CN102107851A - Silica-gold compound nano-fiber - Google Patents
Silica-gold compound nano-fiber Download PDFInfo
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- CN102107851A CN102107851A CN 200910244039 CN200910244039A CN102107851A CN 102107851 A CN102107851 A CN 102107851A CN 200910244039 CN200910244039 CN 200910244039 CN 200910244039 A CN200910244039 A CN 200910244039A CN 102107851 A CN102107851 A CN 102107851A
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- silica
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- 239000002121 nanofiber Substances 0.000 title claims abstract description 33
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims abstract description 142
- 239000000377 silicon dioxide Substances 0.000 claims abstract description 71
- 239000000835 fiber Substances 0.000 claims abstract description 47
- 239000002131 composite material Substances 0.000 claims abstract description 35
- 239000002245 particle Substances 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 24
- 239000000463 material Substances 0.000 claims abstract description 23
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 18
- 239000010931 gold Substances 0.000 claims abstract description 17
- 229910052737 gold Inorganic materials 0.000 claims abstract description 17
- 229920000867 polyelectrolyte Polymers 0.000 claims abstract description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 59
- 235000012239 silicon dioxide Nutrition 0.000 claims description 54
- 239000007864 aqueous solution Substances 0.000 claims description 41
- 239000000243 solution Substances 0.000 claims description 34
- 238000001556 precipitation Methods 0.000 claims description 31
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 claims description 24
- 238000005119 centrifugation Methods 0.000 claims description 21
- 238000005406 washing Methods 0.000 claims description 21
- 229920002518 Polyallylamine hydrochloride Polymers 0.000 claims description 17
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 238000000926 separation method Methods 0.000 claims description 15
- 229960002668 sodium chloride Drugs 0.000 claims description 12
- 235000002639 sodium chloride Nutrition 0.000 claims description 12
- 239000011780 sodium chloride Substances 0.000 claims description 12
- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 claims description 6
- 230000001376 precipitating effect Effects 0.000 claims description 4
- 238000001523 electrospinning Methods 0.000 abstract description 15
- 230000003287 optical effect Effects 0.000 abstract description 9
- 238000010521 absorption reaction Methods 0.000 abstract description 8
- 239000002086 nanomaterial Substances 0.000 abstract description 6
- 239000013078 crystal Substances 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- ZAMOUSCENKQFHK-UHFFFAOYSA-N Chlorine atom Chemical compound [Cl] ZAMOUSCENKQFHK-UHFFFAOYSA-N 0.000 abstract 1
- 229910052801 chlorine Inorganic materials 0.000 abstract 1
- 239000000460 chlorine Substances 0.000 abstract 1
- MDEGNXJQYYHASU-UHFFFAOYSA-N dioxosilane gold Chemical compound [Au].O=[Si]=O MDEGNXJQYYHASU-UHFFFAOYSA-N 0.000 abstract 1
- 229910021505 gold(III) hydroxide Inorganic materials 0.000 abstract 1
- 239000013049 sediment Substances 0.000 description 40
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 20
- 239000011259 mixed solution Substances 0.000 description 20
- 239000012153 distilled water Substances 0.000 description 15
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 description 10
- 238000003756 stirring Methods 0.000 description 10
- 239000002078 nanoshell Substances 0.000 description 8
- 239000002105 nanoparticle Substances 0.000 description 6
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 6
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 6
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 6
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 description 5
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 description 4
- 239000002184 metal Substances 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000002360 preparation method Methods 0.000 description 3
- 239000012212 insulator Substances 0.000 description 2
- 239000000376 reactant Substances 0.000 description 2
- 238000001815 biotherapy Methods 0.000 description 1
- 238000001354 calcination Methods 0.000 description 1
- 230000009514 concussion Effects 0.000 description 1
- 238000002059 diagnostic imaging Methods 0.000 description 1
- 229940126534 drug product Drugs 0.000 description 1
- 239000000413 hydrolysate Substances 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 238000010899 nucleation Methods 0.000 description 1
- 239000000825 pharmaceutical preparation Substances 0.000 description 1
- 230000000704 physical effect Effects 0.000 description 1
- 230000035935 pregnancy Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000000015 thermotherapy Methods 0.000 description 1
- 210000004881 tumor cell Anatomy 0.000 description 1
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- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
本发明公开了一种二氧化硅-金复合纳米纤维。该复合纳米纤维材料是以电纺方法制备所得的二氧化硅纳米纤维为内核，利用聚电解质的静电吸附作用，在二氧化硅纤维外面吸附上纳米金颗粒作为晶种，然后用化学法使氯金酸还原金纳米晶种在二氧化硅纤维上长成一层由纳米金颗粒组成的金外壳。该复合纳米纤维材料突破了现有纳米材料形状的局限，其光学吸收带也由可见光区域(510nm)红移到近红外区域(＞1000nm)，在生物医疗成像、生物治疗和光电开关器件制备方面均具有很好的应用前景。The invention discloses a silicon dioxide-gold composite nanofiber. The composite nanofiber material is based on the silica nanofiber prepared by the electrospinning method as the core, and uses the electrostatic adsorption of polyelectrolyte to adsorb nano-gold particles on the outside of the silica fiber as a crystal seed, and then chemically makes chlorine Auric acid reduced gold nanoseeds to grow a gold shell composed of nano-gold particles on silica fibers. The composite nanofiber material breaks through the limitations of the shape of existing nanomaterials, and its optical absorption band is also red-shifted from the visible light region (510nm) to the near-infrared region (>1000nm). All have good application prospects.
