CN108007988A - Nanocomposite and its electrochemical sensor for specific recognition cadmium ion - Google Patents
Nanocomposite and its electrochemical sensor for specific recognition cadmium ion Download PDFInfo
- Publication number
- CN108007988A CN108007988A CN201711263108.XA CN201711263108A CN108007988A CN 108007988 A CN108007988 A CN 108007988A CN 201711263108 A CN201711263108 A CN 201711263108A CN 108007988 A CN108007988 A CN 108007988A
- Authority
- CN
- China
- Prior art keywords
- graphene oxide
- glass
- gold nano
- nano grain
- carbon electrode
- 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.)
- Granted
Links
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 14
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 123
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 95
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 89
- 229910052737 gold Inorganic materials 0.000 claims abstract description 89
- 239000010931 gold Substances 0.000 claims abstract description 89
- YNHJECZULSZAQK-UHFFFAOYSA-N tetraphenylporphyrin Chemical compound C1=CC(C(=C2C=CC(N2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3N2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 YNHJECZULSZAQK-UHFFFAOYSA-N 0.000 claims abstract description 41
- -1 tetraphenylporphyrin compound Chemical class 0.000 claims abstract description 26
- 238000000034 method Methods 0.000 claims abstract description 10
- 239000002105 nanoparticle Substances 0.000 claims abstract description 9
- 229910052799 carbon Inorganic materials 0.000 claims description 60
- 238000012986 modification Methods 0.000 claims description 38
- 230000004048 modification Effects 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 37
- 150000001875 compounds Chemical class 0.000 claims description 35
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 22
- 239000012498 ultrapure water Substances 0.000 claims description 22
- 238000002360 preparation method Methods 0.000 claims description 19
- 238000001035 drying Methods 0.000 claims description 18
- 229910002804 graphite Inorganic materials 0.000 claims description 18
- 239000010439 graphite Substances 0.000 claims description 18
- 239000007788 liquid Substances 0.000 claims description 16
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 15
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 14
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 14
- 238000002604 ultrasonography Methods 0.000 claims description 12
- 229920001661 Chitosan Polymers 0.000 claims description 11
- 239000011521 glass Substances 0.000 claims description 11
- 239000006185 dispersion Substances 0.000 claims description 10
- 239000000843 powder Substances 0.000 claims description 8
- 244000137852 Petrea volubilis Species 0.000 claims description 7
- WCUXLLCKKVVCTQ-UHFFFAOYSA-M Potassium chloride Chemical compound [Cl-].[K+] WCUXLLCKKVVCTQ-UHFFFAOYSA-M 0.000 claims description 7
- 229910052757 nitrogen Inorganic materials 0.000 claims description 7
- 239000002245 particle Substances 0.000 claims description 7
- 150000001336 alkenes Chemical class 0.000 claims description 6
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 6
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 6
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 6
- SJUCACGNNJFHLB-UHFFFAOYSA-N O=C1N[ClH](=O)NC2=C1NC(=O)N2 Chemical compound O=C1N[ClH](=O)NC2=C1NC(=O)N2 SJUCACGNNJFHLB-UHFFFAOYSA-N 0.000 claims description 5
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 claims description 5
- 125000004106 butoxy group Chemical group [*]OC([H])([H])C([H])([H])C(C([H])([H])[H])([H])[H] 0.000 claims description 5
- 230000005611 electricity Effects 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229910052760 oxygen Inorganic materials 0.000 claims description 5
- 239000001301 oxygen Substances 0.000 claims description 5
- 238000003756 stirring Methods 0.000 claims description 5
- 239000006228 supernatant Substances 0.000 claims description 5
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 3
- SMWDFEZZVXVKRB-UHFFFAOYSA-N Quinoline Chemical compound N1=CC=CC2=CC=CC=C21 SMWDFEZZVXVKRB-UHFFFAOYSA-N 0.000 claims description 3
- 238000003780 insertion Methods 0.000 claims description 3
- 230000037431 insertion Effects 0.000 claims description 3
- 238000005070 sampling Methods 0.000 claims description 3
- 239000012467 final product Substances 0.000 claims description 2
- 235000013339 cereals Nutrition 0.000 claims 15
- 241000208340 Araliaceae Species 0.000 claims 1
- 240000007594 Oryza sativa Species 0.000 claims 1
- 235000007164 Oryza sativa Nutrition 0.000 claims 1
- 235000005035 Panax pseudoginseng ssp. pseudoginseng Nutrition 0.000 claims 1
- 235000003140 Panax quinquefolius Nutrition 0.000 claims 1
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims 1
- 229910052782 aluminium Inorganic materials 0.000 claims 1
- 239000004411 aluminium Substances 0.000 claims 1
- 238000005034 decoration Methods 0.000 claims 1
- 235000008434 ginseng Nutrition 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 235000009566 rice Nutrition 0.000 claims 1
- 238000005406 washing Methods 0.000 claims 1
- 229910001385 heavy metal Inorganic materials 0.000 abstract description 12
- 238000001514 detection method Methods 0.000 abstract description 10
- 230000035945 sensitivity Effects 0.000 abstract description 6
- 239000007864 aqueous solution Substances 0.000 abstract description 3
- 230000004044 response Effects 0.000 description 17
- 239000000463 material Substances 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 150000004032 porphyrins Chemical class 0.000 description 6
- 229910052793 cadmium Inorganic materials 0.000 description 5
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 description 5
- 230000000052 comparative effect Effects 0.000 description 4
- 239000002131 composite material Substances 0.000 description 4
- 238000010586 diagram Methods 0.000 description 4
