CN113740396B - Preparation method and application of electrode used in electrochemical sensor - Google Patents
Preparation method and application of electrode used in electrochemical sensor Download PDFInfo
- Publication number
- CN113740396B CN113740396B CN202110933601.8A CN202110933601A CN113740396B CN 113740396 B CN113740396 B CN 113740396B CN 202110933601 A CN202110933601 A CN 202110933601A CN 113740396 B CN113740396 B CN 113740396B
- Authority
- CN
- China
- Prior art keywords
- electrode
- sulfhydrylation
- graphene oxide
- multiwall carbon
- multiwall
- 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
- 238000002360 preparation method Methods 0.000 title abstract description 9
- 239000002048 multi walled nanotube Substances 0.000 claims abstract description 63
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims abstract description 52
- 229910021389 graphene Inorganic materials 0.000 claims abstract description 47
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims abstract description 43
- 239000010931 gold Substances 0.000 claims abstract description 43
- 229910052737 gold Inorganic materials 0.000 claims abstract description 43
- 239000010949 copper Substances 0.000 claims abstract description 42
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052793 cadmium Inorganic materials 0.000 claims abstract description 38
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052802 copper Inorganic materials 0.000 claims abstract description 38
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 claims abstract description 38
- 229910052753 mercury Inorganic materials 0.000 claims abstract description 38
- 239000002105 nanoparticle Substances 0.000 claims abstract description 37
- 229910021397 glassy carbon Inorganic materials 0.000 claims abstract description 32
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 claims abstract description 30
- 229910001385 heavy metal Inorganic materials 0.000 claims abstract description 26
- 230000009467 reduction Effects 0.000 claims abstract description 22
- 229920000557 Nafion® Polymers 0.000 claims abstract description 19
- 238000000034 method Methods 0.000 claims abstract description 17
- 239000000463 material Substances 0.000 claims abstract description 14
- 238000007603 infrared drying Methods 0.000 claims abstract description 5
- 239000000243 solution Substances 0.000 claims description 44
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 40
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 35
- 238000009210 therapy by ultrasound Methods 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 26
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 239000002244 precipitate Substances 0.000 claims description 14
- 239000002253 acid Substances 0.000 claims description 13
- 235000019441 ethanol Nutrition 0.000 claims description 12
- 238000005406 washing Methods 0.000 claims description 12
- 239000000047 product Substances 0.000 claims description 11
- 238000001035 drying Methods 0.000 claims description 10
- 238000002156 mixing Methods 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 9
- 239000006228 supernatant Substances 0.000 claims description 8
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethyl mercaptane Natural products CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 7
- 238000002386 leaching Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 230000007935 neutral effect Effects 0.000 claims description 7
- DGVVWUTYPXICAM-UHFFFAOYSA-N β‐Mercaptoethanol Chemical compound OCCS DGVVWUTYPXICAM-UHFFFAOYSA-N 0.000 claims description 7
- PWDGLIWNOMOQHM-UHFFFAOYSA-N ethanol;hydrazine;hydrate Chemical compound O.NN.CCO PWDGLIWNOMOQHM-UHFFFAOYSA-N 0.000 claims description 6
- 239000011259 mixed solution Substances 0.000 claims description 6
- QAOWNCQODCNURD-UHFFFAOYSA-N sulfuric acid Substances OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 6
- NWZSZGALRFJKBT-KNIFDHDWSA-N (2s)-2,6-diaminohexanoic acid;(2s)-2-hydroxybutanedioic acid Chemical compound OC(=O)[C@@H](O)CC(O)=O.NCCCC[C@H](N)C(O)=O NWZSZGALRFJKBT-KNIFDHDWSA-N 0.000 claims description 4
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 4
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims description 4
- 239000007795 chemical reaction product Substances 0.000 claims description 4
- 238000004140 cleaning Methods 0.000 claims description 4
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 claims description 4
- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 4
- 239000012528 membrane Substances 0.000 claims description 4
- 229910017604 nitric acid Inorganic materials 0.000 claims description 4
- 238000005498 polishing Methods 0.000 claims description 4
- 239000004810 polytetrafluoroethylene Substances 0.000 claims description 4
- 229920001343 polytetrafluoroethylene Polymers 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000002002 slurry Substances 0.000 claims description 4
- 238000001132 ultrasonic dispersion Methods 0.000 claims description 4
- 238000000967 suction filtration Methods 0.000 claims description 2
- 229910052799 carbon Inorganic materials 0.000 claims 5
- 238000001514 detection method Methods 0.000 abstract description 28
- 230000035945 sensitivity Effects 0.000 abstract description 7
- 230000001360 synchronised effect Effects 0.000 abstract description 4
- 230000004907 flux Effects 0.000 abstract description 3
- 239000011248 coating agent Substances 0.000 abstract 2
- 238000000576 coating method Methods 0.000 abstract 2
- 238000009776 industrial production Methods 0.000 abstract 1
- VNWKTOKETHGBQD-UHFFFAOYSA-N methane Chemical compound C VNWKTOKETHGBQD-UHFFFAOYSA-N 0.000 abstract 1
- 239000011701 zinc Substances 0.000 description 14
- 150000002500 ions Chemical class 0.000 description 11
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 10
- 229910052725 zinc Inorganic materials 0.000 description 10
- 239000007974 sodium acetate buffer Substances 0.000 description 6
- BHZOKUMUHVTPBX-UHFFFAOYSA-M sodium acetic acid acetate Chemical compound [Na+].CC(O)=O.CC([O-])=O BHZOKUMUHVTPBX-UHFFFAOYSA-M 0.000 description 6
- 238000001179 sorption measurement Methods 0.000 description 6
- 238000001291 vacuum drying Methods 0.000 description 6
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 229910021607 Silver chloride Inorganic materials 0.000 description 3
- 150000001768 cations Chemical class 0.000 description 3
- 239000003792 electrolyte Substances 0.000 description 3
- 235000013305 food Nutrition 0.000 description 3
- 210000003734 kidney Anatomy 0.000 description 3
- 229910052709 silver Inorganic materials 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 3
- 238000003950 stripping voltammetry Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- 208000004998 Abdominal Pain Diseases 0.000 description 2
- 241001465754 Metazoa Species 0.000 description 2
- 206010028980 Neoplasm Diseases 0.000 description 2
- 238000003968 anodic stripping voltammetry Methods 0.000 description 2
- 210000004556 brain Anatomy 0.000 description 2
