CN101224434A - Preparing method of nanometer particle carbon nanotube compound catalyst - Google Patents
Preparing method of nanometer particle carbon nanotube compound catalyst Download PDFInfo
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- CN101224434A CN101224434A CNA2007103075809A CN200710307580A CN101224434A CN 101224434 A CN101224434 A CN 101224434A CN A2007103075809 A CNA2007103075809 A CN A2007103075809A CN 200710307580 A CN200710307580 A CN 200710307580A CN 101224434 A CN101224434 A CN 101224434A
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Abstract
The invention relates to a preparation method of a nano particle carbon nanotube compound catalyst. The carbon nanotube with electric charges on surface is obtained from the materials which can generate non-covalent action with the carbon nanotube. Then nano particle with opposite electric charges on surface to that of the non-covalent modified carbon nanotube is added and completely mixed, and excess nano particle is removed to finally obtain the nano particle carbon nanotube catalyst compound. A plurality of nano particle carbon nanotube catalyst compounds can be prepared by the invention, all of which represent very good catalytic activities. The invention adopts the method of non-covalent modified carbon nanotube to obtain carbon nanotube with perfect surface. Meanwhile, the invention provides the nano particle, in particular, the morphology controllable nano particle on the load of carbon nanotube with an effective way by utilizing the electrostatic interaction of carbon nanotube and namo particle, thus extending the applications of morphology controllable nano particle in catalytic field.
Description
Technical field
The present invention relates to provide a kind of preparation method of nanometer particle carbon nanotube compound catalyst.
Background technology
Nano particle (nanoparticles is called for short NPs) is meant that the molecule aggregate of size in 1～100nm scope, the research of nano particle are emerging science, nano particle is with its unique optics, electricity, acoustics, magnetics, character such as catalysis are subject to people's attention day by day.In numerous application of nano particle, nano-catalytic is one of centre sphere of nano particle research.As a class new catalytic agent material, nano particle has high-specific surface area, and the surface energy is so it has very high activity; The kind of nano particle is abundant, and pattern and size are all controlled, make its diversity with catalysis kind and good optionally characteristics, nano particle has been widely used in that catalysis is various types of has reacted, such as oxidation, and hydrogenation reaction, electronics transmits, and many reactions such as fuel cell.Yet in these catalytic reactions, used nano particle generally all is the uncertain nano particle of sphere or pattern, and the controlled nano material of size and pattern is not subjected to enough attention.Because pattern has determined the crystal face structure of nano particle, so the catalytic performance of nano particle also depends on the nano particle pattern at the particle diameter that depends on nano particle simultaneously.Well-known is that the size of the various character of nano particle and nano particle is closely related with pattern, the nano particle that therefore synthetic size pattern is controlled and to use at catalytic field be extremely important.
Under the prerequisite of not sacrificing catalytic performance, use few catalyst as far as possible, thereby save cost, this is important target of catalytic field.Is a kind of approach of effective raising catalyst performance with catalyst cupport to various suprabasil methods.In various substrates, CNT (carbon nanotubes is called for short CNTs) has been subjected to people's very big attention.CNT is by sp
2The hollow tube body of curling and form in the graphite top layer that the carbon atom of hydridization forms. according to the difference of the contained graphite number of plies, CNT can be divided into SWCN (single-walled carbon nanotubes, be called for short: SWNTs), double-walled carbon nano-tube (double-walled carbon nanotubes, be called for short: DWNTs), (Multi-walled carbon nanotubes is called for short: MWNTs) multi-walled carbon nano-tubes.Since 1991, Iijima found that this new material causes physics, chemistry, material scholar's extensive interest since the CNT.CNT one dimension characteristic and with the chiral angle that graphite flake curls causes it to have unique electron transport characteristic, mechanics, elasticity, and character such as Raman spectrum.The peculiar property of CNT makes it be expected to be widely used at catalytic field, there are some researches show that CNT has better anti-corrosion effects than carbon black, hydrogen reduction is had tangible catalytic effect, and these characteristics make CNT be fit to very much do the substrate of nano-particle catalyst.
In recent years, the success of supported nanoparticle catalysts technology and breakthrough have advanced the application of nano material at catalytic field greatly on CNT.Yet CNT is difficult to be dissolved in common solvent and have high radius of curvature, makes at its area load nano-particle catalyst difficult.The common technology of supported nanoparticle catalysts has so several on CNT at present:
(1) infusion process is about to CNT and puts into catalyst precursor solution and fully flood, according to the catalyst type difference, takes reduction respectively, and methods such as hydrolysis are handled the catalyst prerequisite, thereby prepare the dispersed nano material catalyst that loads on the CNT.But the amount of this method supported catalyst on CNT seldom.(2) chemical method and relevant follow-on method thereof.Chemical method is one of basic skills of the carbon nanotube loaded nano-particle catalyst of preparation.Basic process makes carbon nano tube surface produce such as carboxyl carbonyl, function group such as hydroxyl at first CNT being refluxed in nitric acid and sulfuric acid or ultrasonic.Treated afterwards CNT can be by reduction, the different types of nano particles of means load such as hydrolysis.In CNT strong acid treatment process, the SP of CNT
2Hydridization is destroyed, and the physical property of CNT inherence changes.(3) electrochemical deposition.Electrochemical deposition method be a kind of simple and high-quality on CNT the method for depositing nano particle, but exist some such as in electrodeposition process, being accompanied by H
+Reduction, the amount of deposition and theoretical value be difference to some extent.
In sum, traditional method of depositing nano particle catalyst on CNT has a lot of weak points, the above method of what is more important is not nearly all considered the nano material catalyst of controllable appearance and size, uses existent method to be difficult to the nano-particle catalyst of load controllable appearance and size on CNT.No matter success nano material catalyst of load controllable appearance and size on CNT is to improving the catalytic performance of catalyst, still to the application of the nano material of expanding controllable appearance and size, all is significant.
