CN101734614B - Method for manufacturing metal oxide nano-wire/noble metal nanocrystalline composite material - Google Patents
Method for manufacturing metal oxide nano-wire/noble metal nanocrystalline composite material Download PDFInfo
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- CN101734614B CN101734614B CN2009102005333A CN200910200533A CN101734614B CN 101734614 B CN101734614 B CN 101734614B CN 2009102005333 A CN2009102005333 A CN 2009102005333A CN 200910200533 A CN200910200533 A CN 200910200533A CN 101734614 B CN101734614 B CN 101734614B
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Abstract
The invention relates to a method for manufacturing a metal oxide nano-wire/noble metal nanocrystalline composite material. The method comprises the following steps: uniformly dispersing noble metal nanocrystalline in a solvent, dripping the solvent in ethanol solution of 2-mercaptoethylphosphoric acid for reaction overnight so as to obtain solution of phosphoric acid functionalized noble metal nanocrystalline; adding metal oxide nano-wires into the solution of phosphoric acid functionalized noble metal nanocrystal for reaction overnight, filtering the solution, and washing the solution with ethanol and deionized water to obtain the metal oxide nano-wire/noble metal nanocrystal composite material. The method adopts the 2-mercaptoethylphosphoric acid (2-MEPA) as a bonder to ensure that the noble metal nanocrystalline and the metal oxide nano-wires can be bonded through a functional organic group, and regulates and controls light characteristic, electrical characteristic, catalytic characteristic and sensitivity characteristic of the metal oxide nano-wire/noble metal nanocrystalline composite material by regulating the size of the noble metal nanocrystalline and dispersed state thereof on the surface of the metal oxide nano-wires.
Description
Technical field
The present invention relates to a kind of manufacturing approach of metal oxide nano-wire/noble metal nanocrystalline composite material, belong to function nano made field.
Technical background
Metal oxide nano-wire/noble metal nanocrystalline composite material is one type of advanced person's a functionalized nano material, but extensive use is high performance catalysis material, sensitive material, biomaterial and energy and material etc.The type composite is to be substrate with the metal oxide nano-wire, forms through the noble metal nanocrystalline of particular chemical self-assembling method in its area load some.The type composite mainly is through in the metal oxide nano-wire system, having introduced the noble metal nanocrystalline of some; Changed the energy gap of original nano wire system; Thereby make physics, chemistry and the biological nature etc. of this system that peculiar variation take place, thereby have stronger Research Significance.But the manufacturing of the type composite is difficulty relatively.Be mainly reflected in following some: be difficult to the uniform load noble metal nanocrystalline in nanowire surface; The amount of the noble metal nanocrystalline of nanowire surface institute load is difficult to control; Do not have active force etc. between nano wire and the noble metal nanocrystalline, thereby will make relatively difficulty of stable metal oxide nano-wire/noble metal nanocrystalline composite material.Though existing document report adopts methods such as wet chemistry method or vapour deposition can make metal oxide/noble metal nanocrystalline composite material; But owing to adopt noble metal nanocrystalline that wet chemistry method obtains at metal oxide surface not high (the Journal of Materials Chemistry of degree that is evenly distributed; 2008; Vol.18, pp.965-969); And the required equipment more complicated of vapour deposition process, condition is relatively harsher, the more important thing is that the noble metal uniformity coefficient at the metal oxide nano-material surface deposition is difficult to control (Nano Letters, 2005, Vol.5, pp.667-673; Applied PhysicsLetters, 2007, Vol.91, pp.053111).
Summary of the invention
The objective of the invention is to provides a kind of manufacturing approach of metal oxide nano-wire/noble metal nanocrystalline composite material to the deficiency that exists in the prior art.
For achieving the above object, the present invention adopts following technical scheme:
A kind of manufacturing approach of metal oxide nano-wire/noble metal nanocrystalline composite material; The concrete steps that it is characterized in that this method are: noble metal nanocrystalline is dispersed in the solvent; Be mixed with the suspension that concentration is 0.01mg/mL～0.03; Be added drop-wise to concentration again and be in the ethanolic solution of 2-mercaptoethyl phosphoric acid of 0.8mmol/L～2.0mmol/L, reaction overnight obtains the noble metal nanocrystalline solution of phosphoric acid functionalized; Metal oxide nano-wire is joined in the noble metal nanocrystalline solution of this phosphoric acid functionalized, reaction overnight through filtration, and with ethanol and deionized water washing, promptly obtains metal oxide nano-wire/noble metal nanocrystalline composite material; Described solvent is deionized water, ethanol or ethylene glycol; The mass ratio of described noble metal nanocrystalline and 2-mercaptoethyl phosphoric acid is: 100: (1～3); The mass ratio of described noble metal nanocrystalline and metal oxide nano-wire is: (0.2～0.7): 100.
Above-mentioned noble metal is: gold, silver, platinum, palladium, rhodium, iridium, osmium or ruthenium.
Above-mentioned metal oxide nano-wire is: zinc oxide, tin oxide, indium oxide, cupric oxide, iron oxide, tungsten oxide, nickel oxide, titanium oxide or cuprous oxide.
