mV/s, to stable, calculate catalyst electro-chemical activity surface area according to cyclic voltammetry curve to curve.The cyclic voltammetric method of testing is surveyed platinum catalyst anti-carbon monoxide toxicity: feed nitrogen more than half an hour earlier in immersing three-electrode system sulfuric acid methanol mixed solution before the test, carry out repeatedly cyclic voltammetry scan at-0.25V to the 1V interval with the sweep speed of 50mV/s, to stable, scan peak current numerical value (I with negative sense according to the peak current numerical value of the forward scan of cyclic voltammetry curve to curve
f/ I
b) calculate catalyst anti-carbon monoxide toxicity.The electrochemical stability property testing utilizes the timing electric current to send out at this three-electrode system to carry out, and its electrolyte is a sulfuric acid methanol mixed solution, and timing time is 120 minutes.
Embodiment 1
(1) 1 gram CNT (carbon nano-tube) is placed 100ml 60% H
2SO
4In, stir 1h down at 70 ℃, prepare the sulfuric acid solution that contains CNT (carbon nano-tube);
(2) with 5 gram KMnO
4Join in the sulfuric acid solution that contains CNT (carbon nano-tube), continue to stir 1h, obtain containing nanometer carbon ribbon, the KMnO that oxidation is cut open
4And the mixed liquor of sulfuric acid;
(3) in the mixed liquor of step (2), add H successively
2O
2And hydrochloric acid, the deionized water centrifugation, washing precipitate places the dry 12h of 50 ℃ of vacuum drying ovens for several times, obtains the stannic oxide/graphene nano band;
(4) described stannic oxide/graphene nano band is inserted in the deionized water, ultrasonic 30 minutes, add chloroplatinic acid, palladium, nickel acetate again, platinum content is 10% in the catalyst metals, and palladium nickel content is respectively 5%, stir after 20 minutes, add the 0.1g sodium borohydride, 80 ℃ of following reduction reaction 3h filter, vacuumize, cooling promptly obtains described banded carbon-supported metal catalyst under the room temperature; Its electro catalytic activity area (m of unit
2/ g) and positive negative direction peak current ratio I
f/ I
bList in table 1.
(1) 1 gram CNT (carbon nano-tube) is placed 100ml 98%H
2SO
4In, stir 2h down at 80 ℃, prepare the sulfuric acid solution that contains CNT (carbon nano-tube);
(2) with 5 KMnO that restrain
4Join the sulfuric acid solution that contains CNT (carbon nano-tube), continue to stir 0.5 h, obtain containing nanometer carbon ribbon, the KMnO that oxidation is cut open
4And the mixed liquor of sulfuric acid;
(3) in the mixed liquor of step (2), add H successively
2O
2And hydrochloric acid, the deionized water centrifugation, washing precipitate places the dry 12h of 50 ℃ of vacuum drying ovens for several times, obtains pure nanometer carbon ribbon;
(4) described pure nanometer carbon ribbon is inserted in the methyl alcohol, ultrasonic 20 minutes, add chloroplatinic acid, manganese acetate solution again, platinum content is 20% in the catalyst, and manganese content 4% stirs after 20 minutes, 120 ℃ of following reduction reaction 10h, filter, vacuumize, cooling promptly obtains described banded carbon-supported metal catalyst under the room temperature; Its electro catalytic activity area (m of unit
2/ g) and positive negative direction peak current ratio I
f/ I
bList in table 1.
Embodiment 3
(1) 1 gram CNT (carbon nano-tube) is placed 100ml H
3PO
4, 40%H
2SO
4In, stir 1h down at 90 ℃, prepare the sulfuric acid solution that contains CNT (carbon nano-tube);
(2) with 5 KMnO that restrain
4Join the sulfuric acid solution that contains CNT (carbon nano-tube), continue to stir 3h, obtain containing nanometer carbon ribbon, the KMnO that oxidation is cut open
4, sulfuric acid mixed liquor;
(3) in the mixed liquor of step (2), add H successively
2O
2And hydrochloric acid, deionized water is centrifugal, and washing precipitate places the dry 12h of 50 ℃ of vacuum drying ovens for several times, obtains pure nanometer carbon ribbon;
(4) the pure nanometer carbon ribbon of described pure nanometer carbon ribbon is inserted in the ethylene glycol, ultrasonic 20 minutes, add platinum platinic acid, ferric chloride solution again, platinum content is 30% in the catalyst, iron content is 10% to stir after 20 minutes, and 120 ℃ of following reduction reaction 24h filter, vacuumize, cooling promptly obtains described banded carbon-supported metal catalyst under the room temperature; Its electro catalytic activity area (m of unit
2/ g) and positive negative direction peak current ratio I
f/ I
bList in table 1.