Summary of the invention
The present invention provides the preparation method of nanometer particle carbon nanotube compound catalyst.With respect to additive method, non-covalent modification carbon nanotube technology provided by the invention, not only simple to operate, and in operating process the sp of destroying carbon nanometer tube hardly
2Hydridization makes that the exclusive physical property of CNT is preserved.It is in extensive range to be suitable for nano particle, almost contains the nano-particle catalyst of all kinds, and a kind of method of nano-particle catalyst of pay(useful) load controllable appearance and size is provided.Gained nanometer particle carbon nanotube compound catalyst even can be used as precursor is used for further load other types catalyst.The load capacity of catalyst can be achieved by the ratio of regulation and control CNT and catalyst.Obtained nanometer particle carbon nanotube catalyst has showed good catalytic effect.
The invention provides a kind of preparation method of nanometer particle carbon nanotube compound catalyst, step and condition are as follows:
Step (1): the acidifying purification process of CNT
In three neck containers of reflux condensate device are housed, add CNT and nitric acid, the weight of CNT (g): nitric acid volume (ml) is than being 1: (10～100), the concentration of nitric acid is 1M～5M, refluxed 2～48 hours down at 80 ℃～120 ℃, while mechanical agitation or magnetic agitation, mixing time is 2～48 hours, treat that solution is chilled to room temperature, use distilled water diluting, distilled water: the volume ratio of nitric acid is 1: (1～10), leave standstill to precipitating fully to CNT, discard supernatant liquor, the suspension of lower floor is the cellulose nitrate film filtration of 0.22 μ m with the aperture, the pH value that distilled water is washed till the drop that drips is the black filter cake that obtains CNT between 6～7,60 ℃ of following vacuum drying, thus obtain the CNT of purifying;
Step (2): utilization can with the material of CNT generation noncovalent interaction, preparation surface has the water miscible CNT of electric charge
Described material is meant and can is adsorbed on carbon nano tube surface or is wrapped in carbon nano tube surface by hydrogen bond, pi-pi bond, electrostatic interaction, hydrophobic hydrophilic interactional noncovalent interaction, makes the water-soluble and carbon nano tube surface its modification of CNT have the material of electric charge;
Described material is selected from one or more mixtures of polyelectrolyte, surfactant, inorganic compound and organic compound;
Described polyelectrolyte can be divided into cationic polyelectrolyte or anionic polyelectrolyte; Described cationic polyelectrolyte is: diallyl dimethyl ammoniumchloride, polyacrylamide, polypropylene-base amine, protonated poly-Ethylenimine, one or more mixtures such as hydrochloride, polylysine and shitosan of PAH; Described anionic polyelectrolyte is: one or more mixtures such as poly-third vinyl sulfonate, polystyrolsulfon acid, sodium lignin sulfonate and DNA;
Described surfactant is cationic surfactant or anion surfactant; Described cationic surfactant is the myristyl dimethyl benzyl ammonium chloride; Described anion surfactant is a neopelex;
Described inorganic compound has the inorganic compound of positive charge or the inorganic compound that the surface has load for the surface; The inorganic compound that described surface has positive charge is the 3-aminopropyl triethoxysilane; The said inorganic compound of wearing load is that phosphotungstic acid, phosphotungstic acid receive that, Lin Molybdenum acid, Lin Molybdenum acid is received, one or more mixture of silico-tungstic acid and ammonium phosphotungstate;
Described organic compound has the organic compound of positive electricity or the organic compound that the surface has negative electricity for the surface; The organic compound that said surface has positive charge is a 1-pyrene methylamine hydrochloride; The organic compound that said surface has negative electrical charge is a 1-pyrene sodium sulfonate;
With step (1) in the CNT of peracid purification process joins the aqueous solution with the described material of CNT generation noncovalent interaction, the weight of CNT (g): the aqueous solution volume (ml) of described material is than being 1: (10～150), described concentration of material is 0.001～10g/ml, adopt 20～100HZ ultrasonic echography to handle 0.5h～24h, magnetic agitation or electronic stirring 2-24h afterwards, mixing speed is 200-4000r/min, solution is placed on 35-70 ℃ of water-bath leaves standstill 4-24h, obtain homodisperse carbon nano-tube aqueous solutions;
The described material require that is not adsorbed on carbon nano tube surface is removed, the method one that adopts is: with homodisperse carbon nano-tube aqueous solutions directly is the cellulose nitrate film filtration of 0.22 μ m with the aperture, distilled water washing and filtering three times, remove the described material that is not adsorbed on carbon nano tube surface too much in the solution, thereby obtain the treated CNT that has the non-covalent modification of electric charge in surface; Perhaps,
Method two is: homodisperse carbon nano-tube aqueous solutions is placed centrifuge tube, adopting rotating speed is the 5000-20000rpm centrifuge, centrifugal stoste 0.2～2h, obtain the precipitation of black carbon nanotube, after it is scattered in the distilled water, continue adopting rotating speed is that the 5000-20000rpm centrifuge is centrifugal, distilled water is twice of centrifuge washing repeatedly, each centrifugation time is 0.2～2h, obtains the treated CNT that has the non-covalent modification of electric charge in surface;
The surperficial treated CNT that has the non-covalent modification of electric charge of gained will be dispersed in respectively in 0.001～2M salting liquid, and the dispersion concentration of CNT in salting liquid is 0.01～10mg/ml.Adopt the ultrasonic processing 0.5～2h of the ultrasonic device of 20～100HZ, obtain the CNT that the surface has the non-covalent modification of electric charge respectively; Salt in the used salting liquid is NaCl, KCl and CaCl
