CN109490394A - A kind of preparation method of nanogold-carbon nano tube compound material and its application in electro-catalysis - Google Patents
A kind of preparation method of nanogold-carbon nano tube compound material and its application in electro-catalysis Download PDFInfo
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Abstract
The invention discloses a kind of preparation methods of nanogold-carbon nano tube compound material, 1 is successfully synthesized first, 3- bis- (3- bromopropyl) imidazoles bromide ionic liquid, and as Morphological control agent, by adjusting the concentration of ionic liquid and the dosage of reducing agent, it is successfully prepared hollow Nano gold goal, and nanogold-carbon nano tube compound material is compounded to form with carboxylic carbon nano-tube, use above-mentioned composite material modified electrode as working electrode, electrochemical analysis is carried out to kojic acid, the carbon nano-composite material is conductive can be superior, the advantages that bio-compatible performance is good, the cost of material of preparation method of the present invention is relatively low, it is easy to operate and control, it is repeated high, it is environmentally protective, it is easily achieved large-scale production, nanogold-carbon nano tube compound material of preparation is shown to the good electro catalytic activity of kojic acid.
Description
Technical field
The invention belongs to electrocatalysis material technical fields, and in particular to a kind of system of nanogold-carbon nano tube compound material
Preparation Method and its application in electro-catalysis.
Background technique
Carbon nanotube is a kind of One-dimensional Quantum material with special construction, it has been investigated that, carbon nanotube have one layer and
Point of multilayer, i.e. single-walled carbon nanotube (SWNTs) and multi-walled carbon nanotube (MWNTs), either multilayer or single-layered carbon nanotube
Pipe all has good conductive property, mechanical performance, heat transfer property etc., this makes carbon nanotube in electrochemical device, fuel
It has a wide range of applications in terms of battery, field emission apparatus, catalyst carrier.
The extremely strong electric conductivity of carbon nanotube, absorption property and big specific surface area, play it in electro-catalysis field
Important function；On the one hand, carbon nanotube has bigger serface and good biocompatibility, is the fixation of biosensor
The place provided not only can increase the load capacity of bio-sensing substance, but also can effectively keep the biology of sensing element living
Property, help to improve its detection sensitivity and selectivity；On the other hand, the superpower mechanical property of carbon nanotube and electric conductivity,
It can accelerate the electron transmission speed between biomolecule and electrode interface；However carbon nanotube also has certain chemical inertness,
It is difficult to dissolve in a solvent and disperses, which limits its applications in fields such as electro-catalysis；Studies have shown that can by strong acid or
Nitration mixture handles carbon nanotube, makes its surface with carboxyl or hydroxyl isoreactivity functional group, then by electrostatic self-assembled or covalently
The mode of bonding and other materials, which carry out being compounded to form composite material, carries out functional modification to it, this can obviously increase carbon nanometer
The activity and its dispersibility of pipe, expand its application category.
Imidazolium ionic liquid has preferable compared to traditional ionic liquid in empty gas and water and electro-chemical test
Stability, and have wider liquid state range；It can be used as stabilizer modify regulation noble metal nano pattern and
Base group modification is carried out to noble metal nano surface, the functionalized ion liquid for modifying nanoparticle usually has sulfydryl, carboxylic
Base, amino, hydroxyl, due to the presence of these groups, nanoparticle can more easily disperse in the solution, can also pass through covalent bond
Conjunction or Electrostatic Absorption and other materials progress are compound, improve its performance.
Kojic acid (chemical name is 5-hydroxy-2-hydroxamethy-1,4-pyrone) has food fresh keeping, removes free radical, increases
The effects of Bai Meirong, once in the brewing of soy sauce and drinks, thick broad-bean sauce, food additives and some whitening class cosmetics extensively
It uses；In recent years, the numerous studies discovery kojic acid of scientists had certain carcinogenesis, therefore in medicine, cosmetics and food
Great attention is caused to the detection of kojic acid in product field.
