CN103143400A - Preparation method of multi-component porous visible-light-induced photocatalyst with hierarchical structure - Google Patents
Preparation method of multi-component porous visible-light-induced photocatalyst with hierarchical structure Download PDFInfo
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- CN103143400A CN103143400A CN2013101028974A CN201310102897A CN103143400A CN 103143400 A CN103143400 A CN 103143400A CN 2013101028974 A CN2013101028974 A CN 2013101028974A CN 201310102897 A CN201310102897 A CN 201310102897A CN 103143400 A CN103143400 A CN 103143400A
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Abstract
The invention discloses a preparation method of a multi-component porous visible-light-induced photocatalyst with a hierarchical structure. The preparation method comprises the following steps: pre-treating a natural biological material having a three-dimensional porous structure to take the natural biological material as a template; preparing a metal oxide nanometer material having a three-dimensional porous hierarchical structure through the template to take the metal oxide nanometer material as a matrix; and depositing a composite semiconductor nanometer material on the metal oxide matrix to finally prepare a composite nanometer material having a multi-component porous hierarchical structure. According to the method disclosed by the invention, the biological materials having three-dimensional hierarchical structures can be extensively selected as the template, the process is simple and flexible, the cost is low, and the composite nanometer material can be obtained by regulating and controlling the technological parameters and different template structures, and the like. The composite material prepared by the invention can be used as a visible-light-induced photocatalyst, and the composite material can quickly and effectively degrade organic pollutants under the irradiation of visible light, so that the composite material has an important application prospect in such fields as environmental protection, etc.
Description
Technical field
The present invention relates to a kind of preparation method of photochemical catalyst, relate in particular to a kind of preparation method of visible light catalyst of multicomponent porous hierarchical structure
Background technology
When industrial civilization brings the more facilities of the mankind and comfortable life, also caused problem of environmental pollution.Therefore, how to prepare can promote pollutant effectively, the novel environment friendly material of fast degradation is people's outline topic always.
In recent years, photocatalysis oxidation technique is demonstrating tempting application prospect aspect environmental contaminants improvement.The gas ancestor, titanic oxide material possess visible light permeability good, absorb that the ultraviolet light performance is strong, the chemism high, therefore the advantage of uniqueness is arranged at the aspects such as preparation of the environmental treatment of storage of solar energy and utilization, photocatalysis conversion and organic pollution oxidative degradation and new material.But himself also has certain limitation, namely due to TiO
2Energy gap about 3.2eV, can only utilize the ultraviolet light part in sunshine, due to ultraviolet light part in solar spectrum less than 5%, therefore improve the absorption efficiency of visible light part in sunshine (account for sunshine gross energy approximately 50%), be to improve TiO
2The effective way of photoelectrocatalysis efficient.
Semiconductor and the more negative spatia zonularis semiconductor of conduction level by large band gap carry out compound, under visible light, the spatia zonularis semiconductor is because energy gap is less, can be subjected to excited by visible light to produce conduction band electron, and electronics can be injected into the semi-conductive conduction band of large band gap from the semi-conductive conduction band of spatia zonularis, catalytic reaction occurs subsequently, so just can make catalyst realize effectively utilizing accounting for the more visible light of sunshine gross energy.Therefore, those skilled in the art is devoted to develop a kind of composite that can realize effectively utilizing visible light, thereby improves the catalytic efficiency of photochemical catalyst.
Summary of the invention
Because the defects of prior art, technical problem to be solved by this invention is to provide a kind of visible light catalyst that can effectively utilize visible light.
For achieving the above object, the invention provides a kind of multicomponent porous hierarchical structure visible light catalyst and preparation method thereof.Preparation method's technique simple and flexible of the present invention, environmental protection, required raw material easily obtain, with low cost; The catalyst that preparation in accordance with the present invention makes catalyze and degrade organic pollutants effectively under visible light.
On the one hand, the invention provides a kind of preparation method of multicomponent porous hierarchical structure visible light catalyst, this preparation method comprises the following steps:
1) take three-dimensional porous hierarchy as template, and template is carried out pretreatment;
2) pretreated template is put into the slaine precursor liquid and carry out impregnation process;
3) take out after dipping product and successively through cleaning, drying, calcination processing makes the metal oxide materials with three-dimensional porous hierarchy, and with this as matrix material;
4) above-mentioned matrix material is soaked deposition processes, deposition composite semiconductor nano material on the metal oxide matrix; Through cleaning, drying makes the visible light catalyst of multicomponent porous hierarchical structure.