- 238000004364 calculation method Methods 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 239000003153 chemical reaction reagent Substances 0.000 description 2
- 230000005518 electrochemistry Effects 0.000 description 2
- 239000007772 electrode material Substances 0.000 description 2
- 238000011068 loading method Methods 0.000 description 2
- 229910021645 metal ion Inorganic materials 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 229910052697 platinum Inorganic materials 0.000 description 2
- 238000001556 precipitation Methods 0.000 description 2
- 230000004044 response Effects 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 231100000331 toxic Toxicity 0.000 description 2
- 230000002588 toxic effect Effects 0.000 description 2
- 238000003828 vacuum filtration Methods 0.000 description 2
- 208000024172 Cardiovascular disease Diseases 0.000 description 1
- 208000002881 Colic Diseases 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 230000005778 DNA damage Effects 0.000 description 1
- 231100000277 DNA damage Toxicity 0.000 description 1
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- 208000002972 Hepatolenticular Degeneration Diseases 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910020820 NaAc-HAc Inorganic materials 0.000 description 1
- 208000001132 Osteoporosis Diseases 0.000 description 1
- 208000002193 Pain Diseases 0.000 description 1
- 208000018839 Wilson disease Diseases 0.000 description 1
- 239000008351 acetate buffer Substances 0.000 description 1
- 208000005298 acute pain Diseases 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 239000000654 additive Substances 0.000 description 1
- 230000000996 additive effect Effects 0.000 description 1
- 238000001479 atomic absorption spectroscopy Methods 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 239000007853 buffer solution Substances 0.000 description 1
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 230000002498 deadly effect Effects 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 238000004993 emission spectroscopy Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 238000002795 fluorescence method Methods 0.000 description 1
- 230000006870 function Effects 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 238000009616 inductively coupled plasma Methods 0.000 description 1
- 238000001095 inductively coupled plasma mass spectrometry Methods 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 208000017169 kidney disease Diseases 0.000 description 1
- RVPVRDXYQKGNMQ-UHFFFAOYSA-N lead(2+) Chemical compound [Pb+2] RVPVRDXYQKGNMQ-UHFFFAOYSA-N 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
- BQPIGGFYSBELGY-UHFFFAOYSA-N mercury(2+) Chemical compound [Hg+2] BQPIGGFYSBELGY-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000035772 mutation Effects 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 239000003642 reactive oxygen metabolite Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 238000011896 sensitive detection Methods 0.000 description 1
- 230000008786 sensory perception of smell Effects 0.000 description 1
- 238000013112 stability test Methods 0.000 description 1
- 208000011580 syndromic disease Diseases 0.000 description 1
- 125000003396 thiol group Chemical group [H]S* 0.000 description 1
- 230000002110 toxicologic effect Effects 0.000 description 1
- 231100000759 toxicological effect Toxicity 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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
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 invention discloses a preparation method of an electrode used in an electrochemical sensor, which comprises the steps of firstly preparing gold nano particles/sulfhydrylation multiwall carbon nano tube/reduction graphene oxide hybrid material, then dripping the gold nano particles/sulfhydrylation multiwall carbon nano tube/reduction graphene oxide hybrid material on the surface of a glassy carbon electrode, and finally coating the gold nano particles/sulfhydrylation multiwall carbon nano tube/reduction graphene oxide hybrid material on the surface of the glassy carbon electrode, wherein the gold nano particles/sulfhydrylation multiwall carbon nano tube/reduction graphene oxide hybrid material is prepared on the surface of the glassy carbon electrode, and then coating the gold nano particles/sulfhydrylation multiwall carbon nano tube/reduction graphene oxide hybrid material on the surface of the glassy carbon electrode on the surface of the electrode 2 Infrared drying is carried out for 1-2 hours at the temperature of 25-45 ℃ to prepare gold nano particles/sulfhydrylation multi-wall carbon nano tubes/reduced graphene oxide/Nafion modified glassy carbon electrodes; the electrode is used as a working electrode in an electrochemical sensor to synchronously detect heavy metal cadmium, lead, mercury, copper and zinc ions, and experimental results show that the method can synchronously detect the cadmium, lead, mercury, copper and zinc ions, improves synchronous detection flux, has high detection sensitivity, low detection limit and wide linear range, and is suitable for industrial production and market popularization and application.
Description
Technical Field
The invention belongs to the technical field of electrochemical sensors, and particularly relates to a preparation method of an electrode used in an electrochemical sensor and application of the electrode in synchronous detection of heavy metal cadmium, lead, mercury, copper and zinc ions.
Background
With the continuous development of modern society, the release of toxic heavy metals is increasing. Excess heavy metals, such as cadmium, lead, mercury, copper and zinc, in the environment and in foods are becoming increasingly a deadly threat. These heavy metals are non-biodegradable and accumulate in the environment and in human and animal foods. Cadmium is a major carcinogen that causes a variety of cancers, cardiovascular diseases and osteoporosis by inhibiting enzymes, producing DNA mismatches, amplifying cell errors and mutations. Lead can lead to death in children, severely damaging the brain and kidneys, and presenting abdominal pain like kidney disease and colic. Highly toxic mercury threatens the brain, kidneys and lungs and causes acute pain, hunter-raschel syndrome and water tumor. Excessive copper can cause chronic poisoning, such as wilson's disease, as well as acute poisoning, and even death by reactive oxygen species production and DNA damage. Although zinc plays a critical role in humans, excess zinc can cause the liver or kidneys to lose function, thereby triggering the loss of sense of smell. Recent studies have shown that the coexistence of various heavy metals, particularly cadmium, lead, mercury, copper, zinc, induces synergistic and additive toxicological effects in humans and animals. With the increasing problems caused by various heavy metals in the environment and food, it is urgent to develop a rapid, sensitive and simple method for simultaneously detecting various heavy metal ions.
