CN102723504A - Multi-wall carbon nano-tube carried core-shell silver-platinum cathode catalyst and preparation method - Google Patents
Multi-wall carbon nano-tube carried core-shell silver-platinum cathode catalyst and preparation method Download PDFInfo
- Publication number
- CN102723504A CN102723504A CN201210143695XA CN201210143695A CN102723504A CN 102723504 A CN102723504 A CN 102723504A CN 201210143695X A CN201210143695X A CN 201210143695XA CN 201210143695 A CN201210143695 A CN 201210143695A CN 102723504 A CN102723504 A CN 102723504A
- Authority
- CN
- China
- Prior art keywords
- walled carbon
- catalyst
- silver
- carbon nanotube
- platinum
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
Images
Classifications
-
- 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
Landscapes
- Catalysts (AREA)
- Inert Electrodes (AREA)
Abstract
一种多壁碳纳米管载核壳型银-铂阴极催化剂及制备方法，属于燃料电池催化剂技术领域。以多壁碳纳米管为载体，活性金属组分以银为核心、铂为壳层的核壳结构生长在多壁碳纳米管载体的表面。该方法采用硼氢化钠和乙二醇作为溶剂和还原剂，运用两步还原法，即先还原银，得到多壁碳纳米管载银粒子；再还原铂，通过控制反应的温度和pH值，使铂在银的表面沉积，从而制成核壳型催化剂。本发明可以大大提高催化剂的催化效率和贵金属的利用率，提高氧还原的能力，将促进燃料电池的发展。The invention discloses a multi-walled carbon nanotube loaded core-shell silver-platinum cathode catalyst and a preparation method thereof, belonging to the technical field of fuel cell catalysts. The multi-walled carbon nanotube is used as a carrier, and the core-shell structure in which the active metal component takes silver as the core and platinum as the shell grows on the surface of the multi-walled carbon nanotube carrier. The method uses sodium borohydride and ethylene glycol as a solvent and a reducing agent, and uses a two-step reduction method, that is, first reducing silver to obtain multi-walled carbon nanotube silver-loaded particles; then reducing platinum, by controlling the temperature and pH of the reaction, Platinum is deposited on the surface of silver to make a core-shell catalyst. The invention can greatly improve the catalytic efficiency of the catalyst and the utilization rate of precious metals, improve the ability of oxygen reduction, and promote the development of fuel cells.
Description
Technical field
The invention belongs to the fuel-cell catalyst technical field, be specifically related to multi-walled carbon nano-tubes (MWCNTs) supported core-shell silver-platinum catalyst (AgPt/MWCNTs) that a kind of fuel cell uses and preparation method thereof.
Technical background
Fuel cell is a kind of electrochemical appliance that directly chemical energy is transformed into electric energy, and one of its critical material is an electrode catalyst, and for a long time, noble metals such as platinum, ruthenium are widely used because of it has remarkable catalytic performance always.But, cost an arm and a leg, and the interest rate of platinum in battery is not high, thereby has limited the development of fuel cell because the content of platinum metal in the earth's crust is limited.Though alloy catalyst can reduce the carrying capacity of Pt, improve catalytic efficiency, be still waiting at aspects such as catalyst stabilities to improve.Nucleocapsid catalyst more and more receives people's attention in recent years, thereby is widely used in various chemical process owing to have unique catalytic performance.Because the electronics of alloy is different with simple metal with surface texture, so bimetallic catalyst has revealed better catalytic activity to some reaction table.This is because behind the another kind of metal of the surface deposition of metal single crystal, the two kinds of intermetallic interactions in top layer can cause the variation of bimetallic electronics and geometry, thereby the electric charge of the particle that changes, can be functionalized, can carry out advantages such as surface reaction.
US20100197490 has introduced a kind of platinum and has coated a kind of method that base metal prepares nucleocapsid catalyst.This method is reduced into the particle of 2-10nm with base metal salt such as Fe, Co, Ni, W, Ag with the method for electronation earlier, and intensification is carried out annealing in process for 600 ℃ to 800 ℃ behind air drying, and annealing time is decided because of different metal.After annealing is accomplished, this nano particle is immersed in the platinum salting liquid, utilize the electrochemical displacement method at the surface deposition skim Pt of base metal particle shell, thus preparation core-shell type nanocatalyst.Though this method can be made complete hud typed catalyst, operating process is complicated, needs to consume mass energy, and preparation cost is high.
CN200610019303 has introduced a kind of a kind of method that is equipped with nucleocapsid catalyst with the chemical replacement legal system.This method is that base metal salt is mixed with solution, adds certain amount of surfactant, in mixed solution, adds excessive reducing agent then, processes non-noble metal nano metal solution.In non-noble metal nano metal solution, add precious metal salt solution again and carry out chemical replacement, obtain the catalyst with core-casing structure solution that noble metal is wrapped in the base metal nano grain surface, obtain non-supported nucleocapsid catalyst.In non-supported nucleocapsid catalyst solution, add the multi-walled carbon nano-tubes carrier at last and adsorb, obtain loaded nucleocapsid catalyst.The advantage of this method is that operating process is simple, and preparation cost is low, but catalyst particle size is bigger than normal, and catalyst only depends on suction-operated to be connected with the multi-walled carbon nano-tubes carrier, is easy in electrochemical reaction process, come off, thereby reduces catalytic efficiency.
