CN104297318A - Preparation method of network-structure nano-material for gas sensor - Google Patents
Preparation method of network-structure nano-material for gas sensor Download PDFInfo
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- CN104297318A CN104297318A CN201410454502.1A CN201410454502A CN104297318A CN 104297318 A CN104297318 A CN 104297318A CN 201410454502 A CN201410454502 A CN 201410454502A CN 104297318 A CN104297318 A CN 104297318A
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Abstract
The invention relates to a preparation method of a network-structure nano-material for a gas sensor. The preparation method comprises the steps: placing a metal nitrate in a reactor, and adding alcohol and water for volume metering until the concentration is 0.5 mol/L; and then adding an egg membrane into the solution, dipping for 1-2 hours, then taking out the egg membrane, naturally drying in air, then placing in a tubular furnace, controlling the heating-up rate at 3-4 DEG C/s, heating up to 640-660 DEG C, carrying out calcination for 1-2 hours, and naturally cooling to a room temperature. Compared with the prior art, the preparation method has the advantages of simple process, convenient and concise product processing, easily controlled conditions, no pollution to the environment, high sensitivity, and short response and recovery time, can be used for large-scale production, and has strong universality and development prospects.
Description
Technical field
The present invention relates to a kind of nano-oxide synthesis technical field, especially relating to a kind of take eggshell membrane as the method for the three-dimensional netted nano-metal-oxide of template fabricated in situ gas sensor.
Background technology
Sensing technology is the comprehensive branch of learning relating to the multi-door subjects such as physics, electronics, materialogy, chemistry, it is a new and high technology subject, received the concern of many countries such as the U.S., China is also classified as Research on Sensing as one of " 95 " state key science and technology item.Wherein, gas sensing be sensing technology an important branch it can convert the information such as the concentration of gas to electric signal, obtain the exist situation of this gas in atmospheric environment whereby, thus carry out detecting, warning etc.Through the development of over half a century, gas sensing has had hundreds of, have highly sensitive, the response time is fast, the advantage such as easy to use.
In the accident of well ore deposit, 70% is all caused by gas explosion, and methane is the principal ingredient of gas, accounts for 95%.When the methane being mixed with 5-16% in air to be blasted; CO is the principal ingredient causing gas poisoning, poisoning rear death by suffocation; Industrial expansion makes a large amount of coal burning, in air, discharge a large amount of SO
2, H
2s etc., contaminated environment; Detect driver and whether can use gas sensor in drunk driving etc. aspect.
The core of gas sensor is gas sensitive.The more of research is Metal oxide semiconductor gas-sensitiveness material, overcomes the factors such as organic material sensor for temperature is unstable.Wherein, the more and more perfect of research is SnO
2system, ZnO system, Fe
2o
3system, in recent years to In
2o
3research also more.SnO
2be the semiconductor material that investigation and application is maximum, add the noble metals such as Pt, Pd and effectively improve CO, Cl
2, NH
3, H
2s, etc. the detection sensitivity of inorganic gas and the organic gas such as ethanol, toluene and response time, but noble metal is expensive, and in the environment some composition (as NO
2, SO
2deng) effect under to there is catalytic performance decline phenomenon.Poisoning due to catalyzer, can make the long-term reliability of element be damaged.
Have bibliographical information, the nanocrystal of layering, porous and hollow-core construction can promote disperse and the reaction kinetics of gas, and has very high specific surface area, thus can improve sensitivity and the response recovery characteristics of gas sensor.So research layering, porous and hollow structure material have important directive function to new gas sensor.
Summary of the invention
In order to overcome the defect that prior art exists, the invention provides a kind of preparation method of gas sensor network structure nanometer material.
A preparation method for gas sensor network structure nanometer material, is characterized in that, comprise the following steps:
(1) metal nitrate is placed in reactor, adding alcohol and water, to be settled to concentration be 0.5mol/L;
(2) in the obtained solution of step (1), add eggshell membrane, flood taking-up after 1 ~ 2 hour, naturally dry;
(3) be placed in tubular furnace by processing through step (2) the egg shell inner membrance obtained, controlling heating rate is 3 ~ 4 DEG C/s, is warming up to 640 ~ 660 DEG C of calcinings 1 ~ 2 hour, naturally cools to room temperature.
