CN106525933B - Polypyrrole coats the preparation method of cobalt acid nickel nano-wire array Graphene electrodes and detects the application of heavy metal lead ion - Google Patents
Polypyrrole coats the preparation method of cobalt acid nickel nano-wire array Graphene electrodes and detects the application of heavy metal lead ion Download PDFInfo
- Publication number
- CN106525933B CN106525933B CN201610959204.7A CN201610959204A CN106525933B CN 106525933 B CN106525933 B CN 106525933B CN 201610959204 A CN201610959204 A CN 201610959204A CN 106525933 B CN106525933 B CN 106525933B
- Authority
- CN
- China
- Prior art keywords
- graphene
- nico
- nano
- wire array
- polypyrrole
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
- 229910021389 graphene Inorganic materials 0.000 title claims abstract description 138
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 title claims abstract description 137
- 229920000128 polypyrrole Polymers 0.000 title claims abstract description 67
- 238000002360 preparation method Methods 0.000 title claims abstract description 32
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 0.000 title abstract description 26
- 229910001385 heavy metal Inorganic materials 0.000 title abstract description 16
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000002253 acid Substances 0.000 title abstract description 8
- 229910017052 cobalt Inorganic materials 0.000 title abstract description 8
- 239000010941 cobalt Substances 0.000 title abstract description 8
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 title abstract description 8
- 239000002070 nanowire Substances 0.000 claims abstract description 59
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910005949 NiCo2O4 Inorganic materials 0.000 claims abstract description 52
- 238000000034 method Methods 0.000 claims abstract description 28
- 238000010438 heat treatment Methods 0.000 claims abstract description 25
- 229910003266 NiCo Inorganic materials 0.000 claims abstract description 21
- 238000005253 cladding Methods 0.000 claims abstract description 21
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 13
- 239000000126 substance Substances 0.000 claims abstract description 9
- 239000007792 gaseous phase Substances 0.000 claims abstract description 4
- 239000012153 distilled water Substances 0.000 claims description 34
- 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
- 239000007788 liquid Substances 0.000 claims description 22
- 238000006243 chemical reaction Methods 0.000 claims description 15
- 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
- 235000019441 ethanol Nutrition 0.000 claims description 14
- 238000011010 flushing procedure Methods 0.000 claims description 13
- 239000000178 monomer Substances 0.000 claims description 11
- 150000003233 pyrroles Chemical class 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
- 238000006116 polymerization reaction Methods 0.000 claims description 9
- 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
- 229910021586 Nickel(II) chloride Inorganic materials 0.000 claims description 7
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-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
- 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
- 238000009736 wetting Methods 0.000 claims description 3
- 230000005611 electricity Effects 0.000 claims 1
- 238000001514 detection method Methods 0.000 abstract description 39
- 230000035945 sensitivity Effects 0.000 abstract description 12
- 229920001940 conductive polymer Polymers 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 239000000243 solution Substances 0.000 description 18
- 239000000758 substrate Substances 0.000 description 11
- 150000001336 alkenes Chemical class 0.000 description 6
- 239000000463 material Substances 0.000 description 6
- 230000009467 reduction Effects 0.000 description 6
- 238000005229 chemical vapour deposition 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
- 238000012360 testing method Methods 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 4
- 238000002484 cyclic voltammetry Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 4
- 230000005540 biological transmission 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
- 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
- 230000000694 effects 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
- 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
- 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
- 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
- 238000011161 development Methods 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
- 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
- 238000005259 measurement Methods 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
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000002086 nanomaterial Substances 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
- 238000011017 operating method Methods 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 238000001637 plasma atomic emission spectroscopy Methods 0.000 description 1
- 239000004065 semiconductor Substances 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
- 238000003756 stirring Methods 0.000 description 1
- 238000003950 stripping voltammetry Methods 0.000 description 1
- 239000012085 test solution Substances 0.000 description 1
- 230000002485 urinary effect Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
Classifications
-
- 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
Landscapes
- Chemical & Material Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Health & Medical Sciences (AREA)
- Physics & Mathematics (AREA)
- 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 present invention relates to the applications of the preparation method of polypyrrole cladding cobalt acid nickel nano-wire array Graphene electrodes and detection heavy metal lead ion.The hydro-thermal reaction that graphene oxide is carried out first with water heating kettle, obtains the 3D Graphene electrodes with three-dimensional structure, then utilizes second of water-heat process, grows NiCo on 3D Graphene electrodes surface2O4Nano-wire array.Using the method that chemical gaseous phase polymerize in NiCo2O4Nano-wire array surface coats one layer of very thin conductive polymer polypyrrole layer；Obtain final polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes, electrode are used for heavy metal Pb2+Detection.Based on NiCo2O4The transducer sensitivity of@PPy/3D graphene building is 115.621 μ A μM‑1, the range of linearity is 0.709 μM of 0.0125to, and lowest detection is limited to 0.2nM, and sensor has good anti-interference and stability.
Description
Technical field
The invention belongs to electrode material technologies, coat cobalt acid nickel nano-wire array graphene more particularly to a kind of polypyrrole
The preparation method of electrode and the application for detecting heavy metal lead ion.