The measuring method of kojic acid has liquid chromatography, gas chromatography, chromatography and electrochemical process etc., wherein electrochemical process
It is compared with other methods, there are the advantages such as at low cost, easy to operate, response is rapid.
Summary of the invention
In response to the problems existing in the prior art, the purpose of the present invention is to provide a kind of nanogold-carbon nano tube compound materials
Preparation method.
The object of the invention is also to provide a kind of nanometers for having efficient electrocatalysis characteristic made from the preparation method
Application of the gold-carbon nano tube compound material in kojic acid electrochemical analysis.
To achieve the above object, the technical solution adopted by the present invention is that:
A kind of preparation method of nanogold-carbon nano tube compound material, includes the following steps:
The preparation of S1,1,3- bis- (3- bromopropyl) imidazoles bromide ionic liquid: 1,3- dibromopropane is added in sodium hydride, imidazoles
In acetonitrile solution, heating stirring reaction, gained reactant removes acetonitrile to get target crude product；
The preparation of S2, hollow Nano gold goal: by 1,3- bis- made from step S1 (3- bromopropyl) imidazoles bromide ionic liquid solution
HAuCl is added4, NaBH is injected rapidly4Solution, 1,3-, bis- (3- bromopropyl) the imidazoles bromide ionic liquid solution, HAuCl4、
NaBH4Molar ratio be 3:1:6, be stirred to react, gained reactant centrifugation, obtain hollow Nano gold goal；
The preparation of S3, carboxylated single-walled carbon nanotube: under stirring condition, acid with strong oxidizing property is added in single-walled carbon nanotube, institute
Reactant centrifugation is obtained to get carboxylated single-walled carbon nanotube；
S4, the preparation of nanogold-carbon nano tube compound material: under ultrasound condition, by hollow Nano gold goal and carboxylated single wall carbon
Nanotube is dispersed in water and is uniformly mixed, and KOH is added, and heating stirring reaction is cooled to room temperature, precipitating is collected by centrifugation, then pass through
Washing, drying, obtain the nanogold-carbon nano tube compound material, are named as SWNTs/AuNBs.
Preferably, sodium hydride in step S1, imidazoles, 1,3- dibromopropane molar ratio be 2:1:5.
Preferably, heating stirring reaction carries out under the conditions of 60 DEG C in step S1.
Preferably, gained target product is used further to subsequent operation after purification in step S1.
Preferably, further include purification step: being specifically by target crude product obtained through silica gel column chromatography, with by volume ratio
For the eluent that the methylene chloride and methanol of 1 ~ 10:1 form, eluent is evaporated off solvent, obtains object after purification.
It is furthermore preferred that the eluant, eluent is made of the methylene chloride that volume ratio is 5:1 and methanol.
Preferably, 5min is stirred in reaction at 27 DEG C in step S2, and centrifugal condition is that 8000rpm is centrifuged 10min.
Preferably, the solid-to-liquid ratio of single-walled carbon nanotube and acid with strong oxidizing property is 10:3 in step S3.
Preferably, by the concentrated sulfuric acid, 3:1 is mixed the acid with strong oxidizing property by volume with nitric acid.
Preferably, in step S4 hollow nano gold spherical and carboxylated single-walled carbon nanotube mass ratio 1:1.
The present invention also provides nanogold-made from a kind of preparation method of nanogold-carbon nano tube compound material
Carbon nano tube compound material is applied to in the electro-catalysis chemical analysis of kojic acid.
SWNTs/AuNBs nanocomposite is as follows to the electro-catalysis chemical analysis method of kojic acid:
Pre-treatment is carried out to glass-carbon electrode: by glass-carbon electrode (diameter is 3.0mm) always along a direction on abrasive paper for metallograph
It slowly polishes, after electrode surface polishing is clean, is cleaned up repeatedly with water, it is molten to place an electrode within dehydrated alcohol later
Ultrasound 2min, is again cleaned up glassy carbon electrode surface with water in liquid, is then set the electrode and is dried in the air naturally in a cool and dry place
It is dry.