2One or more mixtures;
Step (3): synthetic surface with step (2) gained has the nano particle of carbon nano tube surface opposite charge of the non-covalent modification of electric charge
Nano particle is selected from metal nano material: gold, platinum, palladium, ruthenium, rhodium, iron or cobalt nanometer particle; Perhaps,
Metal binary alloy nano material: golden platinum, platinum ruthenium, platinum palladium, platinum iron or ferrocobalt nano particle; Perhaps,
Metal ternary alloy nano particle: platinum ruthenium tungsten, platinum ruthenium osmium, platinum ruthenium molybdenum, platinum ruthenium nickel or platinum ruthenium iridium nano particle; Perhaps,
Oxide-based nanomaterial: cuprous oxide, titanium dioxide, silica, ruthenic oxide, manganese dioxide, tin ash, ceria, di-iron trioxide or four iron oxide;
Nano particle need be removed the too much surfactant in surface, the nano particle dispersion soln of gained is placed centrifuge tube, adopting rotating speed is the 5000-20000rpm centrifuge, centrifugal stoste 0.1～2h, obtain the precipitation of nano particle, after it is scattered in the distilled water, continuing to adopt rotating speed is the 5000-20000rpm centrifuge, distilled water is twice of centrifuge washing repeatedly, time is 0.1～2h, the nano particle precipitation of last gained is dispersed in the distilled water, obtains the nano particle with the carbon nano tube surface opposite charge of the non-covalent modification of step (2) gained;
Step (4): preparation nanometer particle carbon nanotube compound
In the salting liquid through the non-covalent modification CNT of step (2) gained, add step (3) nano particle with carbon nano tube surface opposite charge non-covalent modification gained, the mass ratio of CNT and nano material is 1: (0.01-20), adopt the ultrasonic processing 0.5～2h of the ultrasonic device of 20～100HZ, magnetic agitation or electronic agitating solution 2～24h, mixing speed is 200～4000r/min; Perhaps adopt oscillator vibration 2～24h, frequency of oscillation is 50～400 commentaries on classics/min.The nanometer particle carbon nanotube compound of last gained need be removed the unnecessary nano material that is not assembled in carbon nano tube surface;
The above-mentioned nano material carbon mano-tube composite dispersion soln of gained is placed centrifuge tube, adopting rotating speed is the 5000-20000rpm centrifuge, centrifugal stoste 0.2～2h, obtain the precipitation of nano material, after it is scattered in the distilled water, continue adopting rotating speed is the 5000-20000rpm centrifuge, distilled water is twice of centrifuge washing repeatedly, 60 ℃ of following vacuum drying of compound precipitation with gained obtain a kind of nanometer particle carbon nanotube catalyst composites;
Gained a kind of nanometer particle carbon nanotube catalyst composites can be used for catalysis such as fuel cell, degradable organic pollutant, hydrogenation reaction, organic addition, fields such as solar cell;
A kind of nanometer particle carbon nanotube catalyst composites of gained showed good catalytic effect, expanded the utilization of the controlled nano particle of pattern at catalytic field.
Description of drawings
Fig. 1 is the 12.0wt% of different platinum load capacity, the field emission scanning electron microscope figure of Pt NCs carbon mano-tube composite.
Fig. 2 is the 39.0wt% of different platinum load capacity, the field emission scanning electron microscope figure of Pt NCs carbon mano-tube composite.
Fig. 3 is the 49.8.0wt% of different platinum load capacity, the field emission scanning electron microscope figure of Pt NCs carbon mano-tube composite.
Fig. 4 is that load capacity is the transmission electron microscope picture of 12.0wt%Pt NCs carbon mano-tube composite.
Fig. 5 is that load capacity is the transmission electron microscope picture of 39.0wt%Pt NCs carbon mano-tube composite.
Fig. 6 is that load capacity is the transmission electron microscope picture of 49.8wt%PtNCs carbon mano-tube composite.
Fig. 7 is that different platinum load capacity are 12.0wt%, and 39.8wt% and 49.8wt%Pt NCs carbon mano-tube composite are at the cyclic voltammogram of the saturated 0.1M sulfuric acid of nitrogen.
Fig. 8 a, 8b are respectively that load capacity is the catalysis figure of 49.8wt%PtNCs carbon mano-tube composite to hydrogen reduction.
The specific embodiment
Embodiment 1:
Step (1): in the three-necked bottle of reflux condensate device is housed, add CNT and nitric acid, the weight of CNT (g): nitric acid volume (ml) is than being 1: 10, the concentration of nitric acid is 1M, refluxed 2 hours down at 80 ℃, while mechanical agitation or magnetic agitation, mixing time is 2 hours, treat that solution is chilled to room temperature, use distilled water diluting, distilled water: the volume ratio of nitric acid is 1: 1, leaves standstill to precipitating fully to CNT, discards supernatant liquor, the suspension of lower floor is the cellulose nitrate film filtration of 0.22 μ m with the aperture, the pH value that distilled water is washed till the drop that drips is the black filter cake that obtains CNT between 6～7,60 ℃ of following vacuum drying, thus obtain the CNT of purifying.
Step (2): preparation non-covalent modification surface has the used preferably poly-third vinyl sulfonate (poly (sodium-p-styrenesulfonate) of molecule of CNT of negative electricity, be called for short PSS), the CNT of the sour purification process of step (1) is joined in the aqueous solution that concentration is 0.005g/ml PSS, the weight of CNT (g): the body of PSS solution (ml) is 1: 10, adopt the ultrasonic processing of the ultrasonic device of 20HZ 0.5h, room temperature magnetic agitation or electronic agitating solution 2h, mixing speed is 200r/min, solution is placed on 35 ℃ of water-baths leaves standstill 4h, obtain the carbon nano-tube aqueous solutions of PSS non-covalent modification.
