CN100588458C - The zinc oxide/titanium dioxide compound photocatalyst having core/case structure and the preparation and the application thereof - Google Patents
The zinc oxide/titanium dioxide compound photocatalyst having core/case structure and the preparation and the application thereof Download PDFInfo
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- CN100588458C CN100588458C CN200710039531A CN200710039531A CN100588458C CN 100588458 C CN100588458 C CN 100588458C CN 200710039531 A CN200710039531 A CN 200710039531A CN 200710039531 A CN200710039531 A CN 200710039531A CN 100588458 C CN100588458 C CN 100588458C
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Abstract
The invention relates to a zinc oxide/titanium dioxide composite photocatalyst with core-shell structure, the preparing method and the application, characterized in that the core layer of core-shell structure is four-legged or multi-legged zinc oxide; the shell layer is the titanium dioxide layer covered in the four-legged or multi-legged zinc oxide and the distance of adjacent leg ends in singlecomposite photocatalyst particle with core-shell structure is more than 10 microns. The four-legged or multi-legged zinc oxide is used as carrier and by gas hydrolysis method nanometer particle of titanium dioxide is fixed on the surface of zinc oxide. The thickness of titanium oxide is from 5 nanometers to several hundred nanometers and it can be adjusted by the dosage of titanium material. The provided composite catalyst has staging structure and holds the characteristic of high catalytic activity of nano-grain. After it is used in liquid phase medium it can be recovered rapidly by low energy consumption method such as normal pressure filtration and so on. The prepared zinc oxide/titanium dioxide photocatalyst with core-shell structure has a comparative photo-catalytic activity with titanium oxide nano-grain prepared by gas phase method.
Description
Technical field
The present invention relates to Zinc oxide/titanium dioxide photochemical catalyst, preparation method and the application of core/shell structure, belong to field of fine chemical.
Background technology
Zinc oxide and titanium dioxide all are the photochemical catalysts of using always, and the conduction band of zinc oxide is more negative than the conduction band of titanium dioxide, so zinc oxide often shows higher photocatalytic activity in photoreduction.In recent years, the zinc oxide for preparing four-footed shape or polypody shape with the method for thermal evaporation oxidation has been obtained bigger progress, the Zinc oxide single crystal of this complicated shape be easy to preparation (Wu Huawu etc., ZL 94107349.1; Zhou Zuowan etc., ZL 98111828.3; ZL such as Chen Erfan 99112867.2).Large-sized zinc oxide is to reclaim fast by the method for low energy consumption such as normal pressure filtration as the great advantage that photochemical catalyst had.These large-sized zinc oxide have higher photocatalytic activity (Q.Wan, T.H.Wang, J.C.Zhao in the reaction of dyestuff photocatalytic degradation, Appl.Phys.Lett., 2005, vol.87,083105) photocatalytic activity is not high, but in some photooxidation reactions.So polypody shape or four-footed shape zinc oxide use as photochemical catalyst still a lot of limitation.The TiOx nano crystalline substance has very high photocatalytic activity, can be carbon dioxide, water and inorganic molecules or ion with multiple organic pollution direct sunshine catalytic degradation, in liquid phase medium the TiOx nano crystalline substance being reclaimed is the process of a high energy consumption, and these intrinsic difficulties have hindered the application of photochemical catalyst in actual sewage is handled.Titanium oxide is fixed on material surfaces such as glass, metal, can solves it and reclaim difficult problem, but the solid-liquid that titanium oxide provided that is fixed or solid-the gas contact area is very little, is not suitable for handling the higher system of pollutant levels.Recently, bar-shaped zinc-oxide film and the bar-shaped zinc-oxide film modified with golden cluster are used to simulate sewage disposal (J.-J.Wu, C.-H.Tseng as immobilized photochemical catalyst, Appl.Catal.B, 2006, vol.66,51-57), and steam promotes the titanium hydrolysis of alkoxide can prepare the existing report of titanium dioxide optical catalyst (Z.L.Wang, L.Q.Mao, the J.Liu of high-specific surface area, J.Photochem.Photobio.A, 2006, vol.177,261-268).The photochemical catalyst of zinc oxide and titanium dioxide coupled mode also has report (G.Marc ì, V.Augugliaro, M.J.
