CN106525933A - Method for producing polypyrrole-coated nickel cobaltate nano wire array graphene electrode and application of graphene electrode for detecting heavy metallic lead ion - Google Patents
Method for producing polypyrrole-coated nickel cobaltate nano wire array graphene electrode and application of graphene electrode for detecting heavy metallic lead ion Download PDFInfo
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- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 132
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 99
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 67
- 239000002070 nanowire Substances 0.000 title claims abstract description 62
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 10
- WABPQHHGFIMREM-UHFFFAOYSA-N lead(0) Chemical compound [Pb] WABPQHHGFIMREM-UHFFFAOYSA-N 0.000 title abstract 2
- 238000004519 manufacturing process Methods 0.000 title abstract 2
- 229910052759 nickel Inorganic materials 0.000 title abstract 2
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims abstract description 54
- 238000000034 method Methods 0.000 claims abstract description 27
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 15
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 238000006116 polymerization reaction Methods 0.000 claims abstract description 10
- 239000000126 substance Substances 0.000 claims abstract description 9
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 56
- 239000012153 distilled water Substances 0.000 claims description 34
- 238000005253 cladding Methods 0.000 claims description 33
- 238000002360 preparation method Methods 0.000 claims description 29
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 claims description 22
- 238000010438 heat treatment Methods 0.000 claims description 22
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 claims description 22
- 239000007788 liquid Substances 0.000 claims description 22
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 14
- ROOXNKNUYICQNP-UHFFFAOYSA-N ammonium persulfate Chemical compound [NH4+].[NH4+].[O-]S(=O)(=O)OOS([O-])(=O)=O ROOXNKNUYICQNP-UHFFFAOYSA-N 0.000 claims description 14
- 150000003233 pyrroles Chemical class 0.000 claims description 12
- 239000000178 monomer Substances 0.000 claims description 11
- 238000002604 ultrasonography Methods 0.000 claims description 10
- 238000001354 calcination Methods 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 8
- DDFHBQSCUXNBSA-UHFFFAOYSA-N 5-(5-carboxythiophen-2-yl)thiophene-2-carboxylic acid Chemical compound S1C(C(=O)O)=CC=C1C1=CC=C(C(O)=O)S1 DDFHBQSCUXNBSA-UHFFFAOYSA-N 0.000 claims description 7
- 229910001870 ammonium persulfate Inorganic materials 0.000 claims description 7
- 239000004202 carbamide Substances 0.000 claims description 7
- 235000013877 carbamide Nutrition 0.000 claims description 7
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 7
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 7
- QMMRZOWCJAIUJA-UHFFFAOYSA-L nickel dichloride Chemical compound Cl[Ni]Cl QMMRZOWCJAIUJA-UHFFFAOYSA-L 0.000 claims description 7
- 239000012299 nitrogen atmosphere Substances 0.000 claims description 7
- 239000004575 stone Substances 0.000 claims description 7
- 150000001875 compounds Chemical class 0.000 claims description 3
- 239000007792 gaseous phase Substances 0.000 claims description 3
- 230000008569 process Effects 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 30
- 230000035945 sensitivity Effects 0.000 abstract description 15
- 229920001940 conductive polymer Polymers 0.000 abstract description 3
- 230000036039 immunity Effects 0.000 abstract 1
- 229910003266 NiCo Inorganic materials 0.000 description 19
- 239000000243 solution Substances 0.000 description 18
- 238000012360 testing method Methods 0.000 description 12
- 239000000758 substrate Substances 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- 239000002253 acid Substances 0.000 description 6
- 150000001336 alkenes Chemical class 0.000 description 6
- 229910017052 cobalt Inorganic materials 0.000 description 6
- 239000010941 cobalt Substances 0.000 description 6
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 6
- 239000000203 mixture Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000005229 chemical vapour deposition Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 description 5
- 239000011259 mixed solution Substances 0.000 description 5
- 230000004044 response Effects 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 238000001291 vacuum drying Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000002848 electrochemical method Methods 0.000 description 3
- -1 graphite Alkene Chemical class 0.000 description 3
- 238000007689 inspection Methods 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 238000011160 research Methods 0.000 description 3
- 238000003756 stirring Methods 0.000 description 3
- 239000008351 acetate buffer Substances 0.000 description 2
- 238000004458 analytical method Methods 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000000840 electrochemical analysis Methods 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 229910002804 graphite Inorganic materials 0.000 description 2
- 239000010439 graphite Substances 0.000 description 2
- 229910052738 indium Inorganic materials 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 2
- 239000002184 metal Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 239000002689 soil Substances 0.000 description 2
- 238000010025 steaming Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 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
