CN104046022B - polypyrrole-Hemin-reduced graphene ternary composite material synthesized by microwave solvothermal method and preparation method thereof - Google Patents
polypyrrole-Hemin-reduced graphene ternary composite material synthesized by microwave solvothermal method and preparation method thereof Download PDFInfo
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- 229940025294 hemin Drugs 0.000 title claims abstract description 52
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 37
- 238000002360 preparation method Methods 0.000 title claims abstract description 23
- 238000004729 solvothermal method Methods 0.000 title claims description 11
- 239000011206 ternary composite Substances 0.000 title abstract 2
- 239000002131 composite material Substances 0.000 claims abstract description 33
- BTIJJDXEELBZFS-QDUVMHSLSA-K hemin Chemical compound CC1=C(CCC(O)=O)C(C=C2C(CCC(O)=O)=C(C)\C(N2[Fe](Cl)N23)=C\4)=N\C1=C/C2=C(C)C(C=C)=C3\C=C/1C(C)=C(C=C)C/4=N\1 BTIJJDXEELBZFS-QDUVMHSLSA-K 0.000 claims abstract description 31
- 238000010438 heat treatment Methods 0.000 claims abstract description 17
- 229910002804 graphite Inorganic materials 0.000 claims abstract description 13
- 239000010439 graphite Substances 0.000 claims abstract description 13
- 238000003756 stirring Methods 0.000 claims abstract description 12
- 239000002904 solvent Substances 0.000 claims abstract description 10
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 25
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 23
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 19
- 239000006185 dispersion Substances 0.000 claims description 13
- 230000015572 biosynthetic process Effects 0.000 claims description 12
- 238000006243 chemical reaction Methods 0.000 claims description 12
- 239000012046 mixed solvent Substances 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 12
- 238000003786 synthesis reaction Methods 0.000 claims description 12
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 10
- KFZMGEQAYNKOFK-UHFFFAOYSA-N Isopropanol Chemical compound CC(C)O KFZMGEQAYNKOFK-UHFFFAOYSA-N 0.000 claims description 10
- 235000011114 ammonium hydroxide Nutrition 0.000 claims description 8
- 238000005119 centrifugation Methods 0.000 claims description 8
- 239000007788 liquid Substances 0.000 claims description 8
- 239000000725 suspension Substances 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 7
- 238000013019 agitation Methods 0.000 claims description 6
- 239000000084 colloidal system Substances 0.000 claims description 6
- 238000005406 washing Methods 0.000 claims description 6
- 239000000203 mixture Substances 0.000 claims description 2
- 238000000034 method Methods 0.000 abstract description 20
- 239000000463 material Substances 0.000 abstract description 14
- 102000004190 Enzymes Human genes 0.000 abstract description 11
- 108090000790 Enzymes Proteins 0.000 abstract description 11
- 229920000128 polypyrrole Polymers 0.000 abstract description 7
- 230000007613 environmental effect Effects 0.000 abstract description 4
- 230000027756 respiratory electron transport chain Effects 0.000 abstract description 4
- 238000001027 hydrothermal synthesis Methods 0.000 abstract description 2
- 230000002255 enzymatic effect Effects 0.000 abstract 1
- 238000012986 modification Methods 0.000 abstract 1
- 230000004048 modification Effects 0.000 abstract 1
- 239000013077 target material Substances 0.000 abstract 1
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 54
- 229910052799 carbon Inorganic materials 0.000 description 18
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 16
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 12
- 230000004044 response Effects 0.000 description 12
- 239000011159 matrix material Substances 0.000 description 10
- 239000000243 solution Substances 0.000 description 10
- 238000002484 cyclic voltammetry Methods 0.000 description 8
- 238000001514 detection method Methods 0.000 description 8
- 229910052757 nitrogen Inorganic materials 0.000 description 8
- ZOMNIUBKTOKEHS-UHFFFAOYSA-L dimercury dichloride Chemical class Cl[Hg][Hg]Cl ZOMNIUBKTOKEHS-UHFFFAOYSA-L 0.000 description 6
- 230000000694 effects Effects 0.000 description 6
- 229910052697 platinum Inorganic materials 0.000 description 6
- 238000013016 damping Methods 0.000 description 5
- 238000010790 dilution Methods 0.000 description 5
- 239000012895 dilution Substances 0.000 description 5
- 239000002270 dispersing agent Substances 0.000 description 5
- 239000012530 fluid Substances 0.000 description 5
- 238000011010 flushing procedure Methods 0.000 description 5
- 235000011194 food seasoning agent Nutrition 0.000 description 5
- TWNQGVIAIRXVLR-UHFFFAOYSA-N oxo(oxoalumanyloxy)alumane Chemical compound O=[Al]O[Al]=O TWNQGVIAIRXVLR-UHFFFAOYSA-N 0.000 description 5
- 230000005540 biological transmission Effects 0.000 description 4
- 230000035484 reaction time Effects 0.000 description 4
- 150000001875 compounds Chemical class 0.000 description 3