C.Mart í n, L.Palmisano, V.Rives, M.Schiavello, R.J.D.Tilley, A.M.Venezia, J.Phys.Chem.B, 2001,105,1026-1932 and 1033-1040), this is a kind of composite photo-catalyst nano particle of similar hetero-junctions.The present invention proposes a kind of preparation method of photochemical catalyst of the Zinc oxide/titanium dioxide for preparing core/shell structure, the zinc oxide that utilizes is large-sized four-footed shape ZnOw, promote the titanium hydrolysis of alkoxide by steam, form one deck anatase phase oxidation titanium layer on the surface of zinc oxide.This composite photo-catalyst has nucleocapsid structure, examines to be zinc oxide, and shell is a titanium oxide, is easy to reclaim by methods such as normal pressure filtrations after using in liquid phase medium.
Summary of the invention
The object of the present invention is to provide a kind of Zinc oxide/titanium dioxide composite photo-catalyst, preparation and application of core/shell structure, this composite photo-catalyst has hierarchy, in the light-catalyzed reaction of majority, have the similar highlight catalytic active of titanium dioxide for preparing with vapor phase method, can reclaim fast by the method for low energy consumption such as normal pressure filtration after in liquid phase medium, using.
The objective of the invention is to implement like this: at first, make the alcoholic solution of titanium alkoxide, then four-footed or polypody shape zinc oxide are joined in the prepared alcoholic solution with in titanium alkoxide and the lower alcohol.The crucible that will fill the titanium alkoxide solution that adds zinc oxide is again put into sealable container top.Sealable container bottom is placed with low amounts of water in advance, and the crucible that fills the alcoholic solution that contains zinc oxide does not directly contact with water.But after inserting in the baking oven after the closed container sealing, be heated to 100 ℃ to 200 ℃, and be incubated 12 to 48 hours.Insulation after temperature is reduced to room temperature, is opened closed container after finishing, and takes out the crucible on upper strata, pours out powder, through washing with dry, obtains the Zinc oxide/titanium dioxide composite photo-catalyst of core/shell structure again.
Now details are as follows with said process:
With the titanium alkoxide is the titanium source, measures a certain amount of titanium alkoxide and is dissolved in the alcoholic solution of making the titanium alkoxide in the lower alcohol.The titanium alkoxide is meant a kind of in tetraethyl titanate, tetraisopropyl titanate and the butyl titanate or their mixture, and lower alcohol is meant a kind of in methyl alcohol, ethanol, normal propyl alcohol and the isopropyl alcohol or their mixture.Take by weighing a certain amount of four-footed shape or polypody shape zinc oxide is poured in the alcoholic solution of titanium alkoxide,, obtain uniform mixture through ultrasonic and stir.But place the top of closed container then, container is airtight.Before airtight, low amounts of water is arranged at the bottom of container, and water does not directly contact with the alcoholic solution of titanium.Closed container is heated to 100 ℃ to 200 ℃, and makes titanium oxide that good degree of crystallinity be arranged through insulating process.The boiling point of above-mentioned lower alcohol all is lower than 100 ℃, so when temperature is higher than its boiling point, the volatilization rapidly of alcohol in the crucible, the titanium alkoxide is concentrated, and when temperature was elevated near the boiling point of water, more water that evaporates with water had promoted the hydrolysis of titanium alkoxide, zinc oxide surface provides a lot of nucleating points, the titanium alkoxide continues hydrolysis then in the zinc oxide surface nucleation around nucleating point, obtain thicker titanium oxide layer.The thickness of titanium oxide layer is that the amount by the titanium alkoxide that is added is determined, according to the amount difference of titanium alkoxide, can form five titanium oxide layers to hundreds of nanometer thickness.
Now the relevant technological parameter of reaction is done some concrete qualifications:
1, the consumption of water: water does not directly contact with the titanium alkoxide in the bottom of closed container, water start vaporizer during heating, and finally make the whole hydrolysis of titanium alkoxide.In the reaction of reality, the ratio of the quality of the material of water and titanium is between 20 to 3000.
2, oxidation zinc concentration: the concentration of zinc oxide in alcoholic solution is between 1.0mg/ml～30.0mg/ml, and excessive concentration is difficult to guarantee the dispersion of zinc oxide, can cause coated by titanium dioxide inhomogeneous like this.