Summary of the invention
The purpose of this invention is to provide a kind of multi-walled carbon nano-tubes supported core-shell silver-platinum cathode catalyst and preparation method, this catalyst has smaller particle size, low Pt carrying capacity, high catalytic activity, can be used as the catalyst for fuel cell material.
The technical scheme that adopts for the present invention of realization above-mentioned purpose is following.
A kind of multi-walled carbon nano-tubes supported core-shell silver-platinum cathode catalyst; It is characterized in that; This catalyst is carrier with the multi-walled carbon nano-tubes, and active metal component is grown in the surface of multi-walled carbon nano-tubes carrier, and active metal component is to be that core, platinum are the material of the nucleocapsid structure of shell with silver.
A kind of multi-walled carbon nano-tubes supported core-shell silver-platinum cathode Preparation of catalysts method is characterized in that, may further comprise the steps:
A, soluble silver salt is dissolved in ethanol and the deionized water mixing material; The concentration of Ag ion is the 0.0005-0.01 mol in the solution; The amount of substance of pressing citric acid or citrate and silver ion then is than being 1-2:1 adding citric acid or citrate; Mass ratio in multi-walled carbon nano-tubes carrier and silver ion is the ratio adding multi-walled carbon nano-tubes carrier of 4-25:1 again, and fully mixing and stirring obtains mixed solution; Wherein the multi-walled carbon nano-tubes carrier is 7-9:1 in the preferable mass ratio of silver ion.
B, sodium borohydride is dissolved in ethanolic solution; Its concentration be the 50-200 mM/liter, be added drop-wise in the above-mentioned reactant liquor, wherein silver ion is 5-10:1 with the ratio of the amount of substance of sodium borohydride; Reaction time 2-6h; With reactant liquor washing, suction filtration, 50 ℃ of-80 ℃ of following vacuumizes obtain multi-walled carbon nano-tubes and carry silver particles (Ag/MWCNTs);
C, the multi-walled carbon nano-tubes among the step B is carried silver particles evenly spread in the ethylene glycol liquid; Add the chloroplatinic acid aqueous solution that concentration is the 0.01-0.02 mol again; Make that the mass ratio of Ag and Pt ion is 0.2-3:1 in the solution; Use the ethylene glycol solution adjusting of NaOH or potassium hydroxide and keep system pH to be 7-9, under 70 ℃-110 ℃, add thermal reduction, reaction time 2-6h;
D, the reactant liquor centrifuge washing that step C is obtained exist up to no chloride ion, 50 ℃ of-80 ℃ of following vacuumizes, obtain multi-walled carbon nano-tubes supported core-shell silver-platinum catalyst (AgPt/MWCNTs).
The multi-walled carbon nano-tubes of the preferred acidified processing of multi-walled carbon nano-tubes.
In ethanol and the deionized water mixing material, the preferred 1:1. of the volume ratio of ethanol and deionized water
Through end product is carried out structural characterization, prove that this product is is carrier with the multi-walled carbon nano-tubes, it is carrier surface that active metal component loads on multi-walled carbon nano-tubes, and reactive metal is to be that core, platinum are the material of the nucleocapsid structure of shell with silver; The quality percentage composition of the preferred Ag of the present invention is 2-30%, and the quality percentage composition of Pt is 5-30%.The quality percentage composition of wherein preferable Ag is 5-15%, and the quality percentage composition of Pt is 5-20%.
Beneficial effect of the present invention: the present invention utilizes sodium borohydride and ethylene glycol to be reducing agent and solvent, and preparation has the AgPt/MWCNTs catalyst of nucleocapsid structure.Sodium borohydride is stronger reducing agent; Can in the process of reduction silver ion, produce silver sol; Be beneficial to the load of silver-colored nanoparticle on multi-walled carbon nano-tubes, in addition, because the viscosity of ethylene glycol is bigger; In the preparation process, can effectively stop the reunion of nano particle, thus the less nanocatalyst of preparation particle diameter.Simultaneously do not need extra reducing agent, the present invention has used two step reduction method, i.e. elder generation's reduction base metal restores noble metal, and temperature and pH value through the control reaction make noble metal at non-noble metal surface deposition, thereby process hud typed catalyst; In addition, the present invention has added the multi-walled carbon nano-tubes carrier in the preparation process, and nano-metal particle is directly grown on carrier, has strengthened the combination of catalyst granules and multi-walled carbon nano-tubes carrier, makes catalyst more stable.The present invention can improve the utilance of the catalytic efficiency and the noble metal of catalyst greatly, improves the ability of hydrogen reduction, with the development that promotes fuel cell.The prepared hud typed cathod catalyst of the present invention is having important use aspect the fuel battery negative pole hydrogen reduction.
