CN104831277A - Preparation method and application of poly-sulfosalicylic acid / titanium dioxide / carbon nanotube nanocomposite with electrode as substrate - Google Patents
Preparation method and application of poly-sulfosalicylic acid / titanium dioxide / carbon nanotube nanocomposite with electrode as substrate Download PDFInfo
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- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 title claims abstract description 120
- 239000002041 carbon nanotube Substances 0.000 title claims abstract description 69
- 229910021393 carbon nanotube Inorganic materials 0.000 title claims abstract description 69
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 59
- 239000004408 titanium dioxide Substances 0.000 title claims abstract description 52
- 238000002360 preparation method Methods 0.000 title claims abstract description 40
- 239000000758 substrate Substances 0.000 title claims abstract description 20
- 239000002114 nanocomposite Substances 0.000 title abstract description 11
- WXHLLJAMBQLULT-UHFFFAOYSA-N 2-[[6-[4-(2-hydroxyethyl)piperazin-1-yl]-2-methylpyrimidin-4-yl]amino]-n-(2-methyl-6-sulfanylphenyl)-1,3-thiazole-5-carboxamide;hydrate Chemical compound O.C=1C(N2CCN(CCO)CC2)=NC(C)=NC=1NC(S1)=NC=C1C(=O)NC1=C(C)C=CC=C1S WXHLLJAMBQLULT-UHFFFAOYSA-N 0.000 title abstract 3
- HVBSAKJJOYLTQU-UHFFFAOYSA-N 4-aminobenzenesulfonic acid Chemical compound NC1=CC=C(S(O)(=O)=O)C=C1 HVBSAKJJOYLTQU-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229950000244 sulfanilic acid Drugs 0.000 claims abstract description 51
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 16
- 239000011259 mixed solution Substances 0.000 claims abstract description 12
- 239000000725 suspension Substances 0.000 claims abstract description 12
- 238000002484 cyclic voltammetry Methods 0.000 claims abstract description 10
- 230000035945 sensitivity Effects 0.000 claims abstract description 10
- 238000000926 separation method Methods 0.000 claims abstract description 7
- 229910052799 carbon Inorganic materials 0.000 claims abstract description 5
- 239000007864 aqueous solution Substances 0.000 claims abstract description 3
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 claims description 31
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 claims description 31
- 229940116269 uric acid Drugs 0.000 claims description 31
- 239000002131 composite material Substances 0.000 claims description 28
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 claims description 15
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 12
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 12
- 238000000034 method Methods 0.000 claims description 10
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 8
- 230000008021 deposition Effects 0.000 claims description 8
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 7
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 7
- 230000004913 activation Effects 0.000 claims description 7
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 7
- 238000003756 stirring Methods 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 5
- 125000004122 cyclic group Chemical group 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 239000002253 acid Substances 0.000 claims description 4
- 238000005516 engineering process Methods 0.000 claims description 4
- 239000000203 mixture Substances 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 230000032683 aging Effects 0.000 claims description 3
- 230000009514 concussion Effects 0.000 claims description 3
- 239000000428 dust Substances 0.000 claims description 3
- 238000011049 filling Methods 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 3
- 230000010355 oscillation Effects 0.000 claims description 3
- 238000005498 polishing Methods 0.000 claims description 3
- 238000010408 sweeping Methods 0.000 claims description 2
- 238000001035 drying Methods 0.000 abstract description 5
- 239000007772 electrode material Substances 0.000 abstract description 4
- 230000006798 recombination Effects 0.000 abstract description 2
- 238000005215 recombination Methods 0.000 abstract description 2
- 239000011248 coating agent Substances 0.000 abstract 1
- 238000000576 coating method Methods 0.000 abstract 1
- 239000002071 nanotube Substances 0.000 abstract 1
- SOQBVABWOPYFQZ-UHFFFAOYSA-N oxygen(2-);titanium(4+) Chemical compound [O-2].[O-2].[Ti+4] SOQBVABWOPYFQZ-UHFFFAOYSA-N 0.000 abstract 1
- 239000000463 material Substances 0.000 description 31
- 239000000243 solution Substances 0.000 description 20
- -1 carbon nano tube compound Chemical class 0.000 description 15
- 230000000694 effects Effects 0.000 description 12
- 150000001875 compounds Chemical class 0.000 description 8
- 238000002203 pretreatment Methods 0.000 description 5
- 239000002238 carbon nanotube film Substances 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000011159 matrix material Substances 0.000 description 4
- 238000002156 mixing Methods 0.000 description 4
- 239000001117 sulphuric acid Substances 0.000 description 4
- 235000011149 sulphuric acid Nutrition 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 3
- BYGOPQKDHGXNCD-UHFFFAOYSA-N tripotassium;iron(3+);hexacyanide Chemical compound [K+].[K+].[K+].[Fe+3].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] BYGOPQKDHGXNCD-UHFFFAOYSA-N 0.000 description 3
