CN102661985B - Application of gold nanoparticle-functionalized kaolinite nanotube composite material - Google Patents
Application of gold nanoparticle-functionalized kaolinite nanotube composite material Download PDFInfo
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- CN102661985B CN102661985B CN201210115851.1A CN201210115851A CN102661985B CN 102661985 B CN102661985 B CN 102661985B CN 201210115851 A CN201210115851 A CN 201210115851A CN 102661985 B CN102661985 B CN 102661985B
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Abstract
The invention relates to the field of materials and discloses a gold nanoparticle-functionalized kaolinite nanotube composite material. The preparation method of the composite material comprises the follow steps: (1) organosilan with an amino group is used for amination to a kaolinite nanotube so as to obtain a functionalized kaolinite nanotube; and (2) gold nanoparticle collosol and functionalized kaolinite nanotube solution are subjected to ultrasound mixing for 20 to 40 Mins. The obtained gold nanoparticle-functionalized kaolinite nanotube composite material can be used for electrochemical catalysis and electrochemical shining detection, and a decorating electrode used for detecting hydrogen peroxide or tripropylamine is prepared.
Description
Technical field
The present invention relates to Material Field, especially golden nanometer particle-functionalized kaolin nanometer tube composite materials, preparation method and the application aspect galvanochemistry.
Background technology
In recent years, the structure of one-dimensional nano-composite material and electrochemical applications research thereof cause concern widely.High-specific surface area, high activity, specific physical character and utmost point smallness that nano material has, environment is very responsive to external world to make it, this property of nano material makes it to become and is applied to the most promising material in chemical sensor aspect, utilizes it can develop the chemical sensor of fast response time, the various different purposes that highly sensitive, selectivity is good.
Gold nano gold particle has good electric conductivity, Bc, the special physicochemical property such as small-size effect, quantum tunneling effect and high chemical mobility of the surface, can greatly reduce the distance between electron donor and acceptor, improve the transfer rate between electronics and electrode, aspect galvanochemistry, have important application.
Porcelain earth is a kind of aluminium silicate salt through crude sedimentation, and its chemical property is similar to smalite, is mainly hollow tubular structures, and kaolin nanotube length is at 1～15 μ m, outer tube diameter 50～70nm, interior caliber 10～30nm.Porcelain earth outside surface is the SiO with negative charge
2inside surface is the Al with positive charge
2o
3, therefore kaolinic outside surface chemical property is similar to SiO
2and pipe internal surface character is similar to Al
2o
3, surface with negative charge and along with the increase of pH current potential more negative.The alchlor of the octahedra shape of the tetrahedral silicon dioxide of outside surface and inside surface is curling through natural deposition, makes porcelain earth become the structure of tubulose, is similar to the large length-diameter ratio that carbon nano-tube is the same, makes it have potential application prospect and wide application.Porcelain earth is as a kind of important raw material of industry, has been widely used in now a lot of fields such as papermaking, coating, rubber, polymkeric substance and nano-reactor, because the industry of the different application of its characteristic is also had any different.On mineralogy, the main character of physics and chemistry and the basis of design feature thereof of kaolin nanotube, in conjunction with kaolin nanotube (HNTs) surface modification, the progress of inorganic coating, and porcelain earth is at the current research of preparing in molecular sieve, stupalith, concrete, catalyst support, filler and other mineral materials, has shown to people the DEVELOPMENT PROSPECT that it is tempting.
Hydrogen peroxide (H
2o
2) there is good Sha Jun ﹑ sterilization and discoloration.In food service industry, hydrogen peroxide is applied in the production runes such as dairy products, beverage, aquatic products, melon and fruit and beer as production and processing auxiliary agent.But hydrogen peroxide exceeds standard, use meeting produces harmful effect to health.The use amount that is clearly defined in hydrogen peroxide in food process process in state health standards should not exceed certain limitation amount.Therefore, the simple hydrogen peroxide detection method of structure Ling Min ﹑ is significant for the effective monitoring of content of hydrogen peroxide in food.At present, the method for detection hydrogen peroxide mainly contains titrimetry, spectrophotometric method, spectroscopic methodology, chemoluminescence method, chromatography, electrochemical process etc.Compare other method, the advantage such as that electrochemical process has is sensitive, Kuai Su ﹑ is simple.
Summary of the invention
The present invention aims to provide a kind of novel golden nanometer particle-functionalized kaolin nanometer tube composite materials (AuNPs-HNTs).