At present, the traditional methods for detecting heavy metal cadmium, lead, mercury, copper and zinc ions mainly comprise an atomic fluorescence method, an atomic absorption spectrometry, an inductively coupled plasma light emission spectrometry, an inductively coupled plasma mass spectrometry and the like. Although the above methods have better selectivity and higher sensitivity, the equipment required by the methods is expensive, the equipment is large in size and unfavorable for carrying, the consumed time for preparing samples is long, the equipment is complex in operation, professional detection is required, and the method cannot be applied to real-time online detection of heavy metal ions. The electrochemical stripping voltammetry has high sensitivity, simple operation, low cost, low detection limit and rapid reaction, can overcome the problems encountered by the traditional technology, has higher sensitivity in various electrochemical stripping voltammetry, and is more suitable for heavy metal ion detection.
The electrochemical anodic stripping voltammetry is used for detecting heavy metals, and comprises two processes of adsorption and dissolution of heavy metal ions on a working electrode, and the modified electrode of the nano material plays an important role in improving the performance of an electrochemical sensor for detecting the heavy metal ions. Currently, commonly used modified electrode materials include multiwall carbon nanotubes, metal nano-ions, metal oxides, and the like. However, the existing electrochemistry has low detection sensitivity to various heavy metals, high detection limit and narrow linear range, and prevents the wide application of the electrochemistry.
Disclosure of Invention
Aiming at the problems existing in the prior art, the invention provides a preparation method of an electrode used in an electrochemical sensor.
The preparation method of the electrode used in the electrochemical sensor comprises the following steps:
(1) Dispersing the multiwall carbon nanotubes in a mixed acid solution, carrying out ultrasonic treatment for 2-4 hours, carrying out vacuum suction filtration on an acid leaching product by using a PTFE filter membrane, washing with water to be neutral, and drying to obtain the acidified multiwall carbon nanotubes; dispersing the acidified multiwall carbon nanotubes in deionized water for ultrasonic treatment at 30-60 ℃ for 24 hours, dispersing the filtered product in hydrazine hydrate-ethanol mixed solution, carrying out ultrasonic treatment at 15-30 ℃ for 20 minutes, finally adding mercaptoethanol into the ultrasonic dispersion solution, stirring for 10-15 minutes, refluxing in a sealed container at 60-100 ℃ for 6 hours, centrifugally washing the reaction product with deionized water to be neutral, washing with ethanol, and drying to obtain the mercaptoated multiwall carbon nanotubes;
the mixed acid solution is prepared by mixing concentrated nitric acid (68%) and concentrated sulfuric acid (98%) according to the volume ratio of 1:1-1:3; the hydrazine hydrate-ethanol mixed solution is prepared by mixing hydrazine hydrate and ethanol according to the volume ratio of 1:1-1:2.5;
the mass ratio of the acidified multiwall carbon nanotube to the mercaptoethanol is 1:0.05-1:0.2;
(2) Dispersing the sulfhydrylation multi-wall carbon nano tube, the reduced graphene oxide and the gold nano particles in deionized water respectively, carrying out ultrasonic treatment for 1-1.5 h to prepare a dispersion solution, then mixing the sulfhydrylation multi-wall carbon nano tube dispersion solution, the reduced graphene oxide dispersion solution and the gold nano particle dispersion solution, carrying out ultrasonic treatment for 1-2 h, centrifuging at 4000-6000 rpm, removing supernatant, adding deionized water into the precipitate, mixing uniformly, centrifuging at 10000-12500 rpm, removing supernatant, drying the obtained precipitate, and obtaining the gold nano particle/sulfhydrylation multi-wall carbon nano tube/reduced graphene oxide hybrid material;
the mass ratio of the sulfhydrylation multiwall carbon nanotube to the reduced graphene oxide to the gold nanoparticles is 5:1:0.01-8:1:0.05;
(3) Adding gold nanoparticle/sulfhydrylation multiwall carbon nanotube/reduction graphene oxide hybrid material into absolute ethyl alcohol, performing ultrasonic treatment for 10-20 min, centrifuging at 4000-6000 rpm, drying the obtained precipitate, dispersing the dried precipitate in Nafion solution with the mass concentration of 0.3-5%, and performing ultrasonic treatment to obtain gold nanoparticle/sulfhydrylation multiwall carbon nanotube/reduction graphene oxide/Nafion dispersionA liquid; (4) Sequentially polishing the surface of the glassy carbon electrode by using alumina slurry with the thickness of 1.0 mu m, 0.3 mu m and 0.05 mu m, sequentially ultrasonically cleaning the glassy carbon electrode by using water, ethanol and deionized water, taking the cleaned glassy carbon electrode as a working electrode, and performing an electrochemical workstation at the scanning speed of 100 mV/s and the scanning speed of 0.5-1 mol/L H 2 SO 4 After 50 cycles of scanning the glassy carbon electrode in the solution, gold nano particles/sulfhydrylation multiwall carbon nano tube/reduced graphene oxide/Nafion dispersion liquid is dripped on the surface of the glassy carbon electrode, and then the gold nano particles/sulfhydrylation multiwall carbon nano tube/reduced graphene oxide/Nafion dispersion liquid is dripped on the surface of the glassy carbon electrode in N 2 And (3) carrying out infrared drying for 1-2 hours at the temperature of 25-45 ℃ to obtain the gold nanoparticle/sulfhydrylation multiwall carbon nanotube/reduced graphene oxide/Nafion modified glassy carbon electrode.
The diameter of the sulfhydrylation multi-wall carbon nano tube is 28-32 nm, and the length is less than 10 mu m; the transverse dimension of the reduced graphene oxide is 100-300 nm, and the layer number is less than 3; the particle size of the gold nanoparticles is 2-20 nm.
