CN104001491A - CeO2/TiO2 nanometer composite hollow sphere catalyst and preparation method thereof - Google Patents

CeO2/TiO2 nanometer composite hollow sphere catalyst and preparation method thereof Download PDF

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CN104001491A
CN104001491A CN201410203860.5A CN201410203860A CN104001491A CN 104001491 A CN104001491 A CN 104001491A CN 201410203860 A CN201410203860 A CN 201410203860A CN 104001491 A CN104001491 A CN 104001491A
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ceo
polystyrene
hollow ball
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CN104001491B (en
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胡静
田婷
邓维钧
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Shanghai Institute of Technology
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Abstract

The invention discloses a CeO2/TiO2 nanometer composite hollow sphere catalyst and a preparation method thereof. The CeO2/TiO2 nanometer composite hollow sphere catalyst is prepared by firstly preparing CeO2/TiO2 coated polystyrene composite microspheres by using polystyrene as a template, and using tetrabutyl titanate and cerium nitrate hexahydrate as wall materials, and through combination of a sol-gel method with a precipitation method, and then performing calcination to obtain the product, wherein the using amount ratio of polystyrene, tetrabutyl titanate and cerium nitrate hexahydrate is 0.1-0.3g:0.2-8*10<-3>mol:1-6*10<-3>mol. The CeO2/TiO2 nanometer composite hollow sphere catalyst prepared in the invention is uniform in size, good in photocatalysis, and good in thermal stability.

Description

A kind of CeO 2/ TiO 2nano combined hollow ball catalyst and preparation method thereof
Technical field
The present invention relates to a kind of inorganic compounding hollow ball catalyst and preparation method thereof, particularly the controlled CeO of a kind of particle diameter 2/ TiO 2nano combined hollow ball catalyst and preparation method thereof.
Background technology
TiO 2to there is good thermal stability, oxidability photochemical catalyst and environmental catalysts strong, cheap and easy to get.There is the TiO of hollow-core construction 2microballoon is owing to having design feature and the TiO that density is low, specific area is large, Surface Permeability is good, light capture rate is high 2the characteristic of self and be widely used in photocatalysis field.But TiO 2the ultraviolet light that can only absorbing wavelength be less than 387nm, low to solar energy utilization ratio, and TiO 2middle photo-generated carrier recombination rate is higher, and quantum efficiency is low, has limited TiO 2the practical application of tiny balloon.By other semiconductors and TiO 2carry out compoundly, can utilize interface coupling effect between the two, photoresponse scope is widened, and can be suppressed the compound of photo-generated carrier, improve photocatalytic activity.Existing about TiO at present 2patent report prepared by composite hollow ball.As the patent that publication number is CN101905153A has been prepared a kind of zinc oxide and titanium oxide composite hollow ball and has been applied to light degradation cationic blue dyestuff taking carbon ball as template; Publication number is that the patent of CN101623644A adopts hydro-thermal method, two step infusion processes and sol-gal process to prepare cadmium sulfide and titanium oxide composite hollow ball and be applied to the hydrogen manufacturing of light degradation water.
Ceria as a kind of important rare earth oxide owing to having compared with high storage oxygen oxygen release and oxygen ion conduction ability and being widely used in fuel cell, pollutant treatment and photocatalysis field compared with strong redox ability.But the good storage oxygen performance of ceria is relevant with its thermal impedance, low-temperature reactivity and structural stability, these influence factors make ceria can not meet the requirement of high temperature application.By CeO 2with TiO 2carry out the compound regulation and control by the interaction between titanium and cerium atom and structure and can improve CeO 2heat endurance, structure and characteristic electron.At present, existing bibliographical information employing sol-gal process, homogeneous coprecipitation method and solvent-thermal method prepare CeO 2with TiO 2nano particle.（Chiara?G,?et?al.?Structural?and?spectroscopic?characterization?of?CeO 2–TiO 2?mixed?oxides[J].?Journal?of?Materials?Chemistry?A,2013,1,10918-10926;?Benjaram?M?R?and?Ataullah?K.?Structural?Characterization?of?CeO 2-TiO 2and?V 2O 5/CeO 2-TiO 2?Catalysts?by?Raman?and?XPS?Techniques[J].?The?Journal?of?Chemical?Physics?B,2003,107,5162-5167;?Chockalingam?K?and?Paramasivan?G.?Solvothermal?Synthesis?of?CeO 2-TiO 2?Nanocomposite?for?VisibleLight?Photocatalytic?Detoxification?of?Cyanide[J].?Sustainable?Chemistry?&?Engineering,2013,1,1555-1563）。
Summary of the invention
One of object of the present invention is to provide a kind of CeO 2/ TiO 2nano combined hollow ball catalyst, has hollow ball-shape structure and common CeO concurrently 2/ TiO 2the feature of composite oxide particle, has high thermal stability, high-specific surface area, good light capture rate and storage oxygen release ability.
