CN104492367B - Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof - Google Patents
Super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure and preparation method thereof Download PDFInfo
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Abstract
The invention provides a preparation method of a super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure, and the method is as follows: 1, synthesis of a micro-nano hierarchical structure comprising ultrathin porous nano single crystal ZnO nanosheets; 2, modification of the ZnO micro-nano hierarchical structure; and 3, preparation of the precious metal-modified ZnO micro-nano hierarchical structure. The super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure prepared by the method has the characteristics of single crystal, ultrathin thin, porous and hierarchical structure and assistant precious metal nanoparticle modification, the points are beneficial to improvement of the sensitivity of ZnO to organic gaseous pollutants, compared with the ZnO materials in the prior art, the super high sensitivity precious metal-modified ZnO micro-nano hierarchical structure has super high gas sensitivity, and the detection limit is less than 1ppb.
Description
Technical field
The present invention relates to the detecting instrument of organic gaseous contamination thing, and in particular to a kind of that there is superelevation spirit to organic pollution
Noble metal decorated ultra thin single crystalline porous ZnO micro-nano hierarchy of sensitivity and preparation method thereof.
Background technology
Organic gaseous contamination thing ethanol, formaldehyde, benzene, toluene brought by finishing material etc., has to the healthy of people
Very big infringement, easily causes the diseases such as respiratory tract disease, pneumonia and tracheitiies, or even also carcinogenic risk.Therefore it is right
The detection of organic gaseous contamination thing is widely paid close attention to always with real-time monitoring.The detection conventional art of current organic gaseous contamination thing
It is chemical analysis, such as gas chromatogram and MS, this detection method workload is big, program is complicated, apparatus expensive,
And can not realize real-time detection.Based on the electricity gas sensor of conductor oxidate, due to low in energy consumption, response is fast, knot
Structure is simple, technical maturity the advantages of, be with a wide range of applications in terms of detection and the real-time monitoring of organic pollution.
ZnO is used as a kind of broad stopband（3.37eV）Quasiconductor, with electron mobility it is high, chemical stability is good the features such as,
It embodies preferable gas-sensitive property to indoor air pollutants.But ZnO that traditional sensors are often based upon block is sensitive
Material, therefore its sensitivity is not high.Research shows, with ultra-thin, monocrystalline, porous, the ZnO material of hierarchy and is aided with
Noble metal nano particles modification can improve sensitivity of the ZnO to indoor air pollutants, because：（1）When ZnO is smaller in size than consumption
When using up 2 times of slice width degree（That is 22nm）, whole granule all becomes depletion layer, and the mobile charge of nearly all semi-conducting material is all
It is bound on the oxygen molecule of absorption, when particle surface capture target molecule release electric charge, electronics is by surface adsorption oxygen molecule
Release, causes the great variety of response current, so as to improve the sensitivity of sensor；（2）Mono-crystalline structures then due to without crystal boundary,
It is not lost when electronics is transmitted in vivo, sensitivity not only can be improved, it can also be ensured that the stability of sensor；（3）Porous
Structure is conducive to increasing the specific surface area of material, so as to increase the activated adoption site to determinand；（4）Hierarchy is then not only
Passage required under test gas diffusion can be provided, and also ensure that ultra-thin materials avoid reuniting；（5）Noble metal nano
Grain is due to high catalytic activity, increasing the reactivity of sensitive material.
The existing sensor based on ZnO is all often to realize spirit using in five mentioned above or several
The lifting of sensitivity, but can simultaneously realize that this five but have no report.Therefore, how to prepare with ultra-thin porous monocrystalline
The hierarchy of ZnO and how to realize one be modified into improve transducer sensitivity of precious metal material nanometer it is huge
Challenge.
The content of the invention
The present invention is for based on traditional ZnO material under-sensitive shortcoming, it is proposed that a kind of noble metal granule modification
The ZnO micro-nano hierarchies of ultra thin single crystalline porous ZnO nanometer sheet composition.