- 230000036541 health Effects 0.000 description 3
- 229910052751 metal Inorganic materials 0.000 description 3
- 239000002184 metal Substances 0.000 description 3
- 229910021645 metal ion Inorganic materials 0.000 description 3
- 238000001237 Raman spectrum Methods 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000011010 flushing procedure Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 210000003734 kidney Anatomy 0.000 description 2
- 238000012544 monitoring process Methods 0.000 description 2
- 238000012545 processing Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000004575 stone Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 1
- 239000000956 alloy Substances 0.000 description 1
- 229910045601 alloy Inorganic materials 0.000 description 1
- 238000004458 analytical method Methods 0.000 description 1
- 238000003321 atomic absorption spectrophotometry Methods 0.000 description 1
- 238000001636 atomic emission spectroscopy Methods 0.000 description 1
- OJIJEKBXJYRIBZ-UHFFFAOYSA-N cadmium nickel Chemical compound [Ni].[Cd] OJIJEKBXJYRIBZ-UHFFFAOYSA-N 0.000 description 1
- 150000001721 carbon Chemical group 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000004737 colorimetric analysis Methods 0.000 description 1
- 238000010668 complexation reaction Methods 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000002384 drinking water standard Substances 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000000840 electrochemical analysis Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 239000003344 environmental pollutant Substances 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 210000004072 lung Anatomy 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 210000000056 organ Anatomy 0.000 description 1
- 230000008520 organization Effects 0.000 description 1
- 239000000575 pesticide Substances 0.000 description 1
- 239000000049 pigment Substances 0.000 description 1
- 238000007747 plating Methods 0.000 description 1
- 238000005498 polishing Methods 0.000 description 1
- 231100000719 pollutant Toxicity 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000008092 positive effect Effects 0.000 description 1
- 210000002307 prostate Anatomy 0.000 description 1
- 238000003900 soil pollution Methods 0.000 description 1
- 238000004611 spectroscopical analysis Methods 0.000 description 1
- PXQLVRUNWNTZOS-UHFFFAOYSA-N sulfanyl Chemical class [SH] PXQLVRUNWNTZOS-UHFFFAOYSA-N 0.000 description 1
- 238000012360 testing method Methods 0.000 description 1
- 238000012546 transfer Methods 0.000 description 1
- 238000003911 water pollution 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
-
- 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
- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
-
- 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
- G01N27/36—Glass electrodes
Landscapes
- Life Sciences & Earth Sciences (AREA)
- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Molecular Biology (AREA)
- Physics & Mathematics (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Electrochemistry (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
- General Physics & Mathematics (AREA)
- Immunology (AREA)
- Pathology (AREA)
- Nanotechnology (AREA)
- Spectroscopy & Molecular Physics (AREA)
- Engineering & Computer Science (AREA)
- Carbon And Carbon Compounds (AREA)
Abstract
The invention discloses the nanocomposite and electrochemical sensor for specific recognition cadmium ion, by graphene oxide, gold nanoparticle, tetraphenylporphyrin is combined to play and acted synergistically, prepare graphene oxide/gold nano grain/tetraphenylporphyrin compound, and it is combined with electrochemical measuring technique, obtain a kind of new high selectivity and high-precision electrochemical sensor is used to measure the heavy metal particularly heavy metal Cd in aqueous solution, detection sensitivity is high, high specificity, and quick and precisely, it is and easy to operate, price is relatively low, avoid using large-scale instrument, and live Emergent detection can be carried out.
Description
Technical field
The invention belongs to electrochemical technology field, and in particular to nanocomposite for specific recognition cadmium ion,
Electrochemical sensor.
Background technology
Heavy metal in the ecosystem because its not biodegradable and indefinitely exist, their existence rings to the mankind
Border and health form great threat, and heavy metal pollution was emphasis pollutant by united nations environment plan column in 1974.Cadmium (Cd)
As one of most heavy heavy metal is endangered in heavy metal pollution, in plating, nickel-cadmium cell, alloy, pigment, fluorescent powder, pesticide etc.
Multiple industry extensive uses, excessive cadmium cause serious water pollution, soil pollution and food pollution.The World Health Organization proposes
Cd (II) ion drinking water standard of 3ng/mL, the intake of excessive cadmium ion can produce the human organs such as liver, lung, kidney and prostate
Raw infringement, and main accumulation, in kidney, the long half time in human body was up to 10~35 years.At present the cadmium developed from
Sub- detection technique, such as fluorescent spectrometry, atomic absorption spectrophotometry, atomic emission spectrometry, colorimetric method, electrochemical analysis
The shortcomings that some are inevitable, such as detection device costliness are faced, operating cost is high, and operating personnel are specialized to require height, divides
Time length is analysed, sensitivity is low, is not easy to rapid field application etc.；But monitoring fast and convenient in terms of cadmium pollution emergency processing
It is very necessary for protection health and environment, therefore, be badly in need of it is a kind of it is quick, simple, can field application high sensitivity point
Analysis method carrys out Monitoring of Cadmium ion concentration.
