CN103364446A - Preparation method of rare earth doped zinc oxide nanowire for gas sensor - Google Patents
Preparation method of rare earth doped zinc oxide nanowire for gas sensor Download PDFInfo
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Abstract
The invention discloses a preparation method of a rare earth doped zinc oxide nanowire for a gas sensor. The zinc oxide nanowire is synthesized under a strong alkali condition by using a chemical solution method; the gas sensor is of a heater-type device structure; an aluminum oxide ceramic tube is used as a carrier and internally provided with a heating wire; a gas sensitive material of the rare earth doped zinc oxide nanowire is coated outside the ceramic tube. The gas sensor can be used for detecting ethanol within different working temperature ranges and is high in response ratio and short in response time. The preparation method of the rare earth doped zinc oxide nanowire is simple; the rare earth doping variety and concentration are easy to control; the obtained rare earth doped zinc oxide nanowire has the advantages such as uniformity in diameter distribution, good stability and the like; the rare earth doped zinc oxide nanowire prepared by the invention can be used for the gas sensor, a solar cell photoanode and the like.
Description
Technical field
The present invention relates to the metal oxide gas sensitive, specifically refer to a kind of preparation method and gas-sensitive property thereof 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, chemical sensitization and biomedical materials.ZnO nano material has larger specific surface area, the more catalyst activity component of energy load, has stronger ion-exchange performance, being conducive to reactant reacts in active sites in catalytic process, detection aspect to gases such as ethanol, acetone, formaldehyde has shown greatly application prospect, so the ZnO nano-structure material is widely used in the sensitive material of gas sensor.
But its working temperature is higher, and gas sensitivity is lower, but better doping of stability is the main method of improving air-sensitive performance, can significantly improve gas sensing property, and preferably response and restorability are arranged.Doping and modification includes precious metal doping, realizes by adding metal oxide or slaine, and is rare earth doped.The precious metal doping thing mostly is greatly Au, Ag, Pd, Pt etc. and has the metal of catalytic, but often has certain toxicity and expensive; Rare earth element is owing to its special atomic shell structure has excellent magnetics and optical characteristics, therefore regulate and control the electrical properties that its physical characteristics can be improved ZnO nano material by rare earth doped ZnO semiconductor, be expected to improve the sensitivity of gas sensor, be used for solar battery photoanode and also can reduce the electron-hole recombination probability and improve its light transfer characteristic.Yet how overcoming semi-conductive self purifying effect and doping at nanocrystalline middle realization Effective Doping, to bring the outstanding key in surface and defect state be a challenge to the destruction of performance always.Therefore be necessary very much to study rare earth doping zinc oxide material preparation technique, a kind of gas sensing materials of high-quality is provided for market.
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides a kind of preparation method of the rare earth doping zinc oxide nano line for gas sensor.
A kind of preparation method of the rare earth doping zinc oxide nano line for gas sensor is characterized in that, comprises the steps:
(1) joins 25 milliliters of NaOH that concentration is 0.5～3M or potassium hydroxide solutions, add 1～8 milliliter diethanolamine in the solution;
(2) in beaker by with the zinc nitrate hexahydrate solution of concentration of sodium hydroxide solution 1:3～5:1, place zinc nitrate solution for 100:10～100:4 takes by weighing the rare-earth compound presoma in molar ratio, obtain zincium-rare earth presoma composite solution;
(3) sodium hydroxide solution is heated to 60～90 ℃, after 20 minutes, injects zincium-rare earth presoma composite solution, continue to keep temperature 30 minutes after injecting, sample is centrifugal, obtain white powder; In 40～80 ℃ of drying boxes, dry, namely obtain rear-earth-doped zinc oxide nanowire;
(4) the rear-earth-doped zinc oxide nanowire of step (3) gained is evenly spread upon on the alumina ceramic tube, alumina ceramic tube is welded, encapsulates, 200～400 ℃ of lower wearing out, make the gas sensor original paper.
Diethanolamine described in the step (2) can replace with triethanolamine or polyglycol.
Six zinc sulphate hydrates described in the step (2) can replace with Zinc vitriol or Zinc diacetate dihydrate.
Zincium-rare earth presoma rare earth elements compound presoma and zinc compound presoma described in the step (2) are combined as:
The dysprosium doped zinc oxide nano-wire adopts five nitric hydrate dysprosiums and the combination of zinc complexes presoma;
The samarium doped zinc oxide nano-wire adopts samaric nitrate and the combination of zinc complexes presoma;
The lanthanum doped zinc oxide nano-wire adopts lanthanum salt and the combination of zinc complexes presoma;
The gadolinium doped zinc oxide nano-wire adopts gadolinium salt and the combination of zinc complexes presoma.
