CN103754929A - Preparation method for TiO2/InVO4 composite porous micro-sphere - Google Patents

Preparation method for TiO2/InVO4 composite porous micro-sphere Download PDF

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CN103754929A
CN103754929A CN201310711687.5A CN201310711687A CN103754929A CN 103754929 A CN103754929 A CN 103754929A CN 201310711687 A CN201310711687 A CN 201310711687A CN 103754929 A CN103754929 A CN 103754929A
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tio
invo4
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申乾宏
杨辉
沈建超
蔡奇风
冯宇
盛建松
程笛
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Zhejiang University ZJU
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Abstract

The invention relates to the field of semiconductor materials and aims to provide a preparation method for a TiO2/InVO4 composite porous micro-sphere. The method comprises the following steps: adding an NH4VO3 water solution into an InCl3 water solution; adjusting the pH value to 4 and agitating to obtain precipitate; adding the precipitate into a CTAB (Cetyltrimethyl Ammonium Bromide) water solution and carrying out a hydrothermal reaction; filtering, washing and drying the obtained precipitate and carrying out heat treatment to obtain an InVO4 porous micro-sphere; dispersing the InVO4 porous micro-sphere into absolute ethyl alcohol to obtain a dispersion system; gradually dripping polymer type TiO2 sol; filtering and drying the precipitate to finish a dip-coating procedure to obtain a TiO2 gel coated InVO4 porous micro-sphere; adding the TiO2 gel coated InVO4 porous micro-sphere into the water, agitating in a water bath, and filtering, washing and drying the precipitate to obtain a product. According to the preparation method for the TiO2/InVO4 composite porous micro-sphere, the nucleation and growth problems of a TiO2 nano crystal are solved so as to accelerate the TiO2 nano crystal to grow in the InVO4 composite porous micro-sphere in an in-situ manner and prevent homogeneous separation of the nano crystal in the solution in a traditional method; the problem that the high specific surface area and the recycling of catalytic materials cannot be considered at the same time is solved and the large specific surface area and apparent size can be obtained simultaneously.

