CN105655607A - High-platinum base-loaded carbon nano tube nanocatalyst and preparation method thereof - Google Patents
High-platinum base-loaded carbon nano tube nanocatalyst and preparation method thereof Download PDFInfo
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- CN105655607A CN105655607A CN201610069833.2A CN201610069833A CN105655607A CN 105655607 A CN105655607 A CN 105655607A CN 201610069833 A CN201610069833 A CN 201610069833A CN 105655607 A CN105655607 A CN 105655607A
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- H—ELECTRICITY
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- H01M4/00—Electrodes
- H01M4/86—Inert electrodes with catalytic activity, e.g. for fuel cells
- H01M4/90—Selection of catalytic material
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- H01M4/925—Metals of platinum group supported on carriers, e.g. powder carriers
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- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
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Abstract
The invention relates to a platinum-based metal-loaded carbon nano tube catalyst for fuel cells and a preparation method and application of the catalyst. According to the catalyst, a multi-wall carbon nano tube is taken as a carbon nano tube, and the loading quantity of platinum-based metal on the carbon nano tube is more than 80%. The catalyst has the advantages that the particle size of active components is as small as about 2.0-4 nm, the active components are evenly distributed on the carbon nano tube, platinum-based nanoparticles are connected into a network structure, the precious metal utilization rate is high, the properties such as the catalytic activity, the life and the carbon monoxide poisoning resistance of the catalyst are high, and the activity of the catalyst for catalyzing and oxidizing methyl alcohol is 4 times or above of that of a commercial Pt-C catalyst.
Description
Technical field
The present invention relates to fuel-cell catalyst field, specifically refer to CNT high capacity platino nanocatalyst for fuel cell and preparation method thereof.
Background technology
Fuel cell is a kind of device that the chemical energy of fuel can directly efficiently and cleanly transform into electric energy, is a kind of more satisfactory generation technology. Due to the fuel cell wide application prospect in vehicle power source, various portable power source, Military Power etc., therefore the research of fuel cell receives the great attention of various countries.
Running into some problems in current commercializing fuel cells process, what wherein highlight the most is the price height of catalyst, and natural reserves are few, and the life-span is short. For the fuel cell being fuel with reformation gas, the problem that there is also the easy poisoning and deactivation of catalyst. And these problems all have with the performance of catalyst and contact closely, therefore the high performance fuel cell catalyst of developmental research a new generation is significant for the research and development promoting fuel cell.
Catalyst material is as one of the most key material of fuel cell, its preparation method mainly has immersion reduction method, ion exchange, the sedimentation method, gas phase reduction process, microwave method, colloid method etc., but these methods can not well control the particle diameter of the active component of catalyst and the surface and interface structure of nano grain surface sometimes, being difficult to obtain surface and interface component controlled, active component high degree of dispersion, granularity are little and disperse highly uniform CNT high capacity platino nanocatalyst (carrying capacity surpasses 90%).
With the carboxylated SWCN of radical reaction (SWCNTs) in the former research of the applicant, then with microwave reaction Supported Pt Nanoparticles (Pt) nano-particle (Pt/SWCNTs) on SWCN. The mass activity of its catalytic oxidation methanol is 3.9 times of business platinum C catalyst, but the anti-poisoning capability of its carbon monoxide oxidation relatively business platinum C catalyst does not significantly improve, and the stability of this scattered Pt nanoparticle is not so good.
Summary of the invention
It is an object of the invention to overcome the shortcoming and defect of above-mentioned prior art, a kind of size tunable is provided, surface and interface is controlled, high dispersive and high activity, anti-poisoning capability is strong, and stability is high, and technique is simple, easy to operate, CNT high capacity platinum nano catalyst for fuel cell with low cost and preparation method thereof.
The purpose of the present invention is achieved through the following technical solutions:
A kind of carbon nano-tube catalyst being loaded with platino metal, it is characterised in that described CNT is multi-walled carbon nano-tubes, described platino metal load capacity on the carbon nanotubes is higher than 80%.