- 239000002994 raw material Substances 0.000 description 3
- 238000006722 reduction reaction Methods 0.000 description 3
- 238000010408 sweeping Methods 0.000 description 3
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 description 2
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 description 2
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 239000011218 binary composite Substances 0.000 description 2
- 238000010531 catalytic reduction reaction Methods 0.000 description 2
- BNIILDVGGAEEIG-UHFFFAOYSA-L disodium hydrogen phosphate Chemical compound [Na+].[Na+].OP([O-])([O-])=O BNIILDVGGAEEIG-UHFFFAOYSA-L 0.000 description 2
- 229910000397 disodium phosphate Inorganic materials 0.000 description 2
- 235000019800 disodium phosphate Nutrition 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- BTIJJDXEELBZFS-UHFFFAOYSA-K hemin Chemical compound [Cl-].[Fe+3].[N-]1C(C=C2C(=C(C)C(C=C3C(=C(C)C(=C4)[N-]3)C=C)=N2)C=C)=C(C)C(CCC(O)=O)=C1C=C1C(CCC(O)=O)=C(C)C4=N1 BTIJJDXEELBZFS-UHFFFAOYSA-K 0.000 description 2
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 description 2
- WGCNASOHLSPBMP-UHFFFAOYSA-N hydroxyacetaldehyde Natural products OCC=O WGCNASOHLSPBMP-UHFFFAOYSA-N 0.000 description 2
- 229940045641 monobasic sodium phosphate Drugs 0.000 description 2
- 239000002114 nanocomposite Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000007800 oxidant agent Substances 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- AJPJDKMHJJGVTQ-UHFFFAOYSA-M sodium dihydrogen phosphate Chemical compound [Na+].OP(O)([O-])=O AJPJDKMHJJGVTQ-UHFFFAOYSA-M 0.000 description 2
- 238000010189 synthetic method Methods 0.000 description 2
- CTENFNNZBMHDDG-UHFFFAOYSA-N Dopamine hydrochloride Chemical compound Cl.NCCC1=CC=C(O)C(O)=C1 CTENFNNZBMHDDG-UHFFFAOYSA-N 0.000 description 1
- 238000005033 Fourier transform infrared spectroscopy Methods 0.000 description 1
- 238000001157 Fourier transform infrared spectrum Methods 0.000 description 1
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 description 1
- -1 Graphene compound Chemical class 0.000 description 1
- 238000003917 TEM image Methods 0.000 description 1
- LEHOTFFKMJEONL-UHFFFAOYSA-N Uric Acid Chemical compound N1C(=O)NC(=O)C2=C1NC(=O)N2 LEHOTFFKMJEONL-UHFFFAOYSA-N 0.000 description 1
- TVWHNULVHGKJHS-UHFFFAOYSA-N Uric acid Natural products N1C(=O)NC(=O)C2NC(=O)NC21 TVWHNULVHGKJHS-UHFFFAOYSA-N 0.000 description 1
- 230000004913 activation Effects 0.000 description 1
- 238000000627 alternating current impedance spectroscopy Methods 0.000 description 1
- 235000010323 ascorbic acid Nutrition 0.000 description 1
- 229960005070 ascorbic acid Drugs 0.000 description 1
- 239000011668 ascorbic acid Substances 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 230000001419 dependent effect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000006073 displacement reaction Methods 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 238000000835 electrochemical detection Methods 0.000 description 1
- 238000002848 electrochemical method Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 229960001031 glucose Drugs 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 229910052742 iron Inorganic materials 0.000 description 1
- BTNMPGBKDVTSJY-UHFFFAOYSA-N keto-phenylpyruvic acid Chemical compound OC(=O)C(=O)CC1=CC=CC=C1 BTNMPGBKDVTSJY-UHFFFAOYSA-N 0.000 description 1
- 229920002521 macromolecule Polymers 0.000 description 1
- 239000002207 metabolite Substances 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000035945 sensitivity Effects 0.000 description 1
- 238000002798 spectrophotometry method Methods 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 229940116269 uric acid Drugs 0.000 description 1
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- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K5/00—Use of organic ingredients
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- C08K5/34—Heterocyclic compounds having nitrogen in the ring
- C08K5/3412—Heterocyclic compounds having nitrogen in the ring having one nitrogen atom in the ring
- C08K5/3415—Five-membered rings
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- C08G—MACROMOLECULAR COMPOUNDS OBTAINED OTHERWISE THAN BY REACTIONS ONLY INVOLVING UNSATURATED CARBON-TO-CARBON BONDS
- C08G73/00—Macromolecular compounds obtained by reactions forming a linkage containing nitrogen with or without oxygen or carbon in the main chain of the macromolecule, not provided for in groups C08G12/00 - C08G71/00
- C08G73/06—Polycondensates having nitrogen-containing heterocyclic rings in the main chain of the macromolecule
- C08G73/0605—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms
- C08G73/0611—Polycondensates containing five-membered rings, not condensed with other rings, with nitrogen atoms as the only ring hetero atoms with only one nitrogen atom in the ring, e.g. polypyrroles
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Abstract