Background technique
It is also increasingly aggravated with the rapid development of modern industry, the mankind pollute caused by nature.Wherein, harmfulness is tight
The big heavy metal pollution of weight, coverage has attracted worldwide attention.Lead is a Heavy Metallic Elements, and heavy metal exists
It will retain, accumulate and migrate after into environment or the ecosystem, will not decompose, have the characteristics that enrichment.So in air
Lead can move in soil and water body, and mankind or animal is directly drunk or water body of the Long Term Contact containing heavy metal ion, can be to mind
Multiple damages are brought through system, blood circulation system, digestive system and urinary system etc..
The method of detection heavy metal mainly has at present: common technique method includes flame emission spectrometry (FES), inductance
It closes plasma atomic emission spectrometry (ICP-AES), hydride generated atomic absorption spectrum (HG-AAS), cold vapor atoms are inhaled
Receive spectrum (CV-AAS) etc..But these traditional method equipment are expensive, and detection cycle is long, and equipment volume is huge, to test sample
The factors such as more are limited, the detection of lead ion is greatly limited., and electrochemical method is quick, sensitive, quasi- due to its
Really, it operates convenient and is easy to the series of characteristics such as miniaturization and networking, become the weight for carrying out concentration of heavy metal ion detection
Want research method, detection of the electrochemical method for heavy metal lead can be applied not only to water, the detection of soil, equally can be with
Detection for 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, material is predominantly detected are as follows: 1. biomolecule classes: enzyme, DNA,
RNA；The nanostructure of 2.Au；3. metal oxide；4. mercury film electrode, dropping-mercury electrode；5. carbon material compound, such as carbon nanometer
Pipe, graphene is as carrier.And for Hg in detectable substance2+Most study, for Pb2+Detection research it is relatively fewer.Lin
Deng utilize the modified electrode of DNA base for Pb2+Detection, DNA fragmentation meeting and Pb2+Specific binding, achievees the purpose that detection,
With good chemical property.Although the detection material of biomolecule class has excellent chemical property, such inspection
It measures and monitor the growth of standing timber and expects easy in inactivation, preparation is complicated, to the more demanding of detection environment, is greatly limited in practical applications.Zhu etc. is utilized
Au nano particle combines half Guang amide, then loads on graphene for Pb2+Detection, reached certain detection effect.
But the utilization of noble metal Au greatly improves the cost of detecting electrode, is unfavorable for Pb2+The extensive use of detection.Aragay etc.
Pb is detected using mercury film electrode2+, alloy can be formed with it when Hg encounters Pb, to achieve the purpose that detection.But due to Hg
Itself also belongs to heavy metal, using such electrode, the problem of being faced with secondary pollution, so such detection material does not meet green
The range of material.Zhou etc. utilizes cysteine and graphene composite material, is electrodeposited in glassy carbon electrode surface, modification obtained
Electrode is used for Pb2+Detection, detection limit has reached 0.12 μ g/L.It is largely to use electronation for grapheme material
Made from graphene oxide, graphene made from such method is easy to stack, 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 for detecting Pb2 +, detection limit reaches 0.0016 μM, but such method preparation process is extremely complex.Li et al. utilizes a kind of novel Fe3O4Nanometer sheet
Shape structure is used for Pb2+Detection.Liu et al. utilizes Co3O4Porous nano chip architecture has reached detection Pb2+Purpose, sensitivity is
71.57μA μM-1, 0.018 μM of detection limit, with more satisfactory sensitivity.But in the detection to actual water sample,
The sensor for needing to have more highly sensitive and lower detection limit simultaneously, this high-performance sensors are badly in need of research.
Summary of the invention
The object of the present invention is to provide a kind of polypyrroles to coat NiCo2O4The preparation method of nano-wire array Graphene electrodes,
Reach the quick detection of lead ion using this electrode, while there is highly sensitive and low detection limit, it is dirty for the water of heavy metal
It is infected with very big significance.We use the structure of cobalt acid nickel nano-wire array, are because three-dimensional matrix structure can increase unit plane
The number of active site in product reduces electron transmission and reaction substrate diffusion resistance；Nanoparticle structure specific surface
Product is big, surface-active site is more, high surface activity, adsorption capacity are strong, high catalytic efficiency, these advantages can be to raising sensor
Stability, sensitivity and selectivity play the role of good, be conducive to the sensor for producing function admirable.Polypyrrole conduct
Conducting polymer be not only able to improve cobalt acid nickel nano-wire array electric conductivity, and pyrroles have nitrogen-containing group, can and lead
Ion complexation, to further increase sensitivity and detection limit.
NiCo is obtained using two one-step hydrothermals2O4Nano-wire array graphene-structured recycles chemical gaseous phase polymerization packet
PPy is covered, final polypyrrole cladding NiCo is obtained2O4Nano-wire array Graphene electrodes.Polypyrrole coats NiCo2O4Nano wire
Array Graphene electrodes have good electro catalytic activity, the wide range of linearity, the low detection limit of high sensitivity.Linear model
It encloses and reaches 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 operating method is easy, obtained modified electrode has excellent chemical property, has in terms of lead ion wide
Wealthy application range.