In preparation method of the present invention, described template is the biomaterial with porous hierarchical structure, is preferably the egg film, but is not limited to this.
In the specific embodiment of the present invention, step 2) the slaine precursor liquid in refers to a kind of metal salt solution, is preferably the inorganic matter salt, such as chloride salt, Sulfates etc., but be not limited to this; Wherein, described salt is preferably titanium salt, but is not limited to this.
In better embodiment of the present invention, the pretreatment described in step 1) comprises the following steps: get described three-dimensional porous hierarchy template, rinsing is clean and dry repeatedly in absolute alcohol.
Preferably, the dipping step 2) refers to: pretreated template is statically placed in the slaine precursor liquid takes out after 1-10h.
In another better embodiment of the present invention, the cleaning described in step 3) refers to: sample is first used ethanol aqueous wash, then clean with deionized water.
Drying described in step 3) refers to: the normal temperature lucifuge, and natural drying.
Preferably, the sintering described in step 3) refers to: dried sample is placed in oxidation furnace, rises to 500-800 ° of C with the heating rate of 10-36 ° of C/min from room temperature, cool to room temperature with the furnace after insulation 90min.
In the specific embodiment of the present invention, preferably, the described deposition of step 4) refers to: first the metal oxide substrate be impregnated in the presoma slaine dipping solution of semi-conducting material, salt described herein is preferably chloride salt, Sulfates, but is not limited to this; Described presoma slaine dipping solution is preferably the salting liquid of cadmium, tin, but is not limited to this.
In better embodiment of the present invention, the cleaning described in step 4) refers to: before each step impregnation with the previous step product with washed with de-ionized water some times.
Preferably, the drying described in step 4) refers to: normal temperature ventilates, lucifuge is natural drying.
On the other hand, the invention provides the as above multicomponent porous hierarchical structure visible light catalyst that makes of preparation method of a kind of basis.
The present invention is by carrying out pretreatment to three-dimensional porous template, with pretreated template after preliminary dipping, through clean, dry, sintering, the more simple and easy to do treatment step of impregnating, thus made the composite of corresponding multicomponent porous hierarchical structure.At present, the preparation method of the catalysis material of the art is complicated, and cost is higher.And catalysis material involved in the present invention is the metal oxide based composites, so its preparation method simple and flexible, and is with low cost, and raw material is drawn materials conveniently, is easy to get; And has good photocatalytic energy efficiency under visible light, effectively degradable organic pollutant.Therefore, the composite of the multicomponent porous hierarchical structure that makes of method produced according to the present invention has application and prospect more widely as visible light catalyst in fields such as environmental protection.
Be described further below with reference to the technique effect of accompanying drawing to design of the present invention, concrete structure and generation, to understand fully purpose of the present invention, feature and effect.
Description of drawings
Fig. 1 is the SEM figure of the multicomponent porous hierarchical structure visible light catalyst that makes take the egg film as template in embodiments of the invention 1;
Fig. 2 is the catalytic effect curve map of multicomponent porous hierarchical structure visible light catalyst under visible light that makes take the egg film as template in embodiments of the invention 1.
The specific embodiment
In preferred embodiment of the present invention, after adopting preliminary dipping, through clean, dry, sintering, the more simple and easy to do treatment step of impregnating has prepared the visible light catalyst of multicomponent porous hierarchical structure.