The invention discloses a polypyrrole-Hemin-reduced graphene ternary composite material synthesized by a microwave solvent heating method and a preparation method thereof. The composite material consists of polypyrrole, hemin and reduced graphene; wherein the hemin accounts for 10.8-19.6% by mass, the graphite oxide accounts for 33.3-60.2% by mass, and the polypyrrole accounts for 20.2-55.9% by mass. According to the invention, the microwave is used for replacing the traditional stirring heating mode and hydrothermal method, and the target material is prepared by changing the parameters such as temperature, time and the like of the microwave; the hemin of the active center of the required enzyme overcomes the harsh requirements of the traditional biological enzyme on external environmental conditions such as temperature, pH value and the like; in addition, PPY and RGO are introduced into the PPY-He-RGO composite material, on one hand, hemin can be fixed to enable the PPY-He-RGO composite material to still retain the enzymatic activity, and on the other hand, the effective area of the electrode is greatly increased, and the electron transfer between the modification material and the surface of the electrode is promoted.
Description
Technical field
Polypyrrole-Hemin-reduced graphene tri compound nano material prepared by modified electrode material that the present invention relates to a kind of sensor and preparation method thereof, particularly a kind of microwave solvent heating method, belongs to Material Field and enzyme biologic sensor technical field.
Background technology
Hydrogen peroxide (H
2o
2) be the meta-bolites of many biomolecules, sensitive rapid detection H
2o
2content in environmental protection, medical science, environment etc., have very important effect.Under normal circumstances, detection method has chemoluminescence method, fluorescent method, spectrophotometry and electrochemical methods etc.Wherein electrochemical techniques due to required instrument simple, can sensitive, directly detect H fast
2o
2rather well received.Be combined with Enzyme sensor and be more expected to show the advantages such as simple and fast, highly sensitive, selectivity is good.
Protohemin (hemin), can effective catalysis H as catalatic active centre
2o
2the reduction of molecule, and cost is low compared with natural biology enzyme, becomes H at present
2o
2one of focus of biosensor research.But enzyme electrodes preparation process is complicated, and its stability and activity are very easily disturbed by ambient conditions, thus limit its application separately in biosensor.How fixed biologically enzyme keeps Activity and stabill at electrode surface, how to improve the supported quantity of enzyme, be devoted to find for these Study on Problems persons and a kind ofly can have larger specific area and have again the fixing hemin molecule of the body material of better biocompatibility absorption.
Functionalized nano matrix material is due to physics, the chemical property of its uniqueness, and being applied in field of biosensors has been trend of the times.The Graphene (GE) of wherein π-pi-conjugated structure has bigger serface, the feature such as good stability and good electroconductibility, can be interacted and the incompatible structure Graphene/hemin nano composite material of hemin molecular juction by π-π.The people such as TengXue use the ultrasonic mixing of GE and hemin obtained by hydrazine hydrate reduction graphite oxide, prepare GE/hemin nano composite material (AngewChemIntEdEngl2012,51,3822).The people such as YujingGuo based on Graphene/hemin binary composite to H
2o
2molecule carries out detecting (SensorsandActuatorsB:Chemical2011,160,295), but the hemin steric hindrance of macromolecule makes greatly again direct electron transfer process be hindered.Select suitable electron transfer mediator can promote the electronic transmission process of enzyme active center and electrode surface, accelerate electron transfer rate, improve the sensitivity of sensor.The people such as HaiyanSong, first at electrode surface deposited Au nano particle, then combine with both Graphene-hemin and obtain tri compound hybrid material (AnalyticaChimicaActa, 2013,788,24).Consider that raw materials cost cost is high, the problems such as surface of metal particles activation energy great Yi reunion, Comparatively speaking the polymer of good electroconductibility is because having the advantages such as synthetic method is simple, raw material is easy to get, and is good selection as electron transmission medium.Polypyrrole (PPY)/hemin binary composite (AppliedMaterialInterfaces2014 is obtained by one-step synthesis method, 6,500), also hydrogen peroxide detection field is used in, so the conducting polymer-polypyrrole that synthetic method is simple, raw material is easy to get is expected to construct the biosensing device that cost is low, performance is high.
