CN110436514A - The preparation method and application of transition metal element doped flower-shaped indium oxide gas sensitive - Google Patents
The preparation method and application of transition metal element doped flower-shaped indium oxide gas sensitive Download PDFInfo
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- CN110436514A CN110436514A CN201810422644.8A CN201810422644A CN110436514A CN 110436514 A CN110436514 A CN 110436514A CN 201810422644 A CN201810422644 A CN 201810422644A CN 110436514 A CN110436514 A CN 110436514A
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- C01G15/00—Compounds of gallium, indium or thallium
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- G01N27/02—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating impedance
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- 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
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- C01P2006/80—Compositional purity
Abstract
The present invention has synthesized the flower-shaped oxidation phosphide material of different transition metal elements (Ni, Cu, Zn) and content (1%, 3%, 5%) doping by hydro-thermal method.The synthetic method is applicable not only to Ni, Cu, Zn, is equally applicable to other transition metal elements that chemical valence is lower than positive trivalent.The present invention is using the different transition metal element doped flower-shaped indium oxide sensing materials of simple one step hydro thermal method synthesis, process is easy, easy to operate, prepared flower-shaped oxidation phosphide material has preferable pattern, and PARA FORMALDEHYDE PRILLS(91,95) response with higher, can be used for making formaldehyde gas sensor.
Description
Technical field
The present invention relates to the preparation method of different transition metal element doped flower-shaped indium oxides and its in gas sensor
In application.The sensing material PARA FORMALDEHYDE PRILLS(91,95) response with higher, can be used for making formaldehyde gas sensor.
Background technique
Indium oxide is a kind of N-type semiconductor metal oxide, may be used as toxic, pernicious gas sensing in detection environment
Material.As a kind of important semiconductor sensing material, indium oxide has lesser resistivity, wider forbidden band and more stable
Physical and chemical performance, and preferable air-sensitive performance is shown to certain gases, has in gas sensor domain and potentially answer
With value.Doping is a kind of simple and effective method for improving air-sensitive performance.Element doping be by certain method by certain
A kind of element is incorporated into material of main part.Since the ionic radius of different elements is different, so that the element of incorporation replaces main body material
Defect sturcture can be formed in material of main part when element in material, to change the physicochemical property of material of main part, improve it in spy
Determine the application performance in field.
A large number of studies show that: element doping produces significant impact to the air-sensitive performance of sensing material.
Duan et al. is adopted in 53 (2018) 3267-3279 of document [1] Journal of Materials Science
Indium oxide (the In of pure and mild Ho doping has been synthesized with electrostatic spinning process2O3) nanotube (NTs) and porous nanotube (PNTs), Ho
Adulterate In2O3The mol% of PNTs(2,4,6 and 8) response to 100 ppm ethyl alcohol is significantly improved, moreover, with Ho doping
Increase, the response of sensor first increases and reduces afterwards, has highest sensitivity when doping is 6 mol%.This may be because
For element Ho doping instead of the position of In, increase the quantity in effective site (Lacking oxygen) of sensing material, cause more
The Lacking oxygen that is increased of electronics captured.When sensor to be placed in air and ethyl alcohol, the response of sensor can change very
Fastly.
Yang etc. in 241 (2017) 806-813 of document [2] Sensors and Actuators B, Chemical
People has synthesized the mesoporous In of pure and mild Zr doping using nanometer casting method2O3, and the long-range order for all having large specific surface area is mesoporous
Structure.At 75 °C of optimum working temperature, Zr doped samples are to 500 ppb NO2Air-sensitive response (65) than pure sample response
(35) 80% is improved.Moreover, the sensor also has preferable selectivity.Zr adulterates In2O3The enhancing of air-sensitive performance can attribution
The chemically adsorbing oxygen of material surface is increased in Zr doping, reduces crystallite dimension, and Jie of ordered pore and high-specific surface area
Pore structure can promote NO2The absorption and diffusion of molecule.
