CN101183116A - Ammoniacal nanometer composite oxides sensitive material - Google Patents
Ammoniacal nanometer composite oxides sensitive material Download PDFInfo
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- CN101183116A CN101183116A CN 200710306935 CN200710306935A CN101183116A CN 101183116 A CN101183116 A CN 101183116A CN 200710306935 CN200710306935 CN 200710306935 CN 200710306935 A CN200710306935 A CN 200710306935A CN 101183116 A CN101183116 A CN 101183116A
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Abstract
The present invention provides the manometer composite oxide sensitive material of ammonia, which is characterized in that the present invention is combined by WO3, Cr2O3 and TiO2; wherein, the atom ratio of W and the Cr is 100 to 45 to 55; the atom ratio of the W and the Ti is 100 to 27 to 36; particle size distribution is between 25 and 45 nm. An ammonia sensor prepared by the sensitive material provided by the present invention has good selectivity and sensitivity for the detection of the trace amount ammonia gas in the air; and no disturbance is caused among common coexistent gases.
Description
Technical field
The present invention relates to a kind of sensitive material that is used for monitoring air ammonia, especially by WO
3, Cr
2O
3And TiO
2The nano composite oxide sensitive material of forming.Belong to field of sensing technologies.
Background technology
Ammonia (NH
3) be a kind of alkalescence, colourless, gas with intense stimulus smell, airborne ammonia often is attracted on human body skin mucous membrane, eye conjunctiva and the respiratory tract mucosa because of soluble in water.Ammonia concentration is 0.5mg/m in air
3The time can make the people feel penetrating odor; Ammonia concentration surpasses 80mg/m in air
3The time, can make in the short time that shedding tears appears in the people, pharyngalgia, cough, uncomfortable in chest, expiratory dyspnea, and with dizzy, headache, feel sick, vomiting, symptom such as weak, pulmonary edema and respiratory disease also can take place in serious.People live in the ammonia environment of low concentration for a long time, can benumb respiratory tract cilium and infringement mucous epithelium tissue gradually, make the pathogeny microorganism be easy to invade, and weaken the resistibility of health to disease.
In recent years, because the use of interior decoration and all kinds of modernized daily necessitiess is on the rise room air pollution.The pollutant of room air mainly contains: ammonia, formaldehyde and radon gas, wherein the exceeding standard rate of ammonia is higher, occupies the first place of pollution.National departments concerned has been spot-check newly-built high-grade office building and home dwelling sub-district, Beijing, and its IAQ (indoor air quality) is detected, and finds that the ammonia exceeding standard rate has reached 80.56% in the room air.The Ministry of Construction and environmental administration spot-check house decorative material, and disqualification rate reaches 68% as a result.The seriously polluted human health that threatening of ammonia.
The conventional sense means of ammonia mainly contain: spectrophotometric method, vapor-phase chromatography, liquid phase chromatography and electrochemical process etc.These method sensitivity are all than higher, but complicated operation must finish in the laboratory, can't on-the-spotly realize.The on-site measurement method of ammonia mainly contains the detector tube colourimetry, and this method stability and sensitivity are all not enough, can't finish the accurate mensuration of micro-ammonia.
Summary of the invention
The objective of the invention is to overcome the deficiency of conventional art, nano composite oxide sensitive material of a kind of ammonia and preparation method thereof is provided, and the ammonia gas sensor of making of this sensitive material can fast, accurately be measured airborne micro-ammonia at the scene and not be subjected to the influence of concurrent.
The preparation method of the nano composite oxide sensitive material of ammonia of the present invention is: with organic or inorganic tungsten salt, chromic salts and titanium salt in can be water-soluble or pure be that initiation material is made stable aqueous solution or alcoholic solution respectively, the solution of preparation is mixed under proper condition, slowly generate precipitation, after ageing, filtration, washing, oven dry and grinding, make nano-powder material by high-temperature calcination.Wherein tungsten salt comprises wolframic acid, ammonium tungstate, ammonium paratungstate, tungsten hexachloride and phosphotungstic acid etc., and chromic salts comprises chromium+oxalic acid, chromic acetate, ammonium dichromate, chromic nitrate and chromium sulfate etc., and titanium salt comprises Titanium Nitrate, titanium phosphate, butyl titanate and titanium tetrachloride etc.
