CN103966697A - Nanocrystalline metal oxide with p-n composite structure, preparation method and application of nanocrystalline metal oxide - Google Patents
Nanocrystalline metal oxide with p-n composite structure, preparation method and application of nanocrystalline metal oxide Download PDFInfo
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- CN103966697A CN103966697A CN201410206765.0A CN201410206765A CN103966697A CN 103966697 A CN103966697 A CN 103966697A CN 201410206765 A CN201410206765 A CN 201410206765A CN 103966697 A CN103966697 A CN 103966697A
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- nanofiber
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Abstract
The invention provides nanocrystalline metal oxide with a p-n composite structure and a preparation method of the nanocrystalline metal oxide. The nanocrystalline metal oxide with the p-n composite structure is prepared from nanofiber which is formed by binding SnO2 nano particles and Co3O4 nano particles in series, has the diameter of 100-200nm and is indicative of n-SnO2@p-Co3O4. The n-SnO2@p-Co3O4 composite nanofiber is prepared by means of electrostatic spinning, cobalt salt and tin salt are dissolved into N,N-dimethylformamide (DMF) to prepare a spinning solution, and the components are spun in electrostatic spinning equipment and are calcined to obtain n-SnO2@p-Co3O4 nanofiber. A gas sensor is made of the n-SnO2@p-Co3O4 nanofiber material, so that the gas sensor is high in sensitivity on low-concentration CO at low operation temperature and is suitable for detecting trace of carbon monoxide in environment.
Description
Technical field
The present invention relates to semiconductor composite nano metal oxide technology of preparing and sensing technology Application Areas, be specifically related to p-n composite construction nano-metal-oxide and preparation method thereof, and used as the sensitive material of semiconductor carbon monoxide transducer, measure micro CO gas content in environment.
Background technology
Up to the present, the research taking metal oxide semiconductor as basic gas sensitive mainly concentrates on SnO
2, ZnO, WO
3and TiO
2on N-shaped semiconductor, and to particularly Co of p-type semiconductor
3o
4the research of sensor is also in the starting stage, and associated documents are also little.Co
3o
4being a kind of transition metal oxide, is cubic system, and space group Fd3m, has normal spinel structure, and divalent cobalt ion occupies four sides position, and trivalent cobalt ions occupies octahedral position, has higher hydration heat.Co
3o
4electrode material, solid electrolyte sensor, electrochromic device, solar absorption and the dyestuff aspect of catalysis in a lot of fields,, lithium battery all have very large potential application.Especially cobaltosic oxide as a kind of p-type semiconductor to environment harmful gas, as CO, NO
2deng there being responsive response, but its remolding sensitivity N-shaped semiconductor is low.Therefore the air-sensitive performance that, how to improve cobaltosic oxide becomes study hotspot.Research in nearly ten years is found when p-type semiconductor and N-shaped semiconductor compound tense, two kinds of crystal grain contact, crystal grain boundary will produce hetero-junctions, for chemically adsorbing oxygen provides extra adsorption plane, and due to the generation of p-n junction, cause crystal boundary potential barrier to raise, and promoted electronics in adsorb oxygen and intercrystalline transfer, be conducive to gas-sensitive reaction, thereby improve air-sensitive performance and be widely used in detecting various gas.
In semiconductor gas sensor field, p-n hetero-junctions composite semiconductor material causes showing great attention to of people, is considered to the novel semi-conductor gas sensitive of the tool prospect of pernicious gas in testing environment.In recent years, people conduct extensive research p-n hetero-junctions, and have made some progress.The people such as Y.Q.Liang (Nanoscale, 2013,5,10916 – 10926) prepare the TiO of homogeneous by anodised method
2nanotube, and as template at 120 DEG C and cobalt nitrate hydro-thermal reaction 5h, generate monodimension nano stick, obtain p-n hetero-junctions Co through calcining
3o
4@TiO
2compound, but the method is carried out hydro-thermal reaction after adopting first anodic oxidation, and synthesis step is loaded down with trivial details.The people such as Z.Lou (New.J.Chem., 2012,36,1003 – 1007), taking stannic chloride and nickel nitrate as raw material, make p-NiO/n-SnO at 140 DEG C of Water Under thermal response 24h
2heterojunction composite.The method reaction time is long.Material prepared by these two kinds of methods is all compound p-type semiconductor on the semi-conductive basis of N-shaped, forms p-n hetero-junctions.
