Background technology
Titanium dioxide is as the most frequently used catalysis material,, good stability nontoxic because of it, the pollutant in the water body of can degrading effectively under the UV-irradiation effect.Yet, because TiO
2Greater band gap (about 3.2ev), TiO
2Problems such as the absorption threshold value is less than 400nm, and is not high to the utilization rate of sunshine, and the light induced electron of material surface and photohole are easily compound have influenced TiO
2The process of multiphase photocatalysis reaction industrialization.
Nano copper particle is little owing to having size, specific area reaches characteristics such as quantum size effect and macro quanta tunnel effect greatly, make it light, electricity, magnetic and chemical aspect represented novel characteristic, the research of therefore relevant in recent years preparation, performance and the application to the copper nano material at home and abroad is subjected to paying close attention to widely always.
Carry out compound by nano copper particle to titanium dioxide, because the energy gap of nano copper particle can be expanded the light absorption of titanium dioxide in visible-range, and two kinds of different semi-conducting materials of energy gap can form heterojunction structure, thereby can effectively reduce the recombination probability of carrier, prolong the life-span of carrier, improve the efficient of opto-electronic conversion.Simultaneously, synthetic binary composite photoelectric catalysis material has novel nucleocapsid structure, this is a kind of orderly package assembly that by chemical bond or other interactions another kind of nano material is coated the nanoscale that forms by a kind of nano material, it is higher level composite nanostructure, composite material of core-shell structure can satisfy people's design to material structure and performance on nanoscale, cut out and optimize, in addition, the material of this structure can also be because of its monodispersity that has, excellent properties such as the operability of nucleocapsid and controllability can be regulated and control many performances of compound to a great extent, utilize the interaction between nuclear and the shell, and the effects such as absorption of checking degradation product, can improve the photocatalysis performance of complex.
By retrieving relevant patent documentation, number of patent application is that ZL 201110258150.9 has reported a kind of copper-titanium dioxide core shell mould nanometer particle process method, though this method and the present invention are about forming copper-titanium dioxide core shell mould nanometer particle process method, but exist more different on synthetic method: method provided by the invention comprises aspect two, at first synthetic zerovalent copper is as the nuclear presoma, utilize the titanium isopropoxide in-situ hydrolysis again, can coat on the zerovalent copper surface and form layer of titanium dioxide, this method can be in the process of synthetic kernel and shell, by selecting different copper sources for use, regulate the concentration of titanium isopropoxide, obtain the copper-titanium dioxide core shell mould nano particle of varying particle size and different thickness of the shells, application 201110258150.9 in reported method to adopt polyethylene glycol be soft template, obtain to have the copper-titanium dioxide nano-particle of nucleocapsid structure by hydro-thermal reaction.Both compare, and method provided by the invention is stronger aspect the operability of nucleocapsid and controllability, and the proof nano particle that utilizes method provided by the invention to prepare has good effect aspect photocatalysis degradation organic contaminant by experiment.
Summary of the invention
The objective of the invention is to, a kind of preparation method with titanium dioxide of core-shell structure clad nano copper is provided, it is cladding titanium dioxide on nano copper particle, formation possesses the preparation method of nuclear shell structure nano complex, this method is based on the principle of in-situ hydrolysis, comprise as the nano copper particle of nuclear matter and mixing of titanium source, utilize the facile hydrolysis in titanium source to form one deck shell structure again on the nano copper particle surface.It is few that this preparation method has a raw material type, method of operating is easy, technology is simple, characteristics such as environmental protection, prepared nano-complex has photocatalysis performance, respectively under visible light and ultraviolet light to 2, the degradation effect of organic pollutions such as 4-two chlorophenols is obvious, has certain actual application value.
A kind of preparation method with titanium dioxide of core-shell structure clad nano copper of the present invention follows these steps to carry out:
A, nano copper particle is scattered in the ethanol solution, ultrasonic 5 minutes, obtains mixed liquor;
B, titanium isopropoxide is dissolved in the 50ml ethanol solution, under agitation, dropwise splashes in the step a mixed liquor, after waiting to dropwise, continue to stir, reacted 1-4 hour, obtain mixed liquor;
C, with water and ethanol solution by volume for 12ml:100-133ml mixes, dropwise be added drop-wise in the step b mixed solution, continue to stir 2 hours, obtain mixed liquor;
D, solution that step c is obtained under 11500rpm centrifugal 10 minutes, resulting sediment respectively washs respectively 3 times with distilled water and absolute ethyl alcohol, place vacuum drying chamber in 30 ℃ of dryings of temperature 12 hours, promptly get target product titanium dioxide of core-shell structure clad nano copper.
