CN104803420A - Method for preparing manganese dioxide nano-material with high ammonia gas specific response - Google Patents
Method for preparing manganese dioxide nano-material with high ammonia gas specific response Download PDFInfo
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- CN104803420A CN104803420A CN201510186075.8A CN201510186075A CN104803420A CN 104803420 A CN104803420 A CN 104803420A CN 201510186075 A CN201510186075 A CN 201510186075A CN 104803420 A CN104803420 A CN 104803420A
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- specificly
- titanium dioxide
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- nanometer titanium
- ammonia
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Abstract
The invention relates to a method for preparing a manganese dioxide nano-material with high ammonia gas specific response. The method comprises the following steps: (1) preparation of solutions: preparing a potassium permanganate solution and a sodium sulfite solution; (2) synthesis of a rodlike manganese dioxide nano-composite material: putting the potassium permanganate solution and the sodium sulfite solution into a reaction kettle, adding polyvinylpyrrolidone into the reaction kettle to serve as a surfactant, carrying out mixing with ultrasonic sound till the obtained mixture is uniform, putting the reaction kettle into an oven, keeping the temperature at a specific value for a certain time, cooling to the room temperature after reaction is finished, centrifuging a sample, carrying out washing and drying, and collecting the product which is the manganese dioxide nano-material with high ammonia gas specific response. Compared with the prior art, the rodlike manganese dioxide nano-composite material is synthesized according to the hydrothermal method, so that the appearance of the product can be controlled. Moreover, the manganese dioxide nano-material has high NH3 specific response, thereby being capable of detecting gas existence under the condition that the gas concentration is very low.
Description
Technical field
The present invention relates to a kind of preparation method of manganese bioxide material, especially relate to a kind of preparation method ammonia to the nanometer titanium dioxide manganese material of specificly-response.
Background technology
The mankind are while material progress high speed development, and the standard of living of people also improves day by day.Meanwhile also bring very serious pollution to the earth, topsoil, water pollutions be all wherein endanger larger.In addition, a lot of people all can be had every year to die from explosion of coal mines, carbon monoxide poisoning etc. mishap, if can check out the existence of these gases in time and give the alarm, so loss of life and personal injury number can greatly reduce.The detection method of past to poisonous and harmful gas-liquid has infrared absorption method, electrochemical methods etc., but these method detection speeds are slow, equipment is complicated, cost is high.Now, cost is low, and highly sensitive gas sensor just arises at the historic moment.
Gas sensor is a kind of sensor detecting specific gas.It mainly comprises semiconductor gas sensor, catalytic combustion type gas sensor and Electro-chemical Gas Sensor etc., and wherein maximum are semiconductor gas sensors.Its application mainly contains: the detection of ethanol in the detection of the detection of CO (carbon monoxide converter) gas, the detection of methane gas, coal gas, the detection of freonll-11, expiration, the detection of human oral cavity halitosis etc.
The oxide compound of manganese has good response to specificity gas, can be used for researching and developing nanometer gas sensitive device.Wherein Manganse Dioxide is as a kind of transition metal oxide, is widely used in a lot of field.It can be applied to ion-exchange, be conventional commercial catalysts.The Manganse Dioxide of nanoscale is good electrode materials, as ultracapacitor, can have good electrical property; The effect of its catalyze and degrade organic pollutants is also fine.
Application number be 200610086152.3 Chinese patent disclose a kind of method preparing nano-manganese dioxide, refer in particular to Sodium Metabisulfite (NA
2s
2o
5) and potassium permanganate (KMNO
4) be raw material, prepare nanometer MNO by W/O emulsion template technology
2microballoon.It is characterized in that preparing three kinds of solution respectively.Aqueous phase 1 (WP-1): prepare a certain amount of 0.5 ~ 1.5MOL/L Sodium Metabisulfite (NA
2s
2o
5) aqueous solution.Oil phase (OP): containing the hexane solution 20 ~ 120ML of appropriate SPAN80.Aqueous phase 2 (WP-2): prepare a certain amount of 0.2 ~ 0.8MOL/LKMNO wherein containing appropriate triton x-100 (TX-100)
4the aqueous solution.Be 1: 1 ~ 6 add emulsification bottle by volume by aqueous phase 1 (WP-1) and oil phase (OP), carry out emulsify at a high speed, obtained w/o type milk sap, slowly join in the aqueous phase (WP-2) of constant temperature 20-80 DEG C again, wherein the ratio of emulsion and aqueous phase (WP-2) is 0.7 ~ 2.4: 1.After mixing ageing 1 ~ 3H, centrifugation, washing, dry.Nanometer MNO prepared by this invention
2pattern be spheroid, smooth surface, size is even, and median size is about 20 ~ 250NM.Because this patent uses W/O emulsion template method, reaction conditions is harsher, is affected by the external environment larger.