Further the atom of the structure cell of Pt the inside is replaced than its big Ag atom by atomic radius, and the argent of nuclear has entered into the inside of platinum, has caused the structure cell of platinum to shrink and the unit cell volume increase, i.e. lattice dilatation, and it is big that lattice constant becomes.
Description of drawings
Fig. 1 be Ag/MWCNTs (curve a), the XRD spectra of AgPt/MWCNTs (c) catalyst of Pt/MWCNTs (curve b) and embodiment 2 preparations;
Fig. 2 is the high-resolution-ration transmission electric-lens photo of the AgPt/MWCNTs catalyst of embodiment 2 preparations;
Fig. 3 is the AgPt/MWCNTs catalyst of embodiment 1,2,3 and 4 preparations and the cyclic voltammetry curve comparison diagram of the Pt/MWCNTs catalyst that Comparative Examples 1 prepares, and wherein b, c, d, e are respectively the curves of embodiment 1,2,3,4, and a is the curve of Comparative Examples 1;
Fig. 4 is the AgPt/MWCNTs of embodiment 2 preparations and the linear volt-ampere curve comparison diagram of Pt/MWCNTs catalyst of Comparative Examples 1 preparation, and wherein a and b are respectively the curves of embodiment 2 and Comparative Examples 1.
Embodiment
Below in conjunction with embodiment and accompanying drawing the present invention is described further.
The prepared hud typed cathod catalyst of the present invention is having important use aspect the fuel battery negative pole hydrogen reduction.The sign of fuel battery cathod catalyst being carried out chemical property adopts cyclic voltammetry curve method and linear volt-ampere curve method usually.
The method of testing of cyclic voltammetry curve is: adopt three-electrode system, reference electrode is a saturated calomel electrode, is platinum electrode to electrode, and work electrode uses polytetrafluoroethylene glass multi-wall carbon nano-tube pipe electrode.Catalyst to be tested and absolute ethyl alcohol and Nafion solution are made into mixed serum, drip on the glass multi-wall carbon nano-tube pipe electrode with micro syringe, air dry in air at room temperature obtains work electrode.Used electrolyte is the H of 0.5mol/L
2SO
4Solution, sweep limits are-0.2-1.2V (relative saturation calomel electrode) that potential scanning speed is 50mV/s.In cyclic voltammetry curve, near the peak-0.2-0V is the absorption and the desorption peaks of hydrogen, and the peak of 0.4-0.45V is the reduction peak of oxygen, and the size of the integral area at redox peak is represented respectively and carried out what of redox reaction electric weight.And the electrochemistry oxygen active area of the Pt that can calculate unit mass by the absorption and the desorption peaks area average of hydrogen in the cyclic voltammetry curve of catalyst (electrochemical active area, EAS), concrete formula is following:
EAS(cm
2mg
-1)=Q
H/(210×[Pt])
Catalyst circulation volt-ampere curve test result is seen Fig. 3, and EAS result of calculation is seen table 1.
Linear volt-ampere scanning is to be recorded under the constant current potential, and the time dependent curve of cathod catalyst is confirmed its steady-state current with this.The work electrode of linear volt-ampere scanning is a rotating disk electrode (r.d.e), and rotating speed is 1600rpm, feeds saturated O
2, eliminate concentration polarization to the full extent.The step of preparation work electrode is tested with cyclic voltammetric.Electrolyte is 0.5molL
-1H
2SO
4Solution.Before test, in solution, feed 30min O earlier
2, keeping electrolyte in the test process is the oxygen saturation condition.The rotating speed of rotating circular disk is 1600rpm, and the scanning potential window is 0.1-0.8 (vs.SCE), and sweep speed is 2mVs
-1, just judge the size of cathod catalyst catalytic oxidation-reduction ability through the initial reduction potential of hydrogen reduction.
Embodiment 1
(1) take by weighing 92.7 milliliters, 1 mM/liter AgNO
3Solution and 84.6 milligrams of citric acids are received and are dissolved in ethanol/deionized water (the preferred 1:1 of volume ratio), after treating to dissolve fully, add 120 milligrams of multi-walled carbon nano-tubes that red fuming nitric acid (RFNA) was handled, and fully stir, and mix;
(2) get 7.9 milligrams of sodium borohydrides and be dissolved in 9.3 milliliters of ethanol, and in above-mentioned reactant liquor, dropwise add, stir, room temperature reaction 2h after reaction finishes, with reacted liquid scrubbing, suction filtration, is dried to constant weight under 60 ℃, obtains multi-walled carbon nano-tubes and carries the Ag particle.