Wang et al. uses simple colloidal crystal mould in 8 (2016) 10622-10631 of document [3] Nanoscale
Plate method is prepared for alkali-metal-doped 3DOM WO3Material tests these materials to low concentration of NO2Air-sensitive performance, the results showed that
3DOM WO3/ Li is at 150 °C of optimum working temperature to 500 ppb NO2Sensitivity is 7 times of pure sample or so.Alkali metal is mixed
Miscellaneous sample especially 3DOM WO3/ Li is increase due to fault of construction and carrier mobility to the improvement of air-sensitive performance and draws
It rises.
The present invention has synthesized the flower-shaped In of different transition metal element (Ni, Cu, Zn) doping using hydro-thermal method2O3Material, and
Be applied to the detection of formaldehyde gas, this it has been reported that data in not yet find.
Summary of the invention
The purpose of the present invention is prepare the transition metal element doped flower-shaped In of difference of uniform morphology2O3Sensing material is ground
Study carefully the influence of different element doping PARA FORMALDEHYDE PRILLS(91,95) gas air-sensitive performances.The sensing material PARA FORMALDEHYDE PRILLS(91,95) has high response, can be used for
Make formaldehyde gas sensor.
Specific preparation process is as follows: the flower-shaped In of different element dopings of favorable dispersibility being prepared using hydro-thermal method2O3Material
Material: 3 mmol lauryl sodium sulfate (SDS) are weighed and are dissolved in the deionized water of 60 mL, are stirring evenly and then adding into 1 mmol's
Inidum chloride (InCl3·4H2) and nickel chloride (NiCl O2·6H2O)/copper nitrate (Cu (NO3)2·3H2O)/zinc nitrate (Zn
(NO3)2·6H2O), so that the molar ratio of Ni/Cu/Zn and In is respectively 1%, 3%, 5%.It states then up and 10 is added in solution
The urea of mmol is transferred in the reaction kettle of 100 mL after 1 h is stirred at room temperature, 12 h is reacted under 120 °C.It naturally cools to
After room temperature, centrifuge separation is spare after dry.The scanning electron microscope (SEM) photograph of product such as Fig. 1-3.
The flower-shaped indium oxide gas sensitive of obtained different element dopings is slurried with ethyl alcohol modulation respectively and is coated in silver-
The surface of the ceramic substrate of palladium interdigital electrode, after dry tack free by this gas sensor 250 °C lower aging 24 hours.Then it surveys
Its air-sensitive performance is tried, the research that different element dopings influence its air-sensitive performance is carried out.Definition response is Ra/Rg, RaAnd RgPoint
It Wei not resistance of the gas sensor in air and formaldehyde gas.
Measurement result is shown in Fig. 4-5, Fig. 4 be the different transition metal elements that synthesize of embodiment 3, embodiment 4 and embodiment 5 most
The flower-shaped In of good doping2O3The pure flower-shaped In synthesized in material and embodiment 12O3The air-sensitive performance of material PARA FORMALDEHYDE PRILLS(91,95) gas
Test result, the operating temperature range of test are 175-275 °C.It is available from figure 4 go out to draw a conclusion: (1) different elements are most preferably mixed
Miscellaneous amount is different, and the optimum doping amount of Ni and Zn are 3%, and Cu is 1%;(2) optimum working temperature is different, and Ni and Cu doping do not change
Become the optimum working temperature of sensor, and it is reduced to 225 °C by 250 °C by Zn doping;(3) PARA FORMALDEHYDE PRILLS(91,95) response mentions
High level is different, and 3%Ni doping response is nearly 4 times of pure sample, and Zn doping is about 7 times undoped with sample, and Cu doping is only
It is to be slightly increased response.
Fig. 5 be pure and mild 3%Zn doping flower-shaped indium oxide sensor to the response of 10-100 ppm formaldehyde gas with gas
Concentration curve.Response increases with the increase of gas concentration, and increases comparatively fast in low concentration.
