CN101393939A - Nano tube hetero-junction constituted by zinc oxide and carbon, preparation thereof - Google Patents
Nano tube hetero-junction constituted by zinc oxide and carbon, preparation thereof Download PDFInfo
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Abstract
The invention discloses a nanotube hetero-junction made up of zinc oxide and carbon, and a preparation method thereof, wherein, the hetero-junction is a one-dimensional heterogeneous nanotube made through connecting a zinc oxide nanotube with a carbon nanotube. The method comprises the following steps: (a), using the secondary anodization method to obtain an alumina template with a through-hole, of which the aperture ranges from 10 to 100 nanometers; (b), using the electron evaporating method, the electro-deposition method, the controllable selective etching method and the metal oxidization technology in sequence to obtain the zinc oxide nanotube which is arranged inside the alumina template; and (c), using the chemical vapor deposition to deposit the carbon nanotube on the end face of the zinc oxide nanotube first, and then placing the zinc oxide nanotube and the carbon nanotube in a strong alkaline solution to have the alumina template etched out, and connecting the zinc oxide nanotube with the carbon nanotube to form the one-dimensional heterogeneous nanotube or the nanotube hetero-junction made up of zinc oxide and carbon. By overcoming the major obstacles in the way of applying the carbon nanotube to a computer chip, a sensor and other microelectronic equipment, the invention can be widely applied to the technical fields of fuel cell catalysis hydrogen manufacturing, solar power dye-sensitized cells, photoelectric devices and the like.
Description
Technical field the present invention relates to a kind of nano tube hetero-junction and method for making, nano tube hetero-junction that especially a kind of zinc oxide and carbon constitute and preparation method thereof.
Background technology zinc oxide is a kind of important semiconductor functional material, belong to electron conductive type (n type) semiconductor, have characteristics such as good photocatalysis, air-sensitive, pressure-sensitive and electromagnetic wave, and possess the nano zinc oxide material of the different shape of nano-scale, have broad application prospects especially at aspects such as optics, electricity, magnetics, catalysis and transducers.People are in order to obtain it, made unremitting effort, a kind of zinc oxide nanowire/pipe and preparation method thereof was once disclosed as " Journal of Inorganic Materials " the 20th volume the 6th interim " preparation of sol-gel template and the sign of zinc oxide nanowire/pipe array " literary composition of publishing in November, 2005, wherein, zinc oxide nanowire/manage is about 15,30,50 into diameter, orderly zinc oxide nanowire/pipe array of 60nm, and the preparation method adopts sol-gel process to prepare the zinc oxide nanowire of high-sequential/pipe array in the hole of alumina formwork.But, no matter be the zinc oxide nano mitron, or its preparation method all exist weak point, at first, if desire gives practical application with the zinc oxide nano mitron, be faced with the technical barrier that the zinc oxide nano mitron that how will have semiconducting behavior is electrically connected with other electronic devices and components or parts.Though carbon nano-tube has good mechanical performance and excellent conducting performance, surplus its stretching resistance exceeds 100 than steel times, the utmost point is suitable for using in various microelectronic components, yet, itself and zinc oxide nano mitron be electrically connected a difficult problem that still needs to be resolved hurrily at present for people; Secondly, the preparation method can not make the nano tube hetero-junction that is made of zinc oxide and carbon.
The summary of the invention the technical problem to be solved in the present invention provides the zinc oxide a kind of simple in structure, easy to use and the nano tube hetero-junction of carbon formation for overcoming weak point of the prior art.
Another technical problem that the present invention will solve is the preparation method of the nano tube hetero-junction that a kind of zinc oxide and carbon are provided constitute.
For solving technical problem of the present invention, the technical scheme that is adopted is: the nano tube hetero-junction that zinc oxide and carbon constitute comprises zinc oxide nano mitron and carbon nano-tube, and particularly said zinc oxide nano mitron and said carbon nano-tube connect into the heterogeneous nanotube of one dimension.