A kind of preparation method of supersensitive noble metal decorated ZnO micro-nano hierarchies, comprises the steps：
（1）Synthesis ZnO micro-nano hierarchies：
By zinc acetate (Zn (CH3COO)2) and carbamide (CO (NH2)2) dissolving form clear solution in a solvent；Then will be saturating
Bright solution is sealed, is incubated after 3-24h, it is centrifuged, is washed, being dried to obtain ultrathin nanometer ZnO precursor；Most
Ultrathin nanometer ZnO precursor is made annealing treatment afterwards, that is, is obtained the ZnO micro-nanos being made up of ultra thin single crystalline porous ZnO nanometer sheet
Hierarchy；
（2）ZnO micro-nano hierarchies it is modified：
By Jing（1）The ZnO micro-nanos hierarchy of preparation is molten for the polymer coupler of 7.5-9 in pH value by ultrasonic disperse
In liquid, after stirring, by centrifugation ZnO micro-nano hierarchies are separated again, and dry the ZnO micro-nanos classification knot that must be modified
Structure；
（3）Prepare noble metal nano particles colloidal sol：
First mass concentration is added for the soluble precious-metal solution of 0.1%-4% and is boiled in deionized water, in boiling process
Middle addition reducing agent, after then proceeding to heat 5-10 minutes, natural cooling is obtained with certain size and favorable dispersibility
Noble metal nano particles colloidal sol；
（4）Prepare noble metal decorated ZnO micro-nano hierarchies：
Modified ZnO micro-nanos hierarchy is mixed with noble metal nano particles colloidal sol, 0.5-4h is stirred, by electrostatic
Interaction modifies noble metal granule on ZnO micro-nano hierarchies, is centrifuged, the noble metal decorated ZnO micro-nanos of drying
Hierarchy.
Further, the step（1）The mass ratio of middle zinc acetate and carbamide is 0.5-2：1-8；
It by deionized water and ethylene glycol is by volume 0.5-5 that the solvent is：1 is constituted.
Further, the step（1）Middle insulation 3-24h is referred to and is incubated 3-24h in temperature is for 70-110 DEG C of baking oven；
The annealing is referred to and made annealing treatment in the Muffle furnace or tube furnace that temperature is 250-500 DEG C.
Further, the step（1）It is 50nm- that middle ultra thin single crystalline porous ZnO nanometer sheet refers to length for 1-20 m, width
10 m, thickness are less than 22nm, the ZnO nano piece that crystalline phase is buergerite phase；
The ZnO micro-nanos hierarchy refers to that flower-shaped or spherical, the particle diameter that are made up of ZnO nano piece are dividing for 1-100 m
Level structure.
Further, the step（2）Middle polymer coupler refers to amino silicane coupling agent, mercaptosilane coupling agents or poly- second
Alkene imines.
Further, the step（2）The time 2-24h stirred after middle ultrasonic disperse；The drying is referred to and is less than in temperature
Dried in 80 DEG C of baking oven.
Further, the step（3）Described in soluble precious-metal refer to granular size be the gold, silver of 5-100nm, platinum or
Palladium；The soluble precious-metal solution includes chlorauric acid solution, silver nitrate solution, platinum acid chloride solution and chlorine palladium acid solution etc..
Further, the step（3）Middle reducing agent is the citric acid solution or trisodium citrate that mass concentration is 0.1%-4%
Solution, the soluble precious-metal solution is 0.5 with the mass ratio of reducing agent:1-1:5.
Further, the step（4）In the be modified weight of ZnO micro-nanos hierarchy and noble metal nano particles compare 1：
0.005-0.05。
It is a further object to provide a kind of noble metal decorated ZnO micro-nanos by prepared by above-mentioned preparation method
Hierarchy, the form of the noble metal decorated ZnO micro-nano hierarchies is that spherical or flower-shaped, particle diameter is 1-100 m, and its is right
Low concentration organic gaseous contamination thing has hypersensitivity.
Because ZnO is amphoteric metal oxide, if the pH of high molecular polymer dispersion liquid is too high, alkalescence is too strong to be caused
The dissolving in a polymer solution of ZnO hierarchies, therefore its pH value must be controlled in 7.5-9 in the range of this.
The present invention by hydro-thermal method by size the smooth ZnO nano piece heap body of 100nm-10 m constitute with spherical or
The ZnO precursor of flower-shaped hierarchy；Carry out annealing by ZnO precursor again to obtain by ultra thin single crystalline porous ZnO nanometer sheet
The ZnO micro-nano hierarchies of composition；Then it is modified.Finally by modified ZnO micro-nanos hierarchy and noble metal nano
Particle colloidal sols are mixed, and are modified by electrostatic interaction, obtain final product noble metal decorated ZnO micro-nano hierarchies.I.e.
Noble metal decorated ZnO micro-nano hierarchies prepared by the present invention are that the characteristics of utilizing its porous with hierarchy improves to be detected
Absorbability of the molecule on ZnO surfaces；Increase the sensitivity of sensor and steady using ultra-thin, monocrystalline and noble metal decorated advantage
It is qualitative, so as to realize that the hypersensitivity to low concentration organic gaseous contamination thing is detected.
So beneficial effects of the present invention have：
1st, noble metal decorated ZnO micro-nano hierarchies prepared by the present invention have ultra-thin, monocrystalline, porous, hierarchy
Feature, and be aided with noble metal nano particles modification and can improve sensitivity of the ZnO to indoor air pollutants, it is relative to existing
Some ZnO materials, have superelevation Gas-sensing measurment to organic gaseous contamination thing ethanol, formaldehyde, acetone etc., and test limit is reachable
1ppb, three orders of magnitude higher than sensitivity in existing ZnO blocks and powder body material, also far above conventional nano material.