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 description 1
- XOLBLPGZBRYERU-UHFFFAOYSA-N SnO2 Inorganic materials O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 1
- 238000000862 absorption spectrum Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 150000001408 amides Chemical class 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000008280 blood Substances 0.000 description 1
- 210000004369 blood Anatomy 0.000 description 1
- 230000017531 blood circulation Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003575 carbonaceous material Substances 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- UBEWDCMIDFGDOO-UHFFFAOYSA-N cobalt(II,III) oxide Inorganic materials [O-2].[O-2].[O-2].[O-2].[Co+2].[Co+3].[Co+3] UBEWDCMIDFGDOO-UHFFFAOYSA-N 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 239000002322 conducting polymer Substances 0.000 description 1
- 238000001816 cooling Methods 0.000 description 1
- XUJNEKJLAYXESH-UHFFFAOYSA-N cysteine Natural products SCC(N)C(O)=O XUJNEKJLAYXESH-UHFFFAOYSA-N 0.000 description 1
- 235000018417 cysteine Nutrition 0.000 description 1
- 230000007423 decrease Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 210000002249 digestive system Anatomy 0.000 description 1
- 238000004821 distillation Methods 0.000 description 1
- 239000007772 electrode material Substances 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000013467 fragmentation Methods 0.000 description 1
- 238000006062 fragmentation reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 229910021397 glassy carbon Inorganic materials 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- SZVJSHCCFOBDDC-UHFFFAOYSA-N iron(II,III) oxide Inorganic materials O=[Fe]O[Fe]O[Fe]=O SZVJSHCCFOBDDC-UHFFFAOYSA-N 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 230000006855 networking Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 230000009870 specific binding Effects 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000003950 stripping voltammetry Methods 0.000 description 1
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- 238000005303 weighing Methods 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
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- Health & Medical Sciences (AREA)
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- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention relates to a method for producing a polypyrrole-coated nickel cobaltate nano wire array graphene electrode and an application of the graphene electrode for detecting heavy metallic lead ion. A hydro-thermal kettle is used for performing a hydro-thermal reaction of graphene oxide to obtain the 3D graphene electrode having a three dimensional structure, a secondary hydro-thermal process is used, and a NiCo2O4 nano wire array is grown on the surface of the 3D graphene electrode. A layer of ultrathin conductive polymer polypyrrole layer is coated on the surface of the NiCo2O4 nano wire array by using a chemical gaseous polymerization method; and the polypyrrole-coated NiCo2O4nano wire array graphene electrode is finally obtained. The electrode is used for detecting heavy metal Pb<2+>. According to the invention, the sensitivity of a sensor constructed based on NiCo2O4-coated PPy/3D graphene is 115.621[mu]A [mu]M<-1>, linearity scope is 0.0125to 0.709 [mu]M, and the lowest detection limit is 0.2 nM, and the sensor has good interference immunity and stability.
Description
Technical field
The invention belongs to electrode material technology, more particularly to a kind of polypyrrole cladding cobalt acid nickel nano-wire array Graphene
The application of the preparation method and detection heavy metal lead ion of electrode.
Background technology
With developing rapidly for modern industry, the pollution that the mankind are caused to nature also increasingly increases.Wherein, hazardness is tight
The big heavy metal pollution of weight, coverage causes global extensive concern.Lead is a Heavy Metallic Elements, and heavy metal exists
Into after environment or ecosystem will retain, accumulate and migrate, will not decompose, with the characteristics of enrichment.So in air
Lead, can move in soil and water body, and the mankind or animal are directly drunk or water body of the Long Term Contact containing heavy metal ion, can be to god
Jing systems, blood circulation, digestive system and urinary system etc. bring multiple damages.
The method of detection heavy metal mainly has at present：Common technique method includes flame emission spectrometry (FES), inductance
Plasma atomic emission spectrometry (ICP-AES) is closed, hydride generated atomic absorption spectrum (HG-AAS), cold vapor atoms are inhaled
Receive spectrum (CV-AAS) etc..But these traditional method apparatus expensives, detection cycle are long, and equipment volume is huge, to detection sample
The factor such as more is limited, its detection to lead ion is greatly limited., and electrochemical method is quick, sensitive, accurate due to which
Really, simple operation and it is easy to the series of characteristics such as miniaturization and networking, becoming carries out the weight of concentration of heavy metal ion detection
Research method is wanted, electrochemical method can be applied not only to water for the detection of heavy metal lead, the detection of soil, equally can be with
For the detection of blood lead.We are exactly to use Electrochemical Detection using polypyrrole cladding cobalt acid nickel nano-wire array Graphene electrodes
Method.
