CN102856562A - Carbon nanotube doped carbon gel catalyst for fuel cell and its application - Google Patents
Carbon nanotube doped carbon gel catalyst for fuel cell and its application Download PDFInfo
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- CN102856562A CN102856562A CN2011101821628A CN201110182162A CN102856562A CN 102856562 A CN102856562 A CN 102856562A CN 2011101821628 A CN2011101821628 A CN 2011101821628A CN 201110182162 A CN201110182162 A CN 201110182162A CN 102856562 A CN102856562 A CN 102856562A
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Abstract
The invention relates to a catalyst for fuel cell and its application, particularly application of a carbon nanotube-carbon gel composite catalyst in fuel cell. The catalyst precursor consists of resorcinol, formaldehyde, carbon nanotube and metal salt, wherein the metal salt includes soluble nitrate, carbonate, sulfate, acetate or halide of one or more of metal elements of group IVB, group VB, group VIB, group VIIB, group VIII, group IB and group IIB, the molar ratio of resorcinol to formaldehyde is 2:1, the mass ratio of carbon nanotube to resorcinol is from 1:1,000 to 1:500, the molar ratio of resorcinol to metal salt is from 5:1 to 1,500:1, and mixed organic gel is subjected to carbonization and nitridation in ammonia gas atmosphere at 500-1,200 DEG C. to obtain high-activity composite carbon gel catalyst. The invention, a nonmetal catalyst, shows good oxygen reduction activity and electrochemical stability when used as cathode catalyst of fuel cell.
Description
Technical field
The present invention relates to catalyst of fuel batter with proton exchange film, specifically a kind of carbon nano tube-doped charcoal gel catalyst and the application in Proton Exchange Membrane Fuel Cells thereof.
Background technology
Fuel cell is a kind of energy conversion device that directly chemical energy of material is converted into electric energy.With the work of heat engine form, power generation process is not subjected to the restriction of Carnot cycle to fuel cell, and the chemical energy of most of fuel wherein can directly be converted to electric energy, and energy conversion efficiency can reach 40～60%.Simultaneously, produce hardly the harmful substances such as sulfur dioxide, nitrogen oxide and suspended matter in the fuel cell power generation process, also do not emit the greenhouse gas carbon dioxide, meet the society environmental protection concept.Simultaneously, the required auxiliary equipment of fuel cell is few, has saved a large amount of power transmission lines, and convenient and reliable operation, flexibility are large.These advantages make fuel cell be acknowledged as the cleaning of 21 century first-selection, efficient generation technology, are subject in recent years the great attention of national governments and enterprise.
The present eelctro-catalyst battery critical material that acts as a fuel, the stability of its material and preparation cost, electrochemical reaction activity and long-time running is to realize the obstacle of fuel cell commercialization maximum.Take common Proton Exchange Membrane Fuel Cells as example, the precious metal materials such as Pt are the catalyst materials that is most widely used in PEMFC, the price that its limited resource, expensive price and complicated preparation technology cause fuel cell can not decrease, becomes the business-like bottleneck of fuel cell.In recent years, no-Pt catalyst was once becoming emphasis and the focus of various countries fuel cell studies personnel research and development, and non-Pt oxygen reduction cathode catalyst mainly comprises transition metal cluster compound, transition metal macrocyclic compound, transition metal oxide and transition metal carboritride etc.No-Pt catalyst preferably catalyst activity and cheap price becomes it to replace Pt the strongest catalyst based being selected, yet because non-Pt material is under the high potential weak acid of operation of fuel cells, alkali condition, the loss that side reaction causes catalyst very easily occurs, thereby also there is very large gap in stable aspect apart from practical application.Therefore, be to realize the Commercialization application of fuel cell, develop a kind of high activity, high stability, cheap non-noble metal fuel cell cathod catalyst is extremely urgent.
Material with carbon element relies on its cheap cost, abundant pore structure, and suitable specific area and good heat-conductivity conducting performance are widely used in the electro-catalyst carrier of fuel cell and the skeleton of porous gas diffusive electrode.Material with carbon element itself does not have activity to oxygen reduction reaction, but by methods such as doping and modifications, improves material with carbon element structure, composition and surface functional group, can make material with carbon element itself that oxygen reduction reaction is produced catalytic activity, yet activity is lower, less stable.Thereby, develop a kind of material with carbon element with higher oxygen reducing activity and antioxidant anticorrosive performance cell catalyst that acts as a fuel, with the decrease material cost, improve the stability of battery long-term work, use significant to the commerce of fuel cell.