The PSS that is not adsorbed on carbon nano tube surface in the solution is removed, can adopt method one to be: with the carbon nano-tube aqueous solutions of the PSS non-covalent modification of gained is that the cellulose nitrate film of 0.22 μ m filters with the aperture directly, distilled water washing and filtering three times, remove poly-third vinyl sulfonate that is not adsorbed on carbon nano tube surface too much in the solution, thereby obtain the CNT that the surface has the PSS modification of negative electricity; Method two is: the carbon nano-tube aqueous solutions that the PSS of gained is modified places centrifuge tube, adopting rotating speed is the 5000rpm centrifuge, centrifugal stoste 0.2h, the CNT centrifugation that obtains is scattered in the distilled water, continuing to adopt rotating speed is the 5000rpm centrifuge, centrifuge washing twice, the time is 0.2h, thereby obtains the CNT that the surface has the PSS modification of negative electricity.The CNT that the PSS of gained modifies is dispersed in the 0.001M NaCl solution, and the dispersion concentration of CNT in salting liquid is 0.01mg/ml.Adopt the ultrasonic processing of the ultrasonic device of 20HZ 0.5h, obtain the CNT that the surface has the electric charge non-covalent modification.
Step (3): synthetic softex kw (hexadecyltrimethylammonium bromide is called for short CTAB), (Platium nanocubes is called for short: Pt NCs) in the foursquare preparation of platinum nanometer of CTAB protection.Contain 0.1M CTAB and 0.75mM chloroplatinic acid in the 10ml solution, this solution is heated to 60 ℃, treat to add 0.01M sodium borohydride 1.1ml fast and stirred 5 minutes after the solution clarification, be placed in 30 ℃ of waters bath with thermostatic control stand-by afterwards.Gained Pt NCs is that 15000 commentaries on classics/min centrifuges are centrifugal at revolution, with distilled water centrifuge washing twice repeatedly, at last Pt NCs is scattered in distilled water.
Step (4): in step (2), add step (3) nano particle with carbon nano tube surface opposite charge non-covalent modification gained in the salting liquid through the non-covalent modification CNT of gained, the mass ratio of CNT and nano material is 1: 0.01, adopt the ultrasonic processing of the ultrasonic device of 20HZ 0.5h, magnetic agitation or electronic agitating solution 2h, mixing speed is 200r/min; Perhaps adopt oscillator vibration 2h, frequency of oscillation is 50 commentaries on classics/min.The nanometer particle carbon nanotube compound of last gained need be removed the unnecessary nano material that is not assembled in carbon nano tube surface.
The above-mentioned nano material carbon mano-tube composite dispersion soln of gained is placed centrifuge tube, adopting rotating speed is the 5000rpm centrifuge, centrifugal stoste 0.2h, obtain the precipitation of nano material, after it is scattered in the distilled water, continue adopting rotating speed is the 5000rpm centrifuge, distilled water is twice of centrifuge washing repeatedly, 60 ℃ of following vacuum drying of compound precipitation with gained obtain nanometer particle carbon nanotube compound.
Embodiment 2:
Step (1): in the three-necked bottle of reflux condensate device is housed, add CNT and nitric acid, the weight of CNT (g): nitric acid volume (ml) is than being 1: 50, the concentration of nitric acid is 3M, refluxed 24 hours down at 100 ℃, while mechanical agitation or magnetic agitation, mixing time is 24 hours, treat that solution is chilled to room temperature, use distilled water diluting, distilled water: the volume ratio of nitric acid is 1: 5, leaves standstill to precipitating fully to CNT, discards supernatant liquor, the suspension of lower floor is the cellulose nitrate film filtration of 0.22 μ m with the aperture, the pH value that distilled water is washed till the drop that drips is the black filter cake that obtains CNT between 6～7,60 ℃ of following vacuum drying, thus obtain the CNT of purifying.
Preparation non-covalent modification surface has the used preferably poly-third vinyl sulfonate (poly (sodium-p-styrenesulfonate) of molecule of CNT of negative electricity, be called for short PSS), the CNT of the sour purification process of step (1) is joined in the aqueous solution that concentration is 0.01g/ml PSS, the weight of CNT (g): the body of PSS solution (ml) is 1: 75, adopt the ultrasonic processing of the ultrasonic device of 50HZ 12h, room temperature magnetic agitation or electronic agitating solution 12h, mixing speed is 2000r/min, solution is placed on 50 ℃ of water-baths leaves standstill 12h, obtain the carbon nano-tube aqueous solutions of PSS non-covalent modification.
The PSS that is not adsorbed on carbon nano tube surface in the solution is removed, can adopt method one to be: with the carbon nano-tube aqueous solutions of the PSS non-covalent modification of gained is that the cellulose nitrate film of 0.22 μ m filters with the aperture directly, distilled water washing and filtering three times, remove poly-third vinyl sulfonate that is not adsorbed on carbon nano tube surface too much in the solution, thereby obtain the CNT that the surface has the PSS modification of negative electricity; Method two is: the carbon nano-tube aqueous solutions that the PSS of gained is modified places centrifuge tube, adopting rotating speed is the 10000rpm centrifuge, centrifugal stoste 1h, the CNT centrifugation that obtains is scattered in the distilled water, continuing to adopt rotating speed is the 10000rpm centrifuge, distilled water is twice of centrifuge washing repeatedly, each time is 1h, thereby obtain the CNT that the surface has the PSS modification of negative electricity. the CNT of the non-covalent modification of gained, be dispersed in the 0.15M NaCl solution, the dispersion concentration of CNT in salting liquid is 1mg/ml.Adopt the ultrasonic processing of the ultrasonic device of 50HZ 1h, obtain the CNT that the surface has the electric charge non-covalent modification.
Step (3): synthetic softex kw (hexadecyltrimethylammonium bromide is called for short CTAB), (Platium nanocubes is called for short: Pt NCs) in the foursquare preparation of platinum nanometer of CTAB protection.Contain 0.1M CTAB and 0.75mM chloroplatinic acid in the 10ml solution, this solution is heated to 60 ℃, treat to add 0.01M sodium borohydride 1.1ml fast and stirred 5 minutes after the solution clarification, be placed in 30 ℃ of waters bath with thermostatic control stand-by afterwards.Gained Pt NCs is 15000 commentaries on classics/min centrifuges at revolution, with distilled water centrifuge washing twice repeatedly, at last Pt NCs is scattered in distilled water.