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 229960001149 dopamine hydrochloride Drugs 0.000 description 2
- 229910021389 graphene Inorganic materials 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 239000000276 potassium ferrocyanide Substances 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 229910019142 PO4 Inorganic materials 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- RTAQQCXQSZGOHL-UHFFFAOYSA-N Titanium Chemical compound [Ti] RTAQQCXQSZGOHL-UHFFFAOYSA-N 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 238000004220 aggregation Methods 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000008901 benefit Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000004567 concrete Substances 0.000 description 1
- 229920001940 conductive polymer Polymers 0.000 description 1
- 230000021615 conjugation Effects 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010790 dilution Methods 0.000 description 1
- 239000012895 dilution Substances 0.000 description 1
- 239000000539 dimer Substances 0.000 description 1
- ZPWVASYFFYYZEW-UHFFFAOYSA-L dipotassium hydrogen phosphate Chemical class [K+].[K+].OP([O-])([O-])=O ZPWVASYFFYYZEW-UHFFFAOYSA-L 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 230000005764 inhibitory process Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002159 nanocrystal Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000956 nontoxicity Toxicity 0.000 description 1
- 239000003921 oil Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 235000021317 phosphate Nutrition 0.000 description 1
- 239000008363 phosphate buffer Substances 0.000 description 1
- 150000003013 phosphoric acid derivatives Chemical class 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 125000002924 primary amino group Chemical group [H]N([H])* 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000000630 rising effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 239000010936 titanium Substances 0.000 description 1
- 229910052719 titanium Inorganic materials 0.000 description 1
- 239000003440 toxic substance Substances 0.000 description 1
Landscapes
- Inorganic Compounds Of Heavy Metals (AREA)
- Carbon And Carbon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention belongs to the technical field of electrode materials, particularly relates to a preparation method and application of a poly-sulfosalicylic acid / titanium dioxide / carbon nanotube nanocomposite with electrode as the substrate. The preparation method includes the following steps: first, uniformly dropwise coating a mixed solution of a nanotube carbon suspension and nano-titanium dioxide colloidal on the surface of an activated white electrode, drying and placing the electrode in an aqueous solution of sulfanilic acid for cyclic voltammetry polymerization, airing the electrode after polymerization to obtain the poly-sulfosalicylic acid / titanium dioxide / carbon nanotube nanocomposite with electrode as the substrate. The nanocomposite prepared by the invention has good electron transport properties, can effectively avoid the fast photo-generated electron-hole recombination of titanium dioxide, and has high selectivity and sensitivity. The nanocomposite prepared by the invention has wide application prospects in biomolecule separation and determination.
Description
Technical field
The present invention relates to the preparation method of matrix material, particularly a kind of take electrode as the preparation method of the poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials of substrate, belongs to electrode materials technical field.
Background technology
The titanium dioxide nano material photo-generate electron-hole that specific surface area is large, light absorption good because having, good dispersity, nontoxicity, chemical stability are high and higher to features such as redox potentials, and is widely used as optical, electrical catalyst application in photochemical catalysis and photodegradation, the structure biosensor of the toxic substances such as organic dye with prepare the fields such as new energy materials.But the catalytic capability of titanium dioxide is subject to aggregation of particles and fast photo-generate electron-hole to the restriction of compound.
Week waits people (K.F. Zhou, Y.H. Zhu, X.L. Yang, X. Jiang, C.Z. Li, Preparation of graphene – TiO
2composites with enhanced photocatalytic activity, New J. Chem. 35 (2011) 353 – 359) titanic oxide nano compound material prepared using Graphene, carbon nanotube etc. as propping material effectively can avoid the gathering of titanium dioxide nano-particle, thus strengthen its catalytic performance, but the right quick compound of photo-generate electron-hole still cannot be avoided.In prior art, in order to reduce the right recombination rate of photo-generate electron-hole, prepared the titanic oxide nano compound material of the semiconductor nanoparticles such as surface deposition CdS, but this matrix material electronics transport performance often decreases.In the preparation process of above matrix material, or directly introduce titanium dioxide, or adopt mechanical grinding method to obtain nano composite material, when being applied to electrode materials, this preparation method is loaded down with trivial details.
