CN104588014B - A kind of method that One-Dimensional ZnO material surface deposits gold nano grain - Google Patents
A kind of method that One-Dimensional ZnO material surface deposits gold nano grain Download PDFInfo
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- CN104588014B CN104588014B CN201510073100.1A CN201510073100A CN104588014B CN 104588014 B CN104588014 B CN 104588014B CN 201510073100 A CN201510073100 A CN 201510073100A CN 104588014 B CN104588014 B CN 104588014B
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Abstract
The invention discloses a kind of method that One-Dimensional ZnO material surface deposits gold nano grain, step includes：By One-Dimensional ZnO material and HAuCl4It is distributed in water, carry out supersound process in the presence of no reducing agent, by Au3+It is reduced to gold nano grain and deposit to One-Dimensional ZnO material surface.The present invention adopts ultrasonic method to reduce gold chloride, load nanometer Au granule in multiple ZnO monodimension nanometer materials, overcome technology prejudice, technological process is simple, raw material is few, gained Au/ZnO is combined Au nano-particle good crystallinity in monodimension nanometer material, particle diameter is little, it is uniformly dispersed, size uniformity, advantageously in the separation of electron hole pair, substantially increases photocatalysis efficiency, better than the product prepared by most liquid phase method, it is widely used in fields such as sensor, battery, catalyst, biology, new forms of energy.
Description
Technical field
The present invention relates to a kind of One-Dimensional ZnO material（I.e. One-Dimensional ZnO nano material）The method that surface deposits gold nano grain,
Specifically related to a kind of no additional reducing agent exists, deposits gold nano grain only with supersound process in One-Dimensional ZnO material surface
Method.
Background technology
ZnO is a kind of n-type semiconductor, and energy gap is 3.2 eV, is II-VI important race's conductor oxidate,
There is higher exciton bind energy, can be widely applied to the numerous areas such as pottery, chemical industry, electronics, optics, biology, medicine.
The pattern of ZnO material is very abundant, and wherein, One-Dimensional ZnO material has higher elevated temperature strength, hardness and excellent chemically stable
Property, for example, has the application in terms of atomic force microscope and scanning tunnelling microscope probe of the ZnO whisker of big L/D ratio and takes
Obtained progress.At present, by a large amount of synthesis and research, its performance test shows huge application to various one-dimensional novel forms
Potentiality.However, due to some limitation of the ZnO of one-dimensional oriented growth itself and in preparation process occur various shakinesses
Determine factor, limit its practical ranges.In order to overcome this shortcoming, ZnO is combined with noble metal Au nano material, to
Prepare the composite having bi-material excellent properties concurrently, and show the performance more excellent than pure ZnO nano material.
At present, One-Dimensional ZnO is more ripe with the preparation method of Au nano material, and can realize commercial production,
The main method preparing Au/ ZnO nano composite of report has high-molecular gel method, dipping light decomposition method, photo-reduction at present
Sedimentation, laser composite heating evaporation technique etc., these methods are required for additionally adding and play the reagent of reduction by Au3+
It is reduced to Au, the different selected reducing agent of method of use is also different.Additionally, these methods there is problems：（1）
In ZnO material compound noble metal Au particle size larger so that active reduction；（2）Au granule disperses uneven leading on ZnO
Cause coupling effect, reduce composite property；（3）The particle diameter preparing is uncontrollable, is susceptible to agglomeration,
Thus being difficult to large-scale production, and its application is confined to the low concentration material in laboratory mostly；（4）Composite
Complicated process of preparation, relatively costly it is difficult to realize commercial production.Therefore, still need to ZnO and Au composite nano materials
Preparation constantly improved and innovated.
Content of the invention
The present invention is directed to the deficiency that the composite nano materials of current One-Dimensional ZnO and Au exist in the preparation, there is provided a kind of
The method that One-Dimensional ZnO material surface deposits gold nano grain, the method is not required to add any electronation reagent, raw materials used
Few, flow process is simple, suitable industrialized great production.
It is known that ultrasonic can make each reaction raw materials dispersion be more uniformly distributed, contact is more abundant, all adopts in a lot of reactions
The carrying out of ultrasonic wave added reaction, also has quickly carrying out using ultrasonic wave added reduction reaction in reduction reaction, but current institute is public
In the reduction reaction opened, especially by HAuCl4In the reaction being reduced to Au in solution environmental, also do not adopt additional going back
Former dose, only to complete reduction reaction by ultrasonic.Inventor is in the improvement of the preparation method to one-dimensional Au/ZnO composite
Find in research, when only with ultrasonic and in the case of being added without additional reducing agent, still can be well by HAuCl4It is reduced to
Au, and successfully by the Au nanoparticle deposition of gained to One-Dimensional ZnO material surface, this result has broken what tradition thought
" the ultrasonic assisted reaction that is only capable of is carried out ", the cognition of " reduction reaction must be added to reducing agent ", overcome technology prejudice.