Description

TiO 2/ InVO 4the preparation method of composite porous microspheres
Technical field
The invention relates to field of semiconductor materials, particularly TiO 2/ InVO 4the preparation method of composite porous microspheres.
Background technology
InVO 4be a kind of important narrow gap semiconductor, energy gap is about 2.0eV.In recent years, due to InVO 4in fields such as sun power utilization, environment protection, gas sensings, there is potential application prospect, caused people's extensive concern.Early stage InVO 4mainly with In 2o 3and V 2o 5for raw material, by high temperature solid-state method, prepare gained, but product coarse grains, specific surface area is very little, and is prone to impurity phase.At present, adopt the wet-chemical means such as hydro-thermal to prepare InVO 4nanocrystal has become a kind of conventional method, and many literature research have all been reported InVO 4the pattern regulation and control of nano material and correlated performance research.But lower quantum yield remains the major cause that limits its practical application.TiO 2because of its nontoxicity, good chemical stability, suitable position of energy band and cheapness, occupy critical role in conductor photocatalysis field, and and InVO 4can be with also comparatively coupling, can be by structure InVO 4/ TiO 2nano composite structure, promotes light induced electron hole to separating, and improves matrix material quantum yield.Existing scientific research personnel carried out both compound research and obtained good effect early stage, but this class research at present still mainly concentrates on the preparation of nano-powder, InVO 4and TiO 2though realized the compound of nanoscale, nano-powder still exist be in actual applications difficult to reclaim problem urgently to be resolved hurrily.
Summary of the invention
The technical problem to be solved in the present invention is, overcomes deficiency of the prior art, and a kind of TiO is provided 2/ InVO 4the preparation method of composite porous microspheres.
For solving the problems of the technologies described above, solution of the present invention is:
A kind of TiO is provided 2/ InVO 4the preparation method of composite porous microspheres, comprises the steps:
Steps A: under agitation condition, by NH 4vO 3the aqueous solution dropwise adds InCl 3in the aqueous solution, form yellow settled solution; Adopt ammoniacal liquor regulator solution system pH to 4, after stirring 2h, obtain precipitation; By sedimentation and filtration, washing 3 times, then add in cetyl trimethylammonium bromide (CTAB) aqueous solution, after continuation stirring 1h, be transferred to hydrothermal reaction kettle and carry out hydro-thermal reaction; Gained sedimentation and filtration after hydro-thermal reaction, and wash respectively three times with distilled water and dehydrated alcohol, after 60 ℃ of dry 4h, in retort furnace, heat-treat, thereby obtain InVO 4porous microsphere;
Wherein, NH 4vO 3the volumetric molar concentration of the aqueous solution is 0.1mol/L～0.5mol/L, InCl 3the volumetric molar concentration of the aqueous solution is 0.1mol/L～0.5mol/L, and the massfraction of the CTAB aqueous solution is 0.5wt%～3wt%; It is 4: 1～1: 1 that the amount of control reactant makes the mol ratio of V and In, and the mol ratio of In and CTAB is 10: 1～2: 1; Hydrothermal temperature is 150～200 ℃, and the hydro-thermal reaction time is 12h～36h; Thermal treatment temp is 350～500 ℃, and heat treatment time is 2～5h;
Step B: by InVO 4porous microsphere is distributed in dehydrated alcohol and obtains dispersion system, after ultrasonic 15min, under the rotating speed of 50r/min, in dispersion system, dropwise adds polymer-type TiO 2colloidal sol, continues to stir after 5h, by sedimentation and filtration, dry, completes InVO 1 time 4porous microsphere is to polymer-type TiO 2the dip-coating operation of colloidal sol, makes TiO 2gel is coated InVO 4microballoon;
Wherein, InVO 4the solid content of porous microsphere in dispersion system is 1%～5%; Control polymer-type TiO 2it is 1: 1～1: 10 that the add-on of colloidal sol makes the mol ratio of In and Ti;
Described polymer-type TiO 2the preparation method of colloidal sol is: it is 2 that butyl (tetra) titanate is added to pH value, and in hydrochloric aqueous ethanolic solution, wherein the mol ratio of butyl (tetra) titanate and water is 1: 4, after mixing, stirs 2h, obtains polymer-type TiO 2colloidal sol;
Step C: by TiO 2gel is coated InVO 4microballoon is added to the water, and under stirring in water bath condition, processes, and gained sedimentation and filtration, washs respectively three times with distilled water and dehydrated alcohol, 60 ℃ of oven dry, obtains TiO 2/ InVO 4composite porous microspheres;
Wherein, TiO 2gel is coated InVO 4the mass ratio of microballoon and water is 1: 80～1: 20; Bath temperature is 70～90 ℃, and the water bath processing time is 2～10h.
As further improvement, repeat as required the InVO of 1～2 described step B 4porous microsphere is to polymer-type TiO 2the dip-coating operation of colloidal sol.