Summary of the invention
Building-up process for titanic oxide nano compound material in prior art cannot avoid the shortcoming of titanium dioxide photo-generate electron-hole compound faster, the invention provides a kind of take electrode as the preparation method of the poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials of substrate, surface deposition one deck Sulphanilic Acid polymeric film of titanium dioxide/carbon nano tube compound material prepared by the method, electronics transport performance is good and effectively can avoid titanium dioxide photo-generate electron-hole compound faster, has high selectivity and sensitivity.
The technical scheme that the present invention is adopted to achieve these goals is:
The invention provides a kind of take electrode as the preparation method of the poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials of substrate, comprises the following steps:
(1) by the nano titanium oxide colloid of the carbon nano tube suspension of 0.5mg/mL and 0.074mmol/mL by volume 3.5:1-5:1 mix after mixed solution, 5-8 μ L mixed solution is dripped uniformly the blank electrode surface being coated in activation, dry under being placed on infrared lamp;
(2) the Sulphanilic Acid aqueous solution electrode after oven dry being placed in 2mmol/L carries out cyclic voltammetric polymerization, polymerizing condition is: potential region-1.5-2.5V, sweep velocity is 100mV/s, sensitivity is 100 μ A, waiting time 2s, the polymerization number of turns is 8 circles, dries, be namely able to poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials that electrode is substrate after being polymerized.
Further, in step (1), the preparation method of described carbon nano tube suspension is: take 0.02g carbon nanotube and be placed in 40mL dehydrated alcohol, is placed in sonic oscillation instrument supersound process 4h.
Further, in step (1), the preparation method of described nano titanium oxide colloid is: in the beaker filling 20mL dehydrated alcohol, drip 1mL tetra-n-butyl titanate under magnetic stirring, stirs 15-30s; Slowly instill the dust technology of 20mL 0.2mol/L with acid buret, dripping speed is 1/s; After dripping off, continue to stir 30min, then beaker to be positioned in 25-40 DEG C of thermostat container after ageing 24h.
Further, in step (1), the preparation method of blank electrode is: rinse after glass-carbon electrode polishing with intermediate water, and in intermediate water ultrasonic vibration 3min, then ultrasonic vibration 3min in dehydrated alcohol, is finally placed in intermediate water excusing from death concussion 3min, dries and obtain blank electrode.
The activation condition of above-mentioned blank electrode is: blank electrode is placed in 1mol/L sulfuric acid, is-0.6-1.2V at potential region, and surface sweeping speed is under 100mV/s condition, adopts cyclic voltammetry to sweep 10 circles.
Poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials prepared by the present invention is for being substrate with electrode, and poly-Sulphanilic Acid uniform deposition is on titanium dioxide/carbon nanotube composite materials surface.
Present invention also offers the application of a kind of poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials in bio-molecular separation measures.
Further, described poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials is at the separation determination of xitix (AA), Dopamine HCL (DA), uric acid (UA) composition.
The present invention is on the preparation basis of titanium dioxide and carbon nano tube compound material, first by Study on Synthesis of Nanocrystal Titanium Dionide colloid, adopt drop-coating that titanium dioxide and carbon nanotube mixed solution are dropped in glassy carbon electrode surface, finally by electrochemical method, at surface deposition one deck Sulphanilic Acid polymeric film of titanium dioxide/carbon nano tube compound material, because poly-Sulphanilic Acid is a kind of conductive polymers with ion-exchange performance, sulfonic group is had in the contraposition of its amino, presence bit inhibition effect and strong sucting electronic effect, effectively can suppress the reset in titanic oxide electronic-hole, extend the lifetime of electron-hole.In addition, the π-electron system of a large amount of height delocalizations that amino phenyl sulfonyl acid dimer can exist with carbon nanotube side-wall forms large conjugated system by pi-pi bond conjugation, promotes the transfer transport of polymeric inner.The synthesized poly-Sulphanilic Acid/katalysis of titanium dioxide/carbon nanotube composite materials to substrate shows stronger synergistic effect, in the separation determination of the compositions such as xitix (AA), Dopamine HCL (DA), uric acid (UA) is analyzed, show and there is higher selectivity and sensitivity.