Embodiment 4
(1) 1 gram CNT (carbon nano-tube) is placed 100ml 68%HNO
3, 30%H
2SO
4In, stir 3h down at 80 ℃, prepare the sulfuric acid solution that contains CNT (carbon nano-tube);
(2) with 3 KMnO that restrain
4Join the sulfuric acid solution that contains CNT (carbon nano-tube), continue to stir 4h, obtain containing nanometer carbon ribbon, the KMnO that oxidation is cut open
4, sulfuric acid mixed liquor;
(3) in the mixed liquor of step (2), add H successively
2O
2And hydrochloric acid, deionized water is centrifugal, and washing precipitate places the dry 12h of 50 ℃ of vacuum drying ovens for several times, obtains pure nanometer carbon ribbon;
(4) the pure nanometer carbon ribbon of described pure nanometer carbon ribbon is inserted in the methyl alcohol, ultrasonic 20 minutes, add again in the acid solution of chloroplatinic acid, chromic acetate, platinum content is 60% in the catalyst, and chromium content 10% stirs after 20 minutes, 120 ℃ of following reduction reaction 16h, filter, vacuumize, cooling promptly obtains described banded carbon-supported metal catalyst under the room temperature; Its electro catalytic activity area (m of unit
2/ g) and positive negative direction peak current ratio I
f/ I
bList in table 1.
Embodiment 5
(1) 1 gram CNT (carbon nano-tube) is placed 100ml 50%H
2SO
4In, under 70 ℃, stir 3h, prepare the sulfuric acid solution that contains CNT (carbon nano-tube);
(2) with 3 gram KMnO
4Join the sulfuric acid solution that contains CNT (carbon nano-tube), continue to stir more than the 3h, obtain containing nanometer carbon ribbon, the KMnO that oxidation is cut open
4, sulfuric acid mixed liquor;
(3) in the compound of step (2), add H successively
2O
2And hydrochloric acid, deionized water is centrifugal, and washing precipitate places the dry 12h of 50 ℃ of vacuum drying ovens for several times, obtains the stannic oxide/graphene nano band;
(4) described stannic oxide/graphene nano band is inserted in the deionized water, ultrasonic 30 minutes, the acid solution that adds chloroplatinic acid, iron chloride, manganese acetate again, platinum content is 30% in the catalyst, iron content is 4%, manganese content is that 8% stirring is after 20 minutes, add the 0.16g sodium borohydride, 90 ℃ of following reduction reaction 6h filter, vacuumize, cooling promptly obtains described catalyst under the room temperature; Its electro catalytic activity area (m of unit
2/ g) and positive negative direction peak current ratio I
f/ I
bList in table 1.
(1) 1 gram CNT (carbon nano-tube) is placed 100ml 98%H
2SO
4In, stir 0.5h down at 70 ℃, prepare the sulfuric acid solution that contains CNT (carbon nano-tube);
(2) with 1 gram KMnO
4Join the sulfuric acid solution that contains CNT (carbon nano-tube), continue to stir more than the 5h, obtain containing nanometer carbon ribbon, the KMnO that oxidation is cut open
4, sulfuric acid mixed liquor;
(3) in the mixed liquor of step (2), add H successively
2O
2And hydrochloric acid, deionized water is centrifugal, and washing precipitate places the dry 12h of 50 ℃ of vacuum drying ovens for several times, obtains the stannic oxide/graphene nano band;
(4) described stannic oxide/graphene nano band is inserted in the deionized water, ultrasonic 30 minutes, the slaine that adds 8mg platinum, molybdenum again, platinum content is 40% in the catalyst, stirs after 20 minutes, adds the 0.64g sodium borohydride, reduction reaction 3h under 80 ℃ of temperature, filter, vacuumize, cooling promptly obtains described catalyst under the room temperature; Its electro catalytic activity area (m of unit
2/ g) and positive negative direction peak current ratio I
f/ I
bList in table 1.
Embodiment 7
(1) 1 gram CNT (carbon nano-tube) is placed 100ml 98%H
2SO
4In, stir 1h down at 70 ℃, prepare the sulfuric acid solution that contains CNT (carbon nano-tube);
(2) with 4.5 gram KMnO
4Join the sulfuric acid solution that contains CNT (carbon nano-tube), continue to stir 1h, obtain containing nanometer carbon ribbon, the KMnO that oxidation is cut open
4Mixed liquor with sulfuric acid;
(3) in the mixed liquor of step (2), add H successively
2O
2And hydrochloric acid, deionized water is centrifugal, and washing precipitate places the dry 12h of 50 ℃ of vacuum drying ovens for several times, obtains the stannic oxide/graphene nano band.
(4) described stannic oxide/graphene nano band is inserted in the deionized water, ultrasonic 30 minutes, add chloroplatinic acid again, platinum content is 40% in the platinum/graphene nano band catalyst, stirs after 20 minutes, adds the 0.64g sodium borohydride, 80 ℃ of following reduction reaction 6h, filter, vacuumize, cooling promptly obtains described catalyst under the room temperature; Its electro catalytic activity area (m of unit
2/ g) and positive negative direction peak current ratio I
f/ I
bList in table 1.