As further improvement, in described step C, by TiO 2gel is coated InVO 4before microballoon is added to the water, take hydrochloric acid, regulate the pH value of water as 1～3.
Principle of work of the present invention: the present invention adopts soft template method successfully to prepare three-D micro-nano hierarchy InVO under hydrothermal condition 4porous microsphere; Then adopt sol-gel technology to pass through polymer-type TiO 2colloidal sol is at InVO 4absorption and gel in porous microsphere pore structure, form TiO 2gel is coated InVO 4microballoon; Finally utilize Ostwald slaking principle, impel TiO 2gel is at InVO 4the hydrolysis of porous microsphere hole situ, forming core grows the TiO with photocatalytic activity 2nanocrystalline, prepare required TiO 2/ InVO 4composite porous microspheres.
Compared with prior art, the invention has the beneficial effects as follows:
1, solved TiO 2nanocrystalline forming core, growth question, impel TiO 2nanocrystalline at InVO 4the growth of porous microsphere hole situ, has avoided the nanocrystalline homogeneous phase in solution of traditional method to separate out;
2, the InVO of three-D micro-nano hierarchy solved the problem that catalytic material high-specific surface area and recoverable are difficult to take into account, by will be there is 4porous microsphere load TiO 2nanocrystalline, can obtain larger specific surface area and apparent size simultaneously, be conducive to realize its recycling when guaranteeing material high catalytic activity.
Embodiment
Below in conjunction with embodiment, the present invention is described in further detail:
TiO 2/ InVO 4the preparation method of composite porous microspheres, comprises the following steps:
Steps A: under agitation condition, by a certain amount of NH 4vO 3the aqueous solution dropwise adds InCl 3in the aqueous solution, form yellow settled solution.Adopt ammoniacal liquor regulator solution system pH to 4, after stirring 2h, obtain precipitation; By sedimentation and filtration, washing 3 times, then add in cetyl trimethylammonium bromide (CTAB) aqueous solution, after continuation stirring 1h, be transferred to hydrothermal reaction kettle and carry out hydro-thermal reaction; Gained sedimentation and filtration after hydro-thermal reaction, and wash respectively three times with distilled water and dehydrated alcohol, after 60 ℃ of dry 4h, in retort furnace, heat-treat, thereby obtain InVO 4porous microsphere.
Wherein, NH 4vO 3the volumetric molar concentration of the aqueous solution is 0.1mol/L～0.5mol/L, InCl 3the volumetric molar concentration of the aqueous solution is 0.1mol/L～0.5mol/L, and the mol ratio of V and In is 4: 1～1: 1; The massfraction of the CTAB aqueous solution is 0.5wt%～3wt%, and the mol ratio of In and CTAB is 10: 1～2: 1; Hydrothermal temperature is 150～200 ℃, and the hydro-thermal reaction time is 12h～36h; Thermal treatment temp is 350～500 ℃, and thermal treatment soaking time is 2～5h.
Step B: by InVO 4porous microsphere is distributed in dehydrated alcohol and obtains system, after ultrasonic 15min, under the rotating speed of 50r/min, in system, dropwise adds a certain amount of polymer-type TiO 2colloidal sol, continues to stir after 5h, by sedimentation and filtration, dry, completes InVO 1 time 4porous microsphere is to polymer-type TiO 2the dip-coating operation of colloidal sol, finally makes TiO 2gel is coated InVO 4microballoon.
Wherein, InVO 4the solid content of porous microsphere in system is 1%～5%; Described polymer-type TiO 2the preparation method of colloidal sol is: it is 2 that butyl (tetra) titanate is added to pH value, and in hydrochloric aqueous ethanolic solution, wherein the mol ratio of butyl (tetra) titanate and water is 1: 4, after mixing, stirs 2h, obtains polymer-type TiO 2colloidal sol; The mol ratio of In and Ti is 1: 1～1: 10.
Step C: by TiO 2gel is coated InVO 4microballoon is added to the water, and under stirring in water bath condition, processes certain hour, and gained sedimentation and filtration washs respectively three times with distilled water and dehydrated alcohol, 60 ℃ of oven dry, obtains TiO 2/ InVO 4composite porous microspheres.
Wherein, TiO 2gel is coated InVO 4the mass ratio of microballoon and water is 1: 80～1: 20; Bath temperature is 70～90 ℃, and the water bath processing time is 2～10h.
The following examples can make this professional professional and technical personnel's comprehend the present invention, but do not limit the present invention in any way.By 8 embodiment, successfully make TiO respectively 2/ InVO 4the preparation method of composite porous microspheres, the testing data in each embodiment sees the following form 1.
Table 1 embodiment data sheet
Figure BDA0000442572100000031
Figure BDA0000442572100000041
Finally, it is also to be noted that, what more than enumerate is only specific embodiments of the invention.Obviously, the invention is not restricted to above examples of implementation, can also have many distortion.All distortion that those of ordinary skill in the art can directly derive or associate from content disclosed by the invention, all should think protection scope of the present invention.