The electrode prepared by the method is applied to synchronously detecting heavy metal cadmium, lead, mercury, copper and zinc ions, and the electrochemical sensor comprises an electrochemical workstation, an electrolytic cell, a counter electrode, a reference electrode and a working electrode (electrode prepared by the method), wherein the counter electrode is a platinum wire counter electrode, and the reference electrode is a silver/silver chloride reference electrode.
The method for synchronously detecting heavy metal cadmium, lead, mercury, copper and zinc ions with high sensitivity comprises the following steps:
1. one end of a working electrode, one end of a counter electrode and one end of a reference electrode are respectively connected to an electrochemical workstation, the other ends of the working electrode, the counter electrode and the reference electrode are respectively placed in electrolyte in an electrolytic cell, and the electrolyte in the electrolytic cell is acetic acid-sodium acetate buffer solution containing cadmium, lead, mercury, copper and zinc ions with the concentration range of 0-35 mu mol/L; selecting an anode stripping voltammetry on an electrochemical workstation, setting an enrichment potential to be-1.15V to-1.45V, mechanically stirring an electrolytic cell while carrying out i-t enrichment, and enriching cadmium, lead, mercury, copper and zinc ions on a working electrode and reducing the ions into simple substances after the enrichment is finished; immediately stopping stirring the solution in the electrolytic cell after the i-t enrichment time is finished, standing, loading a forward scanning voltage with the voltage range of-1.1V to 0.7V on the working electrode, oxidizing the simple substances of cadmium, lead, mercury, copper and zinc enriched on the working electrode into cadmium, lead, mercury, copper and zinc ions, dissolving the cadmium, lead, mercury, copper and zinc ions back into an electrolytic buffer solution, and recording the change condition of current-voltage by an electrochemical workstation to obtain a current-voltage curve; respectively drawing standard curves corresponding to 5 metal ions by taking the concentrations of cadmium, lead, mercury, copper and zinc ions as abscissa and peak current as ordinate, and linearly regressing to obtain the linear relation between the concentrations of cadmium, lead, mercury, copper and zinc ions and the peak current; wherein the pH value of the acetic acid-sodium acetate buffer solution is 3.6-6.5, and the concentration is 0.1mol/L; the electrolyte can be stirred during enrichment, and the stirring speed is 500rpm/min; the enrichment time was 180s.
2. And (3) placing the sample to be detected into an electrolytic cell containing 0.1mol/L acetate buffer solution (NaAc-HAc), detecting peak currents corresponding to cadmium, lead, mercury, copper and zinc ions in the sample to be detected through an electrochemical workstation according to the method, substituting the peak currents into a regression equation, and calculating to obtain the content of the cadmium, lead, mercury, copper and zinc ions in the sample.
The invention has the advantages and technical effects that:
the working electrode prepared by the method has good conductivity and good performance of adsorbing heavy metal cations, can enhance the adsorption of the heavy metal cations under the measured potential condition by the working electrode, ensures that the heavy metal ions are easy to deposit, ensures that the working electrode does not hydrogen evolution, realizes synchronous detection of cadmium, lead, mercury, copper and zinc ions, improves synchronous detection flux, and has the advantages of more sensitive detection, lower detection limit and wider linear range. Specifically, the sulfhydrylation multiwall carbon nanotube in the modified electrode material sulfhydrylation multiwall carbon nanotube/reduced graphene oxide introduces a C-SH bond due to sulfhydrylation, and the semi-ion C-SH bond has a certain negative charge, so that the surface of the sulfhydrylation multiwall carbon nanotube is negatively charged, thereby enhancing the adsorption capacity to cations; meanwhile, the reduced graphene oxide also has good adsorption performance on heavy metal ions, the synergistic effect of the sulfhydrylated multiwall carbon nanotubes/the reduced graphene oxide enhances the adsorption performance on the heavy metal ions, and meanwhile, the reduced graphene oxide is uniformly dispersed on the sulfhydrylated multiwall carbon nanotubes with good conductivity, so that the specific surface area of the composite material is larger, and meanwhile, the electron transfer rate is better, thereby being beneficial to realizing the simultaneous high-sensitivity adsorption of various heavy metal ions; gold nanoparticles uniformly dispersed on the sulfhydryl multiwall carbon nanotube/reduced graphene oxide have excellent catalytic performance and electrochemical response performance;
compared with other methods, the working electrode improves the detection flux, realizes the simultaneous detection of 5 heavy metal ions, and has the advantages of green and environment-friendly materials, wide detection linear range, high detection sensitivity, low detection limit, good stability and the like; the detection limits of heavy metal cadmium, lead, mercury, copper and zinc ions are respectively 0.014, 0.0084, 0.0039, 0.0053 and 0.012 mu mol/L, and the linear ranges are respectively 0.048-35, 0.028-35, 0.013-35.5, 0.017-35.5 and 0.039-35.5 mu mol/L.
Drawings
FIG. 1 is a graph of electrochemical response of an electrochemical sensor to cadmium, lead, mercury, copper, zinc ions (0-35. Mu.M);
FIG. 2 is a graph of concentration of zinc ions versus peak current criteria;
FIG. 3 is a graph of cadmium ion concentration versus peak current criteria;
FIG. 4 is a graph of lead ion concentration versus peak current criteria;
FIG. 5 is a graph of copper ion concentration versus peak current standard;
fig. 6 is a graph of mercury ion concentration versus peak current standard.
Detailed Description
The present invention will be described in further detail with reference to the drawings and examples, but the scope of the present invention is not limited to the above, and the reagents and methods used in the examples, unless otherwise specified, all employ conventional reagents and methods.