In the heavy metal analysis of existing electrochemical method, predominantly detecting material is：1. biomolecule class：Enzyme, DNA,
RNA；The nanostructured of 2.Au；3. metal-oxide；4. mercury film electrode, dropping-mercury electrode；5. carbon material compound, such as carbon nanometer
Pipe, Graphene is used as carrier.And for Hg in detectable substance2+Most study, for Pb2+Detection research it is relatively fewer.Lin
It is used for Pb Deng the modified electrode of DNA bases is utilized2+Detection, DNA fragmentation meeting and Pb2+Specific binding, reaches the purpose of detection,
With good chemical property.Although the detection material of biomolecule class has excellent chemical property, such inspection
Measure and monitor the growth of standing timber material easy in inactivation, prepare complicated, the requirement to detecting environment is higher, is greatly limited in actual applications.Zhu etc. is utilized
Au nano-particle combines half Guang amide, then loads to2+Detection, reached certain Detection results.
But the utilization of noble metal Au, drastically increases the cost of detecting electrode, is unfavorable for Pb2+The extensive application of detection.Aragay etc.
Pb is detected using mercury film electrode2+, alloy can be formed with which when Hg runs into Pb, so as to reach the purpose of detection.But due to Hg
Itself falls within heavy metal, using this kind of electrode, is faced with the problem of secondary pollution, so such detection material does not meet green
The scope of material.Zhou etc. utilizes cysteine and graphene composite material, is electrodeposited in glassy carbon electrode surface, obtained modified
Electrode is used for Pb2+Detection, test limit reached 0.12 μ g/L.For grapheme material, major part is to use electronation
Obtained in graphene oxide, Graphene obtained in this kind of method is easy to stacking, it is difficult to the excellent properties with Graphene itself.
The detection material of metal oxide-type also has certain report：Chen etc. designs a kind of SnO2Tube-in-tube structure is used to detect Pb2 +, test limit reaches 0.0016 μM, but this kind of method preparation process is extremely complex.Li etc. is using a kind of new Fe3O4Nanometer sheet
Shape structure is used for Pb2+Detection.Liu etc. utilizes Co3O4Porous nano chip architecture has reached detection Pb2+Purpose, sensitivity is
71.57μA μM-1, 0.018 μM of test limit, with more gratifying sensitivity.But, in the detection to actual water sample,
The sensor with more high sensitivity and lower test limit, this high-performance sensors is needed to be badly in need of research.
The content of the invention
It is an object of the invention to provide a kind of polypyrrole coats NiCo2O4The preparation method of nano-wire array Graphene electrodes,
The quick detection of lead ion is reached using this electrode, while there is high sensitivity and low test limit, it is dirty for the water of heavy metal
It is infected with very big significance.Using the structure of cobalt acid nickel nano-wire array, we are because that three-dimensional matrix structure can increase unit plane
The number of active site in product, reduce electron transmission and reaction substrate diffusion resistance；Nanoparticle structure specific surface
Long-pending big, many surface activity sites, surface activity height, high adsorption capacity, high catalytic efficiency, these advantages can be to improving sensor
Stability, sensitivity and selectivity play effect well, be conducive to producing the sensor of function admirable.Polypyrrole conduct
Conducting polymer is not only able to the electric conductivity for improving cobalt acid nickel nano-wire array, and pyrroles has nitrogen-containing group, can and lead
Ion complexation, so as to further improve sensitivity and test limit.
NiCo is obtained using two one-step hydrothermals2O4Nano-wire array graphene-structured, recycles chemical gaseous phase polymerization bag
PPy is covered, final polypyrrole cladding NiCo is obtained2O4Nano-wire array Graphene electrodes.Polypyrrole coats NiCo2O4Nano wire
Array Graphene electrodes have a good electro catalytic activity, the wide range of linearity, the low test limit of high sensitivity.Linear model
Enclose and reach 0.0125 μM -0.709 μM, sensitivity is 115.621 μ A μM-1, detect and be limited to 0.2nM.The present invention greatly reduces reality
Cost is tested, and operational approach is easy, the modified electrode for obtaining has excellent chemical property, had extensively at aspects such as lead ion monitorings
Wealthy range of application.
A kind of polypyrrole cladding NiCo of the present invention2O4The preparation of nano-wire array Graphene electrodes and detection heavy metal
Pb2+The application technology scheme of sensor is as follows：
A kind of polypyrrole coats NiCo2O4The preparation method of nano-wire array Graphene electrodes, is obtained using two one-step hydrothermals
NiCo2O4Nano-wire array graphene-structured, recycles chemical gaseous phase polymerization cladding PPy, obtains final polypyrrole cladding
NiCo2O4Nano-wire array Graphene electrodes.