Electrostatic spinning is a kind of unique, and simple and easy, general method, can prepare diameter homogeneous, and draw ratio is large, and have different content, finely dispersed You Ji ∕ inorganic, Wu the 1-dimention nano fiber of Ji ∕ inorganic compounding.As a kind of approach of preparing nanofiber, because low energy efficiently gains great popularity, and the 1-dimention nano fiber of preparing due to method of electrostatic spinning is to be in series by oxide particle, is difficult for reuniting and bonding, can improve better the specific area of material, thereby improve the gas-sensitive property of material.So, utilize method of electrostatic spinning to prepare p-n hetero-junctions composite metal oxide a kind of good method that improves material gas-sensitive property of can yet be regarded as.
The present invention intends adopting method of electrostatic spinning compound N-shaped semiconductor tin ash on p-type cobaltosic oxide, prepares p-n junction composite oxides, thereby improves the air-sensitive of cobaltosic oxide.
Summary of the invention
The object of the present invention is to provide a kind of p-n composite construction nano-metal-oxide and preparation method thereof, and used as the sensing element of semiconductor gas sensor, micro CO gas content in testing environment.
P-n composite construction nano-metal-oxide provided by the invention is by SnO
2and Co
3o
4the diameter that nano particle is connected into is 100-200nm, is expressed as n-SnO
2@p-Co
3o
4nanofiber.
The preparation method of p-n composite construction nano-metal-oxide, concrete steps are as follows:
A. in reactor, solubility cobalt salt is dissolved in to (DMF) in DMF, is made into the solution that concentration is 1.0～2.0mol/L, stir 2～6 hours, under stirring condition, add pink salt, making the mass ratio of cobalt salt and pink salt in solution is 1～10:1, continues to stir 1～3 hour, then add thickener, the addition of thickener adds 0.1～0.5g thickener according to every milliliter of DMF, continues to stir 4～8 hours, obtains clear solution.
Described solubility cobalt salt is cobalt nitrate [Co (NO
3)
26H
2o], cobalt acetate [Co (CH
3cOO)
24H
2o], cobalt chloride (CoCl
26H
2and cobaltous sulfate (CoSO O)
47H
2o) one in; Wherein pink salt is stannous chloride (SnCl
22H
2and stannic chloride (SnCl O)
45H
2o) one in; Wherein thickener is polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylamide (PAM).
B. in electrospinning device, the clear solution by steps A carries out spinning, and under electrostatic pressure 10～20kV, clear solution is pressed 0.0002～0.0008mms by injection-tube
-1fltting speed sprays by spinning head, solidify distance (distance between spinning head and gathering-device) 15～25cm, on masking foil, collect blue fiber membrane, this product room temperature is placed to 12～36h, be warming up to 400～600 DEG C of calcining 2-4 hour according to the heating rate of 4-8 DEG C/min again, obtain n-SnO
2@p-Co
3o
4nanofiber.
The product obtaining is characterized as follows:
With scanning electronic microscope (SEM) observation n-SnO
2@p-Co
3o
4the surface topography of nanofiber, as Fig. 1 and Fig. 2, as seen from the figure, the diameter before the calcining of the product that obtains is 200～300nm, the product after calcining is the nanofiber that the diameter that is in series by nano particle is about 150nm.
With X-ray powder diffraction (XRD) sign n-SnO
2@p-Co
3o
4the phase structure of nanofiber and crystal formation, the results are shown in Figure 3, Co
3o
4each characteristic peak and the PDF#42-1467 of JCPDS basically identical, its main interplanar distance d value (unit: dust) 4.6670,2.8580,2.4370,2.0210,1.5557,1.4290 corresponds respectively to (111), (220), (311), (400), (511), (440) crystal face of cubic system cobaltosic oxide, proves that the cobaltosic oxide obtaining is that a cube cobaltosic oxide is p-Co
3o
4, and SnO
2characteristic peak only occur that three highest peaks are respectively (110), (101), (211), learn as tetragonal crystal system n-SnO according to standard card PDF#41-1445
2, in addition from Fig. 3, do not observe other impurity peaks, illustrate that the product obtaining is pure n-SnO2@p-Co3O4.
