CN105510390B - A kind of multilevel structure nanometer In2O3/ graphene composite material and its preparation method and application - Google Patents
A kind of multilevel structure nanometer In2O3/ graphene composite material and its preparation method and application Download PDFInfo
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- CN105510390B CN105510390B CN201610052042.9A CN201610052042A CN105510390B CN 105510390 B CN105510390 B CN 105510390B CN 201610052042 A CN201610052042 A CN 201610052042A CN 105510390 B CN105510390 B CN 105510390B
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
Abstract
The invention discloses a kind of multilevel structure nanometer In2O3/ graphene composite material and its preparation method and application, multilevel structure nanometer In2O3/ graphene composite material, structure are bricked structure.The present invention also provides multilevel structure nanometer In2O3The preparation method of/graphene composite material, the indium salts and redox graphene for dissolving in ethylene glycol are formed by liquid-vapor interface in ethylene glycol solution and ammonium hydroxide steam under microwave heating condition with precipitating reagent ammonium hydroxide and are chemically reacted, the ethylene glycol solution that reaction product is constantly rolled is taken away, and new product continues to generate.The present invention has the advantage that using nanometer In prepared by microwave liquid-vapor interface method2O3/ graphene raw nanoparticle is small and uniform, and again by these raw nanoparticle portion self-assembles at bricked nanostructure, multilevel structure nanometer In2O3/ graphene composite material has preferable air-sensitive performance at 100 DEG C to oxides of nitrogen gas, and selectivity is good.
Description
Technical field
The present invention relates to novel nitrogen oxide gas sensitive and its preparations and application, and in particular to a kind of multilevel structure nanometer
In2O3/ graphene composite material and its preparation method and application.
Background technique
Nitrogen oxides (NO as air pollutantsx) often refer to NO and NO2Mixed gas.Nitrogen oxides can stimulate lung,
The more difficult respiratory disease for resisting flu etc is made one, the problematic personage of respiratory system such as asthmatics can be easier to meet with
It is influenced by nitrogen oxides.For children, it is impaired that nitrogen oxides is likely to result in lung's development.With nitric oxide and titanium dioxide
Nitrogen oxides based on nitrogen is also the major reason to form photochemical fog and acid rain.Photochemical fog has special gas
Taste stimulates eyes, injures plant, and atmospheric visibility can be made to reduce.In addition, nitrogen oxides reacts generation with the water in air
Nitric acid and nitrous acid are the main components of acid rain.Therefore, new nitrogen oxides gas sensitive and its gas sensing are researched and developed
Device is very necessary.Research report also has many such as nearest use spinning process on the gas sensitive of nitrogen oxides at present
Prepare hetero-junctions NOxGas sensitive (Shuang Xu, Jun Gao, Linlin Wang, Kan Kan, Yu Xie, Pei Kang
Shen,Li Li and Keying Shi.Role of the Heterojunctions in In2O3-composited SnO2
Nanorods Sensor and Their Remarkable Gas-Sensing Performance for NOx at Room
Temperature.2015, Nanoscale, DOI:10.1039/C5NR03796D), operating temperature can drop to room temperature, but should
Technique requires height to equipment control parameter using spining technology, is difficult to control.The present invention uses the base in the hot method of conventional solvent
On plinth, it is changed to that isolating device is added inside reaction kettle, reactant and precipitating reagent is separated, after microwave heating, precipitating reagent gas
Body forms contact interface in solvent surface and carries out quick air-liquid interfacial reaction, generates uniform reaction product, this method reaction
Product is uniform, and granularity is small, controllably, at low cost, environmental-friendly.
Summary of the invention
In order to solve the deficiencies in the prior art, the present invention provides a kind of multilevel structure nanometer In2O3/ graphene composite wood
Material and its preparation method and application.
The technical scheme is that a kind of multilevel structure nanometer In2O3/ graphene composite material, structure are bricked knot
Structure.
Further improvement of the present invention includes:
Multilevel structure nanometer In2O3Graphene content is the 0.05-0.20% of total weight in/graphene composite material.
