CN103112863A - Hollow porous silica nano cuboid particle and preparation method thereof - Google Patents
Hollow porous silica nano cuboid particle and preparation method thereof Download PDFInfo
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- CN103112863A CN103112863A CN2013100841587A CN201310084158A CN103112863A CN 103112863 A CN103112863 A CN 103112863A CN 2013100841587 A CN2013100841587 A CN 2013100841587A CN 201310084158 A CN201310084158 A CN 201310084158A CN 103112863 A CN103112863 A CN 103112863A
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Abstract
The invention discloses a hollow porous silica nano cuboid particle and a preparation method thereof. The preparation method is characterized by comprising the following steps: slowly dropwise adding a cobaltous acetate aqueous solution into an aqueous solution which contains potassium cobaltocyanade and polyvinylpyrrolidone, stirring and then standing; dispersing cobalt thiocyanate and tetraethyl orthosilicate which are obtained through separation in ethanol, dripping ammonia water, thermally insulating in a water bath at 30-45 DEG C for at least 4 hours, vacuum drying and calcinating cobalt thiocyanate nanoparticles wrapped by silica for one hour at 400-600 DEG C; and dispersing cobaltosic oxide nanoparticles wrapped by silica in a hydrochloric acid solution, putting the mixture in a reactor lined by polytetrafluoroethylene to react for 6 hours at 100-160 DEG C, centrifugally separating to obtain the hollow porous silica nano cuboid particles, wherein the size of the particles is 150nm, the shell layer thickness is 20 nm, and irregular cracks are distributed on the surface. The preparation method is simple, produced particles are uniform in appearance, and the nano cuboid particle has an application prospect in electrochemical energy storage.
Description
Technical field
The invention belongs to the silica nano material preparing technical field, particularly hollow porous silica nanometer cubic block particle and preparation method thereof.
Background technology
Silicon-dioxide is a kind of material that is widespread in nature.Due to its stable chemical nature, be easy to controlledly synthesis, have good biocompatibility, and with low cost, therefore at chemical industry, electronic industry, food and medicine industry etc. all is widely used.Holland " applied surface science " magazine (AppliedSurfaceScience, 2008, the 254th volume, 3774 pages) reported the application of silica membrane as lithium ion battery negative material, it adopts the silica membrane of thick 400 nanometers of vacuum magnetic-control sputtering technology preparation to have the first discharge capacity of 539 MAh/gs, and circulating still has later on 416mAhg 100 times
-1Discharge capacity." electrochemistry communication " magazine (Electrochem.Commun. of Holland, 2008, the 10th volume, 1876 pages) introduced the preparation of hard carbon clad nano silicon dioxide granule and as the application of lithium ion battery negative material, this material still has 630mAhg after discharging and recharging for 15 times
-1Discharge capacity.After 500 circulations of the silicon dioxide hollow nanometer ball of Britain's " materials chemistry magazine " (J.Mater.Chem.,, the 21st volume, 13881 pages in 2011) report, discharge capacity is 334mAhg
-1, after quartzy 250 circulations of the grinding of Britain's " energy and environment science " magazine (EnergyEnviron.Sci.,, the 5th volume, 6895 pages in 2012) report, discharge capacity is 734mAhg
-1But due to the cause that has volumetric expansion and the irreversible silicic acid lithium salts of generation in charge and discharge process, the theoretical capacity 1965mAhg of the discharge capacity of these materials and silicon-dioxide
-1Also there is a big difference.And hollow porous nano material is due to unique hollow porous structure being arranged, can effectively alleviate the Volumetric expansion of electrode materials in charge and discharge process, and can shorten the migration path of lithium ion in electrode, improve the lithium ion rate of migration, improve the stability that discharges and recharges of electrode.Therefore, need the method for the synthetic hollow porous Nano particles of silicon dioxide of the new simple and efficient of design to prepare the Nano particles of silicon dioxide with excellent charge-discharge performance.
Summary of the invention
The objective of the invention is to propose a kind of hollow porous silica nanometer cubic block particle and preparation method thereof, to overcome the defects of prior art, alleviate the Volumetric expansion of electrode materials in charge and discharge process, improve charge/discharge capacity, thereby be applied to the electrochemical energy storage aspect.
