CN1207452C - High temperature molten salt reaction process of preparing one-dimensional ordered nano wire and nanotube array - Google Patents
High temperature molten salt reaction process of preparing one-dimensional ordered nano wire and nanotube array Download PDFInfo
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- CN1207452C CN1207452C CN 03148388 CN03148388A CN1207452C CN 1207452 C CN1207452 C CN 1207452C CN 03148388 CN03148388 CN 03148388 CN 03148388 A CN03148388 A CN 03148388A CN 1207452 C CN1207452 C CN 1207452C
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Abstract
The present invention relates to a new process for preparing one-dimensional nanometer materials by the reaction of high-temperature molten salt, which belongs to the technical field of the preparation of inorganic nanometer materials. The present invention particularly relates to a new process for preparing ordered arrays of one-dimensional nanometer lines and nanometer tubes by the reaction of high-temperature molten salt. After blended uniformly according to weight ratio, precursor materials and molten salt dielectric are heated in a tubular furnace to a temperature which is more than a fusing point of the molten salt or are placed on a base attached with a catalyst. The precursor materials and the molten salt dielectric are heated to a temperature more than the fusing point of the molten salt. The atmosphere in a reactor is controlled. The temperature is then maintained properly, and the speed for reducing the temperature is controlled. The precursor materials and molten salt dielectric are cooled gradually, and the molten salt is dissolved and separated by a solvent corresponding to the molten salt. The corresponding one-dimensional nanometer materials such as metal oxide, sulfide, etc., can be respectively obtained, or the one-dimensional nanometer materials with the ordered array characteristics of corresponding materials can be obtained on the surface of the base. The process is simple and is easy to control. The shapes of products can be controlled by adjusting the temperature of a temperature range where the base materials are positioned. The present invention has wide application, and is suitable for the preparation of various compounds.
Description
Technical field
The invention belongs to the inorganic nano material preparing technical field.Be particularly related to a kind of oldered array novel process of utilizing high-temperature molten salt prepared in reaction one-dimensional nano line, nanotube.
Background technology
The discovery of carbon nanotube in 1991 and the many unusual low-dimensional quantum characteristic and the wide application prospect that display subsequently, open up brand-new research field for the 1-dimention nano functional materials, caused the scientific worker's of the ambits such as chemistry, physics and Materials science of being engaged in nanometer material science research both at home and abroad very big interest.Reach in " H.J.Dai et al.Nature375,769 (1995) " report carbon nanotube over past ten years in " S.Iijima, Nature, 354,56 (1991) ", around one dimension Nano structure particularly carbon nanotube synthetic obtained impressive progress.Simultaneously, based on dimensional effect and quantum effect, the nanostructure of many non-carbon compounds, especially some metals and semiconductor material, may produce new performance equally, therefore, develop non-carbon nanotube of novel inorganic and monocrystal nanowire and become one of forward position developing direction most hotly competitive in the international nano materials research field with metal or characteristic of semiconductor.
The high temperature of inorganic non-carbon nanotube and monocrystal nanowire is synthetic to comprise following several technology: (1) template comprises methods " Zhou D, Seraphin S, Chem.Phys.Lett.222,223 (1994) " such as CNT (carbon nano-tube) and porous alumina formwork; (2) crystalline gas-solid (Vapor-Solid, VS) growth method " Yang PD, Lieber CM, Science, 273,1836 (1996) "; (3) Gu laser ablation or metal organic chemical vapor deposition (MOCVD) and crystalline gas-liquid-(Solution-Liquid-Solid, VLS) growth method " R.S.Wagner, W.C.Ellis, Appl.Phys.Lett., 1964,4,89 "; (4) high-temperature laser evaporation or simple physical method of evaporation " Z.W.Pan, Z.R.Dai, and Z.L.Wang, Science, 291,1947 (2001) ".In addition, reported that in " Solid State Communications 122 (2002) 175-179 " the employing organic surface active agent assists ZnC
2O
4The technology that simple thermal decomposition process prepares the ZnO nano wire has realized the growth of ZnO nano wire in the NaCl fused salt, specific embodiment comprises: source material Zn (CH
3COO)
22H
2O and H
2C
2O
42H
2O adds promoting agent NP-9/5 then according to 1: 1 mixed in molar ratio, grinds several minutes in mortar, puts into loft drier oven dry back and obtains ZnC
2O
4, ZnC
2O
4Mix with NaCl, in tube furnace, be heated to 910 ℃, obtained the ZnO nano wire after the cooling.Discover, this method must adopt tensio-active agent as template, granular precursor forms linear structure attached to the tensio-active agent organic molecule surface of wire, in high-temperature process subsequently, form nano wire, belong to the template category, and present technique is the growth of no template nano material, thereby the technology of bibliographical information and present technique have the difference of essence.At present, the high temperature synthesis technique of the array of monodimension nanometer material is a CVD technology, and for example Yang PD etc. is at Advance Materials, 13,113 (2001) go up report utilize VLS mechanism preparation ZnO nano-wire array.Adopt the method for the oldered array of high-temperature molten salt prepared in reaction one-dimensional nano line, nanotube not appear in the newspapers as yet.