A kind of multilevel structure nanometer In2O3/ graphene composite material, the scanning electron microscopy of structure such as attached drawing 1
Shown in mirror figure, XRD spectrum figure is as shown in Figure 2.
Nanometer In2O3Growth in situ, which is carried out, on redox graphene surface forms In2O3/ graphene nano particle,
In2O3The bricked structure of/graphene nano particle portion self-assembles create-rule again.
The present invention also provides a kind of above-mentioned multilevel structure nanometer In2O3The preparation method of/graphene composite material, it is solvable
In ethylene glycol indium salts and redox graphene and precipitating reagent ammonium hydroxide under microwave heating condition in ethylene glycol solution and ammonium hydroxide
Steam is formed by liquid-vapor interface and is chemically reacted, and the ethylene glycol solution that reaction product is constantly rolled is taken away, new product
Continue to generate；The indium salts are InCl3.4H2O。
The multilevel structure nanometer In2O3The preparation method of/graphene composite material, comprising the following steps: first with improvement
Hummers method prepare graphene oxide, then through hydrazine hydrate electronation, obtain redox graphene, appropriate oxygen reduction
Graphite alkene and soluble indium salts are fully dispersed, adsorb, are dissolved in the small container for filling ethylene glycol, and mixed liquor is placed on Sheng
In the rustless steel container for having the polytetrafluoroethyllining lining of appropriate ammonium hydroxide, sealing, microwave procedure heating, and assisting magnetic stirring,
When temperature rises to 170-190 DEG C, 25-40min is kept the temperature, the surface of small container liquid level is contacted with the ammonia that outer wall volatilizes at this time,
Due to the boiling point of ethylene glycol be 197.3 DEG C (maximum temperature of the present invention is 190 DEG C), and microwave heating is from small container outer wall
The ammonia evaporated is insoluble in ethylene glycol, and reaction can only be carried out in liquid-vapor interface.It chemically reacts, obtains in liquid-vapor interface
To In2O3/ graphene composite material presoma is centrifuged, and is washed, dry, and carrying out calcining in Muffle furnace being made has multilevel structure
Nanometer In2O3/ graphene composite material.
Invention further provides according to a kind of multilevel structure nanometer In made from above-mentioned method2O3/ graphene composite wood
Material.
Another object of the present invention is to provide multilevel structure nanometer In2O3/ graphene composite air-sensitive material is for detecting
The application of oxides of nitrogen gas.
The application is further, by the multilevel structure nanometer In2O3/ graphene composite air-sensitive material and deionization
Water is mixed into slurry, then is coated uniformly on the aluminium oxide ceramics pipe surface with forked gold electrode, first in 80-120 DEG C of condition
Lower dry 30-60min, then 1-3h is calcined under conditions of 400-600 DEG C in argon atmosphere, it then welds, dispense, aging, i.e.,
Obtain the oxides of nitrogen gas sensing element.
Compared with the prior art, the invention has the following advantages: the present invention is using prepared by microwave liquid-vapor interface method
Nanometer In2O3/ graphene raw nanoparticle is small and uniform, and is received again by these raw nanoparticle portion self-assembles at bricked
Rice structure, this multi-level nano-structure have the novelty in novelty and appearance structure in preparation method, also, prepared
Multilevel structure nanometer In2O3/ graphene composite material has preferable air-sensitive performance at 100 DEG C to oxides of nitrogen gas, selectivity
It is good.Preparation method uses microwave heating, is aided with stirring, chemically reacts in liquid-vapor interface, and technique is advanced, and the reaction time is short,
Energy consumption is small, at low cost, environmental-friendly.
The present invention is aided with stirring using microwave heating first in preparation process, and is that chemistry occurs in liquid-vapor interface
Reaction, relative to traditional hydro-thermal method, the reaction time is short, and energy consumption is small, and yield is high, at low cost, and can stir during the reaction
It mixes；Obtained primary particle is smaller and uniform, these small and uniform original nanoparticles again portion self-assembles at bricked nanometer
Particle, special construction is due to the small-size effect not only with raw nanoparticle but also has the corner angle of regular bricked structure to gas
The pick up factor of body and have unique contribution to air-sensitive performance.