3, the concentration of titanium alkoxide: the titanium alkoxide can change the thickness of coated by titanium dioxide layer by the concentration that changes the titanium alkoxide in the scope of concentration at 0.0004ml/ml～0.010ml/ml of lower alcohol.
4, the present invention mainly provides a kind of Zinc oxide/titanium dioxide photochemical catalyst, preparation and application of shell/nuclear structure of easy recovery, also can be prepared into the Zinc oxide/titanium dioxide of nucleocapsid structure in this way greater than the zinc oxide of 100nm for crystallite dimension, although also possess very high photocatalytic activity, but, can not it be reclaimed from liquid phase medium with the method that normal pressure filters because the diameter of composite particles still is far smaller than the diameter of filter opening.For carrier is the zinc oxide of crystallite dimension less than 100nm (particularly less than 20nm), and what obtain is the hetero-junctions rather than the core/shell structure of zinc oxide and titanium dioxide.
The chemical equation of this reaction is:
Ti(OC
nH
2n+1)
4(l)+2H
2O(g)→TiO
2(s)+4HOC
nH
2n+1(g)(n＝2，3，4) (1)
L, g and s in the formula bracket represent liquid, gas and solid respectively.
The degree of crystallinity of titanium oxide is main relevant with the heat treated temperature of closed container, and heat treated temperature has good degree of crystallinity in 150 ℃～200 ℃ scopes.The crystallization that changes titanium oxide can be selected a kind of in following three kinds of approach for use: (1) segmentation heating: earlier closed container is heated to 100 ℃, be incubated 12 hours then, make titanium alkoxide complete hydrolysis, and then closed container is warmed up to 150 ℃, be incubated 12 to 36 hours then.(2) one steps heating: closed container directly is heated to 150 ℃ to 200 ℃, is incubated 12 to 48 hours then, make titanium alkoxide complete hydrolysis make the titanium oxide crystallization simultaneously.(3) pass through follow-up calcining after the heat treatment again: earlier closed container is heated to 100 ℃, is incubated 12 hours then, make titanium alkoxide complete hydrolysis.Treat that insulation finishes also to open closed container behind the cool to room temperature, pour out powder, then with distilled water or deionized water washing powder, the filtered and recycled powder, and with its oven dry.Then in air in 450 ℃ to 550 ℃ the calcining 2 hours, titanium oxide wherein is converted into the anatase phase.
For the easy recovery characteristic of this composite photo-catalyst is described, carried out the photocatalytic degradation experiment of phenol.Experiment condition: ambient temperature is about 20 ℃, catalyst concn 0.8g/L, and the initial concentration 1.06mmol/L (100ppm) of phenol, jacket type Photoreactor volume is 400mL, shines from inside to outside with the high-pressure sodium lamp of 300W, feeds O
2, its flow velocity is 100ml/min.Between sampling at regular intervals with the change in concentration of UV-Vis spectrophotometer quantitative assay phenol.After experiment finished, the water that will contain catalyst filtered with quick filter paper, and its turbidity of its filtrate usefulness UV-Vis spectrophotometry may remain in the content of zinc and titanium in the filtrate with inductance linking atom emission spectrum (ICP-AES) mensuration.
The preparation method of the zinc oxide of preparation core/shell structure provided by the present invention/titanium oxide composite photo-catalyst, the feature that possesses is:
1, the stratum nucleare in the core/shell structure is the zinc oxide of four-footed or polypody shape, shell is for evenly being coated on the titanium dioxide layer on the zinc oxide stratum nucleare surface of four-footed or polypody shape, and the distance of adjacent foot end is greater than 10 microns in the composite photo-catalyst particle of single core/shell structure.
2, the thickness of shell arrives hundreds of nanometers for the titania individual layer.
3, form uniform anatase phase oxidation titanium layer on the surface of the zinc oxide of four-footed shape or polypody shape, wherein between the 20nm, temperature of being heated with closed container and follow-up heat treatment temperature are relevant at 5nm for the crystallite dimension of titanium oxide.
