CN105214690A - A kind of tree peony flower-shaped heterojunction structure micron ball photochemical catalyst and Synthesis and applications thereof - Google Patents
A kind of tree peony flower-shaped heterojunction structure micron ball photochemical catalyst and Synthesis and applications thereof Download PDFInfo
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Abstract
The invention provides a kind of tree peony flower-shaped heterojunction structure micron ball photochemical catalyst, because different in width from inside to outside can be with coupling, make catalyst have multiwave absorption to sunshine, thus drastically increase its disposal efficiency to the dyestuff in contaminant water.This catalyst adopts hydro-thermal method and base exchange method to prepare: the flower-shaped Zn-In-S micron ball of tree peony first having utilized hydrothermal synthesis method to prepare to have different specific area; Then utilizing base exchange method the Zn-In-S of surf zone is transformed into Ag-In-S and keeps its pattern constant, regulating the heterogeneous photochemical catalyst that can obtain different extinction wave band by controlling reaction.Compared to traditional TiO
2or single ternary photochemical catalyst, has the good efficiency of light energy utilization, specific area is greater than 100m
2/ g, has very high photodegradation rate when use amount is very little; The inventive method is easy, and generated time is short, and degradation efficiency is high, has obvious superiority and practical value.
Description
Technical field
The invention belongs to micro-nano synthetic material field, be specifically related to a kind of tree peony flower-shaped heterojunction structure micron ball photochemical catalyst and Synthesis and applications thereof.
Background technology
Environment and the energy are 21 century mankind area and significant problem urgently to be resolved hurrily.Dyestuff has application in a lot of fields of mankind's daily life, the industries such as such as clothes, building, food and drink.But, because a lot of dyestuff is all non-natural, chemical industry synthesis, be therefore difficult to by natural degradation.Statistics shows, the dyestuff accounting for Gross World Product 15% is lost in dyeing course, and this has become a global difficult problem.Although a lot of technology can process contaminated water, mostly there is the shortcomings such as cost is high, efficiency is low, byproduct is many.
In recent years, because photocatalysis can make full use of solar energy, make it to become a kind of important practical water-purifying technique.In many photochemical catalysts, titanium dioxide (TiO
2) obtain quote widely owing to having the features such as photolytic activity, safety non-toxic, high chemical stability, cost be low.But due to TiO
2band gap wider, the sunshine of ultraviolet band can only be absorbed, therefore strongly limit its practical application.Although some synthetic method can overcome, such as by surperficial continuous adsorption by quantum point coupling to TiO
2surface, but the shortcoming such as these methods exist complicated process of preparation, and equipment cost is high, and time loss is long, become the bottleneck of suitability for industrialized production.On the other hand, ternary semiconductor, owing to having gap tunable, very high resistance to defective and high stability, obtains the extensive concern of people.But the band gap of the ternary semiconductor of single structure is relatively fixing, can not utilize sunshine fully, the preparation therefore with the photochemical catalyst that multiband absorbs is extremely urgent.
Summary of the invention
In order to realize the broad absorption to sunshine, realizing efficient photocatalytically degradating organic dye, the object of this invention is to provide a kind of tree peony flower-shaped heterojunction structure micron ball photochemical catalyst.A kind of tree peony flower-shaped heterojunction structure micron ball photochemical catalyst, it is followed successively by Zn-In-S core, the Zn-Ag-In-S intermediate layer of 20-200nm and the Ag-In-S skin of 10-50nm from inside to outside; First by the Zn-In-S core micron ball that hydrothermal growth process synthesis tree peony is flower-shaped, make the similar petal layer structure of its surperficial stacking formation of nanometer sheet self assembly for thickness about 50nm, inside is solid; Then utilize partial cation exchange process, the Zn-In-S of Zn-In-S core micron ball surf zone is transformed into Ag-In-S, have a transition zone to be Zn-Ag-In-S intermediate layer in this two-layer centre.
Preferably, the flower-shaped micron ball of the tree peony of described heterojunction structure also comprise the control of contrast table area and optical absorption band gap to microballoon; Described 0.5-10 μm is of a size of to microballoon, pattern is petal stratiform, specific area is 100-150m
2/ g.
Another object of the present invention is to provide a kind of preparation method and application thereof of heterojunction structure micron ball photochemical catalyst.
