CN101085465A - Method for preparing titanium dioxide hollow sphere containing gold nano particles - Google Patents
Method for preparing titanium dioxide hollow sphere containing gold nano particles Download PDFInfo
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- CN101085465A CN101085465A CN 200710023240 CN200710023240A CN101085465A CN 101085465 A CN101085465 A CN 101085465A CN 200710023240 CN200710023240 CN 200710023240 CN 200710023240 A CN200710023240 A CN 200710023240A CN 101085465 A CN101085465 A CN 101085465A
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Abstract
The making of titania hollow ball with nanometer grains features int eh making of carbon balls with gold core through high temperature seal conditions, picking out 1 g of the said carbon ball to scatter inside the water free ethandiol or glycerin in 2.5-20g/L, dropping 30-500 micro litter aqua fortis of 0.01-2 m/l, then butyl titanate 500-5000 micro litter in 0.1-3m/l in the speed of 10-100 micro litter per minute, flowing in the silicon oil for 60-180 minutes, depositing in 600-800deg.C and calcining for 60-200 mintues. The sealed hollow ball has seal volume providing the movement of the gold core. Size of the hollow ball inside gold core and shell thickness can be adjusted.
Description
Technical field:
The invention belongs to the nano material preparation technical field, particularly include the preparation method of the titanium dioxide hollow ball of gold nano grain.
Background technology:
U.S.'s " science " magazine (Science, 2004 the 3rd volumes, 711-714 page or leaf) has been reported and has been utilized the technology that is similar to Tyndall effect, successfully prepares the nucleocapsid structure that cobalt oxide or cobaltous selenide hollow ball structure and oxidation crust of cobalt coat platinum grain nuclear.But the predecessor that this hollow ball adopts is eight carbonyl cobalts, the cost height, and toxicity is big, is not suitable for large-scale industrial production.
American Chemical Society " youth Ge Miuer " magazine (Langumir,, 22 volumes, 1307-1310 page or leaf in 2006) has been reported employing enclosed system Hydrolyze method, prepares uniform coated by titanium dioxide nano silver wire nucleocapsid structure being lower than 200 ℃.But the linear nucleus shell structure of the method preparation is neither enclosed construction, and there is certain difficulty in also non-hollow linear nucleus shell result for the application in fields such as medicine releases later on.
" JACS " (Journal Of The American Chemical Society,, 125 volumes, 2384-2385 page or leaf in 2003) reported and utilized titanium dioxide to make to sacrifice the macromolecule nucleocapsid structure that template prepares removable kernel gold grain.But because the shell high molecular functional of product is single, kernel gold grain size is certain, is unfavorable for the later application of product.
Summary of the invention:
The present invention proposes the method that a kind of simple preparation includes the titanium dioxide hollow ball of gold nano grain, to overcome the above-mentioned shortcoming of prior art.This preparation method does not see bibliographical information so far.
This preparation method who includes the titanium dioxide hollow ball of gold nano grain, the 0.2g saccharide compound is soluble in water to be made into the solution that concentration is the 0.005-0.04 mol according to getting earlier, Dropwise 35 0-2500 microlitre concentration is the aqueous solution of chloraurate of 0.01-0.4 mol again, in 160-200 ℃ of confined reaction 6-20 hour, obtain containing the carbon ball of gold nuclear; It is characterized in that: get this carbon ball 1g that contains gold nuclear and be dispersed in no water glycol or the anhydrous glycerine by 2.5-20g/L, drip the salpeter solution of 30-500 microlitre concentration earlier in the 0.01-2 mol, speed dropping concentration with the 10-100 mul/min is the tetra-n-butyl titanate 500-5000 microlitre of 0.1-3 mol again, 100-180 ℃ of silicone oil bath backflow 60-180 minute, the gained precipitation promptly gets end product through 600-800 ℃ of calcining 60-200 minute.
Described saccharide compound comprises glucose, maltose or sucrose.
The carbon ball of preparation monodispersity is realized for 160-200 ℃ by the control reaction temperature in the inventive method.If reaction temperature is lower than 160 ℃, then can not get the carbon ball, but obtain a large amount of carbon fibers; If reaction temperature is higher than 200 ℃, then can coking serious, cause the symbiosis of carbon ball and carbon fiber.
The formation of prepared titanium dioxide hollow ball shell is to lean against to contain gold nuclear carbon ball concentration control tetra-n-butyl titanate when 2.5-20g/L addition at the 500-5000 microlitre with control rate of addition and realize in the 10-100 mul/min in the inventive method.If the addition of tetra-n-butyl titanate is below 500 microlitres, then outer field titanium dioxide shell does not form, and can not form hollow ball; If it is not in carbon outer surface of ball deposition that the addition of tetra-n-butyl titanate more than 5000 microlitres, then can cause titanium dioxide because of titanium dioxide is excessive, but forms titanium dioxide granule.If rate of addition less than 10 mul/min, then can cause forming hollow ball; If rate of addition greater than 100 mul/min, then can make the titanium dioxide hydrolysis too fast, cause forming a large amount of titanium dioxide granules.