(3) product that takes by weighing step (2) is well-dispersed in the ethylene glycol solution for 65 milligrams, adds 2.325 milliliters, the H of 0.077 mol
2PtCl
66H
2O also fully stirs, and using the pH value of the ethylene glycol solution regulation system of potassium hydroxide is 8, and stir and be warming up to 90 ℃, constant temperature 6h, constantly the ethylene glycol solution of make-up potassium hydroxide keeps the pH value of system constant in course of reaction
(4) with reacted liquid scrubbing, suction filtration, dry to constant weight under 60 ℃, obtain the AgPt/MWCNTs catalyst, wherein the Ag carrying capacity is 5%, the Pt carrying capacity is 35%.
(1) take by weighing 185 milliliters, 1 mM/liter AgNO
3Solution and 168.9 milligrams of citric acids are received and are dissolved in ethanol/deionized water (the preferred 1:1 of volume ratio), after treating to dissolve fully, add 120 milligrams of multi-walled carbon nano-tubes that red fuming nitric acid (RFNA) was handled, and fully stir, and mix;
(2) get 15.7 milligrams of sodium borohydrides and be dissolved in 18.5 milliliters of ethanol, and in above-mentioned reactant liquor, dropwise add, stir; Room temperature reaction 2h is after reaction finishes, with reacted liquid scrubbing, suction filtration; Dry to constant weight under 60 ℃, obtain multi-walled carbon nano-tubes and carry the Ag particle.
(3) product that takes by weighing step (2) is well-dispersed in the ethylene glycol solution for 70 milligrams, adds 1.990 milliliters, the H of 0.077 mol
2PtCl
66H
2O also fully stirs, and using the pH value of the ethylene glycol solution regulation system of potassium hydroxide is 8, and stir and be warming up to 90 ℃, constant temperature 6h, constantly the ethylene glycol solution of make-up potassium hydroxide keeps the pH value of system constant in course of reaction
(4) with reacted liquid scrubbing, suction filtration, dry to constant weight under 60 ℃, obtain the AgPt/MWCNTs catalyst, wherein the Ag carrying capacity is 10%, the Pt carrying capacity is 30%.
(1) take by weighing 278 milliliters, 1 mM/liter AgNO
3Solution and 253.8 milligrams of citric acids are received and are dissolved in ethanol/deionized water (the preferred 1:1 of volume ratio), after treating to dissolve fully, add 120 milligrams of multi-walled carbon nano-tubes that red fuming nitric acid (RFNA) was handled, and fully stir, and mix;
(2) get 23.6 milligrams of sodium borohydrides and be dissolved in 27.8 milliliters of ethanol, and in above-mentioned reactant liquor, dropwise add, stir; Room temperature reaction 2h is after reaction finishes, with reacted liquid scrubbing, suction filtration; Dry to constant weight under 60 ℃, obtain multi-walled carbon nano-tubes and carry the Ag particle.
(3) product that takes by weighing step (2) is well-dispersed in the ethylene glycol solution for 75 milligrams, adds 1.660 milliliters, the H of 0.077 mol
2PtCl
66H
2O also fully stirs, and using the pH value of the ethylene glycol solution regulation system of potassium hydroxide is 8, and stir and be warming up to 90 ℃, constant temperature 6h, constantly the ethylene glycol solution of make-up potassium hydroxide keeps the pH value of system constant in course of reaction
(4) with reacted liquid scrubbing, suction filtration, dry to constant weight under 60 ℃, obtain the AgPt/MWCNTs catalyst, wherein the Ag carrying capacity is 15%, the Pt carrying capacity is 25%.
(1) take by weighing 370 milliliters, 1 mM/liter AgNO
3Solution and 337.8 milligrams of citric acids are received and are dissolved in ethanol/deionized water (the preferred 1:1 of volume ratio), after treating to dissolve fully, add 120 milligrams of multi-walled carbon nano-tubes that red fuming nitric acid (RFNA) was handled, and fully stir, and mix;
(2) get 31.4 milligrams of sodium borohydrides and be dissolved in 37 milliliters of ethanol, and in above-mentioned reactant liquor, dropwise add, stir, room temperature reaction 2h after reaction finishes, with reacted liquid scrubbing, suction filtration, is dried to constant weight under 60 ℃, obtains multi-walled carbon nano-tubes and carries the Ag particle.
(3) product that takes by weighing step (2) is well-dispersed in the ethylene glycol solution for 80 milligrams, adds 1.330 milliliters, the H of 0.077 mol
2PtCl
66H
2O also fully stirs, and using the pH value of the ethylene glycol solution regulation system of potassium hydroxide is 8, and stir and be warming up to 90 ℃, constant temperature 6h, constantly the ethylene glycol solution of make-up potassium hydroxide keeps the pH value of system constant in course of reaction
(4) with reacted liquid scrubbing, suction filtration, dry to constant weight under 60 ℃, obtain the AgPt/MWCNTs catalyst, wherein the Ag carrying capacity is 20%, the Pt carrying capacity is 20%.