The preparation of SWNTs/AuNBs nanocomposite modified glassy carbon electrode: thorough to the glass-carbon electrode Jing Guo pre-treatment
After drying, the SWNTs/AuNBs solution drop coating and glassy carbon electrode surface of 5 μ L 5mg/mL are taken, the modified electrode prepared is set
Naturally dry in a cool and dry place, it is spare.
Electrochemical cyclic voltammetry condition: electrolyte solution is 0.001mol/L acetic acid-sodium acetate solution of pH6.0, is swept
Retouching rate is 100mVs-1。
SWNTs/AuNBs nanocomposite modified glassy carbon electrode pair has been investigated by electrochemistry differential pulse voltammetry
Kojic acid electrocatalytic oxidation peak current is responded with the ever-increasing series of concentration.
Electrochemistry differential pulse voltammetry condition: electrolyte solution is that 0.001mol/L acetic acid-sodium acetate of pH6.0 is molten
Liquid, pulse period are 0.2s, and pulse width is 50ms, and pulse amplitude is 50mV.
Compared with prior art, the beneficial effects of the present invention are:
(1) present invention replaces imidazole radicals by dibromoalkane hydrocarbon, forms branch chain belt bromine atom, and anion is the 1,3- of bromide ion
Two (3- bromopropyl) imidazoles bromide ionic liquids, and as Morphological control agent, by the concentration and reduction that adjust ionic liquid
The dosage of agent is successfully prepared hollow Nano gold goal, due to the excellent stability of ionic liquid and solubility property, nanoparticle energy
More easily disperse in the solution, and due to the electrostatic repulsion that ionic liquid difference group generates, nanoparticle can be allowed
Between generate different spacing, improve the stability of nanoparticle dispersion liquid, avoid solution coagulation.
(2) present invention is by electrostatic adsorption by electronegative carboxylated single-walled carbon nanotube and Ionic Liquid Modified
Hollow gold nanometer ball is compounded to form SWNTs/AuNBs nanocomposite, and one side hollow gold nanometer ball is to single-walled carbon nanotube
Electrocatalysis characteristic play sensitization, the big specific surface energy of another aspect single-walled carbon nanotube improves the negative of hollow gold nanometer ball
Carrying capacity, the two collaboration improves the electrocatalysis characteristic to kojic acid, and then improves the electrochemical analysis detection sensitivity to kojic acid.
Detailed description of the invention
Fig. 1 is the synthetic line figure of 1,3- bis- (3- bromopropyl) imidazoles bromide.
Fig. 2 is the nuclear magnetic resonance spectroscopy phenogram of 1,3- bis- (3- bromopropyl) imidazoles bromide.
Fig. 3 is the infrared absorption spectrum of 1,3- bis- (3- bromopropyl) imidazoles bromide ionic liquid.
Fig. 4 is that the HPLC-MS technology of 1,3- bis- (3- bromopropyl) imidazoles bromide ionic liquid is combined phenogram.
Fig. 5 is the transmission electron microscope figure of hollow Nano gold goal.
Fig. 6 is the scanning electron microscope diagram of hollow Nano gold goal.
Fig. 7 is the ultraviolet-visible absorption spectroscopy figure of hollow Nano gold goal.
Fig. 8 is the X-ray diffraction phenogram of hollow Nano gold goal.
Fig. 9 is that the transmission electron microscope of carboxylated single-walled carbon nanotube characterizes map.
Figure 10 is the x-ray photoelectron spectroscopy phenogram of carboxylated single-walled carbon nanotube.
Figure 11 is that nanogold-carbon nano tube compound material transmission electron microscope characterizes map.
Figure 12 is nanogold-carbon nano tube compound material modified electrode (a), carboxylated single-walled carbon nanotube modified electrode
(b) to the cyclic voltammetric response curve of kojic acid.
Figure 13 is the calibration graph that nanogold-carbon nano tube compound material modified electrode measures kojic acid.
