CN104128209B - A kind of polymer core-shell structure TiO of loaded Ag-AgCl nano particle 2the preparation method of photochemical catalyst - Google Patents
A kind of polymer core-shell structure TiO of loaded Ag-AgCl nano particle 2the preparation method of photochemical catalyst Download PDFInfo
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Abstract
A kind of polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2the preparation method of photochemical catalyst, the present invention relates to TiO
2the preparation method of photochemical catalyst.The present invention's traditional catalysis material that will solve based on existing titanium dioxide has photoresponse narrow range and the not high problem of catalyst activity.Method: by Electrospun TiO
2join in the aqueous solution in silver-colored source, ultrasonic agitation, then centrifugal treating washing, again the product after washing is scattered in distilled water, add in system by polymer monomer and Iron trichloride hexahydrate, centrifugal treating is also washed, and namely obtains the polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2photochemical catalyst.The present invention is used for a kind of polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2the preparation of photochemical catalyst.
Description
Technical field
The present invention relates to TiO
2the preparation method of photochemical catalyst.
Background technology
Metal nanoparticle has attracted the attention of increasing scientific researcher because it has unique physics, chemistry and biological nature.These characteristics make metal nanoparticle be widely used in energy conversion, sensor, biological medicine, especially catalyst aspect.Research display, nano particle has very high specific area, makes it have very high catalytic activity.But nano material also also exists weak point in the process of practical application.Can be there is serious gathering in nano particle, thus result in the obvious reduction of its catalytic activity in the solution, and what this point was serious hinders nano particle in real-life extensive use.
Conducting polymer macromolecular material, polymer is cross-linked polymer, nano particle can be anchored in polymeric system in the course of the polymerization process.Can effectively prevent nano particle from assembling.Polymeric color is dark simultaneously, easily absorbs more visible ray.
Along with economic development and population expansion, environmental pollution threatens human survival, and environmental problem has become global important topic.Compared with conventional method, photocatalysis degradation organic contaminant has nontoxic, and efficiently, the advantage such as inexpensive, is expected to become new energy-efficient environmental pollution improvement's method.At present, the traditional catalysis material based on titanium dioxide has photoresponse narrow range and the not high shortcoming of catalyst activity.
Summary of the invention
The present invention's traditional catalysis material that will solve based on existing titanium dioxide has photoresponse narrow range and the not high problem of catalyst activity, and provides a kind of polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2the preparation method of photochemical catalyst.
A kind of polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2the preparation method of photochemical catalyst, specifically carries out according to following steps:
One, by Electrospun TiO
2join in the aqueous solution in silver-colored source, ultrasonic 1min ~ 60min, then stirs 1h ~ 10h, obtains dispersion soln A;
Described Electrospun TiO
2quality and the volume ratio of the aqueous solution in silver-colored source be 1mg:(0.01 ~ 0.5) mL;
Two, under rotating speed is 1000r/min ~ 8000r/min, dispersion soln A centrifugal treating 3min ~ 15min that step one is obtained, then spend deionized water 1 time ~ 10 times, then the product after washing is scattered in distilled water, and ultrasonic 1min ~ 10min, obtain dispersion soln B;
Described Electrospun TiO
2quality and the volume ratio of distilled water be 1mg:(1 ~ 100) mL;
Three, under agitation, polymer monomer is joined in dispersion soln B, stir 1h ~ 8h, Iron trichloride hexahydrate is added again in system, stirring reaction 3h ~ 20h, then under rotating speed is 1000r/min ~ 8000r/min, centrifugal treating 3min ~ 15min, finally spend deionized water again 1 time ~ 10 times, namely obtain the polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2photochemical catalyst;
The quality of described polymer monomer and the volume ratio of dispersion soln B are 1g:(10 ~ 1000) mL; Described polymer monomer and the mass ratio of Iron trichloride hexahydrate are 1:(1 ~ 10000).