Summary of the invention
Object of the present invention be exactly in order to overcome above-mentioned prior art exist defect and a kind of preparation method ammonia to the nanometer titanium dioxide manganese material of specificly-response is provided.
Object of the present invention can be achieved through the following technical solutions:
Ammonia is had to a preparation method for the nanometer titanium dioxide manganese material of specificly-response, comprises the following steps:
(1) configuration of solution: configuration potassium permanganate solution and sodium sulfite solution;
(2) synthesis of bar-shaped nano material of manganese dioxide: potassium permanganate solution and sodium sulfite solution are put into reactor, add PVP (PVP) as tensio-active agent, ultrasonicly make it mix, put into baking oven, and under specified temp held for some time, reaction terminates, be cooled to room temperature, sample is carried out centrifugal, washing, drying, collects product obtains having ammonia the nanometer titanium dioxide manganese material of specificly-response.
In described potassium permanganate solution and sodium sulfite solution, solvent is deionized water.
Described potassium permanganate solution concentration is 0.01 ~ 0.02mol/L, is preferably 0.01mol/L.
Described sodium sulfite solution concentration is 0.01 ~ 0.02mol/L, is preferably 0.015mol/L.
The volume of taking of described potassium permanganate solution and sodium sulfite solution is 1:1.
Described tensio-active agent PVP and the mass ratio of potassium permanganate solution are 1:(1 ~ 2), be preferably 1:1.58.
Ultrasonic time described in step (2) is 5 ~ 30 minutes.
Specified temp described in step (2) is 160 ~ 200 DEG C, is preferably 180 DEG C.
In step (2), soaking time is 3 ~ 5 hours, is preferably 4 hours.
Nano-manganese dioxide can be explained by transition metal Semiconductive Theory the specificly-response of ammonia.In atmosphere, gas sensitive can oxygen molecule in absorbed air on its surface, the adsorb oxygen of material surface can electronics in attractive material, thus causes carrier concentration and electron mobility to reduce, and then is that the resistance of material increases.When the ammonia of this material, ammonia can with material surface adsorb oxygen generation redox reaction, the quantity of surface adsorbed oxygen is reduced, discharge the electronics that it attracts, increase carrier concentration and electron mobility, be that material resistance value reduces, therefore the response to ammonia can be realized according to the change of measuring material resistance value.In experiment, nano material is prepared to gas sensor.Connect with fixed value resistance and access metering circuit, circuit two ends institute making alive immobilizes, and by measuring before and after material ammonia, the change of fixed value resistance both end voltage, can reflect manganese bioxide material and respond the gas sensing property of ammonia.
Compared with prior art, the present invention has the following advantages and beneficial effect:
1, present invention achieves and utilize common sylvite and sulphite to be presoma, and add tensio-active agent PVP and carry out Morphological control, by hydrothermal method, synthesized bar-shaped nano material of manganese dioxide with this starting material first.
2, the pattern of method of the present invention to product has very high control.
3, the present invention adopts simple inorganic salt as reactant, has very strong versatility.
4, the product that prepared by the present invention as the gas sensitive of air-sensitive original paper, can have comparatively vast potential for future development and application space.
5, technique of the present invention is simple, and preparation condition is general, and product morphology is stable, purity is high, and product process is convenient succinct, is suitable for medium-scale industrial production.
6, method of the present invention has mild condition, homogeneous heating, efficient energy-saving, is easy to the features such as control.
Accompanying drawing explanation
Fig. 1 is the SEM photo of the product that product obtains under the multiple of 5um.