Specific embodiment
In order to make the objectives, technical solutions, and advantages of the present invention clearer, with reference to embodiments, to this hair
It is bright to be further elaborated；It should be appreciated that the specific embodiments described herein are merely illustrative of the present invention, and do not have to
It is of the invention in limiting；Unless stated otherwise, the present invention uses reagent, method and apparatus is the art conventional reagents, side
Method and equipment.
Embodiment 1
A kind of preparation method of nanogold-carbon nano tube compound material, includes the following steps:
The preparation of S1,1,3- bis- (3- bromopropyl) imidazoles bromide ionic liquid: weighing 0.1058g sodium hydride, repeatedly addition contains on a small quantity
In the 30 mL acetonitrile solutions of 1.0 g of imidazoles, ice bath forms the acetonitrile suspension of white imidazole natrium after reacting three hours, is dripped
It adds to and contains 14.845g 1, in the acetonitrile solution of 3- dibromopropane, increase temperature to 60 DEG C, be stirred overnight, contact plate detection reaction
Process, rotary evaporation removes acetonitrile after completion of the reaction, and toluene washing is added, is spin-dried for obtaining crude product；And via silicagel column
(CH2Cl2: MeOH=5:1) isolate and purify after obtain thick pale yellow oily liquids 1,3- bis- (3- bromopropyl) imidazoles bromide mesh
Mark product；
As shown in Fig. 2, be the nuclear magnetic resonance spectroscopy phenogram of above-mentioned 1,3- bis- (3- bromopropyl) imidazoles bromide target product, by1The product synthesized known to the chemical shift of hydrogen corresponding to H-NMR spectrum and attribution analysis is 1,3- bis- (3- bromopropyl) miaow
Azoles bromide.
The infrared absorption spectrum of 1,3- bis- (3- bromopropyl) imidazoles bromide ionic liquid is as shown in figure 3, wherein 3144 cm-1、
3081 cm-1Place is C-H stretching vibration peak on imidazole ring, 1628 cm-1、1566 cm-1Place is the bone of C=N and C=C on imidazole ring
Frame stretching vibration peak, 752 cm-1Place's absorption peak is short chain CH2Stretching vibration, νC-BrStretching vibration is 559 cm-1, thus into
1,3- bis- (3- bromopropyl) imidazoles bromide ionic liquid target product structure of one step card synthesis is correct.
The HPLC-MS technology combination phenogram of 1,3- bis- (3- bromopropyl) imidazoles bromide ionic liquid is as shown in figure 4, spectrogram
Three peaks of middle appearancem/z 308.95255、m/z310.95047 andm/z312.94878 adjacent molecule amounts difference is 2, and peak
Height is than being m:m+2:m+4=1:2:1 this is because containing there are two bromine atom, isotopes in ionic liquid79Br and81Br isotope
Caused by peak, mass spectrographic molecular ion peakm/zWith (3- bromopropyl) the imidazoles bromide ionic liquid cation part 1,3- bis- point
Son amount is coincide, and illustrates that target product structure is correct, no other impurities compound, purity is high.
The preparation of S2, hollow Nano gold goal: under rapid stirring, 0.05mol/L 1,3- bis- (3- bromopropyl) are taken
0.01 mol/L HAuCl is added in 5 mL of imidazoles bromide ionic liquid aqueous solution45 mL, then 0.05 newly prepared is injected rapidly
mol/L NaBH4 6mL is stirred to react 5 min, 8000 r/min centrifugation, and obtains solid powder with second distillation water washing 3 times,
Be stored in 4 DEG C it is spare.
After the hollow Nano gold goal that the present embodiment is prepared is dispersed in water, drips on Tu to copper mesh and silicon wafer, dry in the air respectively
After dry, its structure and surface topography are characterized using transmission electron microscope and scanning electron microscope, as a result distinguished
As shown in Figure 5, Figure 6, by result in figure it is found that the nano gold spherical size synthesized is more uniform and have hollow structure, and surface
With porous configuration.