The invention has the beneficial effects as follows: the catalyst that 1, prepared by the present invention has the stability higher than general catalyst, avoiding material because assembling the low problem of the catalytic activity that causes, can service life of extending catalyst, reduce financial cost.
2, the catalyst prepared by the present invention has the quantum efficiency of the catalysis material of wider response range and Geng Gao than traditional titanium dioxide optical catalyst.
3, the catalyst prepared by the present invention has very strong degradation to dyestuff in sewage.
The present invention is used for a kind of polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2the preparation of photochemical catalyst.
Accompanying drawing explanation
Fig. 1 is Electrospun TiO
2the SEM photo of nano wire;
Fig. 2 is Ag-AgCl/PTTiO prepared by embodiment
2the SEM photo of composite;
Fig. 3 is Ag-AgCl/PTTiO prepared by embodiment
2the TEM photo of composite;
Fig. 4 is the catalytic performance figure of photochemical catalyst prepared by embodiment; A is the curve of titanium dioxide as the ultraviolet-visible absorption spectroscopy test gained of photochemical catalyst; B is the curve of the ultraviolet-visible absorption spectroscopy test gained after the photochemical catalyst catalysis prepared of embodiment;
Fig. 5 is that photochemical catalyst prepared by embodiment carries out catalysis to reaction system, uses different number of times, the curve of the time of dye degrades sodium borohydride reduction methylene blue required for 10% of original vol through reclaiming.
Detailed description of the invention
Technical solution of the present invention is not limited to following cited detailed description of the invention, also comprises any combination between each detailed description of the invention.
Detailed description of the invention one: the polymer core-shell structure TiO of a kind of loaded Ag-AgCl nano particle described in present embodiment
2the preparation method of photochemical catalyst, specifically carries out according to following steps:
One, by Electrospun TiO
2join in the aqueous solution in silver-colored source, ultrasonic 1min ~ 60min, then stirs 1h ~ 10h, obtains dispersion soln A;
Described Electrospun TiO
2quality and the volume ratio of the aqueous solution in silver-colored source be 1mg:(0.01 ~ 0.5) mL;
Two, under rotating speed is 1000r/min ~ 8000r/min, dispersion soln A centrifugal treating 3min ~ 15min that step one is obtained, then spend deionized water 1 time ~ 10 times, then the product after washing is scattered in distilled water, and ultrasonic 1min ~ 10min, obtain dispersion soln B;
Described Electrospun TiO
2quality and the volume ratio of distilled water be 1mg:(1 ~ 100) mL;
Three, under agitation, polymer monomer is joined in dispersion soln B, stir 1h ~ 8h, Iron trichloride hexahydrate is added again in system, stirring reaction 3h ~ 20h, then under rotating speed is 1000r/min ~ 8000r/min, centrifugal treating 3min ~ 15min, finally spend deionized water again 1 time ~ 10 times, namely obtain the polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2photochemical catalyst;
The quality of described polymer monomer and the volume ratio of dispersion soln B are 1g:(10 ~ 1000) mL; Described polymer monomer and the mass ratio of Iron trichloride hexahydrate are 1:(1 ~ 10000).
The catalysis light district scope of titanium dioxide is narrow, by carrying out it can reducing its electronic transition energy when illumination is penetrated with the doping of Nano silver grain, photocatalysis scope is moved to visible region.Silver chloride nanoparticles with titania additive recombination process in can introduce Lattice Oxygen room or part Lacking oxygen is substituted, this makes titanium dioxide forbidden band narrow, thus expand the coverage of radiant light, therefore, prepared catalyst has wider response range than traditional titanium dioxide optical catalyst.The black shell of polypyrrole can absorb more visible ray simultaneously, and this also has certain facilitation to raising photocatalysis efficiency.
The beneficial effect of present embodiment is: the catalyst that 1, prepared by present embodiment has the stability higher than general catalyst, avoids material because assembling the low problem of the catalytic activity that causes, can service life of extending catalyst, reduces financial cost.