According to the present invention, described load capacity is platino metal percentage by weight in platino metal and multi-walled carbon nano-tubes. Preferably, the load capacity of described platino metal is more than 90%.
According to the present invention, described platino metal is Pt or platinum base alloy, and described platinum base alloy is the Pt alloy formed with one or more other metals, and other metals described can be one or more in Rh, Ru, Ir, Cu, Ni.
In another preferred implementation of the present invention, described platino metal is Pt, Pt-Cu alloy, Pt-Ru-Cu alloy, Pt-Ru-Rh-Ni alloy.
According to the present invention, the active component in described catalyst exists with the form of Pt or the nano-particle of platinum base alloy. Its granularity is preferably between 1.0 to 10.0nm, again preferably between 2.0 to 4.0nm.
The preparation method that present invention also offers a kind of above-mentioned carbon nano-tube catalyst amount being loaded with platino metal, including:
(1) multi-walled carbon nano-tubes is carried out free radical functionalization, then carry out carboxylated, obtain carboxylated multi-walled carbon nano-tubes;
(2) the carboxylated multi-walled carbon nano-tubes obtained in corresponding platino metal precursor, step (1) and ethylene glycol are mixed, then by ultrasonic and stirring alternate treatment, obtain mixture;
(3) step (2) gained mixture is heated, obtain described CNT high capacity platino metallic catalyst.
According to the present invention, in step (1), effective for multi-wall carbon nano-tube azodiisobutyronitrile is carried out free radical functionalization in toluene.
According to the present invention, in step (1), carry out carboxylated with sodium hydroxide solution.
According to the present invention, in described step (2), described platino metal precursor is platino slaine, for instance for Pt, and its presoma can be H2PtCl6��6H2O; For Pt-Cu alloy, its presoma can be H2PtCl6��6H2O and CuSO4��5H2O��
According to the present invention, in step (2), described mixing is at room temperature stirring more than 30 minutes. The mol ratio of described platino metal precursor regulates and controls in required ratio and carrying capacity.
According to the present invention, in described step (2), described ultrasonic and stirring alternate treatment time for more than 10 hours, it is preferable that 20-40 hour. After described ultrasonic and stirring, the mixture that obtains is preferably the solution shape mixed liquor of high degree of dispersion.
According to the present invention, in described step (3), by the heating under stirring and nitrogen protection of step (2) gained mixture, then naturally cool to room temperature again.
According to the present invention, in described step (3), the mixture sucking filtration of room temperature will be naturally cooled to, washing, dry, obtain described catalyst. Preferably wash with water. Preferably, dry under vacuo, then cool down again, grind, obtain described catalyst.
The present invention it is preferred that preparation method as follows:
A kind of preparation method of the carbon nano-tube catalyst being loaded with platino metal, including:
(1) multi-walled carbon nano-tubes is carried out free radical functionalization, then carry out carboxylated, obtain carboxylated multi-walled carbon nano-tubes;
(2) corresponding platino metal precursor, carboxylated multi-walled carbon nano-tubes and ethylene glycol are at room temperature stirred mixing, then by ultrasonic and stirring alternate treatment, obtain mixture, the mol ratio of platino metal precursor and carrying capacity in required ratio regulation and control;
(3) in step (2) gained mixture, logical nitrogen microwave heating reflux more than 4 minutes at ambient pressure, or are heated to reflux more than 1 hour in oil bath, and temperature controls between 160 to 197 degrees Celsius;Then under stirring and nitrogen protection, room temperature is naturally cooled to, then sucking filtration, wash with water clean, dry under vacuum, cooling, grind and obtain described CNT high capacity platino nanocatalyst.
The present invention still further provides the purposes of the above-mentioned carbon nano-tube catalyst being loaded with platino metal, and it is used for fuel cell.