The ultraviolet-visible absorption spectroscopy for the hollow Nano gold goal that the present embodiment is prepared is as shown in fig. 7, by result in figure
It is found that hollow Nano gold goal has stronger absorption peak within the scope of 500 ~ 900 nm.
The X-ray diffraction characterization result for the hollow Nano gold goal that the present embodiment is prepared in figure as shown in figure 8, by tying
Fruit is observed that four characteristic diffraction peaks of Au, when 2 θ of the angle of diffraction is located at 38.38 °, 44.56 °, 64.77 °, 77.71 °, point
Not corresponding is gold atom in face-centered cube accumulation (111), (200), (220), (311) crystal face, the standard powder with Au
Diffraction spectrogram matching.
The preparation of S3, carboxylated single-walled carbon nanotube: under stirring condition, 50 mg SWNTs is weighed in a round bottom flask, are added
Enter 15 mL H2SO4And HNO3Nitration mixture (V/V=3:1), 60oC stir 1h, and gained reactant centrifugation is washed with deionized water into
Property is dried for standby, after strong acid treatment, surface can produce largely single-walled carbon nanotube to get carboxylated single-walled carbon nanotube
Carboxyl；
The transmission electron microscope of carboxylated single-walled carbon nanotube made from the present embodiment characterizes as shown in figure 9, can see from figure
Observing the single-walled carbon nanotube after strong acid treatment is still in nano tubular structure, but carbon pipe shortens, and surface is relatively rough.
The x-ray photoelectron spectroscopy characterization of carboxylated single-walled carbon nanotube made from the present embodiment is as shown in Figure 10, by scheming
Middle result is it is found that carboxylated single-walled carbon nanotube contains C1sEnergy level (284.6 eV) and O1sEnergy level (531.7eV), shows single wall carbon
Nanotube contains a large amount of carboxyls through strong acid treatment rear surface.
S4, the preparation of nanogold-carbon nano tube compound material: under ultrasound condition, 5mg hollow Nano gold goal and 5mg are weighed
Carboxylated single-walled carbon nanotube is dispersed in water and is uniformly mixed, and 20mg KOH is added, and reacts 4h in 40 DEG C of heating stirrings, cooling
To room temperature, it is collected by centrifugation precipitating, then is dried in vacuo with second distillation water washing 1-3 times and in 40 DEG C, obtains the nanogold-
Carbon nano tube compound material is named as SWNTs/AuNBs.
The transmission electron microscope characterization such as Figure 11 for SWNTs/AuNBs nanocomposite that the present embodiment is prepared
Shown, by result in figure it is found that the surface of carbon nanotube covers particulate matter, distribution of particles is more uniform, illustrates that carbon is received
Nanotube surface has successfully loaded hollow gold nanometer ball particle, and hollow gold nanometer ball is more uniform in carbon nano tube surface distribution
It is fine and closely woven, and hollow gold nanometer ball particle is mainly distributed on the tube wall of carbon nano pipe array.
In conclusion show that the present embodiment is successfully prepared nanogold-carbon nano tube compound material SWNTs/AuNBs, it should
Nanocomposite has biggish specific surface area, and size uniformity, and hollow gold nanometer ball is distributed in single pipe surface
It is uniform, illustrate through electrostatic interaction, is conducive to hollow gold nanometer ball uniform load on carboxylic carbon nano-tube tube wall, the system
Preparation Method is simply controllable.
Embodiment 2
Nanogold-carbon nano tube compound material made from embodiment 1 is applied to in the electro-catalysis chemical analysis of kojic acid.
SWNTs/AuNBs nanocomposite is as follows to the electro-catalysis chemical analysis method of kojic acid:
(1) pre-treatment is carried out to glass-carbon electrode: by glass-carbon electrode (diameter is 3.0mm) always along a side on abrasive paper for metallograph
To slowly polishing, after electrode surface polishing is clean, is cleaned up repeatedly with water, place an electrode within dehydrated alcohol later
Ultrasound 2min, is again cleaned up glassy carbon electrode surface with water in solution, is then set the electrode natural in a cool and dry place
It dries.