4, prepared composite photo-catalyst has the composite photo-catalyst of the core/shell structure of hierarchy, possesses the brilliant highlight catalytic active of TiOx nano of vapor phase method preparation, and the mode of low energy consumption such as available again normal pressure filtration reclaims fast after using in liquid phase medium.(seeing embodiment 4 and accompanying drawing 5 for details)
Description of drawings
Fig. 1 is the transmission electron microscope photo of the zinc oxide/titanium oxide composite photo-catalyst of embodiment 1 preparation core/shell structure, and titanium oxide evenly is wrapped in the surface of zinc oxide.A is the zinc oxide of the four-footed shape before the titanium oxide parcel, and b is the zinc oxide/titanium oxide of the core/shell structure behind the titanium oxide parcel, and the photo that inserts among the b has provided the higher transmission electron microscope photo of multiplication factor.
Fig. 2 is the high-resolution-ration transmission electric-lens photo and the electronic energy spectrum of zinc oxide/titanium oxide composite photo-catalyst of the preparation core/shell structure of embodiment 1 preparation.Can see the lattice fringe of anatase phase oxidation titanium among the figure, show that titanium oxide has good degree of crystallinity, the grain size of titanium oxide is about 6nm.A is the high resolution electron microscopy of the zinc oxide/titanium oxide of core/shell structure, and b is the power spectrum of respective regions, and showing wherein has titanium elements, zinc element and oxygen element, and copper wherein is from doing the copper mesh that Electronic Speculum is used.Abscissa is Energy (energy) among Fig. 2 (b), and unit is a kilo electron volt, and ordinate Intensity is a relative intensity.
Fig. 3 is the transmission electron microscope photo of the zinc oxide/titanium oxide composite photo-catalyst of embodiment 2 preparation core/shell structures, and titanium oxide evenly is wrapped in the outer surface of zinc oxide, and thickness is about 40nm.
Fig. 4 is the transmission electron microscope photo of the zinc oxide/titanium oxide composite photo-catalyst of embodiment 3 preparation core/shell structures, and mono-layer oxidized titanium evenly is wrapped in the outer surface of zinc oxide.
Fig. 5 be photochemical catalyst among the embodiment 4 through after the quick filter paper filtered and recycled, the absorption spectrum of its filtrate, wavelength 300 in the scope of 800nm nanometer with the transmitance of distilled water similar 100%, the dotted line among the figure be transmitance 100% with reference to reference line.
The specific embodiment
Embodiment 1:
The 0.2ml butyl titanate is joined in the 50ml absolute ethyl alcohol, stirred 2 minutes, take by weighing the four-footed shape zinc oxide of 1.0 gram thermal evaporation oxidizing process preparations, ultrasonic and stirred each 2 minutes.The solution that will contain zinc oxide is poured in the crucible, places the top of sealable container then.Sealable container bottom is placed with 20ml distilled water in advance.With container airtight after, put into baking oven, begin to be heated to 150 ℃, heating rate is 10～20 ℃/minute, temperature reached after the temperature of setting insulation 12 hours.Insulation naturally cools to room temperature after finishing, and opens closed container, takes out crucible, pours out powder, respectively washs 3 times with distilled water and absolute alcohol, through 110 ℃ of oven dry 24 hours.Fig. 1 has provided the transmission electron microscope photo of low multiple, and Fig. 2 has provided its high resolution electron microscopy photo, can know the lattice fringe of seeing anatase phase oxidation titanium.
Embodiment 2:
The 0.16ml butyl titanate is joined in the 50ml absolute ethyl alcohol, stirred 2 minutes, take by weighing the four-footed shape zinc oxide of 1.0 gram thermal evaporation oxidizing process preparations, ultrasonic and stirred each 2 minutes.The solution that will contain zinc oxide is poured in the crucible, places the top of sealable container then.Sealable container bottom is placed with 20ml distilled water in advance.With container airtight after, put into baking oven, begin to be heated to 100 ℃, heating rate is 10～20 ℃/minute, temperature reached after the temperature of setting insulation 24 hours.Insulation naturally cools to room temperature after finishing, and opens closed container, takes out crucible, pours out powder, respectively washs 3 times with distilled water and absolute alcohol, through 110 ℃ of oven dry 24 hours.With powder in air 450 ℃ the calcining 2 hours, obtain the composite photo-catalyst that titanium oxide evenly wraps up zinc oxide, Fig. 3 has provided the transmission electron microscope photo of low power, the thickness of titanium oxide layer is about 40nm.