Microwave solvothermal method is different from conventional heating and solvent-thermal method, and it has homogeneous heating, rapidly and efficiently, is applicable to scale operation.Usually the strong oxidizer that adds of reduction-oxidation graphite is as hydrazine hydrate etc. in addition, and having toxicity, have harm to environment, but use microwave method reduction-oxidation graphite then not need extra strong oxidizer, is a kind of route of synthesis of environmental protection.
Current polypyrrole-Hemin-reduced graphene tri compound nano material have not been reported.
Summary of the invention
For the problem of prior art, the object of this invention is to provide a kind of simple synthesis of microwave solvent heating method efficiently polypyrrole-Hemin-reduced graphene (PPY-He-RGO) trielement composite material.
The technical solution realizing the object of the invention is: a kind of polypyrrole-Hemin-reduced graphene trielement composite material of microwave solvent heating method synthesis, and described matrix material is made up of polypyrrole, protohemin and reduced graphene; Wherein, the massfraction of hemin is 10.8% ~ 19.6%, and graphite oxide massfraction is 33.3% ~ 60.2%, and the massfraction of polypyrrole is 20.2% ~ 55.9%.
The preparation method of polypyrrole-Hemin-reduced graphene trielement composite material for microwave solvothermal method synthesis, with GO/Hemin dispersion liquid in a solvent for presoma, then adds pyrrole monomer and carries out microwave solvent heated polymerizable, comprise the steps:
The first step: graphite oxide colloid is carried out in alcohol-water mixed solvent ultrasonicly obtain finely dispersed graphene oxide (GO) suspension;
Second step: mix with the GO suspension of the first step after hemin being dissolved completely in ammoniacal liquor, and long-time stirring makes it fully adsorb;
3rd step: pyrrole monomer is joined second step and obtains in mixed system, again magnetic agitation, makes it be uniformly dispersed;
4th step: the above-mentioned mixing solutions mixed is transferred in microwave reaction tank and carries out microwave heating reaction;
5th step: the 4th step product is carried out centrifugation, and repeatedly with alcohol washing, obtain PPY-He-RGO trielement composite material.
The ultrasonic disperse time described in step one is 1 ~ 3h, in alcohol-water mixed solvent alcohol used be respectively in Virahol, ethylene glycol or ethanol any one, alcohol and water volume ratio are 1:1.
Ammoniacal liquor pH described in step 2 is 10 ~ 13, and the mass ratio of graphite oxide and hemin is 3.08, and the whip attachment time is 4 ~ 8h.
Pyrrole monomer volumetric molar concentration described in step 3 is 10 ~ 50mmolL
-1, pyrrole monomer and hemin mass ratio 1.03 ~ 5.15, churning time is 0.5h ~ 2h.
Microwave heating temperature described in step 4 is 100 DEG C ~ 180 DEG C; Heat-up time is 10 ~ 30min.
Centrifugation described in step 5 adopts whizzer, and its rotating speed is 1600r/min, is separated into time 10min.
An application for the polypyrrole-Hemin-reduced graphene ternary complex of microwave solvent thermal synthesis, using the polypyrrole-Hemin-reduced graphene ternary complex of said structure as biosensor modified electrode materials application in mensuration content of hydrogen peroxide.
Described measuring method comprises cyclic voltammetry or current versus time curve method.
In said determination step, adopt three-electrode system, take modified electrode as working electrode, saturated calomel electrode is reference electrode, platinum filament is to electrode, and described modified electrode is dripped to be coated on glass-carbon electrode by polypyrrole-Hemin-reduced graphene ternary complex to be prepared from; Wherein, the concentration of polypyrrole-Hemin-reduced graphene dispersion liquid is 1mgmL
-1, dripping quantity is 5 ~ 20 μ L.
The step adopting current versus time curve method to measure content of hydrogen peroxide is: be positioned over by modified electrode in the electrolyzer of pH7.0 containing the Sodium phosphate dibasic/SODIUM PHOSPHATE, MONOBASIC cocktail buffer of 0.1M, logical nitrogen 5 ~ 15min, add hydrogen peroxide continuously, the concentration of hydrogen peroxide in electrolyzer is made to control at 0.13 ~ 70 μM, use current versus time curve method, set initial potential as-0.1V ~-0.35V, detect modified electrode to the response of hydrogen peroxide.