(2) preparation of SWNTs/AuNBs nanocomposite modified glassy carbon electrode: to the glass-carbon electrode Jing Guo pre-treatment
After thoroughly drying, SWNTs/AuNBs solution, SWNTs solution drop coating and the glassy carbon electrode surface of 5 μ L 5mg/mL are taken respectively, it will
The modified electrode prepared sets naturally dry in a cool and dry place, spare.
(3) SWNTs/AuNBs modified electrode that step (2) is prepared, SWNTs modified electrode are being added
Cyclic voltammetry scan is carried out in acetic acid-sodium acetate solution before and after 0.001mol/L kojic acid.
Electrochemical cyclic voltammetry condition: electrolyte solution is 0.001mol/L acetic acid-sodium acetate solution of pH6.0, is swept
Retouching rate is 100mVs-1, as a result as shown in figure 12.
Known to curve 1,3 in Figure 12: in acetic acid-sodium acetate solution of blank, there is no corresponding response peaks to occur；
Known to curve 2,4 in Figure 12: when 0.001mol/L kojic acid is added into acetic acid-sodium acetate solution, SWNTs/AuNBs is repaired
There is the catalysis oxidation peak to kojic acid at 0.474V in decorations electrode, and SWNTs modified electrode occurs at 0.506V to kojic acid
Catalysis oxidation peak, SWNTs/AuNBs modified electrode is negative compared with the oxidation spike potential of SWNTs modified electrode to have moved 0.032V, says
Bright SWNTs/AuNBs composite material has better electrocatalytic oxidation effect to kojic acid than independent SWNTs；This is because by strong
The SWNTs of acid processing preparation has many advantages, such as large specific surface area, high surface activity, in addition the hollow structure of hollow gold nanometer ball,
And surface has porous configuration, further improves the active site on the surface SWNTs, collaboration improves the electrocatalysis to kojic acid
Can, so that SWNTs/AuNBs composite material is shown electrocatalysis characteristic more better than single material, illustrates that SWNTs/AuNBs is multiple
Condensation material modified electrode surface electronic transfer rate is faster.
Embodiment 3
SWNTs/AuNBs nanocomposite modified glassy carbon electrode has been investigated to kojic acid by electrochemistry differential pulse voltammetry
Electrocatalytic oxidation peak current is responded with the ever-increasing series of concentration, electrochemistry differential pulse voltammetry condition: electrolyte solution
For 0.001mol/L acetic acid-sodium acetate solution of pH6.0, the pulse period is 0.2s, and pulse width is 50ms, and pulse amplitude is
50mV。
As a result as shown in figure 13, You Tuzhong as the result is shown: the concentration of kojic acid is 1.0 × 10-9 mol/L ~ 3× 10-5
There is good linear relationship, linear equation within the scope of mol/L are as follows:I (μA ) = 6.58× 10-3 c / (μmol/L) +
5.478 × 10-4 (R=0.9996), detection limit are 8 × 10-10Mol/L (S/N=3), the sensor show kojic acid
Quick out, sensitive biocatalysis response.
Embodiment 4
A large amount of inorganic ions has been investigated using electrochemical cyclic voltammetry and common are the shadow that machine object molecule measures kojic acid
It rings, the results showed that NO3 -、SO4 2-、Ca2+、Cl-And PO4 3-Equal inorganic ions do not influence SWNTs/AuNBs nanocomposite
Measurement of the modified electrode to kojic acid；The organic molecules such as ethyl alcohol, glucose, glyphosate nor affect on the measurement of kojic acid；But first
Base parathion molecule and L-cysteine have a certain impact to the measurement of kojic acid, it may be possible to due to benzene in parathion-methyl molecule
The nitro moiety connected on ring is easy to chemically react, it is caused to occur in conjunction with SWNTs/AuNBs nanocomposite
Electrocatalysis；And containing this group of sulfydryl in L-cysteine, sulfydryl there is certain murder by poisoning to make some metallics
With, can bind metal ion generate mercaptides.