Advantage of the present invention and beneficial effect are:
1. adopt the mode of sol-gel method and electropolymerization, by the nano composite material that poly-Sulphanilic Acid enveloped carbon nanometer tube, nano titanium oxide are formed, mutually collaborative, electro catalytic activity is high, effectively can avoid titanium dioxide photo-generate electron-hole compound faster.
2. the poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials of substrate that what prepared by the present invention with electrode is, has high selectivity and sensitivity, can carry out separation determination to various biomolecules.
Accompanying drawing explanation
Fig. 1 is the scanning electron microscope (SEM) photograph of carbon nano-tube material film prepared by embodiment 1.
Fig. 2 is TiO prepared by embodiment 1
2the scanning electron microscope (SEM) photograph of/carbon nano tube compound material film.
Fig. 3 is the scanning electron microscope (SEM) photograph of poly-Sulphanilic Acid/titanium dioxide/carbon nano tube compound material prepared by embodiment 1.
Fig. 4 is the cyclic voltammogram of electrode at uric acid (UA) solution of the differing materials modification of effect example 1.
Wherein, the poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials modified electrode of a blank electrode, b carbon nano tube modified electrode, c embodiment 1 preparation.
Fig. 5 is the cyclic voltammogram of electrode in the Tripotassium iron hexacyanide and potassium ferrocyanide solution of 1 mmol/L that the differing materials of effect example 2 is modified.
Wherein a blank electrode, b carbon nano tube modified electrode, c polymerization Sulphanilic Acid modified electrode, d nano titanium oxide/carbon nano tube modified electrode, e gather Sulphanilic Acid/nano titanium oxide/carbon nano tube modified electrode.
Fig. 6 is nano composite material differential pulse graphic representation in the solution changing AA and UA concentration of effect example 3.
Wherein, AA concentration is followed successively by 0.25 × 10
-3mol/L, 0.50 × 10
-3mol/L, 0.75 × 10
-3mol/L, 1.00 × 10
-3mol/L, 1.25 × 10
-3mol/L, 1.5 × 10
-3mol/L; The concentration of UA is followed successively by 0.5 × 10
-5mol/L, 1.5 × 10
-5mol/L, 2.5 × 10
-5mol/L, 4.0 × 10
-5mol/L, 5.0 × 10
-5mol/L, 6.0 × 10
-5mol/L.
Fig. 7 be the nano composite material of effect example 4 at fixing AA, UA, change differential pulse graphic representation in the solution of DA concentration.
Wherein, AA concentration is 0.4 × 10
-3mol/L; UA concentration is 1.0 × 10
-5mol/L; The concentration of DA is followed successively by 1.0 × 10
-5mol/L, 2.0 × 10
-5mol/L, 3.0 × 10
-5mol/L, 4.0 × 10
-5mol/L, 5.0 × 10
-5mol/L, 6.0 × 10
-5mol/L, 7.0 × 10
-5mol/L.
Embodiment
Below in conjunction with embodiment, the invention will be further described.The raw materials used Reagent Company that is buys, more than analytical pure.
The preparation of reagent and electrode materials pre-treatment:
1. the preparation of phosphate buffer soln (PBS)
Take 11.4 g dipotassium hydrogen phosphates respectively, 6.8 g potassium primary phosphates, be placed in two beakers respectively, after dissolving with intermediate water, constant volume, in two 500 mL volumetric flasks, in certain proportion by two kinds of solution mixing, prepares the PBS buffered soln of different pH respectively.
2. the preparation of 1 mol/L sulphuric acid soln
Measure 5.4 mL 98% vitriol oils, slowly pour in the beaker filling quantitative intermediate water and dilute, leave standstill and move into constant volume in 100 mL volumetric flasks after solution cooling, for subsequent use;
3. the preparation of the Tripotassium iron hexacyanide/potassium ferrocyanide solution
Take the 0.165 g Tripotassium iron hexacyanide, 0.211 g yellow prussiate of potash and 3.73 g Repone K respectively and be placed in beaker, with pH be the PBS solution constant volume of 7.00 in 500 mL volumetric flasks, the K of obtained 1 mmol/L
3fe (CN)
6/ K
4fe (CN)
6solution.
4.2 × 10
-3the preparation of the Sulphanilic Acid solution of mol/L
Take the anhydrous Sulphanilic Acid of 0.0866 g, use intermediate water dissolved dilution, constant volume, in 250 mL volumetric flasks, obtains 2 × 10
-3the Sulphanilic Acid solution of mol/L.
