CN104492432B - Hollow bimetal nano particles/titanium dioxide core shell structure and its preparation method and application - Google Patents
Hollow bimetal nano particles/titanium dioxide core shell structure and its preparation method and application Download PDFInfo
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Abstract
The invention discloses a kind of hollow bimetal nano particles/titanium dioxide core shell structure, with hollow bimetal nano particles as core, with titanium dioxide as shell, there is space between hollow bimetal nano particles and titanium dioxide.Preparation method the invention also discloses the core shell structure and the application in terms of photocatalytic degradation organic matter, with amphiphilic block copolymer micella as reactor during preparation, the nano-particle of copolymer cladding is prepared first, then using this nano-particle as sacrifice template, prepare the bimetal nano particles with hollow structure, finally with sol-gal process the bimetal nano particles of hollow structure are carried out with coated by titanium dioxide, block copolymer is removed and is obtained product.The present invention realize the bimetal nano particles of hollow structure in titanium dioxide it is dispersed, prevent it from assembling, increased noble metal nano particles and titanic oxide material interfacial area, the catalysis activity of its ultraviolet degradation organic matter is significantly improved.
Description
Technical field
The present invention relates to a kind of hollow bimetal nano particles/titanium dioxide core shell structure and preparation method thereof, further relate to
With the catalyst of the photocatalytic degradation organic matter of the hollow bimetal nano particles/titanium dioxide core shell structure as active ingredient with
And the application of photocatalytic degradation organic matter is carried out with the catalyst.
Background technology
Titanium dioxide is a kind of excellent photochemical catalyst, with catalysis activity is high, heat endurance and chemical stability is good, nothing
Malicious and cheap the features such as, be first-selected environment-friendly photochemical catalyst.Nano-TiO2Photochemical catalyst can decompose hydro carbons, halogen
For materials such as thing, carboxylic acid, surfactant, dyestuff, itrogenous organic substance, organophosphorus insecticides.However, as photochemical catalyst, shadow
It is the quick compound of electric charge-hole in photocatalytic process to ring one of key issue of its practical application.To improve titanium dioxide
The photocatalysis efficiency of material, people are doped using various organic or inorganic compounds to it or surface is modified, wherein your gold
Category nano-particle can promote the migration of light induced electron, the life-span of extension carrier, so as to improve the photocatalysis of titanium dioxide
Activity.
In the prior art to the research using noble metal nano particles raising titanium dioxide optical catalyst catalytic efficiency, mainly
Using traditional carrying method, a kind of is to mix noble metal precursor body with the presoma or solid particle of titanium dioxide, is passed through
High-temperature process or chemical reduction method, obtain the catalyst of carried noble metal nano particle, and such as patent CN102500363A is public
A kind of noble metal orientation load titanium dioxide photocatalyst and preparation method thereof is opened, CN103464150A discloses one kind will be living
Property component be Au, Ag, load to the method on silica, noble metal nano particles are easy to when this kind of method has high-temperature process
Aggregation, in use noble metal nano particles there is a problem of being lost in.Another kind is the method using cladding, using dioxy
Change the noble metal nano particles cladding that be modified on surface by the nano-particle or sol-gel of titanium, form the catalyst of core shell structure,
It is improved photocatalysis performance, this method during cladding the problems such as there is also noble metal nano particles and easily assemble.
The other method for improving catalytic efficiency is the specific surface area for increasing catalyst.Bimetal nano particles are due to surface area
Greatly, adjustable, cost decline of local surface plasma resonance characteristic etc. is valued by people, and in recent years, people's research finds, double
Metal nanoparticle is carried on titanium dioxide granule surface, can improve the efficiency of catalyst.Bimetal nano particles are born at present
It is also that, using above-mentioned traditional carrying method, this method still has bimetal nano particles and is easy to be loaded in titanium dioxide surface
Aggregation, bimetal nano particles and the small problem of titanium dioxide contact area.
The content of the invention
There is metal nanoparticle for catalyst prepared by conventional load mode and be easy to aggregation and titanium dioxide in the present invention
Metal nanoparticle/affected deficiency of titanium dioxide composite construction catalytic performance that contact area is small, formed, there is provided one
Kind hollow bimetal nano particles/titanium dioxide core shell structure, the product with hollow bimetal nano particles as core, with titanium dioxide
Titanium contact area is big, with specific surface area is big, the advantage such as photocatalysis performance is good.
Present invention also offers the preparation method of above-mentioned hollow bimetal nano particles/titanium dioxide core shell structure, the party
Method overcomes hollow bimetal nano particles and is easy to reunite and the small problem of titanium dioxide contact area, and products therefrom performance is good.
Present invention also offers with above-mentioned hollow bimetal nano particles/titanium dioxide core shell structure urging as active ingredient
The application of agent and the catalyst in photocatalytic degradation organic matter.
