CN104841947B - A kind of cable-type silver chlorate wraps up the synthetic method of copper nanostructured - Google Patents
A kind of cable-type silver chlorate wraps up the synthetic method of copper nanostructured Download PDFInfo
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- CN104841947B CN104841947B CN201510215425.9A CN201510215425A CN104841947B CN 104841947 B CN104841947 B CN 104841947B CN 201510215425 A CN201510215425 A CN 201510215425A CN 104841947 B CN104841947 B CN 104841947B
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Abstract
The present invention relates to the synthetic method that a kind of cable-type silver chlorate wraps up copper nanostructured：Specially：First, the preparation of solution.Prepare reaction substrate mantoquita and reducing agent and structure directing agent mixed solution, surfactant solution, silver salt solution.2nd, the synthetic method of copper nano-wire.By the mixed solution containing mantoquita and reducing agent and structure directing agent under normal temperature condition magnetic agitation certain hour, be then transferred in oil bath pan, held for some time under specified temp, reaction terminates, and is cooled to room temperature, and sample is centrifuged, washing, collects to obtain product.3rd, the quantum dot of silver chlorate.Certain density silver salt solution is added dropwise in specific certain density surfactant solution, magnetic agitation certain hour obtains milky white solution.4th, silver chlorate loads the synthetic method of copper nano-wire.Copper nano-wire is added in above-mentioned milky white solution, magnetic agitation certain hour.Present invention process is simple, and preparation condition is general, and product morphology stabilization, purity is high, and product treatment is simple, is adapted to medium-scale industrial production.
Description
Technical field
The invention belongs to technical field of inorganic nanometer material, more particularly to a kind of cable-type silver chlorate parcel copper nanostructured
Synthetic method.
Background technology
Nanoscale science and technology is for producing late 1980s just in the new technology of fast development.So-called nanometer skill
If art refers to use the science and technology of unit --- the nanoparticle of stem molecule or atomic building, manufacture material or microdevice.Receive
Rice structural material（At least 1 dimension（1D）Yardstick is in 1 ~ 100nm) correspond to the property that main body phase material shows many, cause people
Extensive concern.With the development of modern science and technology, the pattern research of nano structural material and preparation method there has also been large development.
Nano effect comes from the limitation of the potential well to electronics of nano-scale structure, it is achieved thereby that electricity, optics, magnetics to solid and
The control of the performances such as thermoelectricity.(2D) nano structural materials are tieed up in the development of recent two decades in 0 dimension (OD) and 2 in the field
Major progress is achieved in development.The quantum dot or SQW of different materials are prepared as there are various methods, and chi can be realized
The good control of degree.Numerous studies inquire into the fundamental characteristics such as chemistry, the physics of material with yardstick using quantum dot as system model
Change.Using quantum dot as active component, have been developed that many types can be used as the nanodevice of cellular construction, such as quantum dot
Laser, single-electronic transistor, mnemon body, sensor, optical detector and light emitting diode.2D nano structural materials
Obtain widely studied in semiconductor applications, molecular beam epitaxy tends to technology and is easier to prepare 2D nano structural materials.
In recent years, 1D nano structural materials have important basic scientific research value and potential technological applications valency because of it
It is worth and turns into new study hotspot.1D nanostructureds are closed between the conduction of research electronics and mechanical characteristic and yardstick and Spatial Dimension
The ideal system of system, this for preparing nanoscale electronic devices and photoelectron device in node and functional unit have it is important
Meaning.There are some researches show, 1D nano structural materials have many peculiar properties, such as superior mechanical toughness, cold light efficiency high, strong
The thermoelectricity capability coefficient of change and relatively low laser threshold.Wherein, nano wire refers to have compared with wide aspect ratio (L/D ratio)
Anisotropy it is nanocrystalline, general its a diameter of 1-200 nm, length is tens microns.Nano wire is spherical nanocrystalline because of shape with its
Looks difference causes the characteristics such as physical property to have larger difference.1D nano structural materials research application in a major issue be as
What effectively prepares 1D nanostructureds by controllable method.Although senior nanometer lithographic techniques, such as electron beam lithography, nearly probe
The technology such as modification and X-ray lithographic can prepare 1D nano structural materials, but these method preparation process are slow and cost is very high,
Cannot be promoted in actual applications.Therefore, at present research focus mostly in by chemical method prepare 1D nano structural materials,
Because such method can realize the control to nanometer dimension, while cost is relatively low, yield is higher.