Summary of the invention
The purpose of this invention is to provide a kind of oldered array novel process of utilizing high-temperature molten salt prepared in reaction one-dimensional nano line, nanotube, it is characterized in that: described technological process is with persursor material Sn, Si, Ti, Zr, ZnS or CdSe; After mixing according to weight ratio with the eutectoid point composition of fused salt NaCl, KCl, KI or several salt, in tube furnace, be heated to more than the fusing point of fused salt, or be placed in the substrate with catalyzer, in High Temperature Furnaces Heating Apparatus, be heated to more than the fused salt fusing point, atmosphere in the controlling reactor, after insulation, control cooling rate, progressively after the cooling, use again with the fused salt corresponding solvent with the fused salt separated and dissolved, then obtain the monodimension nanometer material of corresponding metal oxide, sulfide respectively, or obtain the monodimension nanometer material of the oldered array feature of respective material at substrate surface.
Described catalyzer is for to plate the golden film that a layer thickness is 3nm at substrate surface.
The invention has the beneficial effects as follows and utilize the high-temperature molten salt reaction, obtain to have the novel material of one dimension Nano structure, especially by the catalyzer at substrate surface, make the monodimension nanometer material ordering growth, technological process is simple, easy to control.Adjust the temperature of base material warm area of living in, can control the pattern of product.
Description of drawings
Fig. 1 (a) is for adopting the SnO of fused salt method preparation
2The nano wire scanning electron microscope image; (b) be the XRD diffraction analysis result of Fig. 1 (a).
Fig. 2 (a) is for adopting the TiS of fused salt method preparation
2The nano wire images of transmissive electron microscope; (b) for adopting the TiS of fused salt method preparation
2The nanotube images of transmissive electron microscope.
Fig. 3 (a) is for adopting the ZnO micron tube oldered array scanning electron microscope image of fused salt method preparation: (b) be Fig. 3 (a) XRD diffraction analysis result.
Fig. 4 (a) is for adopting the SiO of fused salt method preparation
2The whisker array scanning electron microscope image; (b) be Fig. 4 (a) EDX EDAX results.
Embodiment
The present invention is a kind of oldered array novel process of utilizing high-temperature molten salt prepared in reaction one-dimensional nano line, nanotube.Its technological process is with persursor material Sn, Si, Ti, Zr, ZnS or CdSe; With fused salt NaCl, KCl, after the eutectoid point composition of KI or several salt mixes according to weight ratio, directly put into containers such as porcelain boat, or be placed on after in the substrate of catalyzer and put into containers such as porcelain boat, in High Temperature Furnaces Heating Apparatus, be heated to more than the fused salt fusing point then, atmosphere in the controlling reactor, after suitably warm area is incubated certain hour, the control cooling rate, progressively cooling, use again with the fused salt corresponding solvent with the fused salt separated and dissolved, can obtain corresponding metal oxide respectively, monodimension nanometer materials such as sulfide, or obtain the monodimension nanometer material of the oldered array feature of respective material at substrate surface.The present invention is actual to be preparation one-dimensional nano line, nanotube and the one-dimensional nano line of being correlated with, two kinds of technologies of oldered array of nanotube.If precedingly a kind ofly prepare one-dimensional nano line, nanotube is not just directly prepared one-dimensional nano line, nanotube by the katalysis that is distributed in the substrate surface catalyzer.
Above-mentioned fused salt can be that salt (NaCl, KCl, KI) and several salt thereof of a certain single composition mixes, as the low melting point congruent melting composition of NaCl and KCl.
Above-mentioned base material is Si, sapphire, quartz.