Description
Technical field
The invention belongs to the composite nano materials field, relating to a kind of is that kernel, metal are the composite nano materials of shell with the insulator, particularly a kind of silica-Jin composite nano-fiber material.
Background technology
Recently, be kernel by the insulating nano particle, the NEW TYPE OF COMPOSITE nano material that metal (particularly gold) is formed for the nanometer shell is more and more paid close attention to.The gold nano shell has the physical property similar with gold colloid, a very strong optical absorption band is particularly arranged in the visible region, this is because the irradiation of light has caused the relevant concussion of gold colloid surface conduction band electron, Electron absorption light energy and being excited, thus produce the phenomenon that strengthens light absorption.The optical absorption of aurosol can make colloidal sol be shiny red, and this character can be used to prepare relevant drug products, tests as home pregnancy.And the optic response of gold nano shell mainly relies on the size of nano particle and the thickness of golden shell.By the thickness of regulation and control kernel and shell, the optical resonance wavelength that can make composite nanometer particle from the near ultraviolet region red shift to mid infrared region.This special optical property of metal nano shell can be used for biomedical imaging and treatment.Document (Technology in Cancer Research﹠amp; Treatment, 2004,3 (1): 33-40) reported that people such as NaomiHalas are used for this nano particle the thermotherapy method of tumour cell.But, according to document (MaterialsChemistry and Physics, 2007,105:419-425; J.Phys.Chem.C 2007,111:6245-6251) report, and it is kernel that present this nano particle all is confined to select spherical nano particle for use, the insulator of other shapes is the rare people's report of the nano material of kernel.
Summary of the invention
The purpose of this invention is to provide a kind of silica-Jin composite nano-fiber material.
Silica provided by the invention-Jin composite nano-fiber material is made up of kernel and shell; Wherein, becoming the material of kernel is silicon dioxide fibre, and the material that constitutes shell is a gold.
In above-mentioned silica-Jin composite nano-fiber material, the diameter of described silica-Jin composite nano-fiber material is the 50-300 nanometer, preferred 100 nanometers.
The method of the above-mentioned silica of preparation provided by the invention-Jin composite nano-fiber material comprises the steps:
1) silicon dioxide fibre is scattered in the water, the polyelectrolyte aqueous solution that adds positively charged reacts, and after the centrifugation, washing gained precipitation obtains precipitating a;
2) described precipitation a is scattered in the water, the aqueous solution that adds nanogold particle reacts, and after the centrifugation, washing gained precipitation obtains precipitating b;
3) described precipitation b is scattered in the water, adds aqueous solution of chloraurate and NH
2The OHHCl aqueous solution reacts, and after the centrifugation, washing gained precipitation obtains described silica-Jin composite nano-fiber material.
In the step 1) of this method, the polyelectrolyte aqueous solution of described positively charged is the sodium-chloride water solution of polyallylamine hydrochloride; The diameter of described silicon dioxide fibre is the 50-300 nanometer, but specifically I am 50-200 nanometer, 70-300 nanometer, 100-250 nanometer, 90-150 nanometer or 80-200 nanometer, preferred 100 nanometers; Described silicon dioxide fibre can have been bought or prepared according to disclosed preparation method by open commercial sources, as preparing: the ethanolic solution of tetraethoxysilance hydrolysate and polyvinylpyrrolidone is carried out electrospinning according to the method that comprises following step, behind described electrospinning step gained fiber calcination, obtain described silicon dioxide fibre.