Embodiment 1
The shell of commercially available egg is cleaned, separated the egg film.With the cleaning, drying of egg film, save backup.Again with the egg film immersion in the solution that is mixed according to the ratio of 12:3:1 by tetra-n-butyl titanate, absolute ethyl alcohol, concentrated hydrochloric acid.Flood after 10 hours and take out, first clean with absolute alcohol, then use washed with de-ionized water, after natural drying, it is put in carries out calcination processing in oxidation furnace, cool to room temperature with the programming rate of 36 ° of C/min with the furnace after room temperature rises to 500 ° of C insulation 90min, obtain the titanium dioxide matrix.CdCl to 0.03mol/L
2In dropwise add concentrated ammonia liquor until solution becomes clarification from white opacity occurring again to solution, obtain cadmium salt dipping precursor liquid.After being put into this cadmium salt dipping precursor liquid dipping 4.5h, takes out matrix material, with the Na that puts into 0.03mol/L after washed with de-ionized water
2Take out after soaking 0.5h in S solution, then clean with deionized water, natural drying.Through above-mentioned steps, obtain take the titanium dioxide of three-dimensional porous structure as matrix and deposit the visible light catalytic agent material of the multicomponent porous hierarchical structure of cadmium sulfide nano layer.Wherein the titania size is about 5nm, and the size of cadmium sulfide crystal grain is about 4nm.
As shown in Figure 1, the visible light catalytic composite of prepared three-dimensional porous hierarchy has kept the three-dimensional porous hierarchy of original egg film.Appropriate product is placed in 100mg/L rhodamine B solution, and take a sample every 10min under radiation of visible light, in its absorbance of 554nm place's measurement, its absorbance size is directly proportional to dye strength, thereby can reflect dyestuff degraded situation, the i.e. catalytic action of catalyst.The variation of absorbance can be tried to achieve its degradation rate (η) per sample, obtains catalytic effect curve as shown in Figure 2.As can be seen from Figure 2, after after a while, the visible light catalyst of prepared three-dimensional porous hierarchy has obvious degradation to organic dyestuff.
The shell of commercially available egg is cleaned, separated the egg film.With the cleaning, drying of egg film, save backup.With the egg film immersion in the solution that is mixed according to the ratio of 12:3:1 by tetra-n-butyl titanate, absolute ethyl alcohol, concentrated hydrochloric acid.Flood after 10 hours and take out, first clean with absolute alcohol, then use washed with de-ionized water, after natural drying, it is put in carries out calcination processing in oxidation furnace, cool to room temperature with the programming rate of 36 ° of C/min with the furnace after room temperature rises to 800 ° of C insulation 90min, obtain the titanium dioxide matrix.CdCl to 0.03mol/L
2In dropwise add concentrated ammonia liquor until solution becomes clarification from white opacity occurring again to solution, obtain cadmium salt dipping precursor liquid.After being put into this cadmium salt dipping precursor liquid dipping 4.5h, takes out matrix material, with the Na that puts into 0.03mol/L after washed with de-ionized water
2Take out after soaking 0.5h in S solution, then clean with deionized water, natural drying.Through above-mentioned steps, obtain take the titanium dioxide of three-dimensional porous structure as matrix and deposit the visible light catalyst of the multicomponent porous hierarchical structure of cadmium sulfide nano layer.Wherein the titania size is about 7nm, and the size of cadmium sulfide crystal grain is about 4.5nm.And prepared multicomponent porous hierarchical structure visible light catalyst also has obvious degradation to organic dye.
The shell of commercially available egg is cleaned, separated the egg film.With the cleaning, drying of egg film, save backup.With the egg film immersion in the solution that is mixed according to the ratio of 12:3:1 by tetra-n-butyl titanate, absolute ethyl alcohol, concentrated hydrochloric acid.Flood after 10 hours and take out, first clean with absolute alcohol, then use washed with de-ionized water, after natural drying, it is put in carries out calcination processing in oxidation furnace, cool to room temperature with the programming rate of 18 ° of C/min with the furnace after room temperature rises to 500 ° of C insulation 90min, obtain the titanium dioxide matrix.CdCl to 0.03mol/L
2In dropwise add concentrated ammonia liquor until solution becomes clarification from white opacity occurring again to solution, obtain cadmium salt dipping precursor liquid.After being put into this cadmium salt dipping precursor liquid dipping 4.5h, takes out matrix material, with the Na that puts into 0.03mol/L after washed with de-ionized water
2Take out after soaking 0.5h in S solution, then clean with deionized water, natural drying.Through above-mentioned steps, obtain take the titanium dioxide of three-dimensional porous structure as matrix and deposit the visible light catalyst of the multicomponent porous hierarchical structure of cadmium sulfide nano layer.Wherein the titania size is about 5nm, and the size of cadmium sulfide crystal grain is about 4.5nm.