Two of object of the present invention is to provide above-mentioned a kind of CeO 2/ TiO 2the preparation method of nano combined hollow ball catalyst.
Know-why of the present invention
Hollow Nano particle is as a kind of special nanostructured, is the research field becoming more and more important in chemistry and material science forward position in recent years, and its obvious characteristic is to have larger internal void.Hollow micro nano structure have many peculiar properties as the specific area compared with large, stability is high, density is low, high index of refraction, good surface chemical property and permeability and be widely used in the aspects such as micro chemical reactor, sensor and catalysis material.
The CeO preparing taking polystyrene spheres as template 2/ TiO 2nano combined hollow ball size homogeneous, good dispersion and pattern are controlled.CeO 2/ TiO 2nano combined hollow ball not only has high thermal stability, and its higher specific area is conducive to improve the performance of storing of cerium oxide.
Technical scheme of the present invention
A kind of CeO 2/ TiO 2nano combined hollow ball catalyst, first taking polystyrene as template, taking butyl titanate and six nitric hydrate ceriums as raw material, by sol-gel process and the precipitation method preparation CeO that combines 2/ TiO 2the complex microsphere of coated polystyrene, then calcining obtains CeO 2/ TiO 2nano combined hollow ball catalyst;
The wherein consumption of polystyrene, butyl titanate and six nitric hydrate ceriums, by polystyrene: butyl titanate: six nitric hydrate ceriums are 0.1-0.3g:0.2-8 × 10 -3mol:1-6 × 10 -3mol.
Above-mentioned CeO 2/ TiO 2the preparation method of nano combined hollow ball catalyst, specifically comprises the steps:
(1), 0.1-0.3g polystyrene, 0.5-2g deionized water, 10-50 μ L concentrated ammonia liquor and 20mL absolute ethyl alcohol are mixed after, controlling temperature is that 60-75 DEG C, rotating speed 300-500r/min react after 2-4h, obtains reactant liquor 1;
Described polystyrene spheres particle diameter is about 200-500nm;
(2), by 0.2-8 × 10 -3mol butyl titanate is dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.01-0.40mol/L tetra-n-butyl titanate ethanolic solution;
Be that 0.01-0.40mol/L tetra-n-butyl titanate ethanolic solution adds in step (1) gained reactant liquor 1 in 0.5-1h by concentration, controlling temperature is that 60-75 DEG C, rotating speed are that 300-500r/min reacts 2-4h, obtains reactant liquor 2;
(3), by 1-6 × 10 -3mol six nitric hydrate ceriums are dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.05-0.3mol/L cerous nitrate ethanolic solution;
Be that 0.05-0.3mol/L cerous nitrate ethanolic solution adds in step (2) gained reactant liquor 2 in 0.5-1h by concentration, controlling temperature is that 60-75 DEG C, rotating speed are that 300-500r/min reacts 2-4h, obtains reactant liquor 3;
By 3 centrifugations of the reactant liquor of gained, gained sediment dry 8-10 h at 60-80 DEG C obtains faint yellow powder;
Faint yellow powder, at 500-800 DEG C of calcining 3-5h, is naturally cooled to room temperature and obtains CeO 2/ TiO 2nano combined hollow ball catalyst.
The CeO of above-mentioned gained 2/ TiO 2nano combined hollow ball catalyst, its grain size evenly, good dispersion, particle diameter be 216nm-580nm, has good photocatalytic degradation ability, particularly photocatalytic degradation rhodamine B.