The present invention replaces single metal nanoparticle to be combined with titanium dioxide using hollow bimetal nano particles, with more
Specific surface area high, can more improve the photocatalytic activity of titanium dioxide.In order to give full play to the excellent of hollow bimetal nano particles
The bimetal nano particles of hollow structure are core by gesture, with titanium dioxide as shell, form core shell structure.It is hollow double in order to overcome
The problem that metal nanoparticle is reunited during cladding and titanium dioxide contact area is reduced, reaches the core shell structure to be formed
Photocatalysis effect is good, hollow bimetal nano particles are dispersed in titanium dioxide, do not assemble and titanium dioxide contact area
Big purpose, amphiphilic block copolymer is added when hollow bimetal nano particles are prepared, and makes hollow bimetal nano particles
Surface connects amphiphilic block copolymer, it is therefore prevented that the reunion of hollow bimetal nano particles.Meanwhile, amphiphilic block copolymer molecule
There is the relation for preferentially interacting with TiO 2 sol, by the combination of amphiphilic block copolymer and TiO 2 sol,
The contact area of hollow bimetal nano particles and titanium dioxide can be improved, accelerates titanium dioxide to hollow bimetal nano grain
The cladding of son, improves the photocatalysis effect of product.
During preparation, with amphiphilic block copolymer micella as reactor, the nano-particle of copolymer cladding is prepared first, then
Using this nano-particle as template is sacrificed, the bimetal nano particles with hollow structure are prepared, finally with sol-gel process pair
The bimetal nano particles of hollow structure carry out coated by titanium dioxide, remove block copolymer and obtain product.
Concrete technical scheme of the present invention is as follows：
A kind of hollow bimetal nano particles/titanium dioxide core shell structure, its with hollow bimetal nano particles as core, with
Titanium dioxide is shell, has space between hollow bimetal nano particles and titanium dioxide.
In above-mentioned core shell structure, the particle diameter of the hollow bimetal nano particles is 5-20nm；The grain of whole core shell structure
Footpath is 10-40nm.
The specific surface area of above-mentioned hollow bimetal nano particles/titanium dioxide core shell structure is more than 100m2/g。
In above-mentioned core shell structure, by controlling hollow bimetal nano particles and TiO2The order by merging of sol-gel and
Proportionate relationship, make hollow bimetal nano particles cladding titanium dioxide shell, it is to avoid the reunion of nano-particle, enhances its property
Energy.
In above-mentioned core shell structure, the hollow bimetal nano particles effect can be capture TiO2Electronics on conduction band,
Suppress compound between electronics and hole, that is, accelerate titanium deoxide catalyst separation of charge, at the same increase metal nanoparticle with
TiO2Between interfacial area.Hollow bimetal nano particles are made up of two kinds of metals, and both metals are deposited in a mixed way
.
In above-mentioned core shell structure, the metal activity of two kinds of metals in the hollow bimetal nano particles is in the presence of poor
Different, the salt of another metal can be reduced to zeroth order by a kind of metal.Two kinds of metals in bimetal nano particles are defined as
More active metal and more inactive metal, wherein more active metal nanoparticle can be by with positive valence state
More inactive reducing metal ions are simple substance.
In above-mentioned hollow bimetal nano particles, more active metal：More inactive metal（Mol ratio）=0.3~
3.0:1, preferably 0.5-2:1.
In above-mentioned core shell structure, two kinds of metals in the hollow bimetal nano particles are selected from：Golden (Au), silver-colored (Ag),
Platinum（Pt）, palladium（Pd）, copper（Cu）Deng.When actually used, the activity according to metal is arranged in pairs or groups, and for example bimetallic can be
Ag-Au, Ag-Pt, Pt-Au, Pd-Pt, Cu-Ag etc..
The preparation of above-mentioned core shell structure is comprised the steps of：Parents are added the more active metallic nanoparticle period of the day from 11 p.m. to 1 a.m is prepared
Block copolymer, the step of forming surface and there is the more active metal nanoparticle of amphiphilic block copolymer；Surface is deposited
Put with the presoma of another more inactive metal in the more active metal nanoparticle of amphiphilic block copolymer
The step of changing reaction and form surface and there are the hollow bimetal nano particles of amphiphilic block copolymer；By coated by titanium dioxide to table
The step of there is the hollow bimetal nano particles surface of amphiphilic block copolymer in face；Amphiphilic block copolymer is removed, in formation
The step of empty bimetal nano particles/titanium dioxide core shell structure.
In above-mentioned core shell structure, during the space existed between hollow bimetal nano particles and titanium dioxide is preparation process
What amphiphilic block copolymer was formed after removing.