Above-mentioned catalyzer is for to plate the golden film that a layer thickness is 3nm at substrate surface.
Below only further specify the present invention for embodiment.
Example 1 SnO
2The preparation of nano wire
(1) 0.2g metal Sn powder is mixed with 1gNaCl, ground 10 minutes, the metal Sn powder is fully disperseed;
(2) above-mentioned powder is placed in the porcelain boat, is placed on the central authorities of tube furnace;
(3) feed Ar gas, wherein sneak into 1% water vapour, flow is 100cm
3/ minute;
(4) tube furnace heats up with temperature control instrument control, and heating schedule is as follows:
Be raised to 860 ℃ from room temperature, 1 hour; Naturally cool to room temperature 860 ℃ of insulations after 2 hours;
(5) remove NaCl with deionized water wash, filter;
(6) SnO of this Experiment Preparation
2The scanning electron microscope result of nano wire as shown in Figure 1.
Example 2 TiS
2The preparation of nano wire and pipe
(1) 0.2g metal Ti powder is mixed with 1gKI, ground 10 minutes, the metal Ti powder is fully disperseed;
(2) above-mentioned powder is placed in the porcelain boat, is placed on the central authorities of tube furnace;
(3) when placing the S powder or feed Ar, the low-temperature end of process furnace feeds about 1%H
2S gas provides S the source;
(4) feed Ar gas, flow is 100cm
3/ minute;
(5) tube furnace heats up with temperature control instrument control, and heating schedule is as follows:
Be raised to 850 ℃ from room temperature, 1 hour; Naturally cool to room temperature 850 ℃ of insulations after 2 hours;
(6) remove KI with deionized water wash, filter;
(7) TiS of this Experiment Preparation
2The transmission electron microscope results of nano wire is shown in Fig. 2 (a);
(8) wherein, contain TiS
2Nanotube, transmission electron microscope results is shown in Fig. 2 (b);
(9) the metal Ti powder is changed to metallic Z r powder, can obtains ZrS
2Nano wire and nanotube.
Example 3 prepares the oldered array of ZnO micron tube on base materials such as Si
(1) with base material supersound washing cleanings in acetone and other organic solvent such as Si sheets, put into vacuum coating film equipment after the drying and plate one deck gold film as catalyzer, the thickness of gold film can be controlled by the time, and the thickness of golden film has significant effects for the size of final product.The golden film thickness that is adopted in this experiment is 3nm;
(2) adopt ZnS as source material, source material can mix with the NaCl fused salt, also can not mix;
(3) ZnS is placed in the porcelain boat, substrate is placed in the porcelain boat and places near source material, then porcelain boat is placed in the tube furnace;
(4) feed Ar gas, flow is 100cm
3/ minute;
(5) tube furnace heats up with temperature control instrument control, and heating schedule is as follows:
Be raised to 860 ℃ from room temperature, 1 hour; Naturally cool to room temperature 860 ℃ of insulations after 2 hours;
(6) substrate is removed NaCl with deionized water wash.
(7) the scanning electron microscope result of the ZnO micron tube oldered array of this Experiment Preparation as shown in Figure 3.
Example 4 prepares the ZnO whisker array in the Si substrate
(1) with base material supersound washing cleanings in acetone and other organic solvent such as Si sheets, put into vacuum coating film equipment after the drying and plate one deck gold film as catalyzer, the thickness of gold film can be controlled by the time, and the thickness of golden film has significant effects for the size of final product.The golden film thickness that is adopted in this experiment is 3nm;
(2) adopt ZnS as source material, source material mixes with the NaCl fused salt, grinds;
(3) step (2) is obtained material and be placed in the porcelain boat, substrate is placed on the place of same porcelain boat middle distance source material 2cm, and with NaCl porcelain boat is filled up;
(4) then porcelain boat is placed in the tube furnace;
(5) feed Ar gas, flow is 100cm
3/ minute;
(6) tube furnace heats up with temperature control instrument control, and heating schedule is as follows:
Be raised to 860 ℃ from room temperature, 1 hour; Naturally cool to room temperature 860 ℃ of insulations after 2 hours;
(7) temperature of substrate position is 830 ℃;
(8) substrate is removed NaCl with deionized water wash;
(9) this Experiment Preparation result is orderly ZnO whisker.