Embodiment 5
The present embodiment is examined by electrochemical cyclic voltammetry has held a memorial ceremony for SWNTs/AuNBs nanocomposite modification electricity in one month
The stability of pole, SWNTs/AuNBs nanocomposite modified electrode is electric to kojic acid catalysis oxidation peak after one month as the result is shown
The size of stream remains at initial 97%, illustrates that SWNTs/AuNBs nanocomposite modified electrode has the detection of kojic acid
There is higher stability.
In conclusion the present invention is prepared for the single-walled carbon nanotube of carboxylated by strong acid oxidation processes single-walled carbon nanotube
Nano material, and with 1,3- bis- (3- bromopropyl) imidazoles bromide ionic liquid, it is Morphological control agent, by adjusting the dense of ionic liquid
The dosage of degree and reducing agent, is successfully prepared hollow Nano gold goal, is then further successfully prepared by aqueous phase synthesis method
SWNTs/AuNBs nanocomposite, preparation method of the present invention is relatively simple, the nano combined material of SWNTs/AuNBs obtained
Expect that pattern is good, stability is stronger, not easy to reunite；Electrochemistry is prepared into SWNTs/AuNBs nanocomposite modified electrode to pass
Sensor has carried out electrocatalysis characteristic detection to kojic acid molecule, the results showed that, SWNTs/AuNBs nanocomposite has kojic acid
Good electrocatalytic oxidation effect, and modified electrode is sensitive to kojic acid response, detection limit reaches 8 × 10-10Mol/L, and this
The sensor good in anti-interference performance of preparation is invented, stability is good, and responsing linear range is wide, is in real life to kojic acid molecule
Electrochemical Detection provides new method.
The above, only of the invention illustrates embodiment, not to the present invention in any form with substantial limitation,
It should be pointed out that for those skilled in the art, under the premise of not departing from the method for the present invention, that makes several changes
It also should be regarded as protection scope of the present invention into supplement；All those skilled in the art, do not depart from spirit of that invention and
In the case where range, using the equivalent variations of a little change, modification and differentiation that disclosed above technology contents are made, it is
Equivalent embodiment of the invention；Meanwhile any equivalent variations that all substantial technologicals according to the present invention do above-described embodiment
Change, modification and differentiation, still fall within protection scope of the present invention.
Claims (10)
1. a kind of preparation method of nanogold-carbon nano tube compound material, which comprises the steps of:
The preparation of S1,1,3- bis- (3- bromopropyl) imidazoles bromide ionic liquid: 1,3- dibromopropane is added in sodium hydride, imidazoles
In acetonitrile solution, heating stirring reaction, gained reactant removes acetonitrile to get target crude product；
The preparation of S2, hollow Nano gold goal: by 1,3- bis- made from step S1 (3- bromopropyl) imidazoles bromide ionic liquid solution
HAuCl is added4, NaBH is injected rapidly4Solution, 1,3-, bis- (3- bromopropyl) the imidazoles bromide ionic liquid solution, HAuCl4、
NaBH4Molar ratio be 3:1:6, be stirred to react, gained reactant centrifugation, obtain hollow Nano gold goal；
The preparation of S3, carboxylated single-walled carbon nanotube: under stirring condition, acid with strong oxidizing property is added in single-walled carbon nanotube, institute
Reactant centrifugation is obtained to get carboxylated single-walled carbon nanotube；
S4, the preparation of nanogold-carbon nano tube compound material: under ultrasound condition, by hollow Nano gold goal and carboxylated single wall carbon
Nanotube is dispersed in water and is uniformly mixed, and KOH is added, and heating stirring reaction is cooled to room temperature, precipitating is collected by centrifugation, then pass through
Washing, drying, obtain the nanogold-carbon nano tube compound material, are named as SWNTs/AuNBs.
2. a kind of preparation method of nanogold-carbon nano tube compound material according to claim 1, which is characterized in that step
Sodium hydride in rapid S1, imidazoles, 1,3- dibromopropane molar ratio be 2:1:5.