The preparation method of above-mentioned hollow bimetal nano particles/titanium dioxide core shell structure, comprises the following steps：
（1）By the presoma of more active metal and amphiphilic block copolymer dissolving in organic solvent, micella is formed
Solution；
（2）More active metal precursor in above-mentioned micellar solution is reduced to by more active gold using reducing process
Category nano-particle, forms the more active metal nanoparticle solution that surface has amphiphilic block copolymer；
（3）Under agitation, the weak solution of the presoma containing another more inactive metal is added drop-wise into surface to deposit
In the more active metal nanoparticle solution of amphiphilic block copolymer, form surface to there are parents embedding by replacing reaction
The hollow bimetal nano particles of section copolymer；
（4）Wrapped on the hollow bimetal nano particles surface that surface has amphiphilic block copolymer by sol-gel process
Titanium dioxide is covered, hollow bimetal nano particles/titanium dioxide core shell structure that surface has amphiphilic block copolymer is formed；
（5）Removing surface is present in the hollow bimetal nano particles/titanium dioxide core shell structure of amphiphilic block copolymer
Amphiphilic block copolymer, form hollow bimetal nano particles/titanium dioxide core shell structure.
In above-mentioned preparation method, the presoma of the more active metal and more inactive metal includes metal
The inorganic acid of salt or metal, such as nitrate, chloride, sulfate etc..
In above-mentioned preparation method, the effect of amphiphilic block copolymer used mainly has following three points：One is hollow double regulation and control
The size of metal nanoparticle；Two is the surface for being present in hollow bimetal nano particles, prevents hollow bimetal nano particles
Reunion, make them dispersed；Three is the presence of the relation for preferentially interacting with titanium dioxide, improves hollow bimetal nano
Particle and the contact area of titanium dioxide, accelerate cladding of the titanium dioxide to hollow bimetal nano particles.Used by the present invention
Amphiphilic block copolymer is that while have any amphiphilic block copolymer of amphipathic property, the amphiphilic block copolymer can be with
It is polyvinylpyridine-polyethylene oxide block copolymer（PVP-b-PEO）, PEG-PEI（PEG-b-
PEI）, polyethylene glycol oxide-poly-（2- methyl oxazolines）（PEO-b-PMO), PVP-PLA（PVP -b-
PLA）Deng.Wherein PVP, PEI, PMO account for less than the 40% of block copolymer cumulative volume respectively.
Above-mentioned steps（1）In, the constitutional repeating unit of a certain block in amphiphilic block copolymer can with it is more active
Metal ion have Specific Interactions, the Specific Interactions refer to constitutional repeating unit in the block can with it is more active
Metal ion there is complexing, the consumption of amphiphilic block copolymer has the repetition knot in the block of Specific Interactions with this
Structure unit is measured.Preferably, metal more active with this in the presoma and amphiphilic block copolymer of more active metal
The mol ratio that ion has the constitutional repeating unit in the block of Specific Interactions is 0.1 ~ 1.0：1, preferably 0.2 ~ 0.6:1.When
During for PVP-b-PEO, the presoma and VP of more active metal（Vinylpyridine）Mol ratio be 0.1 ~ 1.0, when for
During PEG-b-PEI, the presoma and EI of more active metal（Aziridine）Mol ratio be 0.1 ~ 1.0, when being PEO-b-
During PMO, the presoma and MO of more active metal（2- methyl oxazolines）Mol ratio be 0.1 ~ 1.0, when being PVP-b-
During PLA, the presoma and VP of more active metal（Vinyl pyrrolidone）Mol ratio be 0.1 ~ 1.0.
Above-mentioned steps（1）In, the presoma of more active metal concentration in organic solvent is preferably 0.1wt%.
Above-mentioned steps（1）In, the organic solvent is in tetrahydrofuran, benzene, toluene and DMF
Plant or several.
Above-mentioned steps（2）In, the reducing process is that ultraviolet irradiates reducing process, or to add reducing agent（Such as hydrazine hydrate,
Sodium borohydride etc.）The method for being reduced.The ultraviolet irradiation reducing process refers to adding ultra-violet absorber in the solution,
Free radical is produced under the action of uv light, is reduced by free radical, while causing amphiphilic block copolymer to be crosslinked and wrap
It is rolled in surfaces of metal nanoparticles.
Above-mentioned steps（3）In, the presoma of more inactive metal and the presoma of more active metal mole
Than being 0.3 ~ 3.0：1, preferably 0.5 ~ 2.0：1.
Above-mentioned steps（3）In, the displacement reaction time is at least 20h.
Above-mentioned steps（4）In, the sol-gal process is urging in hydrochloric acid or glacial acetic acid etc. by the presoma of titanium dioxide
TiO 2 sol is formed under change, the colloidal sol is added drop-wise to the hollow bimetal nano grain that there is amphiphilic block copolymer containing surface
In the solution of son, the method for realizing the cladding of titanium dioxide.The presoma of the titanium dioxide is the various compounds of titanium, including
Isopropyl titanate（TTIP）, butyl titanate（TBT）, metatitanic acid acetyl acetone titanium and titanium tetrachloride etc..
Above-mentioned steps（4）In, TiO2The TiO that colloidal sol is generated2It is 0.05 ~ 0.15 with the volume ratio of amphiphilic block copolymer：
1, by controlling the use magnitude relation between them, obtain the core shell structure of required size.