2nd, noble metal decorated ZnO micro-nanos hierarchy prepared by the present invention is using raising the characteristics of porous and hierarchy
Molecules detected increases the sensitive of sensor in the absorbability on ZnO surfaces using ultra-thin, monocrystalline and noble metal decorated advantage
Degree and stability, so as to realize that the hypersensitivity to low concentration organic gaseous contamination thing is detected.
3rd, preparation method of the invention can be with its more of the size of precise control ZnO micro-nano hierarchy, pattern and composition
The loose structure of hole ultra thin single crystalline ZnO nano piece, size and thickness, are conducive to the raising of ZnO micro-nano hierarchy sensitivity,
Specifically：By the size and pattern that control ZnO micro-nano hierarchies, can be with the pore structure in Effective Regulation hierarchy, can
So that testing molecule can effectively in ZnO material diffusion inside；The hole of its porous ultra thin single crystalline ZnO nano piece is constituted by control
Structure, can increase the active adsorption sites in ZnO material, so as to effectively catch testing molecule；By controlling nanometer sheet
Size and thickness, can control the ratio of depletion layer on ZnO nano piece, reduce the internal loss of electronics.
4th, the present invention adjusts the dense of polymer coupler solution by controlling polymer coupler solution ph for 7.5-9
Degree, can also effectively prevent due to polymer coupler solution alkaline mistake while realizing that ZnO micro-nanos hierarchy is modified
The ZnO dissolvings for causing by force.
5th, the invention provides a kind of novel method that noble metal granule is modified on ZnO micro-nano hierarchies, can be with
Precise control needs the modification amount of the noble metal granule of modification, and is effectively increased the Gas-sensing measurment of ZnO micro-nano hierarchies.Together
When, Preparation equipment small investment, synthesis technique is simple, processing ease.
6th, the mentality of designing and preparation method of ZnO sensitive materials provided by the present invention, is with superelevation sensitive property
The practical application of sensor sensing material provides new mentality of designing and preparation method.
Description of the drawings
Fig. 1 is the electron-microscope scanning figure of the ZnO micro-nano hierarchies prepared by the present invention.
Fig. 2 is the electron-microscope scanning figure and electronic diffraction of the ultra thin single crystalline porous ZnO nanometer sheet for constituting ZnO micro-nano hierarchies
Figure.
Fig. 3 is the electron-microscope scanning figure and transmission plot of the ZnO micro-nano hierarchies of Argent grain modification.
Fig. 4 is the XRD spectra control of the ZnO micro-nano hierarchies before Argent grain modification and after modification.
Fig. 5 is air-sensitive detection figure of the ZnO micro-nanos hierarchy to ethanol before Argent grain modification and after modification.
Specific embodiment
Embodiment 1
（1）The synthesis of ZnO micro-nano hierarchies：By the zinc acetate (Zn (CH of 1g3COO)2) and 4g carbamide (CO (NH2)2) molten
Solution is by volume 3 by deionized water and ethylene glycol in 40ml:In 1 mixed solvent for constituting, stirring forms clear solution；Again will
It is transferred in the conical flask of a sealing, and is positioned in the baking oven of 90 C temperature, is incubated 10h；Then it is centrifuged
Go out white precipitate, deionized water put it into after being cleaned 2-3 time 60 C vacuum drying ovens it is dry ZnO precursor；Most
Dry ZnO precursor is made annealing treatment in the Muffle furnace or tube furnace of 400 C afterwards, that is, is obtained by ultra thin single crystalline porous ZnO
The ZnO micro-nano hierarchies of nanometer sheet composition.
In ZnO micro-nanos hierarchy such as Fig. 1 manufactured in the present embodiment shown in 1d, it is shaped as flower-shaped.
In addition, the electron-microscope scanning figure of ultra thin single crystalline porous ZnO nanometer sheet manufactured in the present embodiment and electronogram such as Fig. 2
Shown, it is about the m of 5 m, width about 1, thickness about 10nm, and nano aperture is evenly distributed in whole nanometer sheet.Wherein scheme
2a, 2b in 2 is the front of ultra thin single crystalline porous ZnO nanometer sheet manufactured in the present embodiment and side electron-microscope scanning figure, it is seen that single
The cavernous structure and ultra-thin thickness of the ZnO nano piece of piece；2c, 2d are the transmission photos of monolithic ZnO nano piece, its porous knot
Structure is high-visible；2e is the electronogram of monolithic ZnO nano piece, and its diffraction pattern is rendered as the dots structure of rule, and this says
Clear nanometer sheet is mono-crystalline structures；2f is the lattice fringe picture of ZnO nano piece, it is seen that its lattice fringe is arranged in good order,
Demonstrate the mono-crystalline structures of ZnO nano piece.