Example 1: this example is for the preparation of electrodes in electrochemical sensors
(1) Dispersing 100mg of multi-wall carbon nano tubes in 50mL of mixed acid solution (sulfuric acid: nitric acid volume ratio is 3:1), performing water bath ultrasonic treatment for 3 hours at the temperature lower than 50 ℃, performing vacuum filtration on acid leaching products by using a PTFE filter membrane (0.1 mu m), washing the acid leaching products to be neutral by using water, and performing vacuum drying at the temperature of 50 ℃ to obtain acidified multi-wall carbon nano tubes; dispersing 40mg of acidified multiwall carbon nanotubes in 150mL of deionized water at 30 ℃ for 24 hours, dispersing the filtered product in 200mL of hydrazine hydrate-ethanol mixed solution (the volume ratio of hydrazine hydrate to ethanol is 1:1), carrying out water bath ultrasonic treatment for 20 minutes at 30 ℃, adding 20mL of mercaptoethanol into the ultrasonic dispersion solution, stirring for 10 minutes, refluxing for 6 hours at 90 ℃ in a sealed container, centrifuging and washing the reaction product to be neutral by using deionized water, washing by using ethanol, and carrying out vacuum drying at 50 ℃ to obtain the mercaptoized multiwall carbon nanotubes;
(2) Dispersing the sulfhydrylation multi-wall carbon nano tube, the reduction graphene oxide and the gold nano particles in deionized water respectively, carrying out ultrasonic treatment for 1.5 hours to prepare a dispersion solution, then mixing the sulfhydrylation multi-wall carbon nano tube dispersion solution, the reduction graphene oxide dispersion solution and the gold nano particle dispersion solution, wherein the mass ratio of the sulfhydrylation multi-wall carbon nano tube to the reduction graphene oxide to the gold nano particles is 5:1:0.01, carrying out ultrasonic treatment for 1 hour, centrifuging at 5000rpm, removing supernatant, adding deionized water into precipitation, carrying out centrifugal treatment at 12500rpm, removing supernatant, and carrying out vacuum drying at 50 ℃ on obtained precipitate to obtain the gold nano particle/sulfhydrylation multi-wall carbon nano tube/reduction graphene oxide hybrid material;
(3) Adding 10mg of gold nanoparticle/sulfhydrylation multiwall carbon nanotube/reduction graphene oxide hybrid material into 20mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 10min, centrifuging at 5000rpm, drying the obtained precipitate, dispersing the dried precipitate in Nafion solution with the mass concentration of 3%, and carrying out ultrasonic treatment to obtain gold nanoparticle/sulfhydrylation multiwall carbon nanotube/reduction graphene oxide/Nafion dispersion;
(4) Sequentially polishing the surface of a glassy carbon electrode by using alumina slurry with the thickness of 1.0 mu m, 0.3 mu m and 0.05 mu m, sequentially ultrasonically cleaning the glassy carbon electrode by using water, ethanol and deionized water, taking the cleaned glassy carbon electrode as a working electrode, and performing an electrochemical workstation at the scanning speed of 100 mV/s and the scanning speed of 0.5mol/L H at the voltage of 0-2.0V 2 SO 4 After 50 cycles of scanning the glassy carbon electrode in the solution, gold nano particles/sulfhydrylation multiwall carbon nano tube/reduction graphene oxide are subjected toNafion dispersion is dripped on the surface of the glassy carbon electrode and is added with N 2 Infrared drying is carried out for 1.5 hours at 30 ℃ to prepare gold nano particles/sulfhydrylation multiwall carbon nano tube/reduced graphene oxide/Nafion modified glassy carbon working electrode;
(5) Detection applications in electrochemical sensors
a. Test instrument and conditions:
the electrochemical sensor comprises an electrochemical workstation, an electrolytic cell, a working electrode, a counter electrode (platinum electrode) and a silver/silver chloride reference electrode, wherein the working electrode is prepared in the step (4);
b. preparation of a Standard Curve
Placing 30mL of acetic acid-sodium acetate buffer solution containing cadmium, lead, mercury, copper and zinc ions with the concentration of 0, 5, 10, 15, 20, 25, 30 and 35 mu mol/L in the electrolytic cell, wherein the pH value of the acetic acid-sodium acetate buffer solution is 5.0, and the concentration is 0.1mol/L;
(1) selecting an anodic stripping voltammetry on an electrochemical workstation (laniaceae, LK 2010), setting the enrichment potential to-1.3V, and the enrichment time to 180s; placing an electric stirrer into an electrolytic cell, setting the stirring speed of the electric stirrer to be 500rpm/min, and performing i-t enrichment on an electrochemical workstation, wherein cadmium, lead, mercury, copper and zinc ions are enriched on a working electrode modified with a modification solution after the enrichment time is over; (2) immediately stopping stirring the solution in the electrolytic cell after the i-t enrichment time is finished, standing for 30 seconds, loading a forward scanning voltage with a voltage range of-1.1V-0.7V on the working electrode, oxidizing the simple substances of cadmium, lead, mercury, copper and zinc enriched on the working electrode into cadmium, lead, mercury, copper and zinc ions, dissolving out the cadmium, lead, mercury, copper and zinc ions, and recording the change condition of current-voltage by an electrochemical workstation to obtain a current-voltage curve (shown in figure 1); (3) drawing standard curves corresponding to 5 metal ions by taking the concentrations of cadmium, lead, mercury, copper and zinc ions as abscissa and peak current values as ordinate, and linearly regressing to obtain the linear relation between the concentrations of cadmium, lead, mercury, copper and zinc ions and peak current (figures 2-6); the linear relation (standard curve) is used for quantitatively detecting the concentration of cadmium, lead, mercury, copper and zinc ions to be detected; this workThe linear relation between the concentration of cadmium, lead, mercury, copper and zinc ions and the peak current corresponding to the electrode is Zn respectively 2+ :y = 5.3593x + 23.667(R² = 0.9985);Cd 2+ :y = 6.0875x + 28.083(R² = 0.9966);Pb 2+ :y = 3.076x + 22.41(R² = 0.9959);Cu 2+ :y = 7.6738x + 6.8333(R² = 0.9981);Hg 2+ :y = 7.9855x + 29.006(R² = 0.9943);
c. Calculation of detection limits
The detection limit passes formula C L = 3S b Calculated in m, wherein C L 、S b And m is the detection limit (μmol/L), the standard deviation of the blank (μA) and the slope of the standard curve (μA/(μmol/L)), respectively; the slope of the standard curve is obtained by the step b and is respectively Zn 2+ :5.3593;Cd 2+ :6.0875;Pb 2+ :3.076;Cu 2+ :7.6738;Hg 2+ :7.9855. the standard deviation of the blank is obtained by scanning 10 blank water samples and taking the standard deviation of the peak current values, and the standard deviation is Zn respectively 2+ :0.0214;Cd 2+ :0.0284;Pb 2+ :0.00861;Cu 2+ :0.0136;Hg 2+ :0.0104. finally, the slope of the standard curve and the standard deviation of the blank are put into a formula C L = 3S b The detection limit of the electrode is obtained by/m is Zn 2+ :0.012;Cd 2+ :0.014;Pb 2+ :0.0084;Cu 2+ :0.0053;Hg 2+ :0.0039;
d. Sample detection to be tested
The test was carried out on acetic acid-sodium acetate buffer solution containing cadmium, lead, mercury, copper and zinc ions at concentrations of 20. Mu. Mol/L, 25. Mu. Mol/L, 15. Mu. Mol/L and 10. Mu. Mol/L, and the peak currents of cadmium, lead, mercury, copper and zinc were 148.8mA, 99.1mA, 226.7mA, 121.1mA and 76.88mA, respectively, as in step b. And substituting the peak current value into the linear equation of the step b, and calculating to obtain the contents of cadmium, lead, mercury, copper and zinc of 19.83 mu mol/L, 24.93 mu mol/L, 24.76 mu mol/L, 14.89 mu mol/L and 9.93 mu mol/L respectively.
