CN104310466A - Hollow titanium dioxide microsphere based on gel sphere precursor and preparation method of hollow titanium dioxide microsphere - Google Patents
Hollow titanium dioxide microsphere based on gel sphere precursor and preparation method of hollow titanium dioxide microsphere Download PDFInfo
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- CN104310466A CN104310466A CN201410531717.9A CN201410531717A CN104310466A CN 104310466 A CN104310466 A CN 104310466A CN 201410531717 A CN201410531717 A CN 201410531717A CN 104310466 A CN104310466 A CN 104310466A
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G23/00—Compounds of titanium
- C01G23/04—Oxides; Hydroxides
- C01G23/047—Titanium dioxide
- C01G23/053—Producing by wet processes, e.g. hydrolysing titanium salts
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
- B01J21/063—Titanium; Oxides or hydroxides thereof
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- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
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- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
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- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
- C01P2004/32—Spheres
- C01P2004/34—Spheres hollow
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- C01P2006/12—Surface area
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- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/14—Pore volume
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- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/16—Pore diameter
Abstract
The invention belongs to the technical field of inorganic functional material preparation, and particularly relates to a TiO2 hollow microsphere synthesizing technology by using gel spherulite as precursor. A hydrolyzing agent complexed tetra-n-butyl titanate is dispersed into a water solution of starch, and is subjected to hydrothermal treatment at 150 DEG C, the starch reacts with tetra-n-butyl titanate to form a gel sphere with a three-dimensional network structure; a hollow structure is formed in the gel sphere in the mineralizing and carbonizing processes due to volume shrinkage, and the carbon ingredient remained in the gel sphere is removed by a thermal treatment; and the substantial part of the hollow TiO2 microsphere is made of a porous material formed by nano-crystalline grains (8-10nm) and nano-scale passages. According to the synthesized TiO2 spheres, the specific surface area is 230m<2>/g, the porous volume is 0.34cm<3>/g, and the average pore diameter is 6.6nm. By adopting the synthesizing process, water is used as a dispersing medium, and starch participates in the reaction to form the gel spheres, and the process is environment-friendly.
Description
Technical field
The invention belongs to technical field prepared by inorganic functional material, particularly a kind of take gel ball as the TiO of presoma
2the synthetic technology of hollow microsphere.
Background technology
TiO
2because of its chemical physical property stablize, nontoxic, material source is sufficient etc., and feature is widely used as the research of photocatalyst for obnoxious flavour and organic pollutants in air of degrading, be used for the research of dye sensitization solar battery as electrode materials, be used for the research of self-cleaning material as top coat.TiO
2semi-conductor is under the irradiation of UV-light, and the energy jump of the electron absorption photon in its valence band to conduction band, thus forms photo-generate electron-hole pair, and this characteristic is it as the theoretical basis of photocatalyst and dye sensitization solar battery applied research.Semi-conductor TiO
2there are three kinds of crystal formations, be respectively Detitanium-ore-type, brookite type and rutile-type, wherein Detitanium-ore-type is higher compared with the catalytic activity of rutile-type, and brookite type is because being not easy the product of synthesis of high purity and less studied.
Recent two decades comes, around raising TiO
2the catalytic efficiency of photocatalyst and the electricity conversion of dye sensitization solar battery, researcher has done many-sided research work, wherein synthesizes hollow microsphere and can reach good effect.TiO
2hollow microsphere utilizes the reflex action of its internal surface to light to improve the utilising efficiency of incident light, and as photocatalyst, TiO
2microballoon can solve nano-TiO
2the problems such as the loss after powder uses in separation difficulty, use procedure.TiO
2the method of hollow microsphere synthesis is mainly template, and the template of use has SiO
2, hydrated sulfate, carbon ball, polystyrene microsphere, tensio-active agent etc.These methods or the microsphere template needing preparation special, or need to use organic solvent or the higher temperature condition such as ethanol, technique is more complicated, and production cost is higher simultaneously.
Traditional synthetic high polymer and template agent method need synthesize in advance or obtain spheroidal particle template, then form TiO by the hydrolysis of Titanium alkoxides on template surface, polycondensation
2shell.When template shape and structure does not produce substantial variation after the completion of reaction, inner organic formwork agent must be removed by calcining, just can obtain hollow feature.