The mass percentage concentration of the polyelectrolyte solution of described positively charged is 0.05-0.2%, specifically can be 0.05-0.15%, 0.08-0.14%, 0.09-0.15%, 0.1-0.15%, 0.05-0.1% or 0.08-0.15%, preferred 0.1%; Described silicon dioxide fibre is scattered in the step of water, the mass ratio of described silicon dioxide fibre and described water is 1: 500-1: 2000, specifically can be 1: 500-1000,1: 1000-2000,1: 500-1500,1: 800-1200,1: 900-1100,1: 1000-1500 or 1: 1000-1800, preferred 1: 1000; The polyelectrolyte mass ratio of described silicon dioxide fibre and described positively charged 1: 1～1: 3 specifically can be 1: 2,1: 1-2 or 1: 2-3, preferred 1: 1; The temperature of reaction is a normal temperature, and the time of reaction is 0.5～1 hour; In the step with centrifugal separation, centrifugal rotational speed 3000r/min～5000r/min, preferred 3000r/min; The number of times of described step with centrifugal separation is at least 3 times;
Described step 2) in, described precipitation a is scattered in the step in the water, and the mass ratio of described precipitation a and described water is 1: 2000-2: 1000, and preferred 1: 1000; The mass percentage concentration of the aqueous solution of described nanogold particle is 0.005%-0.01%, preferred 0.01%; The mass ratio of the aqueous solution of described precipitation a and the aqueous solution of described nanogold particle is 1: 1-1: 4, and preferred 1: 2; The temperature of reaction is a normal temperature, and the time of reaction is 0.5～1 hour; In the step with centrifugal separation, centrifugal rotational speed 3000r/min～5000r/min, preferred 3000r/min; The number of times of described step with centrifugal separation is at least 3 times.But used nanogold particle reference literature (Jana, N.R in this step; Gearheart, L.; Murphy, C.J.Seeding growth for size control of 5-40nm diameter gold nanoparticles.Langmuir 2001,17 6782-6786) is prepared and obtains.
In the described step 3), described precipitation b is scattered in the step of water, the mass ratio of described precipitation b and described water is 1: 3000-1: 10000, specifically can be 1: 2000-7000,1: 3000-10000,1: 2500-3500,1: 5000-8000,1: 5500-6500 or 1: 5500-7500, preferred 1: 6000; The mass percentage concentration of described aqueous solution of chloraurate is 1-5%, preferred 2%; Described NH
2The mass fraction of the OHHCl aqueous solution is 0.05-0.1%, specifically can be 0.05-0.08%, 1: 0.06-0.09% or 1: 0.065-0.085%, preferred 0.07%; Precipitation b, gold chloride and NH
2The mass ratio of OHHCl is 2.2: 1.3: 0.36-2.2: 2.6: 0.72, specifically can be 2.2: 1.3: 0.38,2.2: 1.3: 0.40,2.2: 1.3: 0.50,2.2: 1.3: 0.60,2.2: 1.3: 0.70,2.2: 1.3: 0.80,2.2: 1.3: 1.0,2.2: 1.3: 1.5,2.2: 1.3: 2.0 or 2.2: 1.3: 2.2, preferred 2.2: 1.3: 0.36; The temperature of reaction is 15-30 ℃, and preferred 25 ℃, the time of reaction is 2-10 minute, preferred 5 minutes; In the step with centrifugal separation, centrifugal rotational speed 3000r/min～5000r/min, preferred 3000r/min; The number of times of described step with centrifugal separation is at least 3 times.In this step, if the precipitation b in water with aqueous solution of chloraurate and NH
2In the gained precipitation, silicon dioxide fibre is outer all not to be covered by gold nano grain behind the OHHCl reactant aqueous solution, and the precipitation that then repeats this reaction is finished is scattered in the water again as reactant, again with aqueous solution of chloraurate and NH
2The OHHCl aqueous solution reacts, and is all covered by gold nano grain until the silicon dioxide fibre skin.
It is kernel that the present invention prepares the silica nano fibrous of gained with the electrospinning method, utilize the electrostatic adsorption of polyelectrolyte, nanogold particle makes gold chloride reduction gold nano crystal seed grow up to the golden shell that one deck is made up of nanogold particle on silicon dioxide fibre with chemical method as crystal seed then in the absorption of silicon dioxide fibre outside.This composite nano-fiber material has been broken through the limitation of existing nano material shape, its optical absorption band also by visible region (510nm) red shift near infrared region (＞1000nm), all have good application prospects at aspects such as biologic medical imaging, biological therapy and photoelectric switching device preparations.
