CN105424763A - Preparation method of nanometer tin dioxide gas sensitive material - Google Patents

Preparation method of nanometer tin dioxide gas sensitive material Download PDF

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Publication number
CN105424763A
CN105424763A CN201510725990.XA CN201510725990A CN105424763A CN 105424763 A CN105424763 A CN 105424763A CN 201510725990 A CN201510725990 A CN 201510725990A CN 105424763 A CN105424763 A CN 105424763A
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China
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gas
carbon
sno
gas sensitive
nanometer
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CN201510725990.XA
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Inventor
王超
徐豹
栾春红
梁莹林
姜晶
杨萍
伍思昕
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University of Electronic Science and Technology of China
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University of Electronic Science and Technology of China
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    • G—PHYSICS
    • G01—MEASURING; TESTING
    • G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
    • G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
    • G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
    • G01N27/04—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance
    • G01N27/12—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance by investigating resistance of a solid body in dependence upon absorption of a fluid; of a solid body in dependence upon reaction with a fluid, for detecting components in the fluid
    • G01N27/125—Composition of the body, e.g. the composition of its sensitive layer
    • G01N27/127—Composition of the body, e.g. the composition of its sensitive layer comprising nanoparticles

Abstract

The invention discloses a preparation method of a nanometer tin dioxide gas sensitive material, and belongs to the field of semiconductor oxide gas sensitive materials. Carbon-coated SnO2 nanometer particles are prepared on the surfaces of SnO2 nanometer particles through acetylene gas by means of a chemical vapor deposition method, then the structure and feature of surface carbon materials are adjusted and controlled through annealing treatment, and the carbon-modified nanometer SnO2 gas sensitive material with the significantly-enhanced gas sensitivity is obtained. The carbon-modified nanometer SnO2 gas sensitive material is applied in the gas detection aspect for the first time. Compared with other methods for improving the performance of gas sensitive materials, such as the method of preparing a metal-oxide semiconductor film through sputtering or evaporation and the method of preparing nanometer particles of special microstructures and features and modified doping precious metal Pt, Pd and Au, the method has the advantages of being simple and low in cost, the gas sensitivity of the obtained carbon-modified SnO2 nanometer gas sensitive material is significantly improved, and the obtained carbon-modified SnO2 nanometer gas sensitive material has the wide application prospect in the field of gas sensitive materials.