Metal nitrate described in step (1) is nitric acid tin, or indium nitrate, or the mixture solution of the two.
Alcohol described in step (1) is one or both mixing in ethanol, isopropyl alcohol, ethylene glycol.
The volume ratio of the alcohol and water described in step (1) is 1:5 ~ 1:9.
Described hydrochloric acid solution is the hydrochloric acid solution of massfraction 7-9%.
In the present invention, described nitrate, alcohol, hydrochloric acid are chemical pure.
The structure of the inventive method products therefrom, pattern, composition characterize, and select X-ray powder diffraction (XRD), scanning electron microscope (SEM), N respectively
2the means such as adsorption specific surface area tester (BET) characterize.
Compared with prior art, the present invention has the following advantages:
(1) current business-like gas sensitive is mixed with catalyzer mostly, as noble metal, metal oxide etc., to improve sensitivity and to shorten response recovery time.The present invention has prepared pure mesh nano indium oxide, tin oxide and tin indium oxide, improves partial sensitivity and shortens partial response time, not carrying out the doping of precious metals pt, Pd or other rare earth metals, be conducive to cost-saving;
(2) indium oxide, tin class N-type semiconductor are occurred in surperficial chemical change and relate to two kinds of key reactions, the oxygen in air captures electronics on surface, becomes chemically adsorbing oxygen: O
2+ 2e → 2 (O
-) ads, the negative oxygen ion of ADSORPTION STATE is that sheet electron concentration reduces, and material surface conductance changes, then with gas generation respective change:
R+ (O
-) ads → R (O) ads+e, the Web materials that the present invention obtains is conducive to obtaining large specific surface, is more conducive to the absorption of gas, diffusion, and the transmission transfer of electronics or negative oxygen ion, shortens the response time; Also be conducive to gas to be pulled out rapidly, shorten release time, make response safer and more effective;
(3) the present invention adopts simple inorganic salts as reactant respectively, has very strong versatility;
(4) product that prepared by the present invention has good chemical property, as the electrode material of fuel cell, can have vast potential for future development and application space;
(5) present invention process is simple, and product process facilitates simple and direct, is suitable for medium scale development.
Accompanying drawing explanation
Fig. 1 is the SEM photo of egg shell inner membrance;
Fig. 2 is the SEM photo that embodiment 1 prepares product;
Fig. 3 is the SEM photo that embodiment 2 prepares product;
Fig. 4 is the SEM photo that embodiment 3 prepares product;
Fig. 5 is the XRD figure that embodiment 1 prepares product;
Fig. 6 is the XRD figure that embodiment 2 prepares product;
Fig. 7 is the XRD figure that embodiment 3 prepares product;
Fig. 8 is that embodiment 2 prepares product to sensitivity concentration curve when 200 of methane DEG C;
Fig. 9 is that embodiment 2 prepares product to sensitivity temperature curve during methane concentration 10ppm;
Figure 10 is that embodiment 3 prepares product to sensitivity concentration curve when 250 of methane DEG C;
Figure 11 is that embodiment 3 prepares product to sensitivity temperature curve during methane concentration 10ppm.
Embodiment
Below in conjunction with the drawings and specific embodiments, the present invention is described in detail.
Embodiment 1:
With the method for egg shell inner membrance for templated synthesis mesh nano metal oxide, the method comprises the following steps:
(1) preparation of egg inner layer film: cleaned by egg shell, all takes off the film of outside, and shell puts into diluted hydrochloric acid solution, and after calcium shell dissolves, inner layer film Automatic-falling, takes out, and cleans;
(2) preparation of mesh nano tin oxide: by Sn grain ultrasonic vibration, clean surface dust, takes 1.4831g, adds 5ml red fuming nitric acid (RFNA), and glass bar stirring and dissolving obtains Sn (NO
3)
4strong solution, all be transferred in 25ml volumetric flask, add 2.5ml isopropyl alcohol, the constant volume that adds water, to shake up, be configured to the solution of concentration 0.5mol/L, appropriate egg membrane is immersed 10h, takes out, naturally dry, 650 DEG C of calcinings, control the heating rate of 3.5 DEG C ∕ s, calcine two hours, namely cooling obtains mesh nano tin oxide naturally.