(4) Electrode stability test
The same electrode is placed at room temperature for 30 days, and the test current values of the electrode are 95.2%, 96.3%, 98.4%, 95.1% and 95.5% of the initial values of the electrode at 30 days, and the electrode corresponds to cadmium, lead, mercury, copper and zinc ions, so that the sensor has better stability.
Example 2: this example is for the preparation of electrodes in electrochemical sensors
(1) Dispersing 100mg of multi-wall carbon nano tubes in 50mL of mixed acid solution (sulfuric acid: nitric acid volume ratio is 2:1), performing water bath ultrasonic treatment for 3 hours at the temperature lower than 50 ℃, performing vacuum filtration on acid leaching products by using a PTFE filter membrane (0.1 mu m), washing the acid leaching products to be neutral by using water, and performing vacuum drying at the temperature of 50 ℃ to obtain acidified multi-wall carbon nano tubes; dispersing 40mg of acidified multiwall carbon nanotubes in 150mL of deionized water at 40 ℃ for ultrasonic treatment for 24 hours, re-dispersing the filtered product in 200mL of hydrazine hydrate-ethanol mixed solution (the volume ratio of hydrazine hydrate to ethanol is 1:2), performing ultrasonic treatment in a water bath at 20 ℃ for 20 minutes, and finally adding mercaptoethanol into the ultrasonic dispersion solution, wherein the mass ratio of the acidified multiwall carbon nanotubes to mercaptoethanol is 1:0.1; stirring for 15min, refluxing at 80deg.C in a sealed container for 6h, centrifuging and washing the reaction product with deionized water to neutrality, washing with ethanol, and vacuum drying at 50deg.C to obtain sulfhydrylation multiwall carbon nanotube;
(2) Dispersing the sulfhydrylation multi-wall carbon nano tube, the reduction graphene oxide and the gold nano particles in deionized water respectively, carrying out ultrasonic treatment for 1h to prepare a dispersion solution, then mixing the sulfhydrylation multi-wall carbon nano tube dispersion solution, the reduction graphene oxide dispersion solution and the gold nano particle dispersion solution, wherein the mass ratio of the sulfhydrylation multi-wall carbon nano tube to the reduction graphene oxide to the gold nano particles is 6:1:0.03, carrying out ultrasonic treatment for 2h, centrifuging at 4000rpm, removing supernatant, adding deionized water into precipitation, carrying out centrifugal treatment at 10000rpm, removing supernatant, and carrying out vacuum drying at 50 ℃ on obtained precipitate to obtain the gold nano particle/sulfhydrylation multi-wall carbon nano tube/reduction graphene oxide hybrid material;
(3) Adding 10mg of gold nanoparticle/sulfhydrylation multiwall carbon nanotube/reduction graphene oxide hybrid material into 20mL of absolute ethyl alcohol, carrying out ultrasonic treatment for 15min, centrifuging at 6000rpm, drying the obtained precipitate, dispersing the dried precipitate in Nafion solution with the mass concentration of 4%, and carrying out ultrasonic treatment to obtain gold nanoparticle/sulfhydrylation multiwall carbon nanotube/reduction graphene oxide/Nafion dispersion;
(4) Sequentially polishing the surface of a glassy carbon electrode by using alumina slurry with the thickness of 1.0 mu m, 0.3 mu m and 0.05 mu m, sequentially ultrasonically cleaning the glassy carbon electrode by using water, ethanol and deionized water, taking the cleaned glassy carbon electrode as a working electrode, and performing an electrochemical workstation at the scanning speed of 100 mV/s and the scanning speed of 1mol/L H at the voltage of 0-2.0V 2 SO 4 After 50 cycles of scanning the glassy carbon electrode in the solution, gold nano particles/sulfhydrylation multiwall carbon nano tube/reduced graphene oxide/Nafion dispersion liquid is dripped on the surface of the glassy carbon electrode, and then the gold nano particles/sulfhydrylation multiwall carbon nano tube/reduced graphene oxide/Nafion dispersion liquid is dripped on the surface of the glassy carbon electrode in N 2 Infrared drying is carried out for 1.5 hours at 30 ℃ to prepare gold nano particles/sulfhydrylation multiwall carbon nano tube/reduced graphene oxide/Nafion modified glassy carbon working electrode;
(5) Detection applications in electrochemical sensors
a. Test instrument and conditions:
the electrochemical sensor comprises an electrochemical workstation, an electrolytic cell, a working electrode, a counter electrode (platinum electrode) and a silver/silver chloride reference electrode, wherein the working electrode is prepared in the step (4);
b. the standard curve was prepared as in example 1;
c. calculation of detection limit was the same as in example 1;
d. sample detection to be tested
The test is carried out on acetic acid-sodium acetate buffer solution containing 25 mu mol/L cadmium, 10 mu mol/L lead, 15 mu mol/L mercury, 15 mu mol/L copper and 20 mu mol/L zinc ion, and the peak currents of cadmium, lead, mercury, copper and zinc are 181.1mA, 79.5mA, 110.5mA, 90.8mA and 160.2mA respectively, which are measured in the same experimental method as the step b. And substituting the peak current value into a linear equation, and calculating to obtain the contents of cadmium, lead, mercury, copper and zinc respectively at 24.63 mu mol/L, 9.77 mu mol/L, 14.72 mu mol/L, 14.83 mu mol/L and 19.91 mu mol/L.