The molar concentration of nano copper particle alcoholic solution is 5.0mM-9.0mM among the step a.
The molar concentration of titanium isopropoxide alcoholic solution is 0.05M-0.25M among the step b.
A kind of preparation method of the present invention with titanium dioxide of core-shell structure clad nano copper, the copper source that is used to prepare nano copper particle in this method is selected from copper chloride, copper sulphate or cupric oxide, reducing agent is selected from the L-ascorbic acid, sodium borohydride, hydrazine or glucose, adopt conventional method to prepare nano copper particle, again nano copper particle is dissolved in the ethanol solution, ultrasonic, under agitation, the ethanol solution that will contain titanium isopropoxide dropwise is added drop-wise in the nanometer copper ethanol solution, stir, solution with water/absolute ethyl alcohol dropwise is added drop-wise in the above-mentioned mixed solution again, continue to stir, under 11500rpm centrifugal 10 minutes, the sediment that obtains washed respectively respectively 3 times with distilled water and absolute ethyl alcohol, be placed in the vacuum drying in 30 ℃ dry 12 hours down, promptly obtain target product.It is few that this preparation method has a raw material type, method of operating is easy, technology is simple, characteristics such as environmental protection, prepared nano-complex has photocatalysis performance, respectively under visible light and ultraviolet light to 2, the degradation effect of organic pollutions such as 4-two chlorophenols is obvious, has certain actual application value.
The specific embodiment
In order to understand the present invention better, further specify by following examples;
Embodiment 1:
The preparation nano copper particle:
Get 100ml 0.04M CuSO
4The aqueous solution joins the NaBH with volume 0.13M
4In the solution, mixed solution at room temperature mixed 1 minute, acquisition be deposited under the 11500rpm centrifugal 10 minutes, wash each respectively 3 times with distilled water and absolute ethyl alcohol again, the product after the washing is placed on 30 ℃ of vacuum drying chamber temperature dry 12h down;
Dioxide coated by nano titanium copper:
The nano copper particle 0.016g that gets preparation is dissolved in the ethanol solution of 50ml, ultrasonic 5 minutes, obtains mixed liquor;
0.74ml isopropoxy titanium solution is dissolved in the 50ml ethanol solution, under agitation, dropwise is added drop-wise in the nanometer copper absolute ethyl alcohol mixed solution, continue to stir, react after 1 hour, obtain mixed liquor;
With volume ratio is that the solution of 0.09(water/absolute ethyl alcohol=12ml/133ml) dropwise is added drop-wise in the mixed solution of titanium isopropoxide alcoholic solution and nanometer copper alcoholic solution, continues to stir 2 hours, obtains mixed liquor;
Again with the mixed liquor that obtains under 11500rpm centrifugal 10 minutes, resulting sediment respectively washs respectively 3 times with distilled water and absolute ethyl alcohol, be placed in the vacuum drying to descend dry 8 hours, promptly obtain target product titanium dioxide of core-shell structure clad nano copper in 40 ℃ of temperature.
Embodiment 2:
The preparation nano copper particle:
Get 50ml 0.4M L-ascorbic acid solution and dropwise be added drop-wise to 50ml 10mM CuCl
22H
2In the O solution, in oil bath, keep 80 ℃ of temperature, continue stirring reaction 16 hours, the sediment of acquisition under 11500rpm centrifugal 10 minutes, respectively wash respectively 3 times with distilled water and absolute ethyl alcohol again, the product after the washing is placed on 30 ℃ of following dry 12h of vacuum drying chamber temperature;
Dioxide coated by nano titanium copper:
The nano copper particle 0.0176g that gets preparation is dissolved in the ethanol solution of 50ml, ultrasonic 5 minutes, obtains mixed liquor;
1.5ml isopropoxy titanium solution is dissolved in the 50ml ethanol solution, under agitation, dropwise is added drop-wise in the nanometer copper absolute ethyl alcohol mixed solution, after waiting to dropwise, continue to stir, reacted 2 hours, obtain mixed liquor;
With volume ratio is that the solution of 0.1(water/absolute ethyl alcohol=12ml/120ml) dropwise is added drop-wise in the mixed solution of titanium isopropoxide alcoholic solution and nanometer copper alcoholic solution, continues to stir 2 hours, obtains mixed liquor;
Again with the mixed solution that obtains under 11500rpm centrifugal 10 minutes, resulting sediment respectively washs respectively 3 times with distilled water and absolute ethyl alcohol, be placed in the vacuum drying to descend dry 12 hours, promptly obtain target product titanium dioxide of core-shell structure clad nano copper in 30 ℃ of temperature.