Summary of the invention
In order to overcome prior art in the process preparing hollow microsphere material, needing special this problem adopting means of calcination removing template, the invention provides a kind of hollow TiO
2microballoon and synthetic method thereof, synthesized TiO
2micropelletoid substantial part has carbon and Detitanium-ore-type TiO
2composite structure, there is large specific surface area; After high-temperature heat treatment decarburization, this hollow TiO
2the substantial part of microballoon becomes and is made up of nano-sized grains and nano-scale passage in microtexture, has the TiO of spacial framework
2porous material.
The method and synthesized microballoon have following characteristics:
(1) adopt the starch that raw materials cost is lower as one of composition forming gel ball;
(2) formation of gel spherolite, hollow structure is unified in hydrothermal condition next step completes: under hydrothermal condition, tetra-n-butyl titanate, starch reaction form the gel ball of three-dimensional net structure, and gel ball produces hollow structure due to volumetric shrinkage in ensuing mineralisation process;
(3) TiO synthesized by hydro-thermal reaction
2spherolite presents black, and it has hollow structure and presents Detitanium-ore-type crystalline phase, and has large specific surface area, can be used as photocatalyst and directly uses; Also can use after 500 DEG C of thermal treatments remove carbon, remove the microballoon after carbon and present white, hollow TiO after decarburization
2the substantial part of microballoon is the TiO that a kind of nanocrystal and nano-scale passage are formed
2porous material;
(4) Titanium alkoxides generally adopts ethanol, propyl alcohol and so on good solvent to disperse, and the present invention utilizes Titanium alkoxides dispersed this characteristic poor in water, can successfully be attached together with the gel spherolite that generates in starch and reflection process; And compared with the technique of conventional organic solvents, the present invention adopts water as dispersion agent on synthesis technique, and the preparation cost of microballoon is lower, avoids the use of organic solvent, environmental protection;
(5) TiO synthesized by the present invention
2microballoon (or the carbon doping TiO before thermal treatment
2microballoon) there is large specific surface area and pore volume, be expected by its adsorption, when organic contamination substrate concentration is lower, plays enrich target material and improve photocatalytic degradation effect.
The concrete technical scheme that the present invention adopts is:
A kind of hollow TiO is provided
2microballoon, has carbon and Detitanium-ore-type TiO
2composite structure, and there is large specific surface area; After the carbon component that doping is removed in thermal treatment, hollow TiO
2the substantial part of microballoon is the porous material that a kind of nanocrystal and nano-scale passage are formed.
Present invention also offers a kind of above-mentioned hollow TiO
2the preparation method of microballoon: adopt water as dispersion medium, simultaneously dispersing starch and organic titanium source, by hydro-thermal reaction, generates the carbon doping TiO of hollow
2microballoon; Again after Overheating Treatment decarburization, obtaining substantial part is the TiO that nanocrystal and nano-scale passage are formed
2porous material hollow microsphere.
Necessary operation comprises: first, preparation amidin and tetra-n-butyl titanate complex compound, under 90 DEG C of conditions, by starch dissolution in deionized water, then room temperature is naturally cooled to, obtain the aqueous solution of starch, as required, appropriate surfactant sodium dodecyl base Phenylsulfonic acid can be added in this amidin; Simultaneously in order to relax the too high hydrolysis rate of tetra-n-butyl titanate, tetra-n-butyl titanate carries out complexing with methyl ethyl diketone hydrolysis inhibitor before using.Secondly, preparation dispersion system, when stirring, is distributed in amidin by the complex compound of tetra-n-butyl titanate, after stirring 1h, obtains uniform milk yellow dispersion system.3rd, hydrothermal treatment consists, proceeds in autoclave by milk yellow dispersion system, and under 150 DEG C of conditions, hydro-thermal reaction 10h, the product be obtained by reacting is after deionized water and ethanol sequential purge, and at 100 DEG C, namely dry 2h obtains the carbon doping TiO of hollow
2microballoon, then after Overheating Treatment decarburization, obtaining substantial part is the TiO that nanocrystal and nano-scale passage are formed
2porous material hollow microsphere.