Description of drawings
The silicon dioxide fibre that Fig. 1 (a) obtains for electrospinning among the embodiment 1; Fig. 1 (b) is for having adsorbed the silicon dioxide fibre of nanogold particle among the embodiment 1; Fig. 1 (c) is silica among the embodiment 1-Jin composite nano fiber; Fig. 1 (d) is the optical absorption peak of silica among the embodiment 1-Jin composite nano fiber at ultraviolet-visible zone (510nm); Fig. 1 (e) is the optical scattering peak of silica among the embodiment 1-Jin composite nano fiber near infrared region (1000nm).
Fig. 2 (a) is for having adsorbed the silicon dioxide fibre of nanogold particle among the embodiment 2; Fig. 2 (b) is silica among the embodiment 2-Jin composite nano fiber.
Fig. 3 is silica among the embodiment 3-Jin composite nano fiber.
Fig. 4 is silica among the embodiment 4-Jin composite nano fiber.
Fig. 5 (a) is for having adsorbed the silicon dioxide fibre of nanogold particle among the embodiment 5; Fig. 5 (b) is silica among the embodiment 5-Jin composite nano fiber.
The specific embodiment
The invention will be further described below in conjunction with specific embodiment, but the present invention is not limited to following examples.Used centrifuge is available from Anting Scientific Instrument Factory, Shanghai among the following embodiment, and model is TGL-16G.
Embodiment 1
(1) the 4.6g ethyl orthosilicate is dissolved in the 2ml ethanol, in the process that stirs, drips 2N aqueous hydrochloric acid solution 0.75ml, reacted 0.5 hour, obtain silicon dioxide gel, standby.Getting 0.7g polyvinylpyrrolidone (molecular weight 1,300,000) is dissolved in the 20ml ethanol, add above-mentioned silicon dioxide gel 1ml in the whipping process, carry out electrospinning after 4 hours, with the 600 ℃ of following roastings 4 hours in Muffle furnace of electrospinning gained silicon dioxide fibre felt, obtain the pure silicon dioxide fiber, see Fig. 1 (a).
(2) above-mentioned silicon dioxide fibre 2mg is distributed in the 2ml water, add the 2ml mass percentage concentration then and be the sodium-chloride water solution of 0.1% polyallylamine hydrochloride (PAH), normal temperature stirred 0.5 hour down, will be then with mixed solution centrifugation three times (rotating speed of centrifuge be 3000r/min), all take out upper solution at every turn, keep the sediment of bottom, add an amount of distilled water washing simultaneously, unnecessary PAH and sodium chloride are removed, and obtaining required sediment a is 2mg.
(3) above-mentioned sediment is distributed in the 2ml water once more, add the 4ml mass percentage concentration and be the aqueous solution of 0.01% nanogold particle, normal temperature stirred 0.5 hour down, with mixed solution centrifugation three times (rotating speed of centrifuge is 3000r/min), all take out upper solution then at every turn, keep the sediment of bottom, add an amount of distilled water washing simultaneously, unnecessary nanogold particle is removed, and obtaining required sediment b is 2.2mg, sees Fig. 1 (b).
(4) above-mentioned sediment is distributed in the 13ml water once more, the adding mass percent is 2% aqueous solution of chloraurate 0.065ml, and under stirring condition, dropwise adding freshly prepd mass percent in this mixed solution is 0.07%NH
2OHHCl aqueous solution 0.5ml behind the 5min, with mixed solution centrifugation three times (rotating speed of centrifuge is 3000r/min), all takes out upper solution at every turn, keeps the sediment of bottom, adds an amount of distilled water washing simultaneously, with unnecessary NH
2OHHCl removes, and obtains required sediment.Repeat this step, all cover up to fibrous outer and go up the gold nano shell, see Fig. 1 (c).
(5) the optical absorption peak of above-mentioned silica-Jin composite nano fiber can be from ultraviolet-visible zone (510nm) Fig. 1 (d) red shift near infrared region (＞1000nm) Fig. 1 (e).