Following steps are adopted specifically：
(1) preparation of 3D Graphene electrodes
Compound concentration is 1～8mg mL-1Graphene oxide solution, 2～4h of ultrasound is transferred in water heating kettle；It is put into horse
Not 120～180 DEG C of heating in stove, obtain 3D Graphenes, then carry out frozen dried；
(2)NiCo2O4The preparation of nano-wire array -3D Graphenes
Configuration 1～2.5mmol of Nickel dichloride., 2～5mmol of cobalt nitrate, 6～15mmol of ammonium fluoride, 10～30mmol of carbamide, plus
Mix in entering distilled water, obtain bright homogeneous pink colour liquid；This pink colour liquid is poured in water heating kettle, 3D Graphenes hang
It is placed in pink colour liquid；The hydro-thermal reaction at a temperature of 60～140 DEG C, reaction are taken out reactor after terminating and are cooled to room temperature, take out
The graphene-based bottoms of 3D, are attached to pink mass on graphene-based bottom, are rinsed with distilled water and ethanol repeatedly, drying at room temperature；So
After be put in tube furnace, calcine in a nitrogen atmosphere, obtain NiCo2O4- 3D Graphenes；
(3) PPy claddings NiCo2O4The preparation of/3D Graphenes
, into distilled water, it is molten that ultrasound makes which fully be dissolved as configuration 3～6mmol Ammonium persulfate .s and 0.1～0.3mmol SDS
Liquid；By NiCo2O4/ 3D Graphenes are dipped to abundant moistening in being put into solution, be placed in culture dish after taking-up, add in culture dish
Enter 10～30 μ L pyrrole monomers, both are not directly contacted with, and cover culture dish, pyrrole monomer volatilization in culture dish produces pyrroles and steams
Vapour；Take out after 3～10min, surface is rinsed repeatedly with distilled water and ethanol, obtain polypyrrole cladding NiCo2O4Nano-wire array stone
Black alkene electrode.
The step (1) heats 5～12h in being put into Muffle furnace.
The step (2) mixes 5～15min in adding distilled water.
The step (2) at a temperature of 60～140 DEG C, 5～8h of hydro-thermal reaction.
The step (3) calcining heat in tube furnace is 200～300 DEG C, and calcination time is 1～4h.
The present invention carries out the hydro-thermal reaction of graphene oxide first with water heating kettle, obtains the 3D Graphenes with three dimensional structure
Electrode, then using second water-heat process, in 3D Graphene electrodes superficial growth NiCo2O4Nano-wire array.Using chemical gas
The method of phase-polymerization is in NiCo2O4The very thin conductive polymer polypyrrole layer of one layer of nano-wire array Surface coating；Obtain final
Polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes (NiCo2O4@PPy/3D Graphenes), the polypyrrole cladding of the present invention
NiCo2O4Nano-wire array Graphene electrodes can be used for heavy metal lead ion transducer, and with high sensitivity and low inspection
Limit is surveyed, has excellent Electrochemical Detection performance.The range of linearity reaches 0.0125 μM -0.709 μM, and sensitivity is 115.621 μ A μM-1, detect and be limited to 0.2nM.Based on NiCo2O4The transducer sensitivity that@PPy/3D Graphenes build is 115.621 μ A μM-1, linearly
Scope is 0.709 μM of 0.0125to, and lowest detection is limited to 0.2nM, and sensor has good anti-interference and stability.
Electro-chemical test is carried out using three-electrode system, at room temperature, is containing K3[Fe(CN)6], K4[Fe(CN)6],
The test of electronics conduction resistance and CV cyclic voltammetry scans are carried out in the solution of KCl.In the lead ion solution of variable concentrations, use
SWASV methods obtain current-responsive and carry out linear fit to response current and concentration, calculate which as enzyme-free glucose sensor
The range of linearity, response sensitivity and test limit.
Description of the drawings
Polypyrrole cladding NiCo in Fig. 1 examples 12O4The scanning electron microscope (SEM) photograph of nano-wire array Graphene electrodes.
Polypyrrole cladding NiCo in Fig. 2 embodiments 12O4The transmission electron microscope picture of nano-wire array Graphene electrodes.
3D Graphene electrodes, NiCo in Fig. 3 embodiments 22O4Nano-wire array Graphene electrodes, polypyrrole cladding NiCo2O4
The CV cyclic voltammetry curve comparison diagrams of nano-wire array Graphene electrodes.
3D Graphene electrodes, NiCo in Fig. 4 embodiments 32O4Nano-wire array Graphene electrodes, polypyrrole cladding NiCo2O4
The impedance contrast figure of nano-wire array Graphene electrodes.
Polypyrrole cladding NiCo in Fig. 5 embodiments 42O4Nano-wire array Graphene electrodes are in variable concentrations Pb2+Under sound
Induced current and Pb2+Concentration relationship figure
Polypyrrole cladding NiCo in Fig. 6 embodiments 42O4The response current of nano-wire array Graphene electrodes and the line of concentration
Property matched curve.
Specific embodiment
The present invention is illustrated by preferred embodiments below, is realized final technology of preparing, but is not only limited to
Following embodiments.