The present invention is as follows only with the ultrasonic concrete technical scheme in One-Dimensional ZnO material surface deposition gold nano grain：
A kind of method that One-Dimensional ZnO material surface deposits gold nano grain, step includes：By One-Dimensional ZnO material with
HAuCl4It is distributed in water, carry out supersound process in the presence of no reducing agent, by Au3+It is reduced to gold nano grain and deposit to one
Dimension ZnO material surface.
Why the present invention can be realized as HAuCl only with ultrasonic4Reduction, have very big pass with the raw material being adopted
System, research finds, when using One-Dimensional ZnO material, the energy of ultrasonic generation can One-Dimensional ZnO material surface produce electronics and
The separation in hole, gold ion is reduced by these detached electronic energies, thus forming the Au nano-particle of 3 ~ 15 nm, makes simultaneously
Gold nano grain is combined with One-Dimensional ZnO material tight, improves the property of composite.And adopt other materials, for example spherical ZnO
When, electronics and hole will not separate, the only ultrasonic reduction that just cannot complete gold ion and deposition.
The present invention is evenly distributed in One-Dimensional ZnO material surface only with the ultrasonic gold nano grain being not added with reducing agent gained.
In said method, the size of nanometer gold grain depositing to One-Dimensional ZnO material surface is homogeneous.
In said method, the particle diameter depositing to the gold nano grain of One-Dimensional ZnO material surface is 3 ~ 15 nm.
In said method, described One-Dimensional ZnO material is ZnO nanorod, ZnO nano-wire, ZnO nano-band, ZnO nano are fine
The monodimension nanometer materials such as dimension, ZnO nano array, ZnO nano whisker.
Said method specifically includes following steps：
（1）One-Dimensional ZnO material is dispersed in water, supersound process 30-60min；
（2）To step（1）Supersound process after mixture in add HAuCl4Aqueous solution, then carries out supersound process again
Make Au3+It is reduced to Au；
（3）By reactant liquor centrifugation, washing after supersound process, obtain Au/ZnO and be combined monodimension nanometer material.
Above-mentioned steps（1）In, concentration in water for the One-Dimensional ZnO material is 1.0～5.0 mmol/L.Within this range, ZnO
Concentration bigger, it is more sparse that Au granule is distributed on ZnO.
Above-mentioned steps（2）In, ZnO and HAuCl4Mol ratio be 40：0.25～5.Within this range, this ratio is bigger,
It is more sparse that Au granule is distributed on ZnO.
Above-mentioned steps（1）With（2）In, ultrasonic power is 50～500 W.Within this range, power is bigger, and Au granule exists
The distribution of ZnO is more closely knit, and particle diameter is bigger, and the required time is fewer.
Above-mentioned steps（2）In, HAuCl4The concentration of aqueous solution is 0.1～5.0 mmol/L.Within this range, HAuCl4's
Concentration is bigger, and it is more closely knit that Au granule is distributed on ZnO.
Above-mentioned steps（2）In, temperature during supersound process is 15～80 DEG C.Within this range, reaction temperature is higher, ZnO
The particle diameter of the Au granule of upper load is bigger.
Above-mentioned steps（2）In, the time of supersound process is 5～30 min.Within this range, the response time is longer, Au
It is more closely knit that grain is distributed on ZnO.
The present invention, only with ultrasonic just Au nano-particle in One-Dimensional ZnO nano-material surface deposition, is carried using ultrasonic
For electron reduction HAuCl4, without adding any other chemical reagent, it is to avoid chemical reagent is as caused by sodium borohydride
Au granular grows too fast, the problems such as skewness, the effective control size of Au nano-particle.
The present invention adopts ultrasonic method to reduce gold chloride, loads nanometer Au granule in multiple ZnO monodimension nanometer materials, overcomes
Technology prejudice, technological process is simple, and raw material is few, and gained Au/ZnO is combined Au nano-particle good crystallinity in monodimension nanometer material,
Particle diameter is little, is uniformly dispersed, size uniformity, advantageously in the separation of electron-hole pair, substantially increases photocatalysis efficiency, excellent
In the product prepared by most liquid phase method, have in fields such as sensor, battery, catalyst, biology, new forms of energy and widely should
With.