Concrete operations are:
(1) by starch dissolution in deionized water, (selectivity adds tensio-active agent) is mixed with starch solution;
(2) tetra-n-butyl titanate and methyl ethyl diketone are carried out complexing, obtain tetra-n-butyl titanate complex compound;
(3) the tetra-n-butyl titanate complex compound obtained in step (2) is joined in the starch solution obtained in step (1), stir and obtain dispersion system;
(4) by the dispersion system that obtains in step (3) under 150 DEG C of conditions, hydro-thermal reaction 10h, reaction product after filtration, washing, dry, obtain the carbon doping TiO of hollow
2microballoon;
(5) the carbon doping TiO will obtained in step (4)
2microballoon thermal treatment 1 hour under 500 DEG C of conditions, obtaining substantial part is the TiO that nanocrystal and nano-scale passage are formed
2porous material hollow microsphere.
Beneficial effect of the present invention is: the TiO synthesized by the present invention
2the hollow structure of microballoon is just formed in synthesis step (being formed based on the volumetric shrinkage effect of gel ball in mineralisation process), prepared hollow TiO
2microballoon not only separation performance is better, and has the characteristics such as high specific surface area, high pore volume and less pore size, has good concentration effect to degraded object.Therefore, the TiO for preparing of the present invention
2microballoon makes TiO on the one hand
2the use of photocatalyst is convenient, overcomes nano-TiO
2separation difficulty after powder uses, the easy shortcoming such as loss in use procedure; Utilize on the other hand the absorption property of microballoon can enrichment organic pollutant molecule, improve photocatalysis efficiency.
Accompanying drawing explanation
Fig. 1 is prepared in embodiment 1, and starch concentration is 27g/L, TiO when not using tensio-active agent
2the SEM photo of hollow microsphere;
Fig. 2 is prepared in embodiment 2, TiO when starch concentration is 27g/L, Witco 1298 Soft Acid concentration is 82.7mg/L
2the SEM photo of hollow microsphere;
Fig. 3 is prepared in embodiment 3, TiO when starch concentration is 163 g/L, Witco 1298 Soft Acid concentration is 82.7mg/L
2the SEM photo of hollow microsphere;
The sem observation of Fig. 2 and Fig. 3 shows, synthesized TiO
2microballoon has hollow structure, and the diameter of microballoon increases with the increase of starch solution concentration.
Fig. 4 is prepared in embodiment 3, TiO when starch concentration is 163g/L, Witco 1298 Soft Acid concentration is 82.7mg/L
2the XRD figure spectrum of hollow microsphere (500 DEG C, before 1h process and after process).
Fig. 5 is prepared in embodiment 3, TiO when starch concentration is 163g/L, Witco 1298 Soft Acid concentration is 82.7mg/L
2hollow microsphere (through 500 DEG C, after 1h process) N
2isothermal adsorption result, this N
2isothermal adsorption analysis shows, TiO
2the substantial part of hollow microsphere is porous network structure.
Fig. 6 is the TiO of preparation in embodiment 2 and embodiment 3
2the EDS ultimate analysis of microballoon.
Embodiment
Embodiment 1:
One, the preparation of starch solution
Get 1.18g starch to be dissolved in the deionized water of 90 DEG C of 40mL, then naturally cool to room temperature;
Two, the complexing of tetra-n-butyl titanate
In 2.5mL tetra-n-butyl titanate, add 1mL methyl ethyl diketone, stirring reaction 0.5h, obtain the complex compound of tetra-n-butyl titanate;
Three, the preparation of dispersion system
When stirring, the tetra-n-butyl titanate complex compound obtained being joined in the starch solution obtained in step one, stir and obtain milk yellow dispersion system in step 2;
Four, hydrothermal treatment consists
Proceed in the autoclave of cup in tetrafluoroethylene by the milk yellow dispersion system obtained in step 3, under 150 DEG C of conditions, hydro-thermal reaction 10h, the product be obtained by reacting is after deionized water and ethanol sequential purge, and at 100 DEG C, dry 2h obtains the TiO of hollow
2microballoon.
Scanning electronic microscope (SEM) is observed and is shown, gained TiO
2particle is hollow microsphere, and diameter about 50 ~ 100 μm, its photo is shown in Fig. 1.