Different from conventional method, electrochemical detection method has that analyze speed is fast, easy to operate, high sensitivity, cost are low
The advantages that.Gold nanoparticle is because having larger specific surface area, and good biocompatibility and excellent electric conductivity are in electrochemistry
It is used widely in detection, gold nanoparticle can strengthen the electricity between biomolecule and the redox center of electrode surface
Son transfer, is also used as the reaction rate that catalyst improves electrochemistry；Graphene be one kind by carbon atom with sp2 hybridized orbits
The flat film that hexangle type is in honeycomb lattice is formed, there is remarkable calorifics, machinery and chemical property, graphene has pole
Big specific surface area, can be with the abundant combination such as metal, polymer and metallorganic, so as to prepare, electric conductivity is excellent, ties
The nanocomposite that structure is stablized, and production cost is relatively low, is very suitable for exploitation high-performance composite materials；Porphyrin has as a kind of
There is the electron mediator of good electrocatalysis characteristic, because its special chemical structure and performance have specificly-response to metal ion；
Graphene oxide, gold nanoparticle, tetraphenylporphyrin are combined there is presently no relevant report and prepare graphene oxide/gold nano
Particle/tetraphenylporphyrin composite material, is combined with electrochemical measuring technique, develops new high selectivity and high-precision electrification
Sensor is learned to be used to measure the cadmium ion in aqueous solution.
The content of the invention
To overcome the drawbacks described above of the prior art, it is an object of the invention to provide receiving for specific recognition cadmium ion
Nano composite material；The present invention also aims to provide the preparation method of above-mentioned nanocomposite.
The present invention also aims to provide the electrochemical sensor prepared by above-mentioned nanocomposite；The mesh of the present invention
Also reside in the preparation method that above-mentioned electrochemical sensor is provided
On the one hand, present inventor combines graphene oxide, gold nanoparticle, tetraphenylporphyrin, plays collaboration
Effect, prepares graphene oxide/gold nano grain/tetraphenylporphyrin composite material, is combined with electrochemical measuring technique, invents
A kind of new high selectivity and high-precision electrochemical sensor are used to measure the heavy metal cadmium ion in aqueous solution.
On the other hand, by using tetraphenylporphyrin, alternatively property biomolecule combination cadmium ion, graphene oxide promote
Into the complexation reaction of cadmium ion and derivatives of porphyrin, the electric conductivity of electrode surface is improved.Further, gold nanoparticle passes through gold
Tetraphenylporphyrin with sulfydryl is connected further to graphene oxide/gold nano grain composite material surface by mercapto key, is improved
The sensitivity of Electrochemical Detection, realizes highly sensitive, the quick detection to heavy metal cadmium ion.
The above-mentioned purpose of the present invention is achieved through the following technical solutions：
For the nanocomposite of specific recognition cadmium ion, including graphene oxide/gold nano grain/tetraphenyl porphin
Quinoline compound.
The preparation method of the above-mentioned nanocomposite for specific recognition cadmium ion, includes the following steps：
(1) graphene oxide/gold nano grain compound is prepared：A certain amount of graphene oxide is distributed to first ultrapure
In water, the yellowish-brown graphene oxide solution that concentration is 1mg/mL is made in ultrasonic 6h；Then take the above-mentioned graphene oxides of 10ml molten
Liquid is mixed with the chlorauric acid solution that 0.04ml concentration is 0.25M/L in round-bottomed flask, is added dropwise into the mixed solution
The sodium hydroxide solution of 0.5M/L, until pH is 10；Then after continuing ultrasound 0.5h at room temperature, the 1h that flows back at 100 DEG C is obtained
Black dispersion liquid, by above-mentioned black dispersion liquid after 30min is centrifuged under rotating speed is 13000rpm, removes supernatant, obtaining concentration is
The graphene oxide of 1mg/mL/gold nano grain compound；
(2) graphene oxide/gold nano grain/tetraphenylporphyrin compound is prepared：Take graphite oxide in 4ml steps (1)
Alkene/gold nano grain compound and 5- [4- (4- sulfydryls butoxy)-phenyl] -10,15,20- triphens that 25uL concentration is 1mM/L
Base porphyrin mixes, and stirs 24h at room temperature, obtains graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex, and will be upper
State compound centrifugal concentrating to obtain the final product.
The method that electrochemical sensor is prepared by above-mentioned nanocomposite, includes the following steps：
(1) graphene oxide/gold nano grain compound is prepared：A certain amount of graphene oxide is distributed to first ultrapure
In water, the yellowish-brown graphene oxide solution that concentration is 1mg/mL is made in ultrasonic 6h；Then take the above-mentioned graphene oxides of 10ml molten
Liquid is mixed with the chlorauric acid solution that 0.04ml concentration is 0.25M/L in round-bottomed flask, is added dropwise into the mixed solution
The sodium hydroxide solution of 0.5M/L, until pH is 10；Then after continuing ultrasound 0.5h at room temperature, the 1h that flows back at 100 DEG C is obtained
Black dispersion liquid, by above-mentioned black dispersion liquid after 30min is centrifuged under rotating speed is 13000rpm, removes supernatant, obtaining concentration is
The graphene oxide of 1mg/mL/gold nano grain compound；
(2) graphene oxide/gold nano grain/tetraphenylporphyrin compound is prepared：Take graphite oxide in 4ml steps (1)
Alkene/gold nano grain compound and 5- [4- (4- sulfydryls butoxy)-phenyl] -10,15,20- triphens that 25uL concentration is 1mM/L
Base porphyrin mixes, and stirs 24h at room temperature, obtains graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex, and will be upper
State compound centrifugal concentrating；
(3) glass-carbon electrode of modification is prepared：The use of sand paper is respectively 1.0um with particle diameter and the alumina powder of 0.05um is to glass
After carbon electrode is polished, each ultrasound 3min in acetone, ultra-pure water is inserted into respectively, then with ultrapure water, nitrogen drying；Will
Graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex that 5uL steps (2) obtain is added drop-wise to treated
Glassy carbon electrode surface, continues that chitosan solution of the 5uL mass fractions for 0.05wt% is added dropwise after drying, then must aoxidize stone after drying
The glass-carbon electrode of black alkene/gold nano grain/tetraphenylporphyrin nano-complex modification；
(4) electrochemical sensor is prepared：The modified electrode prepared in step (3) is inserted into 40ul cadmium-ion solutions and is soaked
Taken out after bubble 30min, water flushes three times, and carries out DPV scannings in the Klorvess Liquid that insertion concentration is 1M/L, makes after the completion of scanning
Above-mentioned modified electrode is rinsed with ultra-pure water, 30min in saturation EDTA solution is then immersed in, finally uses ultra-pure water
Dried after flushing.