The further improvement of the nano tube hetero-junction that constitutes as zinc oxide and carbon, the two ends of described zinc oxide nano mitron all connect into the heterogeneous nanotube of one dimension with carbon nano-tube; The caliber of the heterogeneous nanotube of described one dimension is that 10～100nm, thickness of pipe wall are 5～10nm; The heterogeneous nanotube of described one dimension is arranged in alumina formwork.
For solving another technical problem of the present invention, another technical scheme that is adopted is: the preparation method of the nano tube hetero-junction that zinc oxide and carbon constitute comprises the secondary anode method, electrodeposition process and chemical vapour deposition technique, particularly it is finished according to the following steps: (a) earlier aluminium flake being placed concentration is the acid solution of 0.2～0.4M, in direct voltage is anodic oxidation 4～10h under 20～60v, again it in being the mixed solution of 4～8wt% phosphoric acid of 50～70 ℃ and 1.6～2wt% chromic acid, temperature is soaked 8～12h, then, with it once more after carrying out the anodization second time under the same process conditions, remove the unoxidized aluminium in the back side with copper chloride or tin chloride solution earlier, phosphoric acid solution with 3～7wt% erodes the aluminium oxide barrier layer that is positioned at the bottom, hole again, and obtaining the aperture is the through hole alumina formwork of 10～100nm; (b) the deposited by electron beam evaporation method is placed on earlier in the electroplate liquid at 1.5～2.5mA/cm behind the thick golden film of evaporation a 20～50nm of through hole alumina formwork
2Constant current under electro-deposition 30～70min, wherein, the composition of electroplate liquid is 80g/L ZnSO
4.7H
2O and 20g/L H
3BO
3, its pH is placed on 300～400 ℃ of following oxidation 30～40h again for to be adjusted to 2.5～3.5 with dilute sulfuric acid; (c) alumina formwork that will contain the zinc oxide nano mitron earlier places the argon atmospher under 600～700 ℃, be placed on again in the mixed atmosphere of acetylene and argon gas in 600～700 ℃ of insulation 1～3h down, afterwards, be placed on and erode alumina formwork in the strong base solution, make zinc oxide nano mitron and carbon nano-tube and connect into the zinc oxide of the heterogeneous nanotube of one dimension and the nano tube hetero-junction that carbon constitutes.
The preparation method's of the nano tube hetero-junction that constitutes as zinc oxide and carbon further improvement, the purity of described aluminium flake is 〉=99.9%; Described acid is oxalic acid or phosphoric acid or sulfuric acid; The mixed atmosphere of described acetylene and argon gas is that the ratio of acetylene and argon gas is 1: 10; Described strong base solution is sodium hydroxide solution or potassium hydroxide solution; Described in the through hole of alumina formwork behind the electrodepositing zinc nanotube, deposit the one side 2～4min of zinc nanotube earlier in the dilution heat of sulfuric acid corrosion oxidation aluminum alloy pattern plate with 4～6wt%, again with distilled water or washed with de-ionized water and dry, and then it is carried out oxidation processes, the two ends that make the zinc oxide nano mitron all connect into the zinc oxide of the heterogeneous nanotube of one dimension and the nano tube hetero-junction that carbon constitutes with carbon nano-tube.
Beneficial effect with respect to prior art is, one, use field emission scanning electron microscope, transmission electron microscope and power spectrum tester to characterize respectively to the heterogeneous nanotube of the one dimension that makes, from the stereoscan photograph that obtains, transmission electron microscope photo and scanning can spectrogram as can be known, numerous nanotubes is the array-like of orderly arrangement, wherein, nanotube is to be made of three kinds of different materials, promptly constitute by carbon, zinc oxide and carbon, its caliber is that 10～100nm, thickness of pipe wall are 5～10nm, and zinc oxide nano mitron wherein is a polycrystalline structure.Heterojunction is connected and composed by zinc oxide nano mitron and carbon nano-tube, and its connected mode has two kinds, and one for an end of zinc oxide nano mitron is connected with an end of carbon nano-tube, and another all is connected with carbon nano-tube for the two ends of zinc oxide nano mitron.Its existing way also is two kinds, and one is individualism, and another is for being present among the alumina formwork; They are two years old, preparation method's science, rationally, difficult problem at the electrical connection of zinc oxide nano mitron, with the secondary anode method, electrodeposition process and chemical vapour deposition technique organically integrate in one, semiconductor oxide zinc nanotube and carbon nano-tube are coupled together, formed the structure of the heterogeneous nanotube of one dimension, both overcome carbon nano-tube at computer chip, the major obstacle that transducer and many other microelectronic device application facet exist is again that this novel heterogeneous nanotube is at the fuel cell catalyzing manufacturing of hydrogen, the potential application of aspects such as solar energy dye-sensitized cell and photoelectric device is laid a good foundation; Its three, the preparation method is easy to implement, is suitable for large-scale industrial production.
As the further embodiment of beneficial effect, the one, the two ends of zinc oxide nano mitron are preferably all and connect into the heterogeneous nanotube of one dimension with carbon nano-tube, have expanded the field and the scope of its application; The 2nd, the caliber of the heterogeneous nanotube of one dimension is preferably 10～100nm, thickness of pipe wall is preferably 5～10nm, both has been beneficial to giving full play to of zinc-oxide nano performance, is convenient to preparation again, also is easy to practical application; The 3rd, the heterogeneous nanotube of one dimension is arranged in alumina formwork, is beneficial to its actual use; The 4th, acid is preferably oxalic acid or phosphoric acid or sulfuric acid, not only makes the source of raw material than horn of plenty, also makes the easier enforcement of preparation technology and flexibly; The 5th, the ratio that the mixed atmosphere of acetylene and argon gas is preferably acetylene and argon gas is 1: 10, except that the shaping that is beneficial to carbon nano-tube, has also guaranteed the quality of carbon nano-tube; The 6th, in the through hole of alumina formwork behind the electrodepositing zinc nanotube, deposit the one side 2～4min of zinc nanotube earlier in the dilution heat of sulfuric acid corrosion oxidation aluminum alloy pattern plate with 4～6wt%, again with distilled water or washed with de-ionized water and dry, and then it is carried out oxidation processes, this technology has guaranteed that the two ends of zinc oxide nano mitron all can be connected with carbon nano-tube, and obtains the heterogeneous nanotube of stay-in-grade one dimension.
Description of drawings is described in further detail optimal way of the present invention below in conjunction with accompanying drawing.
Fig. 1 be to the heterogeneous nanotube of the one dimension that makes use take the photograph after the observation of Japanese JEOL 6700 type field emission scanning electron microscopes (SEM) the SEM photo.Image to left in the photo is a macrograph, as seen it is formed by chequered with black and white three sections from top to bottom, and wherein, what the black on top part was corresponding is carbon nano-tube, the white portion at middle part is corresponding to the zinc oxide nano mitron, and the black of bottom part is corresponding to carbon nano-tube.Image to right in the photo is the high power photo that corresponding round frame part divides in the Image to left, wherein, upper right picture is the enlarged photograph that Image to left top round frame part divides, can be clear that the position that carbon nano-tube is connected with the zinc oxide nano mitron by it, the bottom right picture is the enlarged photograph that Image to left bottom round frame part divides, can see the position that the zinc oxide nano mitron is connected with carbon nano-tube by it, also can see the end of broken zinc oxide nano mitron;
Fig. 2 be to the heterogeneous nanotube of the one dimension that makes use take the photograph after JEM-200CX type transmission electron microscope (TEM) observation the TEM photo, wherein, Fig. 2 a is the TEM photo that carbon nano-tube and zinc-oxide nano pipe jointing part divide, and Fig. 2 b is the selected area electron diffraction spot of zinc-oxide nano tube portion;
Fig. 3～Fig. 5 uses the Sirion200FEG type field emission scanning electron microscope of U.S. FEI Co. and incidental power spectrum (EDS) tester that it is observed the figure as a result with the Chosen Point scanning resulting SEM photo in back and EDS to the heterogeneous nanotube of the one dimension that makes, wherein, the EDS right figure among the figure as a result is the SEM photo, bright spot in the SEM photo is selected power spectrum test point, and the test result of this point is shown in EDS as a result among the figure.This point among Fig. 3 is positioned at the top of the heterogeneous nanotube of one dimension, by its EDS as a result figure as can be known, the main component at power spectrum test point place is a carbon, remaining oxygen, zinc, aluminium are that sample corrosion back remaining impurities is polluted, and illustrate that its top is made up of carbon nano-tube.This point among Fig. 4 is positioned at the middle part of the heterogeneous nanotube of one dimension, by its EDS as a result figure as can be known, the main component at power spectrum test point place is zinc and oxygen, aluminium wherein is that the dissolved oxygen aluminum alloy pattern plate obtains, carbon causes by last, two parts carbon pipe, illustrates that its middle part is made up of the zinc oxide nano mitron.This point among Fig. 5 is positioned at the bottom of the heterogeneous nanotube of one dimension, by its EDS as a result figure as can be known, the main component at power spectrum test point place is a carbon, remaining oxygen, zinc, aluminium are that sample corrosion back remaining impurities is polluted, and illustrate that its underpart is made up of carbon nano-tube.
Embodiment at first makes or buys from market aluminium flake with conventional method, as oxalic acid, phosphoric acid and the sulfuric acid of acid, as sodium hydroxide solution and potassium hydroxide solution, acetylene, argon gas, distilled water and the deionized water of strong base solution, and chromic acid, copper chloride solution and tin chloride solution.Then,
Embodiment 1: finish preparation according to the following steps successively: a) earlier aluminium flake being placed concentration is the acid solution of 0.2M, in direct voltage is anodic oxidation 10h under the 20v, again it is soaked 12h in temperature is the mixed solution of 50 ℃ 4wt% phosphoric acid and 1.6wt% chromic acid; Wherein, the purity of aluminium flake is 〉=99.9%, and acid is oxalic acid.Then, with it once more after carrying out the anodization second time under the same process conditions, remove the unoxidized aluminium in the back side with tin chloride solution earlier, the phosphoric acid solution with 3wt% erodes the aluminium oxide barrier layer that is positioned at the bottom, hole again, and obtaining the aperture is the through hole alumina formwork of 30nm.B) first deposited by electron beam evaporation method is placed in the electroplate liquid at 1.5mA/cm behind the thick golden film of an evaporation 20nm of through hole alumina formwork again
2Constant current under electro-deposition 70min, wherein, the composition of electroplate liquid is 80g/L ZnSO
4.7H
2O and 20g/L H
3BO
3, its pH is for to be adjusted to 2.5 with dilute sulfuric acid.Then, deposit the one side 4min of zinc nanotube earlier in the dilution heat of sulfuric acid corrosion oxidation aluminum alloy pattern plate with 4wt%, again with washed with de-ionized water and dry.Afterwards, be placed on 300 ℃ of following oxidation 40h.C) alumina formwork that will contain the zinc oxide nano mitron earlier places the argon atmospher under 600 ℃, is placed in the mixed atmosphere of acetylene and argon gas in 600 ℃ of insulation 3h down again, and wherein, the mixed atmosphere of acetylene and argon gas is that the ratio of acetylene and argon gas is 1: 10.Afterwards, be placed on and erode alumina formwork in the strong base solution, wherein, strong base solution is a sodium hydroxide solution.The two ends that make as Fig. 1, Fig. 2, Fig. 3, Fig. 4 and zinc oxide nano mitron shown in Figure 5 all connect into the zinc oxide of the heterogeneous nanotube of one dimension and the nano tube hetero-junction that carbon constitutes with carbon nano-tube.
Embodiment 2: finish preparation according to the following steps successively: a) earlier aluminium flake being placed concentration is the acid solution of 0.25M, in direct voltage is anodic oxidation 8h under the 30v, again it is soaked 11h in temperature is the mixed solution of 55 ℃ 5wt% phosphoric acid and 1.7wt% chromic acid; Wherein, the purity of aluminium flake is 〉=99.9%, and acid is oxalic acid.Then, with it once more after carrying out the anodization second time under the same process conditions, remove the unoxidized aluminium in the back side with tin chloride solution earlier, the phosphoric acid solution with 4wt% erodes the aluminium oxide barrier layer that is positioned at the bottom, hole again, and obtaining the aperture is the through hole alumina formwork of 40nm.B) first deposited by electron beam evaporation method is placed in the electroplate liquid at 1.8mA/cm behind the thick golden film of an evaporation 30nm of through hole alumina formwork again
2Constant current under electro-deposition 60min, wherein, the composition of electroplate liquid is 80g/L ZnSO
4.7H
2O and 20g/L H
3BO
3, its pH is for to be adjusted to 2.8 with dilute sulfuric acid.Then, deposit the one side 3.5min of zinc nanotube earlier in the dilution heat of sulfuric acid corrosion oxidation aluminum alloy pattern plate with 4.5wt%, again with washed with de-ionized water and dry.Afterwards, be placed on 330 ℃ of following oxidation 38h.C) alumina formwork that will contain the zinc oxide nano mitron earlier places the argon atmospher under 630 ℃, is placed in the mixed atmosphere of acetylene and argon gas in 630 ℃ of insulation 2.5h down again, and wherein, the mixed atmosphere of acetylene and argon gas is that the ratio of acetylene and argon gas is 1: 10.Afterwards, be placed on and erode alumina formwork in the strong base solution, wherein, strong base solution is a sodium hydroxide solution.The two ends that make as Fig. 1, Fig. 2, Fig. 3, Fig. 4 and zinc oxide nano mitron shown in Figure 5 all connect into the zinc oxide of the heterogeneous nanotube of one dimension and the nano tube hetero-junction that carbon constitutes with carbon nano-tube.
Embodiment 3: finish preparation according to the following steps successively: a) earlier aluminium flake being placed concentration is the acid solution of 0.3M, is anodic oxidation 7h under the 40v in direct voltage, again it is soaked 10h in temperature is the mixed solution of 60 ℃ 6wt% phosphoric acid and 1.8wt% chromic acid; Wherein, the purity of aluminium flake is 〉=99.9%, and acid is oxalic acid.Then, with it once more after carrying out the anodization second time under the same process conditions, remove the unoxidized aluminium in the back side with tin chloride solution earlier, the phosphoric acid solution with 5wt% erodes the aluminium oxide barrier layer that is positioned at the bottom, hole again, and obtaining the aperture is the through hole alumina formwork of 60nm.B) first deposited by electron beam evaporation method is placed in the electroplate liquid at 2mA/cm behind the thick golden film of an evaporation 35nm of through hole alumina formwork again
2Constant current under electro-deposition 50min, wherein, the composition of electroplate liquid is 80g/L ZnSO
47H
2O and 20g/L H
3BO
3, its pH is for to be adjusted to 3 with dilute sulfuric acid.Then, deposit the one side 3min of zinc nanotube earlier in the dilution heat of sulfuric acid corrosion oxidation aluminum alloy pattern plate with 5wt%, again with washed with de-ionized water and dry.Afterwards, be placed on 350 ℃ of following oxidation 35h.C) alumina formwork that will contain the zinc oxide nano mitron earlier places the argon atmospher under 650 ℃, is placed in the mixed atmosphere of acetylene and argon gas in 650 ℃ of insulation 2h down again, and wherein, the mixed atmosphere of acetylene and argon gas is that the ratio of acetylene and argon gas is 1:10.Afterwards, be placed on and erode alumina formwork in the strong base solution, wherein, strong base solution is a sodium hydroxide solution.The two ends that make as Fig. 1, Fig. 2, Fig. 3, Fig. 4 and zinc oxide nano mitron shown in Figure 5 all connect into the zinc oxide of the heterogeneous nanotube of one dimension and the nano tube hetero-junction that carbon constitutes with carbon nano-tube.
Embodiment 4: finish preparation according to the following steps successively: a) earlier aluminium flake being placed concentration is the acid solution of 0.35M, is anodic oxidation 5h under the 50v in direct voltage, again it is soaked 9h in temperature is the mixed solution of 65 ℃ 7wt% phosphoric acid and 1.9wt% chromic acid; Wherein, the purity of aluminium flake is 〉=99.9%, and acid is oxalic acid.Then, with it once more after carrying out the anodization second time under the same process conditions, remove the unoxidized aluminium in the back side with tin chloride solution earlier, the phosphoric acid solution with 6wt% erodes the aluminium oxide barrier layer that is positioned at the bottom, hole again, and obtaining the aperture is the through hole alumina formwork of 80nm.B) first deposited by electron beam evaporation method is placed in the electroplate liquid at 2.3mA/cm behind the thick golden film of an evaporation 40nm of through hole alumina formwork again
2Constant current under electro-deposition 40min, wherein, the composition of electroplate liquid is 80g/L ZnSO
4.7H
2O and 20g/L H
3BO
3, its pH is for to be adjusted to 3.3 with dilute sulfuric acid.Then, deposit the one side 2.5min of zinc nanotube earlier in the dilution heat of sulfuric acid corrosion oxidation aluminum alloy pattern plate with 5.5wt%, again with washed with de-ionized water and dry.Afterwards, be placed on 380 ℃ of following oxidation 33h.C) alumina formwork that will contain the zinc oxide nano mitron earlier places the argon atmospher under 680 ℃, is placed in the mixed atmosphere of acetylene and argon gas in 680 ℃ of insulation 1.5h down again, and wherein, the mixed atmosphere of acetylene and argon gas is that the ratio of acetylene and argon gas is 1:10.Afterwards, be placed on and erode alumina formwork in the strong base solution, wherein, strong base solution is a sodium hydroxide solution.The two ends that make as Fig. 1, Fig. 2, Fig. 3, Fig. 4 and zinc oxide nano mitron shown in Figure 5 all connect into the zinc oxide of the heterogeneous nanotube of one dimension and the nano tube hetero-junction that carbon constitutes with carbon nano-tube.
Embodiment 5: finish preparation according to the following steps successively: a) earlier aluminium flake being placed concentration is the acid solution of 0.4M, is anodic oxidation 4h under the 60v in direct voltage, again it is soaked 8h in temperature is the mixed solution of 70 ℃ 8wt% phosphoric acid and 2wt% chromic acid; Wherein, the purity of aluminium flake is 〉=99.9%, and acid is oxalic acid.Then, with it once more after carrying out the anodization second time under the same process conditions, remove the unoxidized aluminium in the back side with tin chloride solution earlier, the phosphoric acid solution with 7wt% erodes the aluminium oxide barrier layer that is positioned at the bottom, hole again, and obtaining the aperture is the through hole alumina formwork of 100nm.B) first deposited by electron beam evaporation method is placed in the electroplate liquid at 2.5mA/cm behind the thick golden film of an evaporation 50nm of through hole alumina formwork again
2Constant current under electro-deposition 30min, wherein, the composition of electroplate liquid is 80g/L ZnSO
4.7H
2O and 20g/L H
3BO
3, its pH is for to be adjusted to 3.5 with dilute sulfuric acid.Then, deposit the one side 2min of zinc nanotube earlier in the dilution heat of sulfuric acid corrosion oxidation aluminum alloy pattern plate with 6wt%, again with washed with de-ionized water and dry.Afterwards, be placed on 400 ℃ of following oxidation 30h.C) alumina formwork that will contain the zinc oxide nano mitron earlier places the argon atmospher under 700 ℃, is placed in the mixed atmosphere of acetylene and argon gas in 700 ℃ of insulation 1h down again, and wherein, the mixed atmosphere of acetylene and argon gas is that the ratio of acetylene and argon gas is 1:10.Afterwards, be placed on and erode alumina formwork in the strong base solution, wherein, strong base solution is a sodium hydroxide solution.The two ends that make as Fig. 1, Fig. 2, Fig. 3, Fig. 4 and zinc oxide nano mitron shown in Figure 5 all connect into the zinc oxide of the heterogeneous nanotube of one dimension and the nano tube hetero-junction that carbon constitutes with carbon nano-tube.