Embodiment 3:
The 0.02ml butyl titanate is joined in the 50ml absolute ethyl alcohol, stirred 2 minutes, take by weighing 1.0 gram thermal evaporation oxidations and obtained four-footed shape zinc oxide, ultrasonic and stirred each 2 minutes.The solution that will contain zinc oxide is poured in the crucible, places the top of sealable container then.Sealable container bottom is placed with 20ml distilled water in advance.With container airtight after, put into baking oven, be warmed up to 100 ℃, heating rate is 10～20 ℃/minute, temperature reached after the temperature of setting insulation 12 hours.Insulation naturally cools to room temperature after finishing, and opens closed container, takes out crucible, pours out powder, respectively washs 3 times with distilled water and absolute alcohol, through 110 ℃ of oven dry 24 hours.Fig. 4 has provided the transmission electron microscope photo of low multiple of the zinc oxide/titanium oxide composite photo-catalyst of core/shell structure, and there is mono-layer oxidized titanium particle on the surface of zinc oxide.
Embodiment 4:
Experiment condition: ambient temperature is about 20 ℃, in the Zinc oxide/titanium dioxide composite photo-catalyst of used core/shell structure, the thickness of titanium dioxide layer is about 40nm, and (embodiment 2, and through 450 ℃ of calcinings in the air two hours), the content of titanium dioxide in composite photo-catalyst is 6.8wt.%, catalyst concn 0.8g/L, the initial concentration 1.06mmol/L (100ppm) of phenol, jacket type Photoreactor volume is 400mL, shines from inside to outside with the high-pressure sodium lamp of 300W, feeds O
2, its flow velocity is 100ml/min.Between at regular intervals time sampling with the change in concentration of UV-Vis spectrophotometer quantitative assay phenol.After experiment finished, the water that will contain catalyst filtered with quick filter paper, and its turbidity of its filtrate usefulness UV-Vis spectrophotometry may remain in the content of zinc and titanium in the filtrate with inductance linking atom emission spectrum (ICP-AES) mensuration.
UV-Vis absorbs light and shows that filtrate is almost near 100% transmitance, the turbidity that the zinc oxide that may exist in the solution and titanium oxide colloid do not increase water is described, and (size is less than the zinc oxide and the titanium oxide of filter paper filter opening or penetrate filter paper, is collected in the filtrate with water.If the concentration of zinc oxide and titanium oxide absorbs ultraviolet light and part scatter visible light than conference in the filtrate, can cause the transmitance of filtrate obviously to descend).The result of ICP-AES show the concentration of titanium be lower than detection resolution (＜0.02mg/L), zinc concentration is 1.51mg/L, mainly since a spot of smooth anodic attack cause.
Claims (8)
1, the Zinc oxide/titanium dioxide composite photo-catalyst of core/shell structure, it is characterized in that the stratum nucleare in the core/shell structure is the zinc oxide of four-footed shape, shell is for evenly being coated on the titanium dioxide layer on four-footed shape zinc oxide stratum nucleare surface, and the distance of adjacent foot end is greater than 10 microns in the composite photo-catalyst particle of single core/shell structure; The crystallite dimension of described stratum nucleare zinc oxide is greater than 100nm.
2, by the Zinc oxide/titanium dioxide composite photo-catalyst of the described core/shell structure of claim 1, the thickness that it is characterized in that described titanium dioxide shell is titania individual layer 5nm-20nm.
3, by the Zinc oxide/titanium dioxide composite photo-catalyst of claim 1 or 2 described core/shell structures, it is characterized in that described shell titanium dioxide is the anatase phase.
