CN1721075A - Preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls - Google Patents
Preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls Download PDFInfo
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- CN1721075A CN1721075A CN 200510040199 CN200510040199A CN1721075A CN 1721075 A CN1721075 A CN 1721075A CN 200510040199 CN200510040199 CN 200510040199 CN 200510040199 A CN200510040199 A CN 200510040199A CN 1721075 A CN1721075 A CN 1721075A
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Abstract
The preparation method for nano carbon hollow carried nano metal particle catalyst comprises three steps: (1) first prepare chitosan nano hollow: add chitosan into omega-olefine acid solution, mix at room temperature, filter and obtain micelle-form polymer solution; use potassium persulfate to initiate polymerization reaction of ethenyl, add 25% glutaral liquid to exchange the non-protonation amido on surface and form product; (2) use metal ion salt to absorb on the hollow; (3) put the dried solid into tube furnace, on the protection of nitrogen or reduced hydrogen, heat to 600-850Deg and keep 0.5-4h, then cool to room temperature and obtain carbon black power. This invention is fast, low cost, simple and controllable.
Description
Technical field
The present invention relates to a kind of method for preparing the hollow Nano carbon balls of catalyst with metal nanoparticles loaded with natural chitosan derivatives hollow nano-sphere, prepared catalyst can be directly used in the cathode and anode material of low temperature proton membrane fuel battery (comprising DMFC), belongs to material science and energy science field.
Background technology
Exploitation for free of contamination low temperature proton membrane fuel battery cathode and anode catalyst is the hot research problem of energy science and material science at present.As low temperature proton membrane fuel battery catalyst, metal platinum is occupied important status.In order to increase the specific area of catalyst, the preparation of nano platinum particle is put into research contents, yet, assemble easily because nano level platinum particles surface energy is higher, cause the reduction of catalytic activity and utilization rate.Again because of the price of metal platinum costliness, make that to use the simple metal platinum cell catalyst that acts as a fuel unrealistic.Therefore, people turn to the emphasis of research the research of carbon load platinum catalyst.Material with carbon element is a kind of good conductor on the one hand, can effectively transmit electronics; On the other hand, the loose structure of carbon can fine dispersed catalyst and is improved activity of such catalysts and utilization rate.Therefore, become the research emphasis of fuel battery anode catalyst preparation as the support materials of metallic catalyst nano particle with porous carbon.Although there is several different methods to prepare the catalyst with metal nanoparticles of carbon load at present, as ion-exchange, colloid, chemical vapour deposition (CVD) and electrochemical method, load comprises carbon black, active carbon, carbon nano-fiber, how empty carbon and CNT etc.But these methods generally all need special equipment, complicated preparation method, harsh preparation condition is as high temperature, high pressure etc., the cost height, and the high degree of dispersion of the particle shape of metal one C catalyst that generates, electrochemical properties, tenor, metal nanoparticle is difficult to control; Therefore, literature method both had been not suitable for breadboard operation, had greatly limited the large-scale production of such catalyst and application widely again.
Summary of the invention
The present invention seeks to propose a kind of low cost, quick, simple, the controlled method for preparing the hollow Nano carbon balls catalyst with metal nanoparticles loaded.
The preparation method of this hollow Nano carbon balls catalyst with metal nanoparticles loaded comprises the steps:
A kind of preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls is characterized in that this preparation method is made up of following three steps: (1) is the preparation of preparation shitosan hollow nano-sphere earlier; The preparation of shitosan hollow nano-sphere: shitosan is added in the aqueous solution of ω-olefin(e) acid, stirring at room, dissolving, the elimination insoluble matter, obtain micella sample polymer solution, filtrate is caused the polymerisation of vinyl with potassium peroxydisulfate, adds 25% glutaraldehyde water solution again and the unprotonated amino in surface is carried out crosslinked, forms the shitosan hollow nano-sphere; (2) adsorb on the shitosan hollow nano-sphere with metal cation salt; The shitosan hollow nano-sphere is placed the metal ion saline solution, stirred 1-10 hour, room temperature leaves standstill the back and filters, and repeatedly washs with distilled water, gets solid after the drying.(3) preparation of catalyst with metal nanoparticles loaded on carbon nano hollow balls; the solid of drying is placed tube furnace; logical nitrogen protection or contain under the hydrogen of reproducibility; be warming up to 600-850 ℃; after keeping 0.5-4 hour under this temperature, be cooled to room temperature; obtain carbon black sample powder, be the hollow Nano carbon balls catalyst with metal nanoparticles loaded.