N-SnO2@p-Co3O4 nanofiber is used as to gas sensitive
The nanofiber of collection is placed in to Muffle furnace, heats up with 3～7 DEG C/min speed, at 300～800 DEG C, keep 1～6h, obtain the n-SnO after roasting
2@p-Co
3o
4nanofiber, it is 10～15mm that this nanofiber is pressed into diameter, the thin rounded flakes that thickness is 0.5～2.0mm, makes gas sensor, the gas sensor of making is placed in to the mobile air-sensitive test macro of temperature control and measures its air-sensitive performance to reducibility gas CO.Concrete measurement result is shown in Fig. 4, shows the gas sensor that this n-SnO2@p-Co3O4 nanofiber is made, and under 180 DEG C of operating temperatures, the sensitivity of 10ppm CO is up to 594.6.This is due to n-SnO
2@p-Co
3o
4nanofiber not only has large specific area, is conducive to the absorption of carbon monoxide at material surface, and due to the generation of p-n hetero-junctions, makes material resistance in the atmosphere of carbon monoxide become rapidly large, has improved detection sensitivity.
Advantage of the present invention and beneficial effect are:
The advantages such as the electrostatic spinning preparation method that the present invention adopts has simply, facilitates, cheapness and environmentally safe, be easy to promote, and p-type semiconductor and N-shaped semi-conducting material composition generation p-n junction can improve the sensitivity that detects gas effectively, have improved significantly the lower shortcoming of p-type semiconductor remolding sensitivity.The method is for the preparation of n-SnO
2@p-Co
3o
4nanofiber there is not yet bibliographical information.This n-SnO2@p-Co3O4 nano-fiber material is made to gas sensor, compared with low concentration CO being had to high sensitivity under low operating temperature, be applicable to micro CO in testing environment.
Brief description of the drawings
Fig. 1 is the n-SnO before the calcining prepared of embodiment 1
2@p-Co
3o
4the SEM figure of nanofiber, illustration is high power SEM.
Fig. 2 is the n-SnO after the calcining prepared of embodiment 1
2@p-Co
3o
4the SEM figure of nanofiber, illustration is high power SEM.
Fig. 3 is the n-SnO after application examples 1 roasting
2@p-Co
3o
4the XRD figure of nanofiber.
Fig. 4 is the n-SnO that application examples 1 records
2@p-Co
3o
4the sensitivity curve of nanofiber to 10ppm CO.
Detailed description of the invention
Below in conjunction with instantiation, further illustrate the present invention, but the invention is not restricted to these examples.
Embodiment 1
Accurately taking 2.6080g cobalt acetate is dissolved in 10mL DMF, stir 2h, add again 0.500g stannous chloride, continue to be stirred to completely and slowly add 1.5g PVP after dissolving, continue to stir after 4h, the dark blue solution obtaining is poured in syringe, is 20kV at electrostatic pressure, and fltting speed is 0.0006mms-
1, under the condition that distance between plates is 20cm, carry out spinning.By at room temperature dry 12h of the masking foil with product, then collect product and product is placed in to Muffle furnace, heat up with 5 DEG C/min speed, at 500 DEG C, roasting 2h, obtains n-SnO
2@p-Co
3o
4product.
Its scanning electronic microscope result, as Fig. 1 and Fig. 2, is calcined front n-SnO
2@p-Co
3o
4the diameter of nanofiber is 200～300nm, and after calcining, the diameter of n-SnO2@p-Co3O4 nanofiber shortens to about 150nm, and is in series by nano particle; The XRD analysis of the n-SnO2@p-Co3O4 making the results are shown in Figure 3, and the product obtaining is the monocline tungsten oxide that degree of crystallinity is high.
Embodiment 2
Accurately take 1.3040g cobalt nitrate and be dissolved in 7mL DMF, stir 4h, then add 0.100g stannic chloride, continue to be stirred to completely after dissolving and slowly add 0.8g PVA, continue to stir after 6h, the dark blue solution obtaining is poured in syringe, be 18kV at electrostatic pressure, fltting speed is 0.0006mms
-1, under the condition that distance between plates is 18cm, carry out spinning.By at room temperature dry 24h of the masking foil with product, then collect product and product is placed in to Muffle furnace, heat up with 10 DEG C/min speed, roasting 4h at 500 DEG C, obtains n-SnO2@p-Co3O4 product.