Description

A kind of preparation method of nano tin dioxide gas-sensitive material
Technical field
The invention belongs to conductor oxidate gas sensitive field, be specifically related to the SnO that a kind of carbon is modified 2the preparation method of gas-sensitive nano material.
Background technology
Tin ash (SnO 2) be a kind of important semiconductor material, have the advantages such as carrier mobility is high, chemical stability good, cheap, be the focus that people study always.Meanwhile, SnO 2stable performance, gas response is high, and realizing the selective response of gas by doping, is one of most study, most popular Semiconductor gas sensors material.SnO 2belong to n-type semiconductor, major defect is Lacking oxygen and tin interstitial atom, works as SnO 2when being in air atmosphere, O 2molecule is with the form (O of chemisorption 2 -, O -, O 2-) attachment be SnO 2surface, forms depleted of electrons layer and space potential barrier, causes SnO 2conductivity reduce; After this, if when there is reducibility gas to be detected in space, surface adsorption state oxygen and reducibility gas react, and are originally got back to SnO again by the electronics that chemical adsorption states oxygen is captured 2in, cause SnO 2conductivity again raise.Therefore, by test SnO 2the change of material electric conductivity just can reach the object detecting gas and concentration thereof.
Summary of the invention
The invention provides the SnO that a kind of carbon is modified 2the preparation method of gas-sensitive nano material, is decomposed by high temperature induction acetylene gas, and the carbon granule of generation is at SnO 2surface deposition forms carbon-coating, then annealing in process in an inert atmosphere, the composition of regulation and control carbon layer on surface and pattern, finally obtains the SnO that carbon that air-sensitive performance strengthens is modified 2gas-sensitive nano material.The present invention and existing Metal oxide semiconductor gas-sensitiveness material preparation method as by sputter or Evaporation preparation metal oxide semiconductor films, sol-gal process prepare special appearance nano particle, modify doped precious metal as compared with the methods such as Pt, Pd, Au, there is the advantage that technique is simple, cost is low, and significantly can promote SnO 2the air-sensitive performance of gas sensitive.
Technical scheme of the present invention is as follows:
A preparation method for nano tin dioxide gas-sensitive material, comprises the following steps:
Step 1: by SnO 2powder is placed in vacuum tube furnace, is warming up to 200 ~ 600 DEG C under an inert atmosphere, insulation 30 ~ 60min;
Step 2: keep temperature-resistant in vacuum tube furnace, passes into the acetylene (C that inert gas that flow is 10 ~ 100mL/min and flow are 20 ~ 150mL/min simultaneously 2h 2) gas, to volume and the SnO of the acetylene passed into 2the ratio of quality when being 20 ~ 3000mL/g, stop passing into acetylene, and it is constant to maintain inert gas flow, with the rate of temperature fall cool to room temperature of 3 ~ 10 DEG C/min, namely obtains the SnO that carbon is coated 2particle powder;
Step 3: the coated SnO of the carbon that step 2 is obtained 2particle powder is placed in vacuum tube furnace, under an inert atmosphere 300 ~ 800 DEG C of annealing in process 1 ~ 12h, namely obtains carbon of the present invention and modifies SnO 2gas-sensitive nano material.
Beneficial effect of the present invention is: the present invention, by aumospheric pressure cvd method, namely passes into acetylene gas in high temperature environments, utilizes acetylene poor heat stability, is easily decomposed into carbon and hydrogen, and the carbon granule generated is at SnO 2surface deposition obtains the coated SnO of carbon 2particle, then annealing in process under an inert atmosphere, obtain the nano SnO that carbon is modified 2gas sensitive.With untreated SnO 2powder is compared, carbon decorated nanometer SnO of the present invention 2the air-sensitive performances such as gas sensitive sensitivity, selectivity are all significantly improved; Relative to other gas sensitive performance improvement method, as by sputtering or Evaporation preparation metal oxide semiconductor films, sol-gal process preparation have special microstructure appearance nano material, modify doped precious metal as methods such as Pt, Pd, Au, the present invention has the advantage that technique is simple, cost is low, and the SnO that the carbon obtained is modified 2the air-sensitive performance of gas-sensitive nano material is significantly increased, and is with a wide range of applications in gas sensitive field.
Accompanying drawing explanation
Fig. 1 is the nano SnO of carbon modification prepared by the embodiment of the present invention 1 ~ 5 2gas sensitive is to the change curve of the acetylene gas response sensitivity of 1000ppm with probe temperature, and wherein S1, S2, S3, S4 and S5 sample is respectively the sample that embodiment 1,2,3,4,5 obtains; S0 is the SnO of unmodified 2sample;
Fig. 2 is the nano SnO of carbon modification prepared by the embodiment of the present invention 1 ~ 5 2the XRD collection of illustrative plates of gas sensitive;
Fig. 3 is the nano SnO of carbon modification prepared by the embodiment of the present invention 3 2the part Raman spectrum of gas sensitive;
Fig. 4 is the nano SnO of carbon modification prepared by the embodiment of the present invention 3 2the HRTEM photo of gas sensitive.
Embodiment
Below in conjunction with drawings and Examples the present invention done and introduce further.
A preparation method for nano tin dioxide gas-sensitive material, comprises the following steps:
Step 1: by SnO 2powder is evenly distributed in quartz boat, and level is placed in vacuum tube furnace flat-temperature zone, is under the inert gas atmosphere of 10 ~ 100mL/min at flow, with the heating rate of 3 ~ 10 DEG C/min by room temperature to 200 ~ 600 DEG C, and insulation 30 ~ 60min;
