CN106290481A - ZnO nano cone gas sensitive of Au load and its production and use - Google Patents
ZnO nano cone gas sensitive of Au load and its production and use Download PDFInfo
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- CN106290481A CN106290481A CN201510235956.4A CN201510235956A CN106290481A CN 106290481 A CN106290481 A CN 106290481A CN 201510235956 A CN201510235956 A CN 201510235956A CN 106290481 A CN106290481 A CN 106290481A
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Abstract
The particle diameter of the Au that the zinc-oxide nano cone gas sensitive of the Au load that the present invention provides is loaded is respectively 3 ~ 14nm；Wherein zinc-oxide nano cone side is isosceles triangle, and a length of about the 200nm of its waist, bottom surface is regular hexagon, and its length of side is that about 100nm, Au nanoparticle is attached to its surface.ZnO nano taper looks prepared by the present invention, size uniform, bore gas sensitive by the Au nanometer particle load of the different-grain diameter prepared to ZnO nano poppet surface, the ZnO nano obtaining Au load by the method for stirring.This gas sensitive has higher sensitivity to ethanol, can be used for the making of alcohol gas sensor.
Description
Technical field
Zinc oxide air-sensitive nano material that the present invention relates to a kind of Au nanometer particle load and preparation method thereof.This gas sensitive has high sensitivity to ethanol, may be used for making alcohol gas sensor.
Background technology
Zinc oxide is a kind of N-type semiconductor metal-oxide, can be as detection environmental toxic, the gas sensitive of harmful gas.Zinc oxide, as a kind of semi-conducting material, has low resistivity, wide forbidden band and stable physical and chemical performance, some gas meter is revealed more preferably air-sensitive performance, have potential using value at gas sensor domain.The nano zinc oxide material exposing particular crystal plane by controlling growth preparation receives much concern.Owing to ZnO difference crystal plane surface atomic arrangement mode is different, the coordination saturated conditions of produced surface atom there are differences, and the crystal face activity causing different crystal face is the most different.ZnO nano cone is main exposes highly active { 10-11} crystal face, thus can improve the gas-sensitive reaction activity of material to a great extent.
The Au of nano-scale has the highest activity, has a wide range of applications in a lot of fields, in terms of catalysis material, electrode material, gas sensor material, biological detection etc..
Numerous studies show: the particle diameter of the Au nanoparticle of load produces significant impact to Au/ZnO composite nano materials gas sensor performance.
Document [1] Sensors and Actuators B, in Chemical 199 (2014) 339-345, T Guo et al. is at zinc oxide nano rod area load Au nanoparticle, drastically increase the sensor sensitivity to ethanol, and find that material has wider detection range to ethanol and sensitivity is the highest, additionally response-recovery time period, selectivity and the stability of sensor are the most fine.But article is not discussed the impact on material air-sensitive performance of the particle diameter of Au nanoparticle.
In document [2] Nano Letters 14 (2014) 6,731 6,736 137., Ding et al. loads the Au nanoparticle of different-grain diameter (7 nm, 10 nm, 15 nm and 20 nm) at titanium dioxide surface and falls the protective agent of Au nanoparticle surface with ligand exchange method exchange.Prepared Au/TiO2 complex is used as the catalyst to methyl orange, and load particle diameter is 10 nm
The TiO2 of Au is the highest to the catalysis activity of methyl orange.Load particle diameter is 7 nm
The density of TiO2 surface A u of Au is very big, how to exist with agglomerate form, and these Au agglomerates play the part of electronics and the role at hole recombination center simultaneously just, thus reduce the catalytic performance of TiO2.
Document [3] Journal of the American Chemical Society 133 (2011)
In 5660-5663, Li et al. utilizes the seed law to be prepared for the Au/ZnO nanocone complex of Au nanoparticle fixed point growth.Au kind is to be reactant with gold chloride, oleyl amine, tetrahedronaphthalene, and formed by the protection of protective agent tert-butylamine.Gained Au kind need are dispersed in hexamethylene standby.ZnO nano cone is that reactant zinc acetate, oleyl amine and lauryl alcohol are made to be pyrolyzed under the conditions of high temperature oil bath.This complex has preferable photocatalysis performance.