Claims (2)
1. A method for preparing an electrode for use in an electrochemical sensor, comprising the steps of:
(1) Dispersing the multiwall carbon nanotubes in a mixed acid solution, performing water bath ultrasonic treatment for 2-4 hours, performing vacuum suction filtration on an acid leaching product by using a PTFE filter membrane, washing the acid leaching product with water to be neutral, and drying to obtain the acidified multiwall carbon nanotubes; dispersing the acidified multiwall carbon nanotubes in deionized water for ultrasonic treatment at 30-60 ℃ for 24 hours, dispersing the filtered product in hydrazine hydrate-ethanol mixed solution, carrying out ultrasonic treatment at 15-30 ℃ for 20 minutes, finally adding mercaptoethanol into the ultrasonic dispersion solution, stirring for 10-15 minutes, refluxing in a sealed container at 60-100 ℃ for 6 hours, centrifugally washing the reaction product with deionized water to be neutral, washing with ethanol, and drying to obtain the mercaptoated multiwall carbon nanotubes;
(2) Dispersing the sulfhydrylation multi-wall carbon nano tube, the reduction graphene oxide and the gold nano particles in deionized water respectively, carrying out ultrasonic treatment for 1-1.5 h to prepare a dispersion solution, then mixing the sulfhydrylation multi-wall carbon nano tube dispersion solution, the reduction graphene oxide dispersion solution and the gold nano particle dispersion solution, carrying out ultrasonic treatment for 1-2 h, centrifuging at 4000-6000 rpm, removing supernatant, adding deionized water into the precipitate, mixing uniformly, centrifuging at 10000-12500 rpm, removing supernatant, drying the obtained precipitate, and obtaining the gold nano particle-sulfhydrylation multi-wall carbon nano tube-reduction graphene oxide hybrid material;
(3) Adding gold nanoparticle-sulfhydrylation multiwall carbon nanotube-reduction graphene oxide hybrid material into absolute ethyl alcohol, carrying out ultrasonic treatment for 10-20 min, centrifuging at 4000-6000 rpm, drying the obtained precipitate, dispersing the dried precipitate into Nafion solution with the mass concentration of 0.3-5%, and carrying out ultrasonic treatment to obtain gold nanoparticle-sulfhydrylation multiwall carbon nanotube-reduction graphene oxide-Nafion dispersion;
(4) Sequentially polishing the surface of the glassy carbon electrode by using alumina slurry with the thickness of 1.0 mu m, 0.3 mu m and 0.05 mu m, sequentially ultrasonically cleaning the glassy carbon electrode by using water, ethanol and deionized water, taking the cleaned glassy carbon electrode as a working electrode, and performing an electrochemical workstation at the scanning speed of 100 mV/s and the scanning speed of 0.5-1 mol/L H 2 SO 4 After 50 cycles of scanning the glassy carbon electrode in the solution, gold nano particles-sulfhydrylation multiwall carbon nano tube-reduction graphene oxide-Nafion dispersion liquid is dripped on the surface of the glassy carbon electrode, and then the gold nano particles-sulfhydrylation multiwall carbon nano tube-reduction graphene oxide-Nafion dispersion liquid is dripped on the surface of the glassy carbon electrode in N 2 Infrared drying at 25-45 DEG C1-2 h, preparing gold nano particles-sulfhydrylation multiwall carbon nano tube-reduced graphene oxide-Nafion modified glassy carbon electrode;
the mixed acid solution is prepared by mixing concentrated nitric acid and concentrated sulfuric acid according to the volume ratio of 1:1-1:3; the hydrazine hydrate-ethanol mixed solution is prepared by mixing hydrazine hydrate and ethanol according to the volume ratio of 1:1-1:2.5; the mass ratio of the acidified multiwall carbon nanotube to the mercaptoethanol is 1:0.05-1:0.2; the mass ratio of the sulfhydrylation multiwall carbon nanotube, the reduced graphene oxide and the gold nanoparticles is 5:1:0.01-8:1:0.05.
2. The use of the electrode prepared by the method for preparing the electrode in the electrochemical sensor according to claim 1 for synchronously detecting heavy metal cadmium, lead, mercury, copper and zinc ions, which is characterized in that: the electrode serves as a working electrode in an electrochemical sensor.