Step (4): in the salting liquid through the non-covalent modification CNT of step (2) gained, add step (3) nano particle with carbon nano tube surface opposite charge non-covalent modification gained, the mass ratio of CNT and nano material is 1: 5, adopt the ultrasonic processing of the ultrasonic device of 50HZ 1h, magnetic agitation or electronic agitating solution 12h, mixing speed is 1000r/min; Perhaps adopt oscillator vibration 12h, frequency of oscillation is that the nanometer particle carbon nanotube compound of the last gained of 200 commentaries on classics/min. need be removed the unnecessary nano material that is not assembled in carbon nano tube surface.
The above-mentioned nano material carbon mano-tube composite dispersion soln of gained is placed centrifuge tube, adopting rotating speed is the 10000rpm centrifuge, centrifugal stoste 1h, obtain the precipitation of nano material, after it is scattered in the distilled water, continue adopting rotating speed is the 10000rpm centrifuge, distilled water is twice of centrifuge washing repeatedly, 60 ℃ of following vacuum drying of compound precipitation with gained obtain nanometer particle carbon nanotube compound.
Embodiment 3:
In the three-necked bottle of reflux condensate device is housed, add CNT and nitric acid, the weight of CNT (g): nitric acid volume (ml) is than being 1: 100, the concentration of nitric acid is 1M～5M, refluxed 48 hours down at 120 ℃, while mechanical agitation or magnetic agitation, mixing time is 48 hours, treat that solution is chilled to room temperature, use distilled water diluting, distilled water: the volume ratio of nitric acid is 1: 10, leaves standstill to precipitating fully to CNT, discards supernatant liquor, the suspension of lower floor is the cellulose nitrate film filtration of 0.22 μ m with the aperture, the pH value that distilled water is washed till the drop that drips is the black filter cake that obtains CNT between 6～7,60 ℃ of following vacuum drying, thus obtain the CNT of purifying.
Step (2): preparation non-covalent modification surface has the used preferably poly-third vinyl sulfonate (poly (sodium-p-styrenesulfonate) of molecule of CNT of negative electricity, be called for short PSS), the CNT of the sour purification process of step (1) is joined in the aqueous solution that concentration is 0.1g/ml PSS, the weight of CNT (g): the body of PSS solution (ml) is 1: 150, adopt the ultrasonic processing of the ultrasonic device of 100HZ 24h, room temperature magnetic agitation or electronic agitating solution 24h, mixing speed is 4000r/min, solution is placed on 70 ℃ of water-baths leaves standstill 24h, obtain the carbon nano-tube aqueous solutions of PSS non-covalent modification.
The PSS that is not adsorbed on carbon nano tube surface in the solution is removed, can adopt method one to be: with the carbon nano-tube aqueous solutions of the PSS non-covalent modification of gained is that the cellulose nitrate film of 0.22 μ m filters with the aperture directly, distilled water washing and filtering three times, remove poly-third vinyl sulfonate that is not adsorbed on carbon nano tube surface too much in the solution, thereby obtain the CNT that the surface has the PSS modification of negative electricity; Method two is: the carbon nano-tube aqueous solutions that the PSS of gained is modified places centrifuge tube, adopting rotating speed is the 20000rpm centrifuge, centrifugal stoste 2h, the CNT centrifugation that obtains is scattered in the distilled water, continuing to adopt rotating speed is the 20000rpm centrifuge, distilled water is centrifuge washing twice repeatedly, and each time is 2h, thereby obtains the CNT that the surface has the PSS modification of negative electricity.The CNT of the non-covalent modification of gained is dispersed in the 2MNaCl solution, and the dispersion concentration of CNT in salting liquid is 10mg/ml.Adopt the ultrasonic processing of the ultrasonic device of 100HZ 2h, obtain the CNT that the surface has the electric charge non-covalent modification.
Step (3): synthetic softex kw (hexadecyltrimethylammonium bromide is called for short CTAB), (Platium nanocubes is called for short: Pt NCs) in the foursquare preparation of platinum nanometer of CTAB protection.Contain 0.1M CTAB and 0.75mM chloroplatinic acid in the 10ml solution, this solution is heated to 60 ℃, treat to add 0.01M sodium borohydride 1.1ml fast and stirred 5 minutes after the solution clarification, be placed in 30 ℃ of waters bath with thermostatic control stand-by afterwards.Gained Pt NCs is 15000 commentaries on classics/min centrifuges at revolution, with distilled water centrifuge washing twice repeatedly, at last Pt NCs is scattered in distilled water.
Step (4): in the salting liquid through the non-covalent modification CNT of step (2) gained, add step (3) nano particle with carbon nano tube surface opposite charge non-covalent modification gained, the mass ratio of CNT and nano material is 1: 20, adopt the ultrasonic processing of the ultrasonic device of 100HZ 2h, magnetic agitation or electronic agitating solution 24h, mixing speed is 4000r/min; Perhaps adopt oscillator vibration 24h, frequency of oscillation is 400 commentaries on classics/min.The nanometer particle carbon nanotube compound of last gained need be removed the unnecessary nano material that is not assembled in carbon nano tube surface.
The above-mentioned nano material carbon mano-tube composite dispersion soln of gained is placed centrifuge tube, adopting rotating speed is the 20000rpm centrifuge, centrifugal stoste 2h, obtain the precipitation of nano material, after it is scattered in the distilled water, continue adopting rotating speed is the 20000rpm centrifuge, distilled water is twice of centrifuge washing repeatedly, 60 ℃ of following vacuum drying of compound precipitation with gained obtain nanometer particle carbon nanotube compound.