With noble metal platinum, palladium etc. is example, the preparation of (1) shitosan hollow nano-sphere: ω-olefin(e) acid is an acrylic acid, shitosan is added in acrylic acid aqueous solution, and stirring at room, dissolving, the elimination insoluble matter obtains micella sample polymer solution.Filtrate is caused the polymerisation of vinyl with potassium peroxydisulfate, adds 25% glutaraldehyde water solution again and the unprotonated amino in surface is carried out crosslinked, forms the shitosan hollow nano-sphere.
(2) absorption of metal cation salt: the shitosan hollow nano-sphere is placed certain density chloroplatinic acid or palladium nitrate aqueous solution, and electromagnetic agitation 5 hours is filtered after the room temperature standing over night, repeatedly washs with distilled water, gets the glassy yellow solid after the drying.
(3) preparation of hollow Nano carbon balls catalyst with metal nanoparticles loaded: the glassy yellow solid of drying is placed homemade tube furnace; the logical nitrogen protection hydrogen of reproducibility (or contain); speed with 5K/min is warming up to 750 ℃; after keeping 1 hour under this temperature, be cooled to room temperature; obtain carbon black sample powder, be hollow Nano carbon balls loaded metal platinum nano-particle catalyst.
As shown from the above technical solution, the Nano carbon balls in the hollow Nano carbon balls catalyst with metal nanoparticles loaded of the present invention is to utilize wide material sources and free of contamination chitosan derivatives through thermal decomposition carbonization gained; Raw material sources are extensive, cheap, pollution-free; Know that from preparation method this technology is without any need for template and any specialized apparatus of complexity, making step is simple, and any laboratory can large-scale production; From products therefrom, the hollow Nano carbon particle all has complete chondritic, and particle diameter is evenly distributed, and particle diameter can be at 30-100nm, and the metal platinum nano-particle high degree of dispersion and the particle diameter that are carried on the hollow Nano carbon balls are even, can be controlled in 1-50nm; Electro-chemical test shows that it has good catalytic activity to methanol oxidation, so the Nano carbon balls preparation method of this loaded metal platinum nano-particle very easily is used more widely.Use different slaines or multiple metal salt mixture can obtain the Nano carbon balls catalyst of other metal nanoparticle or alloy nano particle load.
Description of drawings
Fig. 1 is a hollow Nano carbon balls loaded metal platinum nano-particle Preparation of catalysts process schematic diagram of the present invention.
Fig. 2 is the structural representation of hollow Nano carbon balls loaded metal platinum nano-particle catalyst of the present invention.
Fig. 3 is the transmission electron microscope photo (100,000 times of multiplication factors) that has adsorbed the anionic shitosan hollow nano-sphere of chloroplatinic acid.
Fig. 4 is the transmission electron microscope photo (80,000 times of multiplication factors) of Nano carbon balls of the supported platinum nano particle of embodiment gained.
Fig. 5 is the high-resolution-ration transmission electric-lens photo of nano platinum particle of the single load of embodiment gained.
Fig. 6 is modified at behind the glass-carbon electrode cyclic voltammetry curve to methyl alcohol catalysis for the hollow Nano carbon balls loaded metal platinum nano-particle catalyst of embodiment gained.Dotted line is not have methyl alcohol in the solution; Solid line is by containing 0.5M methyl alcohol in the solution.Sweep speed is 50mV/s.
The specific embodiment
As shown in Figures 1 and 2, the preparation method of preparation hollow Nano carbon balls catalyst with metal nanoparticles loaded provided by the invention mainly comprises following three steps composition: the preparation of (1) shitosan hollow nano-sphere; (2) absorption of metal cation salt on the shitosan hollow nano-sphere; (3) preparation of hollow Nano carbon balls catalyst with metal nanoparticles loaded.