Claims (3)

1.TiO 2/ InVO 4the preparation method of composite porous microspheres, is characterized in that, comprises the steps:
Steps A: under agitation condition, by NH 4vO 3the aqueous solution dropwise adds InCl 3in the aqueous solution, form yellow settled solution; Adopt ammoniacal liquor regulator solution system pH to 4, after stirring 2h, obtain precipitation; By sedimentation and filtration, washing 3 times, then add in cetyl trimethylammonium bromide (CTAB) aqueous solution, after continuation stirring 1h, be transferred to hydrothermal reaction kettle and carry out hydro-thermal reaction; Gained sedimentation and filtration after hydro-thermal reaction, and wash respectively three times with distilled water and dehydrated alcohol, after 60 ℃ of dry 4h, in retort furnace, heat-treat, thereby obtain InVO 4porous microsphere;
Wherein, NH 4vO 3the volumetric molar concentration of the aqueous solution is 0.1mol/L～0.5mol/L, InCl 3the volumetric molar concentration of the aqueous solution is 0.1mol/L～0.5mol/L, and the massfraction of the CTAB aqueous solution is 0.5wt%～3wt%; It is 4: 1～1: 1 that the amount of control reactant makes the mol ratio of V and In, and the mol ratio of In and CTAB is 10: 1～2: 1; Hydrothermal temperature is 150～200 ℃, and the hydro-thermal reaction time is 12h～36h; Thermal treatment temp is 350～500 ℃, and heat treatment time is 2～5h;
Step B: by InVO 4porous microsphere is distributed in dehydrated alcohol and obtains dispersion system, after ultrasonic 15min, under the rotating speed of 50r/min, in dispersion system, dropwise adds polymer-type TiO 2colloidal sol, continues to stir after 5h, by sedimentation and filtration, dry, completes InVO 1 time 4porous microsphere is to polymer-type TiO 2the dip-coating operation of colloidal sol, makes TiO 2gel is coated InVO 4microballoon;
Wherein, InVO 4the solid content of porous microsphere in dispersion system is 1%～5%; Control polymer-type TiO 2it is 1: 1～1: 10 that the add-on of colloidal sol makes the mol ratio of In and Ti;
Described polymer-type TiO 2the preparation method of colloidal sol is: it is 2 that butyl (tetra) titanate is added to pH value, and in hydrochloric aqueous ethanolic solution, wherein the mol ratio of butyl (tetra) titanate and water is 1: 4, after mixing, stirs 2h, obtains polymer-type TiO 2colloidal sol;
Step C: by TiO 2gel is coated InVO 4microballoon is added to the water, and under stirring in water bath condition, processes, and gained sedimentation and filtration, washs respectively three times with distilled water and dehydrated alcohol, 60 ℃ of oven dry, obtains TiO 2/ InVO 4composite porous microspheres;
Wherein, TiO 2gel is coated InVO 4the mass ratio of microballoon and water is 1: 80～1: 20; Bath temperature is 70～90 ℃, and the water bath processing time is 2～10h.
2. method according to claim 1, is characterized in that, repeats as required the InVO of 1～2 described step B 4porous microsphere is to polymer-type TiO 2the dip-coating operation of colloidal sol.
3. method according to claim 1, is characterized in that, in described step C, by TiO 2gel is coated InVO 4before microballoon is added to the water, take hydrochloric acid, regulate the pH value of water as 1～3.
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Cited By (3)

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CN104575625A (en) * 2014-12-25 2015-04-29 浙江大学 Method for preparing lithium metaaluminate porous microsphere serving as solid tritium breeder
CN107998876A (en) * 2017-11-24 2018-05-08 安徽睿知信信息科技有限公司 A kind of nano-sized carbon and InVO4-TiO2The haze cleanser of coupling
CN109678208A (en) * 2017-10-19 2019-04-26 深圳市寒暑科技新能源有限公司 A kind of hollow vanadic anhydride material and preparation method thereof for Zinc ion battery

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Cited By (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104575625A (en) * 2014-12-25 2015-04-29 浙江大学 Method for preparing lithium metaaluminate porous microsphere serving as solid tritium breeder
CN109678208A (en) * 2017-10-19 2019-04-26 深圳市寒暑科技新能源有限公司 A kind of hollow vanadic anhydride material and preparation method thereof for Zinc ion battery
CN107998876A (en) * 2017-11-24 2018-05-08 安徽睿知信信息科技有限公司 A kind of nano-sized carbon and InVO4-TiO2The haze cleanser of coupling

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