Embodiment 3
Accurately take 1.3040g cobaltous sulfate and be dissolved in 7mL DMF, stir 6h, then add 0.300g stannic chloride, continue to be stirred to completely after dissolving and slowly add 1.0g PAM, continue to stir after 8h, the dark blue solution obtaining is poured in syringe, be 18kV at electrostatic pressure, fltting speed is 0.0010mms
-1, under the condition that distance between plates is 20cm, carry out spinning.By at room temperature dry 36h of the masking foil with product, then collect product and product is placed in to Muffle furnace, heat up with 5 DEG C/min speed, roasting 2h at 600 DEG C, obtains n-SnO2@p-Co3O4 product.
Application examples
By the n-SnO after embodiment 1 roasting
2@p-Co
3o
4product is pressed into diameter and is about the thin rounded flakes that 13mm, thickness are 0.5mm, at the both sides of circle sheet welding top electrode, makes gas sensor.The gas sensor of making is placed in to the quartz ampoule in tubular react furnace, pass into air or gas to be measured, constant operating current 10 μ A, the voltage value of surveying respectively them in 30～480 DEG C of Temperature Programmed Processes in air and in gas to be measured, calculate sensitivity by Ohm's law, for reducibility gas (CO), sensitivity is defined as the resistance of element in gas to be measured and the ratio of element resistance in air, and sensitivity result as shown in Figure 4.
As seen from Figure 4, n-SnO
2@p-Co
3o
4the gas sensor sensing element that powder is made is up to 594.6 to the sensitivity of 10ppm CO under 180 DEG C of operating temperatures.Illustrate that this air-sensitive original paper has good sensitivity to CO in environment, is suitable for micro CO in testing environment.
Claims (3)
1. a preparation method for p-n composite construction nano-metal-oxide, concrete steps are as follows:
A. in reactor, solubility cobalt salt is dissolved in to (DMF) in DMF, is made into the solution that concentration is 1.0～2.0mol/L, stir 2～6 hours, under stirring condition, add pink salt, making the mass ratio of cobalt salt and pink salt in solution is 1～10:1, continues to stir 1～3 hour, then add thickener, the addition of thickener adds 0.1～0.5g thickener according to every milliliter of DMF, continues to stir 4～8 hours, obtains clear solution.
Described solubility cobalt salt is cobalt nitrate [Co (NO
3)
26H
2o], cobalt acetate [Co (CH
3cOO)
24H
2o], cobalt chloride (CoCl
26H
2and cobaltous sulfate (CoSO O)
47H
2o) one in; Wherein pink salt is stannous chloride (SnCl
22H
2and stannic chloride (SnCl O)
45H
2o) one in; Wherein thickener is polyvinylpyrrolidone (PVP), polyvinyl alcohol (PVA), polyacrylamide (PAM).
B. in electrospinning device, the clear solution by steps A carries out spinning, and under electrostatic pressure 10～20kV, clear solution is pressed 0.0002～0.0008mms by injection-tube
-1fltting speed sprays by spinning head, and curing distance is 15～25cm, collects blue fiber membrane on masking foil, and this product room temperature is placed to 12～36h, then is warming up to 400～600 DEG C of calcinings 2～4 hours according to the heating rate of 4-8 DEG C/min, obtains n-SnO
2@p-Co
3o
4nanofiber.
2. the p-n composite construction nano-metal-oxide that prepared by method according to claim 1, it is by SnO
2and Co
3o
4the diameter that nano particle is connected into is the fiber of 100～200nm.
3. an application for p-n composite construction nano-metal-oxide claimed in claim 2, this material is for making the gas sensor of sensor, for the detection of environment micro CO.
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| CN105568557A (en) * | 2015-12-22 | 2016-05-11 | 青岛大学 | Humidity-sensitive electrospun cobalt chloride micro-nanofiber membrane as well as preparation method and application thereof |
| CN107640793A (en) * | 2017-11-02 | 2018-01-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of discontinuous two-sided hetero-junctions sandwich tin ash nickel oxide tin ash and products thereof and application |
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| CN107640793A (en) * | 2017-11-02 | 2018-01-30 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of discontinuous two-sided hetero-junctions sandwich tin ash nickel oxide tin ash and products thereof and application |
| CN109085210B (en) * | 2018-07-25 | 2020-12-08 | 中国计量大学 | N-p heterogeneous core-shell structure gas-sensitive material and preparation method thereof |
| CN109085210A (en) * | 2018-07-25 | 2018-12-25 | 徐靖才 | A kind of n-p heterogeneous type core-shell structure gas sensitive and preparation method thereof |
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