Comparative Examples 1
(1) with 2.655 milliliters, the H of 0.077 mol
2PtCl
66H
2O is dissolved in the ethylene glycol solution, and using the pH value of the ethylene glycol solution regulation system of potassium hydroxide is 8;
(2) at ambient temperature, add 60 milligrams of multi-walled carbon nano-tubes that red fuming nitric acid (RFNA) was handled, fully stir, mix, be warming up to 90 ℃, constant temperature 6h, constantly the ethylene glycol solution of make-up potassium hydroxide keeps the pH value of system constant in course of reaction;
(3) with reacted liquid scrubbing, suction filtration, dry to constant weight under 60 ℃, obtain the Pt carrying capacity and be 40% Pt/MWCNTs catalyst.
Table 1 is the tabulation of the concrete calculated value of electro-chemical activity area (EAS) of the AgPt/MWCNTs catalyst of embodiment 1,2,3 and 4 preparations and the Pt/MWCNTs catalyst that Comparative Examples 1 prepares.
Fig. 1 be Ag/MWCNTs (curve a), the XRD spectra of Pt/MWCNTs (curve b) and AgPt/MWCNTs (curve c) eelctro-catalyst.With XRD spectra and PDF card (C:JCPDS75-1621) the comparison 2 θ=26.2 ° characteristic diffraction peak that goes out in (002) for MWCNTs, the characteristic diffraction peak of sharp-pointed carbon has all appearred in three curves.Curve a is the XRD spectra of Ag/MWCNTs eelctro-catalyst, and the characteristic diffraction peak of 2 θ=38.1 °, 44.3 °, 64.4 ° and 77.4 ° appearance is the characteristic diffraction peak of Ag (111), (200), (220), (311) crystal face respectively with standard P DF card (Ag:JCPDS87-0597) contrast.Curve b is the XRD spectra of Pt/MWCNTs eelctro-catalyst, and the characteristic diffraction peak of 2 θ=39.8 °, 46.2 °, 67.4 ° and 81.3 ° appearance is (111), (200), (220) of Pt, the characteristic diffraction peak of (311) crystal face with standard P DF card (Pt:JCPDS04-0802) comparison respectively.Curve c is the XRD spectra of AgPt/MWCNTs eelctro-catalyst, and the characteristic diffraction peak of 2 θ=38.8 °, 43.7 °, 66.5 ° and 80.1 ° appearance is the characteristic diffraction peak of silver-platinum alloy (111), (200), (220), (311) crystal face.The characteristic diffraction peak that metal A g from curve c, do not occur is because the Ag nano particle is included in the inside of AgPt/MWCNTs eelctro-catalyst nano particle; In addition; Correlation curve b and c; Hud typed AgPt/MWCNTs eelctro-catalyst has negative moving to a certain degree than 2 θ angles of the characteristic diffraction peak of Pt/MWCNTs eelctro-catalyst, because the atom of the structure cell of Pt the inside is replaced than its big Ag atom by atomic radius, has caused the structure cell of platinum to shrink and the unit cell volume increase; Be lattice dilatation, it is big that lattice constant becomes.
Fig. 2 is the transmission electron microscope photo of the AgPt/MWCNTs catalyst of embodiment 2 preparations.Fig. 2 a is the transmission electron microscope photo behind the loaded Ag Pt/MWCNTs nano particle eelctro-catalyst, can see that the AgPt/MWCNTs nano particle loads on the surface of CNT, the relative homogeneous of particle, and favorable dispersibility, load capacity is higher.The high-resolution-ration transmission electric-lens photo of Fig. 2 b eelctro-catalyst nano particle, grain shape are circular or oval, and granular size is about 15nm; Can clearly see simultaneously the lattice fringe of nano particle, be about 0.232nm through the spacing of lattice of measuring the nano particle center, the lattice spacing of lattice at nano particle edge is 0.228nm; Known Pt (111) crystal face spacing of lattice is 0.228nm, and Ag (111) crystal face spacing of lattice is 0.236nm, explains that the center of nano particle has formed the structure of nuclear; And the argent as nuclear has entered into the inside of platinum, causes the platinum lattice dilatation, and atomic distance becomes big in the platinum structure cell; And the metal lattice spacing of nano particle shell is consistent with the spacing of lattice of Pt (111) crystal face; Do not change, so shell is a metal platinum, promptly the hud typed eelctro-catalyst of AgPt/MWCNTs is produced out.
Fig. 3 is the AgPt/MWCNTs eelctro-catalyst of embodiment 1,2,3,4 preparations and the cyclic voltammetry curve of the Pt/MWCNTs that Comparative Examples 1 prepares; Can find out increase through Fig. 1 along with platinum content; The absorption and the desorption peaks of the hydrogen of eelctro-catalyst increase gradually; Associative list 1 can find out that the increase along with platinum content is 10wt% when the content of silver, and when the content of platinum was 30wt%, AgPt/MWCNTs eelctro-catalyst electro-chemical activity area (EAS) was for being 70.6m to the maximum
2G
-1, and electro-chemical activity area (EAS) is higher than the electro-chemical activity area of the Pt/MWCNTs catalyst of Comparative Examples 1.