The preparation method of hollow porous silica nanometer cubic block particle of the present invention is characterized in that: 10mL is contained 18mg cobaltous acetate (Co (CH
3COO)
2) the aqueous solution slowly be added drop-wise to 10mL and contain 17mg cobalt potassium cyanate (K
3[Co (CN)
6]) and the aqueous solution of 0.3g polyvinylpyrrolidone (PVP) in, standingly after stirring is no less than 1 hour, centrifugation obtains cobalt cyanic acid cobalt; Getting cobalt cyanic acid cobalt and the 0.3-0.4mL tetraethyl orthosilicate that 50-70mg should make is dispersed in 30mL ethanol, splash into the 4-6mL mass concentration after dispersed with stirring and be 28% ammoniacal liquor, then the water-bath insulation that this mixing solutions is placed in 30-45 ℃ is no less than 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica; With being no less than 1 hour 400-600 ℃ of calcining after above-mentioned particle drying, obtain the cobaltosic oxide nanoparticles of coated with silica; Get this cobaltosic oxide nanoparticles of 30-50mg, being dispersed in 30mL concentration is 3-5molL
-1Hydrochloric acid soln in, be placed in the teflon-lined reactor, be no less than 6 hours 100-160 ℃ of reaction, with the product centrifugation, obtain hollow porous silica nanometer cubic block particle after reaction finishes.
The hollow porous silica nanometer cubic block particle that adopts aforesaid method to prepare, its particle diameter is at 150nm, and shell thickness is 20nm, and profile is the shape of cubic block, and inside is hollow structure, and surface arrangement zigzag cracks.
Compared with prior art, the invention has the advantages that:
The inventive method has been taked with coated with silica outside template, remove again template and obtain hollow porous silica nanometer cubic block particle, by coating---etching method prepares hollow porous silica nanometer piece, owing to having the pattern of homogeneous as the cobalt cyanic acid cobalt nanometer particle of precursor, therefore can obtain the hollow silicon dioxide nano cubic block particle of same pattern homogeneous.Simultaneously, due to the step that calcining and hydrothermal treatment consists are arranged, can form zigzag cracks on the hollow silicon dioxide surface like this in etched process, make the silica nanometer piece become vesicular structure.And the technique of present existing preparation porous silicon dioxide nano particle is difficult to obtain such structure.
The hollow porous silica nanometer piece particle that adopts the inventive method to obtain, owing to having unique hollow porous structure, can effectively alleviate the Volumetric expansion of electrode materials in charge and discharge process, improve the cyclical stability of electrode, simultaneously owing to having larger specific surface, shorten the migration path of lithium ion in electrode, improved the lithium ion rate of migration, made silica nanometer cubic block particle have excellent charge-discharge performance.
Description of drawings
Fig. 1 is the X-ray diffractogram of embodiment 1 hollow core porous silicon dioxide nano cubic block particle;
Fig. 2 is the infrared spectrogram of embodiment 1 hollow core porous silicon dioxide nano cubic block particle;
Fig. 3 is the low range stereoscan photograph of embodiment 1 hollow core porous silicon dioxide nano cubic block particle;
Fig. 4 is the high magnification stereoscan photograph of embodiment 1 hollow core porous silicon dioxide nano cubic block particle;
Fig. 5 is the transmission electron microscope photo of embodiment 1 hollow core porous silicon dioxide nano cubic block particle;
Fig. 6 is the curve of charge/discharge capacity, enclosed pasture efficient and the cycle index of test battery in embodiment 2.