The carbon xerogel material has higher electric conductivity, larger mesopore ratio, the suitable characteristics such as specific area, in the past through being commonly used for the fuel cell carrier.Studies show that, material with carbon element behind the nitrogen treatment has higher hydrogen reduction in oxygen reduction reaction active, and be doped with metal, and it is simple that the carbon xerogel of process nitrogenize has preparation, cheap, be the promising Proton Exchange Membrane Fuel Cells non-platinum catalyst of a kind of tool.In addition, in order further to improve the activity of carbon xerogel non-platinum catalyst in Proton Exchange Membrane Fuel Cells, need to carry out improvement on structure and the performance to it.Show that according to the study carbon nano-tube is because its unique structure and performance, and the composite material that is compounded to form of other materials, in application, shown good performance.Therefore, in the presoma of preparation charcoal gel, add carbon nano-tube, the carbon nano tube-doped carbon xerogel of carbonization that forms through nitrogenize again, show the character better than the carbon xerogel that do not mix, the battery eelctro-catalyst that acts as a fuel can reduce the catalyst material cost greatly, improve the stability of fuel cell, promote the commercial applications of fuel cell.
Summary of the invention
The object of the present invention is to provide a kind of novel carbon nano tube-doped carbon xerogel catalyst and the application in fuel cell thereof; Carbon xerogel has larger specific area, the central hole structure of suitable mass transfer and good electrical and thermal conductivity performance, and carbon nano-tube has the intensity height, the characteristics such as corrosion-resistant, both composite materials cell cathode catalyst that acts as a fuel, long-time running corrosion resistance good stability, oxygen reduction reaction activity are higher than the not carbon xerogel of doped carbon nanometer pipe.
For achieving the above object, the technical solution used in the present invention is:
A kind of carbon nano tube-doped charcoal gel catalyst, take resorcinol, formaldehyde, slaine and carbon nano-tube as raw material, adopt following process to be prepared from:
(1) carbon nano-tube is added the hot reflux surface cleaning with acid solution or hydrogen peroxide and process, described acid solution is one or two or more kinds the mixed solution in red fuming nitric acid (RFNA), concentrated hydrochloric acid or the concentrated sulfuric acid; The concentration of hydrogen peroxide is 5～8M (preferred 6M); 80～140 ℃ of heating-up temperatures (preferred 110 ℃); Heating time, 1～8h (preferred 4～6h)
(2) with resorcinol and the solvent ratio mixed preparing clear solution A in 0.1～10ml solvent/1g resorcinol;
(3) slaine is joined among the mentioned solution A mix, obtain solution B, wherein the mol ratio of metallic atom is 10: 1～1500: 1 in resorcinol and the slaine;
Wherein ambient temperature is 20～100 ℃, is preferably 20～50 ℃.Environmental condition is gentle, reduces the solvent evaporates amount, can obtain the gel rubber material of suitable specific area;
(4) be 1: 200～1: 500 (preferred 1: 200) in mass ratio with carbon nano-tube and water, ultrasonic Uniform Dispersion becomes carbon nano tube suspension, be added drop-wise in the solution B and evenly mix, resorcinol and carbon nano-tube are 500: 1～2000: 1 (preferred 500: 1～1000: 1) in mass ratio, in mixed solution, add formalin, the mol ratio of resorcinol and formaldehyde is 1: 1～4: 1 (preferred 3: 1), continues to stir in 20～100 ℃ of (preferred 50～70 ℃) environment until reaction forms gel C;
Can by adding the ammoniacal liquor that 0.5～30ml mass concentration is 1～28% (preferred 10～15%), be accelerated into glue at lasting whipping process.