Polypyrrole coats NiCo2O4The preparation method of the preparation method 3D Graphene electrodes of nano-wire array Graphene electrodes：
(1) preparation of 3D Graphene electrodes
The graphene oxide powder of purchase is taken, in adding distilled water, mix homogeneously obtains concentration for 1～8mg mL-1It is above-mentioned
The graphene oxide solution of preparation, 2～4h of ultrasound, is transferred in water heating kettle.Be put in Muffle furnace 120～180 DEG C of heating 5～
12h, obtains the graphene oxide (3D Graphenes) of the reduction with network 3D structures, then carries out frozen dried.
(2)NiCo2O4The preparation of nano-wire array -3D Graphenes
3D Graphenes with above-mentioned preparation grow NiCo as substrate in this substrate2O4Presoma nanowire array structure.
Configuration 1～2.5mmol of Nickel dichloride., 2～5mmol of cobalt nitrate, 6～15mmol of ammonium fluoride, 10～30mmol of carbamide, add distilled water
Middle mixing, stirs 5～15min, obtains bright homogeneous pink colour liquid.This pink colour liquid is poured in water heating kettle, 3D stones
Black alkene is suspended in pink colour liquid.At a temperature of 60～140 DEG C, 5～8h of hydro-thermal reaction, reaction take out reactor cooling after terminating
To room temperature, take out the graphene-based bottoms of 3D, it can be seen that pink mass is attached on graphene-based bottom, is rushed with distilled water and ethanol repeatedly
Wash, drying at room temperature.
Sample is transferred in tube furnace, in a nitrogen atmosphere, 200～300 DEG C of 1～4h of calcining obtain NiCo2O4- 3D stones
Black alkene.
(3) PPy claddings NiCo2O4The preparation of/3D Graphenes
Using the method for chemical vapor deposition polymerization in NiCo2O4- 3D graphenic surfaces coat one layer of ultra-thin PPy film：Match somebody with somebody
3～6mmol Ammonium persulfate .s and 0.1～0.3mmol SDS are put into distilled water, 5～10min of ultrasound makes which fully dissolve.Will
NiCo2O4/ 3D Graphenes are dipped to abundant moistening in being put into above-mentioned mixed solution, be placed in culture dish, in culture dish after taking-up
10～30 μ L pyrrole monomers are added, both are not directly contacted with, culture dish on this, pyrrole monomer volatilization in culture dish produces pyrroles and steams
Vapour.Take out after 3～10min, surface is rinsed repeatedly with distilled water and ethanol, obtain polypyrrole cladding NiCo2O4Nano-wire array stone
Black alkene electrode, product are placed in drying for standby in 50～60 DEG C of vacuum drying ovens.
Electro-chemical test is carried out to sample using three electrode test systems：
Wherein working electrode is that polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes, auxiliary electrode are Pt silk electrodes
(diameter 1mm), reference electrode are Ag/AgCl electrodes, set scanning voltage scope as in -0.2～0.6V, in the K of 5mM3[Fe
(CN)6] and 5mM K4[Fe(CN)6] 0.1M KCl solution in carry out CV cyclic voltammetry scans.
Polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes in three-electrode system, in the acetate buffer solution of 0.1M
In be added dropwise over Pb2+Solution, carries out SWASV methods and determines current-responsive under variable concentrations.
Polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes carry out electrochemical impedance in three-electrode system
(EIS) test, used test solution is the K containing 5mM3[Fe(CN)6] and 5mM K4[Fe(CN)6] 0.1M KCl solution.
Embodiment 1
The graphene oxide powder of purchase is taken, in adding 20mL distilled water, mix homogeneously obtains 20mL (8mg mL-1) above-mentioned
The graphene oxide solution of preparation, ultrasound were transferred in 50mL water heating kettles after two hours.It is put into 180 DEG C of heating in Muffle furnace
12h, obtains the graphene oxide (3D Graphenes) of the reduction with network 3D structures, then carries out frozen dried.
3D Graphenes with above-mentioned preparation grow NiCo as substrate in this substrate2O4Presoma nanowire array structure.
Nickel dichloride. 0.12g, cobalt nitrate 0.24g, ammonium fluoride 0.2g, carbamide 1.0g are weighed, are added into 40mL distilled water, stir 15min,
Obtain bright homogeneous pink colour liquid.This pink colour liquid is poured in 50mL water heating kettles, 3D Graphenes are suspended in pink colour liquid.
At a temperature of 100 DEG C, hydro-thermal reaction 5h, reaction are taken out reactor after terminating and are cooled to room temperature, take out the graphene-based bottoms of 3D, can see
Pink mass is attached to on graphene-based bottom, is rinsed with distilled water and ethanol repeatedly, drying at room temperature.Sample is transferred to tubular type
In stove, in a nitrogen atmosphere, 300 DEG C of calcining 2h, obtain NiCo2O4- 3D Graphene electrodes.