The present invention uses solvent-thermal method to be prepared for ZnO nano cone, with it as carrier, load water soluble Au nanoparticle, obtains Au/ZnO nanocone composite air-sensitive material.The ZnO nano cone gas sensitive of load different-grain diameter Au nanoparticle has no document announcement.
Summary of the invention
It is an object of the invention to prepare pattern zinc-oxide nano uniform, favorable dispersibility bore, and at the Au nanoparticle of its area load different-grain diameter, to provide a kind of Au and zinc oxide compound gas-sensitive nano material, thus study Au nano particle diameter to the impact on alcohol gas air-sensitive performance of the Au/ZnO nanocone complex.This gas sensitive has high sensitivity to ethanol, may be used for making alcohol gas sensor.
The particle diameter of the Au that the zinc-oxide nano gas sensitive of the Au load that the present invention provides is loaded is respectively 3 ~ 14 nm；Prepared zinc-oxide nano cone size is uniform, and side is isosceles triangle, its waist a length of 200
About nm, bottom surface is regular hexagon, and its length of side is about 100 nm, and Au nanoparticle is attached to its surface.
Concrete preparation process is as follows:
(1) solvent-thermal method is used to prepare the ZnO nano cone of favorable dispersibility；
(2) 0.1 g is taken
ZnO nano cone is well dispersed in 10 ml deionized waters, adds 5 ~ 20
Ml particle diameter is the Au colloidal sol of 3 ~ 14 nm.Stirring 24 ~ 36 h, obtain Au/ZnO nanocone complex.Gained products therefrom is centrifuged, washs, is dried；
(3) the zinc-oxide nano cone complex gas sensitive loaded by the different-grain diameter obtained spreads upon (earthenware 4mm length on earthenware with ethanol modulation pulping respectively, 1mm diameter, two gold electrodes have been printed at two ends), this gas sensor is aging 24 hours at 300 DEG C.Then measure its air-sensitive performance, carry out the research to the Au/ZnO nanocone quick performance impact of complex alcohol of the Au particle diameter.Definition sensitivity S=Rair/Rgas, Rair and Rgas respectively gas sensor resistance in atmosphere and in the presence of alcohol vapour.
Measurement result is shown in the pure zirconia indium hollow nanometer material of material and the embodiment 1 step A synthesis that Fig. 6, Fig. 6 are embodiment 1, the 2-in-1 one-tenth of the embodiment air-sensitive performance test result to ethanol, and the operating temperature of test is 230 DEG C.Compared with can being concluded that (1) and pure zinc-oxide nano cone by Fig. 6, after load Au nanoparticle, the sensitivity of material is significantly increased, and optimum working temperature also decreases, and the particle diameter of the Au nanoparticle loaded is the least, and sensitivity is the highest；(2) when the particle diameter of the Au nanoparticle loaded is 3.2 nm, Au/ZnO nanocone complex gas sensitive is the highest to the sensitivity of ethanol, and it reaches 157 to the sensitivity of 100 ppm ethanol.
Beneficial effects of the present invention
Preparation method the most of the present invention, process is easy, easily operate, it is easy to accomplish commercial production；
2. the zinc-oxide nano cone gas sensitive of the Au nanometer particle load prepared by can be used for the preparation of alcohol sensible gas sensor.The remolding sensitivity that alcohol gas is detected by prepared gas sensor does not load highly sensitive more than 3 times of the nano zinc oxide material of Au nanoparticle, reaches 157.The load of Au nanoparticle makes the operating temperature of the optimum sensitivity of sensor decline.
Accompanying drawing explanation
Fig. 1 is the SEM figure implementing zinc-oxide nano cone material prepared by 1 step A
Fig. 2 is the TEM figure implementing small particle Au nanoparticle prepared by 1 step B
Fig. 3 is the TEM figure that small particle Au nanoparticle prepared by enforcement 1 step C is combined with ZnO nano cone
Fig. 4 is the TEM figure implementing big particle diameter Au nanoparticle prepared by 2 steps B
Fig. 5 is the TEM figure that big particle diameter Au nanoparticle prepared by enforcement 2 steps C is combined with ZnO nano cone
Fig. 6 is that the ZnO nano of ZnO nano cone and Au nanometer particle load bores the sensitivity curve figure that sensor changes with concentration of alcohol.