The thickness of titanium dioxide hollow ball shell is regulated and control at 60-180 minute with return time at 100-180 ℃ by regulating reflux temperature among the preparation method of the present invention.If reflux temperature is lower than 100 ℃, then can cause the hydrolysis rate of tetra-n-butyl titanate slack-off, can not be adsorbed on carbon ball outer wall well, thereby form a large amount of particles; If reflux temperature is higher than 180 ℃, then can cause the hydrolysis rate of tetra-n-butyl titanate too fast, have little time to be adsorbed on carbon ball outer wall, thereby also form a large amount of particles.If return time is shorter than 60 minutes, can cause the tetra-n-butyl titanate hydrolysis incomplete, can not be adsorbed on carbon ball outer wall well fully, thereby form a large amount of particles; And return time surpasses 180 minutes and there is no need, because positive butyl titanate this moment complete hydrolysis, overlong time only can cause the waste of the energy.
The present invention is controlled at calcination time 60-200 minute.If be shorter than 60 minutes, then Zhong Jian carbon ball can not be removed fully, can not form hollow ball structure; After 200 minutes, the carbon ball is removed fully, and overlong time only can cause the waste of the energy, there is no need.
Calcining heat among the present invention is controlled at 600-800 ℃.Temperature is lower than 600 ℃, and the carbon ball can not be removed in completing combustion, can not form hollow ball structure; Be higher than 800 ℃ of wastes that can cause the energy, there is no need.
Because the present invention utilizes the functional group absorption tetra-n-butyl titanate predecessor on carbon ball surface, adopts enclosed system pyrohydrolysis tetra-n-butyl titanate than prior art, utilizes technique of backflow can more accurately control the hydrolysis rate of tetra-n-butyl titanate.The inventive method can prepare the titanium dioxide hollow ball that includes gold grain, and this hollow ball is a closed structure, and inside cavity has the airtight volume that can move for gold nuclear, this for this reason product provide condition in the application that medicine discharges the field.
Description of drawings:
Fig. 1 is the X diffraction pattern (XRD) of embodiment 1 product;
Fig. 2 is field emission scanning electron microscope (SEM) photo of embodiment 1 product;
Fig. 3 is transmission electron microscope (TEM) photo of embodiment 1 product;
Fig. 4 is the EDAX figure of square frame chosen area among Fig. 3; A among the figure, B, C peak are the detected peaks of gold grain.
Fig. 5 is transmission electron microscope (TEM) photo of embodiment 2 products.
Fig. 6 is transmission electron microscope (TEM) photo of embodiment 3 products.
The specific embodiment:
Below in conjunction with embodiment the present invention is done specific description.
Embodiment 1: preparation includes gold grain and outer wall thickness is the 80nm titanium dioxide hollow ball:
0.2 gram glucose is dissolved in 200 ml waters, stir after 15 minutes and to drip 2500 microlitres to rise concentration be 0.01 mol chlorauric acid solution, stirred again 10 minutes, being transferred to 45 milliliters then has in the teflon-lined autoclave, 160 ℃ of confined reactions 20 hours, products therefrom was dried behind three centrifuge washings.
Get the carbon ball that includes golden kernel 1 gram of above-mentioned preparation, be dispersed in 400 milliliters of no water glycols, Dropwise 5 00 microlitre concentration is the nitric acid of 0.01 mol, stir after 10 minutes, speed Dropwise 5 000 microlitre concentration with 100 mul/min is the tetra-n-butyl titanate of 3 mol, refluxed 60 minutes 180 ℃ of oil baths, in 600 ℃ of calcinings 200 minutes, collect last product and be used for characterizing and test behind the centrifuge washing.
Adopt Philip X ' Pert PRO SUPER X-ray diffractometer (XRD), the H-800 of Hitachi transmission electron microscope (TEM) and the H-2010 of Hitachi high resolution transmission electron microscopy (HRTEM) that sample is carried out elementary composition analysis (EDAX) and field emission scanning electron microscope (SEM) sign respectively:
Fig. 1 is the X diffraction pattern (XRD) of the product for preparing in the present embodiment, with the XRD standard diagram relatively, show that what obtain is titanium dioxide; The minimum detectable activity that is lower than diffractometer owing to the amount of simple substance gold does not have demonstration, can detect by follow-up elementary composition analysis (EDAX).
Fig. 2 is field emission scanning electron microscope (SEM) photo of present embodiment product, the size that shows hollow ball in 350 nanometers between 550 nanometers, wherein most diameters in 400 nanometers between 500 nanometers.