Brief description
Fig. 1 is the transmission electron microscope of the compound monodimension nanometer material of Au/ZnO of the embodiment of the present invention 1 synthesis（TEM）Photo.
Fig. 2 is to be combined monodimension nanometer material with the Au/ZnO that reducing agent obtains in the case of not ultrasonic in comparative example 1 of the present invention
Transmission electron microscope（TEM）Photo.
Specific embodiment
Below by embodiment, the present invention will be further elaborated, the description below merely to explain the present invention, and
Its content is not defined.In following embodiments, ZnO nanorod used, ZnO nano-band, ZnO nano-wire, ZnO nano are fine
Dimension, ZnO nano are brilliant to be commercial, and those skilled in the art can also be using the method synthesis disclosed in document.
Embodiment 1
1.1 weigh 8.1 mg ZnO nanorod powder, are dispersed in 40 mL deionized waters, and the white obtaining 2.5 mM is hanged
Turbid liquid, ultrasonic 30 min in advance, ultrasonic power 50W；
1.2 to step（1）Suspension in add the HAuCl of 2.5 mL4Aqueous solution（1.0 mM）, under room temperature condition, continue
Continuous ultrasonic（50w）5 min；
After 1.3 reactions terminate, it is centrifuged, washs, obtain Au/ZnO composite Nano bar material, wherein Au nano-particle
Particle diameter is 4 nm, and be evenly distributed on ZnO nanorod, more closely knit, concrete shape characteristic is shown in Fig. 1.
Embodiment 2
2.1 weigh 2.01 mg ZnO nano-band powder, are dispersed in 40 mL deionized waters, and the white obtaining 1.0 mM is hanged
Turbid liquid, ultrasonic 60min in advance, ultrasonic power 100W；
2.2 to step（1）Suspended middle addition 2.5 mL HAuCl4Aqueous solution（1.25 mM）, it is heated to 80 DEG C, continue
Continuous ultrasonic（100w）20 min；
After 2.3 reactions terminate, it is centrifuged, washs, obtain Au/ZnO composite Nano carrying material, wherein Au nano-particle grain
Footpath is 4 nm, and be evenly distributed on ZnO nano-band, more sparse.
Embodiment 3
3.1 weigh 3.24 mgZnO nano belt powder, are dispersed in 40 mL deionized waters, and the white obtaining 1.0 mM is hanged
Turbid liquid, ultrasonic 40min in advance, ultrasonic power 400W；
3.2 to step（1）In suspension in add the HAuCl of 2.5 mL4Aqueous solution（1.5 mM）, it is heated to 80 DEG C,
Continue ultrasonic（400w）20 min；
After 3.3 reactions terminate, it is centrifuged, washs, obtain Au/ZnO composite Nano carrying material, wherein Au nano-particle grain
Footpath is 10 nm, and is evenly distributed on ZnO nano-band.
Embodiment 4
4.1 weigh 16.2 mg ZnO nano-wire powder, are dispersed in 40 mL deionized waters, and the white obtaining 5.0 mM is hanged
Turbid liquid, ultrasonic 30 min in advance, ultrasonic power 500W；
4.2 to step（1）In suspension in add the HAuCl of 2.5 mL4Aqueous solution（1.0 mM）, it is heated to 30 DEG C,
Continue ultrasonic（500w）15 min；
After 4.3 reactions terminate, it is centrifuged, washs, obtain Au/ZnO composite Nano wire material, wherein Au nano-particle grain
Footpath is 4 nm, is evenly distributed and sparse on ZnO nano-wire.
Embodiment 5
5.1 weigh 8.1 mg ZnO nano fiber dusts, are dispersed in 40 mL deionized waters, obtain the white of 2.5 mM
Suspension, ultrasonic 30 min in advance, ultrasonic power 80W；
5.2 to step（1）In suspension in add the HAuCl of 2.5 mL4Aqueous solution（0.5 mM）, continue super under room temperature
Sound（80w）React 30 min；
After 5.3 reactions terminate, through centrifugation, washing, obtain Au/ZnO composite nano-fiber material, the wherein grain of Au nano-particle
Footpath is 5 nm, is evenly distributed on ZnO nano fiber.
Embodiment 6
6.1 weigh 8.1 mg ZnO nano whisker powder, are dispersed in 40 mL deionized waters, obtain the white of 2.5 mL
Suspension, ultrasonic 30 min in advance, ultrasonic power 400W；
6.2 to step（1）In suspension in add the HAuCl of 2.5 mL4Aqueous solution（5.0 mM）, it is heated to 40 DEG C
Continue ultrasonic（400w）React 10 min；
After 6.3 reactions terminate, through centrifugation, washing, obtain Au/ZnO composite Nano crystal whisker materials, the wherein grain of Au nano-particle
Footpath is 15 nm to the maximum, is evenly distributed and sparse on ZnO nano whisker.