5. electrode pre-treatment
The preparation method of blank electrode is: by after glass-carbon electrode polishing with intermediate water rinse, and in intermediate water ultrasonic vibration 3min, then ultrasonic vibration 3min in dehydrated alcohol, be finally placed in intermediate water excusing from death concussion 3min, dry and obtain blank electrode.
Embodiment 1
1. the preparation of carbon nano tube suspension: take 0.02 g carbon nanotube and be placed in 40 mL dehydrated alcohols, is placed in sonic oscillation instrument supersound process 4 h, makes it be uniformly dispersed, and obtaining concentration is 0.5 mg/mL carbon nano tube suspension, and microscopic appearance is as Fig. 1.
2. the preparation of colloidal tio 2: adopt sol-gel method (sol-gel) to prepare colloidal tio 2.Pipette 20 mL dehydrated alcohols in small beaker, under magnetic stirring, pipette 1.00 mL tetra-n-butyl titanates with the transfer pipet of drying and be added drop-wise in beaker, stir 20s and make it to mix; Slowly instill the dust technology of 20.00 mL 0.2 mol/L with acid buret, drip speed and be about p.s. one; After dripping off, then stir 30 min, then beaker is positioned over the colloidal tio 2 that can obtain good stability in 25-40 DEG C of thermostat container after ageing 24 h, concentration is 0.074 mmol/mL.
3. be the preparation of the poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials of substrate with electrode:
(1) blank electrode that pre-treatment obtains is placed in 1 mol/L sulphuric acid soln, at potential region-0.6 V ~ 1.2 V, sweep velocity is under 100 mV/s conditions, cyclic voltammetry is adopted to sweep 10 circles, activation, get the scattered carbon nano tube suspension of 6 μ L and nano titanium oxide by volume 4:1 be mixed to get mixed solution, mixed solution is dripped equably and is coated in blank electrode surface, (note: during oven dry is dried under being placed on infrared lamp, electrode can not be too near apart from infrared lamp, otherwise easily destroy the carbon nano-tube film of electrode surface), obtain titanium dioxide/carbon nano tube compound material, microscopic appearance is shown in Fig. 2.
(2) in Sulphanilic Acid, carry out cyclic voltammetric polymerization again after drying, polymerizing condition is: potential region-1.5 V ~ 2.5 V, and sweep velocity is 100 mV/s, and 100 μ A are selected in sensitivity, waiting time 2 s, and the polymerization number of turns is 8 circles, dries after polymerization.Namely poly-Sulphanilic Acid/titanium dioxide/carbon nano tube compound material that electrode is substrate is able to through above two steps, microscopic appearance is shown in Fig. 3, as can be seen from Figure 3 deposition one deck Sulphanilic Acid polymeric film of the surface uniform of titanium dioxide/carbon nano tube compound material.
Embodiment 2 take electrode as the preparation of the poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials of substrate:
(1) blank electrode that pre-treatment obtains is placed in 1 mol/L sulphuric acid soln, at potential region-0.6 V ~ 1.2 V, sweep velocity is under 100 mV/s conditions, cyclic voltammetry is adopted to sweep 10 circles, activation, get the scattered carbon nano tube suspension of 5 μ L and nano titanium oxide by volume 3.5:1 be mixed to get mixed solution, mixed solution is dripped equably and is coated in blank electrode surface, (note: during oven dry is dried under being placed on infrared lamp, electrode can not be too near apart from infrared lamp, otherwise easily destroy the carbon nano-tube film of electrode surface), obtain titanium dioxide/carbon nano tube compound material, microscopic appearance is shown in figure
(2) in Sulphanilic Acid, carry out cyclic voltammetric polymerization again after drying, polymerizing condition is: potential region-1.5 V ~ 2.5 V, and sweep velocity is 100 mV/s, and 100 μ A are selected in sensitivity, waiting time 2 s, and the polymerization number of turns is 8 circles, dries after polymerization.Namely be able to through above two steps poly-Sulphanilic Acid/titanium dioxide/carbon nano tube compound material that electrode is substrate, the nano composite material prepared is deposition one deck Sulphanilic Acid polymeric film of the surface uniform of titanium dioxide/carbon nano tube compound material.
The preparation method of above-mentioned carbon nano tube suspension and colloidal tio 2 is with embodiment 1.