The step of employing cyclic voltammetry content of hydrogen peroxide is: be positioned over by modified electrode in the electrolyzer of pH7.0 containing the Sodium phosphate dibasic/SODIUM PHOSPHATE, MONOBASIC cocktail buffer of 0.1M, logical nitrogen 5 ~ 15min, in the superoxol of 1mM, set scanning current potential as-0.8V ~ 0.2V, sweep velocity is 100mVs
-1, detect modified electrode to the response of hydrogen peroxide.
Compared with prior art, tool of the present invention has the following advantages: the microwave solvothermal method that (1) adopts, replacing traditional stirring heating mode with microwave, preparing polypyrrole-Hemin-reduced graphene trielement composite material by changing the parameters such as the temperature and time of microwave.Compare hydrothermal method, the method has that homogeneous heating, required time are short, utilization ratio advantages of higher, is a kind of simple, efficient and environmental protection, has the preparation method utilizing scale operation; (2) the active centre hemin of required enzyme, overcome traditional biological enzyme to external world envrionment conditions as temperature, the rigors of pH value etc.In PPY-He-RGO matrix material, introduce PPY and RGO, hemin can be fixed on the one hand and make it still retain enzymic activity, substantially increase the useful area of electrode and the electron transmission between promotion decorative material and electrode surface on the other hand; (3) propose one simple to operate, quick and portable, highly sensitive Electrochemical Detection instrument and method, the modified electrode of preparation has strong CV current-responsive to hydrogen peroxide, detects and is limited to 1.3 ~ 7.0 × 10
-7m and linearly dependent coefficient are 0.998.
Accompanying drawing explanation
Accompanying drawing 1 is the TEM photo of the PPY-He-RGO trielement composite material prepared by the embodiment of the present invention 1;
Accompanying drawing 2 is x-ray photoelectron energy spectrograms of the PPY-He-RGO trielement composite material prepared by the embodiment of the present invention 1;
Accompanying drawing 3 is ultraviolet-visible spectrogram (A) and the FTIR spectrum figure (B) of PPY-He-RGO trielement composite material prepared by the embodiment of the present invention 2;
Accompanying drawing 4 is the PPY-He-RGO trielement composite materials prepared by the embodiment of the present invention 2, carries out electro-chemical test to it, and naked glass carbon GEC (a) and modified electrode PPY-He-RGO/GCE (b) are adding H
2o
2after cyclic voltammetry curve;
Accompanying drawing 5 is the PPY-He-RGO trielement composite materials prepared by the embodiment of the present invention 3, the ac impedance spectroscopy (A) of modified electrode and the cyclic voltammogram (B) swept difference in superoxol under speed;
Accompanying drawing 6 is the PPY-He-RGO trielement composite materials prepared by the embodiment of the present invention 3, the current versus time curve (A) when dripping continuously quantitative hydrogen peroxide and corresponding peak current and the linear relationship curve (B) of square root sweeping speed; PPY-He-RGO trielement composite material prepared by accompanying drawing 7 embodiment of the present invention 4, to the current versus time curve figure dripping disturbance material continuously.
Embodiment
The following examples can make the present invention of those skilled in the art comprehend.
Embodiment 1: the present invention, the preparation method of Microwave synthesize PPY-He-RGO under isopropanol/water mixed solvent system, comprises the following steps:
The first step: get massfraction be 4.4% graphite oxide colloid 0.91g in the mixed solvent of 20mL isopropanol/water (1:1v/v), carry out ultrasonic disperse 1h, obtain finely dispersed graphene oxide solution;
Second step: 13mghemin is dissolved completely in (pH13) in ammoniacal liquor and mixes with the GO suspension of the first step, and the long-time 4h that stirs makes it fully adsorb;
3rd step: 10mM pyrrole monomer (13.4mg) is joined second step and obtains in mixed system, again stir 0.5h, make it be uniformly dispersed;
4th step: be transferred in microwave reaction tank by the above-mentioned mixing solutions mixed and carry out microwave heating, temperature of reaction is 120 DEG C, and the reaction times is 30min;
5th step: the 4th step product is carried out centrifugation, and repeatedly with alcohol washing, obtain PPY-He-RGO trielement composite material;
As shown in Figure 1, PPY is nano bar-shape to the TEM image of trielement composite material, and the mean length of rod is 1.1 μm and central diameter is 200nm, and bar-shaped PPY ending is distributed in the surface of Graphene with connecting formula, forms conductive network structure.