3. a kind of preparation method of nanogold-carbon nano tube compound material according to claim 1, which is characterized in that step
Heating stirring reaction carries out under the conditions of 60 DEG C in rapid S1.
4. a kind of preparation method of nanogold-carbon nano tube compound material according to claim 1, which is characterized in that step
Gained target product is used further to subsequent operation after purification in rapid S1.
5. the preparation method of described in any item a kind of nanogold-carbon nano tube compound materials according to claim 1 ~ 4, feature
It is, further includes purification step: is specifically by target crude product obtained through silica gel column chromatography, is 1 ~ 10:1's with by volume ratio
The eluent of methylene chloride and methanol composition, eluent are evaporated off solvent, obtain object after purification.
6. a kind of preparation method of nanogold-carbon nano tube compound material according to claim 1, which is characterized in that step
5min is stirred in reaction at 27 DEG C in rapid S2, and centrifugal condition is that 8000rpm is centrifuged 10min.
7. a kind of preparation method of nanogold-carbon nano tube compound material according to claim 1, which is characterized in that step
The solid-to-liquid ratio of single-walled carbon nanotube and acid with strong oxidizing property is 10:3 in rapid S3.
8. a kind of preparation method of nanogold-carbon nano tube compound material according to claim 1 or claim 7, which is characterized in that
By the concentrated sulfuric acid, 3:1 is mixed the acid with strong oxidizing property by volume with nitric acid.
9. a kind of preparation method of nanogold-carbon nano tube compound material according to claim 1 or claim 7, which is characterized in that
The mass ratio 1:1 of hollow nano gold spherical and carboxylated single-walled carbon nanotube in step S4.
10. nanogold-carbon made from a kind of preparation method of nanogold-carbon nano tube compound material described in claim 1 is received
Mitron composite material is applied to in the electro-catalysis chemical analysis of kojic acid.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115000446A (en) * | 2022-07-22 | 2022-09-02 | 上海电气集团股份有限公司 | Gas diffusion layer, preparation method thereof, membrane electrode, cell and application |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314469A (en) * | 2008-07-03 | 2008-12-03 | 浙江大学 | Preparation of water-soluble carbon nano-tube and nano-precious metal particle load method |
| CN104085876A (en) * | 2014-06-30 | 2014-10-08 | 济南大学 | Preparation method for carbon nano tube-loaded double-metal oxide hollow nano-particles |
| CN104884194A (en) * | 2012-12-27 | 2015-09-02 | Lg化学株式会社 | Hollow metal nanoparticle supported by support body |
-
2018
- 2018-10-24 CN CN201811244628.0A patent/CN109490394A/en active Pending
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101314469A (en) * | 2008-07-03 | 2008-12-03 | 浙江大学 | Preparation of water-soluble carbon nano-tube and nano-precious metal particle load method |
| CN104884194A (en) * | 2012-12-27 | 2015-09-02 | Lg化学株式会社 | Hollow metal nanoparticle supported by support body |
| CN104085876A (en) * | 2014-06-30 | 2014-10-08 | 济南大学 | Preparation method for carbon nano tube-loaded double-metal oxide hollow nano-particles |
Non-Patent Citations (2)
| Title |
|---|
| CAIYUN WANG 等: "Molecularly Imprinted Photo-electrochemical Sensor for Human Epididymis Protein 4 Based on Polymerized Ionic Liquid Hydrogel and Gold Nanoparticle/ZnCdHgSe Quantum Dots Composite Film", 《ANALYTICAL CHEMISTRY》 * |
| 马建春 等: "多壁碳纳米管-纳米金粒子复合材料修饰玻碳电极的研制及其在曲酸测定中的应用", 《理化检验(化学分册)》 * |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115000446A (en) * | 2022-07-22 | 2022-09-02 | 上海电气集团股份有限公司 | Gas diffusion layer, preparation method thereof, membrane electrode, cell and application |
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