Beneficial effect of the present invention
A kind of CeO of the present invention 2/ TiO 2nano combined hollow ball catalyst, has hollow ball-shape structure and common CeO concurrently 2/ TiO 2the feature of composite oxide particle, therefore has high thermal stability, high-specific surface area, good light capture rate and storage oxygen release ability, has potential application prospect in catalysis, fuel cell and sorbing material field.
Further, a kind of CeO of the present invention 2/ TiO 2the preparation method of nano combined hollow ball catalyst, is template because its preparation process adopts polystyrene, titanium salt and cerium salt is dissolved with organic solvent, utilizes Electrostatic Absorption to make nano-titanium oxide and cerium oxide deposition, and calcining is removed template and obtained CeO 2/ TiO 2nano combined hollow ball, therefore to have preparation process simple for preparation method of the present invention, reaction condition gentleness, and can effectively control CeO 2/ TiO 2the features such as the microscopic appearance of nano combined hollow ball, and final gained CeO 2/ TiO 2the size uniform of nano combined hollow ball catalyst, good dispersion.
Brief description of the drawings
The CeO of Fig. 1, embodiment 5 gained 2/ TiO 2the TEM figure of nano combined hollow ball catalyst;
The CeO of Fig. 2, embodiment 5 gained 2/ TiO 2the SEM figure of nano combined hollow ball catalyst;
The CeO of Fig. 3, embodiment 5 gained 2/ TiO 2the light degradation situation of nano combined hollow ball catalyst to rhodamine B.
Detailed description of the invention
Also by reference to the accompanying drawings the present invention is described in further detail below by embodiment , but do not limit the present invention.
In various embodiments of the present invention, reagent used if no special instructions, is commercially available.
Polystyrene spheres, concentration is 2.5% w/v, Aladdin reagent Co., Ltd; Butyl titanate, six nitric hydrate ceriums, absolute ethyl alcohol, concentrated ammonia liquor is analyzes pure level, from traditional Chinese medicines chemical reagent Co., Ltd;
The CeO of prior art 2-TiO 2composite oxides are according to document (Chiara G, et al. Structural and spectroscopic characterization of CeO 2– TiO 2mixed oxides[J]. Journal of Materials Chemistry A, 2013,1,10918-10926) be prepared .
embodiment 1
A kind of CeO 2/ TiO 2nano combined hollow ball catalyst, first taking polystyrene as template, taking butyl titanate and six nitric hydrate ceriums as wall material raw material, by sol-gel process and the precipitation method preparation CeO that combines 2/ TiO 2the complex microsphere of coated polystyrene, then calcining obtains CeO 2/ TiO 2nano combined tiny balloon catalyst;
The wherein consumption of polystyrene, butyl titanate and six nitric hydrate ceriums, by polystyrene: butyl titanate: six nitric hydrate ceriums are 0.1g:0.2 × 10 -3mol:1 × 10 -3mol.
Above-mentioned CeO 2/ TiO 2the preparation method of nano combined hollow ball catalyst, specifically comprises the steps:
(1), 0.1g polystyrene, 0.5g deionized water, 50 μ L concentrated ammonia liquors and 20mL absolute ethyl alcohol are mixed, then controlling temperature is 60 DEG C, and rotating speed is to obtain reactant liquor 1 after 300r/min reacts 2h;
Described polystyrene spheres particle diameter is about 200nm;
(2), by 0.2 × 10 -3mol butyl titanate is dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.01mol/L tetra-n-butyl titanate ethanolic solution;
Be that 0.01mol/L tetra-n-butyl titanate ethanolic solution adds in step (1) gained reactant liquor 1 in 0.5h by concentration, controlling temperature is that 60 DEG C, rotating speed react 2h while being 300r/min, obtains reactant liquor 2;
(3), by 1 × 10 -3mol six nitric hydrate ceriums are dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.05mol/L cerous nitrate ethanolic solution;
Be that 0.05mol/L cerous nitrate ethanolic solution adds in step (2) gained reactant liquor 2 in 0.5h by concentration, controlling temperature is that 60 DEG C, rotating speed react 2h while being 300r/min, obtains reactant liquor 3;
By 3 centrifugations of the reactant liquor of gained, gained sediment dry 8h at 60 DEG C obtains faint yellow powder;
Faint yellow powder, at 500 DEG C of calcining 3h, is naturally cooled to room temperature and obtains the CeO that particle diameter is 216nm 2/ TiO 2nano combined hollow ball catalyst.