（2）ZnO micro-nano hierarchies it is modified：Take 50mg Jing（1）Prepared flower-shaped ZnO micro-nanos hierarchy ultrasound point
Dissipate in the polyethylenimine solution that pH value is 8.5, after stirring 3h by centrifugation by modified ZnO micro-nanos hierarchy from
Separate in solution, and dry in 75 C baking ovens.
（3）Prepare noble metal nano particles colloidal sol：First the silver nitrate solution 100ml of 1wt% is boiled, in boiling process
The mass ratio for adding silver nitrate solution and 1wt% citric acid solutions, silver nitrate solution and citric acid solution is 1:3, continue to heat 10
Natural cooling can obtain the Argent grain colloidal sol with certain size favorable dispersibility after minute.
（4）Prepare noble metal decorated ZnO micro-nano hierarchies：By modified spherical ZnO micro-nanos hierarchy 100mg
It is mixed in proportion with the silver sol of silver-containing nanoparticles 1mg, 0.5h is stirred, by electrostatic interaction i.e. in flower-shaped ZnO micro-nanos
Upper Argent grain is modified on hierarchy, is then centrifuged for, the flower-shaped ZnO micro-nanos point of the Argent grain modification that drying load capacity is 1%
Level structure.
3a, 3b institute in the electron-microscope scanning figure such as Fig. 3 of the flower-shaped ZnO micro-nanos hierarchy of Argent grain modification prepared by the present invention
Show, it is seen that Ag is substantial amounts of to be distributed in the nanometer sheet of micro-nano structure；In its transmission plot such as Fig. 3 shown in 3c, 3d, it can be seen that silver
Grain uniform particle diameter, and be uniformly distributed on ZnO nano piece surface.
In the XRD spectra such as Fig. 4 of modified ZnO micro-nano hierarchies shown in 4a, and the flower-shaped ZnO of Argent grain modification is micro-
Receive in the XRD spectra such as Fig. 4 of hierarchy shown in 4b, it is seen that the XRD diffraction maximums of the ZnO micro-nano hierarchies before Argent grain modification
Buergerite ZnO structures are all belonged to, and a diffraction maximum for belonging to Ag (200) face are substantially occurred in that after Argent grain modification, it was demonstrated that
Modifications of the Ag in the classification of ZnO micro-nanos；And the peak of Ag is also occurred in that except Zn and O in 4b figures, Ag has been also demonstrated
Modification is in the classification of ZnO micro-nanos.
The ZnO micro-nanos hierarchy of the Argent grain modification after preparing to the present embodiment has excellent to organic gaseous contamination thing
Response sensitivity, in its air-sensitive detection such as Fig. 5 to ethanol shown in 5a, its test limit to ethanol is up to 1 ppb；And it rings
Answer in sensitivity and gas concentration linear relationship chart as Fig. 5 shown in 5b, it is seen that the ZnO micro-nano hierarchies of Ag particle modifications are to second
The response of alcohol exists good linear, is expected to be applied to actual ethanol sensor detection.
Embodiment 2
（1）The synthesis of ZnO micro-nano hierarchies：By the zinc acetate (Zn (CH of 0.5g3COO)2) and 3g carbamide (CO (NH2)2)
It is by volume 1 that 50ml is dissolved in by deionized water and ethylene glycol:In 1 mixed solvent for constituting, stirring 3min forms transparent molten
Liquid；In transferring them to the conical flask of a sealing again, and it is positioned in the baking oven of 75 C temperature, is incubated 8h；Then use from
The method of the heart separates the white precipitate for obtaining from solution, and puts it into after deionized water is cleaned 2-3 time
60 C vacuum drying ovens it is dry ZnO precursor；Finally dry ZnO precursor is made annealing treatment under 300 C, you can obtain
Spherical ZnO micro-nanos hierarchy as shown in 1c in Fig. 1, constitutes 2 m that are about of its ultra thin single crystalline porous ZnO nanometer sheet, wide
About 400nm, thickness about 8nm are spent, and nano aperture is evenly distributed in whole nanometer sheet.
（2）ZnO micro-nano hierarchies it is modified：Take 50mg Jing（1）The flower-shaped ZnO micro-nanos hierarchy ultrasonic disperse for preparing
In the polyethylenimine solution that pH value is 7.8,2h is stirred.Then by being centrifuged modified ZnO micro-nanos hierarchy from solution
In separate, in 70 C baking ovens dry.