Embodiment 4:
Step (1): the 20ml 7.1wt%PtNCs/PSS/MWNTs compound of embodiment one gained is scattered in the 0.15M NaCl solution, complex concentration is 0.15mg/ml, 1mg/ml GOD (0.1M phosphate buffer with 20ml, PH=7.4) after the mixing, ultrasonic 20min in the 40HZ ultrasonic wave, concuss 1h in 100 commentaries on classics/min oscillators, the compound of gained is that 15000 commentaries on classics/min centrifuges are centrifugal at revolution, distilled water cyclic washing secondary, the GOD/PtNCs/PSS/MWNTs compound that obtains is scattered in the 0.15M NaCl solution stand-by.
Step (2) is with the PtNCs 0.60mg after the centrifugal treating, GOD/PtNCs/PSS/MWNTs compound (0.15mg/ml) with 20ml, ultrasonic echography 20min at 40HZ, concuss 1h in 100 commentaries on classics/min oscillators, the compound of gained is that 15000 commentaries on classics/min centrifuges are centrifugal at revolution, distilled water washing three times, the PtNCs/MWNTs/GOD/PtNCs compound that obtains is scattered in the 0.15M NaCl solution stand-by.
Step (3):, make (GOD/PtNCs) with (1) and (2) step triplicate
3/ PtNCs/PSS/MWNTs transmission electron microscope shows that the multi-functional compound of compound makes.
Embodiment 5:
Step (1): add the MWNTs of 0.1g and the HNO of 100ml at the 250ml three-necked bottle that reflux condensate device is housed
3Solution (concentration is 3M).120 ℃ of backflow 48h, magnetic agitation or mechanical agitation in the time of backflow are reacted after 48 hours, be cooled to room temperature, add the 100ml distilled water diluting, leave standstill treat that CNT precipitates fully till, take out the upper strata stillness of night, the suspension of lower floor is the cellulose nitrate film filtration of 0.22 μ m with the aperture, using a large amount of distilled water flushings, is 6～7 up to the drop pH that leaches, and obtains the black precipitate of CNT, 60 ℃ of vacuum drying 24h, thus the CNT of purifying obtained.
Step (2): the preparation of PDDA/PSS/MWNTs.Preparation 1wt%PSS aqueous solution 1L, to wherein adding 150mg MWNTs, 40HZ ultrasonic echography 2 hours, stirring is spent the night, and puts it into 50 ℃ water bath with thermostatic control 12 hours afterwards, and the cellulose nitrate film by 0.22 μ m filters elimination and removes too much PSS afterwards.PSS/MWNTs with gained is scattered in the 0.15M sodium chloride solution of 1wt%PDDA afterwards, and solution concentration is 0.15mg/ml.40HZ ultrasonic echography 20min shook 1 hour, and the elimination of the cellulose nitrate film of 0.22 μ m filtration afterwards removes too much PDDA or adopts and remove too much PDDA powerful centrifugal three times, and the PDDA/PSS/MWNTs of gained is dispersed in the 0.15M sodium chloride stand-by, and concentration is
Step (3): the preparation of polyvinyl pyrrolidone protection Pt NCs.Contain 0.1M CTAB and 0.75mM chloroplatinic acid in the 10ml solution, this solution be heated to 60 ℃, treat that solution has been clarified after, add 0.01M NaBH fast
41.1ml stirred 5 minutes, and be placed in the 25 degree waters bath with thermostatic control stand-by afterwards.Getting gained Pt NCs 10ml solution, is that 15000 commentaries on classics/min centrifuges are centrifugal at revolution, and the precipitation of gained is scattered in to stir in the 10ml 0.75mM polyvinyl pyrrolidone solution of (polyviylpyrrolidone is called for short PVP) and spends the night.The CTAB on PtNCs surface is replaced by PVP, and the PVP-Pt NCs of gained is once centrifugal, is that 15000 commentaries on classics/min centrifuges are centrifugal at revolution, and the precipitation of gained is dispersed in the distilled water, and is stand-by.
Step (4): the sodium chloride solution 20ml that gets the PDDA/PSS/MWNTs of first step gained, mix with the Pt NCs of different amounts, the mass ratio of CNT and nano particle is 1: between the 0.01-10, ultrasonic 20min in the 40HZ ultrasonic wave, back 100 commentariess on classics/min oscillators vibration 24 hours, the Pt NCs carbon mano-tube composite of gained is that 15000 commentaries on classics/min centrifuges are centrifugal at revolution, use distilled water is twice of centrifuge washing repeatedly, with 60 ℃ of following vacuum drying of compound precipitation of gained, stand-by.The gained nanometer particle carbon nanotube compound, the sign through transmission electron microscope proves that nano-particle catalyst has loaded on carbon nano tube surface.The catalyst composites of the amount that the percentage composition on the use ICP-AES method mensuration Pt NCs load CNT maybe will be fixed is placed in the chloroazotic acid to be cleared up, and determines the percentage composition of Pt NCs on CNT by ICP-AES or ICP-AAS.
Embodiment 6:
Step (1): add the MWNTs of 0.1g and the HNO of 100ml at the 250ml three-necked bottle that reflux condensate device is housed
3Solution (concentration is 3M).120 ℃ of backflow 48h, magnetic agitation or mechanical agitation in the time of backflow are reacted after 48 hours, be cooled to room temperature, add the 100ml distilled water diluting, leave standstill treat that CNT precipitates fully till, take out the upper strata stillness of night, the suspension of lower floor is the cellulose nitrate film filtration of 0.22 μ m with the aperture, using a large amount of distilled water flushings, is 6～7 up to the drop pH that leaches, and obtains the black precipitate of CNT, 60 ℃ of vacuum drying 24h, thus the CNT of purifying obtained.
Step (2) preparation 1wt%PAH aqueous solution 1L, to wherein adding 150mg MWNTs, the ultrasonic wave of 40HZ was handled 2 hours, stirring is spent the night, after CNT is put into 50 ℃ water bath with thermostatic control 12 hours, by being that the cellulose nitrate film of 0.22 μ m filters elimination and removes too much PSS, filter three times with the distilled water cyclic washing.The MWNTs that PAH is modified is scattered in the 0.15M sodium chloride solution, handles 0.5 hour with the ultrasonic wave of 40HZ, and solution is dissolved fully, and solution concentration is 0.15mg/ml.