The present invention also provides the preparation method of above-mentioned material and the application of (as electrochemical catalysis and electrochemiluminescence detect) aspect galvanochemistry.
Golden nanometer particle-functionalized kaolin nanometer tube composite materials is preparation method comprise the steps:
(1) use, with amino organosilane by kaolin nanotube amination, obtains functionalized kaolin nanotube; The length of kaolin nanotube is 1～15 μ m, outer tube diameter 50～70nm, interior caliber 10～30nm;
Amidized step comprises: kaolin nanotube adds ultrasonic dispersion 20～40min in the mixed liquor of 3-Propylamino triethoxysilane and organic solvent (being preferably toluene), and under 200～500rpm stirring reaction 8～28hr; Get washing of precipitate;
In mixed liquor, be 0.2～0.5mol/L with amino organosilane content, kaolin nanotube be 40～80g/mol with amino organosilane amount ratio; Be preferably 3-Propylamino triethoxysilane (APTES) with amino organosilane.
(2) the ultrasonic 20～40min that mixes of kaolin nanotube of golden nanometer particle colloidal sol and functionalization; Gold nanometer particle grain size is 1～10nm; Functionalized kaolin nanotube and golden nanometer particle amount ratio are 15～30mg/mmol; In the system of the kaolin nanotube solution composition of golden nanometer particle colloidal sol and functionalization, golden nanometer particle content is 0.05～0.2mmol/L, and the content of the kaolin nanotube of functionalization is 1～5mg/ml.
Golden nanometer particle-functionalized kaolin the nanometer tube composite materials obtaining by said method can be used for preparing modified electrode, detects hydrogen peroxide or tripropyl amine (TPA).
The present invention is connected to golden nanometer particle on kaolin nanotube, to prepare novel golden nanometer particle-functionalized kaolin nanometer tube composite materials (AuNPs-HNTs), and this compound substance is applied to electrochemical catalysis and electrochemiluminescence detects.
This compound substance modified electrode is to H
2o
2show high electro catalytic activity and response sensitivity, and there is the features such as long-time stability are good, prepared detection H
2o
2without enzyme type sensor.
This compound substance and Ru (bpy)
3 2+the together Ru (bpy) of preparation
3 2+/ AuNPs-HNTs/Nafion modified electrode can be effectively used to electrogenerated chemiluminescence (ECL) and detects tripropyl amine (TPA) (TPA).This modified electrode shows good electrochemiluminescence character to tripropyl amine (TPA), has brand-new application by detecting at electrochemiluminescence aspect amino medicine.
Kaolin nanotube has special tubular structure, large specific surface area, good biocompatibility, the feature such as inexpensive.Golden nanometer particle has excellent physicochemical characteristics such as good electric conductivity and bioaffinity, high catalytic activity etc.So novel golden nanometer particle-functionalized kaolin nanometer tube composite materials of the present invention has both excellent specific properties.This compound substance modified electrode is to H
2o
2show the features such as high electro catalytic activity and response sensitivity are high, and long-time stability are good.Ru (bpy)
3 2+/ AuNPs-HNTs/Nafion modified electrode can be effectively used to electrogenerated chemiluminescence (ECL) and detects tripropyl amine (TPA) (TPA).This modified electrode shows good electrochemiluminescence character to tripropyl amine (TPA), and the detection of the medicine containing amino is had to huge facilitation.
Feature of the present invention and beneficial effect are:
1. kaolin nanotube is used to APTES functionalization, make it connect amino, current potential is by just bearing change, to inhale mutually by positive negative electricity with the synthetic electronegative golden nanometer particle of Citrate Buffer and covalent bond is connected on functionalized kaolin nanotube again, prepare golden nanometer particle/functionalized kaolin nanometer tube composite materials, and be successfully prepared by the sign such as Zeta potential, ultraviolet compound substance.
2. build based on novel golden nanometer particle-functionalized kaolin nanometer tube composite materials (AuNPs-HNTs) modified electrode, and for H
2o
2detect, thereby prepared without enzyme type H
2o
2sensor.
3.Ru (bpy)
3 2+/ AuNPs-HNTs/Nafion modified electrode can be effectively used to electrogenerated chemiluminescence (ECL) and detects tripropyl amine (TPA) (TPA).There is brand-new application by detecting at electrochemiluminescence aspect amino medicine.