（3）Prepare noble metal nano particles colloidal sol：The chlorauric acid solution 100ml of 0.5 wt % is boiled first.In boiling
During add 0.5% trisodium citrate, the mass ratio of its chlorauric acid solution and trisodium citrate is 1:2, then proceed to heating
Natural cooling can obtain the aurosol with certain size favorable dispersibility after 10 minutes.
（4）Prepare noble metal decorated ZnO micro-nano hierarchies：By modified spherical ZnO micro-nanos hierarchy
1000mg is mixed in proportion with the aurosol containing gold nano grain 10mg, stirs 1h, and by electrostatic interaction gold is capable of achieving
Modification of the granule on spherical ZnO micro-nanos hierarchy, centrifugation, drying load capacity is the spherical of 1% gold grain modification
ZnO micro-nano hierarchies, it has excellent response sensitivity to organic gaseous contamination thing, and the test limit of wherein PARA FORMALDEHYDE PRILLS(91,95) is reachable
0.05 ppm。
Embodiment 3
（1）The synthesis of ZnO micro-nano hierarchies：By the zinc acetate (Zn (CH of 0.5g3COO)2) and 1g carbamide (CO
(NH2)2) be dissolved in 40ml by deionized water and ethylene glycol by volume be 1:In 1 mixed solvent for constituting, stirring forms transparent
Solution, then transfer them in the conical flask of a sealing, and be positioned in the baking oven of 75 C temperature, it is incubated 5h；Then use
The method of centrifugation separates the white precipitate for obtaining from solution, and is put after deionized water is cleaned 2-3 time
Enter 60 C vacuum drying ovens it is dry ZnO precursor；Finally dry ZnO precursor is annealed under 300 C, you can obtain as
Spherical ZnO micro-nanos hierarchy in Fig. 1 shown in 1b, constitute its ultra thin single crystalline porous ZnO nanometer sheet is about 4 m, width
About 500nm, thickness about 12nm, and nano aperture is evenly distributed in whole nanometer sheet.
（2）ZnO micro-nano hierarchies it is modified：Take 50mg Jing（1）The flower-shaped ZnO micro-nanos hierarchy ultrasonic disperse for preparing
In the polyethylenimine solution that pH value is 8,5h is stirred.Then ZnO micro-nano hierarchies are separated from solution by centrifugation
Out, dry in 65 C baking ovens.
（3）Prepare noble metal nano particles colloidal sol：The platinum acid chloride solution 100ml of 1wt % is boiled first.In boiling process
The mass ratio of 1% citric acid of middle addition, its platinum acid chloride solution and citric acid is 1：2；Natural cooling after then proceeding to heat 10 minutes
The platinum grain colloidal sol with certain size favorable dispersibility can be obtained.
（4）Prepare noble metal decorated ZnO micro-nano hierarchies：By modified spherical ZnO micro-nanos hierarchy 100mg
It is mixed in proportion with the platinum colloidal sol containing Pt nanoparticle 2mg, stirs 1h, platinum grain is capable of achieving in ball by electrostatic interaction
Modification on shape ZnO micro-nano hierarchies, centrifugation, drying load capacity is the spherical ZnO micro-nanos point of 2% platinum grain modification
Level structure, it has excellent response sensitivity to organic gaseous contamination thing, wherein to the test limit of acetone up to 10 ppb.
Embodiment 4
（1）The synthesis of ZnO micro-nano hierarchies：By the zinc acetate (Zn (CH of 0.8g3COO)2) and 3.5g carbamide (CO
(NH2)2) be dissolved in 80ml by deionized water and ethylene glycol by volume be 2:In 1 mixed solvent for constituting, stirring forms transparent
Solution, then transfer them in the conical flask of a sealing, and be positioned in the baking oven of 80 C temperature, it is incubated 8h；Then use
The method of centrifugation separates the white precipitate for obtaining from solution.Deionized water puts it into after being cleaned 2-3 time
60 C vacuum drying ovens it is dry ZnO precursor；Finally dry ZnO precursor is annealed under 300 C, you can obtain such as figure
Spherical ZnO micro-nanos hierarchy in 1 shown in 1c, constitute its ultra thin single crystalline porous ZnO nanometer sheet is about 5 m, and width is about
800nm, thickness about 10nm.
（2）ZnO micro-nano hierarchies it is modified：Take 50mg Jing（1）The flower-shaped ZnO micro-nanos hierarchy for preparing, ultrasound point
Dissipate in the polyethylenimine solution that 100ml pH value is 8, stir 12h.Then by centrifugation by ZnO micro-nanos hierarchy from molten
Separate in liquid, dry in 70 C baking ovens.