Fig. 4 is the linear volt-ampere curve of the Pt/MWCNTs eelctro-catalyst for preparing of AgPt/MWCNTs eelctro-catalyst and the Comparative Examples 1 of embodiment 2 preparation, hud typed AgPt/MWCNTs eelctro-catalyst to the initial reduction potential of oxygen with respect to the Pt/MWCNTs eelctro-catalyst to the initial reduction potential of oxygen about 40mV that shuffled.This is because adding has the AgPt/MWCNTs eelctro-catalyst of Transition Metal Ag to be easier to and O than Pt/MWCNTs eelctro-catalyst
2The reaction of hydrogen reduction has been quickened in the absorption of generation dibit; In addition; The standard electrode EMF of " two-electron reduction " key reaction is 0.682V; The standard electrode EMF of " quadrielectron reduction " key reaction is 1.229V; So higher hydrogen reduction current potential can promote to have the reduction reaction of the quadrielectron approach of higher reduction potential, so shuffling of the initial reduction potential of oxygen shown that the AgPt/MWCNTs eelctro-catalyst can promote the generation of " quadrielectron reduction " reaction of oxygen; Simultaneously the initial reduction potential of the oxygen platinum that has shown unit mass in the AgPt/MWCNTs eelctro-catalyst of shuffling has higher utilance; Bigger electro-catalysis interfacial reaction area is provided; Under the quality situation still less of platinum, has higher oxygen reducing ability, so have higher electro-chemical activity area and the catalytic performance of Geng Gao.
Claims (7)
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210143695.XA CN102723504B (en) | 2012-05-09 | 2012-05-09 | Multi-wall carbon nano-tube carried core-shell silver-platinum cathode catalyst and preparation method |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201210143695.XA CN102723504B (en) | 2012-05-09 | 2012-05-09 | Multi-wall carbon nano-tube carried core-shell silver-platinum cathode catalyst and preparation method |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN102723504A true CN102723504A (en) | 2012-10-10 |
| CN102723504B CN102723504B (en) | 2015-04-15 |
Family
ID=46949213
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201210143695.XA Expired - Fee Related CN102723504B (en) | 2012-05-09 | 2012-05-09 | Multi-wall carbon nano-tube carried core-shell silver-platinum cathode catalyst and preparation method |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN102723504B (en) |
Cited By (17)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301860A (en) * | 2013-06-09 | 2013-09-18 | 常州大学 | Preparation method of multiwalled carbon nanotube supported silver phosphate visible light photocatalyst |
| CN103560255A (en) * | 2013-10-23 | 2014-02-05 | 中国科学院金属研究所 | Carrier material of oxygen reduction catalyst for zinc air cell as well as preparation method thereof |
| CN103752328A (en) * | 2014-01-17 | 2014-04-30 | 东华大学 | Preparation method of hollow core-shell catalyst for fuel cell |
| CN103878365A (en) * | 2014-03-11 | 2014-06-25 | 上海交通大学 | Method for preparing core-shell structure nano-particles with silver coated with platinum |
| CN103949251A (en) * | 2014-05-09 | 2014-07-30 | 北京化工大学 | Oxygen reduction catalyst as well as preparation method and application of oxygen reduction catalyst |
| CN104300112A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Positive electrode for lithium sulfur battery |
| CN105363440A (en) * | 2015-11-30 | 2016-03-02 | 北京化工大学 | Carbon black loaded hollow platinum-silver-alloy-nanoparticle composite catalyst and preparation method therefor |
| CN105655603A (en) * | 2015-12-31 | 2016-06-08 | 北京化工大学 | Fuel-cell catalyst and preparation method thereof |
| CN108745350A (en) * | 2018-06-21 | 2018-11-06 | 广东工业大学 | A kind of preparation method and applications of bimetallic nucleocapsid catalyst |
| CN109546168A (en) * | 2018-11-22 | 2019-03-29 | 龙岩学院 | A kind of carbon material supported silver-colored platinum Nanoalloy composite material and preparation method |
| CN109939716A (en) * | 2019-04-10 | 2019-06-28 | 黑龙江大学 | A kind of nitrogen vacancy carbon-based catalyst for hydrogen production and preparation method thereof |
| CN110586090A (en) * | 2019-10-09 | 2019-12-20 | 清华大学 | Noble metal alloy shell-core catalyst prepared by using organic reducing agent and preparation method thereof |
| CN113097500A (en) * | 2019-12-23 | 2021-07-09 | 大连大学 | Preparation method and application of CuO-NiNPs/AgNWs/CNT/PDMS anode |