Embodiment 2
(1) the 4.6g ethyl orthosilicate is dissolved in the 2ml ethanol, in the process that stirs, drips 2N hydrochloric acid solution 0.75ml, reacted 0.5 hour, obtain silicon dioxide gel, standby.Getting 0.7g polyvinylpyrrolidone (molecular weight 1,300,000) is dissolved in the 20ml ethanol, add above-mentioned silicon dioxide gel 1ml in the whipping process, carry out electrospinning after 4 hours, the silicon dioxide fibre felt that electrospinning obtains 600 ℃ of following roastings 4 hours in Muffle furnace obtain the pure silicon dioxide fiber.
(2) above-mentioned silicon dioxide fibre 2mg is distributed in the 2ml water, adding the 1ml mass percentage concentration then is the sodium chloride solution of 0.1% polyallylamine hydrochloride (PAH), normal temperature stirred 0.5 hour down, then with mixed solution centrifugation three times (rotating speed of preferred centrifuge is 3000r/min), all take out upper solution at every turn, keep the sediment of bottom, add an amount of distilled water washing simultaneously, unnecessary PAH and sodium chloride are removed, and obtaining required sediment a is 2mg.
(3) above-mentioned sediment is distributed in the 2ml water once more, add the 4ml mass percentage concentration and be the aqueous solution of 0.01% nanogold particle, normal temperature stirred 0.5 hour down, with mixed solution centrifugation three times (rotating speed of centrifuge is 3000r/min), all take out upper solution then at every turn, keep the sediment of bottom, add an amount of distilled water washing simultaneously, unnecessary nanogold particle is removed, and obtaining required sediment b is 2.1mg, sees Fig. 2 (a).
(4) above-mentioned sediment is distributed in the 13ml water once more, adding mass percentage concentration is 2% chlorauric acid solution 0.065ml, and under stirring condition, dropwise adding freshly prepd mass percentage concentration in this mixed solution is 0.07%NH
2OHHCl aqueous solution 0.5ml behind the 5min, with mixed solution centrifugation three times (centrifuge speed is 3000r/min), all takes out upper solution at every turn, keeps the sediment of bottom, adds an amount of distilled water washing simultaneously, with unnecessary NH
2OHHCl removes, and obtains required sediment.Repeat this step, all cover up to fibrous outer and go up the gold nano shell, see Fig. 2 (b).
Can observe from the figure of embodiment 1 and embodiment 2, obtain the high composite nano fiber of golden coverage, silicon dioxide fibre and polyelectrolyte mass ratio can not be less than 1: 1.
Embodiment 3
(1) the 4.6g ethyl orthosilicate is dissolved in the 2ml ethanol, in the process that stirs, drips 2N hydrochloric acid solution 0.75ml, reacted 0.5 hour, obtain silicon dioxide gel, standby.Getting 0.7g polyvinylpyrrolidone (molecular weight 1,300,000) is dissolved in the 20ml ethanol, add above-mentioned silicon dioxide gel 1ml in the whipping process, carry out electrospinning after 4 hours, the silicon dioxide fibre felt that electrospinning obtains 600 ℃ of following roastings 4 hours in Muffle furnace obtain the pure silicon dioxide fiber.
(2) above-mentioned silicon dioxide fibre 2mg is distributed in the 2ml water, adding the 2ml mass percentage concentration then is the sodium chloride solution of 0.1% polyallylamine hydrochloride (PAH), normal temperature stirred 0.5 hour down, then with mixed solution centrifugation three times (rotating speed of centrifuge is 3000r/min), all take out upper solution at every turn, keep the sediment of bottom, add an amount of distilled water washing simultaneously, unnecessary PAH and sodium chloride are removed, and obtaining required sediment a is 2mg.
(3) above-mentioned sediment is distributed in the 2ml water once more, add the 4ml mass percentage concentration and be the aqueous solution of 0.01% nanogold particle, normal temperature stirred 0.5 hour down, then with mixed solution centrifugation three times (rotating speed of centrifuge is 3000r/min), all take out upper solution at every turn, keep the sediment of bottom, add an amount of distilled water washing simultaneously, unnecessary nanogold particle is removed, and obtaining required sediment b is 2.2mg.
(4) above-mentioned sediment is distributed in the 13ml water once more, adds mass percentage concentration and be 2% chlorauric acid solution 0.033ml, under stirring condition, in this mixed solution, dropwise add the freshly prepd mass percentage concentration of 0.25ml and be 0.07% NH
2The OHHCl aqueous solution behind the 5min, with mixed solution centrifugation three times (rotating speed of centrifuge is 3000r/min), all takes out upper solution at every turn, keeps the sediment of bottom, adds an amount of distilled water washing simultaneously, with unnecessary NH
2OHHCl removes, and obtains required sediment.Repeat this step, all cover up to fibrous outer and go up the gold nano shell, see Fig. 3.