The described ageing environment of step (4) is air atmosphere, and digestion time was at 5 days to 12 days.
The invention has the advantages that: the diameter of nano wire is less, has larger specific surface area and the Size Distribution of homogeneous; The rare earth doping zinc oxide preparation method is simple, does not need expensive equipment, and cost is low, and is easy to rear-earth-doped concentration; The rare earth doping zinc oxide nano line stabilization of the method preparation is strong, can be used for sensitive material and the solar battery photoanode material of gas sensor.
The method is utilized chemical method, has successfully realized the synthetic 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, for gas sensor provides a kind of effective sensitive material.Method of the present invention is to utilize solwution method to prepare rear-earth-doped ZnO nano-wire, the diameter of the variation regulation and control nano wire by coating material in the solution and presoma ratio is regulated and control rear-earth-doped amount by the mol ratio of zinc precursor body in the system and rare earth element presoma.Simple, the cheap and suitable suitability for industrialized production of the method synthesis technique is expected to improve the sensitivity of gas sensor and the production cost that reduces.
Description of drawings
Fig. 1 is the SEM figure of dysprosium doped zinc oxide nano-wire of the present invention.
Fig. 2 is the energy spectrogram of dysprosium doped zinc oxide nano-wire of the present invention.
Fig. 3 is that dysprosium doped zinc oxide nano-wire of the present invention is to the air-sensitive response curve of ethanol.
Embodiment
Embodiment 1:
The NaOH that takes by weighing 4 g places there-necked flask, adds 50 ml deionized waters, adds the triethanolamine of 2 ml in the solution; Take by weighing 15 g zinc nitrate hexahydrates, add 50 ml deionized waters and be made into zinc nitrate aqueous solution, take by weighing the five nitric hydrate dysprosiums of 1 g, place zinc nitrate solution; Heating there-necked flask to 80 ℃ after about 20 minutes, injects zincium-rare earth presoma composite solution, continues to keep temperature about 30 minutes after injecting, and sample is centrifugal, obtains white powder.In 50 ℃ of drying boxes, dry, obtain rear-earth-doped zinc oxide nanowire.
Fig. 1, Fig. 2 have provided respectively SEM figure and the EDS energy spectrogram of the dysprosium doped zinc oxide nano-wire of present embodiment preparation.Can be found out by SEM figure, dysprosium doped zinc oxide nano-wire even size distribution, diameter is less, EDS can spectrogram Zn and the existence of Dy confirmed that this structure is the dysprosium doping zinc-oxide, and the mol ratio of Zn and Dy is 32:1, and is suitable with rate of charge.
Embodiment 2:
The NaOH that takes by weighing 4 g places there-necked flask, adds 50 ml deionized waters, adds the diethanolamine of 2 ml in the solution; Take by weighing 14.3 g Zinc vitriols, add 50 ml deionized waters and be made into zinc sulfate solution, take by weighing the five nitric hydrate dysprosiums of 1 g, place solution of zinc sulfate; Heating there-necked flask to 80
oC after about 20 minutes, injects zincium-rare earth presoma composite solution, continues to keep temperature about 30 minutes after injecting, and sample is centrifugal, obtains white powder.50
oDry in the C drying box, obtain rear-earth-doped zinc oxide nanowire.
Embodiment 3:
The potassium hydroxide that takes by weighing 2.8 g places there-necked flask, adds 50 ml deionized waters, adds the diethanolamine of 3 ml in the solution; Take by weighing 14.3 g Zinc vitriols, add 50 ml deionized waters and be made into zinc sulfate solution, take by weighing the five nitric hydrate dysprosiums of 1 g, place solution of zinc sulfate; Heating there-necked flask to 80 ℃ after about 20 minutes, injects zincium-rare earth presoma composite solution, continues to keep temperature about 30 minutes after injecting, and sample is centrifugal, obtains white powder.In 50 ℃ of drying boxes, dry, obtain rear-earth-doped zinc oxide nanowire.
Embodiment 4:
The NaOH that takes by weighing 8 g places there-necked flask, adds 50 ml deionized waters, adds the diethanolamine of 5 ml in the solution; Take by weighing 14.3 g Zinc vitriols, add 50 ml deionized waters and be made into zinc sulfate solution, take by weighing the five nitric hydrate dysprosiums of 0.5 g, place solution of zinc sulfate; Heating there-necked flask to 80 ℃ after about 20 minutes, injects zincium-rare earth presoma composite solution, continues to keep temperature about 30 minutes after injecting, and sample is centrifugal, obtains white powder.In 50 ℃ of drying boxes, dry, obtain rear-earth-doped zinc oxide nanowire.