The glass-carbon electrode modified described in step (3) further include graphene oxide modification glass-carbon electrode, graphene oxide/
The glass-carbon electrode of gold nano grain compound modification, the glass-carbon electrode of gold nano grain/tetraphenylporphyrin compound modification and/or
The glass-carbon electrode of graphene oxide/tetraphenylporphyrin compound modification.
The glass-carbon electrode preparation method of the graphene oxide modification includes：The use of sand paper is respectively 1.0um with particle diameter
After polishing with the alumina powder of 0.05um glass-carbon electrode, each ultrasound 3min, Ran Houyong in acetone, ultra-pure water are inserted into respectively
Ultrapure water, nitrogen drying；The yellowish-brown graphene oxide solution that concentration in 5uL steps (1) is 1mg/mL is added drop-wise to
The glassy carbon electrode surface after processing is stated, continues that chitosan solution of the 5uL mass fractions for 0.05wt% is added dropwise after drying, then dry
The glass-carbon electrode of graphene oxide modification is obtained afterwards；
The glass-carbon electrode preparation method of the graphene oxide/gold nano grain compound modification includes：Use sand paper
Respectively with after particle diameter is 1.0um and the alumina powder of 0.05um polishes glass-carbon electrode, it is inserted into respectively in acetone, ultra-pure water
Each ultrasound 3min, then with ultrapure water, nitrogen drying；By concentration in 5uL steps (1) be 1mg/mL graphene oxide/
Gold nano grain compound is added drop-wise to treated glassy carbon electrode surface, continues dropwise addition 5uL mass fractions after drying and is
The chitosan solution of 0.05wt%, then the glass-carbon electrode of graphene oxide/gold nano grain compound modification is obtained after drying；
DPV sweep parameters include described in step (4)：Scanning range is -1.0V -0.15V, and impulse amplitude 50mV, shakes
Width is 4mV, burst length 0.2S, sampling period 2S.
A kind of electrochemical sensor as made from above-mentioned preparation method.
Compared with prior art, positive effect of the invention is：
(1) electrochemical sensor for preparing of the present invention is used to detecting heavy metal particularly heavy metal Cd, detection sensitivity is high,
High specificity, and quick and precisely；(2) electrochemical sensor of the invention is easy to operate, and price is relatively low, avoids using large-scale instrument
Device, and live Emergent detection can be carried out.
Brief description of the drawings
Fig. 1 is the fundamental diagram that electrochemical sensor of the present invention is used to detect heavy metal Cd；
Fig. 2 for graphite oxide in the present invention it is dilute/gold nano grain/tetraphenylporphyrin nano-complex (a), graphite oxide
The Raman spectrogram of dilute/gold nano grain compound (b), graphene oxide (c), wherein, 828,995,1055,1134,1236cm-1
Place's Raman peaks are the characteristic peaks of tetraphenylporphyrin；
Fig. 3 be graphite oxide it is dilute/electron microscope of gold nano grain compound (b)；
Fig. 4 be graphite oxide it is dilute/energy spectrum diagram of gold nano grain compound (b)；
Fig. 5 is DPV response curve of the glass-carbon electrode of different materials modification to 1mM cadmium ions in 1M KCl solution, its
In, graphene oxide/gold nano grain/tetraphenylporphyrin (a), graphene oxide/gold nano grain (b), gold nano grain/tetra-
Phenyl porphyrin (c), chitosan (d), graphene oxide/tetraphenylporphyrin (e)；
Fig. 6 is the glass-carbon electrode of graphene oxide/gold nano grain/tetraphenylporphyrin compound modification to 1mM cadmium ions
The DPV response curves of continuous five times in 1M KCl solution；
Fig. 7 is that the glass-carbon electrode of graphene oxide/gold nano grain/tetraphenylporphyrin compound modification is 1mM to concentration
The DPV response curves of dissimilar metals ion, wherein, (a) Fe3+, (b) Na+, (c) Mg2+, (d) Ca2+, (e) Mn2+, (f) Hg2 +, (g) Ag+, (h) Pb2+, (i) Cd2+；
Fig. 8 is that the glass-carbon electrode of graphene oxide/gold nano grain/tetraphenylporphyrin compound thing modification distinguishes concentration
For 0, the DPV response curves of 0.05,0.25,0.5,1,2.5,5,7.5,10mM cadmium ion；
Fig. 9 is that the glass-carbon electrode of graphene oxide/gold nano grain/tetraphenylporphyrin compound thing modification distinguishes concentration
For 0, the linear relationship chart of 0.05,0.25,0.5,1,2.5,5,7.5,10mM cadmium ion DPV responses.
Embodiment
It is used to illustrate the present invention below in conjunction with the drawings and specific embodiments, but is not limited to the scope of the present invention.