A kind of polypyrrole of the invention coats NiCo2O4The 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 cladding 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 to coat PPy, obtains final polypyrrole cladding
NiCo2O4Nano-wire array Graphene electrodes.
Specifically use 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 horse
Not 120~180 DEG C of heating in furnace, obtain 3D graphene, then carry out frozen dried；
(2)NiCo2O4The preparation of nano-wire array -3D graphene
1~2.5mmol of nickel chloride, 2~5mmol of cobalt nitrate, 6~15mmol of ammonium fluoride are configured, 10~30mmol of urea adds
Enter in distilled water and be mixed, obtains the pink colour liquid for becoming clear uniform；This pink colour liquid is poured into water heating kettle, 3D graphene is outstanding
It is placed in pink colour liquid；Hydro-thermal reaction at a temperature of 60~140 DEG C is taken out reaction kettle after reaction and is cooled to room temperature, takes out
The graphene-based bottom 3D, is attached to pink mass on graphene-based bottom, with distilled water and ethyl alcohol repeated flushing, drying at room temperature；So
After be put into tube furnace, calcine in a nitrogen atmosphere, obtain NiCo2O4- 3D graphene；
(3) PPy coats NiCo2O4The preparation of/3D graphene
3~6mmol ammonium persulfate and 0.1~0.3mmol SDS are configured into distilled water, it is molten that ultrasound is dissolved as it sufficiently
Liquid；By NiCo2O4/ 3D graphene, which is put into solution, is dipped to abundant wetting, and taking-up is placed in culture dish, adds in culture dish
Enter 10~30 μ L pyrrole monomers, the two is not directly contacted with, and covers culture dish, and pyrrole monomer volatilization generates pyrroles and steams in culture dish
Vapour；It is taken out after 3~10min, with distilled water and ethyl alcohol repeated flushing surface, obtains polypyrrole cladding NiCo2O4Nano-wire array stone
Black alkene electrode.
The step (1) is put into 5~12h of heating in Muffle furnace.
The step (2), which is added in distilled water, is mixed 5~15min.
The step (2) is at a temperature of 60~140 DEG C, 5~8h of hydro-thermal reaction.
The step (3) calcination temperature 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 graphene with three-dimensional structure
Electrode then utilizes second of water-heat process, grows NiCo on 3D Graphene electrodes surface2O4Nano-wire array.Use chemical gas
The method of phase-polymerization is in NiCo2O4Nano-wire array surface coats one layer of very thin conductive polymer polypyrrole layer；It obtains final
Polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes (NiCo2O4@PPy/3D graphene), polypyrrole cladding of the invention
NiCo2O4Nano-wire array Graphene electrodes can be used for heavy metal lead ion transducer, and have high sensitivity and low inspection
Limit is surveyed, there is 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 of@PPy/3D graphene building is 115.621 μ A μM-1, linearly
Range 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 and is containing K at room temperature3[Fe(CN)6], K4[Fe(CN)6],
The test of electronics conduction resistance and CV cyclic voltammetry scan are carried out in the solution of KCl.In the lead ion solution of various concentration, use
SWASV method obtains current-responsive and carries out linear fit to response current and concentration, calculates it as huge sum of money lead ion sensor
The range of linearity, response sensitivity and detection limit.
Detailed description of the invention
Polypyrrole coats NiCo in Fig. 1 example 12O4The scanning electron microscope (SEM) photograph of nano-wire array Graphene electrodes.
Polypyrrole coats NiCo in Fig. 2 embodiment 12O4The transmission electron microscope picture of nano-wire array Graphene electrodes.
3D Graphene electrodes, NiCo in Fig. 3 embodiment 22O4Nano-wire array Graphene electrodes, polypyrrole coat NiCo2O4
The CV cyclic voltammetry curve comparison diagram of nano-wire array Graphene electrodes.
3D Graphene electrodes, NiCo in Fig. 4 embodiment 32O4Nano-wire array Graphene electrodes, polypyrrole coat NiCo2O4
The impedance contrast figure of nano-wire array Graphene electrodes.
Polypyrrole coats NiCo in Fig. 5 embodiment 42O4Nano-wire array Graphene electrodes are in various concentration Pb2+Under sound
Answer electric current and Pb2+Concentration relationship figure
Polypyrrole coats NiCo in Fig. 6 embodiment 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, realizes final technology of preparing, but be 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, is added in distilled water, being uniformly mixed and obtaining concentration is 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 into Muffle furnace 120~180 DEG C of heating 5~
12h obtains the graphene oxide (3D graphene) with the reduction of network 3D structure, then carries out frozen dried.
(2)NiCo2O4The preparation of nano-wire array -3D graphene
Using the 3D graphene of above-mentioned preparation as substrate, NiCo is grown in this substrate2O4Presoma nanowire array structure.
1~2.5mmol of nickel chloride, 2~5mmol of cobalt nitrate, 6~15mmol of ammonium fluoride, 10~30mmol of urea are configured, distilled water is added
Middle mixing stirs 5~15min, obtains the pink colour liquid for becoming clear uniform.This pink colour liquid is poured into water heating kettle, 3D stone
Black alkene is suspended in pink colour liquid.At a temperature of 60~140 DEG C, it is cooling to take out reaction kettle after reaction by 5~8h of hydro-thermal reaction
To room temperature, the graphene-based bottom 3D is taken out, it can be seen that be attached to pink mass on graphene-based bottom, rushed repeatedly with distilled water and ethyl alcohol
It washes, 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 stone
Black alkene.