Detailed description of the invention
Embodiment 1
First, 100 ml there-necked flasks add 3 ml oil ammonia and 6 ml lauryl alcohols, then oil bath pan temperature is increased to 120 DEG C, constant temperature 10 min.Rapidly join 0.1 mol Zinc diacetate dihydrate solid.Oil bath pan temperature is increased to 180 DEG C, and constant temperature two hours at this temperature, obtain ZnO nano cone, such as Fig. 1.Products therefrom is centrifugal, washing, washing solvent for use is 75 DEG C of hot ethanols, and washing times is six times.Washing the single hot ethanol of first three time, the 4th washing needs to add a small amount of hexamethylene in hot ethanol, and follow-up secondary washing still uses single 75 DEG C of hot ethanols.Products therefrom is placed in 60 DEG C of vacuum drying ovens, takes out after being dried 12h；
B. taking a there-necked flask is reaction vessel.First, add 95ml deionized water, and this reaction vessel is placed in ice-water bath stirring constant temperature half an hour.Then, in reaction vessel, add 2.5 ml (10 mM) HAuCl4•4H2O solution & stir 10 min.Then, in reaction vessel, add 2.5 ml(10 mM) sodium citrate aqueous solution stir 10 min.Finally, by 1.5
Ml(100 mM) NaBH4Aqueous solution rapidly joins in reaction vessel, it can be observed that solution is become orange red from faint yellow, obtains aurosol, such as Fig. 2.This aurosol is stirred 12 h, standby；
First, being joined in 10 ml deionized waters by 0.1 g ZnO nano cone, in order to make ZnO nano cone fully dispersed, the method that experiment uses is stirring 10
Min, ultrasonic 10 min.Dropwise adding small particle Au colloidal sol prepared by 10 ml in above-mentioned ZnO nano cone aqueous solution, stir the mixture for 24 h, products therefrom is centrifuged, washs, is drying to obtain small particle Au nanoparticle and ZnO nano cone complex, such as Fig. 3.
Embodiment 2
A. with embodiment 1
B. the HAuCl of 5 ml 10 mM is taken4Aqueous solution, joins in 45 ml deionized waters, is configured to the HAuCl of 50 ml 1 mM4Aqueous solution.This aqueous solution is heated to 100 DEG C, under conditions of high degree of agitation, rapidly joins 5 ml 38.8 mM sodium citrate aqueous solutions.Reacting 15 min after adding sodium citrate, the color of aqueous solution will be from the colourless peony that becomes, and it is 14.0 that gained is particle diameter
The Au colloidal sol of nm, such as Fig. 4.Now, do not continue to heating, allow solution can carry out subsequent experimental after naturally cooling to room temperature；
First, being joined in 10 ml deionized waters by 0.1 g ZnO nano cone, in order to make ZnO nano cone fully dispersed, the method that experiment uses is stirring 10
Min, ultrasonic 10 min.Dropwise boring the Au colloidal sol adding the big particle diameter prepared by 2.5 ml in aqueous solution to above-mentioned ZnO nano, stir 36 hours, products therefrom is centrifuged and uses the alternately washing of deionized water and ethanol, puts and is dried in an oven.Products therefrom is big particle diameter Au nanoparticle and bores complex with ZnO nano, such as Fig. 5.
Embodiment 3
A. with embodiment 1
B. with embodiment 1
First, 0.1 g ZnO nano cone is joined in 10 ml deionized waters, stirs 10 min, ultrasonic 10 min so that it is fully dispersed.Dropwise adding small particle Au colloidal sol prepared by 20 ml in above-mentioned ZnO nano cone aqueous solution, stir the mixture for 24 h, products therefrom is centrifuged, washs, is drying to obtain small particle Au nanoparticle and ZnO nano cone complex.