Fig. 2 is the SEM photo of the product that product obtains under the multiple of 10um.
Fig. 3 is the Fourier transform infrared spectroscopy figure (FTIR) of product.
Fig. 4 is X-ray diffraction (XRD) collection of illustrative plates of product.
Fig. 5 be product at 200 DEG C, ammonia concentration is under the condition of 500ppm, the time dependent curve of voltage.
Fig. 6 be product at 200 DEG C, ammonia concentration is under the condition of 500ppm, the time dependent curve of resistance.
Fig. 7 be product at 200 DEG C, ammonia concentration is under the condition of 500ppm, and this air-sensitive original paper is to the response collection of illustrative plates of gas with various.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment
Ammonia is had to a preparation method for the nanometer titanium dioxide manganese material of specificly-response, concrete steps are as follows:
(1) configuration of solution: take deionized water as solvent, the configuration potassium permanganate solution of 0.01mol/L and each 8ml of sodium sulfite solution of 0.015mol/L, and mix.
(2) synthesis of bar-shaped nano material of manganese dioxide:
Potassium permanganate solution and sodium sulfite solution are put into the reactor of 20ml, add PVP (PVP) 0.01g as tensio-active agent, within ultrasonic 5 minutes, make it mix.Put into baking oven, and be incubated 4 hours at 180 DEG C of temperature, obtain nanometer titanium dioxide manganese material ammonia to specificly-response.
Fig. 1 is the SEM photo that product obtains product under the multiple of 5um; Fig. 2 is the SEM photo that product obtains product under the multiple of 10um, and from above-mentioned picture, the cross-sectional diameter of the bar-shaped dioxy that we synthesize under can seeing this condition is about 900nm.Fig. 3 is the FTIR collection of illustrative plates of product, in figure 3417 and 1600-1700cm
-1the corresponding Manganse Dioxide in peak in the flexible and flexural vibration of O-H key of molecular water; 523 and 463cm
-1the corresponding MnO in peak
6the stretching vibration of Mn-O key in octahedron.Fig. 4 is the XRD figure sheet of product, illustrates that product is Manganse Dioxide really.
The present embodiment product is at 200 DEG C, ammonia concentration is under the condition of 500ppm, the time dependent curve of voltage as shown in Figure 5, the time dependent curve of resistance as shown in Figure 6, this air-sensitive original paper to the response collection of illustrative plates of gas with various as shown in Figure 7, can find out, the present embodiment product has specificly-response to ammonia, to other test gas if methane, nitrogen, oxygen are all without response.
Embodiment 2
Ammonia is had to a preparation method for the nanometer titanium dioxide manganese material of specificly-response, comprises the following steps:
(1) configuration of solution: take deionized water as solvent, configuration concentration is the potassium permanganate solution of 0.01mol/L and concentration is the sodium sulfite solution of 0.01mol/L, gets same volume and mixes;
(2) synthesis of bar-shaped nano material of manganese dioxide: potassium permanganate solution and sodium sulfite solution are put into reactor, add PVP (PVP) as tensio-active agent, the mass ratio of tensio-active agent PVP and potassium permanganate solution is 1:1, within ultrasonic 15 minutes, it is made to mix, put into baking oven, and 5 hours are incubated at 160 DEG C, reaction terminates, be cooled to room temperature, sample is carried out centrifugal, washing, dry, collect product obtains having ammonia the nanometer titanium dioxide manganese material of specificly-response.
Embodiment 3
Ammonia is had to a preparation method for the nanometer titanium dioxide manganese material of specificly-response, comprises the following steps:
(1) configuration of solution: take deionized water as solvent, configuration concentration is the potassium permanganate solution of 0.02mol/L and concentration is the sodium sulfite solution of 0.02mol/L, gets same volume and mixes;
(2) synthesis of bar-shaped nano material of manganese dioxide: potassium permanganate solution and sodium sulfite solution are put into reactor, add PVP (PVP) as tensio-active agent, the mass ratio of tensio-active agent PVP and potassium permanganate solution is 1:2, within ultrasonic 30 minutes, it is made to mix, put into baking oven, and 3 hours are incubated at 200 DEG C, reaction terminates, be cooled to room temperature, sample is carried out centrifugal, washing, dry, collect product obtains having ammonia the nanometer titanium dioxide manganese material of specificly-response.