In numerous 1D nano structural materials, metal nanometer line increasingly causes extensive concern.From German Gleiter in
Since 1984 Fe nanometer particles for preparing 6 nm first, in the world to the research mushroom development of nano metal, and achieve very
Big progress.Wherein, copper nano material increasingly causes the concern of researcher.Silver halide is widely used in manufacturing photo film, glue
Silver chlorates also have very important application in electrochemistry in version and gummed paper, and silver-colored monochlor(in)ate silver reference electrode is difficult polarization, thus
The photosensitivity of more accurate data silver halides can be provided and its application in terms of photocatalysis is instability limit, such as
Fruit can make silver halide stable existence can just be applied to photocatalysis aspect under light illumination and the argent of nanoscale exists
There is stronger absorption in black light area, and by adjusting the size of argent, the environment residing for shape and nano particle can make
There is red shift in its absorption spectrum.In theory, it is possible to use silver nano-grain strengthens absorption of the catalysis material to sunshine.This
Copper is effectively combined with silver chlorate in experiment, the network structure of Cu/AgCl is formed, firstly, since metallic copper and chlorination
The close contact of silver, makes electronic energy produced in system be easier to be delivered in metallic silver particles, has been effectively promoted electronics
Separation with hole and then improve quantum efficiency, it is ensured that the stability of system；Secondly, this novel network structure have compared with
Big specific surface area, can provide more light-catalysed avtive spots, improve catalytic efficiency；Again, the nano-cable knot of Cu@AgCl
Structure has effectively expanded response of the system to visible ray, it is had very strong absorption in whole visible region, substantially increases
To the utilization rate of sunshine.This method has been widened can by metal surface plasmon resonance effect reinforcement catalysis material pair
See the approach of light absorbs, and then improve the performance of catalysis material.
The content of the invention
It is an object of the invention to provide the synthetic method that a kind of cable-type silver chlorate wraps up copper nanostructured.
To achieve these goals, technical scheme is as follows：
Cable-type silver chlorate proposed by the present invention wraps up the synthetic method of copper nanostructured, comprises the following steps that：
（1）The configuration of solution
Reaction substrate mixed solution, surfactant solution and silver salt solution are prepared respectively；Wherein：The reaction substrate is mixed
Close solution to be made up of mantoquita, reducing agent and structure directing agent, the mol ratio of mantoquita, reducing agent and structure directing agent is 1:4:6；
（2）The synthetic method of copper nano-wire
By reaction substrate mixed solution under normal temperature condition magnetic agitation 12h, be then transferred in oil bath pan, at 110 DEG C
At a temperature of oil bath pan in be incubated 6 hours, reaction terminates, and is cooled to room temperature, and sample is centrifuged, washing, collect copper is received
Rice noodles；
（3）The quantum dot of silver chlorate
By step（1）The silver salt solution for obtaining is added dropwise in surfactant solution, magnetic agitation under normal temperature condition
30min, obtains milky white solution；
（4）Silver chlorate loads the synthetic method of copper nano-wire
Copper nano-wire is added to step（3）In the milky white solution of gained, magnetic agitation 12 hours under normal temperature condition, instead
Should terminate, be cooled to room temperature, sample is centrifuged, wash, dry, collect, obtain final product product.
In the present invention, step（1）, step (2), solvent described in step (3) and step (4) be deionized water.
In the present invention, the mantoquita is Copper dichloride dihydrate, and its concentration is 0.01mol/L.
In the present invention, described reducing agent is glucose, and its concentration is 0.04mol/L.
In the present invention, described structure directing agent is cetylamine, and its concentration is 0.06mol/L.
In the present invention, described surfactant is DTAC, and its concentration is 0.121mol/L.
In the present invention, described silver salt is silver nitrate, and its concentration is 0.101mol/L.
In the present invention, step（2）And step（4）The washing distinguishes washed product using ethanol and deionized water.
In the present invention, step（4）The drying is to dry 10h in 60 DEG C of vacuum drying chambers.
Due to using such scheme, the invention has the advantages that：
1st, it is presoma that the present invention is realized using common mantoquita and nitrate, is synthesized first by oil bath heating
The composite of Cu@AgCl network structures.
2nd, the method for the present invention has control very high to the pattern of product.
3rd, the present invention uses simple inorganic salts as reactant, with very strong versatility.
4th, product prepared by the present invention has the good Photocatalytic Degradation Property to organic pollution, can be as property high
Energy photochemical catalyst, there is more vast potential for future development and application space.
5th, process is simple of the invention, preparation condition is general, and product morphology stabilization, purity are high, and the convenient letter of product treatment
It is clean, it is suitable for medium-scale industrial production.
6th, the method for the present invention have mild condition, homogeneous heating, efficient energy-saving, it is easily controllable the features such as.
Brief description of the drawings
Fig. 1 is the SEM photograph of intermediate product obtained under the multiple of 50nm in embodiment 1.
Fig. 2 is the SEM photograph of product obtained under the multiple of 50nm in embodiment 1.
Fig. 3 is the TEM photos of product obtained under the multiple of 500nm in embodiment 1.
Fig. 4 is the XRD spectrum of products therefrom in embodiment 1.