Embodiment 1: prepare hollow porous silica nanometer cube cubic block particle
10mL is contained 18mg cobaltous acetate (Co (CH
3COO)
2) the aqueous solution be added drop-wise to 10mL and contain 17mg cobalt potassium cyanate (K
3[Co (CN)
6]) and the aqueous solution of the polyvinylpyrrolidone (PVP) of 0.3g in, after magnetic agitation, static 24 hours, centrifugation obtained cobalt cyanic acid cobalt.Cobalt cyanic acid cobalt particle and 0.35ml tetraethyl orthosilicate that 60mg should be made are dispersed in 30ml ethanol, pour in Erlenmeyer flask, after magnetic agitation ten minutes, slowly splash into the 6ml mass concentration and be 28% ammoniacal liquor, after this water-bath that this mixing solutions is placed in 45 ℃ is incubated 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica.To calcine 1 hour under 550 ℃ after this product vacuum-drying, cobalt cyanic acid cobalt can be converted into tricobalt tetroxide, therefore can obtain the cobaltosic oxide nanoparticles of coated with silica.Get this particle of 30mg, being dispersed in the 30ml volumetric molar concentration is 5molL
-1Hydrochloric acid soln in, being placed in volume is the teflon-lined reactor of 50ml, reaction is 6 hours under 110 ℃, with the product centrifugation, can obtain hollow porous silica nanometer cubic block particle after reaction finishes.
The composition of particle can be determined by X-ray diffraction and infrared spectra.Fig. 1 is the X-ray diffractogram of the present embodiment hollow core porous silicon dioxide nano cubic block particle.As shown in Figure 1, the peak of a broadening is arranged near 20 °, show in product and contain amorphous compound, be i.e. soft silica.Fig. 2 is the infrared spectrogram of hollow porous silica nanometer cubic block particle.As can be seen from Figure 2, at 1071cm
-1There is the absorption peak of a broadening at the place, shows the existence of soft silica.
Fig. 3 is the low range stereoscan photograph of the present embodiment hollow core porous silicon dioxide nano cubic block particle.Low range stereoscan photograph by (Fig. 3) product can find out, particle has particle diameter and the shape of homogeneous, and particle diameter is about 150nm, and profile is a cube cubic block particle.Fig. 4 is the high magnification stereoscan photograph of the present embodiment hollow core porous silicon dioxide nano cubic block particle.Can be seen by this high magnification stereoscan photograph, zigzag cracks in the surface arrangement of particle, and can see inner hollow structure by the damaged particle of part.Fig. 5 is the transmission electron microscope photo of the present embodiment hollow core porous silicon dioxide nano cubic block particle, the hollow structure that can clearly see product from this transmission electron microscope photo, and the thickness of shell is 20nm as can be known.
The application of the hollow porous silica nanometer cubic block of embodiment 2. particle in lithium ion battery negative
Hollow porous silica nanometer cubic block particle and the acetylene black that will make by method in embodiment 1, polyvinylidene difluoride (PVDF) (PVDF) 5:3:2 in mass ratio is mixed and made into the muddy material, material is evenly coated on Copper Foil, after oven dry, Copper Foil is cut into the circular electric pole piece that diameter is 14mm in the baking oven of 100 ℃.The electrode slice of hollow porous silicon dioxide nano cubic block particle is arranged as anodal take load, the circular metal lithium sheet take diameter as 14mm is negative pole, take concentration as 1mol/L lithium hexafluoro phosphate (LiPF
6) ethylene carbonate (EC) and diethyl carbonate (DEC) (mass ratio EC:DEC=1:1) solution be electrolytic solution, the circular polypropylene film take diameter as 16mm is barrier film.Be assembled into button cell in the glove box of argon atmosphere protection.Battery test system is NewareBTS-610, and discharging current is 100mAg
-1Fig. 6 is the curve of charge/discharge capacity, enclosed pasture efficient and the cycle index of test battery in the present embodiment.The discharge capacity first of test battery has reached 3084mAhg
– 1, the initial charge amount has reached 1457mAhg
– 1, having circulated after 30 times, 919mAhg is arranged still
– 1Discharge capacity.This capacity is far above the theoretical capacity (372mAhg of existing commercial graphite cathode
– 1).And the enclosed pasture efficient of electrode maintains more than 90% after the 5th circulation, has shown that hollow porous silica nanometer has excellent charge-discharge performance and stability.