Embodiment
The electrochemical sensor system of the glass-carbon electrode of graphene oxide/gold nano grain/tetraphenylporphyrin compound modification
Preparation Method, includes the following steps：
(1) graphene oxide/gold nano grain compound is prepared：A certain amount of graphene oxide is distributed to first ultrapure
In water, the yellowish-brown graphene oxide solution that concentration is 1mg/mL is made in ultrasonic 6h；Then take the above-mentioned graphene oxides of 10ml molten
Liquid is mixed with the chlorauric acid solution that 0.04ml concentration is 0.25M/L in round-bottomed flask, is added dropwise into the mixed solution
The sodium hydroxide solution of 0.5M/L, until pH is 10；Then after continuing ultrasound 0.5h at room temperature, the 1h that flows back at 100 DEG C is obtained
Black dispersion liquid, by above-mentioned black dispersion liquid after 30min is centrifuged under rotating speed is 13000rpm, removes supernatant, obtaining concentration is
The graphene oxide of 1mg/mL/gold nano grain compound；
(2) graphene oxide/gold nano grain/tetraphenylporphyrin compound is prepared：Take graphite oxide in 4ml steps (1)
Alkene/gold nano grain compound and 5- [4- (4- sulfydryls butoxy)-phenyl] -10,15,20- triphens that 25uL concentration is 1mM/L
Base porphyrin mixes, and stirs 24h at room temperature, obtains graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex, and will be upper
State compound centrifugal concentrating；
(3) glass-carbon electrode of modification is prepared：The use of sand paper is respectively 1.0um with particle diameter and the alumina powder of 0.05um is to glass
After carbon electrode is polished, each ultrasound 3min in acetone, ultra-pure water is inserted into respectively, then with ultrapure water, nitrogen drying；Will
Graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex that 5uL steps (2) obtain is added drop-wise to treated
Glassy carbon electrode surface, continues that chitosan solution of the 5uL mass fractions for 0.05wt% is added dropwise after drying, then must aoxidize stone after drying
The glass-carbon electrode of black alkene/gold nano grain/tetraphenylporphyrin nano-complex modification；
(4) electrochemical sensor is prepared：The modified electrode prepared in step (3) is inserted into 40ul cadmium-ion solutions and is soaked
Taken out after bubble 30min, water flushes three times, and carries out DPV scannings in the Klorvess Liquid that insertion concentration is 1M/L, makes after the completion of scanning
Above-mentioned modified electrode is rinsed with ultra-pure water, 30min in saturation EDTA solution is then immersed in, finally uses ultra-pure water
Dried after flushing；Wherein DPV sweep parameters include：Scanning range is -1.0V -0.15V, impulse amplitude 50mV, and amplitude is
4mV, burst length 0.2S, sampling period 2S.
Comparative example 1
For preparation method with embodiment 1, the glass-carbon electrode that difference is to modify is graphene oxide/gold nano grain
(b) glass-carbon electrode of modification.
Comparative example 2
For preparation method with embodiment 1, the glass-carbon electrode that difference is to modify is gold nano grain/tetraphenylporphyrin
(c) glass-carbon electrode of modification.
Comparative example 3
For preparation method with embodiment 1, the glass-carbon electrode that difference is to modify is electric for the glass carbon that chitosan (d) is modified
Pole.
Comparative example 4
For preparation method with embodiment 1, the glass-carbon electrode that difference is to modify is graphene oxide/tetraphenylporphyrin
(e) glass-carbon electrode of modification.
Referring to attached drawing 1, the fundamental diagram for detecting heavy metal Cd is used for for electrochemical sensor of the present invention.
Referring to attached drawing 2, for graphite oxide in the present invention it is dilute/gold nano grain/tetraphenylporphyrin nano-complex (a), oxygen
Graphite is dilute/gold nano grain compound (b), the Raman spectrogram of graphene oxide (c), wherein, 828,995,1055,1134,
1236cm-1Place's Raman peaks are the characteristic peaks of tetraphenylporphyrin；By being contrasted to its above-mentioned Raman spectrum, in graphite oxide
828,995,1055,1134 can be clearly visible in dilute/gold nano grain/tetraphenylporphyrin nano-complex (a) Raman spectrum,
1236cm-1Locate the Characteristic Raman peak of tetraphenylporphyrin, with graphite oxide it is dilute/gold nano grain compound (b), graphene oxide
(c) Raman spectrogram is contrasted, and further illustrates that tetraphenylporphyrin is successfully combined with graphene oxide/gold nano grain, oxygen
Graphite is dilute/and gold nano grain/tetraphenylporphyrin nano-complex is successfully prepared.
Referring to attached drawing 3, be graphite oxide it is dilute/electron microscope of gold nano grain compound (b)；As we can clearly see from the figure
The gold nano grain of membranaceous surface of graphene oxide, show graphite oxide it is dilute/gold nano grain compound is successfully prepared.
Referring to attached drawing 4, be graphite oxide it is dilute/energy spectrum diagram of gold nano grain compound (b)；As we can clearly see from the figure
Containing carbon, oxygen, gold element in the material, further prove that graphene oxide/gold nano grain compound is successfully prepared.