Fig. 5 is the EDS collection of illustrative plates of products therefrom in embodiment 1.
Fig. 6 is the SEM photograph of intermediate product obtained under the multiple of 200nm in embodiment 2.
Fig. 7 is the SEM photograph of intermediate product obtained under the multiple of 500nm in embodiment 3.
Specific embodiment
The present invention is further detailed explanation for illustrated embodiment below in conjunction with the accompanying drawings.
Embodiment 1
The first step：0.16g DTACs are weighed respectively（) and 0.086g AgNO DTAC3It is respectively placed in
Label is respectively in the 25ml reaction bulbs of B and C, 5ml deionized waters and magneton dissolving is separately added into, by AgNO3Solution dropwise adds
Enter in DTAC solution, magnetic agitation 30min obtains milky white solution.0.0220g CuCl are weighed respectively2•2H2O, 0.1846g
Cetylamine（HAD）, 0.0754g glucose is placed in the 25ml reaction bulbs marked as A, adds 10ml deionized waters and magneton,
Normal temperature magnetic agitation 12h is to being dissolved as blue solution.
Second step：Blue solution is fixed on iron stand, is placed in oil bath pan, open oil bath pan switch, temperature is set
It is 110 DEG C, and opens magnetic agitation.
3rd step：Setting temperature and stabilization, magnetic agitation reaction 6h are reached Deng oil bath pan, solution becomes brick-red.Close
Oil bath pan, and reaction bulb is removed into liquid level, room temperature is cooled to, respectively washed once brick-red solid with absolute ethyl alcohol and deionized water
Body.
4th step：Brick-red solid is added in milky white solution, magneton, normal temperature magnetic agitation is added.
5th step：Reaction 12h, is washed for several times with absolute ethyl alcohol and deionized water, is placed in vacuum drying chamber and is dried.
Fig. 1 is the SEM photograph of intermediate product obtained under the multiple of 50nm in embodiment 1；Fig. 2 be embodiment 1 in
The SEM photograph of the product obtained under the multiple of 50nm；Fig. 3 is the TEM of product obtained under the multiple of 500nm in embodiment 1
Photo；Fig. 4 is the XRD spectrum of the products therefrom of embodiment 1, the existing AgCl in compound is illustrated, again with the presence of Cu.Fig. 5 is real
Apply the EDS collection of illustrative plates of the products therefrom of example 1.
Embodiment 2
The first step：0.16g DTACs are weighed respectively（) and 0.086g AgNO DTAC3It is respectively placed in
Label is respectively in the 25ml reaction bulbs of B and C, 5ml deionized waters and magneton dissolving is separately added into, by AgNO3Solution dropwise adds
Enter in DTAC solution, magnetic agitation 30min obtains milky white solution.0.0880g CuCl are weighed respectively2•2H2O, 0.7384g
Cetylamine（HAD）, 0.3016g glucose is placed in the 25ml reaction bulbs marked as A, adds 10ml deionized waters and magneton,
Normal temperature magnetic agitation 12h is to being dissolved as blue solution.
Second step：Blue solution is fixed on iron stand, is placed in oil bath pan, open oil bath pan switch, temperature is set
It is 110 DEG C, and opens magnetic agitation.
3rd step：Setting temperature and stabilization, magnetic agitation reaction 6h are reached Deng oil bath pan, solution becomes brick-red.Close
Oil bath pan, and reaction bulb is removed into liquid level, room temperature is cooled to, respectively washed once brick-red solid with absolute ethyl alcohol and deionized water
Body.
4th step：Brick-red solid is added in milky white solution, magneton, normal temperature magnetic agitation is added.
5th step：Reaction 12h, is washed for several times with absolute ethyl alcohol and deionized water, is placed in vacuum drying chamber and is dried.
Fig. 6 is the SEM photograph of product obtained under the multiple of 200nm in embodiment 2.By picture as can be seen that herein
Under the conditions of can still form the nano cable structure of Cu/AgCl, the chlorination silver particles for simply loading are less.
Embodiment 3
The first step：0.16g DTACs are weighed respectively（) and 0.086g AgNO DTAC3It is respectively placed in
Label is respectively in the 25ml reaction bulbs of B and C, 5ml deionized waters and magneton dissolving is separately added into, by AgNO3Solution dropwise adds
Enter in DTAC solution, magnetic agitation 30min obtains milky white solution.0.440g CuCl are weighed respectively2•2H2O, 3.692g ten
Hexamine（HAD）, 1.508g glucose is placed in the 25ml reaction bulbs marked as A, adds 10ml deionized waters and magneton, normal temperature
Magnetic agitation 12h is to being dissolved as blue solution.
Second step：Blue solution is fixed on iron stand, is placed in oil bath pan, open oil bath pan switch, temperature is set
It is 110 DEG C, and opens magnetic agitation.