Using the method for chemical vapor deposition polymerization in NiCo2O4- 3D graphenic surfaces coat one layer of ultra-thin PPy film：Claim
Take in 0.1g Ammonium persulfate .s and 0.01g SDS addition 20mL distilled water, ultrasonic 10min makes which fully dissolve.By NiCo2O4- 3D stones
Black alkene soaks 30min in being put into above-mentioned mixed solution, be placed in culture dish after taking-up, and 30 μ L pyrroles's lists are added in culture dish
Body, both are not directly contacted with, culture dish on this, and pyrrole monomer volatilization in culture dish produces pyrroles's steam.Take out after 10min, use
Distilled water and ethanol rinse surface repeatedly, obtain polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes, product are placed in 50
3h is dried in DEG C vacuum drying oven standby.The polypyrrole cladding NiCo for obtaining2O4Nano-wire array Graphene electrodes scanning electron microscope shape
Looks figure as shown in Figure 1, from the figure, it can be seen that NiCo2O41～2 μm of nano-wire array height, growth is uniform, and polypyrrole is equal
It is even to be coated on NiCo2O4Nano wire forms cylindric.Polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes transmission electron microscope
Shape appearance figure as shown in Figure 2, polypyrrole layer (PPy), NiCo as we can see from the figure2O4Nanometer rods, 3D graphene-structureds, by
This can be determined that we successfully synthesize polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes.
Embodiment 2
The graphene oxide powder of purchase is taken, in adding 40mL distilled water, mix homogeneously obtains 40mL (1mg mL-1) above-mentioned
The graphene oxide solution of preparation, ultrasound were transferred in 50mL water heating kettles after two hours.It is put into 180 DEG C of heating in Muffle furnace
12h, obtains the graphene oxide (3D Graphenes) of the reduction with network 3D structures, then carries out frozen dried.
3D Graphenes with above-mentioned preparation grow NiCo as substrate in this substrate2O4Presoma nanowire array structure.
Nickel dichloride. 0.4g, cobalt nitrate 0.8g, ammonium fluoride 0.4g, carbamide 0.5g are weighed, is added into 40mL distilled water, stirred 15min, obtain
To bright homogeneous pink colour liquid.This pink colour liquid is poured in 50mL water heating kettles, 3D Graphenes are suspended in pink colour liquid.
At a temperature of 140 DEG C, hydro-thermal reaction 8h, reaction are taken out reactor after terminating and are cooled to room temperature, take out the graphene-based bottoms of 3D, it can be seen that
Pink mass is attached on graphene-based bottom, is rinsed with distilled water and ethanol repeatedly, drying at room temperature.Sample is transferred to tube furnace
In, in a nitrogen atmosphere, 200 DEG C of calcining 4h obtain NiCo2O4- 3D Graphene electrodes.
Using the method for chemical vapor deposition polymerization in NiCo2O4- 3D graphenic surfaces coat one layer of ultra-thin PPy film：Claim
Take in 1.2g Ammonium persulfate .s and 0.1g SDS addition 20mL distilled water, ultrasonic 5min makes which fully dissolve.By NiCo2O4/ 3D graphite
Alkene soaks 30min in being put into above-mentioned mixed solution, be placed in culture dish after taking-up, and 30 μ L pyrrole monomers are added in culture dish,
Both are not directly contacted with, culture dish on this, and pyrrole monomer volatilization in culture dish produces pyrroles's steam.Take out after 3min, with distillation
Water and ethanol rinse surface repeatedly, obtain polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes, product are placed in 60 DEG C very
3h is dried in empty drying baker standby.
NiCo is coated by polypyrrole of working electrode2O4Nano-wire array Graphene electrodes, auxiliary electrode are Pt silk electrodes
(diameter 1mm), reference electrode are Ag/AgCl electrodes, set scanning voltage scope as in -0.2～0.6V, in the K of 5mM3[Fe
(CN)6] and 5mM K4[Fe(CN)6] 0.1M KCl solution in carry out CV cyclic voltammetry scans.As shown in Figure 3,3D graphite
Alkene electrode, NiCo2O4- 3D Graphene electrodes, polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes all occur in that oxidation
Reduction peak.3D Graphene electrodes modify NiCo2O4Nano-wire array CV redox peaks occur in that reduction is because NiCo2O4For
Quasiconductor, causes electric conductivity to decline, but after modification polypyrrole, polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes have
There are most strong redox peaks, it is shown that polypyrrole coats NiCo2O4There is nano-wire array Graphene electrodes bigger catalysis to live
Property and electric conductivity.