Embodiment 3. uses the tetraethyl orthosilicate of different amounts to prepare hollow porous silicon-dioxide cubic block particle
60mg is dispersed in 30ml ethanol according to the cobalt cyanic acid cobalt that makes in embodiment 1 and 0.4ml tetraethyl orthosilicate, pour in Erlenmeyer flask, after magnetic agitation ten minutes, slowly splash into the 6ml mass concentration and be 28% ammoniacal liquor, after this water-bath that this mixing solutions is placed in 45 ℃ is incubated 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica.To calcine 1 hour under 550 ℃ after this product vacuum-drying, cobalt cyanic acid cobalt can be converted into tricobalt tetroxide, therefore can obtain the cobaltosic oxide nanoparticles of coated with silica.Get this particle of 30mg, being dispersed in the 30ml volumetric molar concentration is 5molL
-1Hydrochloric acid soln in, being placed in volume is the teflon-lined reactor of 50ml, reaction is 6 hours under 110 ℃, with the product centrifugation, can obtain hollow porous silica nanometer cubic block particle after reaction finishes.The pattern of product is similar to the product appearance in embodiment 1, and has the part particle that reunion has occured.
60mg is dispersed in 30ml ethanol according to the cobalt cyanic acid cobalt particle that makes in embodiment 1 and 0.35ml tetraethyl orthosilicate, pour in Erlenmeyer flask, after magnetic agitation ten minutes, slowly splash into the 4ml mass concentration and be 28% ammoniacal liquor, after this water-bath that this mixing solutions is placed in 45 ℃ is incubated 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica.To calcine 1 hour under 550 ℃ after this product vacuum-drying, cobalt cyanic acid cobalt can be converted into tricobalt tetroxide, therefore can obtain the cobaltosic oxide nanoparticles of coated with silica.Get this particle of 30mg, being dispersed in the 30ml volumetric molar concentration is 5molL
-1Hydrochloric acid soln in, being placed in volume is the teflon-lined reactor of 50ml, reaction is 6 hours under 110 ℃, with the product centrifugation, can obtain hollow porous silica nanometer cubic block particle after reaction finishes.The pattern of product is similar to the product appearance in embodiment 1.
Embodiment 5. uses different calcining temperatures to prepare hollow porous silicon-dioxide cubic block particle
60mg is dispersed in 30ml ethanol according to the cobalt cyanic acid cobalt particle that makes in embodiment 1 and 0.35ml tetraethyl orthosilicate, pour in Erlenmeyer flask, after magnetic agitation ten minutes, slowly splash into the 6ml mass concentration and be 28% ammoniacal liquor, after this water-bath that this mixing solutions is placed in 45 ℃ is incubated 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica.To calcine 1 hour under 400 ℃ after this product vacuum-drying, cobalt cyanic acid cobalt can be converted into tricobalt tetroxide, therefore can obtain the cobaltosic oxide nanoparticles of coated with silica.Get this particle of 30mg, being dispersed in the 30ml volumetric molar concentration is 5molL
-1Hydrochloric acid soln in, being placed in volume is the teflon-lined reactor of 50ml, reaction is 6 hours under 110 ℃, with the product centrifugation, can obtain hollow porous silica nanometer cubic block particle after reaction finishes.The pattern of product is similar to the product appearance in embodiment 1.
60mg is dispersed in 30ml ethanol according to the cobalt cyanic acid cobalt particle that makes in embodiment 1 and 0.35ml tetraethyl orthosilicate, pour in the Erlenmeyer flask that volume is 50ml, after magnetic agitation ten minutes, slowly splash into the 6ml mass concentration and be 28% ammoniacal liquor, after this water-bath that this mixing solutions is placed in 45 ℃ is incubated 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica.To calcine 1 hour under 550 ℃ after this product vacuum-drying, cobalt cyanic acid cobalt can be converted into tricobalt tetroxide, therefore can obtain the cobaltosic oxide nanoparticles of coated with silica.Get this particle of 30mg, being dispersed in the 30ml volumetric molar concentration is 5molL
-1Hydrochloric acid soln in, being placed in volume is the teflon-lined reactor of 50ml, reaction is 6 hours under 160 ℃, with the product centrifugation, can obtain hollow porous silica nanometer cubic block particle after reaction finishes.The pattern of product is similar to the product appearance in embodiment 1, but damaged particle is more.