Embodiment 2:
One, the preparation of starch solution
Get 1.18g starch to be dissolved in the deionized water of 90 DEG C of 40mL, then naturally cool to room temperature (25 DEG C) and obtain starch solution, then add the Witco 1298 Soft Acid of 3.6mg in this starch solution, stir;
Two, the complexing of tetra-n-butyl titanate
In 2.5mL tetra-n-butyl titanate, add 1mL methyl ethyl diketone, stirring reaction 0.5h, obtain the complex compound of tetra-n-butyl titanate;
Three, the preparation of dispersion system
When stirring, the tetra-n-butyl titanate complex compound obtained being joined in the starch solution obtained in step one, stir and obtain milk yellow dispersion system in step 2;
Four, hydrothermal treatment consists
Proceed in the autoclave of cup in tetrafluoroethylene by the milk yellow dispersion system obtained in step 3, under 150 DEG C of conditions, hydro-thermal reaction 10h, the product be obtained by reacting is after deionized water and ethanol sequential purge, and at 100 DEG C, dry 2h obtains the TiO of hollow
2microballoon.
Fig. 2 is the TiO of preparation in embodiment 2
2scanning electronic microscope (SEM) photo of hollow microsphere, larger-size microballoon presents honeycomb structure, and less microballoon is then solid construction.
Comparison diagram 1, Fig. 2 show: although add the diameter that tensio-active agent can regulate microballoon, along with the reduction of microsphere diameter, its internal structure also there occurs change.During microsphere diameter less than 20 μm, inside changes honeycomb structure into by hollow; During microsphere diameter less than about 10 μm, inside changes solid construction into by honeycomb.
The ultimate analysis of Fig. 6 shows, microballoon in chemical constitution containing Ti, O, C element (in figure, the corresponding peak of Pt is caused by the Pt layer that plated by sample pre-treatments).
Embodiment 3:
One, the preparation of starch solution
Get 7.1g starch to be dissolved in the deionized water of 90 DEG C of 40mL, then naturally cool to room temperature (25 DEG C) and obtain starch solution, then add the Witco 1298 Soft Acid of 3.6mg in this starch solution, stir;
Two, the complexing of tetra-n-butyl titanate
In 2.5mL tetra-n-butyl titanate, add 1mL methyl ethyl diketone, stirring reaction 0.5h, obtain the complex compound of tetra-n-butyl titanate;
Three, the preparation of dispersion system
When stirring, the tetra-n-butyl titanate complex compound obtained being joined in the starch solution obtained in step one, stir and obtain milk yellow dispersion system in step 2;
Four, hydrothermal treatment consists
The milk yellow dispersion system obtained in step 3 is proceeded in the autoclave of cup in tetrafluoroethylene, under 150 DEG C of conditions, hydro-thermal reaction 10h, the product be obtained by reacting is after deionized water and ethanol sequential purge, and at 100 DEG C, dry 2h obtains the hollow TiO of surface for black
2microballoon, its specific surface area is 265m
2/ g,
Power spectrum (EDS) analysis of Fig. 6 shows, the shell of hollow microsphere is except Ti, O element, and also containing C element, this shows to contain starch in the gel ball that hydro-thermal reaction is formed, and leaves the C element of doping after starch carbonizing; The inner C element content of microballoon is higher, has stayed the inside of microballoon after showing relatively many starch carbonizings;
Five, thermal treatment
By the black hollow TiO prepared in step 4
2microballoon (temperature rise rate is 15 DEG C/min) at 500 DEG C processes 1h, naturally cools to room temperature (25 DEG C), obtains the microballoon of surface in white.
Scanning electronic microscope (SEM) photo of Fig. 3 shows, gained TiO after step 5 thermal treatment
2microballoon has hollow feature, its diameter about 120 μm.
X-ray diffraction (XRD) analysis of Fig. 4 shows, before thermal treatment, the microballoon synthesized by embodiment 3 is Detitanium-ore-type TiO
2, grain-size is about 8nm; After 500 DEG C of process 1h, grain-size is increased to 10nm.
The N of Fig. 5
2isothermal adsorption analysis shows, TiO
2the substantial part of hollow microsphere (removing after carbon through thermal treatment) is vesicular structure, and its specific surface area, pore volume and hole diameter are respectively 230m
2/ g, 0.34cm
3/ g and 6.6nm.
Claims (8)
1. a hollow TiO
2microballoon, is characterized in that: described hollow TiO
2the substantial part of microballoon is Detitanium-ore-type TiO
2the matrix material of doping carbon.