Brief description of the drawings
Fig. 1 is the synthetic schematic diagram of golden nanometer particle-functionalized kaolin nanometer tube composite materials of the present invention
Fig. 2 is golden nanometer particle-functionalized kaolin nanometer tube composite materials TEM figure, and its orbicular spot is the golden nanometer particle being connected on functionalized kaolin nanotube.
Fig. 3 be kaolin nanotube (a), golden nanometer particle/functionalized kaolin nanometer tube composite materials (b) modified electrode in saturated PBS (PH7.0) solution, under-0.3V condition, add continuously 15mol/L H
2o
2chronoamperogram.
Fig. 4 is Ru (bpy)
3 2+the electrogenerated chemiluminescence spectrogram of/AuNPs-HNTs/Nafion modified electrode in 0.68mmol/L tripropyl amine (TPA), photomultiplier high pressure 600V.
Embodiment
Kaolin nanotube (HNTs, Natural Nano.Inc.), 30% hydrogen peroxide (H
2o
2) solution (Solution on Chemical Reagents in Shanghai company).Gold chloride (HAuCl
4) and sodium citrate buy from traditional Chinese medicines.Organosilane (3-Propylamino triethoxysilane, APTES, 25K), six hydration tris (bipyridine) rutheniums (Ru (bpy)
3 2+) purchased from Sigma-Aldrich.The phosphate buffer solution (PBS, 0.1mol/L) of different pH is by Na
2hPO
4and NaH
2pO
4press different proportion formulated.Agents useful for same is analytical reagent, and all solution is all prepared with redistilled water.
The preparation of embodiment 1 golden nanometer particle-functionalized kaolin nanotube-compound substance
1. the functional modification of kaolin nanotube: 2mL APTES (0.01mol) is dispersed in 25mL toluene, ultrasonic mixing.Take in the toluene solution that 0.6g kaolin nanotube joins APTES ultrasonic dispersion 30 minutes.Under above-mentioned mixed liquor 350rpm rotating speed, stir 12 hours.Repeatedly centrifugal and by toluene wash precipitation, remove unreacted organosilane, 120 DEG C of dried overnight are stand-by.After dry, be dispersed in distilled water for subsequent use.
2. golden nanometer particle preparation: application Citrate Buffer, first, by clean 250mL conical flask soaked overnight in acid solution, then clean up oven dry, stand-by.Add wherein 100mL0.01wt% (0.294mmol/L) HAuCl
4boil, under agitation add rapidly 2mL1wt% trisodium citrate, continue heating until solution colour celadon stops heating while becoming aubergine and stirs, obtain golden nanometer particle colloidal sol, cooling stand-by.Prepared gold nanometer particle grain size is evenly distributed, good stability, and difficult reunion, particle diameter is at 1～10nm.
3. the preparation of golden nanometer particle functionalized kaolin nanometer tube composite materials: the kaolin nanotube aqueous solution of getting the functionalization of 0.5mL3mg/mL is mixed ultrasonic 30min with 0.25mL golden nanometer particle colloidal sol (0.0735mmol).By the sign such as Zeta potential, ultraviolet composite A, uNPs-HNTs is successfully prepared.
Prepare synthesis step as shown in Figure 1.Golden nanometer particle-functionalized kaolin nanometer tube composite materials the TEM obtaining schemes as Fig. 2, and the round dot in figure is the golden nanometer particle being connected on functionalized kaolin nanotube.
The preparation of embodiment 2 compound substance modified electrodes
First use 2#, 5# abrasive paper for metallograph polishing grinding glass-carbon electrode, then use the Al of 0.3 and 0.05 μ m
2o
3burnishing powder polishing, rinses and removes surface contaminants, then successively at the HNO of 1:1
3, ultrasonic 1-2 minute respectively in absolute ethyl alcohol, redistilled water, finally by the electrode high-purity N of handling well
2dry up.The preparation process of compound substance modified electrode is as follows: get 8 μ L2mgmL
-1compound substance solution drip at twice on the glass-carbon electrode of handling well, the natural drying compound substance modified electrode that obtains under room temperature.Test as a comparison for HNTs modified electrode with legal system, for H
2o
2detection.
Embodiment 3Ru (bpy)
3 2+the preparation of/AuNPs-HNTs/Nafion modified electrode
On above-mentioned compound substance modified electrode, drip 8 μ L0.5%Nafion, naturally dry, be then dipped into 1.0*10-
3m Ru (bpy)
3 2+in solution 1.5 hours.