The present invention is by improving platino metal load capacity on multi-walled carbon nanotubes, network structure is connected between platino metal nanoparticle, improve active component platinum resisting CO poisoning ability by the interface between platino metal nanoparticle on the one hand, improved the stability of active component platinum catalysis Oxidation of Methanol on the other hand by described network structure.
The present invention compared with prior art, at least has the advantage that and beneficial effect:
(1) the invention provides a class CNT high capacity platino metallic catalyst (load capacity is higher than 80%), it can not only improve the catalysis activity of platinum, life-span; The anti-poisoning capability improving platinum is worked in coordination with simultaneously also by the contact surface between the platino nano-particle of surface. The peak current density of described catalyst Oxidation of Methanol exceeds more than 4 times than the high-performance Pt/C catalyst of JohnsonMatthey company.
(2) making spent glycol high temperature reduction, can prepare active component particles degree high activated catalyst between 1.0 to 10.0nm, the distribution of particle sizes of active component is extremely uniform, and distribution, in two dimensional height dispersing character, is effectively increased the utilization rate of noble metal.
(3) in the CNT high capacity platino nanocatalyst synthesized, described platino metal is on the carbon nanotubes in one-dimensional porous platinum Specific surface area, connect into network loose structure between platino nano-particle, be effectively increased catalytic life and the resisting CO poisoning ability of platinum.
(4) adopting microwave heating alcohol reducing process or oil bath heating alcohol reducing process to prepare this catalyst, technique is simple, environmental friendliness, and the response rate is high, reduces catalyst cost.
Accompanying drawing explanation
Fig. 1 is the XRD spectra of the Pt/MWCNTs catalyst of embodiment 1 preparation, and MWCNTs is the English abbreviation of carboxylated multi-walled carbon nano-tubes;
Fig. 2 be embodiment 1 prepare Pt/MWCNTs catalyst transmission electron microscope and in water scattered photo a, b, c, d and e be the electromicroscopic photograph of Pt/MWCNTs catalyst, f is Pt/MWCNTs catalyst scattered photo in water;
Fig. 3 is the x-ray photoelectron energy spectrogram that embodiment 1 prepares the Pt element in Pt/MWCNTs catalyst;
Fig. 4 is the Pt/MWCNTs catalyst of embodiment 1 preparation, on carboxylated SWCN the platinum (Pt/SWCNTs, 20%) of load 20% and business Pt/C catalyst at 0.5mol/LH2SO4+1.0mol/LCH3Cyclic voltammetry spectrum in OH solution;
Fig. 5 be embodiment 1 preparation Pt/MWCNTs catalyst and business Pt/C catalyst at 0.5mol/LH2SO4+1.0mol/LCH3Steady-state current time graph when 0.09 volt in OH solution;
Fig. 6 is the Pt/MWCNTs catalyst of embodiment 1 preparation, on carboxylated SWCN the platinum (Pt/SWCNTs, 20%) of load 20% and business Pt/C catalyst at 0.5mol/LH2SO4Carbon monoxide cycle voltammogram in solution.
Fig. 7 is that the Pt/MWCNTs catalyst of embodiment 1 preparation is at 0.5mol/LH2SO4+1.0mol/LCH3Cyclic voltammetric in OH solution stablizes collection of illustrative plates.
Fig. 8 is that embodiment 1 business Pt/C catalyst is at 0.5mol/LH2SO4+1.0mol/LCH3Cyclic voltammetric in OH solution stablizes collection of illustrative plates.
Detailed description of the invention
Below in conjunction with embodiment and accompanying drawing, the present invention is described in further detail, but embodiments of the present invention are not limited to this. Any those skilled in the art, a little change done on technical scheme basis and modification, thus forming new inventive technique scheme, all still fall within the scope of technical solution of the present invention.