Embodiment 7: use different calcining temperatures to prepare hollow porous silica nanometer cubic block particle
60mg is dispersed in 30mL ethanol according to the cobalt cyanic acid cobalt particle that makes in embodiment 1 and 0.35mL tetraethyl orthosilicate, pour in Erlenmeyer flask, after magnetic agitation ten minutes, slowly splash into the 6mL mass concentration and be 28% ammoniacal liquor, after this water-bath that this mixing solutions is placed in 45 ℃ is incubated 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica.To calcine 1 hour under 400 ℃ after this product vacuum-drying, cobalt cyanic acid cobalt can be converted into tricobalt tetroxide, therefore can obtain the cobaltosic oxide nanoparticles of coated with silica.Get this particle of 30mg, being dispersed in the 30mL volumetric molar concentration is 5molL
-1Hydrochloric acid soln in, being placed in volume is the teflon-lined reactor of 50mL, reaction is 6 hours under 110 ℃, with the product centrifugation, can obtain hollow porous silica nanometer cubic block particle after reaction finishes.The pattern of product is similar to the product appearance in embodiment 1.
Embodiment 8: use the cobaltosic oxide nanoparticles of the coated with silica of different amounts to prepare hollow porous silica nanometer cubic block particle
60mg is dispersed in 30mL ethanol according to the cobalt cyanic acid cobalt particle that makes in embodiment 1 and 0.35mL tetraethyl orthosilicate, pour in the Erlenmeyer flask that volume is 50mL, after magnetic agitation ten minutes, slowly splash into the 6mL mass concentration and be 28% ammoniacal liquor, after this water-bath that this mixing solutions is placed in 45 ℃ is incubated 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica.To calcine 1 hour under 550 ℃ after this product vacuum-drying, cobalt cyanic acid cobalt can be converted into tricobalt tetroxide, therefore can obtain the cobaltosic oxide nanoparticles of coated with silica.Get this particle of 50mg, being dispersed in the 30mL volumetric molar concentration is 5molL
-1Hydrochloric acid soln in, being placed in volume is the teflon-lined reactor of 50mL, reaction is 6 hours under 110 ℃, with the product centrifugation, can obtain hollow porous silica nanometer cubic block particle after reaction finishes.The pattern of product is similar to the product appearance in embodiment 1.
Embodiment 9: use different hydrothermal treatment consists temperature to prepare hollow porous silica nanometer cubic block particle
60mg is dispersed in 30mL ethanol according to the cobalt cyanic acid cobalt particle that makes in embodiment 1 and 0.35mL tetraethyl orthosilicate, pour in the Erlenmeyer flask that volume is 50mL, after magnetic agitation ten minutes, slowly splash into the 6mL mass concentration and be 28% ammoniacal liquor, after this water-bath that this mixing solutions is placed in 45 ℃ is incubated 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica.To calcine 1 hour under 550 ℃ after this product vacuum-drying, cobalt cyanic acid cobalt can be converted into tricobalt tetroxide, therefore can obtain the cobaltosic oxide nanoparticles of coated with silica.Get this particle of 30mg, being dispersed in the 30mL volumetric molar concentration is 5molL
-1Hydrochloric acid soln in, being placed in volume is the teflon-lined reactor of 50mL, reaction is 6 hours under 160 ℃, with the product centrifugation, can obtain hollow porous silica nanometer cubic block particle after reaction finishes.The pattern of product is similar to the product appearance in embodiment 1, but damaged particle is more.