Composite air-sensitive material of the present invention has the following characteristics that
1) operating temperature is low: utilizing multilevel structure nanometer In2O3The nitrogen oxides sensing element of/graphene composite material preparation
Part is 100 DEG C to nitrogen oxides optimum working temperature, purer In2O3It works with common metal oxide semiconductor gas sensor
Temperature is greatly lowered；
2) high sensitivity: in 100 DEG C of high sensitivities to 10ppm oxides of nitrogen gas up to 54；
3) the response-recovery time is fast: response time of the gas sensor within the scope of 300ppm within 10s, recovery time
Also within 120s；
4) selectivity is good: relative to some common organic solvents such as ethyl alcohol, methanol, benzene, toluene, H2S and amine gas,
The gas sensor has significant sensibility to oxides of nitrogen gas.
Detailed description of the invention
Fig. 1 a is the nanometer In that graphene content is 0.052O3The SEM of/graphene composite material schemes；
Fig. 1 b is the nanometer In that graphene content is 0.12O3The SEM of/graphene composite material schemes；
Fig. 1 c is the nanometer In that graphene content is 0.22O3The SEM of/graphene composite material schemes；
Fig. 2 multilevel structure nanometer In of the present invention2O3The XRD diagram of/graphene composite air-sensitive material；
Sensitivity curve of Fig. 3 gas sensor of the present invention to 10ppm oxides of nitrogen gas at a temperature of different operating；
The air-sensitive selectivity test result of Fig. 4 gas sensor of the present invention.
Specific embodiment
It elaborates below with reference to embodiment to the present invention.
Experimental material and method: experimental method described in following embodiments is unless otherwise specified conventional method；Institute
Reagent and material are stated, unless otherwise specified, is commercially obtained.
Embodiment 1
The present invention provides a kind of multilevel structure nanometer In2O3/ graphene composite air-sensitive material, nanometer In2O3In reduction-oxidation
Graphene surface carries out growth in situ, and final product is nanometer In2O3Wrap up the raw nanoparticle of graphene and original by these
The regular bricked structure I n that nano particle is self-assembled into again2O3/ graphene composite material, wherein graphene content is total weight
0.05-0.2%.A kind of multilevel structure nanometer In2O3The structure of/graphene composite air-sensitive material such as attached drawing 1 (including Fig. 1 a,
Fig. 1 b and Fig. 1 c)；Its XRD spectrum figure is as shown in Figure 2.
Composite material preparation:
First prepare graphene oxide with improved Hummers method, with hydrazine hydrate reduction graphene oxide, then it is appropriate also
Former graphene oxide is evenly spread in ethylene glycol, and InCl is added3·4H2O, magnetic agitation 1h will fill the 50ml of mixed solution
Beaker is put into inner liner polytetrafluoroethylene reaction kettle, and a certain amount of ammonium hydroxide is then added on the outside of beaker, this reaction kettle is put into
Microwave chemical reaction is carried out by program in microwave reaction instrument.