In sum, the inventive method adopts 2-mercaptoethyl phosphoric acid (2-MEPA) as coupler, and noble metal nanocrystalline and metal oxide nano-wire can be combined through functional organic group; Through the size of adjusting noble metal nanocrystalline and in the surperficial dispersity of metal oxide nano-wire, and then light, electricity, catalysis and the sensitivity characteristic of regulation and control metal oxide nano-wire/noble metal nanocrystalline composite material.
Description of drawings
Fig. 1 is WO
3The transmission electron microscope photo of nano wire/Au nanocrystalline composite material
Fig. 2 is SnO
2The transmission electron microscope photo of nano wire/Pt nanocrystalline composite material
Fig. 3 is the transmission electron microscope photo of ZnO nano wire/Pd nanocrystalline composite material
The transmission electron microscope photo of ZnO nano wire/Pd nanocrystalline composite material that Fig. 4 obtains for the wet-chemical dipping method
The specific embodiment
Embodiment one: oxide nano thread is WO
3Nano wire, noble metal nanocrystalline are that Au is nanocrystalline.
WO
3The preparation method of nano wire is referring to document---Chemical Physics Letters, 2003, Vol.377, pp.317-321.
The Au preparation of nano crystal is: with 0.01g gold chloride (HAuCl
44H
2O) be dissolved in the 100mL deionized water, be heated to and boil, stir down accurately adding 2mL 1% trisodium citrate (Na
3C
6H
5O
72H
2O) aqueous solution; Continue heated and boiled 15min; Return to original volume with distilled water after being cooled to room temperature.The gained solution centrifugal is separated, and wash with deionized water, it is nanocrystalline to obtain Au.
0.1mg Au is nanocrystalline behind the deionized water for ultrasonic dispersion 10-50min of 5mL; Evenly being added drop-wise to 30mL concentration is in the 2-MEPA ethanolic solution of 1mmol/L; The stirred overnight reaction; Centrifugal in the 3000r/min supercentrifuge, and spend deionised water, the Au that promptly can be made into phosphoric acid functionalized is nanocrystalline.
Be scattered in the 10mL ethanol the Au of phosphoric acid functionalized is nanocrystalline, to wherein adding 50mg WO
3Nano wire, after the ultrasonic dispersion, stirring reaction spends the night, the centrifugal or filtration with its process, and, can obtain WO with ethanol and deionized water washing
3Nano wire/Au nanocrystalline composite material (referring to accompanying drawing 1).
Embodiment two: oxide nano thread is SnO
2Nano wire, noble metal nanocrystalline are that Pt is nanocrystalline.
SnO
2The preparation method of nano wire is referring to document---Nanotechnology, 2008, Vol.19, pp.185705 (8pp).
The Pt preparation of nano crystal is: 0.08g polyvinylpyrrolidone (PVP) is dissolved in the ethylene glycol (EG) of 7mL, then above-mentioned solution is changed in the 50mL three-necked bottle, is warming up to 160 ℃, insulation 10min, rapid chloroplatinic acid (H to its adding 1mL 80mmol/L
2PtCl
66H
2O), treat solution becomes to black, stop reaction.The gained solution centrifugal is separated, and use washing with acetone, it is nanocrystalline to obtain Pt.
0.14mg Pt is nanocrystalline in the ethanol of 5mL behind the ultrasonic dispersion 10-50min; Evenly being added drop-wise to 30mL concentration is in the 2-MEPA ethanolic solution of 2mmol/L; The stirred overnight reaction; Centrifugal in the 3000r/min supercentrifuge, and spend deionised water, the Pt that promptly can be made into phosphoric acid functionalized is nanocrystalline.
Be scattered in the 10mL ethylene glycol the Pt of phosphoric acid functionalized is nanocrystalline, to wherein adding 40mg SnO
2Nano wire, after the ultrasonic dispersion, stirring reaction spends the night, the centrifugal or filtration with its process, and, can obtain SnO with ethanol and deionized water washing
2Nano wire/Pt nanocrystalline composite material (referring to accompanying drawing 2).
Embodiment three: oxide nano thread is the ZnO nano wire, and noble metal nanocrystalline is that Pd is nanocrystalline.
The preparation method of ZnO nano wire is referring to document---Materials Chemistry and Physics, 2007, Vol.106, pp.58-62.
The Pd preparation of nano crystal is referring to document---Journal of the American Chemical Society, 2005, Vol.127, pp.7332-7333.
0.12mg Pd is nanocrystalline in the ethanol of 5mL behind the ultrasonic dispersion 10-50min; Evenly being added drop-wise to 30mL concentration is in the 2-MEPA ethanolic solution of 1.5mmol/L; The stirred overnight reaction; Centrifugal in the 3000r/min supercentrifuge, and spend deionised water, the Pd that promptly can be made into phosphoric acid functionalized is nanocrystalline.
Be scattered in the 10mL ethanol the Pd of phosphoric acid functionalized is nanocrystalline, to wherein adding 60mg ZnO nano wire, after the ultrasonic dispersion; Stirring reaction spends the night; Centrifugal or the filtration with its process, and, can obtain ZnO nano wire/Pd nanocrystalline composite material (referring to accompanying drawing 3) with ethanol and deionized water washing.