(3) PPy coats NiCo2O4The preparation of/3D graphene
Using the method for chemical vapor deposition polymerization in NiCo2O4- 3D graphene surface coats one layer of ultra-thin PPy film: matching
3~6mmol ammonium persulfate and 0.1~0.3mmol SDS are set into distilled water, 5~10min of ultrasound dissolves it sufficiently.It will
NiCo2O4/ 3D graphene, which is put into above-mentioned mixed solution, is dipped to abundant wetting, and taking-up is placed in culture dish, in culture dish
10~30 μ L pyrrole monomers are added, the two is not directly contacted with, culture dish on this, and pyrrole monomer volatilization generates pyrroles and steams in culture dish
Vapour.It is taken out after 3~10min, with distilled water and ethyl alcohol repeated flushing surface, obtains polypyrrole cladding NiCo2O4Nano-wire array stone
Black alkene electrode, product are placed in drying for standby in 50~60 DEG C of vacuum 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 electrodes
(diameter 1mm), reference electrode are Ag/AgCl electrode, set scanning voltage range 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 scan.
Polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes are in three-electrode system, in the acetate buffer solution of 0.1M
In Pb is added dropwise2+Solution carries out current-responsive under SWASV method measurement various concentration.
Polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes carry out electrochemical impedance in three-electrode system
(EIS) it tests, 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, is added in 20mL distilled water, is uniformly mixed and obtains 20mL (8mg mL-1) above-mentioned
The graphene oxide solution of preparation, ultrasound are transferred in 50mL water heating kettle after two hours.It is put into 180 DEG C of heating in Muffle furnace
12h obtains the graphene oxide (3D graphene) with the reduction of network 3D structure, then carries out frozen dried.
Using the 3D graphene of above-mentioned preparation as substrate, NiCo is grown in this substrate2O4Presoma nanowire array structure.
Nickel chloride 0.12g, cobalt nitrate 0.24g, ammonium fluoride 0.2g, urea 1.0g are weighed, is added into 40mL distilled water, 15min is stirred,
Obtain the pink colour liquid for becoming clear uniform.This pink colour liquid is poured into 50mL water heating kettle, 3D graphene is suspended in pink colour liquid.
At a temperature of 100 DEG C, hydro-thermal reaction 5h takes out reaction kettle after reaction and is cooled to room temperature, takes out the graphene-based bottom 3D, can see
It is attached to pink mass on to graphene-based bottom, with distilled water and ethyl alcohol repeated flushing, drying at room temperature.Sample is transferred to tubular type
In furnace, 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 graphene surface coats one layer of ultra-thin PPy film: claiming
0.1g ammonium persulfate and 0.01g SDS is taken to be added in 20mL distilled water, ultrasonic 10min dissolves it sufficiently.By NiCo2O4- 3D stone
Black alkene, which is put into above-mentioned mixed solution, impregnates 30min, and taking-up is placed in culture dish, and it is single that 30 μ L pyrroles are added in culture dish
Body, the two are not directly contacted with, culture dish on this, and pyrrole monomer volatilization generates pyrroles's steam in culture dish.It takes out, uses after 10min
Distilled water and ethyl alcohol repeated flushing surface obtain polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes, product are placed in 50
Dry 3h is spare in DEG C vacuum oven.Obtained polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes scanning electron microscope shape
Looks figure is as shown in Fig. 1, from the figure, it can be seen that NiCo2O41~2 μm of nano-wire array height, uniformly, polypyrrole is equal for growth
It is even to be coated on NiCo2O4Nano wire forms cylindric.Polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes transmission electron microscope
Shape appearance figure is as shown in Fig. 2, as we can see from the figure polypyrrole layer (PPy), NiCo2O4Nanometer rods, 3D graphene-structured, 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, is added in 40mL distilled water, is uniformly mixed and obtains 40mL (1mg mL-1) above-mentioned
The graphene oxide solution of preparation, ultrasound are transferred in 50mL water heating kettle after two hours.It is put into 180 DEG C of heating in Muffle furnace
12h obtains the graphene oxide (3D graphene) with the reduction of network 3D structure, then carries out frozen dried.
Using the 3D graphene of above-mentioned preparation as substrate, NiCo is grown in this substrate2O4Presoma nanowire array structure.
Nickel chloride 0.4g, cobalt nitrate 0.8g, ammonium fluoride 0.4g, urea 0.5g are weighed, is added into 40mL distilled water, 15min is stirred, obtains
To the pink colour liquid for becoming clear uniform.This pink colour liquid is poured into 50mL water heating kettle, 3D graphene is suspended in pink colour liquid.?