The nano composite oxide sensitive material of best ammonia of the present invention is with ammonium tungstate ((NH
4)
5H
5[H
2(WO
4)
6] H
2O), ammonium dichromate ((NH
4)
2Cr
2O
7) and butyl titanate (C
16H
36O
4Ti) make for initiation material.By the atomic ratio of W and Cr is that 100: 45～55 amount takes by weighing ammonium tungstate respectively and ammonium dichromate is dissolved in the appropriate amount of deionized water, in 60 ℃ of heated and stirred, it is dissolved fully, with butyl titanate, the uniform mix of isopropyl alcohol and concentrated hydrochloric acid dropwise joins in the above-mentioned solution, keep temperature constantly to stir, being added dropwise to complete the atomic ratio that makes W and Ti is 100: 27～36, being chilled to room temperature continues to stir 1 hour, left standstill 10 hours, to precipitate filtration under diminished pressure, extremely do in 2 hours in 110 ℃ of bakings, after fully grinding, in high temperature box type resistance furnace, slowly be warming up to 450 ℃ and calcined 4 hours down, promptly obtain nano-powder material.
The present invention has following advantage:
(1) preparation process is simple, good reproducibility;
(2) utilize the Acidity of Aikalinity of different reagent self can reach the precipitation requirement, precipitation process is slow, and particle growth is even, gained powder body material size distribution less (25～42nm);
(3) prepared sensitive material has very high sensitivity (0.1mg/m to ammonia
3);
(4) ammoniacal sensor made from prepared sensitive material is still very stable after using 100 hours continuously;
(5) prepared sensitive material has good selectivity to ammonia, and airborne concurrent is interference measurement not.
Embodiment
Embodiment one: by the atomic ratio of W and Cr is that 100: 45 amount takes by weighing ammonium tungstate respectively and the ammonium dichromate general assembly (TW) is that 200g is dissolved in the 150mL deionized water, to dissolving fully, makes solution (I) in 60 ℃ of heated and stirred.Butyl titanate and concentrated hydrochloric acid are dissolved in the isopropyl alcohol, make solution (II), wherein the concentration of butyl titanate and hydrochloric acid is respectively 0.75 and 0.3mol/L.Keep 60 ℃ constantly to stir down, solution (II) is dropwise joined in the solution (I), making the atomic ratio of W and Ti is 100: 30, is chilled to room temperature and continues to stir 1 hour, leaves standstill 10 hours, to precipitate filtration under diminished pressure, extremely did in 2 hours in 110 ℃ of bakings, after fully grinding, in high temperature box type resistance furnace, slowly be warming up to 450 ℃ of calcinings 4 hours, obtain nano-powder material, particle diameter 25～35nm.
Embodiment two: by the atomic ratio of W and Cr is that 100: 50 amount takes by weighing ammonium tungstate respectively and the chromic acetate general assembly (TW) is that 200g is dissolved in 1: 1 the ethanol water of 200mL, to dissolving fully, makes solution (I) in 65 ℃ of heated and stirred.Butyl titanate and concentrated hydrochloric acid are dissolved in the ethanol, make solution (II), wherein the concentration of butyl titanate and hydrochloric acid is respectively 0.65 and 0.25mol/L.Keep 65 ℃ constantly to stir down, solution (II) is dropwise joined in the solution (I), making the atomic ratio of W and Ti is 100: 27, is chilled to room temperature and continues to stir after 1 hour, leaves standstill 10 hours, to precipitate filtration under diminished pressure, and, after fully grinding, in high temperature box type resistance furnace, slowly be warming up to 400 ℃ of calcinings 4 hours in 110 ℃ of oven dry 2 hours, obtain nano-powder material, particle diameter 28～41nm.