In order further to show the advantage of the inventive method; Adopt traditional wet-chemical dipping method (detailed preparation process is referring to document---Sensor and Actuators B; 2000, Vol.66 pp.161) has prepared ZnO nano wire/Pd nanocrystalline composite material (referring to accompanying drawing 4).From accompanying drawing 4, can find out, the Pd particle size heterogeneity of ZnO nanowire surface, and also the Pd particle is also inhomogeneous in the degree of scatter of nanowire surface.
Claims (3)
1. the manufacturing approach of a metal oxide nano-wire/noble metal nanocrystalline composite material; The concrete steps that it is characterized in that this method are: noble metal nanocrystalline is dispersed in the solvent; Be mixed with the suspension that concentration is 0.01mg/mL～0.03mg/mL; Be added drop-wise to concentration again and be in the ethanolic solution of 2-mercaptoethyl phosphoric acid of 0.8mmol/L～2.0mmol/L, reaction overnight obtains the noble metal nanocrystalline solution of phosphoric acid functionalized; Metal oxide nano-wire is joined in the noble metal nanocrystalline solution of this phosphoric acid functionalized, reaction overnight through filtration, and with ethanol and deionized water washing, promptly obtains metal oxide nano-wire/noble metal nanocrystalline composite material; Described solvent is deionized water, ethanol or ethylene glycol; The mass ratio of described noble metal nanocrystalline and 2-mercaptoethyl phosphoric acid is: 100: (1～3); The mass ratio of described noble metal nanocrystalline and metal oxide nano-wire is: (0.2～0.7): 100.
2. the manufacturing approach of a kind of metal oxide nano-wire/noble metal nanocrystalline composite material according to claim 1 is characterized in that described noble metal is: gold, silver, platinum, palladium, rhodium, iridium, osmium or ruthenium.
3. the manufacturing approach of a kind of metal oxide nano-wire/noble metal nanocrystalline composite material according to claim 1 is characterized in that described metal oxide nano-wire is: zinc oxide, tin oxide, indium oxide, cupric oxide, iron oxide, tungsten oxide, nickel oxide, titanium oxide or cuprous oxide.
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| CN103331453B (en) * | 2013-07-01 | 2015-03-25 | 南京邮电大学 | Preparation method for precious metal/tin dioxide nano composite |
| CN105628748B (en) * | 2015-12-24 | 2018-10-30 | 东北师范大学 | A kind of the tin dioxide nano fiber gas sensitive and its gas sensor of Supported Pt Nanoparticles |
| CN106299391B (en) * | 2016-08-10 | 2019-01-08 | 上海师范大学 | A kind of palladium-cuprous oxide mesh nano catalysis material and its preparation and application |
| CN106693990B (en) * | 2016-12-31 | 2019-09-03 | 浙江工业大学 | Pt-Cu2O wraps up Cu nano wire and the preparation method and application thereof |
| CN106925771B (en) * | 2017-03-14 | 2018-12-07 | 中国科学技术大学先进技术研究院 | Ultra-fine PtRh nano wire and its method for preparing catalyst, application |
| CN109994624B (en) * | 2017-12-29 | 2020-12-11 | Tcl科技集团股份有限公司 | Composite nano-particles and preparation method and application thereof |
| CN110116008A (en) * | 2018-02-07 | 2019-08-13 | 中国科学院兰州化学物理研究所苏州研究院 | The regulatable Au-Cu in interface2O photochemical catalyst and preparation method thereof |
| CN109467127A (en) * | 2018-10-31 | 2019-03-15 | 青岛大学 | A kind of preparation method of more Metal Supported tungsten oxide composite nano-lines |
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| CN101058858A (en) * | 2007-05-24 | 2007-10-24 | 昆明贵金属研究所 | Method for preparing oxide dispersion intensifying platinum-base composite material |
| CN101319101A (en) * | 2008-06-03 | 2008-12-10 | 河南大学 | Method of preparing water-soluble nanocrystalline |
| CN101374980A (en) * | 2005-12-21 | 2009-02-25 | 纽约州州立大学研究基金会 | Non-spherical semiconductor nanocrystals and methods of making them |
| CN101560669A (en) * | 2009-04-24 | 2009-10-21 | 同济大学 | Method for preparing noble metal nanocrystalline chemically based on titanium dioxide nanotube array |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101374980A (en) * | 2005-12-21 | 2009-02-25 | 纽约州州立大学研究基金会 | Non-spherical semiconductor nanocrystals and methods of making them |
| CN101058858A (en) * | 2007-05-24 | 2007-10-24 | 昆明贵金属研究所 | Method for preparing oxide dispersion intensifying platinum-base composite material |
| CN101319101A (en) * | 2008-06-03 | 2008-12-10 | 河南大学 | Method of preparing water-soluble nanocrystalline |
| CN101560669A (en) * | 2009-04-24 | 2009-10-21 | 同济大学 | Method for preparing noble metal nanocrystalline chemically based on titanium dioxide nanotube array |
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