Above-mentioned is can understand and use invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiments and need not through performing creative labour.Therefore, the invention is not restricted to above-described embodiment, those skilled in the art, according to announcement of the present invention, do not depart from improvement that scope makes and amendment all should within protection scope of the present invention.
Claims (9)
1. ammonia is had to a preparation method for the nanometer titanium dioxide manganese material of specificly-response, it is characterized in that, comprise the following steps:
(1) configuration of solution: configuration potassium permanganate solution and sodium sulfite solution;
(2) synthesis of bar-shaped nano material of manganese dioxide: potassium permanganate solution and sodium sulfite solution are put into reactor, add PVP as tensio-active agent, ultrasonicly make it mix, put into baking oven, and under specified temp held for some time, reaction terminates, be cooled to room temperature, sample is carried out centrifugal, washing, drying, collects product obtains having ammonia the nanometer titanium dioxide manganese material of specificly-response.
2. a kind of preparation method ammonia to the nanometer titanium dioxide manganese material of specificly-response according to claim 1, is characterized in that, in described potassium permanganate solution and sodium sulfite solution, solvent is deionized water.
3. a kind of preparation method ammonia to the nanometer titanium dioxide manganese material of specificly-response according to claim 1, it is characterized in that, described potassium permanganate solution concentration is 0.01 ~ 0.02mol/L.
4. a kind of preparation method ammonia to the nanometer titanium dioxide manganese material of specificly-response according to claim 1, it is characterized in that, described sodium sulfite solution concentration is 0.01 ~ 0.02mol/L.
5. a kind of preparation method ammonia to the nanometer titanium dioxide manganese material of specificly-response according to claim 1, is characterized in that, the volume of taking of described potassium permanganate solution and sodium sulfite solution is 1:1.
6. a kind of preparation method ammonia to the nanometer titanium dioxide manganese material of specificly-response according to claim 1, is characterized in that, described tensio-active agent PVP and the mass ratio of potassium permanganate solution are 1:(1 ~ 2).
7. a kind of preparation method ammonia to the nanometer titanium dioxide manganese material of specificly-response according to claim 1, it is characterized in that, the ultrasonic time described in step (2) is 5 ~ 30 minutes.
8. a kind of preparation method ammonia to the nanometer titanium dioxide manganese material of specificly-response according to claim 1, it is characterized in that, the specified temp described in step (2) is 160 ~ 200 DEG C.
9. a kind of preparation method ammonia to the nanometer titanium dioxide manganese material of specificly-response according to claim 1, is characterized in that, in step (2), soaking time is 3 ~ 5 hours.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686679A (en) * | 2020-06-01 | 2020-09-22 | 山西大学 | Preparation method and application of manganese dioxide aerogel material |
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| CN101950682A (en) * | 2010-09-09 | 2011-01-19 | 江西财经大学 | Preparation method of super-capacitor manganese oxide material |
| CN102259929A (en) * | 2011-06-27 | 2011-11-30 | 北京工业大学 | Method for preparing porous nano or submicron rod-like manganese oxide |
| CN102583560A (en) * | 2011-01-06 | 2012-07-18 | 河南师范大学 | Spherical gamma-MnO2 particle and preparation method thereof |
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2015
- 2015-04-17 CN CN201510186075.8A patent/CN104803420A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101950682A (en) * | 2010-09-09 | 2011-01-19 | 江西财经大学 | Preparation method of super-capacitor manganese oxide material |
| CN102583560A (en) * | 2011-01-06 | 2012-07-18 | 河南师范大学 | Spherical gamma-MnO2 particle and preparation method thereof |
| CN102259929A (en) * | 2011-06-27 | 2011-11-30 | 北京工业大学 | Method for preparing porous nano or submicron rod-like manganese oxide |
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| SHUHUI LIANG ET AL.: "Effect of Phase Structure of MnO2 Nanorod Catalyst on the Activity for CO Oxidation", 《J. PHYS. CHEM. C》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111686679A (en) * | 2020-06-01 | 2020-09-22 | 山西大学 | Preparation method and application of manganese dioxide aerogel material |
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