Embodiment 4
A. with embodiment 1
B. with embodiment 2
First, 0.1 g ZnO nano cone is joined in 10 ml deionized waters, stirs 10 min, ultrasonic 10 min so that it is fully dispersed.Dropwise adding small particle Au colloidal sol prepared by 5 ml in above-mentioned ZnO nano cone aqueous solution, stir the mixture for 36 h, products therefrom is centrifuged, washs, is drying to obtain big particle diameter Au nanoparticle and ZnO nano cone complex.
Embodiment 5
A. with embodiment 1
B. with embodiment 1
First, being joined in 10 ml deionized waters by 0.1 g ZnO nano cone, in order to make ZnO nano cone fully dispersed, the method that experiment uses is stirring 10
Min, ultrasonic 10 min.Dropwise adding small particle Au colloidal sol prepared by 10 ml in above-mentioned ZnO nano cone aqueous solution, stir the mixture for 24 h, products therefrom is centrifuged, washs, is drying to obtain small particle Au nanoparticle and ZnO nano cone complex.Gained Au/ZnO composite nano materials is calcined 2 h at 300 DEG C.
Embodiment 6
A. with embodiment 1
B. with embodiment 1
First, being joined in 10 ml deionized waters by 0.1 g ZnO nano cone, in order to make ZnO nano cone fully dispersed, the method that experiment uses is stirring 10
Min, ultrasonic 10 min.Dropwise adding small particle Au colloidal sol prepared by 10 ml in above-mentioned ZnO nano cone aqueous solution, stir the mixture for 24 h, products therefrom is centrifuged, washs, is drying to obtain small particle Au nanoparticle and ZnO nano cone complex.Gained Au/ZnO composite nano materials is calcined 2 h at 400 DEG C.
Claims (3)
1. a zinc-oxide nano cone gas sensitive for Au load, the particle diameter of the Au loaded is respectively 3 ~ 14 nm；Wherein zinc-oxide nano cone side is isosceles triangle, and a length of about 200 nm of its waist, bottom surface is regular hexagon, and its length of side is about 100 nm, and pattern is single, size uniform, and Au nanoparticle is attached to its surface.
The preparation method of the zinc-oxide nano cone gas sensitive of Au the most according to claim 1 load, concrete preparation process is as follows:
A. using solvent-thermal method to prepare the ZnO nano cone of favorable dispersibility, gained zinc-oxide nano cone side is isosceles triangle, and a length of about 200 nm of its waist, bottom surface is regular hexagon, and its length of side is about 100 nm, and pattern is single, size uniform；
B. take 0.1 g ZnO nano cone to be well dispersed in 10 ml deionized waters, add the Au colloidal sol that 20 ml particle diameters are 3 ~ 14 nm, stirring 24 ~ 36 h, obtaining Au/ZnO nanocone complex, gained products therefrom is centrifuged, washs, is drying to obtain the ZnO nano cone gas sensitive of different-grain diameter Au nanometer particle load.
The application of the zinc-oxide nano cone gas sensitive of Au the most according to claim 1 load, this gas sensitive is used for making alcohol gas sensor.
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Cited By (2)
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| CN107064220A (en) * | 2017-01-23 | 2017-08-18 | 吉林大学 | Using the spherical multi-slice structure ZnO of ultra-fine Au Nanoparticle Modifieds as the acetylene gas sensor and preparation method of sensitive layer |
| CN112362701A (en) * | 2020-11-16 | 2021-02-12 | 吉林大学 | N-amyl alcohol sensor of Au-loaded ZnO nano composite material synthesized based on one-step solvothermal method and preparation method thereof |
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| CN107064220A (en) * | 2017-01-23 | 2017-08-18 | 吉林大学 | Using the spherical multi-slice structure ZnO of ultra-fine Au Nanoparticle Modifieds as the acetylene gas sensor and preparation method of sensitive layer |
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| CN112362701A (en) * | 2020-11-16 | 2021-02-12 | 吉林大学 | N-amyl alcohol sensor of Au-loaded ZnO nano composite material synthesized based on one-step solvothermal method and preparation method thereof |
| CN112362701B (en) * | 2020-11-16 | 2022-03-08 | 吉林大学 | N-amyl alcohol sensor of Au-loaded ZnO nano composite material synthesized based on one-step solvothermal method and preparation method thereof |
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