As shown in Figure 2, containing carbon in x-ray photoelectron power spectrum (XPS), oxygen, nitrogen and iron four kinds of elements, describe hemin and be still entrained in hybrid material, trielement composite material is by polypyrrole, and hemin and reduced graphene are formed.
Embodiment 2: the present invention, the preparation method of Microwave synthesize PPY-He-RGO under glycol/water mixed solvent system, comprises the following steps:
The first step: get massfraction be 4.4% graphite oxide colloid 0.91g in the mixed solvent of 20mL glycol/water (1:1v/v), carry out ultrasonic disperse 2h, obtain finely dispersed graphene oxide solution;
Second step: 1.3mghemin is dissolved completely in (pH11) in ammoniacal liquor and mixes with the GO suspension of the first step, and the long-time 6h that stirs makes it fully adsorb;
3rd step: 25mM pyrrole monomer (33.5mg) is joined second step and obtains in mixed system, again stir 1h, make it be uniformly dispersed;
4th step: be transferred in microwave reaction tank by the above-mentioned mixing solutions mixed and carry out microwave heating, temperature of reaction is 150 DEG C, and the reaction times is 15min;
5th step: the 4th step product is carried out centrifugation, and repeatedly with alcohol washing, obtain PPY-He-RGO trielement composite material;
As shown in fig. 3 a, the ultraviolet absorption peak of hemin there occurs displacement, indicates to there is conjugative effect trielement composite material PPY-He-RGO redox graphene and hemin and PPY from 389nm red shift to 413nm.
The infrared spectra (FTIR) of contrast different components is as Fig. 3 B, and in known PPY-He-RGO matrix material, the charateristic avsorption band of existing hemin has again 1521 and 1442cm
-1pyrrole ring charateristic avsorption band, confirm, under different solvents condition, equally also successfully to have prepared PPY-He-RGO trielement composite material.
Embodiment 3: the present invention, the preparation method of Microwave synthesize PPY-He-RGO under ethanol/water mixed solvent system, comprises the following steps:
The first step: get massfraction be 4.4% graphite oxide colloid 0.91g in the mixed solvent of 20mL ethanol/water (1:1v/v), carry out ultrasonic disperse 3h, obtain finely dispersed graphene oxide solution;
Second step: 1.3mghemin is dissolved completely in (pH10) in ammoniacal liquor and mixes with the GO suspension of the first step, and the long-time 8h that stirs makes it fully adsorb;
3rd step: 50mM pyrrole monomer (67.0mg) is joined second step and obtains in mixed system, again stir 2h, make it be uniformly dispersed;
4th step: be transferred in microwave reaction tank by the above-mentioned mixing solutions mixed and carry out microwave heating, temperature of reaction is 180 DEG C, and the reaction times is 10min;
5th step: the 4th step product is carried out centrifugation, and repeatedly with alcohol washing, obtain polypyrrole-Hemin-reduced graphene trielement composite material;
Accompanying drawing 4 is that it is to H
2o
2electrochemical response, in PBS buffered soln, sweep speed for 100mV/s time, by PPY-He-RGO modified electrode cyclic voltammetry (CV) curve, can draw after adding 1mM hydrogen peroxide ,-0.15V place occur obvious H
2o
2reduction peak, illustrates that ternary hybrid material is to H
2o
2there is good catalytic reduction effect.
Embodiment 4: the present invention, the preparation method of Microwave synthesize PPY-He-RGO under isopropanol/water mixed solvent system, comprises the following steps:
The first step: get massfraction be 4.4% graphite oxide colloid 0.91g in the mixed solvent of 20mL isopropanol/water (1:1v/v), carry out ultrasonic disperse 1h, obtain finely dispersed graphene oxide solution;
Second step: 1.3mghemin is dissolved completely in (pH10) in ammoniacal liquor and mixes with the GO suspension of the first step, and the long-time 4h that stirs makes it fully adsorb;
3rd step: 50m pyrrole monomer (67.0mg) is joined second step and obtains in mixed system, again stir 0.5h, make it be uniformly dispersed;
4th step: be transferred in microwave reaction tank by the above-mentioned mixing solutions mixed and carry out microwave heating, temperature of reaction is 120 DEG C, and the reaction times is 30min;
5th step: the 4th step product is carried out centrifugation, and repeatedly with alcohol washing, obtain PPY-He-RGO trielement composite material.