More than describe preferred embodiment of the present invention in detail.The ordinary skill that should be appreciated that this area need not creative work and just can design according to the present invention make many modifications and variations.Therefore, all technical staff in the art all should be in the determined protection domain by claims under this invention's idea on the basis of existing technology by the available technical scheme of logical analysis, reasoning, or a limited experiment.
Claims (10)
1. the preparation method of a multicomponent porous hierarchical structure visible light catalyst, is characterized in that, comprises the following steps:
1) take three-dimensional porous hierarchy as template, and template is carried out pretreatment;
2) pretreated template is put into the slaine precursor liquid and carry out impregnation process;
3) take out impregnation product and successively through cleaning, drying, calcination processing makes the metal oxide materials with three-dimensional porous hierarchy, with this as matrix material;
4) described matrix material is soaked deposition processes, deposition composite semiconductor nano material on the metal oxide matrix; Through cleaning, drying makes the visible light catalyst of multicomponent porous hierarchical structure;
Wherein, described template is the biomaterial with porous hierarchical structure.
2. the method for claim 1, wherein described template is the egg film.
3. the method for claim 1, wherein step 2) described slaine precursor liquid refers to the inorganic matter salting liquid of slaine.
4. method as claimed in claim 3, wherein, step 2) described slaine precursor liquid refers to titanium chloride solution.
5. the method for claim 1, wherein step 2) described dipping refers to: pretreated template is statically placed in described slaine precursor liquid takes out after 1-10h.
6. the method for claim 1, wherein the described sintering of step 3) refers to: dried sample is placed in oxidation furnace, rises to 500-800 ° of C with the heating rate of 10-36 ° of C/min from room temperature, cool to room temperature with the furnace after insulation 90min.
7. the method for claim 1, wherein the described deposition of step 4) refers to: first the metal oxide substrate be impregnated in the presoma slaine dipping solution of semi-conducting material;
Described presoma slaine dipping solution is chloride salt or the sulfate of cadmium or tin.
8. the method for claim 1, wherein the described cleaning of step 4) refers to, each step impregnation is before with washed with de-ionized water some times of previous step product.
9. the method for claim 1, wherein the described drying of step 4) refers to: normal temperature ventilates, lucifuge is natural drying.
10. the multicomponent porous hierarchical structure visible light catalyst for preparing according to the described method of above-mentioned arbitrary claim.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| CN105800679A (en) * | 2016-03-08 | 2016-07-27 | 南京大学 | Method for preparing TiO2 spherical three-level hierarchical structure |
| CN106282982A (en) * | 2016-08-26 | 2017-01-04 | 上海交通大学 | A kind of method preparing three-dimensional order micro-nano hierarchy noble metal composite-material |
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| CN101007269A (en) * | 2007-01-25 | 2007-08-01 | 上海交通大学 | Preparation method of crystal phase controllable three dimensional hierarchical structure photocatalytic material |
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| CN101007269A (en) * | 2007-01-25 | 2007-08-01 | 上海交通大学 | Preparation method of crystal phase controllable three dimensional hierarchical structure photocatalytic material |
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| QUN DONG, ET AL: "Synthesis and characterizations of hierarchical biomorphic titania oxide by a bio-inspired bottom-up assembly solution technique", 《JOURNAL OF SOLID STATE CHEMISTRY》 * |
| QUN DONG, ET AL: "Synthesis of hierarchical mesoporous titania with interwoven networks by eggshell membrane directed sol–gel technique", 《MICROPOROUS AND MESOPOROUS MATERIALS》 * |
| 张传照: "CdS/TiO2的制备及其光催化转化CO2-H2O的性能研究", 《上海交通大学硕士学位论文》 * |
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Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105800679A (en) * | 2016-03-08 | 2016-07-27 | 南京大学 | Method for preparing TiO2 spherical three-level hierarchical structure |
| CN106282982A (en) * | 2016-08-26 | 2017-01-04 | 上海交通大学 | A kind of method preparing three-dimensional order micro-nano hierarchy noble metal composite-material |
| CN106282982B (en) * | 2016-08-26 | 2018-11-20 | 上海交通大学 | A method of preparing three-dimensional order micro-nano hierarchical structure noble metal composite-material |
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