Above-mentioned steps（4）In, in there is the solution of hollow bimetal nano particles of amphiphilic block copolymer containing surface, institute
The concentration for stating the hollow bimetal nano particles that surface has amphiphilic block copolymer is 0.01-0.05wt%.
Above-mentioned steps（4）In, TiO 2 sol is added drop-wise to the hollow bimetallic that surface has amphiphilic block copolymer
Continue to stir 0.5-1h in nano-particle solution, after being added completely into.
Above-mentioned steps（5）In, parents are removed by the method for ultraviolet irradiation degraded, high-temperature calcination or plasma etching embedding
Section copolymer.
It is organic in photocatalytic degradation present invention also offers above-mentioned hollow bimetal nano particles/titanium dioxide core shell structure
Application in thing, the hollow bimetal nano particles/titanium dioxide core shell structure can be used as photochemical catalyst, the drop of catalyzing organic
Solution.
It is the structure of shell for core, titanium dioxide that the present invention uses hollow bimetal nano particles, hollow bimetal nano grain
Sub- specific surface area is big, can cause efficiently separating for light induced electron and hole, extends the life-span of photogenerated charge, so as to accelerate organic
The degradation rate of pollutant, adds amphiphilic block copolymer in preparation process, it is to avoid the group of hollow bimetal nano particles
It is poly-, the contact area of nano-particle and titanium dioxide is increased, in hollow double gold during amphiphilic block copolymer is removed
Many spaces can be also produced between category nano-particle and titanium dioxide, Molecular Adsorption and motion beneficial to organic pollution enter one
Step increased degradation effect.Additionally, in preparation process, by controlling reaction condition, can adjust bimetallic proportionate relationship,
The particle diameter of hollow bimetal nano particles and the thickness of titanium dioxide shell, can make catalytic effect more preferably.
The inventive method process is simple, mild condition, products therefrom good degrading effect compared with prior art, is realized
The bimetal nano particles of hollow structure are dispersed in titanium dioxide, increased bimetal nano particles and titanium dioxide
The interfacial area of material, the catalysis activity of gained core shell structure ultraviolet degradation organic matter is significantly improved.
Brief description of the drawings
The UV-visible spectrum of each nano-particle prepared by Fig. 1 embodiments 1.
The TEM pictures of hollow Ag-Au nano-particles prepared by Fig. 2 embodiments 1.
The TEM figures of the hollow Ag-Au nano-particles/titanium dioxide of removing block copolymer prepared by Fig. 3 embodiments 1
Piece.
Hollow bimetal nano particles/titanium dioxide optical catalyst catalytic degradation methylene blue prepared by Fig. 4 embodiments 1
Effect curve.
Specific embodiment
The present invention is described in further detail with reference to specific embodiment.
In following embodiments, polyvinylpyridine-polyethylene oxide block copolymer used（PVP-b-PEO）It is purchased from
Polymer Source companies, molecular weight is 130000 g/mol, and PVP blocks account for the 24% of block copolymer volume；Poly- second used
Vinyl pyrrolidone-PLA（PVP-b-PLA）Block copolymer, molecular weight is that 22000, PVP blocks account for block copolymerization object
Long-pending 28%.
In the present embodiment, using methylene blue（MB）Ultraviolet degradation experimental evaluation prepared by hollow bimetal nano
Photocatalysis effect when particle/titanium dioxide core shell structure is as photochemical catalyst.MB is a kind of organic dyestuff, in the useless of textile industry
It is widely present in water, the catalytic degradation effect of titanium dioxide is evaluated usually as standard substance.Experimental technique is as follows：
Take 8 × 10-4Hollow bimetal nano particles/titanium dioxide core the shell structure of mg is put into and fills 5.0 milliliters of concentration and be
In the quartzy bottle of the MB solution of 5.0mg/L, with the 254nm ultraviolet lights different time, purple is carried out every 30min taking-up solution
External spectrum is measured, and draws the concentration of MB and the curve of degradation time, calculates MB degradation amounts.
Embodiment 1
（1）Hollow bimetal nano particles preparation process：Weigh polyvinylpyridine-polyethylene oxide block copolymer
（PVP-b-PEO）0.5g, adds silver nitrate 0.12g（Wherein Ag/VP=0.6）, add solvents tetrahydrofurane to prepare block copolymer
Concentration is the solution of 0.05 wt%, and stirring obtains clear transparent solutions in 2 days, and a certain amount of ultraviolet radiation absorption is added on this basis
Agent 2,4 dihydroxyl benzophenone（BPH）, during above-mentioned solution moved into quartzy bottle, ultraviolet light（254nm）Irradiation 10-20 hours,
Obtain the silver nano-particle solution of yellow；The silver nano-particle solution of 40g preparations is weighed, adds 1mg/mL's under agitation
HAuCl4190 microlitres of THF solution, enter line replacement reaction, react at least 24 h, obtain surface and contain the hollow of block copolymer
The mol ratio of Doré metal nano-particle, wherein Au and Ag is 0.5.Fig. 1 (a) and (b) are Nano silver grain and hollow gold and silver
The ultraviolet spectra of bimetal nano particles, Fig. 2 is corresponding transmission electron microscope picture, and profit is can be seen that by Fig. 1 (a) ~ (b) and Fig. 2
Hollow bimetal nano particles have been prepared with the method.