4, the method for the Zinc oxide/titanium dioxide composite photo-catalyst of preparation core/shell structure as claimed in claim 1 is characterized in that preparation process is:
(1) be the titanium source with the titanium alkoxide, be dissolved in methyl alcohol, ethanol, normal propyl alcohol and the isopropyl alcohol in a kind of or their mixture, make the alcoholic solution of titanium alkoxide, described titanium alkoxide is a kind of in tetraethyl titanate, tetraisopropyl titanate and the butyl titanate or their mixture; The concentration of titanium alkoxide is 0.0004ml/ml～0.010ml/ml:
(2) crystallite dimension is poured the titanium alkoxide solution of step (1) preparation into greater than the four-footed shape zinc oxide of 100nm, through ultrasonic and stirring, obtains even mixture; The concentration of zinc oxide in alcoholic solution is 1.0mg/ml～30.0mg/ml;
(3) alcoholic solution that contains zinc oxide that step (2) is made is contained in the crucible, and put into sealable container top, the bottom of container is placed with water in advance, and crucible directly do not contact with water, and closed container is inserted in the baking oven, be heated to 100-200 ℃ of heat treatment, insulation is reduced to room temperature after finishing, and opens container, takes out crucible, pour out powder, through washing and dry; The mass ratio of water of putting in advance and titanium alkoxide is 20-3000.
5, press the preparation method of the Zinc oxide/titanium dioxide composite photo-catalyst of the described core/shell structure of claim 4, it is characterized in that the heat treated temperature retention time of step (3) is 12-48 hour.
6,, it is characterized in that describedly being heated to 100 ℃ of-200 ℃ of heat treatments and selecting a kind of in following two kinds of methods by the preparation method of the Zinc oxide/titanium dioxide composite photo-catalyst of the described core/shell structure of claim 4;
Method 1: the segmentation heating, earlier closed container is heated to 100 ℃ of-200 ℃ of heat treatments, be incubated 12 hours, make titanium alkoxide complete hydrolysis, and then closed container is warmed up to 150 ℃, be incubated 12-36 hour;
Method 2: one steps heating directly is heated to 150 ℃ to 200 ℃ with closed container, is incubated 12-48 hour then, makes titanium alkoxide complete hydrolysis crystallization simultaneously.
7, press the application of the Zinc oxide/titanium dioxide composite photo-catalyst of the described core/shell structure of claim 1, it is characterized in that described composite photo-catalyst has hierarchy, is applied in the light-catalyzed reaction; Have the similar high catalytic activity of titanium dioxide for preparing with vapor phase method, can reclaim by the normal pressure filter method after in liquid phase medium, using.
8, press the application of the Zinc oxide/titanium dioxide composite photo-catalyst of the described core/shell structure of claim 7, it is characterized in that filtrate absorption spectrum transmitance in the scope of 300-800nm is 100%.
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| CN102029140B (en) * | 2009-09-28 | 2012-07-18 | 中国石油化工股份有限公司 | Desulfurizing agent with nuclear/shell structure and preparation method |
| JP5459624B2 (en) * | 2010-12-16 | 2014-04-02 | 株式会社豊田中央研究所 | CO oxidation catalyst and exhaust gas purification method using the same |
| CN102350353A (en) * | 2011-08-25 | 2012-02-15 | 东华大学 | Preparation method of Fe3O4/C/TiO2 composite photocatalyst |
| CN102784632B (en) * | 2012-07-30 | 2015-10-28 | 东华大学 | The preparation method of the diatomite/titanium dioxide composite photocatalyst of core/shell structure |
| CN103359774B (en) * | 2013-07-28 | 2014-10-29 | 桂林理工大学 | Preparation method of castor-oil-coated zinc oxide nano particle |
| CN107376975A (en) * | 2017-08-17 | 2017-11-24 | 中国科学院生态环境研究中心 | Visible light catalysis activity N doping nucleocapsid shape titanium dioxide and preparation method thereof |
| CN109107562B (en) * | 2018-09-19 | 2021-12-10 | 安庆师范大学 | Preparation method of zinc oxide/titanium dioxide composite microspheres |
| CN112094622B (en) * | 2020-09-27 | 2022-03-11 | 山东大学 | Titanium dioxide coated ferroferric oxide hollow microsphere composite material and preparation method and application thereof |
| CN113929306B (en) * | 2021-10-29 | 2023-07-07 | 佛山欧神诺陶瓷有限公司 | Photocatalyst antibacterial ceramic glaze, preparation method thereof and light ceramic tile |
| CN114231254B (en) * | 2021-12-14 | 2023-12-22 | 佛山欧神诺陶瓷有限公司 | Composite ceramic material with phase-change temperature regulation and preparation method and application thereof |
| CN115700145A (en) * | 2022-11-21 | 2023-02-07 | 中国人民解放军海军特色医学中心 | Photocatalyst material and preparation method and application thereof |
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