Example 5 prepares SiO on silicon base
2Whisker array
(1) with base material supersound washing cleanings in acetone and other organic solvent such as Si sheets, put into vacuum coating film equipment after the drying and plate one deck gold film as catalyzer, the thickness of gold film can be controlled by the time, and the thickness of golden film has significant effects for the size of final product.The golden film thickness that is adopted in this experiment is 3nm;
(2) adopt Si powder or Si sheet as source material, mix with the NaCl fused salt;
(3) step (2) is obtained material and be placed in the porcelain boat, substrate is placed on the place of same porcelain boat middle distance source material 3cm, and whole porcelain boat fills up with NaCl;
(4) then porcelain boat is placed in the tube furnace.
(5) feed Ar gas, flow is 100cm
3/ minute;
(6) tube furnace heats up with temperature control instrument control, and heating schedule is as follows:
Be raised to 1000 ℃ from room temperature, 1 hour; Naturally cool to room temperature 1000 ℃ of insulations after 2 hours;
(7) temperature of substrate position is 850 ℃;
(8) substrate is removed NaCl with deionized water wash;
(9) the orderly SiO of this Experiment Preparation
2The scanning electron microscope result of whisker as shown in Figure 4.
Example 6 prepares CdSe nanometer rod oldered array in the Si substrate
(1) with the supersound washing cleaning in acetone and other organic solvent of Si base material, put into vacuum coating film equipment after the drying and plate one deck gold film as catalyzer, the thickness of gold film can be controlled by the time, and the thickness of golden film has significant effects for the size of final product.The golden film thickness that is adopted in this experiment is 3nm;
(2) adopt CdSe as source material, source material mixes with the KCl fused salt;
(3) will be placed in the porcelain boat source material after step on the surface coverage (2) is handled through the Si substrate that step (1) is handled;
(4) then porcelain boat is placed in the tube furnace;
(5) feed Ar gas, flow is 100cm
3/ minute;
(6) tube furnace heats up with temperature control instrument control, and heating schedule is as follows:
Be raised to 850 ℃ from room temperature, 1 hour; Naturally cool to room temperature 850 ℃ of insulations after 2 hours;
(7) substrate is removed KCl with deionized water wash;
(8) experimental result is for having obtained CdSe nanometer rod oldered array in the Si substrate.
Claims (2)
1. oldered array novel process of utilizing high-temperature molten salt prepared in reaction one-dimensional nano line, nanotube, it is characterized in that: described technological process is with persursor material Sn, Si, Ti, Zr, ZnS or CdSe; After mixing according to weight ratio with the eutectoid point composition of fused salt NaCl, KCl, KI or several salt, in tube furnace, be heated to more than the fusing point of fused salt, or be placed in the substrate with catalyzer, in High Temperature Furnaces Heating Apparatus, be heated to more than the fused salt fusing point, atmosphere in the controlling reactor, after insulation, control cooling rate, progressively after the cooling, use again with the fused salt corresponding solvent with the fused salt separated and dissolved, then obtain the monodimension nanometer material of corresponding metal oxide, sulfide respectively, or obtain the monodimension nanometer material of the oldered array feature of respective material at substrate surface.
2. according to the described oldered array novel process of utilizing high-temperature molten salt prepared in reaction one-dimensional nano line, nanotube of claim 1, it is characterized in that: described catalyzer is for to plate the golden film that a layer thickness is 3nm at substrate surface.
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Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN101337654B (en) * | 2007-07-04 | 2010-04-21 | 中国科学院合肥物质科学研究院 | Micron grade blocky silicone base composite body assembled by silicon oxide or willemite nano-wires and method for preparing same |
| CN101532178B (en) * | 2009-03-09 | 2011-11-23 | 合肥工业大学 | CdS nano line array preparation method based on flexible metal base plate |
| CN110092407B (en) * | 2019-04-11 | 2020-11-10 | 浙江大学 | Method for preparing metal oxide or metal hydroxide nano film material by molten salt method |
| CN111172743B (en) * | 2020-01-16 | 2021-10-19 | 浙江大学 | Method for rapidly preparing composite metal oxide nano film material at low temperature |
| CN112620644B (en) * | 2020-12-15 | 2022-03-01 | 紫金矿业集团股份有限公司 | Method for chemically synthesizing silver nanowires by using molten salt |
| CN115537907A (en) * | 2022-09-02 | 2022-12-30 | 北京仿生界面科学未来技术研究院 | Size-controllable inorganic micro-single crystal array and melting preparation method thereof |
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