Application example 1:
1. the preparation of modified electrode, comprises the following steps:
(1) glass-carbon electrode is ground to respectively on the aluminum oxide of 0.1 and 0.03 μm smooth, clean with water and alcohol flushing, dry under room temperature, for subsequent use;
(2) by matrix material PPY-He-RGO through supersound process 1h, heavily dispersion dilution after, join to obtain 1.0mgmL
-1uniform dispersion;
(3) getting 5 μ L dispersant liquid drops with liquid-transfering gun applies on the glass-carbon electrode got ready in advance, and seasoning, obtains PPY-He-RGO modified electrode;
2. modified electrode is to the detection method of hydrogen peroxide, comprises the following steps:
Use three-electrode system, saturated calomel electrode is reference electrode, platinum electrode is to electrode, glass-carbon electrode is working electrode, is positioned over by step (3) gained modified electrode in the PBS damping fluid of 10mLpH=7 and soaks, after passing into nitrogen 15min, add 1mM hydrogen peroxide and magnetic agitation, use cyclic voltammetry, potential window is set to-0.8 ~ 0.2V, sweep speed for 100mVs
-1, detect modified electrode to H
2o
2electrochemical response.
Application example 2:
1. the preparation of modified electrode, comprises the following steps:
(1) glass-carbon electrode is ground to respectively on the aluminum oxide of 0.1 and 0.03 μm smooth, clean with water and alcohol flushing, dry under room temperature, for subsequent use;
(2) by matrix material PPY-He-RGO through ultrasonic 1h, heavily dispersion dilution after, join to obtain 1.0mgmL
-1uniform dispersion;
(3) getting 5 μ L dispersant liquid drops with liquid-transfering gun applies on the glass-carbon electrode got ready in advance, and seasoning, obtains PPY-He-RGO modified electrode;
2. modified electrode is to the detection method of hydrogen peroxide, comprises the following steps:
Use three-electrode system, saturated calomel electrode is reference electrode, platinum electrode is to electrode, glass-carbon electrode is working electrode, step (3) gained modified electrode is positioned in the PBS damping fluid of 10mLpH=7 and soaks, after passing into nitrogen 15min, use AC impedence method, arranging range of frequency is 1.0 ~ 10
6hz, as Fig. 5 A can observe significantly, the electrode that hemin modifies has maximum impedance, and after Graphene compound, impedance is obviously lower.But compare unitary, two yuan of matrix materials, the impedance of trielement composite material PPY-He-RGO is less, illustrate that trielement composite material can promote the electron transmission between electrode surface and decorative material significantly, improve current responsing signal.
Application example 3:
1. the preparation of modified electrode, comprises the following steps:
(4) glass-carbon electrode is ground to respectively on the aluminum oxide of 0.1 and 0.03 μm smooth, clean with water and alcohol flushing, dry under room temperature, for subsequent use;
(5) by matrix material PPY-He-RGO through ultrasonic 1h, heavily dispersion dilution after, join to obtain 1.0mgmL
-1uniform dispersion;
(6) getting 10 μ L dispersant liquid drops with liquid-transfering gun applies on the glass-carbon electrode got ready in advance, and seasoning, obtains PPY-He-RGO modified electrode;
2. modified electrode is to the detection method of hydrogen peroxide, comprises the following steps:
Use three-electrode system, saturated calomel electrode is reference electrode, platinum electrode is to electrode, and glass-carbon electrode is working electrode, is positioned over by step (3) gained modified electrode in the PBS damping fluid of 10mLpH=7 and soaks, after passing into nitrogen 10min, add 2mM hydrogen peroxide and magnetic agitation, use cyclic voltammetry, potential window is set to-0.8 ~ 0.2V, as shown in Figure 5 B, at 30 ~ 200mVs
-1in scope, along with the increase of sweeping speed, the response of a pair redox peak current of hemin increases all thereupon, illustrates that the stability of electrode is better.Hydrogen peroxide peak point current is linear with the square root sweeping speed, illustrates that hydrogen peroxide belongs to surface diffusion process on modified electrode surface.
Application example 4:
1. the preparation of modified electrode, comprises the following steps:
(1) glass-carbon electrode is ground to respectively on the aluminum oxide of 0.1 and 0.03 μm smooth, clean with water and alcohol flushing, dry under room temperature, for subsequent use;
(2) by matrix material PPY-He-RGO through ultrasonic 1h, heavily dispersion dilution after, join to obtain 1.0mgmL
-1uniform dispersion;
(3) getting 5 μ L dispersant liquid drops with liquid-transfering gun applies on the glass-carbon electrode got ready in advance, and seasoning, obtains PPY-He-RGO modified electrode;
2. modified electrode is to the detection method of hydrogen peroxide, comprises the following steps:
Use three-electrode system, saturated calomel electrode is reference electrode, platinum electrode is to electrode, and glass-carbon electrode is working electrode, is positioned over by step (3) gained modified electrode in the PBS damping fluid of 10mLpH=7 and soaks, after passing into nitrogen 15min, the hydrogen peroxide that continuous dropping is quantitative also, after magnetic agitation 5min, as shown in Figure 6, uses current versus time curve method, arranging initial potential is-0.15V, detects modified electrode to the response of hydrogen peroxide.As shown in Fig. 6 (A), once there is response step immediately after adding hydrogen peroxide, show that modified electrode is rapid to the response of hydrogen peroxide, catalytic reduction also occurs thereupon, and within the scope of 1.3 ~ 70 μMs, response current and H
2o
2concentration has good linear relationship (Fig. 6 (B)).