Fig. 3 is the transmission electron microscope photo of present embodiment product, shows to contain movably gold grain kernel in the preparation-obtained titanium dioxide hollow ball, and it is of a size of the 20-25 nanometer, wherein the EDAX test zone of the zone of choosing in the square frame for going on foot down.
Fig. 4 is the EDAX figure of square frame chosen area among Fig. 3, and the A among the figure, B, C peak are the feature detection peak of gold grain.This figure shows that this zone of kernel contains gold grain.
By the result of above-mentioned detection and sign as can be known, what prepare in the present embodiment includes the 20-25nm gold grain, and the titanium dioxide outer casing thickness is the 40-50 nanometer, and whole sphere diameter is that 400 nanometers are to the titanium dioxide hollow ball between 500 nanometers.
Embodiment 2: preparation includes gold grain and outer wall thickness is the 15nm titanium dioxide hollow ball:
Carbon source is example with sucrose in the present embodiment, 0.2 gram sucrose is dissolved in 25 ml waters, stir that Dropwise 35 0 microlitre concentration is the gold chloride of 0.4 mol after 15 minutes, stirred again 10 minutes, being transferred to 45 milliliters then has in the teflon-lined autoclave, 200 ℃ of confined reactions 6 hours, product was dried behind three centrifuge washings.
The carbon ball that includes golden kernel 1 gram of getting above-mentioned preparation is dispersed in 50 milliliters of anhydrous glycerine, dripping 30 microlitre concentration is the nitric acid of 2 mol, stir after 10 minutes, with 10 mul/min speed Dropwise 5s, 00 microlitre concentration is the tetra-n-butyl titanate of 0.1 mol, in 100 ℃ of oil baths, refluxed 180 minutes, in 800 ℃ of calcinings 60 minutes, collect last product and be used for characterizing and test behind the centrifuge washing.
Adopt the H-800 of Hitachi transmission electron microscope (TEM), sample characterized:
Fig. 5 is the TEM figure of present embodiment product, shows and contains a gold grain that movably is of a size of the 20-25 nanometer in the prepared titanium dioxide hollow ball, and the hollow ball outer casing thickness is the 15-20 nanometer, and diameter is the titanium dioxide hollow ball of 350-450 nanometer.
Embodiment 3: preparation includes gold grain and outer wall thickness is the 45nm titanium dioxide hollow ball:
Carbon source is example with maltose in the present embodiment, 0.2 gram maltose is dissolved in 100 ml waters, stirring and dripping 1200 microlitre concentration after 15 minutes is the gold chloride of 0.1 mol, stirred again 10 minutes, being transferred to 45 milliliters then has in the teflon-lined autoclave, 180 ℃ of confined reactions 10 hours, product was dried behind three centrifuge washings.
The carbon ball that includes golden kernel 1 gram of getting above-mentioned preparation is dispersed in 100 milliliters of no water glycols, dripping 200 microlitre concentration is the nitric acid of 0.1 mol, stir after 10 minutes, dripping 2000 microlitre concentration with the speed of 50 mul/min is the tetra-n-butyl titanate of 1 mol, in 150 ℃ of oil baths, refluxed 120 minutes, in 700 ℃ of calcinings 90 minutes, collect last product and be used for characterizing and test behind the centrifuge washing.
Adopt the H-800 of Hitachi transmission electron microscope (TEM), sample characterized:
Fig. 6 is the TEM figure of present embodiment product, shows and contains a gold grain that movably is of a size of the 50-60 nanometer in the prepared titanium dioxide hollow ball, and the hollow ball outer casing thickness is the 30-35 nanometer, and sphere diameter is the titanium dioxide hollow ball of 200-350 nanometer.
Claims (2)
1. preparation method who includes the titanium dioxide hollow ball of gold nano grain, the 0.2g saccharide compound is soluble in water to be made into the solution that concentration is the 0.005-0.04 mol according to getting earlier, Dropwise 35 0-2500 microlitre concentration is the aqueous solution of chloraurate of 0.01-0.4 mol again, in 160-200 ℃ of confined reaction 6-20 hour, obtain containing the carbon ball of gold nuclear; It is characterized in that: get this carbon ball 1g that contains gold nuclear and be dispersed in no water glycol or the anhydrous glycerine by 2.5-20g/L, drip the salpeter solution of 30-500 microlitre concentration earlier in the 0.01-2 mol, speed dropping concentration with the 10-100 mul/min is the tetra-n-butyl titanate 500-5000 microlitre of 0.1-3 mol again, 100-180 ℃ of silicone oil bath backflow 60-180 minute, the gained precipitation promptly gets end product through 600-800 ℃ of calcining 60-200 minute.
2. the preparation method of titanium dioxide hollow ball according to claim 1 is characterised in that described saccharide compound comprises glucose, maltose or sucrose.