Referring to attached drawing 5, DPV of the 1mM cadmium ions in 1M KCl solution is responded for the glass-carbon electrode of different materials modification
Curve, wherein, graphene oxide/gold nano grain/tetraphenylporphyrin (a), graphene oxide/gold nano grain (b), gold nano
Particle/tetraphenylporphyrin (c), chitosan (d), graphene oxide/tetraphenylporphyrin (e)；From the figure, it can be seen that oxygen is modified
Response of the glass-carbon electrode of graphite alkene/gold nano grain/tetraphenylporphyrin (a) material to cadmium ion is apparently higher than having modified oxygen
Graphite alkene/gold nano grain (b), gold nano grain/tetraphenylporphyrin (c), chitosan (d) or graphene oxide/tetraphenyl
The glass-carbon electrode of porphyrin (e) material, shows to modify the glass carbon electricity of graphene oxide/gold nano grain/tetraphenylporphyrin (a) material
Pole combines graphene oxide, gold nano grain, the good characteristic of tetraphenylporphyrin, has sensitive response to cadmium ion.
It is the glass-carbon electrode of graphene oxide/gold nano grain/tetraphenylporphyrin compound modification to 1mM referring to attached drawing 6
Cadmium ion DPV response curves of continuous five times in 1M KCl solution；It can be seen that good reproduction is presented in five DPV tests
Property, show that the glass-carbon electrode stability of graphene oxide/gold nano grain/tetraphenylporphyrin compound modification is good, carrying out cadmium
With good reappearance during ion detection.
It is the glass-carbon electrode of graphene oxide/gold nano grain/tetraphenylporphyrin compound modification to dense referring to attached drawing 7
Spend for the DPV response curves of 1mM dissimilar metals ions, wherein, (a) Fe3+, (b) Na+, (c) Mg2+, (d) Ca2+, (e) Mn2 +, (f) Hg2+, (g) Ag+, (h) Pb2+, (i) Cd2+；Cd as we can see from the figure2+(i) DPV response curves differ markedly from it
The response of his metal ion, avoids the presence of other metal ions to Cd2+Detection produce interference, ensure this method prepare glass
Carbon electrode is to Cd2+Sensitive response.
It is the glass-carbon electrode pair that graphene oxide/gold nano grain/tetraphenylporphyrin compound thing is modified referring to attached drawing 8
Concentration is respectively the DPV response curves of 0,0.05,0.25,0.5,1,2.5,5,7.5,10mM cadmium ion；Can from figure
Go out as concentration of cadmium ions increases, the glass-carbon electrode DPV response enhancings of this method modification, illustrate DPV signals and concentration of cadmium ions
Present obvious related.
It is the glass-carbon electrode pair that graphene oxide/gold nano grain/tetraphenylporphyrin compound thing is modified referring to attached drawing 9
Concentration is respectively the linear relationship chart of 0,0.05,0.25,0.5,1,2.5,5,7.5,10mM cadmium ion DPV responses；From figure
It can be seen that DPV response of the glass-carbon electrode of this method modification to the cadmium ion of 0.05-10Mm has well with concentration of cadmium ions
Linear relationship, further demonstrate that this method can be detected the cadmium ion in the range of 0.05-10Mm.
Although above with general explanation and specific embodiment, the present invention is described in detail, at this
On the basis of invention, it can be made some modifications or improvements, this will be apparent to those skilled in the art.Therefore,
These modifications or improvements without departing from theon the basis of the spirit of the present invention, belong to the scope of protection of present invention.
Claims (8)
1. the nanocomposite for specific recognition cadmium ion, it is characterised in that including graphene oxide/gold nano
Grain/tetraphenylporphyrin compound.
2. it is used for the preparation method of the nanocomposite of specific recognition cadmium ion as claimed in claim 1, it is characterised in that
Include the following steps：
(1) a certain amount of graphene oxide is distributed in ultra-pure water first, the yellowish-brown that concentration is 1mg/mL is made in ultrasonic 6h
Graphene oxide solution；Then chlorauric acid solution of the above-mentioned graphene oxide solutions of 10ml with 0.04ml concentration for 0.25M/L is taken
Mixed in round-bottomed flask, the sodium hydroxide solution of 0.5M/L is added dropwise into the mixed solution, until pH is 10；Then exist
After continuing ultrasound 0.5h at room temperature, the 1h that flows back at 100 DEG C obtains black dispersion liquid, is in rotating speed by above-mentioned black dispersion liquid
After centrifuging 30min under 13000rpm, supernatant is removed, obtains graphene oxide/gold nano grain compound that concentration is 1mg/mL；
(2) graphene oxide/gold nano grain compound and 5- [4- (the 4- mercaptos that 25uL concentration is 1mM/L in 4ml steps (1) are taken
Base butoxy)-phenyl] -10, the mixing of 15,20- Triphenylporphyrins, stirs 24h, obtains graphene oxide/gold nano at room temperature
Grain/tetraphenylporphyrin nano-complex, and to obtain the final product by above-mentioned compound centrifugal concentrating.