Embodiment 3 take electrode as the preparation of the poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials of substrate:
(1) blank electrode that pre-treatment obtains is placed in 1 mol/L sulphuric acid soln, at potential region-0.6 V ~ 1.2 V, sweep velocity is under 100 mV/s conditions, cyclic voltammetry is adopted to sweep 10 circles, activation, get the scattered carbon nano tube suspension of 8 μ L and nano titanium oxide by volume 5:1 be mixed to get mixed solution, mixed solution is dripped equably and is coated in blank electrode surface, (note: during oven dry is dried under being placed on infrared lamp, electrode can not be too near apart from infrared lamp, otherwise easily destroy the carbon nano-tube film of electrode surface), obtain titanium dioxide/carbon nano tube compound material, microscopic appearance is shown in figure
(2) in Sulphanilic Acid, carry out cyclic voltammetric polymerization again after drying, polymerizing condition is: potential region-1.5 V ~ 2.5 V, and sweep velocity is 100 mV/s, and 100 μ A are selected in sensitivity, waiting time 2 s, and the polymerization number of turns is 8 circles, dries after polymerization.Namely be able to through above two steps poly-Sulphanilic Acid/titanium dioxide/carbon nano tube compound material that electrode is substrate, the nano composite material prepared is deposition one deck Sulphanilic Acid polymeric film of the surface uniform of titanium dioxide/carbon nano tube compound material.
The preparation method of above-mentioned carbon nano tube suspension and colloidal tio 2 is with embodiment 1.
effect example 1(different electrodes is 1 × 10 to concentration
-5the katalysis of the uric acid (UA) of mol/L)
Different electrodes is 1 × 10 to concentration
-5the katalysis (the poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials modified electrode c of blank electrode a, carbon nano tube modified electrode b, embodiment 1 preparation) of the uric acid (UA) of mol/L, as shown in Figure 4.As shown in Figure 4, in UA solution, comparatively blank electrode spike potential is obviously negative moves for complex film modified electrode, and peak current obviously raises, and illustrates that complex film modified electrode effectively can reduce the overpotential of reaction in the katalysis to UA solution, promote that electronics moves, reaction is more easily carried out; And the rising of peak current also illustrates that the sensitivity of complex film modified electrode is sensitiveer compared with blank electrode.
effect example 2(the cyclic voltammetry of the electrode that differing materials is modified characterizes)
Take pH as the PBS solution of 7.00 being buffered soln, take concentration as the KCl solution of 0.1 mol/L is end liquid, is the K of 1 mmol/L in concentration
3fe (CN)
6respectively cyclic voltammetry scan is carried out to poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials modified electrode (e) prepared by blank electrode (a), carbon nano tube modified electrode (b), poly-Sulphanilic Acid modified electrode (c), carbon nano-tube/titanic oxide modified electrode (d), embodiment 1 in solution, potential region is-0.2 ~ 0.6 V, and scanning speed is 100 mVs
-1, to characterize the electrochemical activity of various material, concrete outcome is shown in Fig. 5.As shown in Figure 5, blank electrode (a) current-responsive is not good and spike potential difference is very large, shows irreversible electrochemical behavior.And through modification after electrode (b ~ e) higher than the peak of blank electrode, the difference of spike potential is little, illustrates that Sulphanilic Acid film, carbon nano-tube film and nano titanium oxide all can promote the transmission of electronics.Further analysis is known, the electrode peak current that Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials is modified is the highest, spike potential difference is minimum, show that Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials has the stronger Electron Transfer of promotion, thus there is more efficient electrochemical activity.
effect example 3(the differential pulse method scanning carried out when uric acid (UA) and xitix (AA) solution melting concn change simultaneously)
Poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials embodiment 1 prepared carries out the scanning of differential pulse method to the uric acid (UA) and the mixing of xitix (AA) solution that change concentration simultaneously, as shown in Figure 6.The mensuration of AA is not substantially by the impact of UA as seen from Figure 6, and the mensuration of UA is not substantially by the impact of AA, and two kinds of materials all can be measured out.Respectively according to the oxidation peak current of AA
i pto the working curve that concentration c is made, the linear fit equation obtained is respectively:
i p(μ A)=10.338
c(10
-3mol/L)+15.507 (coefficient R=0.9997);
i p(μ A)=6.799
c(10
-5mol/L)+9.861 (coefficient R=0.9991).Can prove that matrix material modified electrode can carry out measuring and mutually not disturb the mixing solutions of AA and UA from this working curve, show that the peak current of AA and UA is all proportional with concentration simultaneously, and then the mensuration of practical application can be carried out according to working curve.