From the figure of embodiment 1 and embodiment 3, can observe, obtain the composite nano fiber of continuous golden shell, silicon dioxide fibre, gold chloride and NH
2The optimum quality ratio of OHHCl is 2.2: 1.3: 0.36.
Embodiment 4
(1) the 4.6g ethyl orthosilicate is dissolved in the 2ml ethanol, in the process that stirs, drips 2N hydrochloric acid solution 0.75ml, reacted 0.5 hour, obtain silicon dioxide gel, standby.Getting 0.7g polyvinylpyrrolidone (molecular weight 1,300,000) is dissolved in the 20ml ethanol, add above-mentioned silicon dioxide gel 1ml in the whipping process, carry out electrospinning after 4 hours, the silicon dioxide fibre felt that electrospinning obtains 600 ℃ of following roastings 4 hours in Muffle furnace obtain the pure silicon dioxide fiber.
(2) above-mentioned silicon dioxide fibre 2mg is distributed in the 2ml water, adding the 2ml mass percentage concentration then is the sodium chloride solution of 0.1% polyallylamine hydrochloride (PAH), normal temperature stirred 0.5 hour down, then with mixed solution centrifugation three times (rotating speed of centrifuge is 3000r/min), all take out upper solution at every turn, keep the sediment of bottom, add an amount of distilled water washing simultaneously, unnecessary PAH and sodium chloride are removed, and obtaining required sediment a is 2mg.
(3) above-mentioned sediment is distributed in the 2ml water once more, add the 4ml mass percentage concentration and be mass percentage concentration and be the aqueous solution of 0.01% nanogold particle, normal temperature stirred 0.5 hour down, then with mixed solution centrifugation three times (rotating speed of centrifuge is 3000r/min), all take out upper solution at every turn, keep the sediment of bottom, add an amount of distilled water washing simultaneously, unnecessary nanogold particle is removed, and obtaining required sediment b is 2.2mg.
(4) above-mentioned sediment is distributed in the 13ml water once more, adds mass percentage concentration and be 2% chlorauric acid solution 0.165ml, under stirring condition, in this mixed solution, dropwise add the freshly prepd mass percentage concentration of 0.25ml and be 0.07% NH
2The OHHCl aqueous solution behind the 5min, with mixed solution centrifugation three times (rotating speed of centrifuge is 3000r/min), all takes out upper solution at every turn, keeps the sediment of bottom, adds an amount of distilled water washing simultaneously, with unnecessary NH
2OHHCl removes, and obtains required sediment.Repeat this step, all cover up to fibrous outer and go up the gold nano shell, see Fig. 4.
Can observe from the figure of embodiment 1 and embodiment 4, the golden shell of the silica that embodiment 4 obtains than embodiment 1-Jin composite nano-fiber material is thick, illustrates that the thickness of golden shell can be by gold chloride and the NH that adds
2The consumption regulation and control of OHHCl.
Embodiment 5
(1) the 4.6g ethyl orthosilicate is dissolved in the 2ml ethanol, in the process that stirs, drips 2N hydrochloric acid solution 0.75ml, reacted 0.5 hour, obtain silicon dioxide gel, standby.Getting 0.7g polyvinylpyrrolidone (molecular weight 1,300,000) is dissolved in the 20ml ethanol, add above-mentioned silicon dioxide gel 1ml in the whipping process, carry out electrospinning after 4 hours, the silicon dioxide fibre felt that electrospinning obtains 600 ℃ of following roastings 4 hours in Muffle furnace obtain the pure silicon dioxide fiber.
(2) above-mentioned silicon dioxide fibre 2mg is distributed in the 2ml water, adding the 2ml mass percentage concentration then is the sodium chloride solution of 0.1% polyallylamine hydrochloride (PAH), normal temperature stirred 0.5 hour down, then with mixed solution centrifugation three times (rotating speed of preferred centrifuge is 3000r/min), all take out upper solution at every turn, keep the sediment of bottom, add an amount of distilled water washing simultaneously, unnecessary PAH and sodium chloride are removed, and obtaining required sediment a is 2mg.