Comparative Examples
Catalyst in Comparative Examples 1 and the Comparative Examples 2 is the commercial catalysts platinum/C catalyst of the gloomy company in river, the carrier of Comparative Examples 1 is the platinum/multi-arm carbon nano-tube catalyst (platinum content is 40%) to be carrier from the organic multi-arm carbon nano-tube of being bought in Chinese Academy of Sciences Chengdu, the carrier of Comparative Examples 2 is 40% for the XC-72(platinum content), with, the electro catalytic activity area (m of unit that uses said method to measure
2/ g) and positive negative direction peak current ratio I
f/ I
bList in table 1, initial electro-chemical activity test result as shown in Figure 1, anti-carbon monoxide toxicity is positive negative direction peak current ratio I
f/ I
bTest result as shown in Figure 2.Electrochemical stability be the timing current curve as shown in Figure 3.
As can be seen from Figure 1, contain the initial electro-chemical activity area maximum of oxygen-containing functional group graphitization nano carbon ribbon platinum catalyst,, illustrate and contain oxygen-containing functional group graphitization nano carbon ribbon to do the catalyst ability of carrier the strongest apparently higher than Comparative Examples 1 and 2.
As can be seen from Figure 2, contain oxygen-containing functional group graphitization nano carbon ribbon platinum catalyst, forward peak current and negative sense peak current ratio are the highest, apparently higher than Comparative Examples 1 and 2, the anti-CO poisoning capability of its platinum grain is the highest, and longer service life can reduce cost to a greater extent.
As can be seen from Figure 3, the electric current that contains oxygen-containing functional group graphitization carbon ribbon platinum catalyst all is higher than Comparative Examples 1 and 2 in whole test specification, and its catalytic stability is strong, still has very big current density after 120 minutes, and useful life is strong.
Wherein, the carrier of embodiment 1～7 is graphene oxide, and the carrier of Comparative Examples 1 is a multi-arm carbon nano-tube, and Comparative Examples 2 carriers are XC72.
Claims (10)
1. a banded carbon-supported metal catalyst is characterized in that, described banded carbon be bonding oxygen-containing functional group and carbon-to-oxygen ratio are arranged is the nanometer carbon ribbon of 1000:5～100:50, the surface deposition of described nanometer carbon ribbon has the nano metal that is of a size of 0.1～100nm; Described nano metal is one or more the mixture in transition metal, lanthanide series metal, the actinide metals.
2. catalyst according to claim 1 is characterized in that, described nanometer carbon ribbon is made of the banded Graphene of single or multiple lift, and the thickness of described single or multiple lift Graphene is 1～10nm, and banded area is 0.05～0.2 μ m
2
3. catalyst according to claim 1 is characterized in that, described transition metal is platinum, palladium, rhodium, manganese, chromium, nickel, gold or molybdenum.
4. catalyst according to claim 1 is characterized in that, the mass ratio of described nano metal and described banded carbon is 1:100～100:1.
5. the arbitrary described Preparation of catalysts method of claim 1 to 4 is characterized in that, comprises following steps: carbon nano-tube is placed sulfuric acid solution, and 30～120 ℃ are stirred 0.5～6h down, add KMnO
4Continue to stir 0.5～8h, the solid H that obtains after the reaction
2O
2Washing adds metal acid or slaine again, and regulating the pH value with alkaline aqueous solution is 9～13, after the stirred for several minute, add reducing agent and deionized water and under 20～180 ℃, carry out 3～24h reduction reaction, filter, 60～100 ℃ of following vacuumize sediments promptly obtain described catalyst after the cooling; Described carbon nano-tube: sulfuric acid solution: KMnO
4: metal acid or slaine: reducing agent: the mass ratio of deionized water is 1:5～500:0.5～20:2.66～15.93:160～640:5000～10000; The mass percentage concentration of described sulfuric acid solution is 20～100%; Described carbon nano-tube is single armed or multi-arm carbon pipe.
6. preparation method according to claim 5 is characterized in that, the mass percentage concentration of described sulfuric acid solution is 90～98%.
7. preparation method according to claim 5 is characterized in that, described KMnO
4With the mass ratio of described carbon nano-tube be 1:1～8:1.
8. preparation method according to claim 5 is characterized in that, described reducing agent is sodium borohydride, ethylene glycol or methyl alcohol, 60～160 ℃ of the temperature of described reduction reaction.
9. preparation method according to claim 5 is characterized in that, described alkaline aqueous solution is 0.5～4M potassium hydroxide aqueous solution.
10. a fuel cell is characterized in that, described fuel cell packets contains right and requires 1 to 4 arbitrary described banded carbon-supported metal catalyst.
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| CN107096536A (en) * | 2017-04-26 | 2017-08-29 | 山东师范大学 | A kind of controllable method for preparing of the monatomic catalyst of base metal |
| CN104437278B (en) * | 2014-11-18 | 2017-11-17 | 复旦大学 | A kind of carbon nanoporous aerogel material of the leaf shape structure of Heteroatom doping and its preparation method and application |
| CN109786129A (en) * | 2019-03-21 | 2019-05-21 | 西京学院 | A kind of ribbon-shaped nano-graphene ternary composite material and its preparation method and use |
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