Embodiment 1: the preparation of carbon multi-wall nano tube loaded high carrying capacity platinum nano catalyst Pt/MWCNTs (platinum percentage by weight in platinum and multi-walled carbon nano-tubes is 91%)
(1) multi-walled carbon nano-tubes (MWCNTs) is dispersed in toluene, add azodiisobutyronitrile, pass into nitrogen, cold filtration after reacting more than 4 hours in the oil bath of 75 degrees Celsius, is then dispersed in the aqueous solution of sodium hydroxide in the oil bath of 70 degrees Celsius and stirs more than 48 hours.Finally being washed by reacting liquid filtering, it is standby that dried grinding obtains carboxylated multi-walled carbon nano-tubes;
(2) by H2PtCl6��6H2O, the carboxylated multi-walled carbon nano-tubes of step (1) and ethylene glycol at room temperature stir and make it fully dispersed in more than 30 minutes, and continue ultrasonic. By stirring being used alternatingly and ultrasonic, obtain the solution shape mixed liquor of high degree of dispersion. H simultaneously2PtCl6��6H2Also commercial weight accounting in the weight of multi-walled carbon nano-tubes and Pt of O is 91%;
(3) step (2) gained mixed solution is put in microwave reactor, logical nitrogen deoxygenation, simultaneously logical upper condensed water, and stir 30 minutes;
(4) step (3) gained solution microwave heating more than 3 minutes, room temperature is then naturally cooled to;
(5) by step (4) gained mixed solution vacuum filtration, filter cake redistilled water washes clean, and dry 10 hours in vacuum drying oven, cooling, grind, thus obtaining multi-walled carbon nano-tubes high capacity platino nanocatalyst Pt/MWCNTs, this catalyst is the nanocatalyst with network loose structure.
Pt/MWCNTs and the X-ray powder diffraction spectrogram of business Pt/C catalyst prepared by the present embodiment are shown in Fig. 1; It can be seen that in the material of preparation, platinum is pure phase in the present embodiment.
Pt/MWCNTs catalyst prepared by the present embodiment scattered photo and transmission electron microscope thereof in water are shown in Fig. 2; It can be seen that in the material of preparation, Pt nanoparticle is evenly distributed in the present embodiment, good crystallinity, and all on the carbon nanotubes, form the Pt nanoparticle network interconnected. And material disperses very well in water.
The x-ray photoelectron energy spectrogram of the Pt element in the Pt/MWCNTs and business Pt/C of embodiment 1 preparation is shown in Fig. 3; It can be seen that the platinum in the material of preparation is pure platinum in the present embodiment, owing to Pt nanoparticle connects into network structure, the surface of platinum can reduce, and the surface electronic of platinum combines can red shift.
Further, the catalytic performance of the Pt/MWCNTs catalyst that the present embodiment is prepared has detected, also compare with the platinum that load content on carboxylated SWCN is 20%, this content is that the platinum of 20% is formed without network structure on SWCN, and Pt nanoparticle is that single load is on SWCN. Having better catalytic performance by comparative descriptions the present embodiment, testing result is referring to Fig. 4-Fig. 7.
Fig. 4 is the Pt/MWCNTs catalyst of embodiment 1 preparation, and the platinum (Pt/SWCNTs, 20%) of load 20% on carboxylated SWCN and business Pt/C catalyst are at 0.5mol/LH2SO4+1.0mol/LCH3Cyclic voltammetry spectrum in OH solution; It can be seen that the mass activity of the material catalytic oxidation methanol of preparation is greatly improved in the present embodiment, it is 4.4 times of business Pt/C. And the performance of Pt/SWCNTs (20%) catalytic oxidation methanol is relatively low, this is single isolated existence due to Pt nanoparticle on SWCN, and Pt nanoparticle is to form network structure in the present embodiment, the contact surface between Pt nanoparticle has the performance of good catalytic oxidation methanol.
Fig. 5 be embodiment 1 preparation Pt/MWCNTs catalyst and business Pt/C catalyst at 0.5mol/LH2SO4+1.0mol/LCH3Steady-state current time graph when 0.09 volt in OH solution; It can be seen that the stability of material catalytic oxidation methanol of preparation is greatly improved in the present embodiment, current attenuation slower.
Fig. 6 is the Pt/MWCNTs catalyst of embodiment 1 preparation, and the platinum (Pt/SWCNTs, 20%) of load 20% on carboxylated SWCN and business Pt/C catalyst are at 0.5mol/LH2SO4Carbon monoxide cycle voltammogram in solution.As can be seen from the figure, although the material load capacity of preparation is up to 91% in the present embodiment, but the spike potential that rises of its CO catalytic oxidation substantially reduces, only-400 millivolts, and business platinum C catalyst is 0 millivolt, Pt/SWCNTs (20%) is 39 millivolts. The spike potential of material CO catalytic oxidation prepared by the present embodiment is 38.6 millivolts, and business platinum C catalyst is 180 millivolts, and Pt/SWCNTs (20%) is 235 millivolts of spike potentials. This is that nano-particle is little, connects into network structure owing in the material of the present embodiment synthesis, Pt nanoparticle is evenly distributed on the carbon nanotubes.
Fig. 7 is that the Pt/MWCNTs catalyst of embodiment 1 preparation is at 0.5mol/LH2SO4+1.0mol/LCH3Cyclic voltammetric in OH solution stablizes collection of illustrative plates. It can be seen that in the present embodiment preparation the stability of material catalytic oxidation methanol obtain considerable degree of raising. After 6000 circulate, the mass activity of its catalytic oxidation methanol is also up to the 68% of initial mass activity.
Fig. 8 is that embodiment 1 business Pt/C catalyst is at 0.5mol/LH2SO4+1.0mol/LCH3Cyclic voltammetric in OH solution stablizes collection of illustrative plates. As can be seen from the figure business Pt/C is after 6000 circulate, and the mass activity of its catalytic oxidation methanol only has the 39% of initial mass activity, and material prepared by speed ratio the present embodiment of its performance degradation wants fast.
Embodiment 2: carbon multi-wall nano tube loaded high carrying capacity platinum copper catalyst PtCu3The preparation of/MWCNTs (platinum percentage by weight in platinum, copper and multi-walled carbon nano-tubes surpasses 90%)
(1) by H2PtCl6��6H2O��CuSO4��5H2O, functionalized multi-wall carbonnanotubes and ethylene glycol at room temperature stir 30 minutes and make it fully dispersed. In mixed solution, the mol ratio of Pt and Cu is 1:3. Simultaneously Pt metal carbon, Cu and Pt weight in accounting for surpassing 90%;
(2) step (1) gained mixed solution alternately with stirring and supersound process, then regulating its pH value with sodium hydroxide ethylene glycol solution is 10;
(3) step (2) gained mixed solution is continued ultrasonic and stirring is used alternatingly, until forming the dispersion liquid of solution shape;
(4) it is put in microwave reactor to step (3) gained mixed solution, logical nitrogen deoxygenation, simultaneously logical upper condensed water, and stir 30 minutes;
(5) step (4) gained solution microwave heating more than 3 minutes, room temperature is then naturally cooled to;
(6) by step (5) gained mixed solution vacuum filtration, filter cake redistilled water washes clean, and in vacuum drying oven 90 degrees Celsius dry 10 hours, cooling, grind, obtain sample P tCu3/ C;
(7) step (6) gained sample is placed in 5.0M sulphuric acid and stirs and after ultrasonic each 30 minutes, preserve more than 2 days;
(8) step (7) gained acid dispersion secondary deionized water is diluted, vacuum filtration, filter cake redistilled water washes clean, and dry 10 hours in vacuum drying oven, cooling, grind, thus obtaining carbon multi-wall nano tube loaded high carrying capacity platinum base alloy nanocatalyst PtCu3-A/MWCNTs (accounting is for surpassing 90% in the weight of carbon and Pt for Pt metal, and A represents the process through strong acid corrosion), this catalyst is also the platinum base alloy nuclear shell structure nano catalyst with surface texture defect.