The preparation method who makes the hollow Nano carbon balls catalyst with metal nanoparticles loaded is that example is illustrated with acrylic acid participation preparation hollow Nano carbon balls catalyst with metal nanoparticles loaded.
The preparation method of hollow Nano carbon balls catalyst with metal nanoparticles loaded is an example with the hollow Nano carbon balls of supported platinum nano particle, can carry out as follows:
(1) preparation of shitosan hollow nano-sphere: shitosan (a) is added in the aqueous solution of acrylic acid (b), the ratio of shitosan/ω-olefin(e) acid amount of substance is 1: 1～1: 2, and optimal proportion is 1: 1.1.Shitosan/ω-the concentration of olefin(e) acid compound in solution is 0.5gL
-1～20gL
-1As 13gL
-1, be lower than or surpass form and the character that this concentration range all can influence product.Stirring at room, dissolving, the elimination insoluble matter obtains micella sample polymer (c) solution.Filtrate is caused the polymerisations of vinyl at 80 ℃ with potassium peroxydisulfate, reaction 2h, be cooled to room temperature after, add 25% glutaraldehyde water solution again and the unprotonated amino in surface carried out crosslinked, form shitosan hollow nano-sphere (d).
Described ω-olefin(e) acid, molecular formula are CH
2=CH-(CH
2) m-COOH, m=0 wherein, 1,2,3,4,5, the shitosan hollow nano-sphere particle diameter minimum that when m is 0, obtains.The chitosan molecule formula is as follows:
x＝90～100％
Deacetylation is 90～100%, and molecular weight is 25,000～200,000D.
(2) the anionic absorption of chloroplatinic acid: the shitosan hollow nano-sphere is placed certain density chloroplatinic acid aqueous solution, chloroplatinic acid concentration is 0～100mg/mL, and electromagnetic agitation 5 hours is filtered after the room temperature standing over night, repeatedly wash with distilled water, get glassy yellow solid (e) after the drying.Metal cation salt can be chloroplatinic acid, gold chloride, ruthenium trichloride, palladium nitrate etc., adopt the metal ion salt solution of variable concentrations or the chloroplatinic acid/ruthenium trichloride aqueous solution of different proportion, can prepare the metal nanoparticles loaded hollow Nano carbon balls of different metal content or contain the hollow Nano carbon balls of the load platinum ruthenium nanometer particle of different platinum/ruthenium ratio.
The hollow Nano carbon balls average grain diameter is about 30-100nm, and the nano platinum particle high degree of dispersion is in carbon ball surface and carbon ball layer, and average grain diameter is 1-50nm, and the content of metal nanoparticle is 0～36% (w/w).
(3) preparation of the carbon hollow nanospheres of supported platinum nano particle: the glassy yellow solid of drying is placed homemade tube furnace; logical nitrogen (or containing reductive hydrogen) protection; speed with 5K/min is warming up to 750 ℃; after keeping 1 hour, this temperature is cooled to room temperature; get carbon black sample powder, be hollow Nano carbon balls catalyst with metal nanoparticles loaded (f).Logical nitrogen protection, or utilize the nitrogen atmosphere high temperature reduction will obtain same result.
The carbon hollow nanospheres average grain diameter is about 30-100nm; Metal nanoparticle is dispersed in carbon ball surface and the hollow carbon sphere layer, and particle size dispersion is good, can be controlled in 1～50nm, and tenor is 0～36% (w/w).By to the shitosan hollow nano-sphere of adsorbing metal ions in nitrogen atmosphere, pyrolytic or get by the hydrogen high temperature reduction.
The hollow ball shape structure that the anionic chitosan nano ball of transmission electron microscope observing absorption chloroplatinic acid is a regular shape, the shell average-size is about 50nm, boring nuclear is of a size of about 30nm.Nano carbon balls through the thermal decomposition carbonization is the spherical structure of rule under transmission electron microscope, and average grain diameter is about 50nm, and there is ferrous metal particle spot on the surface, and this metallic spot average-size is about 5nm.