(3) above-mentioned sediment is distributed in the 2ml water once more, add the 0.5ml mass percentage concentration and be the aqueous solution of 0.01% nanogold particle, normal temperature stirred 0.5 hour down, with mixed solution centrifugation three times (rotating speed of centrifuge is 3000r/min), all take out upper solution then at every turn, keep the sediment of bottom, add an amount of distilled water washing simultaneously, unnecessary nanogold particle is removed, and obtaining required sediment b is 2.05mg, sees Fig. 5 (a).
(4) above-mentioned sediment is distributed in the 13ml water once more, adding mass percentage concentration is 2% chlorauric acid solution 0.065ml, under stirring condition, dropwise adds the freshly prepd mass percentage concentration of 0.5ml and be 0.07% NH in this mixed solution
2The OHHCl aqueous solution behind the 5min, with mixed solution centrifugation three times (centrifuge speed is 3000r/min), all takes out upper solution at every turn, keeps the sediment of bottom, adds an amount of distilled water washing simultaneously, with unnecessary NH
2OHHCl removes, and obtains required sediment.Repeat this step, all cover up to fibrous outer and go up the gold nano shell, see Fig. 5 (b).
From the figure of embodiment 5 and embodiment 1, can observe, obtain the high composite nano fiber of golden coverage, preferred 1: 2 of the mass ratio of the aqueous solution of silicon dioxide fibre and the aqueous solution of described nanogold particle.
Claims (10)
1. silica-Jin composite nano-fiber material is made up of kernel and shell; It is characterized in that: the material that constitutes described kernel is a silicon dioxide fibre, and the material that constitutes described shell is gold.
2. silica according to claim 1-Jin composite nano-fiber material is characterized in that: the diameter of described silica-Jin composite nano-fiber material is the 50-300 nanometer.
3. silica according to claim 1 and 2-Jin composite nano-fiber material is characterized in that: the diameter of described silica-Jin composite nano-fiber material is 100 nanometers.
4. a method for preparing the arbitrary described silica of claim 1-3-Jin composite nano-fiber material comprises the steps:
1) silicon dioxide fibre is scattered in the water, the polyelectrolyte aqueous solution that adds positively charged reacts, and after the centrifugation, washing gained precipitation obtains precipitating a;
2) described precipitation a is scattered in the water, the aqueous solution that adds nanogold particle reacts, and after the centrifugation, washing gained precipitation obtains precipitating b;
3) described precipitation b is scattered in the water, adds aqueous solution of chloraurate and NH
2The OHHCl aqueous solution reacts, and after the centrifugation, washing gained precipitation obtains described silica-Jin composite nano-fiber material.
5. method according to claim 4 is characterized in that: in the described step 1), the polyelectrolyte aqueous solution of described positively charged is the sodium-chloride water solution of polyallylamine hydrochloride; The diameter of described silicon dioxide fibre is the 50-300 nanometer.
6. method according to claim 5 is characterized in that: the diameter of described silicon dioxide fibre is 100 nanometers.
7. according to the arbitrary described method of claim 4-6, it is characterized in that: in the described step 1), the mass percentage concentration of the polyelectrolyte aqueous solution of described positively charged is 0.05-0.2%; Described silicon dioxide fibre is scattered in the step of water, and the mass ratio of described silicon dioxide fibre and described water is 1: 500-2000; The mass ratio of the polyelectrolyte of described silicon dioxide fibre and described positively charged 1: 1～1: 3;
Described step 2) in, described precipitation a is scattered in the step in the water, and the mass ratio of described precipitation a and described water is 1: 2000-2: 1000; The mass percentage concentration of the aqueous solution of described nanogold particle is 0.005%-0.01%; The mass ratio of the aqueous solution of described precipitation a and described nanogold particle is 1: 1-1: 4;
In the described step 3), described precipitation b is scattered in the step of water, and the mass ratio of described precipitation b and described water is 1: 3000-1: 10000; The mass percentage concentration of described aqueous solution of chloraurate is 1-5%; Described NH
2The mass percentage concentration of the OHHCl aqueous solution is 0.05-0.1%; Precipitation b, gold chloride and NH
2The mass ratio of OHHCl is 2.2: 1.3: 0.36-2.2.