| CN113388846A (en) * | 2021-06-11 | 2021-09-14 | 广东电网有限责任公司 | Au @ Pt/CNT catalyst and preparation method and application thereof |
| CN114588915A (en) * | 2020-12-04 | 2022-06-07 | 中国科学院大连化学物理研究所 | A supported platinum-based catalyst and its preparation and application |
| CN114985755A (en) * | 2022-04-21 | 2022-09-02 | 江苏大学 | A kind of preparation method of PtPd alloy nanowire |
| CN115863669A (en) * | 2023-02-09 | 2023-03-28 | 江苏皇冠新材料科技有限公司 | Method for preparing nano particle catalyst by liquid phase deposition and application thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872417A (en) * | 2006-06-08 | 2006-12-06 | 武汉理工大学 | Nucleocapsid catalyst in use for fuel cell and preparation method |
| CN101664685A (en) * | 2009-09-27 | 2010-03-10 | 西北师范大学 | Low-platinum high active core-shell structure catalyst and preparation method thereof |
| CN102088091A (en) * | 2010-12-17 | 2011-06-08 | 北京化工大学 | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof |
-
2012
- 2012-05-09 CN CN201210143695.XA patent/CN102723504B/en not_active Expired - Fee Related
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1872417A (en) * | 2006-06-08 | 2006-12-06 | 武汉理工大学 | Nucleocapsid catalyst in use for fuel cell and preparation method |
| CN101664685A (en) * | 2009-09-27 | 2010-03-10 | 西北师范大学 | Low-platinum high active core-shell structure catalyst and preparation method thereof |
| CN102088091A (en) * | 2010-12-17 | 2011-06-08 | 北京化工大学 | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof |
Cited By (29)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103301860B (en) * | 2013-06-09 | 2015-04-22 | 常州大学 | Preparation method of multiwalled carbon nanotube supported silver phosphate visible light photocatalyst |
| CN103301860A (en) * | 2013-06-09 | 2013-09-18 | 常州大学 | Preparation method of multiwalled carbon nanotube supported silver phosphate visible light photocatalyst |
| CN104300112A (en) * | 2013-07-18 | 2015-01-21 | 中国科学院大连化学物理研究所 | Positive electrode for lithium sulfur battery |
| CN104300112B (en) * | 2013-07-18 | 2016-12-28 | 中国科学院大连化学物理研究所 | A kind of lithium-sulfur cell positive pole |
| CN103560255A (en) * | 2013-10-23 | 2014-02-05 | 中国科学院金属研究所 | Carrier material of oxygen reduction catalyst for zinc air cell as well as preparation method thereof |
| CN103560255B (en) * | 2013-10-23 | 2015-10-07 | 中国科学院金属研究所 | Carrier material of a kind of oxygen reduction catalyst for zinc-air battery and preparation method thereof |
| CN103752328A (en) * | 2014-01-17 | 2014-04-30 | 东华大学 | Preparation method of hollow core-shell catalyst for fuel cell |
| CN103752328B (en) * | 2014-01-17 | 2016-04-06 | 东华大学 | A kind of preparation method of the hollow core-shell catalyst for fuel cell |
| CN103878365B (en) * | 2014-03-11 | 2016-08-24 | 上海交通大学 | A kind of preparation method of platinum coated with silver Core-shell Structure Nanoparticles |
| CN103878365A (en) * | 2014-03-11 | 2014-06-25 | 上海交通大学 | Method for preparing core-shell structure nano-particles with silver coated with platinum |
| CN103949251A (en) * | 2014-05-09 | 2014-07-30 | 北京化工大学 | Oxygen reduction catalyst as well as preparation method and application of oxygen reduction catalyst |
| CN105363440B (en) * | 2015-11-30 | 2018-10-23 | 北京化工大学 | Hollow platinum-silver alloys nano-particle composite catalyst of carbon black loadings and preparation method thereof |
| CN105363440A (en) * | 2015-11-30 | 2016-03-02 | 北京化工大学 | Carbon black loaded hollow platinum-silver-alloy-nanoparticle composite catalyst and preparation method therefor |
| CN105655603B (en) * | 2015-12-31 | 2018-06-12 | 北京化工大学 | A kind of fuel-cell catalyst and preparation method thereof |
| CN105655603A (en) * | 2015-12-31 | 2016-06-08 | 北京化工大学 | Fuel-cell catalyst and preparation method thereof |
| CN108745350B (en) * | 2018-06-21 | 2021-03-16 | 广东工业大学 | A kind of preparation method and application of bimetallic core-shell catalyst |
| CN108745350A (en) * | 2018-06-21 | 2018-11-06 | 广东工业大学 | A kind of preparation method and applications of bimetallic nucleocapsid catalyst |
| CN109546168A (en) * | 2018-11-22 | 2019-03-29 | 龙岩学院 | A kind of carbon material supported silver-colored platinum Nanoalloy composite material and preparation method |
| CN109546168B (en) * | 2018-11-22 | 2021-12-03 | 龙岩学院 | Carbon material loaded silver-platinum nano alloy composite material and preparation method thereof |
| CN109939716B (en) * | 2019-04-10 | 2022-04-29 | 黑龙江大学 | A kind of nitrogen vacancy carbon-based catalyst for hydrogen production and preparation method thereof |