Step 2: keep temperature-resistant in vacuum tube furnace, passes into the acetylene (C that inert gas that flow is 10 ~ 100mL/min and flow are 20 ~ 150mL/min simultaneously 2h 2) gas, the amount passing into acetylene gas is: every 1gSnO 2correspondence passes into 20 ~ 3000mL acetylene; Then stop passing into acetylene, and it is constant to maintain inert gas flow, with the rate of temperature fall cool to room temperature of 3 ~ 10 DEG C/min, namely obtains the SnO that carbon is coated 2powder;
Step 3: the coated SnO of the carbon that step 2 is obtained 2powder puts into quartz boat, and is placed in vacuum tube furnace, 300 ~ 800 DEG C of annealing in process 1 ~ 12h under inert gas shielding, namely obtains the nano SnO that carbon of the present invention is modified 2gas sensitive;
Step 4: the nano SnO that carbon step 3 obtained is modified 2gas sensitive is coated on Al 2o 3ceramic pipe surface, welding pin and heater strip make gas sensor, room temperature to 500 DEG C temperature range build-in test its to the response of gas; Wherein, test gas is ethanol, methane, acetylene (C 2h 2), hydrogen (H 2) etc.
Embodiment 1
A preparation method for nano tin dioxide gas-sensitive material, comprises the following steps:
Step 1: take 0.3gSnO 2powder is evenly distributed in quartz boat, quartz boat is put into vacuum tube furnace flat-temperature zone, passes into the Ar gas of 30mL/min as blanket gas, then with the speed of 5 DEG C/min by room temperature to 200 DEG C, insulation 30min;
Step 2: keep electron tubes type in-furnace temperature 200 DEG C constant, pass into the C that flow is 30mL/min simultaneously 2h 2gas and flow are the Ar oxygen mixture of 60mL/min, after 3min, stop passing into acetylene, and the flow maintaining Ar gas 60mL/min are constant, with the rate of temperature fall cool to room temperature of 3 DEG C/min, namely obtains the SnO that carbon is coated 2particle powder;
Step 3: the SnO that carbon step 2 obtained is coated 2particle powder is put into quartz boat and is placed on vacuum tube furnace, and under the Ar protection that flow is 60mL/min, 500 DEG C of annealing 2h, namely obtain the nano SnO that carbon of the present invention is modified 2gas sensitive;
Step 4: the nano SnO that carbon step 3 obtained is modified 2gas sensitive is coated on Al 2o 3ceramic pipe surface, welding pin and heater strip make gas sensor, room temperature to 500 DEG C temperature range build-in test its to the response of acetylene gas.
Fig. 1 is the nano SnO of carbon modification prepared by embodiment 1 ~ 5 2gas sensitive is to the change curve of the acetylene gas response sensitivity of 1000ppm with probe temperature; As shown in Figure 1, when temperature of reaction is 400 DEG C (embodiment 3) to prepare the air-sensitive performance of sample to acetylene of gained best, and its sensitivity first increases rear reduction with probe temperature, 370 DEG C time, reach maximal value 106.3.Fig. 2 is the nano SnO of carbon modification prepared by embodiment 1 ~ 5 2the XRD collection of illustrative plates of gas sensitive; As shown in Figure 2, contrast can obtain with standard card (PDF#41-1445), SnO 2diffraction peak is obvious, has no obvious carbon peak, illustrates that in the rear powder of reaction, carbon content is little.
Embodiment 2:
Tubular furnace in embodiment 1 step 1 is warming up to 300 DEG C under Ar compression ring border, and all the other operations are all identical with embodiment 1.
Embodiment 3:
Tubular furnace in embodiment 1 step 1 is warming up to 400 DEG C under Ar compression ring border, and all the other operations are all identical with embodiment 1.
Fig. 3 is the nano SnO of carbon modification prepared by embodiment 3 2the part Raman spectrum of gas sensitive; Wherein be positioned at 1345cm -1neighbouring sp 2hydridization represents the D peak of disordered carbon structure and is positioned at 1590cm -1neighbouring sp 2hydridization represent orderly carbon structure G peak, SnO is described 2the carbon of finishing is the carbon complex of graphite state and unformed shape.Fig. 4 is the nano SnO of carbon modification prepared by the embodiment of the present invention 3 2the HRTEM photo of gas sensitive; As shown in Figure 4, at SnO 2particle surface deposits many hemispheric carbon granules, and random lattice fringe also demonstrate that SnO 2the carbon that particle surface is modified has complicated structure.
Embodiment 4:
Tubular furnace in embodiment 1 step 1 is warming up to 500 DEG C under Ar compression ring border, and all the other operations are all identical with embodiment 1.
Embodiment 5:
Tubular furnace in embodiment 1 step 1 is warming up to 600 DEG C under Ar compression ring border, and all the other operations are all identical with embodiment 1.
Embodiment 6:
C is passed into by embodiment 3 step 2 2h 2the time of gas is adjusted to 1min, and all the other operations are all identical with embodiment 3.
Embodiment 7:
C is passed into by embodiment 3 step 2 2h 2the time of gas is adjusted to 5min, and all the other operations are all identical with embodiment 3.
Embodiment 8
C is passed into by embodiment 3 step 2 2h 2the time of gas is adjusted to 10min, and all the other operations are all identical with embodiment 3.
Embodiment 9
C is passed into by embodiment 3 step 2 2h 2the flow of gas is adjusted to 30mL/min, and the flow passing into Ar gas is adjusted to 30mL/min, passes into C 2h 2the time of gas is adjusted to 3min, and all the other operations are all identical with embodiment 3.
Embodiment 10
C is passed into by embodiment 3 step 2 2h 2the flow of gas is adjusted to 90mL/min, and the flow passing into Ar gas is adjusted to 30mL/min, passes into C 2h 2the time of gas is adjusted to 3min, and all the other operations are all identical with embodiment 3.