In order to realize object of the present invention, the invention provides a kind of preparation scheme with the high efficiency photocatalyst of high specific surface area:
(1) preparation of Zn-In-S micron ball:
By hydrothermal growth process, the amount mol ratio in control reactant zinc salt, indium salt, sulphur source is 1:2 (± 1.2): 6 (± 2); Control the pH value of reactant liquor, reaction time and reaction temperature, obtain the Zn-In-S micron ball that the tree peony of different size is flower-shaped; The alternately washing of product ethanol and deionized water, centrifugal, be then kept in ethanol or deionized water; The micron ball of different component and pattern is synthesized by the amount and reaction temperature changing reactant;
(2) preparation of the heterogeneous microballoon of Zn-In-S/Ag-In-S:
Zn-In-S micron ball reflection step (1) obtained, in the mixed liquor of first alcohol and water, by part cation exchange, controls to add AgNO
3amount and the control in solution acid alkalinity pH value, reaction temperature, reaction time is obtained to the Ag-In-S layer of different-thickness; The alternately washing of product ethanol and deionized water, centrifugal, be then kept in ethanol or deionized water.
Preferential, zinc salt is selected from one of analogs such as zinc sulfate, zinc nitrate, zinc acetate or zinc chloride; Indium salt is selected from one of analogs such as indium sulfate, indium nitrate, indium acetate or inidum chloride, and sulphur source is selected from one of analogs such as thioacetamide, thiocarbamide or vulcanized sodium or composition; The mol ratio of indium salt and zinc salt is between 0.8-2.5, and the scope of pH value is between 0.5-3, and the amount of substance in sulphur source is 4-8 times of zinc salt amount of substance.
Preferential, the preparation of described Zn-In-S micron ball and the heterogeneous microballoon of Zn-In-S/Ag-In-S is synthesized in the stainless steel autoclave of teflon lined, and reaction temperature is 100-180 DEG C, and the reaction time is 2-8 hour.
Preferential, in base exchange method synthesis, the amount of added silver nitrate is 0.2-5mmol.
Preferential further, the reaction temperature of cation exchange reaction is 120-160 DEG C, and the reaction time is 4-6 hour.
Meanwhile, the invention provides the application of described heterogeneous type micron ball dyestuff in photocatalytic degradation contaminant water.Be specially and the photochemical catalyst of different structure, component is joined in the dye discoloration aqueous solution, then irradiate to realize the light degradation to dyestuff under natural daylight or tungsten halogen lamp.
Good effect of the present invention is as follows:
(1) the simple water heat transfer of employing of the present invention has the flower-shaped micron ball photochemical catalyst of the tree peony of different specific area, makes material have high absorption efficiency to ultraviolet band;
(2) adopt the photochemical catalyst of base exchange method synthesis heterojunction structure first, there is while keeping high specific area the strong absorption to visible light wave range, thus make use of sunshine fully;
(3) this tree peony flower-shaped heterojunction structure micron ball photochemical catalyst effectively can utilize the degraded of light realization to dyestuff in contaminant water.
Accompanying drawing explanation
The scanning electron microscope image of the different-shape of Fig. 1: ZIS/AIS micron ball, correspond to embodiment 1 to embodiment 4, and the pattern of visible product is very homogeneous, and surface is assembled by a large amount of nanometer sheet;
Fig. 2: the x-ray photoelectron energy spectrogram of microballoon before and after ion-exchange, after reaction, the characteristic peak of Zn weakens, and has occurred the characteristic peak of Ag;
Fig. 3: the ultraviolet-visible-near infrared absorption spectrum of micron ball, as shown in the figure, along with the difference of reaction condition, the absorption characteristic of product is obviously different, absorption spectra after reaction is wider, shows there is stronger absorption to visible ray, and this is conducive to making full use of luminous energy to realize high efficiency photocatalysis.
Fig. 4: micron ball surface apertures measurement data, shows that the aperture of product is all belong to mesoporous material between 3-10nm, can fully adsorb and hold a large amount of pollutants.
Over time, as seen from the figure, along with the prolongation of light application time, the fluorescence of dyestuff declines Fig. 5: light degradation fluorescent dyes rhodamine B efficiency gradually, and this illustrates that molecular structure is destroyed, decomposes, and the degradation rate after degraded in 50 minutes reaches 99.5%.
Detailed description of the invention
The present invention is introduced in detail below in conjunction with accompanying drawing and detailed description of the invention thereof.
1, chemicals
Zinc acetate, zinc chloride, zinc nitrate, indium acetate, inidum chloride, indium nitrate, vulcanized sodium, thiocarbamide, thioacetamide, silver nitrate, is analysis pure, is provided by Chemical Reagent Co., Ltd., Sinopharm Group.