| CN109939716A (en) * | 2019-04-10 | 2019-06-28 | 黑龙江大学 | A kind of nitrogen vacancy carbon-based catalyst for hydrogen production and preparation method thereof |
| CN110586090B (en) * | 2019-10-09 | 2021-04-27 | 清华大学 | A kind of precious metal alloy shell-core catalyst prepared by using organic reducing agent and preparation method thereof |
| CN110586090A (en) * | 2019-10-09 | 2019-12-20 | 清华大学 | Noble metal alloy shell-core catalyst prepared by using organic reducing agent and preparation method thereof |
| CN113097500A (en) * | 2019-12-23 | 2021-07-09 | 大连大学 | Preparation method and application of CuO-NiNPs/AgNWs/CNT/PDMS anode |
| CN113097500B (en) * | 2019-12-23 | 2022-06-07 | 大连大学 | A kind of preparation method of CuO-NiNPs/AgNWs/CNT/PDMS anode and its application |
| CN114588915A (en) * | 2020-12-04 | 2022-06-07 | 中国科学院大连化学物理研究所 | A supported platinum-based catalyst and its preparation and application |
| CN113388846A (en) * | 2021-06-11 | 2021-09-14 | 广东电网有限责任公司 | Au @ Pt/CNT catalyst and preparation method and application thereof |
| CN114985755A (en) * | 2022-04-21 | 2022-09-02 | 江苏大学 | A kind of preparation method of PtPd alloy nanowire |
| CN115863669A (en) * | 2023-02-09 | 2023-03-28 | 江苏皇冠新材料科技有限公司 | Method for preparing nano particle catalyst by liquid phase deposition and application thereof |
Also Published As
| Publication number | Publication date |
|---|---|
| CN102723504B (en) | 2015-04-15 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN102723504A (en) | Multi-wall carbon nano-tube carried core-shell silver-platinum cathode catalyst and preparation method | |
| CN102088091A (en) | Carbon-carrying shell type copper-platinum catalyst for fuel cell and preparation method thereof | |
| CN105170169B (en) | A kind of nitrogen-doped graphene iron-based nano-particles reinforcement type catalyst and preparation method thereof | |
| CN111933960B (en) | PtCo @ N-GNS catalyst and preparation method and application thereof | |
| CN105633425B (en) | A kind of Pdx@Pt/C nucleocapsid fuel battery cathod catalysts and preparation method thereof | |
| CN100531914C (en) | Preparation method of solid-phase reduction of platinum-carbon catalysts for fuel cells | |
| CN103050715B (en) | Preparation method for Palladium-copper-tin ternary alloy nano-catalyst and thereof | |
| CN101572316A (en) | Modified catalyst for low-temperature fuel cell and preparation method thereof | |
| CN104368357B (en) | A kind of PdPtNi/C metal nano Catalysts and its preparation method and purposes | |
| CN101733094A (en) | Pt-CeO2/graphene electro-catalyst and preparation method thereof | |
| CN102380400B (en) | Direct borohydride fuel cell core-shell structure anode catalyst and preparation method thereof | |
| CN103331172B (en) | Preparation method for non-Pt non-H anode catalyst of proton exchange membrane fuel cell (PEMFC) | |
| CN110201662A (en) | The electrochemical preparation method of carbon load monoatomic metal catalyst | |
| CN101607197A (en) | A kind of preparation method of fuel-cell catalyst | |
| CN110787823B (en) | Three-dimensional nitrogen-doped flower-shaped carbon spheres supported ultrafine nitrogen-doped molybdenum carbide nanoparticles and preparation method and application | |
| CN108155392B (en) | Preparation method of reduced graphene oxide loaded Pd-M nano composite catalyst | |
| CN112421063A (en) | A kind of preparation method of one-dimensional porous hollow low platinum nano chain catalyst | |
| CN108746659B (en) | Flower-shaped AgPd nano alloy and preparation and use methods thereof | |
| CN104525189A (en) | Polyhedral Pd-Pt alloy nano catalyst and preparation method and application of nano catalyst | |
| CN103394346A (en) | Preparation method for small-size high-dispersion fuel battery catalyst | |
| CN105655603B (en) | A kind of fuel-cell catalyst and preparation method thereof | |
| CN113809344B (en) | A highly stable nano-platinum-based intermetallic compound direct methanol fuel cell electrocatalyst and preparation method thereof | |
| RU2324538C1 (en) | Catalyst with nanoparticles on carrier and method of its production | |
| CN104037427B (en) | A kind of preparation method of high active core shell structure catalyst and application thereof | |
| CN103041857A (en) | Preparation method of graphite nano-plate-loaded nano-noble metal catalyst |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20150415 Termination date: 20170509 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |