CN103364446B - A kind of preparation method of the rare earth doping zinc oxide nano line for gas sensor - Google Patents
A kind of preparation method of the rare earth doping zinc oxide nano line for gas sensor Download PDFInfo
- Publication number
- CN103364446B CN103364446B CN201310264269.6A CN201310264269A CN103364446B CN 103364446 B CN103364446 B CN 103364446B CN 201310264269 A CN201310264269 A CN 201310264269A CN 103364446 B CN103364446 B CN 103364446B
- Authority
- CN
- China
- Prior art keywords
- zinc oxide
- zinc
- earth
- presoma
- rare earth
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Expired - Fee Related
Links
Abstract
A kind of preparation method of the rear-earth-doped zinc oxide nanowire for gas sensor, zinc oxide nanowire uses chemical solution method to synthesize under strongly alkaline conditions, gas sensor uses heater-type device architecture, with alumina ceramic tube as carrier, ceramic tube inside has heater strip, and external coated have rear-earth-doped zinc oxide nanowire gas sensitive.The gas-sensitive sensor device of the present invention can detect ethanol in different operating temperature range, and responsiveness is high, and response time is short.Rear-earth-doped zinc oxide nanowire preparation method is simple, easily controllable rear-earth-doped kind and doping content, gained rare earth doping zinc oxide nano line have diameter Distribution uniformly, good stability etc. a little, rare earth doping zinc oxide nano line prepared by this invention can be used for gas sensor, solar battery photoanode etc..
Description
Technical field
The present invention relates to metal-oxide gas sensitive, specifically refer to preparation method and the gas-sensitive property thereof of a kind of rare earth doping zinc oxide nano line.
Background technology
Nano zinc oxide material has higher specific surface area and good photoelectricity, photocatalysis performance, has boundless application prospect in fields such as gas sensor, dye-sensitized solar cells, photocatalyst, the photosensitive and biomedical materials of chemistry.ZnO nano material has bigger specific surface area, more catalyst activity component can be loaded, there is stronger ion-exchange performance, reactant is conducive to react in active sites in catalytic process, the detection aspect of the gases such as ethanol, acetone, formaldehyde is shown greatly application prospect, and therefore ZnO nano-structure material is widely used in the sensitive material of gas sensor.
But, its operating temperature is higher, and gas sensitivity is relatively low, the main method being to improve air-sensitive performance but stability is preferably adulterated, and can significantly improve gas sensing property, and have preferably response and restorability.Doping and modification includes precious metal doping, realizes by adding metal-oxide or slaine, rare earth doped.Precious metal doping thing is mostly Au, Ag, Pd, Pt etc. and has a metal of catalytic, but often has certain toxicity and expensive；Rare earth element has magnetics and the optical characteristics of excellence due to its special atomic shell structure, therefore regulate and control its physical characteristic by rare earth doped ZnO quasiconductor and can improve the electrical properties of ZnO nano material, it is expected to improve the sensitivity of gas sensor, electron-hole recombination probability can also be reduced for solar battery photoanode and improve its light transfer characteristic.But middle realize how Effective Doping overcomes the autologous purified effect of quasiconductor and doping to bring the destruction always challenge to performance of surface dangling bond and defect state nanocrystalline.Therefore it is highly desirable to study the preparation technology of rare earth doping zinc oxide material, the gas sensing materials of a kind of high-quality is provided for market.
Summary of the invention
In order to overcome the deficiencies in the prior art, the present invention provides the preparation method of a kind of rare earth doping zinc oxide nano line for gas sensor.
The preparation method of a kind of rare earth doping zinc oxide nano line for gas sensor, it is characterised in that comprise the steps:
(1) join sodium hydroxide or potassium hydroxide solution 25 milliliters that concentration is 0.5～3M, in solution, add the diethanolamine of 1～8 milliliter；
(2) put in beaker with concentration of sodium hydroxide solution than the zinc nitrate hexahydrate solution for 1:3～5:1, it is that 100:10～100:4 weighs rare-earth compound presoma and is placed in zinc nitrate solution by zinc nitrate and rare-earth compound presoma mol ratio, obtains zincium-rare earth presoma composite solution；
(3) willStep ( 1 ) prepareSolution is heated to 60～90 DEG C, after 20 minutes, injects zincium-rare earth presoma composite solution, continues to keep temperature 30 minutes, be centrifuged by sample, obtain white powder after injection；40～80 DEG C of drying baker are dried, i.e. obtains rear-earth-doped zinc oxide nanowire；
(4) the rear-earth-doped zinc oxide nanowire uniform application of step (3) gained on alumina ceramic tube, carry out alumina ceramic tube welding, encapsulating, aging at 200～400 DEG C, make gas sensor original paper.
Diethanolamine described in step (2) can replace with triethanolamine or Polyethylene Glycol.
Six hydrations described in step (2)NitreAcid zinc can replace with Zinc vitriol or Zinc diacetate dihydrate.
Zincium-rare earth presoma rare earth elements compounds precursors described in step (2) is combined as with zinc compound presoma:
Dysprosium doped zinc oxide nanowire uses five nitric hydrate dysprosiums and the combination of zinc complexes presoma；
Samarium doping zinc oxide nanowire uses samaric nitrate and the combination of zinc complexes presoma；
La doped zinc oxide nanowire uses lanthanum salt and the combination of zinc complexes presoma；
Gd2 O3 zinc oxide nanowire uses gadolinium salt and the combination of zinc complexes presoma.
Ageing environment described in step (4) is air atmosphere, and ageing time was at 5 days to 12 days.
It is an advantage of the current invention that: the diameter of nano wire is less that there is bigger specific surface area and homogeneous distribution of sizes；Rare earth doping zinc oxide preparation method is simple, it is not necessary to expensive equipment, low cost, and is prone to regulate and control rear-earth-doped concentration；Rare earth doping zinc oxide nano line stabilization prepared by the method is strong, can be used for sensitive material and the solar battery photoanode material of gas sensor.
The method utilizes chemical method, is successfully realized the synthesis of rare earth doping zinc oxide nano line, the zinc oxide nanowire even size distribution that gained is rear-earth-doped, and diameter is less, provides a kind of effective sensitive material for gas sensor.The method of the present invention is to utilize solwution method to prepare rear-earth-doped ZnO nano-wire, by the diameter of the change regulation and control nano wire of coating material in solution and presoma ratio, regulates and controls rear-earth-doped amount by the mol ratio of zinc precursor in system and rare earth element presoma.The method synthesis technique is simple, cheap and applicable industrialized production, is expected to the sensitivity improving gas sensor the production cost reduced.
Accompanying drawing explanation
Fig. 1 is the SEM figure of the dysprosium doped zinc oxide nanowire of the present invention.
Fig. 2 is the energy spectrogram of dysprosium doped zinc oxide nanowire of the present invention.
Fig. 3 is the dysprosium doped zinc oxide nanowire of the present invention air-sensitive response curve to ethanol.
Detailed description of the invention
Embodiment 1:
The sodium hydroxide weighing 4 g is placed in there-necked flask, adds 50 ml deionized waters, adds the triethanolamine of 2 ml in solution；Weigh 15 g zinc nitrate hexahydrates, add 50 ml deionized waters and be made into zinc nitrate aqueous solution, weigh the five nitric hydrate dysprosiums of 1 g, be placed in zinc nitrate solution；Heating there-necked flask is to 80 DEG C, after about 20 minutes, injects zincium-rare earth presoma composite solution, continues to keep temperature about 30 minutes, be centrifuged by sample, obtain white powder after injection.50 DEG C of drying baker are dried, obtains rear-earth-doped zinc oxide nanowire.
Fig. 1, Fig. 2 sets forth SEM figure and the EDS energy spectrogram of dysprosium doped zinc oxide nanowire prepared by the present embodiment.Being schemed by SEM it can be seen that dysprosium doped zinc oxide nanowire even size distribution, diameter is less, and the existence of EDS energy spectrogram Zn and Dy confirms that this structure is dysprosium doped zinc oxide, and the mol ratio of Zn and Dy is 32:1, suitable with rate of charge.
Embodiment 2:
The sodium hydroxide weighing 4 g is placed in there-necked flask, adds 50 ml deionized waters, adds the diethanolamine of 2 ml in solution；Weigh 14.3 g Zinc vitriols, add 50 ml deionized waters and be made into zinc sulfate solution, weigh the five nitric hydrate dysprosiums of 1 g, be placed in solution of zinc sulfate；Heating there-necked flask is to 80oC, after about 20 minutes, injects zincium-rare earth presoma composite solution, continues to keep temperature about 30 minutes, be centrifuged by sample, obtain white powder after injection.50oC drying baker is dried, obtains rear-earth-doped zinc oxide nanowire.
Embodiment 3:
The potassium hydroxide weighing 2.8 g is placed in there-necked flask, adds 50 ml deionized waters, adds the diethanolamine of 3 ml in solution；Weigh 14.3 g Zinc vitriols, add 50 ml deionized waters and be made into zinc sulfate solution, weigh the five nitric hydrate dysprosiums of 1 g, be placed in solution of zinc sulfate；Heating there-necked flask is to 80 DEG C, after about 20 minutes, injects zincium-rare earth presoma composite solution, continues to keep temperature about 30 minutes, be centrifuged by sample, obtain white powder after injection.50 DEG C of drying baker are dried, obtains rear-earth-doped zinc oxide nanowire.
Embodiment 4:
The sodium hydroxide weighing 8 g is placed in there-necked flask, adds 50 ml deionized waters, adds the diethanolamine of 5 ml in solution；Weigh 14.3 g Zinc vitriols, add 50 ml deionized waters and be made into zinc sulfate solution, weigh the five nitric hydrate dysprosiums of 0.5 g, be placed in solution of zinc sulfate；Heating there-necked flask is to 80 DEG C, after about 20 minutes, injects zincium-rare earth presoma composite solution, continues to keep temperature about 30 minutes, be centrifuged by sample, obtain white powder after injection.50 DEG C of drying baker are dried, obtains rear-earth-doped zinc oxide nanowire.
Performance: dysprosium doped zinc oxide nanowire does the voltage response curves of gas sensor prepared by catalysis material as it is shown on figure 3, test temperature is 330oC, concentration of alcohol is 100 ppm, and as seen from the figure, the zinc oxide nanowire of dysprosium doped shows the response of obvious ethanol air-sensitive.Under this test condition, resistance sensitivity is 10, and response time is 20 s.
Claims (1)
1. the preparation method for the rare earth doping zinc oxide nano line of gas sensor, it is characterised in that comprise the steps:
(1) join sodium hydroxide or potassium hydroxide solution 25 milliliters that concentration is 0.5～3M, in solution, add the diethanolamine of 1～8 milliliter；
(2) put in beaker with concentration of sodium hydroxide solution than the zinc nitrate hexahydrate solution for 1:3～5:1, it is that 100:10～100:4 weighs rare-earth compound presoma and is placed in zinc nitrate solution by zinc nitrate and rare-earth compound presoma mol ratio, obtains zincium-rare earth presoma composite solution；
(3) willStep ( 1 ) prepareSolution is heated to 60～90 DEG C, after 20 minutes, injects zincium-rare earth presoma composite solution, continues to keep temperature 30 minutes, be centrifuged by sample, obtain white powder after injection；40～80 DEG C of drying baker are dried, i.e. obtains rear-earth-doped zinc oxide nanowire；
(4) the rear-earth-doped zinc oxide nanowire uniform application of step (3) gained on alumina ceramic tube, carry out alumina ceramic tube welding, encapsulating, aging at 200～400 DEG C, make gas sensor original paper；
Diethanolamine described in step (2) can replace with triethanolamine or Polyethylene Glycol；
Six hydrations described in step (2)NitreAcid zinc can replace with Zinc vitriol or Zinc diacetate dihydrate；
Zincium-rare earth presoma rare earth elements compounds precursors described in step (2) is combined as with zinc compound presoma:
Dysprosium doped zinc oxide nanowire uses five nitric hydrate dysprosiums and the combination of zinc complexes presoma；
Samarium doping zinc oxide nanowire uses samaric nitrate and the combination of zinc complexes presoma；
La doped zinc oxide nanowire uses lanthanum salt and the combination of zinc complexes presoma；
Gd2 O3 zinc oxide nanowire uses gadolinium salt and the combination of zinc complexes presoma；
Ageing environment described in step (4) is air atmosphere, and ageing time is 5 days to 12 days.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310264269.6A CN103364446B (en) | 2013-06-28 | 2013-06-28 | A kind of preparation method of the rare earth doping zinc oxide nano line for gas sensor |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201310264269.6A CN103364446B (en) | 2013-06-28 | 2013-06-28 | A kind of preparation method of the rare earth doping zinc oxide nano line for gas sensor |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN103364446A CN103364446A (en) | 2013-10-23 |
| CN103364446B true CN103364446B (en) | 2016-08-17 |
Family
ID=49366270
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201310264269.6A Expired - Fee Related CN103364446B (en) | 2013-06-28 | 2013-06-28 | A kind of preparation method of the rare earth doping zinc oxide nano line for gas sensor |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN103364446B (en) |
Families Citing this family (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104458886B (en) * | 2014-12-09 | 2018-01-16 | 江苏师范大学 | A kind of nanometer respiration transducer and preparation method thereof |
| CN104764772B (en) * | 2015-04-01 | 2017-09-22 | 哈尔滨学院 | A kind of preparation method of loose acicular type zinc oxide gas sensor |
| CN105424759A (en) * | 2015-10-22 | 2016-03-23 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc oxide nanotube array gas sensitive sensor |
| CN109853030B (en) * | 2017-11-30 | 2020-11-20 | 中国科学院福建物质结构研究所 | Metal oxide nanocrystalline coated by metal organic framework film and preparation method and application thereof |
| CN109502630A (en) * | 2018-12-21 | 2019-03-22 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of zinc oxide nanowire and products thereof and application |
| CN113120947A (en) * | 2019-12-30 | 2021-07-16 | Tcl集团股份有限公司 | Composite material, preparation method thereof and quantum dot light-emitting diode |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320648A (en) * | 2011-08-15 | 2012-01-18 | 天津理工大学 | Preparation method and application of lanthanum ion-doped zinc oxide porous hollow sphere |
| CN102992389A (en) * | 2012-12-13 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for growing zinc oxide nano wire arrays |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| KR100750933B1 (en) * | 2005-08-14 | 2007-08-22 | 삼성전자주식회사 | Top-emitting White Light Emitting Devices Using Nano-structures of Rare-earth Doped Transparent Conducting ZnO And Method Of Manufacturing Thereof |
| CN101786653B (en) * | 2010-02-26 | 2012-05-09 | 中山大学 | Preparation method and applications of rare earth element-doped zinc oxide one-dimensional nanomaterial |
-
2013
- 2013-06-28 CN CN201310264269.6A patent/CN103364446B/en not_active Expired - Fee Related
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102320648A (en) * | 2011-08-15 | 2012-01-18 | 天津理工大学 | Preparation method and application of lanthanum ion-doped zinc oxide porous hollow sphere |
| CN102992389A (en) * | 2012-12-13 | 2013-03-27 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method for growing zinc oxide nano wire arrays |
Non-Patent Citations (1)
| Title |
|---|
| "The magnetic properties of Gd doped ZnO nanowires";Xiying Ma;《Thin Solid Films》;20120420;第520卷;第5752-5755页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN103364446A (en) | 2013-10-23 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN103364446B (en) | A kind of preparation method of the rare earth doping zinc oxide nano line for gas sensor | |
| Qiao et al. | Tunable MoS2/SnO2 P–N heterojunctions for an efficient trimethylamine gas sensor and 4-nitrophenol reduction catalyst | |
| Baek et al. | Simple but effective way to enhance photoelectrochemical solar-water-splitting performance of ZnO nanorod arrays: charge-trapping Zn (OH) 2 annihilation and oxygen vacancy generation by vacuum annealing | |
| Yao et al. | Oxygen-defective ultrathin BiVO4 nanosheets for enhanced gas sensing | |
| He et al. | One-step solvothermal synthesis of petalous carbon-coated Cu+-doped CdS nanocomposites with enhanced photocatalytic hydrogen production | |
| Yang et al. | Fabrication of highly sensitive gas sensor based on Au functionalized WO3 composite nanofibers by electrospinning | |
| Lu et al. | UV-enhanced room temperature NO2 sensor using ZnO nanorods modified with SnO2 nanoparticles | |
| Lv et al. | Sb-doped three-dimensional ZnFe2O4 macroporous spheres for N-butanol chemiresistive gas sensors | |
| Wang et al. | Humidity-sensing performance of 3DOM WO3 with controllable structural modification | |
| GUO et al. | Low-temperature NO2 sensors based on polythiophene/WO3 organic-inorganic hybrids | |
| Zhai et al. | Visible-light-induced photoelectric gas sensing to formaldehyde based on CdS nanoparticles/ZnO heterostructures | |
| Ma et al. | A simple absorbent cotton biotemplate to fabricate SnO2 porous microtubules and their gas-sensing properties for chlorine | |
| Umar et al. | Composite CdO-ZnO hexagonal nanocones: Efficient materials for photovoltaic and sensing applications | |
| Long et al. | Layered double hydroxide onto perovskite oxide-decorated ZnO nanorods for modulation of carrier transfer behavior in photoelectrochemical water oxidation | |
| CN103400699B (en) | A kind of quantum dot modifies ZnO nanorod array electrode and preparation method thereof | |
| CN107469824A (en) | A kind of preparation method of the ethanol oxidation catalyst of the hollow crystal nickel oxide of carbon coating | |
| Mokoena et al. | Fabrication of a propanol gas sensor using p-type nickel oxide nanostructures: The effect of ramping rate towards luminescence and gas sensing characteristics | |
| Li et al. | UV excited gas sensing SnO2-ZnO aerogels to ppb-level ethanol detection | |
| Jana et al. | A comparative study on the dye sensitized solar cell performance of solution processed ZnO | |
| CN102539487A (en) | Air-sensitive material compounded by titanium dioxide nanometer lines and stannic oxide nanometer particles and preparation method thereof | |
| CN103713016A (en) | Palladium-doped stannic oxide wrapped carbon nano tube as well as preparation method and application of nano tube | |
| Li et al. | Versatile nanobead-scaffolded N-SnO 2 mesoporous microspheres: one-step synthesis and superb performance in dye-sensitized solar cell, gas sensor, and photocatalytic degradation of dye | |
| CN103675026B (en) | For the preparation method of the Hierarchical self-assembly zinc paste micro-nano structure of gas sensor | |
| Li et al. | Strongly coupled Ag/TiO 2 heterojunction: from one-step facile synthesis to effective and stable ethanol sensing performances | |
| CN106093142B (en) | With SnO2Electric potential type NH is blended together for the YSZ base of sensitive electrode3Sensor and preparation method thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| C10 | Entry into substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| C14 | Grant of patent or utility model | ||
| GR01 | Patent grant | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20160817 Termination date: 20190628 |
|
| CF01 | Termination of patent right due to non-payment of annual fee |