（2）The hollow bimetal nano particles of coated by titanium dioxide：Hollow pair that the block copolymer of above-mentioned preparation is coated
Metal nanoparticle solution, is then added dropwise over the colloidal sol of TTIP formation, wherein titanium dioxide and block copolymer under agitation
Volume ratio be 5.0%, continue to stir 30min to 1h after adding, its ultraviolet spectra shows（Fig. 1 (c)）, hollow bimetal nano
The surface plasma resonance peak of particle disappears substantially, shows that the sol-gel of the oxidized titanium of bimetal nano particles is uniformly coated；
（3）Will（2）The cladding product utilization spin coating for obtaining or the method for cast are coated in solid substrate（Silicon chip, sheet glass etc.）
On, drying and remove solvent, the method degraded using ultraviolet irradiation removes the organic principles such as block copolymer, obtains hollow double gold
Category nano-particle/titanic oxide nano compound material photochemical catalyst, its transmission electron microscope picture is shown in Fig. 3.Detected through TEM methods, should
In core shell structure, the size of hollow bimetal nano particles is 12.8nm, and the particle diameter of whole core shell structure is 26nm.
The photocatalysis effect of products obtained therefrom, the change of gained methylene blue concentration and exposure time are detected using methylene blue
Although curve is as shown in figure 4, it can be seen that catalyst（I.e. hollow bimetal nano particles/titanium dioxide core-shell knot
Structure）Consumption seldom, MB solution after UV irradiations 420min, the ratio of MB concentration and initial concentration（C/C0）Drop to for
0.395, i.e. MB have degraded 60.5%.
Embodiment 2
（1）Weigh 100mg PVP-b-PEO block copolymers（That is polyvinylpyridine-polyethylene oxide block copolymerization
Thing）, 24.0 mg silver nitrates and solvents tetrahydrofurane 10g are added, stir at least 1 day, colourless transparent solution is formed, add BPH
（2,4 dihydroxyl benzophenone）20 mg, 16h is irradiated by the ultraviolet that above-mentioned solution wavelength is 254nm, is obtained yellow Ag and is received
Contain block copolymer in rice corpuscles solution, the surface of the Ag nano-particles.
（2）The mg of silver nano-particle solution 400 of preparation is taken, HAuCl is added4Solution（1mg/ml）18 μ l, enter line replacement
Reaction, reacts at least 24 h, obtains the hollow bimetallic Ag-Au that block copolymer is contained on surface（The mol ratio of wherein Au and Ag
It is 0.39）Nano-particle.
（3）The hollow bimetal nano particles containing block copolymer of above-mentioned preparation are diluted further into concentration is
0.05wt%, then under agitation to the TiO 2 sol that the formation of TTIP hydrochloric acid catalysis is added dropwise in the solution, wherein dioxy
The volume ratio for changing titanium with block copolymer is 5.0%, continues to stir 50min after adding, and hollow bimetal nano particles are by titanium dioxide
The colloidal sol of titanium is uniformly coated, and forms the hollow bimetal nano particles/titanium dioxide core shell structure containing block copolymer；
（4）Take step（3）The hollow bimetal nano particles/titanium dioxide core shell structure containing block copolymer it is molten
Liquid, volatilization removes solvent, recycles the method for ultraviolet irradiation degraded to remove block copolymer, forms hollow bimetal nano grain
Son/titanium dioxide core shell structure.Detect that in the core shell structure, the size of hollow bimetal nano particles is through TEM methods
13nm, the particle diameter of whole core shell structure is 25nm, and hollow bimetal nano particles are 0.6 with the weight ratio of titanium dioxide.
Embodiment 3
100mgPVP-b-PEO block copolymers are weighed, 24 mg silver nitrates and solvents tetrahydrofurane 20g is added, stirring is extremely
It is few 1 day, colourless transparent solution is formed, the mg of BPH 20 are added, the ultraviolet that above-mentioned solution wavelength is 254nm is irradiated into 16h,
Obtain yellow Ag nano-particle solutions.The mg of silver nano-particle solution 400 of preparation is taken, HAuCl is added4Solution（1mg/ml ）
24 μ l, enter line replacement reaction at least 24h, obtain hollow bimetallic Ag-Au nano-particles（The mol ratio of wherein Au and Ag is
1.0）.By the hollow bimetal nano particles containing block copolymer of above-mentioned preparation, being diluted further to concentration is
0.05wt%, is then added dropwise over the colloidal sol of TTIP formation under agitation, and wherein titanium dioxide is with the volume ratio of block copolymer
5.0%, continue to stir 50min after adding, hollow bimetal nano particles are uniformly coated by the sol-gel of titanium dioxide；By 10
Sample after μ l claddings is coated on silicon chip, and after solvent volatilization, the method degraded using ultraviolet irradiation removes block copolymer, in obtaining
Empty bimetal nano particles/titanium dioxide core shell structure.Detected through TEM methods, in the core shell structure, hollow bimetal nano grain
The size of son is 14nm, and the particle diameter of whole core shell structure is 28nm.