Claims (1)

1. a preparation method for nano tin dioxide gas-sensitive material, comprises the following steps:
Step 1: by SnO 2powder is placed in vacuum tube furnace, is warming up to 200 ~ 600 DEG C under an inert atmosphere, insulation 30 ~ 60min;
Step 2: keep temperature-resistant in vacuum tube furnace, passes into inert gas that flow is 10 ~ 100mL/min simultaneously and flow is the acetylene gas of 20 ~ 150mL/min, to volume and the SnO of the acetylene passed into 2the ratio of quality when being 20 ~ 3000mL/g, stop passing into acetylene, and it is constant to maintain inert gas flow, with the rate of temperature fall cool to room temperature of 3 ~ 10 DEG C/min, namely obtains the SnO that carbon is coated 2particle powder;
Step 3: the coated SnO of the carbon that step 2 is obtained 2particle powder is placed in vacuum tube furnace, under an inert atmosphere 300 ~ 800 DEG C of annealing in process 1 ~ 12h, namely obtains carbon of the present invention and modifies SnO 2gas-sensitive nano material.
CN201510725990.XA 2015-10-30 2015-10-30 Preparation method of nanometer tin dioxide gas sensitive material Pending CN105424763A (en)

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Cited By (8)

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CN105928983A (en) * 2016-06-17 2016-09-07 吉林大学 Acetylene gas sensor and preparation method thereof
CN106556624A (en) * 2016-08-17 2017-04-05 安徽建筑大学 A kind of preparation method of nanostructured gas sensitive
CN107807151A (en) * 2017-09-20 2018-03-16 全球能源互联网研究院 A kind of acetylene gas sensor and preparation method
CN109437288A (en) * 2018-12-13 2019-03-08 东莞理工学院 A kind of carbon wraps up the preparation method of golden doping stannic oxide composite material
CN109655499A (en) * 2019-01-23 2019-04-19 中物院成都科学技术发展中心 A kind of gas sensitive and preparation method thereof for nitrogen dioxide sensor
CN109930133A (en) * 2019-03-21 2019-06-25 西南大学 A kind of preparation method of the graphene zirconium oxide composite material for gas sensing
CN109975368A (en) * 2019-03-21 2019-07-05 西南大学 A kind of preparation method of the graphene oxidation tin composite material for gas sensing
CN111044582A (en) * 2019-12-04 2020-04-21 中国工程物理研究院化工材料研究所 Fluorocarbon film/metal oxide gas-sensitive film composite laminated device and preparation method thereof

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Cited By (10)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN105928983A (en) * 2016-06-17 2016-09-07 吉林大学 Acetylene gas sensor and preparation method thereof
CN105928983B (en) * 2016-06-17 2018-11-09 吉林大学 A kind of acetylene gas sensor and preparation method thereof
CN106556624A (en) * 2016-08-17 2017-04-05 安徽建筑大学 A kind of preparation method of nanostructured gas sensitive
CN107807151A (en) * 2017-09-20 2018-03-16 全球能源互联网研究院 A kind of acetylene gas sensor and preparation method
CN109437288A (en) * 2018-12-13 2019-03-08 东莞理工学院 A kind of carbon wraps up the preparation method of golden doping stannic oxide composite material
CN109655499A (en) * 2019-01-23 2019-04-19 中物院成都科学技术发展中心 A kind of gas sensitive and preparation method thereof for nitrogen dioxide sensor
CN109655499B (en) * 2019-01-23 2021-06-15 中物院成都科学技术发展中心 Gas-sensitive material for nitrogen dioxide sensor and preparation method thereof
CN109930133A (en) * 2019-03-21 2019-06-25 西南大学 A kind of preparation method of the graphene zirconium oxide composite material for gas sensing
CN109975368A (en) * 2019-03-21 2019-07-05 西南大学 A kind of preparation method of the graphene oxidation tin composite material for gas sensing
CN111044582A (en) * 2019-12-04 2020-04-21 中国工程物理研究院化工材料研究所 Fluorocarbon film/metal oxide gas-sensitive film composite laminated device and preparation method thereof

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Application publication date: 20160323