(5) with the dry burin-in process 3～12 days (preferred 7 days) of gel C, pulverize after taking out and grind, obtain pressed powder D;
(6) pressed powder D is processed 1～10 hour (preferred 5～8 hours) in 600～1200 ℃ of (optimum condition is 600～900 ℃) nitriding atmospheres, inert blowing gas is swept to room temperature, adopt the unreacted slaine of 0.5～5M acid solution (deciding according to the acid solution kind) eccysis, namely get charcoal gel catalyst of the present invention after the drying.
Described slaine is the soluble-salt of one or more metallic elements in IVB, VB, VIB, VIIB, VIII, IB and the IIB family; Soluble-salt is nitrate, carbonate, sulfate, acetate, halide, dinitroso diamine salts, the acetylacetonate of metal or encircles greatly in complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and the polymer thereof one or more; Described metallic element is one or two or more kinds among Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, W, Ti, La, the Ce.
Described carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes;
Single Walled Carbon Nanotube caliber scope is 0.5-5.5nm, and length range is 3-50 μ m.
Multi-walled carbon nano-tubes external diameter scope is 15-40nm, and inside diameter ranges is 3-10nm, and length range is 20-70 μ m.
Described nitriding atmosphere is N
2, NH3, CH
3Among CN or the HCN one or two or more kinds.
Described dry aging method can be CO
2Supercritical drying, CO
240～55 ℃ of supercritical drying conditions, 11～16Mpa can get aeroge; Vacuumize, 50～90 ℃ of vacuumize conditions ,-0.1～-0.09Mpa, can get xerogel; Or freeze drying, freeze drying condition temperature is lower than solvent condensation point, normal pressure, can congeal glue.
During obtain solution A, described solvent is that the stirring ambient temperature of water is 20～80 ℃ (preferred 40 ℃), solvent is that the stirring ambient temperature of ethanol is 20～78 ℃ (preferred 40～50 ℃), solvent is that the stirring ambient temperature of isopropyl alcohol is 20～82 ℃ (preferred 40～50 ℃), and solvent is that the stirring ambient temperature of ethylene glycol is 60～100 ℃ (preferred 70～90 ℃); Ethanol and isopropyl alcohol have dispersed preferably, and reactant is uniformly dispersed, and ethylene glycol is applicable to higher temperature environment.
The inert gas purge pressed powder is during to room temperature, and selected inert gas can be nitrogen, argon gas, carbon dioxide, or the gaseous mixture that mixes with arbitrary proportion of above-mentioned three gases.The acid solution of eccysis slaine can be hydrochloric acid, sulfuric acid, and nitric acid, its hydrogen ion concentration is 1M/L.
The application of described catalyst in Proton Exchange Membrane Fuel Cells or alkaline membrane cell.When the present invention is used as fuel battery cathod catalyst as a kind of non-metallic catalyst, show good hydrogen reduction activity and electrochemical stability.
Beneficial effect of the present invention
1. carbon nano tube-doped charcoal gel catalyst is as a kind of non-metal kind eelctro-catalyst, and when fuel battery negative pole was used, it was active and stable for a long time to show higher oxygen reduction reaction;
2. technological process of the present invention is simple, the cycle short, with the once simultaneously carbonization nitrogenize of precursor component, can prepare high-specific surface area, the charcoal gel catalyst of high stability; The solvent safety that uses in the charcoal gel preparation course, nontoxic, environmentally safe; Slaine evenly distributes in presoma, improves the homogeneity of carbonization nitrogenize, and even carbon nanotube is dispersed in the colloid.Improve stability and the corrosion resistance of colloid;
3. charcoal gel of the present invention is in the gel-forming process, by the adding of controlling different amount slaines, adding, adjusting precursor solution concentration and the reaction environment temperature of carbon nano-tube, and carbonization nitrogen treatment temperature, can prepare the controllable charcoal gel rubber material of pore structure and specific area;
Catalyst of the present invention with low cost, have wide range of applications.Carbon nano tube-doped charcoal gel catalyst is a kind of nonmetal electrocatalysis material, compares with the noble metals such as Pt in the past, and material cost reduces greatly; In addition, this catalyst material not only can be used the acid proton exchange film fuel battery, and the catalytic activity in alkaline environment is higher, and is suitable with the catalytic activity of the noble metals such as Pt.
Description of drawings
Fig. 1 is the cyclic voltammogram of the carbon nano-tube of embodiment 1 preparation.