Performance: the dysprosium doped zinc oxide nano-wire do catalysis material preparation gas sensor voltage response curves as shown in Figure 3, probe temperature is 330
oC, concentration of alcohol are 100 ppm, and as seen from the figure, the zinc oxide nanowire that dysprosium mixes shows obvious ethanol air-sensitive response.Resistance sensitivity is 10 under this test condition, and the response time is 20 s.
Claims (5)
1. a preparation method who is used for the rare earth doping zinc oxide nano line of gas sensor is characterized in that, comprises the steps:
(1) joins 25 milliliters of NaOH that concentration is 0.5～3M or potassium hydroxide solutions, add 1～8 milliliter diethanolamine in the solution;
(2) in beaker by with the zinc nitrate hexahydrate solution of concentration of sodium hydroxide solution 1:3～5:1, place zinc nitrate solution for 100:10～100:4 takes by weighing the rare-earth compound presoma in molar ratio, obtain zincium-rare earth presoma composite solution;
(3) sodium hydroxide solution is heated to 60～90 ℃, after 20 minutes, injects zincium-rare earth presoma composite solution, continue to keep temperature 30 minutes after injecting, sample is centrifugal, obtain white powder; In 40～80 ℃ of drying boxes, dry, namely obtain rear-earth-doped zinc oxide nanowire;
(4) the rear-earth-doped zinc oxide nanowire of step (3) gained is evenly spread upon on the alumina ceramic tube, alumina ceramic tube is welded, encapsulates, 200～400 ℃ of lower wearing out, make the gas sensor original paper.
2. the preparation method of described a kind of rare earth doping zinc oxide nano line for gas sensor according to claim 1 is characterized in that the diethanolamine described in the step (2) can replace with triethanolamine or polyglycol.
3. the preparation method of described a kind of rare earth doping zinc oxide nano line for gas sensor according to claim 1 is characterized in that six zinc sulphate hydrates described in the step (2) can replace with Zinc vitriol or Zinc diacetate dihydrate.
4. the preparation method of described a kind of rare earth doping zinc oxide nano line for gas sensor according to claim 1 is characterized in that zincium-rare earth presoma rare earth elements compound presoma and zinc compound presoma described in the step (2) are combined as:
The dysprosium doped zinc oxide nano-wire adopts five nitric hydrate dysprosiums and the combination of zinc complexes presoma;
The samarium doped zinc oxide nano-wire adopts samaric nitrate and the combination of zinc complexes presoma;
The lanthanum doped zinc oxide nano-wire adopts lanthanum salt and the combination of zinc complexes presoma;
The gadolinium doped zinc oxide nano-wire adopts gadolinium salt and the combination of zinc complexes presoma.
5. the preparation method of described a kind of rare earth doping zinc oxide nano line for gas sensor according to claim 1 is characterized in that the described ageing environment of step (4) is air atmosphere, and digestion time is 5 days to 12 days.
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Cited By (7)
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| CN104458886A (en) * | 2014-12-09 | 2015-03-25 | 江苏师范大学 | Nano respiration sensor and preparation method thereof |
| CN104764772A (en) * | 2015-04-01 | 2015-07-08 | 张有科 | Method for preparing pine-needle-shaped 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 |
| 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 |
| CN109853030A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院福建物质结构研究所 | A kind of metallic oxide nanocrystal and its preparation method and application of metal organic frame film coated |
| 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 |
| CN115266847A (en) * | 2022-08-03 | 2022-11-01 | 吉林大学 | High-performance NO based on ZnO nanowire sensitive material loaded with metal Pd 2 Sensor and manufacturing method |
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104458886A (en) * | 2014-12-09 | 2015-03-25 | 江苏师范大学 | Nano respiration sensor and preparation method thereof |
| CN104458886B (en) * | 2014-12-09 | 2018-01-16 | 江苏师范大学 | A kind of nanometer respiration transducer and preparation method thereof |
| CN104764772A (en) * | 2015-04-01 | 2015-07-08 | 张有科 | Method for preparing pine-needle-shaped zinc oxide gas sensor |
| 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 |
| CN109853030A (en) * | 2017-11-30 | 2019-06-07 | 中国科学院福建物质结构研究所 | A kind of metallic oxide nanocrystal and its preparation method and application of metal organic frame film coated |
| 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 |
| CN115266847A (en) * | 2022-08-03 | 2022-11-01 | 吉林大学 | High-performance NO based on ZnO nanowire sensitive material loaded with metal Pd 2 Sensor and manufacturing method |
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