（3）Prepare noble metal nano particles colloidal sol：The chlorine palladium acid solution 100ml of 0.1 wt % is boiled first.In boiling
During add 0. 1% citric acid solution, the mass ratio of its chlorine palladium acid solution and citric acid solution is by 1:1 ratio addition,
Natural cooling can obtain the palladium particle colloidal sols with certain size favorable dispersibility after then proceeding to heat 10 minutes.
（4）Prepare noble metal decorated ZnO micro-nano hierarchies：By modified spherical ZnO micro-nanos hierarchy 100mg
It is mixed in proportion with the palladium colloidal sol containing palladium nano-particles 2mg, stirs 2h, palladium granule is capable of achieving in ball by electrostatic interaction
Modification on shape ZnO micro-nano hierarchies, centrifugation, drying load capacity is the spherical ZnO micro-nanos point of 2% palladium particle modification
Level structure, it has excellent response sensitivity to organic gaseous contamination thing, wherein to the test limit of acetone up to 5 ppb.
Embodiment 5
（1）The synthesis of ZnO micro-nano hierarchies：By the zinc acetate (Zn (CH of 1g3COO)2) and 1g carbamide (CO (NH2)2)
It is by volume 0.5 that 30ml is dissolved in by deionized water and ethylene glycol:In 1 mixed solvent for constituting, stir 5min to be formed
Bright solution, then transfer them in the conical flask of a sealing, and be positioned in the baking oven of 70 C temperature, it is incubated 8h；Then make
The white precipitate for obtaining is separated from solution with the method for centrifugation.Deionized water is put after being cleaned 2-3 time
Enter 60 C vacuum drying ovens it is dry ZnO precursor；Finally dry ZnO precursor is annealed under 300 C, you can obtain as
Spherical ZnO micro-nanos hierarchy in Fig. 1 shown in 1a, constitutes its ultra thin single crystalline porous ZnO nanometer sheet and is about 1 m, and width is about
50nm, thickness about 8nm, and nano aperture is evenly distributed in whole nanometer sheet.
（2）ZnO micro-nano hierarchies it is modified：Take 50mg Jing（1）The flower-shaped ZnO micro-nanos hierarchy for preparing, ultrasound point
Dissipate in the polyethylenimine solution that 100ml pH value is 8, stir 18h.Then by centrifugation by ZnO micro-nanos hierarchy from molten
Separate in liquid, dry in 75 C baking ovens.
（3）Prepare noble metal nano particles colloidal sol：The chlorauric acid solution 100ml of 0.1 wt % is boiled first.In boiling
During add 0.1% citric acid solution, the mass ratio of its chlorauric acid solution and citric acid solution is 1：1, then proceed to heating 10
Natural cooling can obtain the gold grain colloidal sol with certain size favorable dispersibility after minute.
（4）Prepare noble metal decorated ZnO micro-nano hierarchies：By modified spherical ZnO micro-nanos hierarchy
1000mg is mixed in proportion with the aurosol containing gold nano grain 5mg, stirs 0.5h, and by electrostatic interaction gold is capable of achieving
Modification of the granule on spherical ZnO micro-nanos hierarchy, centrifugation, drying load capacity is the spherical of 0.5% gold grain modification
ZnO micro-nano hierarchies, it has excellent response sensitivity to organic gaseous contamination thing, and the test limit of wherein PARA FORMALDEHYDE PRILLS(91,95) is reachable
0.05 ppm。
Embodiment 6
（1）The synthesis of ZnO micro-nano hierarchies：By the zinc acetate (Zn (CH of 1.3g3COO)2) and 5.5g carbamide (CO
(NH2)2) be dissolved in 40ml by deionized water and ethylene glycol by volume be 4:In 1 mixed solvent for constituting, stirring a period of time
To form clear solution, then this transparent solution is transferred in the conical flask of a sealing, and is positioned over the baking of 100 C temperature
In case, 12h is incubated；Then the white precipitate for obtaining is separated from solution using the method for centrifugation.Deionized water will
Its cleaning 2-3 time after put it into 60 C vacuum drying ovens it is dry ZnO precursor；Finally by dry ZnO precursor 400
Anneal under C, you can obtain flower-shaped ZnO micro-nanos hierarchy, constitute its ultra thin single crystalline porous ZnO nanometer sheet is about 10 m,
The m of width about 2, thickness about 8nm.
（2）ZnO micro-nano hierarchies it is modified：50mg Jing（1）The flower-shaped ZnO micro-nanos hierarchy for preparing takes, ultrasound point
Dissipate in the polyethylenimine solution that 100ml pH value is 9, stir 3h.Then by centrifugation by ZnO micro-nanos hierarchy from molten
Separate in liquid, dry in 80 C baking ovens.