Embodiment three: by the atomic ratio of W and Cr is that 100: 55 amount takes by weighing tungsten hexachloride respectively and the chromium+oxalic acid general assembly (TW) is that 200g is dissolved in the ethanol water of 200mL30%, to dissolving fully, makes solution (I) in 60 ℃ of heated and stirred.Titanium Nitrate is soluble in water, be made into 0.45mol/L solution (II).Keep 60 ℃ constantly to stir down, solution (II) is joined in the solution (I), the atomic ratio that makes W and Ti is 100: 35, subsequently, dropwise slowly dropping ammonia is 7 until PH, is chilled to room temperature and continues to stir after 1 hour, leaves standstill 8 hours, to precipitate filtration under diminished pressure, and, after fully grinding, in high temperature box type resistance furnace, slowly be warming up to 420 ℃ of calcinings 4 hours in 110 ℃ of oven dry 2 hours, obtain nano-powder material, particle diameter 30～42nm.
Embodiment four: by the atomic ratio of W and Cr is that 100: 52 amount takes by weighing ammonium paratungstate respectively and the chromic nitrate general assembly (TW) is that 150g is dissolved in the 150mL deionized water, to dissolving fully, makes solution (I) in 60 ℃ of heated and stirred.Titanium tetrachloride and concentrated hydrochloric acid are dissolved in the deionized water, make solution (II), wherein the concentration of titanium tetrachloride and hydrochloric acid is respectively 0.55 and 0.35mol/L.Keep 60 ℃ constantly to stir down, solution (II) is dropwise joined in the solution (I), making the atomic ratio of W and Ti is 100: 30, is chilled to room temperature and continues to stir 1 hour, leaves standstill 10 hours, to precipitate filtration under diminished pressure, extremely did in 2 hours in 110 ℃ of bakings, after fully grinding, in high temperature box type resistance furnace, slowly be warming up to 460 ℃ of calcinings 3 hours, obtain nano-powder material, particle diameter 25～40nm.
Embodiment five: by the atomic ratio of W, Cr and Ti be 100: 50: 30 amount to take by weighing tungsten hexachloride, chromic nitrate and Titanium Nitrate general assembly (TW) respectively be that 300g is dissolved in the hydrochloric acid solution of 300mL10%, under 50 ℃, be stirred to dissolving fully at a slow speed.Be cooled to room temperature, under stirring, dropwise drip 20% ammonia spirit till PH about 7.5 with the speed that is no more than 2mL/min, continue to stir 2 hours, left standstill then 10 hours, will precipitate filtration under diminished pressure, and in 110 ℃ of oven dry 2 hours, after fully grinding, in high temperature box type resistance furnace, slowly be warming up to 440 ℃ of calcinings 4 hours, obtain nano-powder material, particle diameter 30～45nm.
Embodiment six: by the atomic ratio of W, Cr and Ti be 100: 55: 40 amount to take by weighing phosphotungstic acid, chromic acetate and titanium tetrachloride general assembly (TW) respectively be that 300g is dissolved in the hydrochloric acid solution of 300mL15%, under 55 ℃, be stirred to dissolving fully at a slow speed.Be cooled to room temperature, under stirring, dropwise drip 20% ammonia spirit till PH about 7.5 with the speed that is no more than 2mL/min, continue to stir 2 hours, left standstill then 10 hours, will precipitate filtration under diminished pressure, and in 115 ℃ of oven dry 1.5 hours, after fully grinding, in high temperature box type resistance furnace, slowly be warming up to 450 ℃ of calcinings 4 hours, obtain nano-powder material, particle diameter 27～42nm.