2. a hollow TiO
2microballoon, is characterized in that: described hollow TiO
2the substantial part of microballoon is the TiO that a kind of nanocrystal and nano-scale passage are formed
2porous material.
3. hollow TiO as claimed in claim 1
2the preparation method of microballoon, is characterized in that: described preparation method is,
(1) by starch dissolution in deionized water, be mixed with starch solution;
(2) tetra-n-butyl titanate and methyl ethyl diketone are carried out complexing, obtain tetra-n-butyl titanate complex compound;
(3) the tetra-n-butyl titanate complex compound obtained in step (2) is joined in the starch solution obtained in step (1), stir and obtain dispersion system;
(4) by the dispersion system that obtains in step (3) under 150 DEG C of conditions, hydro-thermal reaction 10h, reaction product after filtration, washing, dry, obtain the carbon doping TiO of hollow
2microballoon.
4. hollow TiO as claimed in claim 2
2the preparation method of microballoon, is characterized in that: described preparation method is,
(1) by starch dissolution in deionized water, be mixed with starch solution;
(2) tetra-n-butyl titanate and methyl ethyl diketone are carried out complexing, obtain tetra-n-butyl titanate complex compound;
(3) the tetra-n-butyl titanate complex compound obtained in step (2) is joined in the starch solution obtained in step (1), stir and obtain dispersion system;
(4) by the dispersion system that obtains in step (3) under 150 DEG C of conditions, hydro-thermal reaction 10h, reaction product after filtration, washing, dry, obtain the carbon doping TiO of hollow
2microballoon;
(5) the carbon doping TiO will obtained in step (4)
2microballoon thermal treatment 1 hour under 500 DEG C of conditions, obtaining substantial part is the TiO that nanocrystal and nano-scale passage are formed
2porous material hollow microsphere.
5. the hollow TiO as described in claim 3 or 4
2the preparation method of microballoon, is characterized in that: the concentration of the starch solution described in step (1) is 27 ~ 163mg/L.
6. the hollow TiO as described in claim 3 or 4
2the preparation method of microballoon, is characterized in that: the washing described in step (4) is, adopts the order of deionized water, ethanol, washs described reaction product.
7. the hollow TiO as described in claim 3 or 4
2the preparation method of microballoon, is characterized in that: the drying described in step (4) is, dry 2h at 100 DEG C.
8. the hollow TiO as described in claim 3 or 4
2the preparation method of microballoon, is characterized in that: in step (1), in described starch solution, add tensio-active agent.
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Cited By (6)
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| CN105883915A (en) * | 2016-04-08 | 2016-08-24 | 湖北工程学院 | Nano-crystal titanium dioxide microspheres and application thereof as ozonation catalyst |
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| CN106140123A (en) * | 2015-03-16 | 2016-11-23 | 中智环保新材料江苏有限公司 | A kind of preparation method and applications of mesopore titania photocatalyst |
| CN106732653A (en) * | 2016-12-30 | 2017-05-31 | 雷笑天 | A kind of preparation method of low-temperature denitration catalyst |
| CN107021522A (en) * | 2017-05-05 | 2017-08-08 | 常州大学 | A kind of single dispersing TiO based on microemulsion2The synthetic method of microballoon |
| CN111320204A (en) * | 2020-02-24 | 2020-06-23 | 常州大学 | Preparation method of titanium dioxide microspheres with high specific surface area |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN106140123A (en) * | 2015-03-16 | 2016-11-23 | 中智环保新材料江苏有限公司 | A kind of preparation method and applications of mesopore titania photocatalyst |
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| CN106082357A (en) * | 2016-06-08 | 2016-11-09 | 淮阴师范学院 | A kind of preparation method of Cobalto-cobaltic oxide Multi-layer hollow microsphere |
| CN106732653A (en) * | 2016-12-30 | 2017-05-31 | 雷笑天 | A kind of preparation method of low-temperature denitration catalyst |
| CN107021522A (en) * | 2017-05-05 | 2017-08-08 | 常州大学 | A kind of single dispersing TiO based on microemulsion2The synthetic method of microballoon |
| CN111320204A (en) * | 2020-02-24 | 2020-06-23 | 常州大学 | Preparation method of titanium dioxide microspheres with high specific surface area |
| CN111320204B (en) * | 2020-02-24 | 2022-03-25 | 常州大学 | Preparation method of titanium dioxide microspheres with high specific surface area |
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