At a temperature of 140 DEG C, hydro-thermal reaction 8h takes out reaction kettle after reaction and is cooled to room temperature, takes out the graphene-based bottom 3D, it can be seen that
It is attached to pink mass on graphene-based bottom, with distilled water and ethyl alcohol repeated flushing, 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 graphene surface coats one layer of ultra-thin PPy film: claiming
1.2g ammonium persulfate and 0.1g SDS is taken to be added in 20mL distilled water, ultrasonic 5min dissolves it sufficiently.By NiCo2O4/ 3D graphite
Alkene, which is put into above-mentioned mixed solution, impregnates 30min, and taking-up is placed in culture dish, and 30 μ L pyrrole monomers are added in culture dish,
The two is not directly contacted with, culture dish on this, and pyrrole monomer volatilization generates pyrroles's steam in culture dish.It is taken out after 3min, with distillation
Water and ethyl alcohol repeated flushing surface obtain polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes, product are placed in 60 DEG C very
Dry 3h is spare in empty drying box.
NiCo is coated by polypyrrole of working electrode2O4Nano-wire array Graphene electrodes, auxiliary electrode are Pt electrodes
(diameter 1mm), reference electrode are Ag/AgCl electrode, set scanning voltage range 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 scan.As shown in Fig. 3,3D graphite
Alkene electrode, NiCo2O4- 3D Graphene electrodes, polypyrrole coat NiCo2O4All there is oxidation in nano-wire array Graphene electrodes
Reduction peak.3D Graphene electrodes modify NiCo2O4It is because of NiCo that reducing, which occur, in nano-wire array CV redox peaks2O4For
Semiconductor causes electric conductivity to decline, but after modifying polypyrrole, polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes tool
There are strongest redox peaks, it is shown that polypyrrole coats NiCo2O4Nano-wire array Graphene electrodes have bigger catalysis living
Property and electric conductivity.
Embodiment 3
The graphene oxide powder of purchase is taken, is added in 40mL distilled water, is uniformly mixed and obtains 40mL (6mg mL-1) above-mentioned
The graphene oxide solution of preparation, ultrasound are transferred in 50mL water heating kettle after two hours.120 DEG C of heating 5h in Muffle furnace are put into,
The graphene oxide (3D graphene) with the reduction of network 3D structure is obtained, frozen dried is then carried out.
Using the 3D graphene of above-mentioned preparation as substrate, NiCo is grown in this substrate2O4Presoma nanowire array structure.
Nickel chloride 0.1g, cobalt nitrate 0.8g, ammonium fluoride 0.1g, urea 0.8g are weighed, is added into 40mL distilled water, 15min is stirred, obtains
To the pink colour liquid for becoming clear uniform.This pink colour liquid is poured into 50mL water heating kettle, 3D graphene is suspended in pink colour liquid.?
At a temperature of 60 DEG C, hydro-thermal reaction 8h takes out reaction kettle after reaction and is cooled to room temperature, takes out the graphene-based bottom 3D, it can be seen that
It is attached to pink mass on graphene-based bottom, with distilled water and ethyl alcohol repeated flushing, 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 graphene surface coats one layer of ultra-thin PPy film: claiming
0.66g ammonium persulfate and 0.05g SDS is taken to be added in 20mL distilled water, ultrasonic 10min dissolves it sufficiently.By NiCo2O4-3D
Graphene, which is put into above-mentioned mixed solution, impregnates 30min, and taking-up is placed in culture dish, and it is single that 10 μ L pyrroles are added in culture dish
Body, the two are not directly contacted with, culture dish on this, and pyrrole monomer volatilization generates pyrroles's steam in culture dish.It is taken out after 5min, with steaming
Distilled water and ethyl alcohol repeated flushing surface obtain polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes, product are placed in 60 DEG C
Dry 3h is spare in vacuum oven.
NiCo is coated by polypyrrole of working electrode2O4Nano-wire array Graphene electrodes, auxiliary electrode are Pt electrodes
(diameter 1mm), reference electrode are Ag/AgCl electrode, 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 attached drawing 4, can be with from figure
Find out, polypyrrole coats NiCo2O4The impedance value of nano-wire array Graphene electrodes and 3D Graphene electrodes is close, far smaller than
NiCo2O4- 3D Graphene electrodes illustrate that it has good electron transport ability, are beneficial to the raising of sensitivity.
Embodiment 4
The graphene oxide powder of purchase is taken, is added in 40mL distilled water, is uniformly mixed and obtains 40mL (4mg mL-1) above-mentioned
The graphene oxide solution of preparation, ultrasound are transferred in 50mL water heating kettle after two hours.It is put into 160 DEG C of heating in Muffle furnace
10h obtains the graphene oxide (3D graphene) with the reduction of network 3D structure, then carries out frozen dried.
Using the 3D graphene of above-mentioned preparation as substrate, NiCo is grown in this substrate2O4Presoma nanowire array structure.
Nickel chloride 0.3g, cobalt nitrate 0.68g, ammonium fluoride 0.3g, urea 0.78g are weighed, is added into 40mL distilled water, 5min is stirred,
Obtain the pink colour liquid for becoming clear uniform.This pink colour liquid is poured into 50mL water heating kettle, 3D graphene is suspended in pink colour liquid.