embodiment 2
A kind of CeO 2/ TiO 2nano combined hollow ball catalyst, first taking polystyrene as template, taking butyl titanate and six nitric hydrate ceriums as wall material raw material, by sol-gel process and the precipitation method preparation CeO that combines 2/ TiO 2the complex microsphere of coated polystyrene, then calcining obtains CeO 2/ TiO 2nano combined hollow ball catalyst;
The wherein consumption of polystyrene, butyl titanate and six nitric hydrate ceriums, by polystyrene: butyl titanate: six nitric hydrate ceriums are 0.3g:8 × 10 -3mol:4 × 10 -3mol.
Above-mentioned CeO 2/ TiO 2the preparation method of nano combined hollow ball catalyst, specifically comprises the steps:
(1), 0.3g polystyrene, 2g deionized water, 10 μ L concentrated ammonia liquors and 20mL absolute ethyl alcohol are mixed, controlling temperature is 70 DEG C, and rotating speed is that 400r/min reacts after 4h, obtains reactant liquor 1;
Described polystyrene spheres particle diameter is about 400nm;
(2), by 8 × 10 -3mol butyl titanate is dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.40mol/L tetra-n-butyl titanate ethanolic solution;
Be that 0.40mol/L tetra-n-butyl titanate ethanolic solution adds in step (1) gained reactant liquor 1 in 1h by concentration, controlling temperature is that 70 DEG C, rotating speed react 4h while being 400r/min, obtains reactant liquor 2;
(3), by 4 × 10 -3mol six nitric hydrate ceriums are dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.2mol/L cerous nitrate ethanolic solution;
Be that 0.2mol/L cerous nitrate ethanolic solution adds in step (2) gained reactant liquor 2 in 1h by concentration, controlling temperature is that 70 DEG C, rotating speed react 4h while being 400r/min, obtains reactant liquor 3;
By 3 centrifugations of the reactant liquor of gained, gained sediment dry 9h at 80 DEG C obtains faint yellow powder;
Faint yellow powder, at 500 DEG C of calcining 5h, is naturally cooled to room temperature and obtains the CeO that particle diameter is 440nm 2/ TiO 2nano combined hollow ball catalyst.
embodiment 3
A kind of CeO 2/ TiO 2nano combined hollow ball catalyst, first taking polystyrene as template, taking butyl titanate and six nitric hydrate ceriums as wall material raw material, by sol-gel process and the precipitation method preparation CeO that combines 2/ TiO 2the complex microsphere of coated polystyrene, then calcining obtains CeO 2/ TiO 2nano combined hollow ball catalyst;
The wherein consumption of polystyrene, butyl titanate and six nitric hydrate ceriums, by polystyrene: butyl titanate: six nitric hydrate ceriums are 0.2g:4 × 10 -3mol:6 × 10 -3mol.
Above-mentioned CeO 2/ TiO 2the preparation method of nano combined hollow ball catalyst, specifically comprises the steps:
(1), 0.2g polystyrene, 1g deionized water, 30 μ L concentrated ammonia liquors and 20mL absolute ethyl alcohol are mixed, controlling temperature is 75 DEG C, and rotating speed is that 500r/min reacts after 3h, obtains reactant liquor 1;
Described polystyrene spheres particle diameter is about 500nm;
(2), by 4 × 10 -3mol butyl titanate is dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.2mol/L tetra-n-butyl titanate ethanolic solution;
Be that 0.2mol/L tetra-n-butyl titanate ethanolic solution adds in step (1) gained solution 1 in 0.8h by concentration, controlling temperature is that 75 DEG C, rotating speed react 3h while being 500r/min, obtains reactant liquor 2;
(3), by 6 × 10 -3mol six nitric hydrate ceriums are dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.3mol/L cerous nitrate ethanolic solution;
Be that 0.3mol/L cerous nitrate ethanolic solution adds in step (2) gained solution 2 in 0.8h by concentration, controlling temperature is that 75 DEG C, rotating speed react 3h while being 500r/min, obtains reactant liquor 3;
Then by 3 centrifugations of the reactant liquor of gained, gained sediment dry 10 h at 70 DEG C obtain faint yellow powder;
Then faint yellow powder is calcined to 4h at 800 DEG C, naturally cool to room temperature and obtain the CeO that particle diameter is 580nm 2/ TiO 2nano combined hollow ball catalyst.