The electrochemical properties of hollow Nano carbon balls loaded metal platinum nano-particle catalyst is measured: get the ultrasonic dispersion of Nafion solution of this carbon ball of 1mg and 10 μ l1%, get 2 μ l mixtures and drip and be coated on the glass-carbon electrode of surface finish, dry.With the modified glassy carbon is working electrode, and reversible hydrogen electrode is a reference electrode, and platinum electrode is to electrode, at 0.5MH
2SO
4In the sulfuric acid solution, repeatedly scanning cleaning electrode surface in 0.05～1.2V potential range is again in 0.5MH
2SO
4Among/0.5M the MeOH, in 0.05～1.2V potential range, measure cyclic voltammetry curve.The result shows, load the hollow Nano carbon balls of nano platinum particle methanol oxidation is had good catalytic action, and under experiment condition, show stable catalytic capability.
Claims (8)
1, a kind of preparation method of catalyst with metal nanoparticles loaded on carbon nano hollow balls is characterized in that this preparation method is made up of following three steps: (1) is the preparation of preparation shitosan hollow nano-sphere earlier; The preparation of shitosan hollow nano-sphere: shitosan is added in the aqueous solution of ω-olefin(e) acid, stirring at room, dissolving, the elimination insoluble matter, obtain micella sample polymer solution, filtrate is caused the polymerisation of vinyl with potassium peroxydisulfate, adds 25% glutaraldehyde water solution again and the unprotonated amino in surface is carried out crosslinked, forms the shitosan hollow nano-sphere; (2) adsorb on the shitosan hollow nano-sphere with metal cation salt; The shitosan hollow nano-sphere is placed the metal ion saline solution, stirred 1-10 hour, room temperature leaves standstill the back and filters, and repeatedly washs with distilled water, gets solid after the drying.(3) preparation of catalyst with metal nanoparticles loaded on carbon nano hollow balls; the solid of drying is placed tube furnace; logical nitrogen protection or contain under the hydrogen of reproducibility; be warming up to 600-850 ℃; after keeping 0.5-4 hour under this temperature, be cooled to room temperature; obtain carbon black sample powder, be the hollow Nano carbon balls catalyst with metal nanoparticles loaded.
2, according to the preparation method of the described carried metal nano hollow ball catalyst of claim 1, it is characterized in that shitosan is added in the aqueous solution of ω-olefin(e) acid, the ratio of shitosan/ω-olefin(e) acid amount of substance is 1: 1～1: 2, optimal proportion is 1: 1.1.Shitosan/ω-the concentration of olefin(e) acid compound in solution is 0.5gL
-1～20gL
-1
3, according to the preparation method of claim 1 or 2 described carried metal nano hollow ball catalysts, it is characterized in that filtrate is 60-100 ℃ of polymerisation that causes vinyl with potassium peroxydisulfate, reaction 2h, after being cooled to room temperature, add 25% glutaraldehyde water solution again and the unprotonated amino in surface is carried out crosslinked, form the shitosan hollow nano-sphere.
4, according to the preparation method of claim 1 or 2 described carried metal nano hollow ball catalysts, it is characterized in that described ω-olefin(e) acid, molecular formula is CH
2=CH-(CH
2) m-COOH, m=0 wherein, 1,2,3,4,5, the shitosan hollow nano-sphere particle diameter minimum that when m is 0, obtains; The chitosan molecule formula is as follows:
x＝90～100％
Deacetylation is 90～100%, and molecular weight is 25,000～200,000D.
5, according to the preparation method of claim 1 or 3 described carried metal nano hollow ball catalysts, it is characterized in that preparing with the following method: it is 0～100mg/mL chloroplatinic acid aqueous solution that the shitosan hollow nano-sphere is placed concentration.
6, according to the preparation method of claim 1 or 3 described carried metal nano hollow ball catalysts; the preparation that it is characterized in that hollow Nano carbon balls is that the glassy yellow solid with drying places tube furnace; logical nitrogen protection or nitrogen atmosphere high temperature reduction; speed with 5K/min is warming up to 750 ℃; kept 1 hour in this temperature; be cooled to room temperature, obtain carbon black sample powder.