At a temperature of 120 DEG C, hydro-thermal reaction 6h takes out reaction kettle after reaction and is cooled to room temperature, takes out the graphene-based bottom 3D, can see
It is attached to pink mass on to graphene-based bottom, with distilled water and ethyl alcohol repeated flushing, drying at room temperature.Sample is transferred to tubular type
In furnace, 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 graphene surface coats one layer of ultra-thin PPy film: claiming
0.4g ammonium persulfate and 0.03g SDS is taken to be added in 20mL distilled water, ultrasonic 10min dissolves it sufficiently.By NiCo2O4- 3D stone
Black alkene, which is put into above-mentioned mixed solution, impregnates 30min, and taking-up is placed in culture dish, and it is single that 20 μ L pyrroles are added in culture dish
Body, the two are not directly contacted with, culture dish on this, and pyrrole monomer volatilization generates pyrroles's steam in culture dish.It is taken out after 7min, with steaming
Distilled water and ethyl alcohol repeated flushing surface obtain polypyrrole cladding NiCo2O4Nano-wire array Graphene electrodes, product are placed in 60 DEG C
Dry 3h is spare in vacuum oven.
NiCo is coated by polypyrrole of working electrode2O4Nano-wire array Graphene electrodes, auxiliary electrode are Pt electrodes
(diameter 1mm), reference electrode is Ag/AgCl electrode, using Pb is added dropwise in the acetate buffer solution of 0.1M2+Solution utilizes
Square wave stripping voltammetry (SWASV) measures current-responsive under various concentration.It is as shown in Fig. 5 to obtain result, 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.Response current and the linear fit curve of concentration are as shown in Fig. 6, and the range of linearity is 0.0125~0.709 μ
M is 115.621 μ A μM by can be calculated sensitivity-1, lowest detection is limited to 0.2nM.Show polypyrrole cladding
NiCo2O4Nano-wire array Graphene electrodes have fabulous application value in lead ion detection.
The preparation method and inspection for the polypyrrole cladding cobalt acid nickel nano-wire array Graphene electrodes that the present invention is disclosed and proposed
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
Etc. links realize, although methods and applications of the invention are described by preferred embodiment, related technical personnel are bright
Show off one's talent or competence and do not departing from the content of present invention, method described herein and application be modified or are reconfigured in spirit and scope,
To realize final technology of preparing.In particular, it should be pointed out that 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 that invention, range and content.
Claims (6)
1. a kind of polypyrrole coats NiCo2O4The preparation method of nano-wire array Graphene electrodes, it is characterised in that first with hydro-thermal
Kettle carries out the hydro-thermal reaction of graphene oxide, obtains the 3D Graphene electrodes with three-dimensional structure, then utilizes second of hydro-thermal
Process grows NiCo on 3D Graphene electrodes surface2O4Nano-wire array obtains NiCo using two one-step hydrothermals2O4Nanometer linear array
Column graphene-structured recycles chemical gaseous phase polymerization to coat PPy, obtains final polypyrrole cladding NiCo2O4Nanometer linear array
Column Graphene electrodes.
2. the method as described in claim 1；It is characterized in that using 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 graphene, then carry out frozen dried；
(2)NiCo2O4The preparation of nano-wire array -3D graphene
1~2.5mmol of nickel chloride, 2~5mmol of cobalt nitrate, 6~15mmol of ammonium fluoride, 10~30mmol of urea are configured, is added and steams
It is mixed in distilled water, obtains the pink colour liquid for becoming clear uniform；This pink colour liquid is poured into water heating kettle, 3D graphene is suspended in
In pink colour liquid；Hydro-thermal reaction at a temperature of 60~140 DEG C is taken out reaction kettle after reaction and is cooled to room temperature, takes out 3D stone
Mertenyl bottom is attached to pink mass on graphene-based bottom, with distilled water and ethyl alcohol repeated flushing, drying at room temperature；Then it puts
Enter in tube furnace, calcine in a nitrogen atmosphere, obtains NiCo2O4- 3D graphene；
(3) PPy coats NiCo2O4The preparation of/3D graphene
3~6mmol ammonium persulfate and 0.1~0.3mmol SDS are configured into distilled water, ultrasound makes it sufficiently be dissolved as solution；
By NiCo2O4/ 3D graphene, which is put into solution, is dipped to abundant wetting, and taking-up is placed in culture dish, and 10 are added in culture dish
~30 μ L pyrrole monomers, the two are not directly contacted with, and cover culture dish, and pyrrole monomer volatilization generates pyrroles's steam in culture dish；3~
It is taken out after 10min, with distilled water and ethyl alcohol repeated flushing surface, obtains polypyrrole cladding NiCo2O4Nano-wire array graphene electricity
Pole.
3. method according to claim 2, it is characterized in that the step (1) is put into 5~12h of heating in Muffle furnace.
4. method according to claim 2, it is characterized in that the step (2), which is added in distilled water, is mixed 5~15min.