（3）Prepare noble metal nano particles colloidal sol：The chlorauric acid solution 100ml of 1wt % is boiled first.In boiling process
The mass ratio of 1% citric acid solution of middle addition, its chlorauric acid solution and citric acid solution is 1：4, after then proceeding to heating 10 minutes
Natural cooling can obtain the gold grain colloidal sol with certain size favorable dispersibility.
（4）Prepare noble metal decorated ZnO micro-nano hierarchies：By modified spherical ZnO micro-nanos hierarchy 100mg
It is mixed in proportion with the aurosol containing gold nano grain 3mg, stirs 3h, gold grain is capable of achieving in ball by electrostatic interaction
Modification on shape ZnO micro-nano hierarchies, centrifugation, drying load capacity is the spherical ZnO micro-nanos point of 3% gold grain modification
Level structure, it has excellent response sensitivity to organic gaseous contamination thing, and wherein the test limit of PARA FORMALDEHYDE PRILLS(91,95) is up to 0.08 ppm.
Embodiment 7
（1）The synthesis of ZnO micro-nano hierarchies：By the zinc acetate (Zn (CH of 1.5g3COO)2) and 6g carbamide (CO
(NH2)2) be dissolved in 40ml by deionized water and ethylene glycol by volume be 5:In 1 mixed solvent for constituting, stirring a period of time
To form clear solution, then transfer them in the conical flask of a sealing, and be positioned in the baking oven of 110 C temperature, be incubated
18h；Then the white precipitate for obtaining is separated from solution using the method for centrifugation.Deionized water is cleaned 2-3
Put it into after secondary 60 C vacuum drying ovens it is dry ZnO precursor；Finally dry ZnO precursor is annealed under 500 C,
Flower-shaped ZnO micro-nanos hierarchy is obtained, 15 m that are about of its ultra thin single crystalline porous ZnO nanometer sheet, width about 5 is constituted
M, thickness about 8nm.
（2）ZnO micro-nano hierarchies it is modified：Take 50mg Jing（1）The flower-shaped ZnO micro-nanos hierarchy for preparing, ultrasound point
Dissipate in the polyethylenimine solution that 100ml pH value is 8, stir 24h.Then by centrifugation by ZnO micro-nanos hierarchy from molten
Separate in liquid, dry in 75 C baking ovens.
（3）Prepare noble metal nano particles colloidal sol：The chlorauric acid solution 100ml of 4 wt % is boiled first.Boiled
2% citric acid solution is added in journey, the mass ratio of its chlorauric acid solution and citric acid solution is 1：5, then proceed to heating 10 minutes
Afterwards natural cooling can obtain the gold grain colloidal sol with certain size favorable dispersibility.
（4）Prepare noble metal decorated ZnO micro-nano hierarchies：By modified spherical ZnO micro-nanos hierarchy 100mg
It is mixed in proportion with the aurosol containing gold nano grain 5mg, stirs 4h, gold grain is capable of achieving in ball by electrostatic interaction
Modification on shape ZnO micro-nano hierarchies, centrifugation, drying load capacity is the spherical ZnO micro-nanos point of 5% gold grain modification
Level structure, it has excellent response sensitivity to organic gaseous contamination thing, wherein to the test limit of ethanol up to 0.01 ppm.
Embodiment 8
（1）The synthesis of ZnO micro-nano hierarchies：By the zinc acetate (Zn (CH of 2g3COO)2) and 8g carbamide (CO (NH2)2)
It is by volume 8 that 40ml is dissolved in by deionized water and ethylene glycol:In 1 mixed solvent for constituting, stirring forms clear solution, then
In transferring them to the conical flask of a sealing, and it is positioned in the baking oven of 110 C temperature, is incubated 24h；Then using centrifugation
Method separates the white precipitate for obtaining from solution.Deionized water puts it into 60 C after being cleaned 2-3 time true
Empty drying baker it is dry ZnO precursor；Finally dry ZnO precursor is annealed under 500 C, you can obtain flower-shaped ZnO micro-
Receive hierarchy, constitute 20 m that are about of its ultra thin single crystalline porous ZnO nanometer sheet, the m of width about 10, thickness about 22nm.
（2）ZnO micro-nano hierarchies it is modified：Take 50mg Jing（1）The flower-shaped ZnO micro-nanos hierarchy for preparing, ultrasound point
Dissipate in the polyethylenimine solution that 100ml pH value is 7.5, stir 4h.Then by centrifugation by ZnO micro-nanos hierarchy from
Separate in solution, dry in 80 C baking ovens.
（3）Prepare noble metal nano particles colloidal sol：The chlorauric acid solution 100ml of 4wt % is boiled first.In boiling process
The mass ratio of 2% citric acid solution of middle addition, its chlorauric acid solution and citric acid solution is 1：5, after then proceeding to heating 10 minutes
Natural cooling can obtain the gold grain colloidal sol with certain size favorable dispersibility.