Embodiment 2
Specific preparation method of the invention is the InCl for weighing 1.1326 parts in mass ratio3·4H2O (0.002mol) is dissolved in
In 20 parts of ethylene glycol, stirring is allowed to sufficiently dissolve, and obtains clear solution.Separately accurately weighing 0.0008 part of graphene is dissolved in another 20
In part ethylene glycol, dispersion is uniformly mixed.It is fully dispersed into ethylene glycol solution to graphene, then by InCl3·4H2O's is clear
Clear solution is slowly added into graphene solution in whipping process, and is continued stirring and be allowed to be sufficiently mixed, adsorb, and will finally be contained
There is the container of mixed solution to be put into inner liner polytetrafluoroethylene reaction kettle, the ammonia of 0.8 part of 15mol/L is then added in outside of containers
This reaction kettle is put into microwave reaction instrument and is reacted by water.Using microwave heating, and assisting magnetic stirring, temperature rise to
At 180 DEG C, 30min is kept the temperature, 100 DEG C are cooled in microwave reaction instrument and naturally cools to room temperature hereinafter, taking out reaction kettle, is obtained
Sediment, centrifugation, washing, precipitating is transferred in evaporating dish, 60 DEG C of dry 10h in air dry oven, 400 DEG C in argon atmosphere
3h is calcined, natural cooling obtains multilevel structure nanometer In2O3/ graphene composite material (such as scheme than being 0.2% by graphene doping
1c)。
Specific experiment:
Weigh the InCl of 1.1326g3·4H2O (0.002mol) is dissolved in 20ml ethylene glycol, is allowed to using rotor agitator
Sufficiently dissolution, obtains clear solution.Separately accurately weigh graphene 0.7mg and be dissolved in 20ml ethylene glycol, in cell crushing instrument into
Row dispersion is allowed to uniformly mixed, time 30min, interval 2s.It is fully dispersed into ethylene glycol solution to graphene, then will
InCl3.4H2The mixed solution of O is added dropwise in graphene solution in whipping process, and is continued stirring and be allowed to sufficiently inhale
It is attached, finally the 50ml beaker for filling mixed solution is put into inner liner polytetrafluoroethylene reaction kettle, is then added on the outside of beaker
This reaction kettle is put into microwave reaction instrument and is reacted by a certain amount of ammonium hydroxide.Microwave reaction instrument temperature from room temperature 20min it
When being inside warming up to 170-190 DEG C, 25-40min is kept the temperature, three groups of experiment embodiments are as follows.
Experiment detailed process between each mass ratio is as described above, the difference is that the additional amount of graphene is different and warm
Degree system is different.
Experiment one:
Weigh InCl3·4H2O mass: 1.1326g ammonium hydroxide volume 0.8ml (molar concentration 15mol/ml).
The quality of graphene: 0.05% weighs 0.0002g；Microwave temperature is raised to 190 DEG C from room temperature in 20min, heat preservation
Room temperature is naturally cooled to after 25min.
Experiment two:
Weigh InCl3·4H2O mass: 1.1326g ammonium hydroxide volume 0.8ml (molar concentration 15mol/ml).
The quality of graphene: 0.1% weighs 0.0004g；Microwave temperature is raised to 180 DEG C from room temperature in 20min, heat preservation
Room temperature is naturally cooled to after 30min.
Experiment three:
Weigh InCl3·4H2O mass: 1.1326g ammonium hydroxide volume 0.8ml (molar concentration 15mol/ml).
The quality of graphene: 0.05% weighs 0.0002g；
Microwave temperature is raised to 170 DEG C from room temperature in 20min, naturally cools to room temperature after keeping the temperature 40min.
By multilevel structure nanometer In obtained above2O3/ graphene composite material is tuned into slurry with pure water, uniformly applies
It overlays on aluminium oxide airsensitive porcelain pipe, dry in 105 DEG C of baking ovens, aging, encapsulation obtains gas sensor.It is tested in gas sensor
The quick performance test of the enterprising promoting the circulation of qi of instrument (Zhengzhou Wei Sheng Electronic Technology Co., Ltd WS-30A), result is respectively such as Fig. 3 and Fig. 4 institute
Show.
In conjunction with the above results it is found that composite air-sensitive material of the present invention has the following characteristics that
1) operating temperature is low: to oxides of nitrogen gas, optimum working temperature is 100 DEG C, purer In2O3With general gold
The operating temperature for belonging to oxide is low；
2) high sensitivity: in 100 DEG C of high sensitivities to 10ppm oxides of nitrogen gas up to graphene doping than being 0.2%
Composite material up to 43, doping than the composite material for 0.1% up to 54, doping than for 0.05% composite material it is reachable
27；
3) the response-recovery time is fast: gas sensor within 10s, restores the response time of 10ppm oxides of nitrogen gas
Time is also within 120s；
4) selectivity is good: relative to some common organic solvents such as ethyl alcohol, acetone, benzene, toluene, H2The gas such as S and amine
The body gas sensor has significant sensibility to oxides of nitrogen gas.