2, concrete operations are as follows
(1) preparation of the flower-shaped Zn-In-S micron ball of the tree peony of different specific area
The configuration 20-40mL aqueous solution, wherein the concentration of zinc salt is 0.025 ~ 0.05mol/L, the concentration 0.020-0.125mol/L of indium salt, namely the mol ratio of In and Zn is between 0.8 ~ 2.5, with hydrochloric acid, its pH value is adjusted to 0.5-3, then add 10mL and contain 4 ~ 8mmol sulphur source, sulphur source is selected from thioacetamide, vulcanized sodium or thiocarbamide, or the solution of their combination.Mixed liquor is transferred in the stainless steel autoclave of teflon lined, at 100-180 DEG C of reaction 2-8 hour.Cooling reactant liquor, centrifugal, add excessive ethanol washing, product dispersion is preserved in ethanol.
(2) preparation of the ZIS/AIS microballoon of different band gap
The a certain amount of Zn-In-S micron ball prepared is dispersed in the mixed liquor of 20mL first alcohol and water, preferably, the amount of described ZIS is as the criterion being dispersed in mixed liquor preferably, wherein the volume ratio of first alcohol and water is preferably 1:5, add a certain amount of 0.2-5mmol liquor argenti nitratis ophthalmicus contained under magnetic agitation, stir 10-40 minute.Then mixed liquor is transferred in the stainless steel autoclave of teflon lined, 120-180 DEG C of reaction 3-8 hour.Product processing mode is the same.
Below choose embodiment and do concrete explaination:
embodiment 1
(1) zinc acetate of 1mmol and the indium acetate of 2mmol are dissolved in 40mL water, with hydrochloric acid, its pH are adjusted to 2.5; Then the solution that 10mL contains 4mmol thioacetamide and 2mmol thiocarbamide is added.Mixed liquor was transferred in the stainless steel autoclave of teflon lined, 100 DEG C of reactions 3 hours.Cooling reactant liquor, centrifugal, add excessive ethanol washing, product dispersion is preserved in ethanol.
(2) a certain amount of Zn-In-S micron ball prepared is dispersed in the mixed liquor of 20mL first alcohol and water, preferably, the amount of described ZIS is as the criterion being dispersed in mixed liquor preferably, wherein the volume ratio of first alcohol and water is preferably 1:5, add the liquor argenti nitratis ophthalmicus of a certain amount of 0.2mmol contained under magnetic agitation, stir 10 minutes.Then transfer in the stainless steel autoclave of teflon lined by mixed liquor, 120 DEG C are reacted 3 hours.Product processing mode is the same.
Product S EM figure is Fig. 1 upper left, and within 50 minutes, degradation rate is 99.3%.
embodiment 2
(1) zinc nitrate of 2mmol and the indium nitrate of 2mmol are dissolved in 40mL water, with hydrochloric acid, its pH are adjusted to 1; Then add 10mL and contain 4mmol thioacetamide.Mixed liquor was transferred in the stainless steel autoclave of teflon lined, 100 DEG C of reactions 3 hours.Cooling reactant liquor, centrifugal, add excessive ethanol washing, product dispersion is preserved in ethanol.
(2) a certain amount of Zn-In-S micron ball prepared is dispersed in the mixed liquor of 20mL first alcohol and water, preferably, the amount of described ZIS is as the criterion being dispersed in mixed liquor preferably, wherein the volume ratio of first alcohol and water is preferably 1:5, add the liquor argenti nitratis ophthalmicus of a certain amount of 1mmol contained under magnetic agitation, stir 10 minutes.Then transfer in the stainless steel autoclave of teflon lined by mixed liquor, 150 DEG C are reacted 4 hours.Product processing mode is the same.
Product S EM figure is Fig. 1 upper right, and within 50 minutes, degradation rate is 99.1%.
embodiment 3
(1) zinc chloride of 2mmol and the inidum chloride of 1mmol are dissolved in 40mL water, with hydrochloric acid, its pH are adjusted to 2, then add the solution that 10mL contains 2mmol thioacetamide and 4mmol thiocarbamide.Mixed liquor was transferred in the stainless steel autoclave of teflon lined, 100 DEG C of reactions 4 hours.Cooling reactant liquor, centrifugal, add excessive ethanol washing, product dispersion is preserved in ethanol.
(2) a certain amount of Zn-In-S micron ball prepared is dispersed in the mixed liquor of 20mL first alcohol and water, preferably, the amount of described ZIS is as the criterion being dispersed in mixed liquor preferably, wherein the volume ratio of first alcohol and water is preferably 1:5, add the liquor argenti nitratis ophthalmicus of a certain amount of 5mmol contained under magnetic agitation, stir 10 minutes.Then transfer in the stainless steel autoclave of teflon lined by mixed liquor, 120 DEG C are reacted 5 hours.Product processing mode is the same.