Comparative example 1
Weigh 8.1 mg ZnO nanorod powder, be dispersed in stirring in 40 mL deionized waters, the white obtaining 2.5 mM is hanged
Turbid liquid；
The HAuCl of 4 mL is added in the suspension of above-mentioned steps4Aqueous solution（1.0 mM）, under room temperature condition, continue to stir
Mix 5 min；Add sodium borohydride reduction agent afterwards and stir 10min.
After reaction terminates, it is centrifuged, washs, obtain Au/ZnO composite Nano bar material, wherein Au nano particle diameter
It is 20 nm to the maximum, and skewness, concrete shape characteristic are shown in Fig. 2 on ZnO nanorod.
Comparative example 2
Weigh 8.1 mg ZnO micron ball powder, be dispersed in 40 mL deionized waters, the white obtaining 2.5 mM is suspended
Liquid, ultrasonic 30 min in advance, ultrasonic power 50W；
The HAuCl of 2.5 mL is added in the suspension of above-mentioned steps4Aqueous solution（1.0 mM）, under room temperature condition, continue
Ultrasonic（50w）5 min；
Reaction terminate after, be centrifuged, wash after through electron microscopic observation find do not have Au nanoparticle deposition, illustrate one
Dimension material is the detached key in ultrasonic acquisition electron hole.
Claims (10)
1. a kind of method that One-Dimensional ZnO material surface deposits gold nano grain, is characterized in that：By One-Dimensional ZnO material and HAuCl4Point
It is scattered in water, carry out supersound process in the presence of no reducing agent, by Au3+It is reduced to gold nano grain and deposit to One-Dimensional ZnO material
Material surface.
2. method according to claim 1, is characterized in that：Gold nano grain is evenly distributed in One-Dimensional ZnO material surface.
3. method according to claim 1 and 2, is characterized in that：Gold nano grain particle diameter is 3 ~ 15 nm.
4. method according to claim 1 and 2, is characterized in that：Described One-Dimensional ZnO material is ZnO nanorod, ZnO nano
Line, ZnO nano-band, ZnO nano fiber, ZnO nano array or ZnO nano whisker.
5. method according to claim 1 and 2, is characterized in that comprising the following steps：
（1）One-Dimensional ZnO material is dispersed in water, supersound process 30-60min；
（2）To step（1）Supersound process after mixture in add HAuCl4Aqueous solution, then carry out supersound process and make Au3+Also
Originally it was Au；
（3）By reactant liquor centrifugation, washing after supersound process, obtain Au/ZnO and be combined monodimension nanometer material.
6. method according to claim 5, is characterized in that：Step（1）In, concentration in water for the One-Dimensional ZnO material is 1.0
～5.0 mmol/L.
7. method according to claim 5, is characterized in that：ZnO and HAuCl4Mol ratio be 40：0.25～5.
8. method according to claim 5, is characterized in that：Step（1）With（2）In, ultrasonic power is 50～500 W.
9. method according to claim 5, is characterized in that：HAuCl4The concentration of aqueous solution is 0.1～5.0 mmol/L.
10. method according to claim 5, is characterized in that：Step（2）In, temperature during supersound process is 15～80 DEG C；
The time of supersound process is 5～30 min.
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| CN105215347B (en) * | 2015-09-07 | 2017-03-29 | 济南大学 | A kind of Zinc Oxide and gold nano grain composite and preparation method thereof |
| CN105195144B (en) * | 2015-10-15 | 2017-07-11 | 吉林大学 | A kind of method of the bar-shaped heterojunction photocatalysts of synthesis Au/ZnO |
| CN106391008A (en) * | 2016-09-21 | 2017-02-15 | 苏州大学 | Method for loading three-dimensional zinc oxide surface with metal nanoparticles |
| CN107175339A (en) * | 2017-05-23 | 2017-09-19 | 天津工业大学 | A kind of method and device without reducing agent Fast back-projection algorithm gold nano grain |
| CN108440767A (en) * | 2018-04-18 | 2018-08-24 | 西北大学 | It is a kind of that nanometer Au is combined to the new method for preparing Au@MOF composite materials with porous MOF |
| CN110150317B (en) * | 2019-05-30 | 2021-12-07 | 吉林大学 | PDMS-ZnO/Au sterilization material with noble metal modified semiconductor nano-pillar array structure and preparation method thereof |
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