The above shows and describes the basic principles and main features of the present invention and the advantages of the present invention.The technology of the industry
Personnel are it should be appreciated that the present invention is not limited to the above embodiments, and the above embodiments and description only describe this
The principle of invention, without departing from the spirit and scope of the present invention, various changes and improvements may be made to the invention, these changes
Change and improvement all fall within the protetion scope of the claimed invention.The claimed scope of the invention by appended claims and its
Equivalent thereof.
Claims (2)
1. a kind of multilevel structure nanometer In2O3The preparation method of/graphene composite material, which is characterized in that weigh in mass ratio
1.1326 the InCl of part3·4H2O is dissolved in 20 parts of ethylene glycol, and stirring is allowed to sufficiently dissolve, and obtains clear solution；Separately accurately weigh
0.0008 part of graphene is dissolved in another 20 parts of ethylene glycol, and dispersion is uniformly mixed；It is fully dispersed to ethylene glycol solution to graphene
In, then by InCl3·4H2The clear solution of O is slowly added into graphene solution in whipping process, and continue stirring make
Be sufficiently mixed, adsorb, finally the container for filling mixed solution is put into inner liner polytetrafluoroethylene reaction kettle, then in container
The ammonium hydroxide of 0.8 part of 15mol/L is added in outside, this reaction kettle is put into microwave reaction instrument and is reacted；Using microwave heating, and
And assisting magnetic stirring, when temperature rises to 170-190 DEG C, 30min is kept the temperature, 100 DEG C are cooled in microwave reaction instrument hereinafter, taking
Reaction kettle naturally cools to room temperature out, obtains sediment, and precipitating is transferred in evaporating dish, in air dry oven by centrifugation, washing
60 DEG C of dry 10h, 400 DEG C of calcining 3h in argon atmosphere, natural cooling obtain multilevel structure nanometer In2O3/ graphene composite wood
Material.
2. a kind of multilevel structure nanometer In2O3/ graphene composite material, which is characterized in that according to the method for claim 1
It is made.
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| US10212932B2 (en) * | 2016-07-28 | 2019-02-26 | eXion labs Inc. | Antimicrobial photoreactive composition comprising organic and inorganic multijunction composite |
| CN108130589B (en) * | 2016-12-01 | 2020-11-20 | 北京理工大学 | Hydrothermal method capable of controlling preparation of single crystal |
| CN107340367A (en) * | 2017-07-11 | 2017-11-10 | 济南大学 | A kind of preparation method of three-dimensional rGO/In2O3 composite room temperature gas sensitive |
| CN108562615B (en) * | 2018-01-02 | 2020-12-15 | 深圳市安泰安防技术有限公司 | Nitrogen dioxide leakage detection device working at room temperature |
| CN108445049B (en) * | 2018-05-08 | 2019-12-10 | 公安部天津消防研究所 | Preparation method of graphene oxide modified composite metal oxide gas-sensitive material |
| CN109187686B (en) * | 2018-09-12 | 2020-05-12 | 南昌航空大学 | Preparation method of electrode modification material silver disulfide/reduced graphene oxide and application of electrode modification material silver disulfide/reduced graphene oxide in detection of ciprofloxacin |
| CN113092545B (en) * | 2021-04-13 | 2022-12-09 | 哈尔滨理工大学 | Based on CuO/In 2 O 3 Preparation method of modified graphene MEMS gas sensor |
| CN113686928A (en) * | 2021-08-24 | 2021-11-23 | 华北电力大学 | GO/In2O3Composite nano material and preparation and application thereof |
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| CN102602917A (en) * | 2012-03-19 | 2012-07-25 | 华南理工大学 | Preparation method of nitrogen doped graphene/ metal oxide nanometer composite material |
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