Select sour phosphoric acid of conduct or sulfuric acid, potassium hydroxide solution, distilled water more respectively for use as strong base solution, and select chromic acid, copper chloride solution for use, repeat the foregoing description 1～5, the two ends that make the zinc oxide nano mitron shown in Fig. 1～5 equally all connect into the zinc oxide of the heterogeneous nanotube of one dimension and the nano tube hetero-junction that carbon constitutes with carbon nano-tube.
If desire obtains to be arranged in the heterogeneous nanotube of one dimension of alumina formwork, only need in step c), to save the process that the alumina formwork that will be equipped with the heterogeneous nano-tube array of one dimension in the through hole places strong base solution to corrode and get final product.
Obviously, those skilled in the art's nano tube hetero-junction that can constitute zinc oxide of the present invention and carbon and preparation method thereof carries out various changes and modification and does not break away from the spirit and scope of the present invention.Like this, if of the present invention these are revised and modification belongs within the scope of claim of the present invention and equivalent technologies thereof, then the present invention also is intended to comprise these changes and modification interior.
Claims (10)
1, the nano tube hetero-junction of a kind of zinc oxide and carbon formation comprises zinc oxide nano mitron and carbon nano-tube, it is characterized in that said zinc oxide nano mitron and said carbon nano-tube connect into the heterogeneous nanotube of one dimension.
2, the nano tube hetero-junction of zinc oxide according to claim 1 and carbon formation is characterized in that the two ends of zinc oxide nano mitron all connect into the heterogeneous nanotube of one dimension with carbon nano-tube.
3, the nano tube hetero-junction of zinc oxide according to claim 1 and 2 and carbon formation, the caliber that it is characterized in that the heterogeneous nanotube of one dimension is that 10～100nm, thickness of pipe wall are 5～10nm.
4, the nano tube hetero-junction of zinc oxide according to claim 3 and carbon formation is characterized in that the heterogeneous nanotube of one dimension is arranged in alumina formwork.
5, the preparation method of the nano tube hetero-junction of zinc oxide according to claim 1 and carbon formation comprises secondary anode method, electrodeposition process and chemical vapour deposition technique, it is characterized in that finishing according to the following steps:
(a) earlier aluminium flake being placed concentration is the acid solution of 0.2～0.4M, in direct voltage is anodic oxidation 4～10h under 20～60v, again it in being the mixed solution of 4～8wt% phosphoric acid of 50～70 ℃ and 1.6～2wt% chromic acid, temperature is soaked 8～12h, then, with it once more after carrying out the anodization second time under the same process conditions, remove the unoxidized aluminium in the back side with copper chloride or tin chloride solution earlier, phosphoric acid solution with 3～7wt% erodes the aluminium oxide barrier layer that is positioned at the bottom, hole again, and obtaining the aperture is the through hole alumina formwork of 10～100nm;
(b) the deposited by electron beam evaporation method is placed on earlier in the electroplate liquid at 1.5～2.5mA/cm behind the thick golden film of evaporation a 20～50nm of through hole alumina formwork
2Constant current under electro-deposition 30～70min, wherein, the composition of electroplate liquid is 80g/L ZnSO
47H
2O and 20g/L H
3BO
3, its pH is placed on 300～400 ℃ of following oxidation 30～40h again for to be adjusted to 2.5～3.5 with dilute sulfuric acid;
(c) alumina formwork that will contain the zinc oxide nano mitron earlier places the argon atmospher under 600～700 ℃, be placed on again in the mixed atmosphere of acetylene and argon gas in 600～700 ℃ of insulation 1～3h down, afterwards, be placed on and erode alumina formwork in the strong base solution, make zinc oxide nano mitron and carbon nano-tube and connect into the zinc oxide of the heterogeneous nanotube of one dimension and the nano tube hetero-junction that carbon constitutes.
6, the preparation method of the nano tube hetero-junction of zinc oxide according to claim 5 and carbon formation, the purity that it is characterized in that aluminium flake is 〉=99.9%.