Embodiment 3
The graphene oxide powder of purchase is taken, in adding 40mL distilled water, mix homogeneously obtains 40mL (6mg mL-1) above-mentioned
The graphene oxide solution of preparation, ultrasound were transferred in 50mL water heating kettles after two hours.120 DEG C of heating 5h in Muffle furnace are put into,
The graphene oxide (3D Graphenes) of the reduction with network 3D structures is obtained, frozen dried is then carried out.
3D Graphenes with above-mentioned preparation grow NiCo as substrate in this substrate2O4Presoma nanowire array structure.
Nickel dichloride. 0.1g, cobalt nitrate 0.8g, ammonium fluoride 0.1g, carbamide 0.8g are weighed, is added into 40mL distilled water, stirred 15min, obtain
To bright homogeneous pink colour liquid.This pink colour liquid is poured in 50mL water heating kettles, 3D Graphenes are suspended in pink colour liquid.
At a temperature of 60 DEG C, hydro-thermal reaction 8h, reaction are taken out reactor after terminating and are cooled to room temperature, take out the graphene-based bottoms of 3D, it can be seen that
Pink mass is attached on graphene-based bottom, is rinsed with distilled water and ethanol repeatedly, drying at room temperature.Sample is transferred to tube furnace
In, in a nitrogen atmosphere, 300 DEG C of calcining 3h obtain NiCo2O4- 3D Graphene electrodes.
Using the method for chemical vapor deposition polymerization in NiCo2O4- 3D graphenic surfaces coat one layer of ultra-thin PPy film：Claim
Take in 0.66g Ammonium persulfate .s and 0.05g SDS addition 20mL distilled water, ultrasonic 10min makes which fully dissolve.By NiCo2O4-3D
Graphene soaks 30min in being put into above-mentioned mixed solution, be placed in culture dish after taking-up, and 10 μ L pyrroles's lists are added in culture dish
Body, both are not directly contacted with, culture dish on this, and pyrrole monomer volatilization in culture dish produces pyrroles's steam.Take out after 5min, with steaming
Distilled water and ethanol rinse surface repeatedly, obtain polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes, product are placed in 60 DEG C
3h is dried in vacuum drying oven standby.
NiCo is coated by polypyrrole of working electrode2O4Nano-wire array Graphene electrodes, auxiliary electrode are Pt silk electrodes
(diameter 1mm), reference electrode are Ag/AgCl electrodes, in [the Fe (CN) that solution is 5mM6]3-/4-1M KCl solution in, to sample
Product electrode carries out impedance analysis.The frequency range of test is 105Hz～10-2Hz.Its comparing result is shown in accompanying drawing 4, can be with from figure
Find out, polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes are close to the resistance value of 3D Graphene electrodes, far smaller than
NiCo2O4- 3D Graphene electrodes, illustrate which has good electron transport ability, are beneficial to the raising of sensitivity.
Embodiment 4
The graphene oxide powder of purchase is taken, in adding 40mL distilled water, mix homogeneously obtains 40mL (4mg mL-1) above-mentioned
The graphene oxide solution of preparation, ultrasound were transferred in 50mL water heating kettles after two hours.It is put into 160 DEG C of heating in Muffle furnace
10h, obtains the graphene oxide (3D Graphenes) of the reduction with network 3D structures, then carries out frozen dried.
3D Graphenes with above-mentioned preparation grow NiCo as substrate in this substrate2O4Presoma nanowire array structure.
Nickel dichloride. 0.3g, cobalt nitrate 0.68g, ammonium fluoride 0.3g, carbamide 0.78g are weighed, are added into 40mL distilled water, stir 5min,
Obtain bright homogeneous pink colour liquid.This pink colour liquid is poured in 50mL water heating kettles, 3D Graphenes are suspended in pink colour liquid.
At a temperature of 120 DEG C, hydro-thermal reaction 6h, reaction are taken out reactor after terminating and are cooled to room temperature, take out the graphene-based bottoms of 3D, can see
Pink mass is attached to on graphene-based bottom, is rinsed with distilled water and ethanol repeatedly, drying at room temperature.Sample is transferred to tubular type
In stove, in a nitrogen atmosphere, 300 DEG C of calcining 1h, obtain NiCo2O4- 3D Graphene electrodes.
Using the method for chemical vapor deposition polymerization in NiCo2O4- 3D graphenic surfaces coat one layer of ultra-thin PPy film：Claim
Take in 0.4g Ammonium persulfate .s and 0.03g SDS addition 20mL distilled water, ultrasonic 10min makes which fully dissolve.By NiCo2O4- 3D stones
Black alkene soaks 30min in being put into above-mentioned mixed solution, be placed in culture dish after taking-up, and 20 μ L pyrroles's lists are added in culture dish
Body, both are not directly contacted with, culture dish on this, and pyrrole monomer volatilization in culture dish produces pyrroles's steam.Take out after 7min, with steaming
Distilled water and ethanol rinse surface repeatedly, obtain polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes, product are placed in 60 DEG C
3h is dried in vacuum drying oven standby.