Fig. 2 is the polarization curves of oxygen reduction of the carbon nano-tube of embodiment 1 preparation.
Fig. 3 is the prepared catalyst circulation voltammogram of embodiment 1 and Comparative Examples 1.
Fig. 4 is the prepared former polarization curve of catalyst oxidation of embodiment 1 and Comparative Examples 1.
Fig. 5 is the battery performance comparison diagram that embodiment 1 and Comparative Examples 1 prepared catalyst are assembled.
Embodiment
Below by embodiment the present invention is described in detail, but the present invention is not limited only to embodiment.
Embodiment 1
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.815g cabaltous nitrate hexahydrate solid and add among the above-mentioned clear solution A, mix and obtain solution B; Get 0.012g process 8M hydrogen peroxide under 120 ℃ of conditions, the carbon nano-tube that adds hot reflux 5h, be uniformly dispersed in ultrasonic with the 4ML deionized water, dropwise drip scattered carbon nano-tube in the solution B in stir, further mix and form suspension C, drip the 9.08g mass concentration in the suspension C and be 37% formalin, drip the 3mL mass concentration and be 28% ammoniacal liquor in 20 ℃ of environment and continue sealing and stir, reaction forms gel D; Gel D is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 7d, pulverizes after taking out and grind, obtain pressed powder E; With pressed powder E 800 ℃ of carbonization nitrogen treatment 1h in acetonitrile atmosphere, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains resorcinol and cobalt nitrate mol ratio 20: 1, adds the carbon xerogel catalyst WCNTS500-Co-NO of carbon nano-tube (specification: external diameter 25nm, internal diameter 8nm, length 50 μ m) 0.012g
3-20.
Comparative Examples 1
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.815g cabaltous nitrate hexahydrate solid and add among the above-mentioned clear solution A, mix and obtain solution B; Drip the 9.08g mass concentration in the solution B and be 37% formalin, drip the 3mL mass concentration and be 28% ammoniacal liquor in 20 ℃ of environment and continue sealing and stir, reaction forms gel C; Gel C is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 7d, pulverizes after taking out and grind, obtain pressed powder D; With pressed powder D 800 ℃ of carbonization nitrogen treatment 1h in acetonitrile atmosphere, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains resorcinol and cobalt nitrate mol ratio 20: 1, adds the carbon xerogel catalyst WCNTS-Co-NO of carbon nano-tube 0.01g
3-20.
From Fig. 1, can find out among Fig. 2 that carbon nano-tube itself does not have the hydrogen reduction activity, the main cause that improves carbon xerogel hydrogen reduction activity is because the adding of carbon nano-tube has improved the structure of carbon xerogel.
As can be seen from Figure 3, added after the carbon nano-tube, the electric double layer of catalyst increases, and chemism area ECA increases, and specific area is larger, and the aperture increases, and mass transfer is better.
As can be seen from Figure 4, after the interpolation carbon nano-tube, compare with the carbon xerogel that does not add carbon nano-tube, hydrogen reduction is active obviously to improve.
The catalyst of embodiment 1 and Comparative Examples 1 preparation is assembled into Proton Exchange Membrane Fuel Cells, and working temperature is 80 ℃, and as anode catalyst, anode and cathode pressure is H with Pt/C
2/ O
2=0.2/0.2Mpa.As can be seen from Figure 5, equally as base metal negative electrode fuel battery cathode with proton exchange film catalyst, carbon nano tube-doped carbon xerogel has better mass transfer effect owing to be better than unadulterated carbon xerogel on the structure, has shown better performance at battery.
Embodiment 2
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.930g four hydration cobalt acetate solids and add among the above-mentioned clear solution A, mix and obtain solution B; Get 0.012g process 8M hydrogen peroxide under 120 ℃ of conditions, the carbon nano-tube that adds hot reflux 5h, be uniformly dispersed in ultrasonic with the 4ML deionized water, dropwise drip scattered carbon nano-tube in the solution B in stir, further mix and form suspension C, drip the 9.08g mass concentration in the suspension C and be 37% formalin, drip the 3mL mass concentration and be 28% ammoniacal liquor in 20 ℃ of environment and continue sealing and stir, reaction forms gel D; Gel D is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 7d, pulverizes after taking out and grind, obtain pressed powder E; With pressed powder E 800 ℃ of carbonization nitrogen treatment 1h in acetonitrile atmosphere, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains resorcinol and cobalt acetate mol ratio 15: 1, adds the carbon xerogel catalyst WCNTS500-Co-COOH-15 of carbon nano-tube 0.012g.
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.697g four hydration cobalt acetate solids and add among the above-mentioned clear solution A, mix and obtain solution B; Get 0.012g process 8M hydrogen peroxide under 120 ℃ of conditions, the carbon nano-tube that adds hot reflux 5h, be uniformly dispersed in ultrasonic with the 4ML deionized water, dropwise drip scattered carbon nano-tube in the solution B in stir, further mix and form suspension C, drip the 9.08g mass concentration in the suspension C and be 37% formalin, drip the 3mL mass concentration and be 28% ammoniacal liquor in 20 ℃ of environment and continue sealing and stir, reaction forms gel D; Gel D is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 7d, pulverizes after taking out and grind, obtain pressed powder E; With pressed powder E 800 ℃ of carbonization nitrogen treatment 1h in acetonitrile atmosphere, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains resorcinol and cobalt acetate mol ratio 20: 1, adds the carbon xerogel catalyst WCNTS500-Co-COOH-20 of carbon nano-tube 0.012g.
Embodiment 4
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.466g four hydration cobalt acetate solids and add among the above-mentioned clear solution A, mix and obtain solution B; Get 0.012g process 8M hydrogen peroxide under 120 ℃ of conditions, the carbon nano-tube that adds hot reflux 5h, be uniformly dispersed in ultrasonic with the 4ML deionized water, dropwise drip scattered carbon nano-tube in the solution B in stir, further mix and form suspension C, drip the 9.08g mass concentration in the suspension C and be 37% formalin, drip the 3mL mass concentration and be 28% ammoniacal liquor in 20 ℃ of environment and continue sealing and stir, reaction forms gel D; Gel D is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 7d, pulverizes after taking out and grind, obtain pressed powder E; With pressed powder E 800 ℃ of carbonization nitrogen treatment 1h in acetonitrile atmosphere, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains resorcinol and cobalt acetate mol ratio 30: 1, adds the carbon xerogel catalyst WCNTS500-Co-COOH-30 of carbon nano-tube 0.012g.
Embodiment 5
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.815g cabaltous nitrate hexahydrate solid and add among the above-mentioned clear solution A, mix and obtain solution B; Get 0.062g process 8M hydrogen peroxide under 120 ℃ of conditions, the carbon nano-tube that adds hot reflux 5h, be uniformly dispersed in ultrasonic with the 4ML deionized water, dropwise drip scattered carbon nano-tube in the solution B in stir, further mix and form suspension C, drip the 9.08g mass concentration in the suspension C and be 37% formalin, drip the 3mL mass concentration and be 28% ammoniacal liquor in 20 ℃ of environment and continue sealing and stir, reaction forms gel D; Gel D is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 7d, pulverizes after taking out and grind, obtain pressed powder E; With pressed powder E 800 ℃ of carbonization nitrogen treatment 1h in acetonitrile atmosphere, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains resorcinol and cobalt nitrate mol ratio 20: 1, adds the carbon xerogel catalyst WCNTS1000-Co-NO of carbon nano-tube 0.0062g
3-20.
Embodiment 6
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.930g four hydration cobalt acetate solids and add among the above-mentioned clear solution A, mix and obtain solution B; Get 0.0062g process 8M hydrogen peroxide under 120 ℃ of conditions, the carbon nano-tube that adds hot reflux 5h, be uniformly dispersed in ultrasonic with the 4ML deionized water, dropwise drip scattered carbon nano-tube in the solution B in stir, further mix and form suspension C, drip the 9.08g mass concentration in the suspension C and be 37% formalin, drip the 3mL mass concentration and be 28% ammoniacal liquor in 20 ℃ of environment and continue sealing and stir, reaction forms gel D; Gel D is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 7d, pulverizes after taking out and grind, obtain pressed powder E; With pressed powder E 800 ℃ of carbonization nitrogen treatment 1h in acetonitrile atmosphere, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains resorcinol and cobalt acetate mol ratio 15: 1, adds the carbon xerogel catalyst WCNTS1000-Co-COOH-15 of carbon nano-tube 0.0062g.
Embodiment 7
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.697g four hydration cobalt acetate solids and add among the above-mentioned clear solution A, mix and obtain solution B; Get 0.0062g process 8M hydrogen peroxide under 120 ℃ of conditions, the carbon nano-tube that adds hot reflux 5h, be uniformly dispersed in ultrasonic with the 4ML deionized water, dropwise drip scattered carbon nano-tube in the solution B in stir, further mix and form suspension C, drip the 9.08g mass concentration in the suspension C and be 37% formalin, drip the 3mL mass concentration and be 28% ammoniacal liquor in 20 ℃ of environment and continue sealing and stir, reaction forms gel D; Gel D is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 7d, pulverizes after taking out and grind, obtain pressed powder E; With pressed powder E 800 ℃ of carbonization nitrogen treatment 1h in acetonitrile atmosphere, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains resorcinol and cobalt acetate mol ratio 20: 1, adds the carbon xerogel catalyst WCNTS1000-Co-COOH-20 of carbon nano-tube 0.012g.
Embodiment 8
The 6.16g resorcinol is dissolved in the 7mL deionized water, forms clear solution A; Get in the stirring of 0.697g four hydration cobalt acetate solids and add among the above-mentioned clear solution A, mix and obtain solution B; Get 0.0062g process 8M hydrogen peroxide under 120 ℃ of conditions, the carbon nano-tube that adds hot reflux 5h, be uniformly dispersed in ultrasonic with the 4ML deionized water, dropwise drip scattered carbon nano-tube in the solution B in stir, further mix and form suspension C, drip the 9.08g mass concentration in the suspension C and be 37% formalin, drip the 3mL mass concentration and be 28% ammoniacal liquor in 20 ℃ of environment and continue sealing and stir, reaction forms gel D; Gel D is transferred to vacuum drying chamber at 60 ℃ of lower vacuumize burin-in process 7d, pulverizes after taking out and grind, obtain pressed powder E; With pressed powder E 800 ℃ of carbonization nitrogen treatment 1h in acetonitrile atmosphere, N
2Air-blowing is swept to room temperature, 2M HNO
3Solution eccysis slaine obtains resorcinol and cobalt acetate mol ratio 20: 1, adds the carbon xerogel catalyst WCNTS1000-Co-COOH-30 of carbon nano-tube 0.012g.
Claims (9)
1. a fuel cell is with carbon nano tube-doped charcoal gel catalyst, and it is characterized in that: described catalyst adopts following process to be prepared from take resorcinol, formaldehyde, slaine and carbon nano-tube as raw material:
(1) carbon nano-tube being added the hot reflux surface cleaning with acid solution or hydrogen peroxide processes;
(2) with resorcinol and the solvent ratio mixed preparing clear solution A in 0.1～10ml solvent/1g resorcinol;
(3) slaine is joined among the mentioned solution A mix, obtain solution B, wherein the mol ratio of metallic atom is 10: 1～1500: 1 in resorcinol and the slaine;
(4) be to become carbon nano tube suspension at ultrasonic middle Uniform Dispersion in 1: 200～1: 500 in mass ratio with carbon nano-tube and water, be added drop-wise to again in the solution B and evenly mix that wherein resorcinol and carbon nano-tube mass ratio are 500: 1～2000: 1; Add mass concentration in the mixed solution and be 20～40% formalin, the mol ratio of resorcinol and formaldehyde is 1: 1～4: 1, continues to stir in 20～100 ℃ of environment until reaction forms gel C;
(5) with the dry burin-in process of gel C 3～12 days, pulverize after taking out and grind, obtain pressed powder D;
(6) pressed powder D was processed 1～10 hour in 600～1200 ℃ of nitriding atmospheres, be cooled to room temperature; Namely get charcoal gel catalyst of the present invention after the drying.
2. according to catalyst claimed in claim 1, it is characterized in that: described slaine is the soluble-salt of one or more metallic elements in IVB, VB, VIB, VIIB, VIII, IB or the IIB family;
But described soluble-salt is nitrate, carbonate, sulfate, acetate, halide, dinitroso diamine salts, the acetylacetonate of metal or encircles greatly one or more cosolvency salt in complex compound porphyrin, the phthalein mountain valley with clumps of trees and bamboo and the polymer thereof.