embodiment 4
A kind of CeO 2/ TiO 2nano combined hollow ball catalyst, first taking polystyrene as template, taking butyl titanate and six nitric hydrate ceriums as wall material raw material, by sol-gel process and the precipitation method preparation CeO that combines 2/ TiO 2the complex microsphere of coated polystyrene, then calcining obtains CeO 2/ TiO 2nano combined hollow ball catalyst;
The wherein consumption of polystyrene, butyl titanate and six nitric hydrate ceriums, by polystyrene: butyl titanate: six nitric hydrate ceriums are 0.3g:2 × 10 -3mol:3 × 10 -3mol.
Above-mentioned CeO 2/ TiO 2the preparation method of nano combined hollow ball catalyst, specifically comprises the steps:
(1), 0.3g polystyrene, 0.5g deionized water, 40 μ L concentrated ammonia liquors and 20mL absolute ethyl alcohol are mixed, controlling temperature is 65 DEG C, and rotating speed is that 400r/min reacts after 2h, obtains reactant liquor 1;
Described polystyrene spheres particle diameter is about 300nm;
(2), by 2 × 10 -3mol butyl titanate is dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.10mol/L tetra-n-butyl titanate ethanolic solution;
Be in 0.10mol/L tetra-n-butyl titanate ethanolic solution 1h, to add in step (1) gained solution 1 by concentration, controlling temperature is that 65 DEG C, rotating speed react 3h while being 400r/min, obtains reactant liquor 2;
(3), by 3 × 10 -3mol six nitric hydrate ceriums are dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.15mol/L cerous nitrate ethanolic solution;
Be that 0.15mol/L cerous nitrate ethanolic solution adds in step (2) gained reactant liquor 2 in 1h by concentration, controlling temperature is that 65 DEG C, rotating speed react 2-4h while being 400r/min, obtains reactant liquor 3;
By 3 centrifugations of the reactant liquor of gained, gained sediment dry 8 h at 70 DEG C obtain faint yellow powder;
Faint yellow powder, at 600 DEG C of calcining 4h, is naturally cooled to room temperature and obtains the CeO that particle diameter is 326nm 2/ TiO 2nano combined hollow ball catalyst.
embodiment 5
A kind of CeO 2-TiO 2nano combined hollow ball catalyst, first taking polystyrene as template, taking butyl titanate and six nitric hydrate ceriums as wall material raw material, by sol-gel process and the precipitation method preparation CeO that combines 2/ TiO 2the complex microsphere of coated polystyrene, then calcining obtains CeO 2/ TiO 2nano combined hollow ball catalyst;
The wherein consumption of polystyrene, butyl titanate and six nitric hydrate ceriums, by polystyrene: butyl titanate: six nitric hydrate ceriums are 0.2g:1 × 10 -3mol:1 × 10 -3mol.