7, according to the preparation method of claim 1 or 3 described carried metal nano hollow ball catalysts, it is characterized in that the hollow Nano carbon balls average grain diameter is about 30-100nm, the nano platinum particle high degree of dispersion is in carbon ball surface and carbon ball layer, average grain diameter is 1-50nm, and the content of metal nanoparticle is 0～36% (w/w).
8, according to the preparation method of claim 1 or 3 described carried metal nano hollow ball catalysts, it is characterized in that metal cation salt is chloroplatinic acid, gold chloride or ruthenium trichloride, adopt the metal ion salt solution of variable concentrations or the chloroplatinic acid/trichlorine chemotherapy aqueous solution of different proportion, can prepare the metal nanoparticles loaded hollow Nano carbon balls of different metal content or contain the hollow Nano carbon balls of the load platinum ruthenium nanometer particle of different platinum/ruthenium ratio.
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Cited By (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100455507C (en) * | 2006-03-15 | 2009-01-28 | 哈尔滨工业大学 | Carbon hollow ball with ferrocene and ammonium chloride as raw material and its prepn |
| CN1970203B (en) * | 2006-12-11 | 2010-05-19 | 哈尔滨工业大学 | Method for preparing hollow carbon ball with iron filler |
| CN102211204A (en) * | 2011-05-06 | 2011-10-12 | 中国科学院化学研究所 | Method for preparing nano-gold |
| CN102891326A (en) * | 2012-10-23 | 2013-01-23 | 南京交通职业技术学院 | Nitrogen-doped hollow carbon ball loaded palladium-based catalyst and preparation method thereof, and alcohol fuel cell applying same |
| CN101815563B (en) * | 2007-07-18 | 2013-02-13 | 新加坡南洋理工大学 | Hollow porous microspheres |
| CN108531932A (en) * | 2018-04-11 | 2018-09-14 | 郑州大学 | A kind of hollow carbon sphere encapsulation Ru nano particle electrolysis water catalyst and preparation method thereof |
| CN110743539A (en) * | 2019-09-29 | 2020-02-04 | 济南大学 | Method for preparing carbon platinum hollow spheres by using haematococcus pluvialis as reduction template agent |
| CN115285972A (en) * | 2022-08-05 | 2022-11-04 | 湖南师范大学 | Porous carbon-loaded metal type nano material and preparation method thereof |
-
2005
- 2005-05-24 CN CNB2005100401991A patent/CN100484631C/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100455507C (en) * | 2006-03-15 | 2009-01-28 | 哈尔滨工业大学 | Carbon hollow ball with ferrocene and ammonium chloride as raw material and its prepn |
| CN1970203B (en) * | 2006-12-11 | 2010-05-19 | 哈尔滨工业大学 | Method for preparing hollow carbon ball with iron filler |
| CN101815563B (en) * | 2007-07-18 | 2013-02-13 | 新加坡南洋理工大学 | Hollow porous microspheres |
| CN102211204A (en) * | 2011-05-06 | 2011-10-12 | 中国科学院化学研究所 | Method for preparing nano-gold |
| CN102891326A (en) * | 2012-10-23 | 2013-01-23 | 南京交通职业技术学院 | Nitrogen-doped hollow carbon ball loaded palladium-based catalyst and preparation method thereof, and alcohol fuel cell applying same |
| CN108531932A (en) * | 2018-04-11 | 2018-09-14 | 郑州大学 | A kind of hollow carbon sphere encapsulation Ru nano particle electrolysis water catalyst and preparation method thereof |
| CN108531932B (en) * | 2018-04-11 | 2020-02-21 | 河南郑大催化技术研究院有限公司 | Hollow carbon sphere packaged Ru nanoparticle electrolytic water catalyst and preparation method thereof |
| CN110743539A (en) * | 2019-09-29 | 2020-02-04 | 济南大学 | Method for preparing carbon platinum hollow spheres by using haematococcus pluvialis as reduction template agent |
| CN115285972A (en) * | 2022-08-05 | 2022-11-04 | 湖南师范大学 | Porous carbon-loaded metal type nano material and preparation method thereof |
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