As it has been described above, the present invention just can be realized preferably.
Claims (10)
1. the carbon nano-tube catalyst being loaded with platino metal, it is characterised in that described CNT is multi-walled carbon nano-tubes, described platino metal load capacity on the carbon nanotubes is higher than 80%.
2. catalyst according to claim 1, wherein, described platino metal load capacity on the carbon nanotubes is higher than 90%.
3. catalyst according to claim 1 and 2, wherein, described platino metal is Pt or platinum base alloy, and described platinum base alloy is the Pt alloy formed with one or more other metals, and other metals described are preferably as one or more in Rh, Ru, Ir, Cu, Ni.
4. the catalyst according to any one of claim 1-3, wherein, described platino metal is Pt, Pt-Cu alloy, Pt-Ru-Cu alloy, Pt-Ru-Rh-Ni alloy.
5. the catalyst according to any one of claim 1-4, wherein, active component in described catalyst exists with the form of platinum or platinum base alloy nano-particle, its granularity is preferably between 1.0 to 10.0nm, again preferably between 2.0 to 4.0nm, preferably, described platino metal forms network structure on the carbon nanotubes.
6. a preparation method for the catalyst described in any one of claim 1-5, including:
(1) multi-walled carbon nano-tubes is carried out free radical functionalization, then carry out carboxylated, obtain carboxylated multi-walled carbon nano-tubes;
(2) the carboxylated multi-walled carbon nano-tubes obtained in corresponding platino metal precursor, step (1) and ethylene glycol are mixed, then by ultrasonic and stirring alternate treatment, obtain mixture;
(3) step (2) gained mixture is heated, obtain described CNT high capacity platino metallic catalyst.
7. preparation method according to claim 6, wherein, in described step (1), carries out free radical functionalization by effective for multi-wall carbon nano-tube azodiisobutyronitrile in toluene; Carry out carboxylated with sodium hydroxide solution.
Preferably, in described step (2), described platino metal precursor is platino slaine, and the mol ratio of described platino metal precursor regulates and controls in required ratio and carrying capacity.
8. preparation method according to claim 6, wherein, in described step (2), described ultrasonic and stirring alternate treatment time for more than 10 hours, it is preferable that 20-40 hour.
9. preparation method according to claim 6, wherein, in described step (3), is heated step (2) gained mixed solution under stirring and nitrogen protection, then naturally cools to room temperature again;
Preferably, in described step (3), the mixed liquor sucking filtration that reacting by heating is obtained, washing, dry, obtain described catalyst; Preferably wash with water; Dry under vacuo, cooling, grind.
10. the purposes of the catalyst described in any one of claim 1-5, it is used for fuel cell.
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CN106602092A (en) * | 2017-02-28 | 2017-04-26 | 中国科学院福建物质结构研究所 | Preparation method for single-walled carbon nanotube (SWCNT) hollow ball oxygen reduction catalyst, and application of SWCNT hollow ball oxygen reduction catalyst |
CN106784900A (en) * | 2016-12-12 | 2017-05-31 | 中国科学院福建物质结构研究所 | CNT of platinum base nano particle cladding tin ash covering and preparation method thereof |
CN107649148A (en) * | 2017-10-26 | 2018-02-02 | 湘潭大学 | A kind of preparation method and application using multi-walled carbon nanotube as the carrier loaded auxiliary agent Pt Ni base catalyst being modified |
CN110741497A (en) * | 2017-09-19 | 2020-01-31 | 株式会社Lg化学 | Method for preparing catalyst for fuel cell and catalyst for fuel cell prepared thereby |
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