Product S EM figure is Fig. 1 lower-left, and within 50 minutes, degradation rate is 99.9%.
embodiment 4
(1) zinc acetate of 1mmol and the indium acetate of 1mmol are dissolved in 40mL water, with hydrochloric acid, its pH are adjusted to 2, then add the solution that 10mL contains 4mmol thioacetamide and 4mmol thiocarbamide.Mixed liquor was transferred in the stainless steel autoclave of teflon lined, 100 DEG C of reactions 6 hours.Cooling reactant liquor, centrifugal, add excessive ethanol washing, product dispersion is preserved in ethanol.
(2) a certain amount of Zn-In-S micron ball prepared is dispersed in the mixed liquor of 20mL first alcohol and water, preferably, the amount of described ZIS is as the criterion being dispersed in mixed liquor preferably, wherein the volume ratio of first alcohol and water is preferably 1:5, add the liquor argenti nitratis ophthalmicus of a certain amount of 2mmol contained under magnetic agitation, stir 10 minutes.Then transfer in the stainless steel autoclave of teflon lined by mixed liquor, 130 DEG C are reacted 7 hours.Product processing mode is the same.
Product S EM figure is Fig. 1 bottom right, and within 50 minutes, degradation rate is 99.5%.
embodiment 5
(1) zinc nitrate of 1mmol and the indium nitrate of 1mmol are dissolved in 40mL water, with hydrochloric acid, its pH are adjusted to 2, then add the solution that 10mL contains 4mmol thioacetamide and 4mmol thiocarbamide.Mixed liquor was transferred in the stainless steel autoclave of teflon lined, 80 DEG C of reactions 4 hours.Cooling reactant liquor, centrifugal, add excessive ethanol washing, product dispersion is preserved in ethanol.
(2) a certain amount of Zn-In-S micron ball prepared is dispersed in the mixed liquor of 20mL first alcohol and water, preferably, the amount of described ZIS is as the criterion being dispersed in mixed liquor preferably, wherein the volume ratio of first alcohol and water is preferably 1:5, add the liquor argenti nitratis ophthalmicus of a certain amount of 0.2mmol contained under magnetic agitation, stir 10 minutes.Then transfer in the stainless steel autoclave of teflon lined by mixed liquor, 180 DEG C are reacted 8 hours.Product processing mode is the same.
embodiment 6
(1) zinc nitrate of 1mmol and the indium nitrate of 1mmol are dissolved in 40mL water, with hydrochloric acid, its pH are adjusted to 3, then add the solution that 10mL contains 4mmol thioacetamide, 2mmol thiocarbamide and 2mmol vulcanized sodium.Mixed liquor was transferred in the stainless steel autoclave of teflon lined, 80 DEG C of reactions 4 hours.Cooling reactant liquor, centrifugal, add excessive ethanol washing, product dispersion is preserved in ethanol.
(2) a certain amount of Zn-In-S micron ball prepared is dispersed in the mixed liquor of 20mL first alcohol and water, preferably, the amount of described ZIS is as the criterion being dispersed in mixed liquor preferably, wherein the volume ratio of first alcohol and water is preferably 1:5, add the liquor argenti nitratis ophthalmicus of a certain amount of 0.2mmol contained under magnetic agitation, stir 10 minutes.Then transfer in the stainless steel autoclave of teflon lined by mixed liquor, 150 DEG C are reacted 5 hours.Product processing mode is the same.
Above-mentioned 6 embodiments are to show, by controlling reaction condition: the amount of substance proportioning of reaction temperature, time and reactant, can obtain the photochemical catalyst of different surface morphology and optical band gap, thus be applied to different light-catalyzed reactions.
application examples 1
The photochemical catalyst of the embodiment 1 of 20mg is joined in the aqueous solution of 50ppm rhodamine B, stir a period of time, dye molecule is made to reach adsorption equilibrium in photocatalyst surface, control group does not add any photochemical catalyst, then under natural daylight or under 500W tungsten halogen lamp, different time is irradiated, by measuring the absorption spectra of solution.As shown in Figure 5, almost degradable in 20 minutes, degradation rate is 99.5%, and the dyestuff not adding catalyst only has the minimizing of 5%, and this is destroyed to a certain extent due to molecular structure of dye, is commonly called as photobleaching.