3. according to catalyst claimed in claim 2, it is characterized in that: described metallic element is one or two or more kinds among Fe, Co, Ni, Cu, Zn, Ir, V, Cr, Mn, Zr, W, Ti, La, the Ce.
4. according to catalyst claimed in claim 1, it is characterized in that: carbon nano-tube is Single Walled Carbon Nanotube or multi-walled carbon nano-tubes;
Single Walled Carbon Nanotube caliber scope is 0.5-5.5nm, and length range is 3-50 μ m.
Multi-walled carbon nano-tubes external diameter scope is 15-40nm, and inside diameter ranges is 3-10nm, and length range is 20-70 μ m.
5. according to catalyst claimed in claim 1, it is characterized in that: described nitriding atmosphere is N
2, NH3, CH
3Among CN or the HCN one or two or more kinds.
6. according to catalyst claimed in claim 1, it is characterized in that: described dry aging method can be CO
2Supercritical drying, CO
240～55 ℃ of supercritical drying conditions, 11～16Mpa can get aeroge; Vacuumize, 50～90 ℃ of vacuumize conditions ,-0.1～-0.09Mpa, can get xerogel; Or freeze drying, freeze drying condition temperature is lower than solvent condensation point, normal pressure, can congeal glue.
7. according to catalyst claimed in claim 1, it is characterized in that: during obtain solution A, solvent is one or two or more kinds in water, ethanol, isopropyl alcohol, the ethylene glycol.
8. according to catalyst claimed in claim 7, it is characterized in that: the preparation temperature when described solvent is water is 20～80 ℃, preparation temperature when solvent is ethanol is 20～78 ℃, preparation temperature when solvent is isopropyl alcohol is 20～82 ℃, and solvent is that the stirring preparation temperature of ethylene glycol is 60～100 ℃.
9. the application of the arbitrary described catalyst of claim 1-8 is characterized in that:
Arbitrary catalyst all can be used as Proton Exchange Membrane Fuel Cells or alkaline membrane fuel battery cathod catalyst and is used for fuel cell among the described claim 1-8.
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| CN103752277A (en) * | 2014-02-25 | 2014-04-30 | 海南大学 | Oil-absorbing aerogel and preparation method thereof |
| CN107398274A (en) * | 2016-05-20 | 2017-11-28 | 香港纺织及成衣研发中心有限公司 | The catalyst and preparation method of organic pollution in a kind of degraded dyeing waste water |
| CN112701303A (en) * | 2020-12-31 | 2021-04-23 | 杭州电子科技大学 | Preparation method and application of carbon tube intercalation nitrogen-doped carbon-coated cobalt particle catalyst |
| CN113584514A (en) * | 2021-08-27 | 2021-11-02 | 中国人民解放军国防科技大学 | Preparation method of monoatomic metal-nitrogen doped carbon aerogel electrocatalyst |
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Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103752277A (en) * | 2014-02-25 | 2014-04-30 | 海南大学 | Oil-absorbing aerogel and preparation method thereof |
| CN103752277B (en) * | 2014-02-25 | 2016-01-20 | 海南大学 | A kind of oil suction aeroge and preparation method thereof |
| CN107398274A (en) * | 2016-05-20 | 2017-11-28 | 香港纺织及成衣研发中心有限公司 | The catalyst and preparation method of organic pollution in a kind of degraded dyeing waste water |
| CN112701303A (en) * | 2020-12-31 | 2021-04-23 | 杭州电子科技大学 | Preparation method and application of carbon tube intercalation nitrogen-doped carbon-coated cobalt particle catalyst |
| CN112701303B (en) * | 2020-12-31 | 2022-03-25 | 杭州电子科技大学 | Preparation method and application of carbon tube intercalation nitrogen-doped carbon-coated cobalt particle catalyst |
| CN113584514A (en) * | 2021-08-27 | 2021-11-02 | 中国人民解放军国防科技大学 | Preparation method of monoatomic metal-nitrogen doped carbon aerogel electrocatalyst |
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