（4）Prepare noble metal decorated ZnO micro-nano hierarchies：By modified spherical ZnO micro-nanos hierarchy 100mg
Mix with the aurosol containing gold nano grain 2.5mg, stir 4h, gold grain is capable of achieving spherical by electrostatic interaction
Modification on ZnO micro-nano hierarchies, centrifugation, drying load capacity is the spherical ZnO micro-nanos point of 2.5% gold grain modification
Level structure, its test limit to PARA FORMALDEHYDE PRILLS(91,95) is up to 0.01 ppm.
Above example is not limited only to protection scope of the present invention, all to be modified based on the basic thoughts invented
Or change belong to protection scope of the present invention.
Claims (7)
1. a kind of preparation method of supersensitive noble metal decorated ZnO micro-nano hierarchies, it is characterised in that：Including under
State step：
（1）Synthesis ZnO micro-nano hierarchies：
By zinc acetate (Zn (CH3COO)2) and carbamide (CO (NH2)2) in mass ratio it is 0.5-2：1-8 dissolvings form in a solvent saturating
Bright solution；Then clear solution is sealed, is placed in being incubated after 3-24h in 70-110 DEG C of baking oven, it is centrifuged
Separate, wash, being dried to obtain ultrathin nanometer ZnO precursor；Finally ultrathin nanometer ZnO precursor is made annealing treatment, is obtained final product
To the ZnO micro-nano hierarchies being made up of ultra thin single crystalline porous ZnO nanometer sheet；The solvent be by deionized water and ethylene glycol by
Volume ratio is 0.5-5：1 is constituted；
（2）ZnO micro-nano hierarchies it is modified：
By Jing steps（1）The ZnO micro-nanos hierarchy of preparation is molten for the polymer coupler of 7.5-9 in pH value by ultrasonic disperse
In liquid, after stirring, by centrifugation ZnO micro-nano hierarchies are separated again, and dry the ZnO micro-nanos classification knot that must be modified
Structure；The polymer coupler is polyethyleneimine；
（3）Prepare noble metal nano particles colloidal sol：
First mass concentration is added for the soluble precious-metal solution of 0.1%-4% and is boiled in deionized water, added in boiling process
Enter reducing agent, then proceed to heat 5-10 minutes after, natural cooling obtain with certain size and favorable dispersibility your gold
Metal nano-particle colloidal sol；
（4）Prepare noble metal decorated ZnO micro-nano hierarchies：
By modified ZnO micro-nanos hierarchy and noble metal nano particles colloidal sol by weight 1：0.005-0.05 is mixed, and is stirred
0.5-4h is mixed, noble metal granule is modified on ZnO micro-nano hierarchies by electrostatic interaction, be centrifuged, drying is expensive
The ZnO micro-nano hierarchies of metal-modified.
2. preparation method according to claim 1：It is characterized in that：The step（1）Annealing refers in temperature and is
Annealing in 250-500 DEG C of Muffle furnace or tube furnace.
3. preparation method according to claim 1：It is characterized in that：The step（1）Middle ultra thin single crystalline porous ZnO nanometer
Piece refer to length for 1-20 m, width be 50nm-10 m, thickness less than 22nm, crystalline phase for buergerite phase ZnO nano piece；
The ZnO micro-nanos hierarchy refers to that flower-shaped or spherical, the particle diameter that are made up of ZnO nano piece are tied for the classification of 1-100 m
Structure.
4. preparation method according to claim 1：It is characterized in that：The step（2）After middle ultrasonic disperse stir when
Between 2-24h；The drying is referred to is dried in baking oven of the temperature less than 80 DEG C.
5. preparation method according to claim 1：It is characterized in that：The step（3）Described in soluble precious-metal refer to
Granular size is gold, silver, platinum or the palladium of 5-100nm；The soluble precious-metal solution includes that chlorauric acid solution, silver nitrate are molten
Liquid, platinum acid chloride solution and chlorine palladium acid solution.
6. preparation method according to claim 1：It is characterized in that：The step（3）Middle reducing agent is that mass concentration is
The citric acid solution or citric acid three sodium solution of 0.1%-4%, the soluble precious-metal solution is with the mass ratio of reducing agent
0.5:1-1:5。
7. the noble metal decorated ZnO micro-nanos classification prepared by a kind of preparation method by described in any one of claim 1-6 is tied
Structure, it is characterised in that：It is 1-100 that the form of the noble metal decorated ZnO micro-nano hierarchies is spherical or flower-shaped, particle diameter
M, it has hypersensitivity to low concentration organic gaseous contamination thing.
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