Embodiment 4
100mgPVP-b-PEO block copolymers are weighed, 24 mg silver nitrates and solvents tetrahydrofurane 10g is added, stirring is extremely
It is few 1 day, colourless transparent solution is formed, the mg of BPH 20 are added, the ultraviolet that above-mentioned solution wavelength is 254nm is irradiated into 16h,
Obtain yellow Ag nano-particle solutions.The mg of silver nano-particle solution 400 of preparation is taken, HAuCl is added4Solution（1mg/ml ）
28 μ l, enter line replacement reaction at least 24h, obtain hollow bimetallic Ag-Au nano-particles（The mol ratio of wherein Au and Ag is 3）.
By the hollow bimetal nano particles containing block copolymer of above-mentioned preparation, concentration is diluted further to for 0.05wt%, then
The colloidal sol of TTIP formation is added dropwise under agitation, and wherein titanium dioxide and the volume ratio of block copolymer is 5.0%, after adding
Continue to stir 50min, the sol-gel that hollow bimetal nano particles are oxidized titanium is uniformly coated；Sample after 10 μ l are coated
Product are coated on silicon chip, and after solvent volatilization, the method degraded using ultraviolet irradiation removes block copolymer, obtains hollow bimetal nano
Particle/titanium dioxide core shell structure.Detect that in the core shell structure, the size of hollow bimetal nano particles is through TEM methods
16nm, the particle diameter of whole core shell structure is 32nm.
Embodiment 5,6,7
Bimetal nano particles solution prepared by Example 1, for preparing the hollow bimetal nano of coated by titanium dioxide
Particle, simply changes the volume ratio of titanium dioxide and block copolymer, and titanium dioxide is respectively with the volume ratio of block copolymer
10.0%（Embodiment 5）、15.0%（Embodiment 6）With 20.0%（Embodiment 7）, other preparation processes are same as Example 1.Gained
Product cut size is as follows：
Embodiment 8,9,10
Ag nano-particle solutions are prepared by the preparation method of embodiment 1, simply changes the consumption of silver nitrate and block copolymer
（Calculated with the ratio of Ag/VP）, when when during Ag/VP=0.2 as embodiment 8, Ag/VP=0.4 as embodiment 9, Ag/VP=1.0
Used as embodiment 10, other steps are same as Example 1.
Products obtained therefrom particle diameter is as follows：
Embodiment 11
Ag nano-particle solutions prepared by Example 1, replace gold chloride to prepare hollow Ag-Pt nanoparticles with potassium chloroplatinate
Son, other preparation processes are same as Example 1.Detected through TEM methods, in gained core shell structure, hollow bimetal nano particles
Size be 14nm, the particle diameter of whole core shell structure is 26nm.
Embodiment 12
100mg PVP-PEO block copolymers are weighed, 34 mg potassium chloroplatinates and solvents tetrahydrofurane 200g, stirring is added
At least 1 day, clear transparent solutions are formed, add the mg of BPH 240, by the ultraviolet irradiation 20 that above-mentioned solution wavelength is 254nm
H, obtains Pt nano-particle solutions.The ml of Pt nano-particle solutions 400 of preparation is taken, HAuCl is added4The μ l of solution 10, are carried out
Displacement reaction at least 24 h, obtain hollow bimetallic Pt-Au nano-particles（The mol ratio 3 of wherein Pt and Au:1）Nano-particle.