The preparation of the nano platinum particle of step (3) natrium citricum protection: contain the 0.25mM chloroplatinic acid in the 20ml distilled water, in the 2.5mM sodium citrate solution, add the 0.01M sodium borohydride of 0.6ml, solution reaction continues ten minutes.
Step (4): the sodium chloride solution 20ml that gets the PAH/MWNTs of first step gained, concentration is 0.15mg/ml. and the nano platinum particle aqueous solution of different amounts, the mass ratio of CNT and nano platinum particle is 1: between the 0.01-10, ultrasonic 20min in the 40HZ ultrasonic wave, back 100 commentaries on classics/min oscillators vibration 24 hours, the Pt nano platinum particle of gained and carbon mano-tube composite are that 15000 commentaries on classics/min centrifuges are centrifugal at revolution, use distilled water twice of centrifuge washing repeatedly, with 60 ℃ of following vacuum drying of compound precipitation of gained, stand-by.The gained nanometer particle carbon nanotube compound, the sign through transmission electron microscope proves that nano-particle catalyst has loaded on carbon nano tube surface.The percentage composition that uses the ICP-AES method to measure on the Pt NCs load CNT is cleared up in the chloroazotic acid for the catalyst composites of the amount that maybe will fix is placed on, and determines the percentage composition of Pt NCs on CNT by ICP-AES or ICP-AAS.
Embodiment 7:
Step (1): add the multi-walled carbon nano-tubes of 0.1g and the HNO of 100ml at the 250ml three-necked bottle that reflux condensate device is housed
3Solution (concentration is 3M).120 ℃ of backflow 48h, magnetic agitation or mechanical agitation in the time of backflow are reacted after 48 hours, be cooled to room temperature, add the 100ml distilled water diluting, leave standstill treat that CNT precipitates fully till, take out the upper strata stillness of night, the suspension of lower floor is the cellulose nitrate film filtration of 0.22 μ m with the aperture, using a large amount of distilled water flushings, is 6～7 up to the drop pH that leaches, and obtains the black precipitate of CNT, 60 ℃ of vacuum drying 24h, thus the CNT of purifying obtained.
Step (2) preparation 1wt%PAH aqueous solution 1L, to wherein adding 150mg MWNTs, the ultrasonic wave of 40HZ was handled 2 hours, stirring is spent the night, after CNT is put into 50 ℃ water bath with thermostatic control 12 hours, by being that the cellulose nitrate film of 0.22 μ m filters elimination and removes too much PSS, filter three times with the distilled water cyclic washing.The MWNTs that PAH is modified is scattered in the 0.15M sodium chloride solution, handles 0.5 hour with the ultrasonic wave of 40HZ, and solution is dissolved fully, and solution concentration is 0.15mg/ml.
Step (3): the preparation of the nano platinum particle of natrium citricum protection.In water of 20ml, contain the 0.25mM gold chloride, in the 2.5mM sodium citrate solution, add the 0.01M sodium borohydride of 0.6ml, solution reaction ten minutes.
Step (4): the sodium chloride solution 20ml that gets the PAH/MWNTs of first step gained, concentration is 0.15mg/ml. and the nano platinum particle aqueous solution of different amounts, the mass ratio of CNT and nano platinum particle is 1: between the 0.01-10, ultrasonic 20min in the 40HZ ultrasonic wave, back 100 commentaries on classics/min oscillators vibration 24 hours, the Pt nano platinum particle of gained and carbon mano-tube composite are that 15000 commentaries on classics/min centrifuges are centrifugal at revolution, use distilled water twice of centrifuge washing repeatedly, with 60 ℃ of following vacuum drying of compound precipitation of gained, stand-by.The gained nanometer particle carbon nanotube compound, the sign through transmission electron microscope proves that nano-particle catalyst has loaded on carbon nano tube surface.The percentage composition that uses the ICP-AES method to measure on the Pt NCs load CNT is cleared up in the chloroazotic acid for the catalyst composites of the amount that maybe will fix is placed on, and determines the percentage composition of Pt NCs on CNT by ICP-AES or ICP-AAS.