Above-mentioned CeO 2/ TiO 2the preparation method of nano combined hollow ball catalyst, specifically comprises the steps:
(1), 0.2g polystyrene, 1g deionized water, 40 μ L concentrated ammonia liquors and 20mL absolute ethyl alcohol are mixed, controlling temperature is 60 DEG C, and rotating speed is that 300r/min reacts after 2h, obtains reactant liquor 1;
Described polystyrene spheres particle diameter is about 200nm;
(2), by 1 × 10 -3mol butyl titanate is dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.05mol/L tetra-n-butyl titanate ethanolic solution;
Be that 0.05mol/L tetra-n-butyl titanate ethanolic solution adds in step (1) gained reactant liquor 1 in 1h by concentration, controlling temperature is that 60 DEG C, rotating speed react 4h while being 300r/min, obtains reactant liquor 2;
(3), by 1 × 10 -3mol six nitric hydrate ceriums are dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.05mol/L cerous nitrate ethanolic solution;
Be that 0.05mol/L cerous nitrate ethanolic solution adds in step (2) gained solution 2 in 1h by concentration, controlling temperature is that 60 DEG C, rotating speed react 2h while being 300r/min, obtains reactant liquor 3;
By 3 centrifugations of the reactant liquor of gained, gained sediment dry 9h at 60 DEG C obtains faint yellow powder;
Faint yellow powder, at 500 DEG C of calcining 3h, is naturally cooled to room temperature and obtains the CeO that particle diameter is 220nm 2/ TiO 2nano combined hollow ball catalyst.
Adopt the CeO of transmission electron microscope instrument (Hitachi H-600, high and new technology company of Hitachi) to above-mentioned gained 2/ TiO 2nano combined hollow ball is tested, and the TEM of gained schemes as shown in Figure 1, as can be seen from Figure 1 CeO 2/ TiO 2nano combined hollow ball particle diameter is 220nm.
Adopt the CeO of ESEM instrument (Hitachi S-3400N, high and new technology company of Hitachi) to above-mentioned gained 2/ TiO 2nano combined hollow ball is tested, and the SEM of gained schemes as shown in Figure 2, and as can be seen from Figure 2 products therefrom of the present invention is hollow ball structure, i.e. the CeO of its structure and prior art 2-TiO 2the structure difference of composite oxides.
application Example 1
Getting 25mL concentration is that 20mg/L rhodamine B solution is placed in 50ml quartz socket tube, to the CeO that adds 20mg embodiment 5 gained in quartz socket tube 2/ TiO 2composite hollow sphere catalyst, adopts SB-5200 supersonic wave cleaning machine, the ultrasonic 5min of 300W.
Separately getting 25mL concentration is that 20mg/L rhodamine B solution is placed in 50ml quartz socket tube, does not add CeO 2/ TiO 2composite hollow ball, does blank assay.
Separately getting 25mL concentration is that 20mg/L rhodamine B solution is placed in 50ml quartz socket tube, adds the CeO of prior art 2-TiO 2composite oxides, do control experiment.
Quartz socket tube is placed in to BL-GHX photochemical reaction instrument, in dark, adsorbs after 30min, sampling 5ml.After absorption, light degradation reaction 60min under 600W ultraviolet source, every 10min sampling 5ml.
To after the centrifugal 5min of the sample thief 10000r/min of institute, get supernatant liquor, adopt UV-2100 ultraviolet specrophotometer test absorbance.CeO 2/ TiO 2the CeO of nano combined hollow ball catalyst and prior art 2-TiO 2as shown in Figure 3, in Fig. 3, composite hollow ball is CeO to the photocatalytic activity of composite oxides 2/ TiO 2nano combined hollow ball catalyst, composite granule is according to document (Chiara G, et al. Structural and spectroscopic characterization of CeO 2– TiO 2mixed oxides[J]. Journal of Materials Chemistry A, 2013,1,10918-10926) CeO of the prior art that is prepared 2-TiO 2composite oxides.As can be seen from Figure 3 the CeO that prepared by the present invention 2/ TiO 2nano combined hollow ball has the ability of stronger light degradation rhodamine B.
In sum, a kind of CeO of the present invention 2/ TiO 2nano combined hollow ball catalyst particle diameter is even, and average grain diameter is 216nm-580nm, and cavity is obvious, under 600W ultraviolet source in 60min, and CeO of the present invention 2/ TiO 2nano combined hollow ball catalyst is 30% to the disposal efficiency of 20mg/L rhodamine B solution, and the CeO of prior art 2-TiO 2composite oxides are 20% to the disposal efficiency of 20mg/L rhodamine B solution, i.e. a kind of CeO of the present invention 2/ TiO 2composite hollow sphere catalyst, because it is hollow-core construction, compares CeO 2-TiO 2the solid construction of composite oxides has improved 10% to the degradation capability of rhodamine B.