Claims (3)
1. the nano sensitive material of an ammonia is characterized in that by Cr
2O
3, WO
3And TiO
2Be composited, wherein the atomic ratio of Cr and W is 100: 45～55, and the atomic ratio of Ti and W is 100: 27～36.
2. nano sensitive material according to claim 1, the size distribution that it is characterized in that described nano sensitive material is 25～42nm.
3. nano sensitive material according to claim 1, it is characterized in that described nano sensitive material the preparation ammonia sensor in use.
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| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN200710306935A CN100580455C (en) | 2007-12-28 | 2007-12-28 | Ammoniacal nanometer composite oxides sensitive material |
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|---|---|---|---|
| CN200710306935A CN100580455C (en) | 2007-12-28 | 2007-12-28 | Ammoniacal nanometer composite oxides sensitive material |
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| Publication Number | Publication Date |
|---|---|
| CN101183116A true CN101183116A (en) | 2008-05-21 |
| CN100580455C CN100580455C (en) | 2010-01-13 |
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|---|---|---|---|
| CN200710306935A Expired - Fee Related CN100580455C (en) | 2007-12-28 | 2007-12-28 | Ammoniacal nanometer composite oxides sensitive material |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102807862A (en) * | 2012-05-29 | 2012-12-05 | 北京联合大学生物化学工程学院 | Nano sensitive material for monitoring hydrogen cyanide |
| CN102809557A (en) * | 2012-01-18 | 2012-12-05 | 北京联合大学生物化学工程学院 | Nanometer sensitive material for detecting hydrogen sulfide |
| CN103969249A (en) * | 2014-04-14 | 2014-08-06 | 北京联合大学生物化学工程学院 | Composite oxide sensitive material used for monitoring formaldehyde and ammonia simultaneously |
| CN112345590A (en) * | 2020-09-30 | 2021-02-09 | 西安工业大学 | Three-dimensional layered multi-stage TiO2Nanoflower NH3Sensitive sensor and preparation method thereof |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102809554B (en) * | 2011-11-08 | 2015-08-12 | 北京联合大学生物化学工程学院 | The nano sensitive material of biconjugate chlorphenyl trichloroethanes agricultural chemicals |
| CN102809555B (en) * | 2012-01-18 | 2015-08-12 | 北京联合大学生物化学工程学院 | A kind of nano sensitive material of monitoring carbon monoxide |
-
2007
- 2007-12-28 CN CN200710306935A patent/CN100580455C/en not_active Expired - Fee Related
Cited By (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102809557A (en) * | 2012-01-18 | 2012-12-05 | 北京联合大学生物化学工程学院 | Nanometer sensitive material for detecting hydrogen sulfide |
| CN102809557B (en) * | 2012-01-18 | 2015-01-28 | 北京联合大学生物化学工程学院 | Nanometer sensitive material for detecting hydrogen sulfide |
| CN102807862A (en) * | 2012-05-29 | 2012-12-05 | 北京联合大学生物化学工程学院 | Nano sensitive material for monitoring hydrogen cyanide |
| CN103969249A (en) * | 2014-04-14 | 2014-08-06 | 北京联合大学生物化学工程学院 | Composite oxide sensitive material used for monitoring formaldehyde and ammonia simultaneously |
| CN103969249B (en) * | 2014-04-14 | 2016-07-13 | 北京联合大学生物化学工程学院 | For monitoring the composite oxides sensitive material of formaldehyde and ammonia simultaneously |
| CN112345590A (en) * | 2020-09-30 | 2021-02-09 | 西安工业大学 | Three-dimensional layered multi-stage TiO2Nanoflower NH3Sensitive sensor and preparation method thereof |
| CN112345590B (en) * | 2020-09-30 | 2024-01-26 | 西安工业大学 | Three-dimensional layered multi-stage TiO 2 Nano flower NH 3 Sensor and preparation method thereof |
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| Publication number | Publication date |
|---|---|
| CN100580455C (en) | 2010-01-13 |
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