7, the preparation method of the nano tube hetero-junction of zinc oxide according to claim 5 and carbon formation is characterized in that acid is oxalic acid or phosphoric acid or sulfuric acid.
8, the preparation method of the nano tube hetero-junction of zinc oxide according to claim 5 and carbon formation, the mixed atmosphere that it is characterized in that acetylene and argon gas is that the ratio of acetylene and argon gas is 1:10.
9, the preparation method of the nano tube hetero-junction of zinc oxide according to claim 5 and carbon formation is characterized in that strong base solution is sodium hydroxide solution or potassium hydroxide solution.
10, the preparation method of the nano tube hetero-junction of zinc oxide according to claim 5 and carbon formation, it is characterized in that in the through hole of alumina formwork behind the electrodepositing zinc nanotube, deposit the one side 2～4min of zinc nanotube earlier in the dilution heat of sulfuric acid corrosion oxidation aluminum alloy pattern plate with 4～6wt%, again with distilled water or washed with de-ionized water and dry, and then it is carried out oxidation processes, the two ends that make the zinc oxide nano mitron all connect into the zinc oxide of the heterogeneous nanotube of one dimension and the nano tube hetero-junction that carbon constitutes with carbon nano-tube.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN102157358A (en) * | 2010-12-30 | 2011-08-17 | 北京理工大学 | Method for synthesizing carbon nano tube and zinc oxide heterostructure by hydrothermal method |
| CN102345162A (en) * | 2011-04-19 | 2012-02-08 | 中国科学院合肥物质科学研究院 | One-dimensional axial type nano zinc oxide / zinc sulfide heterojunction and preparation method thereof |
| CN104445047A (en) * | 2014-11-05 | 2015-03-25 | 天津大学 | Tungsten oxide/vanadium oxide heterojunction nanowire array and manufacturing method thereof |
| CN105926019A (en) * | 2016-06-12 | 2016-09-07 | 南开大学 | Preparation method for cypress leaf shaped platinoid superlattice nano structure |
| CN107104040A (en) * | 2016-02-23 | 2017-08-29 | 北京大学 | The anode fabrication method of gallium nitride Schottky diode |
| CN108950521A (en) * | 2018-06-06 | 2018-12-07 | 湖北大学 | Red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization |
-
2007
- 2007-09-20 CN CN2007101331020A patent/CN101393939B/en not_active Expired - Fee Related
Cited By (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102157358A (en) * | 2010-12-30 | 2011-08-17 | 北京理工大学 | Method for synthesizing carbon nano tube and zinc oxide heterostructure by hydrothermal method |
| CN102157358B (en) * | 2010-12-30 | 2012-08-29 | 北京理工大学 | Method for synthesizing carbon nano tube and zinc oxide heterostructure by hydrothermal method |
| CN102345162A (en) * | 2011-04-19 | 2012-02-08 | 中国科学院合肥物质科学研究院 | One-dimensional axial type nano zinc oxide / zinc sulfide heterojunction and preparation method thereof |
| CN102345162B (en) * | 2011-04-19 | 2014-04-09 | 中国科学院合肥物质科学研究院 | One-dimensional axial type nano zinc oxide / zinc sulfide heterojunction and preparation method thereof |
| CN104445047A (en) * | 2014-11-05 | 2015-03-25 | 天津大学 | Tungsten oxide/vanadium oxide heterojunction nanowire array and manufacturing method thereof |
| CN107104040A (en) * | 2016-02-23 | 2017-08-29 | 北京大学 | The anode fabrication method of gallium nitride Schottky diode |
| CN105926019A (en) * | 2016-06-12 | 2016-09-07 | 南开大学 | Preparation method for cypress leaf shaped platinoid superlattice nano structure |
| CN108950521A (en) * | 2018-06-06 | 2018-12-07 | 湖北大学 | Red phosphorus-ZnO heterojunction film preparation method of rapid photocatalytic sterilization |
| CN108950521B (en) * | 2018-06-06 | 2020-05-08 | 湖北大学 | Preparation method of red phosphorus-zinc oxide heterojunction film with rapid photocatalytic sterilization |
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