Embodiment 10: use different hydrothermal treatment consists temperature to prepare hollow porous silica nanometer cubic block particle
60mg is dispersed in 30mL ethanol according to the cobalt cyanic acid cobalt particle that makes in embodiment 1 and 0.35mL tetraethyl orthosilicate, pour in the Erlenmeyer flask that volume is 50mL, after magnetic agitation ten minutes, slowly splash into the 6mL mass concentration and be 28% ammoniacal liquor, after this water-bath that this mixing solutions is placed in 45 ℃ is incubated 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica.To calcine 1 hour under 550 ℃ after this product vacuum-drying, cobalt cyanic acid cobalt can be converted into tricobalt tetroxide, therefore can obtain the cobaltosic oxide nanoparticles of coated with silica.Get this particle of 30mg, being dispersed in the 30mL volumetric molar concentration is 3molL
-1Hydrochloric acid soln in, being placed in volume is the teflon-lined reactor of 50mL, reaction is 6 hours under 110 ℃, with the product centrifugation, can obtain hollow porous silica nanometer cubic block particle after reaction finishes.The pattern of product is similar to the product appearance in embodiment 1
In a word, the present invention is simple, and repeatability is high, can produce hollow porous silica nanometer cubic block particle in enormous quantities, and resulting particle has the pattern of homogeneous and unique structure, can be applied at aspects such as electrochemical energy storages.
Claims (2)
1. the preparation method of a hollow porous silica nanometer cubic block particle, it is characterized in that: the aqueous solution that 10mL is contained the 18mg cobaltous acetate slowly is added drop-wise in the aqueous solution that 10mL contains 17mg cobalt potassium cyanate and 0.3g polyvinylpyrrolidone, stirring is standing afterwards is no less than 1 hour, and centrifugation obtains cobalt cyanic acid cobalt; Getting cobalt cyanic acid cobalt and the 0.3-0.4mL tetraethyl orthosilicate that 50-70mg should make is dispersed in 30mL ethanol, splash into the 4-6mL mass concentration after dispersed with stirring and be 28% ammoniacal liquor, then the water-bath insulation that this mixing solutions is placed in 30-45 ℃ is no less than 4 hours, and after reaction finishes, centrifugation obtains the cobalt cyanic acid cobalt nanometer particle of coated with silica; With being no less than 1 hour 400-600 ℃ of calcining after above-mentioned particle drying, obtain the cobaltosic oxide nanoparticles of coated with silica; Get this cobaltosic oxide nanoparticles of 30-50mg, being dispersed in 30mL concentration is 3-5molL
-1Hydrochloric acid soln in, be placed in the teflon-lined reactor, be no less than 6 hours 100-160 ℃ of reaction, with the product centrifugation, namely obtain hollow porous silica nanometer cubic block particle after reaction finishes.
2. the hollow porous silica nanometer cubic block particle that adopts claim 1 method to prepare is characterized in that particle diameter at 150nm, and shell thickness is 20nm, and profile is the shape of cubic block, and inside is hollow structure, and surface arrangement zigzag cracks.
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Cited By (3)
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| CN105879897A (en) * | 2016-05-27 | 2016-08-24 | 中国科学技术大学 | Carbon-base shell coated palladium-cobalt binary alloy nano-particle and preparation method and application thereof |
| CN106378449A (en) * | 2016-10-11 | 2017-02-08 | 中国科学技术大学 | Ruthenium-cobalt alloy nanoparticle as well as preparation method and application thereof |
| CN106953093A (en) * | 2017-04-17 | 2017-07-14 | 新乡学院 | The method that anode of lithium ion battery is prepared using colloid core shell structure α Fe2O3 materials |
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| CN101037205A (en) * | 2007-02-08 | 2007-09-19 | 上海交通大学 | Preparation method of nuclear/hull type functional nano micro-ball using silicon dioxide as hull |
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105879897A (en) * | 2016-05-27 | 2016-08-24 | 中国科学技术大学 | Carbon-base shell coated palladium-cobalt binary alloy nano-particle and preparation method and application thereof |
| CN106378449A (en) * | 2016-10-11 | 2017-02-08 | 中国科学技术大学 | Ruthenium-cobalt alloy nanoparticle as well as preparation method and application thereof |
| CN106378449B (en) * | 2016-10-11 | 2019-05-14 | 中国科学技术大学 | A kind of ruthenium cobalt alloy nanoparticles, preparation method and application as elctro-catalyst |
| CN106953093A (en) * | 2017-04-17 | 2017-07-14 | 新乡学院 | The method that anode of lithium ion battery is prepared using colloid core shell structure α Fe2O3 materials |
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Application publication date: 20130522 |