Embodiment 3:
The preparation nano copper particle:
Stir down, hydrazine solution dropwise is added drop-wise in the copper chloride solution of 45ml 0.43mM (mol ratio of hydrazine and copper chloride solution is 20), reaction temperature maintains 35 ℃, when changing yellow into by blueness, solution colour have nano copper particle to produce, with be deposited under the 11500rpm centrifugal 10 minutes that obtain, respectively wash respectively 3 times with distilled water and absolute ethyl alcohol again, the product after the washing is placed on 50 ℃ of following dry 4h of vacuum drying chamber temperature;
Dioxide coated by nano titanium copper:
The nano copper particle 0.0224g that gets preparation is dissolved in the ethanol solution of 50ml, ultrasonic 5 minutes, obtains mixed liquor;
3.0ml isopropoxy titanium solution is dissolved in the 50ml ethanol solution, under agitation, dropwise is added drop-wise in the nanometer copper absolute ethyl alcohol mixed solution, after waiting to dropwise, continue to stir, reacted 3 hours, obtain mixed liquor;
With volume ratio is that the solution of 0.105(water/absolute ethyl alcohol=12ml/114ml) dropwise is added drop-wise in the mixed solution of titanium isopropoxide alcoholic solution and nanometer copper alcoholic solution, continues to stir 2 hours, obtains mixed liquor;
Again with the mixed solution that obtains under 11500rpm centrifugal 10 minutes, resulting sediment respectively washs respectively 3 times with distilled water and absolute ethyl alcohol, be placed in the vacuum drying to descend dry 10 hours, promptly obtain target product titanium dioxide of core-shell structure clad nano copper in 35 ℃ of temperature.
Embodiment 4
The preparation nano copper particle::
1.246g cupric oxide and excessive a-D-glucose are placed the reactor of 50ml, add the 40ml deionized water, place baking oven to react 20 hours down for 150 ℃ reactor in temperature, the question response still is cooled to room temperature, the precipitation that obtains is filtered, respectively wash respectively 3 times with distilled water and absolute ethyl alcohol again, the product after the washing is placed on 50 ℃ of following dry 4h of vacuum drying chamber temperature;
Dioxide coated by nano titanium copper:
The nano copper particle 0.0288g that gets preparation is dissolved in the ethanol solution of 50ml, ultrasonic 3 minutes, obtains mixed liquor;
3.7ml isopropoxy titanium solution is dissolved in the 50ml ethanol solution, under agitation, dropwise is added drop-wise in the nanometer copper absolute ethyl alcohol mixed solution, after waiting to dropwise, continue to stir, reacted 4 hours, obtain mixed liquor;
With volume ratio is that the solution of 0.12(water/absolute ethyl alcohol=12ml/100ml) dropwise is added drop-wise in the mixed solution of titanium isopropoxide alcoholic solution and nanometer copper alcoholic solution, continues to stir 2 hours, obtains mixed liquor;
With the mixed solution that obtains under 11500rpm centrifugal 10 minutes, resulting sediment respectively washs respectively 3 times with distilled water and absolute ethyl alcohol, be placed in the vacuum drying to descend dry 12 hours, promptly obtain target product titanium dioxide of core-shell structure clad nano copper in 30 ℃ of temperature.
By the titanium dioxide of core-shell structure clad nano copper that embodiment 1-4 obtains, observe dioxide coated by nano titanium copper by transmission electron microscope method commonly used and have nucleocapsid structure (Fig. 2).