Above said content is only the basic explanation of the present invention under conceiving, and according to any equivalent transformation that technical scheme of the present invention is done, all should belong to protection scope of the present invention.

Claims (3)

1. a CeO 2/ TiO 2nano combined hollow ball catalyst, is characterized in that described CeO 2/ TiO 2nano combined hollow ball catalyst, first taking polystyrene as template, taking butyl titanate and six nitric hydrate ceriums as wall material raw material, by sol-gel process and the precipitation method preparation CeO that combines 2/ TiO 2the complex microsphere of coated polystyrene, then controlling temperature is that 500-800 DEG C of calcining 3-5h obtains CeO 2/ TiO 2nano combined hollow ball catalyst;
The wherein consumption of polystyrene, butyl titanate and six nitric hydrate ceriums, by polystyrene: butyl titanate: six nitric hydrate ceriums are 0.1-0.3g:0.2-8 × 10 -3mol:1-6 × 10 -3mol.
2. CeO as claimed in claim 1 2/ TiO 2nano combined hollow ball catalyst, is characterized in that its particle diameter is 216nm-580nm.
3. CeO as claimed in claim 1 or 2 2/ TiO 2the preparation method of nano combined hollow ball catalyst, is characterized in that specifically comprising the steps:
(1), 0.1-0.3g polystyrene, 0.5-2g deionized water, 10-50 μ L concentrated ammonia liquor and 20mL absolute ethyl alcohol are mixed after, controlling temperature is that 60-75 DEG C, rotating speed 300-500r/min react after 2-4h, obtains reactant liquor 1;
Described polystyrene spheres particle diameter is about 200-500nm;
(2), by 0.2-8 × 10 -3mol butyl titanate is dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.01-0.40mol/L tetra-n-butyl titanate ethanolic solution;
Be that 0.01-0.40mol/L tetra-n-butyl titanate ethanolic solution adds in step (1) gained reactant liquor 1 in 0.5-1h by concentration, controlling temperature is that 60-75 DEG C, rotating speed are that 300-500r/min reacts 2-4h, obtains reactant liquor 2;
(3), by 1-6 × 10 -3mol six nitric hydrate ceriums are dissolved in 20mL absolute ethyl alcohol, and being mixed with concentration is 0.05-0.3mol/L cerous nitrate ethanolic solution;
Be that 0.05-0.3mol/L cerous nitrate ethanolic solution adds in step (2) gained reactant liquor 2 in 0.5-1h by concentration, controlling temperature is that 60-75 DEG C, rotating speed are that 300-500r/min reacts 2-4h, obtains reactant liquor 3;
By 3 centrifugations of the reactant liquor of gained, gained sediment dry 8-10 h at 60-80 DEG C obtains faint yellow powder;
Faint yellow powder, at 500-800 DEG C of calcining 3-5h, is naturally cooled to room temperature and obtains CeO 2/ TiO 2nano combined hollow ball catalyst.
CN201410203860.5A 2014-05-15 2014-05-15 A kind of CeO2/ TiO2nano combined hollow ball catalyst and preparation method thereof Expired - Fee Related CN104001491B (en)

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CN105642332A (en) * 2016-03-15 2016-06-08 辽宁大学 g-C3N4/TiO2 composite photochemical catalyst and preparation method thereof
CN105869897A (en) * 2016-06-29 2016-08-17 扬州大学 Preparation method and application of hollow material CeO2@TiO2
CN105869897B (en) * 2016-06-29 2017-12-08 扬州大学 A kind of hollow material CeO2@TiO2Preparation method and applications
CN107159182A (en) * 2017-05-31 2017-09-15 中盐金坛盐化有限责任公司 A kind of preparation method of hollow microsphere SCR denitration
CN112295515A (en) * 2020-11-30 2021-02-02 江南大学 Preparation method of zinc oxide/cerium oxide hollow microspheres with inverted blueberry-shaped structures
CN116747154A (en) * 2023-08-15 2023-09-15 广东药科大学 Cerium oxide-based sun-screening material capable of resisting blue light and preparation method thereof

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