5. method according to claim 2, it is characterized in that the step (2) is at a temperature of 60~140 DEG C, hydro-thermal reaction 5~
8h。
6. method according to claim 2, it is characterized in that the step (3) calcination temperature in tube furnace is 200~300
DEG C, calcination time is 1~4h.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610959204.7A CN106525933B (en) | 2016-11-03 | 2016-11-03 | Polypyrrole coats the preparation method of cobalt acid nickel nano-wire array Graphene electrodes and detects the application of heavy metal lead ion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201610959204.7A CN106525933B (en) | 2016-11-03 | 2016-11-03 | Polypyrrole coats the preparation method of cobalt acid nickel nano-wire array Graphene electrodes and detects the application of heavy metal lead ion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN106525933A CN106525933A (en) | 2017-03-22 |
| CN106525933B true CN106525933B (en) | 2019-08-13 |
Family
ID=58326061
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201610959204.7A Active CN106525933B (en) | 2016-11-03 | 2016-11-03 | Polypyrrole coats the preparation method of cobalt acid nickel nano-wire array Graphene electrodes and detects the application of heavy metal lead ion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN106525933B (en) |
Families Citing this family (8)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107732206B (en) * | 2017-10-18 | 2020-06-30 | 安徽工业大学 | Preparation method of bimetallic oxide composite negative electrode material with multilevel structure |
| CN111936854A (en) * | 2018-03-29 | 2020-11-13 | 塞洛蒂克斯公司 | Improved electrode for electrochemical devices |
| CN109632908B (en) * | 2019-02-13 | 2020-11-03 | 天津商业大学 | Three-dimensional porous structure C @ NiCo2O4@ PPy composite material and preparation method and application thereof |
| CN109709173B (en) * | 2019-02-13 | 2020-11-27 | 天津商业大学 | Electrochemical sensor for detecting bisphenol A and preparation method and detection method thereof |
| CN111307916A (en) * | 2020-03-02 | 2020-06-19 | 宁波职业技术学院 | Preparation method of bimetallic nickel cobaltate molecular imprinting array sensor and application of bimetallic nickel cobaltate molecular imprinting array sensor in detection of residual sulfonamides |
| CN112786870B (en) * | 2021-02-10 | 2022-05-13 | 广西师范大学 | Polypyrrole coated MoS2/C composite material and preparation method thereof |
| CN114166911B (en) * | 2021-11-17 | 2023-12-12 | 大连民族大学 | Microfluidic-based ocean metal ion detection system and preparation method of coating of electrochemical sensor |
| CN115568850B (en) * | 2022-12-06 | 2023-03-28 | 北京深纳普思人工智能技术有限公司 | Implantable enzyme-free sensor electrode material and enzyme-free sensor |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101706471A (en) * | 2008-12-12 | 2010-05-12 | 烟台海岸带可持续发展研究所 | Electrochemical sensor for determining concentration of heavy metal ions in water sample |
| CN105651836A (en) * | 2016-02-26 | 2016-06-08 | 浙江大学 | Self-driven all-solid-state glucose biosensor and preparation method thereof |
| CN105717174A (en) * | 2016-02-22 | 2016-06-29 | 山东省科学院新材料研究所 | Electrochemical detection method for detecting trace heavy metal ions in water with modified graphene oxide composite modified electrode |
| CN105842318A (en) * | 2016-03-25 | 2016-08-10 | 大连理工大学 | Preparation method and application of graphene/polypyrrole electrochemical sensor for trace-amount lead ion detection |
-
2016
- 2016-11-03 CN CN201610959204.7A patent/CN106525933B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN101706471A (en) * | 2008-12-12 | 2010-05-12 | 烟台海岸带可持续发展研究所 | Electrochemical sensor for determining concentration of heavy metal ions in water sample |
| CN105717174A (en) * | 2016-02-22 | 2016-06-29 | 山东省科学院新材料研究所 | Electrochemical detection method for detecting trace heavy metal ions in water with modified graphene oxide composite modified electrode |
| CN105651836A (en) * | 2016-02-26 | 2016-06-08 | 浙江大学 | Self-driven all-solid-state glucose biosensor and preparation method thereof |
| CN105842318A (en) * | 2016-03-25 | 2016-08-10 | 大连理工大学 | Preparation method and application of graphene/polypyrrole electrochemical sensor for trace-amount lead ion detection |
Non-Patent Citations (2)
| Title |
|---|
| Facile Synthesis of Urchin-like NiCo2O4 Hollow Microspheres with Enhanced Electrochemical Properties in Energy and Environmentally Related Applications;Xin-Yao Yu等;《Applied Materials & Interfaces》;20140217;第3689-3695页 |
| Preparation of spinel nickel-cobalt oxide nanowrinkles/reduced graphene oxide hybrid for nonenzymatic glucose detection at physiological level;Guangran Ma 等;《Electrochimica Acta》;20161024;第545-553页 |
Also Published As
| Publication number | Publication date |
|---|---|
| CN106525933A (en) | 2017-03-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN106525933B (en) | Polypyrrole coats the preparation method of cobalt acid nickel nano-wire array Graphene electrodes and detects the application of heavy metal lead ion | |
| Qiu et al. | An electrochemical ratiometric sensor based on 2D MOF nanosheet/Au/polyxanthurenic acid composite for detection of dopamine | |