As shown in Figure 1, as shown in Figure 2, XRD figure as shown in Figure 5 for the SEM photo of the mesh nano tin oxide prepared for the SEM photo of common egg inner layer film.
Embodiment 2:
With the method for egg shell inner membrance for templated synthesis mesh nano metal oxide, the method comprises the following steps:
(1) preparation of egg inner layer film: cleaned by egg shell, all takes off the film of outside, and shell puts into diluted hydrochloric acid solution, and after calcium shell dissolves, inner layer film Automatic-falling, takes out, and cleans;
(2) preparation of mesh nanometer indium oxide: take 3.7603g In (NO
3)
3, solution transfer enters in 25ml volumetric flask, adds 2.5ml ethanol, the constant volume that adds water, shakes up, be configured to the solution of concentration 0.5mol/L, appropriate egg membrane is immersed 10h, take out, naturally dry, 650 DEG C of calcinings, control the heating rate of 3.5 DEG C ∕ s, calcine two hours, naturally cool.
As shown in Figure 3, XRD figure as shown in Figure 6 for the SEM photo of the mesh nano indium oxide prepared.
Embodiment 3:
With the method for egg shell inner membrance for templated synthesis mesh nano metal oxide, the method comprises the following steps:
(1) preparation of egg inner layer film: cleaned by egg shell, all takes off the film of outside, and shell puts into diluted hydrochloric acid solution, and after calcium shell dissolves, inner layer film Automatic-falling, takes out, and cleans;
(2) preparation of mesh nanometer tin indium oxide: the Sn grain taking 1.4831g ultrasonic cleaning, adds 5ml red fuming nitric acid (RFNA), and glass bar stirring and dissolving obtains Sn (NO
3)
4solution, takes 3.7603g In (NO
3)
3, dissolve, be transferred in 25ml volumetric flask, add 2.5ml ethylene glycol, add water constant volume, shake up, be configured to the solution of concentration 0.5mol/L, appropriate egg membrane is immersed 10h, take out, naturally dry, 650 DEG C of calcinings, control the heating rate of 3.5 DEG C ∕ s, calcine two hours, naturally cool.
As shown in Figure 4, XRD figure as shown in Figure 7 for the SEM photo of the mesh nano indium tin oxide target prepared.
Embodiment 1 ~ 3 is mixed with a small amount of water, sonic oscillation 5min, obtain pastel, draw with micro syringe on the ceramic pipe spread upon on a small quantity with platinum filament, 80 DEG C of oven dry, repeatedly smear, dry, until ceramic pipe surface scribbles uniform thin layer, be welded on pedestal together with heater strip, be placed on aging 72h on agingtable.Then three kinds of materials are measured respectively to CO, CH
4, NH
3, H
2s, ethanol, toluene air-sensitive performance, draw same concentration time sensitivity temperature curve and optimum temperature under sensitivity concentration curve.
Mesh nano indium oxide to sensitivity temperature curve when sensitivity concentration curve when 200 of methane DEG C and concentration 10ppm respectively as shown in Figure 8 and Figure 9.According to s=(Vg-Va)/Va, in known Fig. 8, the sensitivity of variable concentrations is respectively 6.80,6.90,10.49,11.12,11.92, and along with the increase of concentration, sensitivity also increases; Sensitivity in Fig. 9 during different temperatures is respectively 6.89,7.67,8.10,16.17, and along with the rising of temperature, sensitivity increases.
Mesh nano tin indium oxide to sensitivity temperature curve when sensitivity concentration curve when 250 of methane DEG C and concentration 10ppm as shown in Figure 10 and Figure 11.According to s=(Vg-Va)/Va, in known Figure 10, the sensitivity of variable concentrations is respectively 7.29,10.20,28.06,41.79,41.00, and along with the increase of concentration, sensitivity first increases, after have downtrending; Sensitivity in Figure 11 during different temperatures is respectively 82.56,28.09,9.23, along with the rising of temperature, and sensitivity decrease.