Beneficial effects of the present invention: 1. preparation methods of the present invention, process is easy, easy to operate, is easy to real
Existing industrial production.The transient metal doped flower-shaped In of difference prepared by 2.2O3Gas sensitive can be used for the system of formaldehyde gas sensor
It is standby.The response of prepared gas sensor PARA FORMALDEHYDE PRILLS(91,95) gas is up to about pure In2O37 times of material response value, reach 207, and
Zn adulterates the optimum working temperature for reducing sensor.
Detailed description of the invention
Fig. 1 is the scanning electron microscope (SEM) photograph implemented the 3%Ni that 3 prepare and adulterate flower-shaped indium oxide.
Fig. 2 is the scanning electron microscope (SEM) photograph implemented the 1%Cu that 4 prepare and adulterate flower-shaped indium oxide.
Fig. 3 is the scanning electron microscope (SEM) photograph implemented the 3%Zn that 5 prepare and adulterate flower-shaped indium oxide.
Fig. 4 is the flower-shaped indium oxide sensing of pure and mild different transition metal element optimum doping amounts (3%Ni/1%Cu/3%Zn)
Device varies with temperature curve to the response of 100 ppm formaldehyde gas.
Fig. 5 be pure and mild 3%Zn doping flower-shaped indium oxide sensor to the response of 10-100 ppm formaldehyde gas with gas
Bulk concentration change curve.
Specific embodiment
Embodiment 1
1 mmol inidum chloride (InCl is accurately weighed with assay balance3·4H2O), 10 mmol urea, a certain amount of dodecyl
Sodium sulphate (SDS), making the molar ratio of In and SDS is respectively 1:2,1:3 and 1:4, is dissolved in 60 mL distilled water, is stirred at room temperature 1
Then h is transferred in 100 mL reaction kettles, 12 h is reacted under 120 °C.After reaction, cooled to room temperature, centrifugation
Product is separated and collected, is washed several times with deionized water and dehydrated alcohol, it is then dry in 60 °C of vacuum ovens, it obtains not
With the flower-shaped In of amount of surfactant2O3。
Embodiment 2
Accurately weigh 1 mmol inidum chloride (InCl3·4H2O), 10 mmol urea, 3 mmol SDS are dissolved in 60 mL distillation
In water, 1 h is stirred at room temperature, is then transferred in 100 mL reaction kettles, reacts 12 under 100 °C, 120 °C, 140 °C respectively
H, reaction terminate after being cooled to room temperature, and product is collected in centrifuge separation, is washed several times with deionized water and dehydrated alcohol, at 60 °C
It is dry in vacuum oven, obtain the flower-shaped In reacted under different temperatures2O3。
Embodiment 3
It weighs 3 mmol SDS to be dissolved in the deionized water of 60 mL, is stirring evenly and then adding into the inidum chloride (InCl of 1 mmol3·
4H2) and nickel chloride (NiCl O2·6H2O), so that the molar ratio of Ni and In is respectively 1%, 3%, 5%.It states in solution and adds then up
The urea for entering 10 mmol is transferred in the reaction kettle of 100 mL after 1 h is stirred at room temperature, 12 h is reacted under 120 °C.Naturally cold
But it to after room temperature, is centrifugated, it is dry.Sample after drying is put into tube furnace, is heated up with the heating rate of 5 °C/min
To 400 °C, and 2 h are kept at such a temperature, cooled to room temperature adulterates flower-shaped In to get to Ni2O3Sample is denoted as respectively
In2O3/1%Ni、In2O3/3%Ni、In2O3/ 5%Ni, such as Fig. 1.