Modified electrode is to the response of common interference material:
1. the preparation of modified electrode, comprises the following steps:
(4) glass-carbon electrode is ground to respectively on the aluminum oxide of 0.1 and 0.03 μm smooth, clean with water and alcohol flushing, dry under room temperature, for subsequent use;
(5) by matrix material PPY-He-RGO through ultrasonic 1h, heavily dispersion dilution after, join to obtain 1.0mgmL
-1uniform dispersion;
(6) using liquid-transfering gun to get 5 μ L dispersant liquid drops applies on the glass-carbon electrode got ready in advance, and seasoning, obtains PPY-He-RGO modified electrode;
2. modified electrode is to the detection method of hydrogen peroxide, comprises the following steps:
Use three-electrode system, saturated calomel electrode is reference electrode, platinum electrode is to electrode, glass-carbon electrode is working electrode, is positioned over by step (3) gained modified electrode in the PBS damping fluid of 10mLpH=7 and soaks, after passing into nitrogen 15min, add 10 μMs of hydrogen peroxide and magnetic agitation 5min, use current versus time curve method, arranging initial potential is-0.15V, detects modified electrode to the response of common interference material; As shown in Figure 7, modified electrode all without obviously response, shows that modified electrode is detected hydrogen oxide and has good selectivity to the common interference material Dopamine HCL of 10 times of concentration, uric acid, ascorbic acid and glucose.
Claims (6)
1. the preparation method of the polypyrrole-Hemin-reduced graphene trielement composite material of a microwave solvothermal method synthesis, it is characterized in that, with GO/Hemin dispersion liquid in a solvent for presoma, then add pyrrole monomer and carry out microwave solvent heated polymerizable, comprise the steps:
The first step: graphite oxide colloid is carried out in alcohol-water mixed solvent ultrasonicly obtain finely dispersed GO suspension;
Second step: mix with the GO suspension of the first step after hemin being dissolved completely in ammoniacal liquor, and long-time stirring makes it fully adsorb;
3rd step: pyrrole monomer is joined second step and obtains in mixed system, again magnetic agitation, makes it be uniformly dispersed;
4th step: the above-mentioned mixing solutions mixed is transferred in microwave reaction tank and carries out microwave heating reaction;
5th step: the 4th step product is carried out centrifugation, and repeatedly with alcohol washing, obtain PPY-He-RGO trielement composite material.
2. the preparation method of the polypyrrole-Hemin-reduced graphene trielement composite material of microwave solvothermal method synthesis according to claim 1, it is characterized in that, the ultrasonic disperse time in step one is 1 ~ 3h, in alcohol-water mixed solvent alcohol used be respectively in Virahol, ethylene glycol or ethanol any one, alcohol and water volume ratio are 1:1.
3. the preparation method of the polypyrrole-Hemin-reduced graphene trielement composite material of microwave solvothermal method synthesis according to claim 1, it is characterized in that, the pH value of the ammoniacal liquor described in step 2 is 10 ~ 13, the mass ratio of graphite oxide and hemin is 3.08, and the whip attachment time is 4 ~ 8h.
4. the preparation method of the polypyrrole-Hemin-reduced graphene trielement composite material of microwave solvothermal method synthesis according to claim 1, it is characterized in that, the pyrrole monomer volumetric molar concentration described in step 3 is 10 ~ 50mmolL
-1, pyrrole monomer and hemin mass ratio 1.03 ~ 5.15, churning time is 0.5h ~ 2h.
5. the preparation method of the polypyrrole-Hemin-reduced graphene trielement composite material of microwave solvothermal method synthesis according to claim 1, it is characterized in that, the microwave heating temperature described in step 4 is 100 DEG C ~ 180 DEG C; Heat-up time is 10 ~ 30min.
6. the preparation method of the polypyrrole-Hemin-reduced graphene trielement composite material of microwave solvothermal method synthesis according to claim 1, it is characterized in that, centrifugation described in step 5 adopts whizzer, and its rotating speed is 1600r/min, is separated into time 10min.
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