3rd step：Setting temperature and stabilization, magnetic agitation reaction 6h are reached Deng oil bath pan, solution becomes brick-red.Close
Oil bath pan, and reaction bulb is removed into liquid level, room temperature is cooled to, respectively washed once brick-red solid with absolute ethyl alcohol and deionized water
Body.
4th step：Brick-red solid is added in milky white solution, magneton, normal temperature magnetic agitation is added.
5th step：Reaction 12h, is washed for several times with absolute ethyl alcohol and deionized water, is placed in vacuum drying chamber and is dried.
Fig. 7 is the SEM photograph of product obtained under the multiple of 500nm in embodiment 3.By picture as can be seen that herein
Under the conditions of can still form the nano cable structure of Cu AgCl, the chlorination silver particles for simply loading are more rare.
The above-mentioned description to embodiment is to be understood that and apply this hair for ease of those skilled in the art
It is bright.Person skilled in the art obviously easily can make various modifications to these embodiments, and described herein
General Principle is applied in other embodiment without by performing creative labour.Therefore, the invention is not restricted to implementation here
Example, in the modification made without departing from the scope of the invention all within protection scope of the present invention.
Claims (6)
1. a kind of cable-type silver chlorate wraps up the synthetic method of copper nanostructured, it is characterised in that comprise the following steps that：
(1) configuration of solution
Reaction substrate mixed solution, surfactant solution and silver salt solution are prepared respectively;Wherein:The reaction substrate mixing is molten
Liquid is made up of mantoquita, reducing agent and structure directing agent, and the mol ratio of mantoquita, reducing agent and structure directing agent is 1:4:6；
（2）The synthetic method of copper nano-wire
By reaction substrate mixed solution under normal temperature condition magnetic agitation 12h, be then transferred in oil bath pan, in 110 DEG C of temperature
Under oil bath pan in be incubated 6 hours, reaction terminates, and is cooled to room temperature, and sample is centrifuged, washing, collect to obtain copper nano-wire；
（3）The quantum dot of silver chlorate
By step（1）The silver salt solution for obtaining is added dropwise in surfactant solution, magnetic agitation under normal temperature condition
30min, obtains milky white solution；
(4) silver chlorate loads the synthetic method of copper nano-wire
Copper nano-wire is added to step（3）In the milky white solution of gained, magnetic agitation 12 hours under normal temperature condition, reaction knot
Beam, is cooled to room temperature, and sample is centrifuged, washing, dries, and collects, and obtains final product product；
Wherein：Described surfactant is DTAC, and its concentration is 0.121mol/L, described silver salt
It is silver nitrate, its concentration in reaction substrate mixed solution is 0.101mol/L.
2. a kind of cable-type silver chlorate according to claim 1 wraps up the synthetic method of copper nanostructured, it is characterised in that：Institute
Mantoquita is stated for Copper dichloride dihydrate, its concentration in reaction substrate mixed solution is 0.01mol/L.
3. a kind of cable-type silver chlorate according to claim 1 wraps up the synthetic method of copper nanostructured, it is characterised in that：Institute
The reducing agent stated is glucose, and its concentration in reaction substrate mixed solution is 0.04mol/L.
4. a kind of cable-type silver chlorate according to claim 1 wraps up the synthetic method of copper nanostructured, it is characterised in that：Institute
The structure directing agent stated is cetylamine, and its concentration in reaction substrate mixed solution is 0.06mol/L.
5. a kind of cable-type silver chlorate according to claim 1 wraps up the synthetic method of copper nanostructured, it is characterised in that：Step
Suddenly（2）And step（4）The washing distinguishes washed product using ethanol and deionized water.
6. a kind of cable-type silver chlorate according to claim 1 wraps up the synthetic method of copper nanostructured, it is characterised in that：Step
Suddenly（4）The drying is to dry 10h in 60 DEG C of vacuum drying chambers.
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| CN101962205B (en) * | 2009-07-24 | 2012-07-04 | 烟台海岸带可持续发展研究所 | Halogenated silver nano-particles and synthesis method and application thereof |
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| CN102787347B (en) * | 2012-09-04 | 2015-10-21 | 上海师范大学 | The preparation method of a kind of super long copper nano wire and copper nano-wire conductive film |
| CN103193265A (en) * | 2013-04-09 | 2013-07-10 | 河海大学 | Preparation method of spiral titanium dioxide (TiO2) nano wire doped with silver/silver chloride (Ag/AgCl) |
| CN103934007B (en) * | 2014-03-31 | 2016-04-06 | 同济大学 | The oxidation synthesis method of the network structure of a kind of surface plasma visible light catalyst Ag/AgCl |
| CN104034775B (en) * | 2014-06-27 | 2016-03-30 | 安徽师范大学 | A kind of polypyrrole/silver-colored silver chloride nuclear shell structure nano line, preparation method and application thereof |
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