3. the nanocomposite for specific recognition cadmium ion prepares the side of electrochemical sensor as claimed in claim 1
Method, it is characterised in that include the following steps：
(1) graphene oxide/gold nano grain compound is prepared：A certain amount of graphene oxide is distributed to ultra-pure water first
In, the yellowish-brown graphene oxide solution that concentration is 1mg/mL is made in ultrasonic 6h；Then the above-mentioned graphene oxide solutions of 10ml are taken
Mixed with the chlorauric acid solution that 0.04ml concentration is 0.25M/L in round-bottomed flask, 0.5M/ is added dropwise into the mixed solution
The sodium hydroxide solution of L, until pH is 10；Then after continuing ultrasound 0.5h at room temperature, the 1h that flows back at 100 DEG C obtains black point
Dispersion liquid, by above-mentioned black dispersion liquid after 30min is centrifuged under rotating speed is 13000rpm, removes supernatant, it is 1mg/mL to obtain concentration
Graphene oxide/gold nano grain compound；
(2) graphene oxide/gold nano grain/tetraphenylporphyrin compound is prepared：Take graphene oxide/gold in 4ml steps (1)
Nano-particle complex and 5- [4- (4- sulfydryls butoxy)-phenyl] -10,15,20- triphenyl porphins that 25uL concentration is 1mM/L
Quinoline mixes, and stirs 24h at room temperature, obtains graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex, and will be above-mentioned multiple
Compound centrifugal concentrating；
(3) glass-carbon electrode of modification is prepared：Using sand paper be respectively 1.0um with particle diameter and the alumina powder of 0.05um is to glass carbon electricity
After pole is polished, each ultrasound 3min in acetone, ultra-pure water is inserted into respectively, then with ultrapure water, nitrogen drying；By 5uL
Graphene oxide/gold nano grain/tetraphenylporphyrin nano-complex that step (2) obtains is added drop-wise to treated glass carbon
Electrode surface, continues that chitosan solution of the 5uL mass fractions for 0.05wt% is added dropwise after drying, then obtains graphite oxide after drying
The glass-carbon electrode of alkene/gold nano grain/tetraphenylporphyrin nano-complex modification；
(4) electrochemical sensor is prepared：The modified electrode prepared in step (3) is inserted into 40ul cadmium-ion solutions and is soaked
Taken out after 30min, water flushes three times, and carries out DPV scannings in the Klorvess Liquid that insertion concentration is 1M/L, is used after the completion of scanning
Ultra-pure water is rinsed above-mentioned modified electrode, is then immersed in 30min in saturation EDTA solution, is finally rushed with ultra-pure water
Dried after washing.
4. the preparation method of electrochemical sensor as claimed in claim 3, it is characterised in that the glass modified described in step (3)
Carbon electrode further includes the glass carbon electricity of the glass-carbon electrode of graphene oxide modification, graphene oxide/gold nano grain compound modification
Pole, the glass-carbon electrode and/or graphene oxide/tetraphenylporphyrin compound of gold nano grain/tetraphenylporphyrin compound modification
The glass-carbon electrode of modification.
5. the preparation method of electrochemical sensor as described in claim 3 or 4, it is characterised in that the graphene oxide is repaiied
The glass-carbon electrode preparation method of decorations includes：Using sand paper be respectively 1.0um with particle diameter and the alumina powder of 0.05um is to glass carbon electricity
After pole is polished, each ultrasound 3min in acetone, ultra-pure water is inserted into respectively, then with ultrapure water, nitrogen drying；By 5uL
Concentration is that the yellowish-brown graphene oxide solution of 1mg/mL is added drop-wise to treated glassy carbon electrode surface in step (1), is dried in the air
Continue that chitosan solution of the 5uL mass fractions for 0.05wt% is added dropwise after dry, then the glass carbon of graphene oxide modification is obtained after drying
Electrode.
6. the preparation method of electrochemical sensor as claimed in claim 4, it is characterised in that the graphene oxide/Jenner
The glass-carbon electrode preparation method of rice grain compound modification includes：The use of sand paper is respectively 1.0um with particle diameter and the oxygen of 0.05um
Change after aluminium powder polishes glass-carbon electrode, be inserted into each ultrasound 3min in acetone, ultra-pure water respectively, then with ultrapure water,
Nitrogen is dried；Graphene oxide/gold nano grain compound that concentration in 5uL steps (1) is 1mg/mL is added drop-wise to above-mentioned place
Glassy carbon electrode surface after reason, continues that chitosan solution of the 5uL mass fractions for 0.05wt% is added dropwise after drying, then is obtained after drying
The glass-carbon electrode of graphene oxide/gold nano grain compound modification.
7. the preparation method of electrochemical sensor as claimed in claim 4, it is characterised in that the scanning ginsengs of DPV described in step (4)
Number includes：Scanning range is -1.0V -0.15V, impulse amplitude 50mV, amplitude 4mV, burst length 0.2S, the sampling period
For 2S.