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110933601.8A CN113740396B (en) | 2021-08-14 | 2021-08-14 | Preparation method and application of electrode used in electrochemical sensor |
Applications Claiming Priority (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
CN202110933601.8A CN113740396B (en) | 2021-08-14 | 2021-08-14 | Preparation method and application of electrode used in electrochemical sensor |
Publications (2)
Publication Number | Publication Date |
---|---|
CN113740396A CN113740396A (en) | 2021-12-03 |
CN113740396B true CN113740396B (en) | 2024-03-22 |
Family
ID=78731113
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
CN202110933601.8A Active CN113740396B (en) | 2021-08-14 | 2021-08-14 | Preparation method and application of electrode used in electrochemical sensor |
Country Status (1)
Country | Link |
---|---|
CN (1) | CN113740396B (en) |
Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106692971A (en) * | 2017-01-17 | 2017-05-24 | 苏州大学 | Gold nano-grade heat radiotherapy medicine carrier and preparation method and application thereof |
CN106892896A (en) * | 2017-03-21 | 2017-06-27 | 山东大学 | One kind has the multifarious gold nano grain series compound in surface |
CN108219019A (en) * | 2018-02-08 | 2018-06-29 | 华中科技大学 | A kind of sulfhydrylation hydroxyethyl starch and its nano material and preparation method of modification |
CN109884143A (en) * | 2018-12-31 | 2019-06-14 | 中国农业科学院油料作物研究所 | It is a kind of to detect heavy metal cadmium, lead, mercury, copper, the electrochemical sensor of zinc ion and preparation method for highly sensitive synchronization |
CN110441365A (en) * | 2019-09-16 | 2019-11-12 | 石河子大学 | A kind of iron-based spinelle is used for the detection method of heavy metal ion electrochemical sensor |
CN111781268A (en) * | 2020-07-15 | 2020-10-16 | 吉林省海森博科技有限公司 | Voltammetry-based method for detecting heavy metal ions in brackish water |
-
2021
- 2021-08-14 CN CN202110933601.8A patent/CN113740396B/en active Active
Patent Citations (6)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
CN106692971A (en) * | 2017-01-17 | 2017-05-24 | 苏州大学 | Gold nano-grade heat radiotherapy medicine carrier and preparation method and application thereof |
CN106892896A (en) * | 2017-03-21 | 2017-06-27 | 山东大学 | One kind has the multifarious gold nano grain series compound in surface |
CN108219019A (en) * | 2018-02-08 | 2018-06-29 | 华中科技大学 | A kind of sulfhydrylation hydroxyethyl starch and its nano material and preparation method of modification |
CN109884143A (en) * | 2018-12-31 | 2019-06-14 | 中国农业科学院油料作物研究所 | It is a kind of to detect heavy metal cadmium, lead, mercury, copper, the electrochemical sensor of zinc ion and preparation method for highly sensitive synchronization |
CN110441365A (en) * | 2019-09-16 | 2019-11-12 | 石河子大学 | A kind of iron-based spinelle is used for the detection method of heavy metal ion electrochemical sensor |
CN111781268A (en) * | 2020-07-15 | 2020-10-16 | 吉林省海森博科技有限公司 | Voltammetry-based method for detecting heavy metal ions in brackish water |
Also Published As
Publication number | Publication date |
---|---|
CN113740396A (en) | 2021-12-03 |
Similar Documents
Publication | Publication Date | Title |
---|---|---|
CN109164151B (en) | Preparation method of nano material modified glassy carbon electrode | |
CN102435662B (en) | Method for detecting target mercury ions in water body | |
Zhang et al. | An electrochemical sensor based on plasma-treated zinc oxide nanoflowers for the simultaneous detection of dopamine and diclofenac sodium | |
CN109884143B (en) | Electrochemical sensor for high-sensitivity synchronous detection of heavy metal cadmium, lead, mercury, copper and zinc ions and preparation method thereof | |
CN111239214B (en) | Three-electrode type Pb (II) and Cu (II) electrochemical sensor, preparation method and application thereof | |
Ensafi et al. | NiFe 2 O 4 nanoparticles decorated with MWCNTs as a selective and sensitive electrochemical sensor for the determination of epinephrine using differential pulse voltammetry | |
CN110441365B (en) | Detection method of iron-based spinel for heavy metal ion electrochemical sensor | |
Sadeghi et al. | Electrochemical determination of vitamin B6 in water and juice samples using an electrochemical sensor amplified with NiO/CNTs and Ionic liquid | |
CN109187679B (en) | Electrochemical sensor and preparation method and application thereof | |
Ramki et al. | Hierarchical multi-layered molybdenum carbide encapsulated oxidized carbon nanofiber for selective electrochemical detection of antimicrobial agents: inter-connected path in multi-layered structure for efficient electron transfer | |
Tamilalagan et al. | A sonochemical assisted synthesis of hollow sphere structured tin (IV) oxide on graphene oxide sheets for the low-level detection of environmental pollutant mercury in biological samples and foodstuffs | |
WO2021000422A1 (en) | Preparation method and application of two-dimensional metal-organic framework nanosheet | |
CN113504283B (en) | Preparation method and application of composite material modified electrode for detecting gallic acid | |
Moghadam et al. | Electrochemical sensor for the determination of thiourea using a glassy carbon electrode modified with a self-assembled monolayer of an oxadiazole derivative and with silver nanoparticles | |
CN105973956A (en) | Graphene-cuprous oxide composite film modified acetylene black electrode and detection method for detection of vanillin in food | |
Mardani et al. | Design and construction of a carbon paste electrode modified with molecularly imprinted polymer-grafted nanocomposites for the determination of thyroxin in biological samples | |
CN105136883A (en) | Preparation method of silver-loaded graphene sensor used for detecting lead ions in water | |
CN113740396B (en) | Preparation method and application of electrode used in electrochemical sensor | |
Mehri-Talarposhti et al. | Determination of bisphenol in food samples using an electrochemical method based on modification of a carbon paste electrode with CdO nanoparticle/ionic liquid | |
Nguyen et al. | Glucose sensors based on chitosan capped Zns doped Mn nanomaterials | |
CN107328834B (en) | Composite material modified electrode for detecting lead ions in livestock and poultry drinking water and preparation method thereof | |
CN107478695B (en) | Electrode modified based on nano copper sulfide-multiwalled carbon nanotube compound and preparation method and application thereof | |
See et al. | Highly Sensitive Aluminium (III) ion sensor based on a self-assembled monolayer on a gold nanoparticles modified screen-printed carbon electrode | |
CN116482194A (en) | Uric acid detection electrochemical sensor and preparation method and application thereof | |
Ji et al. | Electrocatalysis of puerarin on a nano‐CeO2/MWCNTs composite modified electrode and its determination in pharmaceutical preparations |
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 |