2, the catalyst prepared by present embodiment has the quantum efficiency of the catalysis material of wider response range and Geng Gao than traditional titanium dioxide optical catalyst.
3, the catalyst prepared by present embodiment has very strong degradation to dyestuff in sewage.
Detailed description of the invention two: present embodiment and detailed description of the invention one are unlike the Electrospun TiO described in step one
2diameter be 100nm ~ 1000nm.Other is identical with detailed description of the invention one.
Detailed description of the invention three: one of present embodiment and detailed description of the invention one or two unlike: the concentration of the aqueous solution in the silver-colored source described in step one is 0.01mol/L ~ 10mol/L.Other is identical with detailed description of the invention one or two.
Detailed description of the invention four: one of present embodiment and detailed description of the invention one to three unlike: the aqueous solution in the silver-colored source described in step one is a kind of or wherein several mixture in the aqueous solution of the aqueous solution of silver sulfate, the aqueous solution of silver cyanide, the aqueous solution of silver oxide and silver nitrate.Other is identical with detailed description of the invention one to three.
Detailed description of the invention five: one of present embodiment and detailed description of the invention one to four unlike: the polymer monomer described in step 3 is thiophene monomer, pyrrole monomer or aniline monomer.Other is identical with detailed description of the invention one to four.
Detailed description of the invention six: one of present embodiment and detailed description of the invention one to five unlike: in step 2 under rotating speed is 1000r/min ~ 8000r/min, the dispersion soln A centrifugal treating 15min that step one is obtained.Other is identical with detailed description of the invention one to five.
Present embodiment act as removing and is not attached to TiO
2on silver ion.
Detailed description of the invention seven: one of present embodiment and detailed description of the invention one to six unlike: in step 3 under rotating speed is 1000r/min ~ 8000r/min, centrifugal treating 15min.Other is identical with detailed description of the invention one to six.
Present embodiment act as the responseless polymer monomer of removing and iron ion.
Following examples are adopted to verify beneficial effect of the present invention:
Embodiment:
The polymer core-shell structure TiO of a kind of loaded Ag-AgCl nano particle described in the present embodiment
2the preparation method of photochemical catalyst, specifically carries out according to following steps:
One, by 100mg diameter be the Electrospun TiO of 300nm
2joining 10mL concentration is in the silver nitrate aqueous solution of 0.5mol/mL, and ultrasonic 30min, then stirs 1h, dispersion soln A;
Two, under rotating speed is 6000r/min, the dispersion soln A centrifugal treating 5min that step one is obtained, then wash 3 times by deionized water, then the product after washing is scattered in 120mL distilled water, and ultrasonic 20min, obtain dispersion soln B;
Three, under agitation, 0.05mg thiophene monomer is joined in dispersion soln B, stir 5h, 100mg Iron trichloride hexahydrate is added again in system, stirring reaction 20h, then under rotating speed is 7000r/min, centrifugal treating 10min, finally spend deionized water again 3 times, obtain the polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2photochemical catalyst, i.e. Ag-AgCl/PTTiO
2composite.
Fig. 1 is Electrospun TiO
2the SEM photo of nano wire, Fig. 2 is Ag-AgCl/PTTiO prepared by embodiment
2the SEM photo of composite, as seen from the figure, its diameter increases to some extent, and outward appearance is mellow and full, and the composite of synthesis is very well apparent.
Fig. 3 is Ag-AgCl/PTTiO prepared by embodiment
2the TEM photo of composite, as seen from the figure, nano wire is nucleocapsid structure, outside coated PT has been described, can have found out that on housing, some inorganic matter nano particles in grappling simultaneously in picture.