All above-mentioned this intellectual properties of primary enforcement, not setting restriction this new product of other forms of enforcement and/or new method.Those skilled in the art will utilize this important information, and foregoing is revised, to realize similar implementation status.But all modifications or transformation belong to the right of reservation based on new product of the present invention.
The above is only preferred embodiment of the present invention, and be not restriction the present invention being made to other form, any those skilled in the art may utilize the technology contents of above-mentioned announcement to be changed or be modified as the Equivalent embodiments of equivalent variations.But everyly do not depart from technical solution of the present invention content, any simple modification, equivalent variations and the remodeling done above embodiment according to technical spirit of the present invention, still belong to the protection domain of technical solution of the present invention.
Claims (8)
1. a tree peony flower-shaped heterojunction structure micron ball photochemical catalyst, is characterized in that, it is followed successively by Zn-In-S core, the Zn-Ag-In-S intermediate layer of 20-200nm and the Ag-In-S skin of 10-50nm from inside to outside; First by the Zn-In-S core micron ball that hydrothermal growth process synthesis tree peony is flower-shaped, make the similar petal layer structure of its surperficial stacking formation of nanometer sheet self assembly for thickness about 50nm, inside is solid; Then utilize partial cation exchange process, the Zn-In-S of Zn-In-S core micron ball surf zone is transformed into Ag-In-S, have a transition zone to be Zn-Ag-In-S intermediate layer in this two-layer centre.
2. tree peony according to claim 1 flower-shaped heterojunction structure micron ball photochemical catalyst, is characterized in that, described heterojunction structure micron ball photochemical catalyst also comprises microballoon; Described 0.5-10 μm is of a size of to microballoon, pattern is petal stratiform, specific area is 100-150m
2/ g.
3. a preparation method for the arbitrary described tree peony flower-shaped heterojunction structure micron ball photochemical catalyst of claim 1 or 2, specifically comprises the following steps:
The preparation of Zn-In-S micron ball:
By hydrothermal growth process, the amount mol ratio in control reactant zinc salt, indium salt, sulphur source is 1:2 (± 1.2): 6 (± 2); Control the pH value of reactant liquor, reaction time and reaction temperature, obtain the Zn-In-S micron ball that the tree peony of different size is flower-shaped; The alternately washing of product ethanol and deionized water, centrifugal, be then kept in ethanol or deionized water;
The preparation of the heterogeneous microballoon of Zn-In-S/Ag-In-S:
Zn-In-S micron ball reflection step (1) obtained, in the mixed liquor of first alcohol and water, by part cation exchange, controls to add AgNO
3amount and the control in solution acid alkalinity pH value, reaction temperature, reaction time is obtained to the Ag-In-S layer of different-thickness; The alternately washing of product ethanol and deionized water, centrifugal, be then kept in ethanol or deionized water.
4. the preparation method of tree peony flower-shaped heterojunction structure micron ball photochemical catalyst as claimed in claim 3, it is characterized in that, zinc salt is selected from one of analogs such as zinc sulfate, zinc nitrate, zinc acetate or zinc chloride; Indium salt is selected from one of analogs such as indium sulfate, indium nitrate, indium acetate or inidum chloride, and sulphur source is selected from one of analogs such as thioacetamide, thiocarbamide or vulcanized sodium or composition; The mol ratio of indium salt and zinc salt is between 0.8-2.5, and the scope of pH value is between 0.5-3, and the amount of substance in sulphur source is 4-8 times of zinc salt amount of substance.
5. the preparation method of tree peony flower-shaped heterojunction structure micron ball photochemical catalyst as claimed in claim 3, it is characterized in that, the preparation of described Zn-In-S micron ball and the heterogeneous microballoon of Zn-In-S/Ag-In-S is synthesized in the stainless steel autoclave of teflon lined, reaction temperature is 100-180 DEG C, and the reaction time is 2-8 hour.
6. the preparation method of tree peony flower-shaped heterojunction structure micron ball photochemical catalyst as claimed in claim 3, is characterized in that, in base exchange method synthesis, the amount of added silver nitrate is 0.2-5mmol.
7. the preparation method of tree peony flower-shaped heterojunction structure micron ball photochemical catalyst as claimed in claim 3, it is characterized in that, the reaction temperature of cation exchange reaction is 120-160 DEG C, and the reaction time is 4-6 hour.
8. the application of tree peony according to claim 1 flower-shaped heterojunction structure micron ball photochemical catalyst dyestuff in photocatalytic degradation contaminant water.
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| CN111790404A (en) * | 2020-07-08 | 2020-10-20 | 齐鲁工业大学 | Defective type sulfur indium zinc microsphere visible light catalyst, preparation method and application |
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