Embodiment 4AuNPs-HNTs modified electrode is to H
2o
2detection
AuNPs-HNTs modified electrode can be used to quantitatively detect the content of hydrogen peroxide, and catalytic current value and H
2o
2linear in concentration 5.0 μ M-255 μ M, linearly dependent coefficient is 0.997, detects and is limited to 1 μ M, compared with HNTs modified electrode, has higher sensitivity and detectability.
Kaolin nanotube (a), golden nanometer particle-functionalized kaolin nanometer tube composite materials (b) modified electrode, in saturated PBS (PH7.0) solution, add 15mol/LH continuously under-0.3V condition
2o
2chronoamperogram as shown in Figure 3.
Embodiment 5Ru (bpy)
3 2+the electrochemiluminescdetection detection of/AuNPs-HNTs/Nafion modified electrode to TPA
Ru (bpy)
3 2+/ AuNPs-HNTs/Nafion modified electrode is electrogenerated chemiluminescence spectrogram (the photomultiplier high pressure 600V) as shown in Figure 4 in 0.68mmol/L tripropyl amine (TPA) in concentration, shows that this modified electrode shows good electrochemiluminescence character to tripropyl amine (TPA).
Claims (1)
1. the application of golden nanometer particle-functionalized kaolin nanometer tube composite materials in the modified electrode of preparation detection tripropyl amine (TPA), is characterized in that, described golden nanometer particle-functionalized kaolin nanometer tube composite materials is prepared by the following method:
(1) use, with amino organosilane by kaolin nanotube amination, obtains functionalized kaolin nanotube;
(2) the ultrasonic 20～40min that mixes of kaolin nanotube solution of golden nanometer particle colloidal sol and functionalization; The particle diameter of golden nanometer particle is 1～10nm; Functionalized kaolin nanotube and golden nanometer particle amount ratio are 15～30mg/mmol;
In step (1), the amination of kaolin nanotube comprises the steps:
Kaolin nanotube adds ultrasonic dispersion 20～40min in the mixed liquor of 3-Propylamino triethoxysilane and organic solvent, and under 200～500rpm stirring reaction 8～28hr; Get washing of precipitate;
The length of kaolin nanotube is 1～15 μ m, outer tube diameter 50～70nm, interior caliber 10～30nm;
Be 3-Propylamino triethoxysilane with amino organosilane, organic solvent is toluene.
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| CN109432425B (en) * | 2018-11-27 | 2021-03-19 | 暨南大学 | Targeted gold nanorod halloysite nanotube compound and preparation method thereof |
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| EP2045214A2 (en) * | 2007-10-04 | 2009-04-08 | Gwangju Institute of Science and Technology | Gold nanoparticle-halloysite nanotube and method of forming the same |
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| EP2045214A2 (en) * | 2007-10-04 | 2009-04-08 | Gwangju Institute of Science and Technology | Gold nanoparticle-halloysite nanotube and method of forming the same |
Non-Patent Citations (6)
| Title |
|---|
| Li Mao et al.Multi-walled carbon nanotubes and Ru(bpy)32+/nano-Au nano-sphere as efficient matrixes for a novel solid-state electrochemiluminescence sensor.《Talanta》.2009,第80卷1692–1697. |
| Multi-walled carbon nanotubes and Ru(bpy)32+/nano-Au nano-sphere as efficient matrixes for a novel solid-state electrochemiluminescence sensor;Li Mao et al;《Talanta》;20091013;第80卷;1692–1697 * |
| 基于Ru(bpy)32+印刷电极的电致化学发光传感器的研制;林振宇等;《光谱学与光谱分析》;20061130;第26卷(第11期);1996-1999 * |
| 基于功能化高岭土纳米管的生物电化学研究;孙秀梅;《中国优秀硕士学位论文全文数据库 信息科技辑》;20111031(第10期);正文第38页第3.1节、第40页第3.2.3节及41页图3.2b、第45页第3.35节 * |
| 孙秀梅.基于功能化高岭土纳米管的生物电化学研究.《中国优秀硕士学位论文全文数据库 信息科技辑》.2011,(第10期),正文第38页第3.1节、第40页第3.2.3节及41页图3.2b、第45页第3.35节. |
| 林振宇等.基于Ru(bpy)32+印刷电极的电致化学发光传感器的研制.《光谱学与光谱分析》.2006,第26卷(第11期),1996-1999. |
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