By the hollow bimetal nano particles containing block copolymer of above-mentioned preparation, the molten of TTIP formation is added dropwise under agitation
Glue, wherein titanium dioxide are 5.0% with the volume ratio of block copolymer, continue to stir 50min, hollow bimetal nano after adding
The sol-gel that particle is oxidized titanium is uniformly coated；Sample after 10 μ l are coated is coated on silicon chip, after solvent volatilization, is utilized
The method of ultraviolet irradiation degraded removes block copolymer, obtains hollow bimetal nano particles/titanium dioxide core shell structure.Through TEM
Method is detected, in the core shell structure, the size of hollow bimetal nano particles is 13nm, and the particle diameter of whole core shell structure is
27nm。
Embodiment 13
100mgPVP-PEO block copolymers are weighed, 34 mg platinum chlorides potassium and solvents tetrahydrofurane 200g, stirring is added
At least 1 day, clear transparent solutions are formed, add the mg of BPH 240, by the ultraviolet irradiation 20 that above-mentioned solution wavelength is 254nm
H, obtains Pt nano-particle solutions.The ml of Pt nano-particle solutions 400 of preparation is taken, HAuCl is added4The μ l of solution 20, are put
Reaction at least 20 h are changed, hollow bimetallic Pt-Au is obtained（The mol ratio 2 of wherein Pt and Au:1）Nano-particle.By above-mentioned preparation
The hollow bimetal nano particles containing block copolymer, the colloidal sol of TTIP formation, wherein dioxy are added dropwise under agitation
The volume ratio for changing titanium with block copolymer is 5.0%, continues to stir 50min after adding, and hollow bimetal nano particles are oxidized titanium
Sol-gel uniformly coat；Sample after 10 μ l are coated is coated on silicon chip, after solvent volatilization, is degraded using ultraviolet irradiation
Method remove block copolymer, obtain hollow bimetal nano particles/titanium dioxide core shell structure.Detected through TEM methods, the core
In shell structure, the size of hollow bimetal nano particles is 12nm, and the particle diameter of whole core shell structure is 26nm.
Embodiment 14
100mgPVP-PEO block copolymers are weighed, 34 mg platinum chlorides potassium and solvents tetrahydrofurane, stirring at least 1 is added
My god, clear solution is formed, the mg of BPH 24 are added, the ultraviolet that above-mentioned solution wavelength is 254nm is irradiated into 16h, obtain yellow
Pt nano-particle solutions.The ml of Pt nano-particle solutions 400 of preparation is taken, HAuCl is added4The μ l of solution 40, enter line replacement reaction
At least 24 h, obtain hollow bimetallic Pt-Au（Mol ratio 1:1）Nano-particle.By above-mentioned preparation containing block copolymer
Hollow bimetal nano particles, are diluted further to concentration for 0.05wt%, and the molten of TTIP formation is then added dropwise under agitation
Glue, wherein titanium dioxide are 5.0% with the volume ratio of block copolymer, continue to stir 50min, hollow bimetal nano after adding
The sol-gel that particle is oxidized titanium is uniformly coated；Sample after 10 μ l are coated is coated on silicon chip, solvent volatilization, using purple
After the method for external irradiation degraded removes block copolymer, hollow bimetal nano particles/titanium dioxide core shell structure is obtained.Through TEM
Method is detected, in the core shell structure, the size of hollow bimetal nano particles is 13nm, and the particle diameter of whole core shell structure is
27nm。
Embodiment 15
Weigh 100mg PVPs-PLA（PVP-b-PLA）Block copolymer, adds silver nitrate and molten
Agent tetrahydrofuran, stirring obtains colourless transparent solution, and the wherein mol ratio of Ag/VP is 0.6, for the preparation of Nano silver grain.
Prepared by hollow bimetal nano particles, prepared by the hollow bimetal nano particles of coated by titanium dioxide and the removing method of copolymer
Carried out according to embodiment 1.
Embodiment 16
The mixed solution of block copolymer and silver nitrate is prepared by embodiment 1, the tetrahydrofuran that hydrazine hydrate is then added dropwise is molten
Liquid, it is 20 with the mol ratio of silver to control hydrazine, obtains silver nano-particle solution.Prepared by hollow bimetal nano particles, titanium dioxide
Prepared by the hollow bimetal nano particles of cladding and the removing method of copolymer is carried out according to embodiment 1.
Embodiment 17
Bimetal nano particles solution prepared by Example 1, for preparing the hollow bimetal nano of coated by titanium dioxide
Particle.The colloidal sol of titanium dioxide uses butyl titanate（TBT）Prepare, other steps are with embodiment 1.
Embodiment 18,19
The hollow bimetal nano particles of coated by titanium dioxide prepared by Example 1, unlike：Using oxygen plasma
Treatment 20 minutes（Embodiment 18）Or 400 degree of high-temperature calcinations 4 hours（Embodiment 19）Remove block copolymer.
Comparative example 1
During embodiment 1 prepares bimetal nano particles, block copolymer is added without, then more active metal
Nano-particle less stable, with more inactive metal precursor is entering when line replacement reacts that bimetal nano can not be obtained
Particle.
Comparative example 2-4
The sol-gel that PVP-b-PEO block copolymers are formed with TTIP is directly mixed, Titanium Dioxide is prepared
Agent, carries out photocatalytic degradation MB experiments, as comparative example 2 as described in Example 1.
The Nano silver grain that will be prepared using PVP-PEO block copolymers in example 1, the sol-gel formed with TTIP
Directly mix, coated, photocatalytic degradation MB experiments are carried out as described in Example 1, as comparative example 3.
The Pt nano-particles that will be prepared using PVP-PEO block copolymers in example 4, the sol-gel formed with TTIP
Directly mix, coated, photocatalytic degradation MB experiments are carried out as described in Example 1, as comparative example 4.