8. one kind electrochemical sensor made from preparation method as described in claim any one of 3-7.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711263108.XA CN108007988B (en) | 2017-12-04 | 2017-12-04 | Nanocomposite and its electrochemical sensor for specific recognition cadmium ion |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201711263108.XA CN108007988B (en) | 2017-12-04 | 2017-12-04 | Nanocomposite and its electrochemical sensor for specific recognition cadmium ion |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108007988A true CN108007988A (en) | 2018-05-08 |
| CN108007988B CN108007988B (en) | 2019-08-02 |
Family
ID=62056369
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201711263108.XA Expired - Fee Related CN108007988B (en) | 2017-12-04 | 2017-12-04 | Nanocomposite and its electrochemical sensor for specific recognition cadmium ion |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108007988B (en) |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108918629A (en) * | 2018-09-21 | 2018-11-30 | 浙江理工大学 | A kind of copper graphene quantum dot loads the preparation method of ultra-thin porphyrin nano sheet modified electrode altogether |
| CN110895278A (en) * | 2019-11-28 | 2020-03-20 | 北京乐普医疗科技有限责任公司 | Preparation method and application of electrochemical immunosensor based on graphene oxide-chitosan/nanogold |
Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104345043A (en) * | 2014-07-16 | 2015-02-11 | 天津工业大学 | Porphyrin optical sensing functional film suitable for detecting heavy metal ions and preparation method of porphyrin optical sensing functional film |
| CN106198664A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院烟台海岸带研究所 | A kind of solid polymer membrane ion-selective electrode based on alkane functionalized nano material |
| CN106996945A (en) * | 2016-01-23 | 2017-08-01 | 江南石墨烯研究院 | A kind of noble metal decorated method of lead ion sensor |
| CN107064034A (en) * | 2017-05-19 | 2017-08-18 | 深圳市绿恩环保技术有限公司 | The detection method of cadmium in a kind of water |
| CN107219280A (en) * | 2017-07-21 | 2017-09-29 | 济南大学 | A kind of Metalloporphyrins gas sensor element and its preparation method and application |
-
2017
- 2017-12-04 CN CN201711263108.XA patent/CN108007988B/en not_active Expired - Fee Related
Patent Citations (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104345043A (en) * | 2014-07-16 | 2015-02-11 | 天津工业大学 | Porphyrin optical sensing functional film suitable for detecting heavy metal ions and preparation method of porphyrin optical sensing functional film |
| CN106198664A (en) * | 2015-05-06 | 2016-12-07 | 中国科学院烟台海岸带研究所 | A kind of solid polymer membrane ion-selective electrode based on alkane functionalized nano material |
| CN106996945A (en) * | 2016-01-23 | 2017-08-01 | 江南石墨烯研究院 | A kind of noble metal decorated method of lead ion sensor |
| CN107064034A (en) * | 2017-05-19 | 2017-08-18 | 深圳市绿恩环保技术有限公司 | The detection method of cadmium in a kind of water |
| CN107219280A (en) * | 2017-07-21 | 2017-09-29 | 济南大学 | A kind of Metalloporphyrins gas sensor element and its preparation method and application |
Non-Patent Citations (1)
| Title |
|---|
| CHUNLI YANG等: "Conjugates of graphene oxide covalently linked ligands and gold nanoparticles to construct silver ion graphene paste electrode", 《TALANTA》 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108918629A (en) * | 2018-09-21 | 2018-11-30 | 浙江理工大学 | A kind of copper graphene quantum dot loads the preparation method of ultra-thin porphyrin nano sheet modified electrode altogether |
| CN110895278A (en) * | 2019-11-28 | 2020-03-20 | 北京乐普医疗科技有限责任公司 | Preparation method and application of electrochemical immunosensor based on graphene oxide-chitosan/nanogold |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108007988B (en) | 2019-08-02 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Agnihotri et al. | Transition metal oxides in electrochemical and bio sensing: A state-of-art review | |
| Tian et al. | MnO2 nanowires-decorated reduced graphene oxide modified glassy carbon electrode for sensitive determination of bisphenol A | |
| Ramachandran et al. | A review of the advanced developments of electrochemical sensors for the detection of toxic and bioactive molecules | |
| Song et al. | Facile preparation of urchin-like NiCo2O4 microspheres as oxidase mimetic for colormetric assay of hydroquinone | |
| Huang et al. | Electrostatically assembling 2D hierarchical Nb2CTx and zifs-derivatives into Zn-Co-NC nanocage for the electrochemical detection of 4-nitrophenol | |
| CN103235019B (en) | Cyclodextrin/grapheme nanometer compound modified electrode, preparation method and usage | |
| Jiang et al. | Recent advances in sensors for electrochemical analysis of nitrate in food and environmental matrices | |
| Zhao et al. | Electroactive Cu2O nanoparticles and Ag nanoparticles driven ratiometric electrochemical aptasensor for prostate specific antigen detection | |
| Guo et al. | Carbon nanotube/silica coaxial nanocable as a three-dimensional support for loading diverse ultra-high-density metal nanostructures: facile preparation and use as enhanced materials for electrochemical devices and SERS | |
| Niu et al. | Electrochemical stripping analysis of trace heavy metals using screen-printed electrodes | |
| Guo et al. | Recent developments in electrochemical determination of arsenic | |
| CN105572196B (en) | Nickel cobalt (alloy)/polypyrrole/reduced graphene nanocomposite and its application | |
| Yi et al. | Recent developments in electrochemical detection of cadmium | |
| CN107389767A (en) | The preparation method without enzyme electrochemical glucose sensor based on Nano Silver copper oxide particle/graphene | |
| CN105277528A (en) | Construction of algal toxin Raman sensor adopting gold nanoflower-silver nanoparticle bimetallic nano assembly | |
| Khalifa et al. | Mucilage-capped silver nanoparticles for glucose electrochemical sensing and fuel cell applications | |
| Duan et al. | Non-enzymatic sensors based on a glassy carbon electrode modified with Au nanoparticles/polyaniline/SnO 2 fibrous nanocomposites for nitrite sensing | |
| CN105203612A (en) | Biosensor based on metal organic skeleton material and application thereof | |
| CN105628764A (en) | Uric acid detection electrochemical sensor and preparation and application thereof | |
| Benjamin et al. | Graphene-Based electrochemical sensors for detection of environmental pollutants | |
| CN108007988A (en) | Nanocomposite and its electrochemical sensor for specific recognition cadmium ion | |
| Chen et al. | Advanced metal–organic frameworks-based catalysts in electrochemical sensors | |
| Zhang et al. | Progress and opportunities for metal–organic framework composites in electrochemical sensors | |
| CN108802122A (en) | A kind of preparation method of chitosan-graphene/gold nanoparticle@carbon nanotube ionic trace sensors | |
| Cao et al. | An electrochemical sensor based on a glassy carbon electrode modified with optimized Cu–Fe3O4 nanocomposite for 4-nitrophenol detection |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | 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 | ||
| CF01 | Termination of patent right due to non-payment of annual fee |
Granted publication date: 20190802 |