Claims (1)
1. the preparation method of a nanometer particle carbon nanotube compound catalyst is characterized in that, step and condition are as follows:
Step (1): the acidifying purification process of CNT
In three neck containers of reflux condensate device are housed, add CNT and nitric acid, the weight of CNT (g): nitric acid volume (ml) is than being 1: (10～100), the concentration of nitric acid is 1M～5M, refluxed 2～48 hours down at 80 ℃～120 ℃, while mechanical agitation or magnetic agitation, mixing time is 2～48 hours, treat that solution is chilled to room temperature, use distilled water diluting, distilled water: the volume ratio of nitric acid is 1: (1～10), leave standstill to precipitating fully to CNT, discard supernatant liquor, the suspension of lower floor is the cellulose nitrate film filtration of 0.22 μ m with the aperture, the pH value that distilled water is washed till the drop that drips is the black filter cake that obtains CNT between 6～7,60 ℃ of following vacuum drying, thus obtain the CNT of purifying;
Step (2): utilization can with the material of CNT generation noncovalent interaction, preparation surface has the water miscible CNT of electric charge
Described material is meant and can is adsorbed on carbon nano tube surface or is wrapped in carbon nano tube surface by hydrogen bond, pi-pi bond, electrostatic interaction, hydrophobic hydrophilic interactional noncovalent interaction, makes the water-soluble and carbon nano tube surface its modification of CNT have the material of electric charge;
Described material is selected from one or more mixtures of polyelectrolyte, surfactant, inorganic compound and organic compound;
Described polyelectrolyte can be divided into cationic polyelectrolyte or anionic polyelectrolyte; Described cationic polyelectrolyte is: diallyl dimethyl ammoniumchloride, polyacrylamide, polypropylene-base amine, protonated poly-Ethylenimine, one or more mixtures such as hydrochloride, polylysine and shitosan of PAH; Described anionic polyelectrolyte is: one or more mixtures such as poly-third vinyl sulfonate, polystyrolsulfon acid, sodium lignin sulfonate and DNA;
Described surfactant is cationic surfactant or anion surfactant; Described cationic surfactant is the myristyl dimethyl benzyl ammonium chloride; Described anion surfactant is a neopelex;
Described inorganic compound has the inorganic compound of positive charge or the inorganic compound that the surface has load for the surface; The inorganic compound that described surface has positive charge is the 3-aminopropyl triethoxysilane; The said inorganic compound of wearing load is that phosphotungstic acid, phosphotungstic acid receive that, Lin Molybdenum acid, Lin Molybdenum acid is received, one or more mixture of silico-tungstic acid and ammonium phosphotungstate;
Described organic compound has the organic compound of positive electricity or the organic compound that the surface has negative electricity for the surface; The organic compound that said surface has positive charge is a 1-pyrene methylamine hydrochloride; The organic compound that said surface has negative electrical charge is a 1-pyrene sodium sulfonate;
With step (1) in the CNT of peracid purification process joins the aqueous solution with the described material of CNT generation noncovalent interaction, the weight of CNT (g): the aqueous solution volume (ml) of described material is than being 1: (10～150), described concentration of material is 0.001～10g/ml, adopt 20～100HZ ultrasonic echography to handle 0.5h～24h, magnetic agitation or electronic stirring 2-24h afterwards, mixing speed is 200-4000r/min, solution is placed on 35-70 ℃ of water-bath leaves standstill 4-24h, obtain homodisperse carbon nano-tube aqueous solutions;
The described material require that is not adsorbed on carbon nano tube surface is removed, the method one that adopts is: with homodisperse carbon nano-tube aqueous solutions directly is the cellulose nitrate film filtration of 0.22 μ m with the aperture, distilled water washing and filtering three times, remove the described material that is not adsorbed on carbon nano tube surface too much in the solution, thereby obtain the treated CNT that has the non-covalent modification of electric charge in surface; Perhaps,
Method two is: homodisperse carbon nano-tube aqueous solutions is placed centrifuge tube, adopting rotating speed is the 5000-20000rpm centrifuge, centrifugal stoste 0.2～2h, obtain the precipitation of black carbon nanotube, after it is scattered in the distilled water, continue adopting rotating speed is that the 5000-20000rpm centrifuge is centrifugal, distilled water is twice of centrifuge washing repeatedly, each centrifugation time is 0.2～2h, obtains the treated CNT that has the non-covalent modification of electric charge in surface;
The surperficial treated CNT that has the non-covalent modification of electric charge of gained will be dispersed in respectively in 0.001～2M salting liquid, and the dispersion concentration of CNT in salting liquid is 0.01～10mg/ml.Adopt the ultrasonic processing 0.5～2h of the ultrasonic device of 20～100HZ, obtain the CNT that the surface has the non-covalent modification of electric charge respectively; Salt in the used salting liquid is NaCl, KCl and CaCl
2One or more mixtures;
Step (3): synthetic surface with step (2) gained has the nano particle of carbon nano tube surface opposite charge of the non-covalent modification of electric charge
Nano particle is selected from metal nano material: gold, platinum, palladium, ruthenium, rhodium, iron or cobalt nanometer particle; Perhaps,
Metal binary alloy nano material: golden platinum, platinum ruthenium, platinum palladium, platinum iron or ferrocobalt nano particle; Perhaps,
Metal ternary alloy nano particle: platinum ruthenium tungsten, platinum ruthenium osmium, platinum ruthenium molybdenum, platinum ruthenium nickel or platinum ruthenium iridium nano particle; Perhaps,
Oxide-based nanomaterial: cuprous oxide, titanium dioxide, silica, ruthenic oxide, manganese dioxide, tin ash, ceria, di-iron trioxide or four iron oxide;
Nano particle need be removed the too much surfactant in surface, the nano particle dispersion soln of gained is placed centrifuge tube, adopting rotating speed is the 5000-20000rpm centrifuge, centrifugal stoste 0.1～2h, obtain the precipitation of nano particle, after it is scattered in the distilled water, continuing to adopt rotating speed is the 5000-20000rpm centrifuge, distilled water is twice of centrifuge washing repeatedly, time is 0.1～2h, the nano particle precipitation of last gained is dispersed in the distilled water, obtains the nano particle with the carbon nano tube surface opposite charge of the non-covalent modification of step (2) gained;
Step (4): preparation nanometer particle carbon nanotube compound
In the salting liquid through the non-covalent modification CNT of step (2) gained, add step (3) nano particle with carbon nano tube surface opposite charge non-covalent modification gained, the mass ratio of CNT and nano material is 1: (0.01-20), adopt the ultrasonic processing 0.5～2h of the ultrasonic device of 20～100HZ, magnetic agitation or electronic agitating solution 2～24h, mixing speed is 200～4000r/min; Perhaps adopt oscillator vibration 2～24h, frequency of oscillation is that the nanometer particle carbon nanotube compound of the last gained of 50～400 commentaries on classics/min. need be removed the unnecessary nano material that is not assembled in carbon nano tube surface;
The above-mentioned nano material carbon mano-tube composite dispersion soln of gained is placed centrifuge tube, adopting rotating speed is the 5000-20000rpm centrifuge, centrifugal stoste 0.2～2h, obtain the precipitation of nano material, after it is scattered in the distilled water, continue adopting rotating speed is the 5000-20000rpm centrifuge, distilled water is twice of centrifuge washing repeatedly, 60 ℃ of following vacuum drying of compound precipitation with gained obtain a kind of nanometer particle carbon nanotube catalyst composites.
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