Using methylene blue each embodiment of experiment detection and the photocatalysis effect of comparative example products obtained therefrom, 1 is as a result see the table below.
Each embodiment of table 1 and comparative example product catalytic effect
Claims (12)
1. a kind of preparation method of hollow bimetal nano particles/titanium dioxide core shell structure, it is characterized in that comprising the following steps：
（1）By the presoma of more active metal and amphiphilic block copolymer dissolving in organic solvent, micellar solution is formed；
（2）The more active metal precursor in above-mentioned micellar solution is reduced into more active metal using reducing process to receive
Rice corpuscles, forms the more active metal nanoparticle solution that surface has amphiphilic block copolymer；
（3）Under agitation, the solution of the presoma containing more inactive metal is added drop-wise to surface and there is parents' block and be total to
In the more active metal nanoparticle solution of polymers, formed during surface has an amphiphilic block copolymer by replacing reaction
Empty bimetal nano particles；
（4）There is the hollow bimetal nano particles Surface coating two of amphiphilic block copolymer on surface by sol-gel process
Titanium oxide, forms hollow bimetal nano particles/titanium dioxide core shell structure that surface has amphiphilic block copolymer；
（5）Remove surface exist it is double in the hollow bimetal nano particles/titanium dioxide core shell structure of amphiphilic block copolymer
Close block copolymer, forms hollow bimetal nano particles/titanium dioxide core shell structure；The hollow bimetal nano particles/
Titanium dioxide core shell structure with hollow bimetal nano particles as core, with titanium dioxide as shell, hollow bimetal nano particles with
There is space between titanium dioxide；
In the hollow bimetal nano particles, more active metal can be by the positive valence state ion of more inactive metal
Zeroth order is reduced to, both metals are selected from Au Ag Pt Pd, copper.
2. preparation method according to claim 1, it is characterized in that：More active metal and more inactive metal
Mol ratio is：3.0~0.3：1.
3. preparation method according to claim 1, it is characterized in that：Two kinds of metals in the hollow bimetal nano particles
Selected from silver and gold.
4. preparation method according to claim 2, it is characterized in that：More active metal and more inactive metal
Mol ratio is 2.0 ~ 0.5：1.
5. the preparation method according to any one of claim 1-4, it is characterized in that：The amphiphilic block copolymer is poly- second
Alkenyl pyridine-polyethylene oxide block copolymer, PEG-PEI, polyethylene glycol oxide-poly-（2- methyl oxazolines）
Or PVP-PLA.
6. preparation method according to claim 1, it is characterized in that：Step（1）In, in amphiphilic block copolymer can with more
There is rubbing for constitutional repeating unit in the block of complexing and the presoma of more active metal in active metal ion
You are than being 1：0.1~1.0；Step（4）In, TiO2The TiO that colloidal sol is generated2With the volume ratio of amphiphilic block copolymer for 0.05 ~
0.15：1.
7. preparation method according to claim 6, it is characterized in that：Step（1）In, in amphiphilic block copolymer can with more
There is rubbing for constitutional repeating unit in the block of complexing and the presoma of more active metal in active metal ion
You are than being 1：0.2~0.6.
8. the preparation method according to any one of claim 1-4, it is characterized in that：The more active metal and more
The presoma of inactive metal includes the salt of metal or the inorganic acid of metal；Step（2）In, the reducing process is using purple
Outside line irradiation reducing process is reduced, or to add reducing agent to be reduced；Step（4）In, the sol-gal process be by
The presoma of titanium dioxide forms TiO 2 sol under the catalysis of hydrochloric acid or glacial acetic acid, and the colloidal sol is added drop-wise into surface is present
In the solution of the hollow bimetal nano particles of amphiphilic block copolymer, the method for realizing the cladding of titanium dioxide；Step（4）
In, the presoma of the titanium dioxide includes isopropyl titanate, butyl titanate, acetyl acetone titanium or titanium tetrachloride；Step
（5）In, amphiphilic block copolymer is removed by the method for ultraviolet irradiation degraded, high-temperature calcination or plasma etching.
9. preparation method according to claim 1, it is characterized in that：Step（3）In, the time for replacing reaction is at least 20h；
Step（4）In, it is 0.01- that the surface has the hollow bimetal nano particles of amphiphilic block copolymer concentration in the solution
0.05wt%。
10. according to the preparation of the hollow bimetal nano particles/titanium dioxide core shell structure any one of claim 1-9
Hollow bimetal nano particles/titanium dioxide core shell structure obtained in method.
11. hollow bimetal nano particles/titanium dioxide core shell structures according to claim 10, it is characterized in that：It is described
The particle diameter of hollow bimetal nano particles is 5-20nm；The particle diameter of hollow bimetal nano particles/titanium dioxide core shell structure is
10-40nm。
Hollow bimetal nano particles/titanium dioxide core shell structure described in a kind of 12. claims 10 or 11 is used as photocatalysis
The application of the photochemical catalyst in degradation of organic substances.
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