| Song et al. | Metal− organic frameworks-derived MnO2/Mn3O4 microcuboids with hierarchically ordered nanosheets and Ti3C2 MXene/Au NPs composites for electrochemical pesticide detection | |
| Li et al. | Facile synthesis of Au-embedded porous carbon from metal-organic frameworks and for sensitive detection of acetaminophen in pharmaceutical products | |
| Liu et al. | Procalcitonin sensitive detection based on graphene–gold nanocomposite film sensor platform and single-walled carbon nanohorns/hollow Pt chains complex as signal tags | |
| Jiang et al. | A non-enzymatic hydrogen peroxide sensor based on a glassy carbon electrode modified with cuprous oxide and nitrogen-doped graphene in a nafion matrix | |
| Qian et al. | Research progress of electrochemical detection of heavy metal ions | |
| Qu et al. | Nanoflower-like CoS-decorated 3D porous carbon skeleton derived from rose for a high performance nonenzymatic glucose sensor | |
| Ni et al. | In-situ growth of Co 3 O 4 nanoparticles on mesoporous carbon nanofibers: a new nanocomposite for nonenzymatic amperometric sensing of H 2 O 2 | |
| CN102910621B (en) | Preparation methods and applications of multilayer graphene and multilayer graphene modified electrode | |
| Cao et al. | Ultrathin nanosheet-assembled accordion-like Ni-MOF for hydrazine hydrate amperometric sensing | |
| CN103811775A (en) | Porous nano composite material for fuel cell oxygen reduction catalyst | |
| CN106908498B (en) | A kind of Co4S3The preparation method and applications of/nitrogen-doped graphene composite material | |
| Pan et al. | Electrochemical sensor using methimazole imprinted polymer sensitized with MWCNTs and Salen-Co (III) as recognition element | |
| CN112285174A (en) | Enzyme-free glucose sensor and preparation method and application thereof | |
| Jia et al. | Electrocatalytically active cuprous oxide nanocubes anchored onto macroporous carbon composite for hydrazine detection | |
| US11733199B2 (en) | Fabrication method of enzyme-free glucose sensor and use of enzyme-free glucose sensor fabricated by the same | |
| Lu et al. | Cobalt-decorated 3D hybrid nanozyme: A catalytic amplification platform with intrinsic oxidase-like activity | |
| CN105606684B (en) | A kind of graphene based on protein-single-walled carbon nanotube-nano-Au composite preparation method and applications | |
| CN112824884A (en) | Photoelectrochemical aptamer sensor and preparation method and application thereof | |
| CN108982626A (en) | It is a kind of for detecting the nano electrochemical enzyme sensor and its preparation method and application of trichloroacetic acid or sodium nitrite | |
| CN105572200B (en) | It is a kind of existing for ascorbic acid under the conditions of the detection modified glassy carbon electrode of dopamine, preparation method and application | |
| Ma et al. | Voltammetric determination of hydrogen peroxide using AuCu nanoparticles attached on polypyrrole-modified 2D metal-organic framework nanosheets | |
| Lin et al. | Fabrication of bimetallic ZIF/carbon nanofibers composite for electrochemical sensing of adrenaline | |
| Wang et al. | High-performance non-enzymatic catalysts based on 3D hierarchical hollow porous Co 3 O 4 nanododecahedras in situ decorated on carbon nanotubes for glucose detection and biofuel cell application |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| C06 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20220412 Address after: 300304 room 1-2050, Block E, No. 6, Huafeng Road, Huaming high tech Industrial Zone, Dongli District, Tianjin Patentee after: Zhongzhi online Co.,Ltd. Address before: 300072 Tianjin City, Nankai District Wei Jin Road No. 92, Tianjin University Patentee before: Tianjin University |
|
| TR01 | Transfer of patent right |
Effective date of registration: 20221019 Address after: Room 107, Building 6, No. 91, Fahuasi Street, Dongcheng District, Beijing 100062 Patentee after: Beijing Legend Yousheng Culture Media Co.,Ltd. Address before: 300304 room 1-2050, Block E, No. 6, Huafeng Road, Huaming high tech Industrial Zone, Dongli District, Tianjin Patentee before: Zhongzhi online Co.,Ltd. |
|
| TR01 | Transfer of patent right | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20170322 Assignee: TIANJIN FEYE UAV TECHNOLOGY CO.,LTD. Assignor: Beijing Legend Yousheng Culture Media Co.,Ltd. Contract record no.: X2023980037927 Denomination of invention: Preparation of Polypyrrole coated nickel cobalt oxide nanowire array Graphene electrode and its application in the detection of heavy metal lead ions Granted publication date: 20190813 License type: Common License Record date: 20230711 |
|
| EE01 | Entry into force of recordation of patent licensing contract | ||
| EE01 | Entry into force of recordation of patent licensing contract |
Application publication date: 20170322 Assignee: TIANJIN BAOGANG RARE EARTH RESEARCH INSTITUTE Co.,Ltd. Assignor: Beijing Legend Yousheng Culture Media Co.,Ltd. Contract record no.: X2023980040543 Denomination of invention: Preparation method and application of polypyrrole coated nickel cobalt oxide nanowire array graphene electrode for detecting heavy metal lead ions Granted publication date: 20190813 License type: Common License Record date: 20230825 |
|
| EE01 | Entry into force of recordation of patent licensing contract |