Embodiment 4:
With the method for egg shell inner membrance for templated synthesis mesh nano metal oxide, the method comprises the following steps:
(1) tin grain is gone out surface dirt through sonic oscillation, then adding red fuming nitric acid (RFNA) preparation, to obtain concentration be 0.28g/ml, and be then placed in volumetric flask, add the isopropyl alcohol of 1/10 liquor capacity, adding water and being settled to concentration is 0.5mol/L;
(2) cleaned by egg shell, all taken off by the film of outside, shell puts into the hydrochloric acid solution that massfraction is 7%, after calcium shell dissolves, inner layer film Automatic-falling, takes out afterwash, then in the obtained solution of step (1), add the inner membrance of egg shell, take out after dipping 8h, naturally dry;
(3) be placed in tubular furnace by processing through step (2) the egg shell inner membrance obtained, controlling heating rate is 3.5 DEG C/s, is warming up to 650 DEG C of calcinings two hours, naturally cools to room temperature.
Embodiment 5:
With the method for egg shell inner membrance for templated synthesis mesh nano metal oxide, it is characterized in that, the method comprises the following steps:
(1) tin grain is gone out surface dirt through sonic oscillation, then adding red fuming nitric acid (RFNA) preparation, to obtain concentration be 0.3g/ml, add indium nitrate wherein again, the concentration controlling indium nitrate is 0.76 g/ml, then be placed in volumetric flask, add the ethanol of 1/10 liquor capacity, adding water and being settled to concentration is 0.5mol/L;
(2) cleaned by egg shell, all taken off by the film of outside, shell puts into the hydrochloric acid solution that massfraction is 9%, after calcium shell dissolves, inner layer film Automatic-falling, takes out afterwash, then in the obtained solution of step (1), add the inner membrance of egg shell, take out after dipping 10h, naturally dry;
(3) being placed in tubular furnace by processing through step (2) the egg shell inner membrance obtained, controlling heating rate 3.5 DEG C/s, be warming up to 650 DEG C of calcining 2h, naturally cool to room temperature.
Claims (5)
1. a gas sensor preparation method for network structure nanometer material, is characterized in that, comprise the following steps:
(1) metal nitrate is placed in reactor, adding alcohol and water, to be settled to concentration be 0.5mol/L;
(2) in the obtained solution of step (1), add eggshell membrane, flood taking-up after 1 ~ 2 hour, naturally dry;
(3) be placed in tubular furnace by processing through step (2) the egg shell inner membrance obtained, controlling heating rate is 3 ~ 4 DEG C/s, is warming up to 640 ~ 660 DEG C of calcinings 1 ~ 2 hour, naturally cools to room temperature.
2. the gas sensor preparation method of network structure nanometer material according to claim 1, it is characterized in that, the metal nitrate described in step (1) is nitric acid tin, or indium nitrate, or the mixture solution of the two.
3. the gas sensor preparation method of network structure nanometer material according to claim 1, is characterized in that, the alcohol described in step (1) is one or both mixing in ethanol, isopropyl alcohol, ethylene glycol.
4. the gas sensor preparation method of network structure nanometer material according to claim 1, it is characterized in that, the volume ratio of the alcohol and water described in step (1) is 1:5 ~ 1:9.
5. the gas sensor preparation method of network structure nanometer material according to claim 1, it is characterized in that, described hydrochloric acid solution is the hydrochloric acid solution of massfraction 7-9%.
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Cited By (2)
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| CN107880318A (en) * | 2017-11-07 | 2018-04-06 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of hydrogen sulfide gas sensing material of biomass carrying inorganic particle and products thereof and application |
| CN110455978A (en) * | 2019-06-30 | 2019-11-15 | 北京联合大学 | A kind of low-temperature catalyzed luminous cross sensitivity material of benzene and ammonia |
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