8. method according to claim 7 is characterized in that: in the described step 1), the mass percentage concentration of the polyelectrolyte solution of described positively charged is 0.1%; Described silicon dioxide fibre is scattered in the step of water, and the mass ratio of described silicon dioxide fibre and described water is 1: 1000; The mass ratio of the polyelectrolyte of described silicon dioxide fibre and described positively charged is 1: 1;
Described step 2) in, described precipitation a is scattered in the step in the water, and the mass ratio of described precipitation a and described water is 1: 1000; The mass percentage concentration of the aqueous solution of described nanogold particle is 0.01%; The mass ratio of the aqueous solution of described precipitation a and described nanogold particle is 1: 2;
In the described step 3), described precipitation b is scattered in the step of water, and the mass ratio of described precipitation b and described water is 1: 6000; The mass percentage concentration of described aqueous solution of chloraurate is 2%; Described NH
2The mass percentage concentration of the OHHCl aqueous solution is 0.07%; Precipitation b, gold chloride and NH
2The mass ratio of OHHCl is 2.2: 1.3: 0.36.
9. according to the arbitrary described method of claim 4-8, it is characterized in that: in the described step 1), the temperature of reaction is 15-30 ℃, and the time of reaction is 0.5～1 hour; In the step with centrifugal separation, centrifugal rotational speed 3000r/min～5000r/min; The number of times of described step with centrifugal separation is at least 3 times;
Described step 2) in, the temperature of reaction is 15-30 ℃, and the time of reaction is 0.5～1 hour; In the step with centrifugal separation, centrifugal rotational speed is 3000r/min～5000r/min; The number of times of described step with centrifugal separation is at least 3 times;
In the described step 3), the temperature of reaction is 15-30 ℃, and the time of reaction is 2-10 minute; In the step with centrifugal separation, centrifugal rotational speed 3000r/min～5000r/min; The number of times of described step with centrifugal separation is at least 3 times.
10. method according to claim 9 is characterized in that: in the described step 1), in the step with centrifugal separation, centrifugal rotational speed is 3000r/min;
Described step 2) in, in the step with centrifugal separation, centrifugal rotational speed is 3000r/min;
In the described step 3), the temperature of reaction is 25 ℃, and the time of reaction is 5 minutes; In the step with centrifugal separation, centrifugal rotational speed is 3000r/min.
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Cited By (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN102851877A (en) * | 2012-09-11 | 2013-01-02 | 中国科学技术大学 | Method for assembling gold and silver one-dimensional nano-material by adopting electrostatic spinning technology and application thereof |
| US20140228201A1 (en) * | 2011-10-17 | 2014-08-14 | Universitat Politecnica De Catalunya | PROCEDURE FOR OBTAINING A SUBSTRATE WITH Au NANOCLUSTERS ATTACHED TO ITS SURFACE, AND THE SUBSTRATE AND CATALYST OBTAINED THROUGH THIS PROCEDURE |
| CN104550941A (en) * | 2014-11-26 | 2015-04-29 | 东华大学 | A preparation method of silica@noble metal nanocomposite microspheres |
| CN106974627A (en) * | 2017-04-12 | 2017-07-25 | 中国科学院东北地理与农业生态研究所 | Preparation method of 3D nanomaterials applied to wrist pulse sensor |
Family Cites Families (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN100544823C (en) * | 2007-12-29 | 2009-09-30 | 中国科学院长春应用化学研究所 | A kind of preparation method of nanoparticle carbon nanotube composite catalyst |
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Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20140228201A1 (en) * | 2011-10-17 | 2014-08-14 | Universitat Politecnica De Catalunya | PROCEDURE FOR OBTAINING A SUBSTRATE WITH Au NANOCLUSTERS ATTACHED TO ITS SURFACE, AND THE SUBSTRATE AND CATALYST OBTAINED THROUGH THIS PROCEDURE |
| US9782764B2 (en) * | 2011-10-17 | 2017-10-10 | Universitat Politècnica De Catalunya | Procedure for obtaining a substrate with Au nanoclusters attached to its surface, and the substrate and catalyst obtained through this procedure |
| CN102851877A (en) * | 2012-09-11 | 2013-01-02 | 中国科学技术大学 | Method for assembling gold and silver one-dimensional nano-material by adopting electrostatic spinning technology and application thereof |
| CN104550941A (en) * | 2014-11-26 | 2015-04-29 | 东华大学 | A preparation method of silica@noble metal nanocomposite microspheres |
| CN106974627A (en) * | 2017-04-12 | 2017-07-25 | 中国科学院东北地理与农业生态研究所 | Preparation method of 3D nanomaterials applied to wrist pulse sensor |
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