Fig. 4 is the catalytic performance figure of photochemical catalyst prepared by embodiment; A is the curve of titanium dioxide as the ultraviolet-visible absorption spectroscopy test gained of photochemical catalyst; B is the curve of the ultraviolet-visible absorption spectroscopy test gained after the photochemical catalyst catalysis prepared of embodiment; As seen from the figure, photochemical catalyst prepared by the present embodiment can be found out to the photocatalytic activity of dye degrades sodium borohydride reduction methylene blue from curve far away higher than the photochemical catalyst not carrying out modification, confirm that the photochemical catalyst that the present embodiment synthesizes has higher photocatalytic activity.
Fig. 5 is that photochemical catalyst prepared by embodiment carries out catalysis to reaction system, uses different number of times, the curve of the time of dye degrades sodium borohydride reduction methylene blue required for 10% of original vol through reclaiming.As seen from the figure, the catalysis time of catalyst increases to some extent through increasing of access times, but the time that six tests increase does not have too great fluctuation process, and this illustrates that catalyst has good stability.
Claims (6)
1. the polymer core-shell structure TiO of a loaded Ag-AgCl nano particle
2the preparation method of photochemical catalyst, is characterized in that a kind of polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2the preparation method of photochemical catalyst carries out according to following steps:
One, by Electrospun TiO
2join in the aqueous solution in silver-colored source, ultrasonic 1min ~ 60min, then stirs 1h ~ 10h, obtains dispersion soln A;
Described Electrospun TiO
2quality and the volume ratio of the aqueous solution in silver-colored source be 1mg:(0.01 ~ 0.5) mL;
Two, under rotating speed is 1000r/min ~ 8000r/min, dispersion soln A centrifugal treating 3min ~ 15min that step one is obtained, then spend deionized water 1 time ~ 10 times, then the product after washing is scattered in distilled water, and ultrasonic 1min ~ 10min, obtain dispersion soln B;
Described Electrospun TiO
2quality and the volume ratio of distilled water be 1mg:(1 ~ 100) mL;
Three, under agitation, polymer monomer is joined in dispersion soln B, stir 1h ~ 8h, Iron trichloride hexahydrate is added again in system, stirring reaction 3h ~ 20h, then under rotating speed is 1000r/min ~ 8000r/min, centrifugal treating 3min ~ 15min, finally spend deionized water again 1 time ~ 10 times, namely obtain the polymer core-shell structure TiO of loaded Ag-AgCl nano particle
2photochemical catalyst;
The quality of described polymer monomer and the volume ratio of dispersion soln B are 1g:(10 ~ 1000) mL; Described polymer monomer and the mass ratio of Iron trichloride hexahydrate are 1:(1 ~ 10000);
Polymer monomer described in step 3 is thiophene monomer, pyrrole monomer or aniline monomer.
2. the polymer core-shell structure TiO of a kind of loaded Ag-AgCl nano particle according to claim 1
2the preparation method of photochemical catalyst, is characterized in that the Electrospun TiO described in step one
2diameter be 100nm ~ 1000nm.
3. the polymer core-shell structure TiO of a kind of loaded Ag-AgCl nano particle according to claim 1
2the preparation method of photochemical catalyst, is characterized in that the concentration of the aqueous solution in the silver-colored source described in step one is 0.01mol/L ~ 10mol/L.
4. the polymer core-shell structure TiO of a kind of loaded Ag-AgCl nano particle according to claim 1
2the preparation method of photochemical catalyst, is characterized in that the aqueous solution in the silver-colored source described in step one is a kind of or wherein several mixture in the aqueous solution of the aqueous solution of silver sulfate, the aqueous solution of silver cyanide and silver nitrate.
5. the polymer core-shell structure TiO of a kind of loaded Ag-AgCl nano particle according to claim 1
2the preparation method of photochemical catalyst, is characterized in that in step 2 under rotating speed is 1000r/min ~ 8000r/min, dispersion soln A centrifugal treating 15min step one obtained.
6. the polymer core-shell structure TiO of a kind of loaded Ag-AgCl nano particle according to claim 1
2the preparation method of photochemical catalyst, is characterized in that in step 3 under rotating speed is 1000r/min ~ 8000r/min, centrifugal treating 15min.
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