Embodiment 4
It weighs 3 mmol SDS to be dissolved in the deionized water of 60 mL, is stirring evenly and then adding into the inidum chloride (InCl of 1 mmol3·
4H2) and copper nitrate (Cu (NO O3)2·3H2O), so that the molar ratio of Cu and In is respectively 1%, 3%, 5%.Solution is stated then up
The middle urea that 10 mmol are added, is transferred in the reaction kettle of 100 mL after 1 h is stirred at room temperature, 12 h is reacted under 120 °C.From
After being so cooled to room temperature, it is centrifugated, it is dry.Sample after drying is put into tube furnace, with the heating rate of 5 °C/min
400 °C are warming up to, and keeps 2 h at such a temperature, cooled to room temperature adulterates flower-shaped In to get to Cu2O3Sample, respectively
It is denoted as In2O3/1%Cu、In2O3/3%Cu、In2O3/ 5%Cu, such as Fig. 2.
Embodiment 5
It weighs 3 mmol SDS to be dissolved in the deionized water of 60 mL, is stirring evenly and then adding into the inidum chloride (InCl of 1 mmol3·
4H2) and zinc nitrate (Zn (NO O3)2·6H2O), so that the molar ratio of Zn and In is respectively 1%, 3%, 5%.Solution is stated then up
The middle urea that 10 mmol are added, is transferred in the reaction kettle of 100 mL after 1 h is stirred at room temperature, 12 h is reacted under 120 °C.From
After being so cooled to room temperature, it is centrifugated, it is dry.Sample after drying is put into tube furnace, with the heating rate of 5 °C/min
400 °C are warming up to, and keeps 2 h at such a temperature, cooled to room temperature adulterates flower-shaped In to get to Zn2O3Sample, respectively
It is denoted as In2O3/1%Zn、In2O3/ 3%Zn and In2O3/ 5%Zn, such as Fig. 3.
Claims (4)
1. variety classes transition metal element (Ni, Cu, Zn) and the flower-shaped indium oxide sensing material of content (1%, 3%, 5%) doping.
2. Zn according to claim 1 adulterates the preparation method of flower-shaped indium oxide sensing material, specific preparation process is as follows:
Flower-shaped oxidation phosphide material is adulterated using the Zn that favorable dispersibility is prepared in hydro-thermal method: weighing 3 mmol dodecyl sulphates
Sodium (SDS) is dissolved in the deionized water of 60 mL, is stirring evenly and then adding into the inidum chloride (InCl of 1 mmol3·4H2) and zinc nitrate O
(Zn (NO3)2·6H2O), so that the molar ratio of Zn and In is respectively 1%, 3%, 5%, stated in solution then up and 10 mmol are added
Urea, be transferred in the reaction kettle of 100 mL after 1 h is stirred at room temperature, 12 h, cooled to room temperature reacted under 120 °C
Afterwards, it is centrifugated, after washing, drying to obtain the final product.
3. it is low that the preparation method that Zn as stated in claim 2 adulterates flower-shaped indium oxide sensing material is equally applicable to other valence states
In In3+Transition metal element, such as Ni and Cu.
4. the application of the transition metal element doped flower-shaped indium oxide sensing material of difference according to claim 1, the gas
Quick material is for making formaldehyde gas sensor.
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Cited By (2)
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CN113564812A (en) * | 2021-07-20 | 2021-10-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde, product and application thereof |
CN113916944A (en) * | 2021-09-30 | 2022-01-11 | 北京化工大学 | Nano graphite powder doped flower-like indium oxide material, preparation method and application thereof, and nitrogen dioxide gas sensor |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN113564812A (en) * | 2021-07-20 | 2021-10-29 | 上海纳米技术及应用国家工程研究中心有限公司 | Preparation method of alkalescent indium oxide for detecting ultralow-concentration formaldehyde, product and application thereof |
CN113916944A (en) * | 2021-09-30 | 2022-01-11 | 北京化工大学 | Nano graphite powder doped flower-like indium oxide material, preparation method and application thereof, and nitrogen dioxide gas sensor |
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