NiCo is coated by polypyrrole of working electrode2O4Nano-wire array Graphene electrodes, auxiliary electrode are Pt silk electrodes
(diameter 1mm), reference electrode are Ag/AgCl electrodes, adopt and are added dropwise over Pb in the acetate buffer solution of 0.1M2+Solution, utilizes
Square wave stripping voltammetry (SWASV) determines current-responsive under variable concentrations.Obtain result as shown in Figure 5, polypyrrole cladding
NiCo2O4Nano-wire array Graphene electrodes are for Pb2+Response current increase with the increase of plumbum ion concentration, and have very
Good linear relationship.As shown in Figure 6, the range of linearity is 0.0125～0.709 μ to the linear fit curve of response current and concentration
M, through can be calculated sensitivity for 115.621 μ A μM-1, lowest detection is limited to 0.2nM.Show polypyrrole cladding
NiCo2O4Nano-wire array Graphene electrodes have fabulous using value in lead ion detection.
The preparation method of the polypyrrole cladding cobalt acid nickel nano-wire array Graphene electrodes for disclosing and proposing of the invention and inspection
The application of check weighing metal lead ion, those skilled in the art can be by using for reference present disclosure, appropriate feed change and process route
Realize etc. link, although the method for the present invention and application are described by preferred embodiment, person skilled is bright
Show off one's talent or competence and method described herein and application be modified or reconfigured in without departing from present invention, spirit and scope,
To realize final technology of preparing.Specifically, all similar replacements and change are to those skilled in the art
For be it will be apparent that they are considered as being included in spirit of the invention, scope and content.
Claims (7)
1. a kind of polypyrrole coats NiCo2O4The preparation method of nano-wire array Graphene electrodes, it is characterised in that using two step water
Full-boiled process obtains NiCo2O4Nano-wire array graphene-structured, recycles chemical gaseous phase polymerization cladding PPy, obtains final gathering
Pyrroles coats NiCo2O4Nano-wire array Graphene electrodes.
2. the method for claim 1；It is characterized in that adopting following steps：
(1) preparation of 3D Graphene electrodes
Compound concentration is 1～8mg mL‐1Graphene oxide solution, 2～4h of ultrasound is transferred in water heating kettle；It is put into Muffle furnace
In 120～180 DEG C heating, obtain 3D Graphenes, then carry out frozen dried；
(2)NiCo2O4The preparation of nano-wire array 3D Graphenes
Configuration 1～2.5mmol of Nickel dichloride., 2～5mmol of cobalt nitrate, 6～15mmol of ammonium fluoride, 10～30mmol of carbamide, add and steam
Mix in distilled water, obtain bright homogeneous pink colour liquid；This pink colour liquid is poured in water heating kettle, 3D Graphenes are suspended in
In pink colour liquid；The hydro-thermal reaction at a temperature of 60～140 DEG C, reaction are taken out reactor after terminating and are cooled to room temperature, take out 3D stones
Mertenyl bottom, is attached to pink mass on graphene-based bottom, is rinsed with distilled water and ethanol repeatedly, drying at room temperature；Then put
Enter in tube furnace, calcine in a nitrogen atmosphere, obtain NiCo2O43D Graphenes；
(3) PPy claddings NiCo2O4The preparation of/3D Graphenes
, into distilled water, ultrasound makes which fully be dissolved as solution for configuration 3～6mmol Ammonium persulfate .s and 0.1～0.3mmol SDS；
By NiCo2O4/ 3D Graphenes are dipped to abundant moistening in being put into solution, be placed in culture dish after taking-up, and 10 are added in culture dish
～30 μ L pyrrole monomers, both are not directly contacted with, and cover culture dish, and pyrrole monomer volatilization in culture dish produces pyrroles's steam；3～
Take out after 10min, surface is rinsed repeatedly with distilled water and ethanol, obtain polypyrrole cladding NiCo2O4Nano-wire array Graphene electricity
Pole.
3. method as claimed in claim 2, is characterized in that the step (1) heats 5～12h in being put into Muffle furnace.
4. method as claimed in claim 2, is characterized in that the step (2) mixes 5～15min in adding distilled water.
5. method as claimed in claim 2, is characterized in that the step (2) at a temperature of 60～140 DEG C, hydro-thermal reaction 5～
8h。
6. method as claimed in claim 2, is characterized in that the step (3) calcining heat in tube furnace is 200～300
DEG C, calcination time is 1～4h.
7. polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes are used for heavy metal lead ion transducer.
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