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Cited By (10)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102672169A (en) * | 2012-06-07 | 2012-09-19 | 北京科技大学 | Method for preparing gold/titanium dioxide core-shell nanoparticle |
| CN102806055A (en) * | 2012-07-26 | 2012-12-05 | 华中科技大学 | Method for preparing core-shell type composite with nano material coated with titanium dioxide |
| CN103241763A (en) * | 2013-04-15 | 2013-08-14 | 天津大学 | Preparation method of gold/metal oxide core-shell structural nano material |
| CN103252502A (en) * | 2012-02-17 | 2013-08-21 | 国家纳米科学中心 | Hollow core shell structure Au@TiO2 nano-composite material and preparation method thereof |
| CN106115779A (en) * | 2016-07-07 | 2016-11-16 | 西安交通大学苏州研究院 | A kind of hollow nano-TiO2the preparation method of bag carbon Yolk shell structure |
| CN106890638A (en) * | 2017-03-01 | 2017-06-27 | 海南大学 | A kind of gold/nano titania compound and its preparation method and application |
| CN107140606A (en) * | 2017-05-25 | 2017-09-08 | 中国科学院广州能源研究所 | A kind of preparation method of oxide hollow microsphere |
| CN108615884A (en) * | 2018-04-25 | 2018-10-02 | 国家纳米科学中心 | A kind of KFeF of hollow structure3Nano material and its preparation method and application |
| CN108956715A (en) * | 2018-07-19 | 2018-12-07 | 东北大学 | A kind of Au@WO3Core-shell nanospheres and its preparation method and application |
| CN110882725A (en) * | 2019-12-06 | 2020-03-17 | 北京科技大学 | Metal organic framework loaded titanium dioxide photocatalytic material and preparation method thereof |
Family Cites Families (2)
| Publication number | Priority date | Publication date | Assignee | Title |
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| JP2001513697A (en) * | 1997-02-24 | 2001-09-04 | スーペリア マイクロパウダーズ リミテッド ライアビリティ カンパニー | Aerosol method and apparatus, particle product, and electronic device manufactured from the particle product |
| CN100471601C (en) * | 2006-10-24 | 2009-03-25 | 中国科学技术大学 | Synthetic method for silicon dioxide hollow bal lincluding noble metal nano particles |
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2007
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Cited By (15)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN103252502A (en) * | 2012-02-17 | 2013-08-21 | 国家纳米科学中心 | Hollow core shell structure Au@TiO2 nano-composite material and preparation method thereof |
| CN103252502B (en) * | 2012-02-17 | 2015-07-15 | 国家纳米科学中心 | Hollow core shell structure Au@TiO2 nano-composite material and preparation method thereof |
| CN102672169A (en) * | 2012-06-07 | 2012-09-19 | 北京科技大学 | Method for preparing gold/titanium dioxide core-shell nanoparticle |
| CN102672169B (en) * | 2012-06-07 | 2014-04-02 | 北京科技大学 | Method for preparing gold/titanium dioxide core-shell nanoparticle |
| CN102806055A (en) * | 2012-07-26 | 2012-12-05 | 华中科技大学 | Method for preparing core-shell type composite with nano material coated with titanium dioxide |
| CN103241763A (en) * | 2013-04-15 | 2013-08-14 | 天津大学 | Preparation method of gold/metal oxide core-shell structural nano material |
| CN106115779A (en) * | 2016-07-07 | 2016-11-16 | 西安交通大学苏州研究院 | A kind of hollow nano-TiO2the preparation method of bag carbon Yolk shell structure |
| CN106890638A (en) * | 2017-03-01 | 2017-06-27 | 海南大学 | A kind of gold/nano titania compound and its preparation method and application |
| CN106890638B (en) * | 2017-03-01 | 2019-06-11 | 海南大学 | A kind of gold/nano titania compound and its preparation method and application |
| CN107140606A (en) * | 2017-05-25 | 2017-09-08 | 中国科学院广州能源研究所 | A kind of preparation method of oxide hollow microsphere |
| CN108615884A (en) * | 2018-04-25 | 2018-10-02 | 国家纳米科学中心 | A kind of KFeF of hollow structure3Nano material and its preparation method and application |
| CN108615884B (en) * | 2018-04-25 | 2020-10-23 | 国家纳米科学中心 | KFeF with hollow structure3Nano material and preparation method and application thereof |
| CN108956715A (en) * | 2018-07-19 | 2018-12-07 | 东北大学 | A kind of Au@WO3Core-shell nanospheres and its preparation method and application |
| CN108956715B (en) * | 2018-07-19 | 2020-10-02 | 东北大学 | Au @ WO3Core-shell structure nanosphere and preparation method and application thereof |
| CN110882725A (en) * | 2019-12-06 | 2020-03-17 | 北京科技大学 | Metal organic framework loaded titanium dioxide photocatalytic material and preparation method thereof |
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