effect example 4(the differential pulse method scanning carried out during dopamine hydrochloride (DA) change in concentration when xitix (AA), uric acid (UA) exist simultaneously)
Poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials embodiment 1 prepared is to xitix (AA), the uric acid (UA) of fixed concentration, dopamine hydrochloride (DA) mixing solutions changing concentration carries out the scanning of differential pulse method, as shown in Figure 7.The mensuration of DA is not substantially by the impact of AA, UA as seen from Figure 7.According to the oxidation peak current of DA
i pto the working curve that concentration c is made, obtaining linear fit equation is:
i p(μ A)=5.235
c(10
-5mol/L)+14.137 (coefficient R=0.9998).Can prove that complex film modified electrode can measure the concentration of DA under fixing AA, UA concentration from this working curve, draw simultaneously the peak current of DA and concentration proportional, and then the mensuration of practical application can be carried out according to working curve.
Claims (8)
1. be a preparation method for the poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials of substrate with electrode, it is characterized in that, comprise the following steps:
(1) after the nano titanium oxide colloid of the carbon nano tube suspension of 0.5mg/mL and 0.074mmol/mL being mixed according to volume ratio 3.5:1-5:1 mixed solution, 5-8 μ L mixed solution is dripped uniformly the blank electrode surface being coated in activation, dry under being placed on infrared lamp;
(2) the Sulphanilic Acid aqueous solution electrode after oven dry being placed in 2mmol/L carries out cyclic voltammetric polymerization, polymerizing condition is: potential region-1.5-2.5V, sweep velocity is 100mV/s, sensitivity is 100 μ A, waiting time 2s, the polymerization number of turns is 8 circles, dries, be namely able to poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials that electrode is substrate after being polymerized.
2. preparation method according to claim 1, is characterized in that, in step (1), the preparation method of described carbon nano tube suspension is: take 0.02g carbon nanotube and be placed in 40mL dehydrated alcohol, is placed in sonic oscillation instrument supersound process 4h.
3. preparation method according to claim 1, is characterized in that, in step (1), the preparation method of described nano titanium oxide colloid is: in the beaker filling 20mL dehydrated alcohol, drip 1mL tetra-n-butyl titanate under magnetic stirring, stirs 15-30s; Slowly instill the dust technology of 20mL 0.2mol/L with acid buret, dripping speed is 1/s; After dripping off, continue to stir 30min, then beaker to be positioned in 25-40 DEG C of thermostat container after ageing 24h.
4. preparation method according to claim 1, it is characterized in that, in step (1), the preparation method of blank electrode is: rinse after glass-carbon electrode polishing with intermediate water, and in intermediate water ultrasonic vibration 3min, then ultrasonic vibration 3min in dehydrated alcohol, is finally placed in intermediate water excusing from death concussion 3min, dries and obtain blank electrode.
5. preparation method according to claim 4, it is characterized in that, the activation condition of described blank electrode is: blank electrode is placed in 1mol/L sulfuric acid, is-0.6-1.2V at potential region, surface sweeping speed is under 100mV/s condition, adopts cyclic voltammetry to sweep 10 circles.
6. preparation method according to claim 1, it is characterized in that: described poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials is for being substrate with electrode, and poly-Sulphanilic Acid uniform deposition is on titanium dioxide/carbon nanotube composite materials surface.
7. the application of poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials in bio-molecular separation measures prepared of the preparation method as described in any one of claim 1-6.
8. application according to claim 7, is characterized in that: described poly-Sulphanilic Acid/titanium dioxide/carbon nanotube composite materials is at the separation determination of xitix, Dopamine HCL, uric acid composition.
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| CN107326358A (en) * | 2017-06-26 | 2017-11-07 | 华南理工大学 | A kind of highly conductive corrosion-resistant silver-colored carbon nanotube/nano diamond compound film layer and preparation and application |
| CN108918611A (en) * | 2018-06-06 | 2018-11-30 | 江西农业大学 | It is a kind of for detecting the electrode and preparation method thereof of coffee acid content |
| CN109930136A (en) * | 2019-04-10 | 2019-06-25 | 广东新劲刚新材料科技股份有限公司 | The chemical plating method and nano-composite plate of nano-composite plate |
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