CN114660144B - Palladium nanoparticle-polyacid composite material, electrochemical sensor, and preparation methods and applications thereof - Google Patents
Palladium nanoparticle-polyacid composite material, electrochemical sensor, and preparation methods and applications thereof Download PDFInfo
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- CN114660144B CN114660144B CN202210277700.XA CN202210277700A CN114660144B CN 114660144 B CN114660144 B CN 114660144B CN 202210277700 A CN202210277700 A CN 202210277700A CN 114660144 B CN114660144 B CN 114660144B
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- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 title claims abstract description 64
- 239000002131 composite material Substances 0.000 title claims abstract description 36
- 229910052763 palladium Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- MGSRCZKZVOBKFT-UHFFFAOYSA-N thymol Chemical compound CC(C)C1=CC=C(C)C=C1O MGSRCZKZVOBKFT-UHFFFAOYSA-N 0.000 claims abstract description 94
- 239000005844 Thymol Substances 0.000 claims abstract description 46
- 229960000790 thymol Drugs 0.000 claims abstract description 46
- WJJMNDUMQPNECX-UHFFFAOYSA-N dipicolinic acid Chemical compound OC(=O)C1=CC=CC(C(O)=O)=N1 WJJMNDUMQPNECX-UHFFFAOYSA-N 0.000 claims abstract description 20
- 238000001514 detection method Methods 0.000 claims abstract description 17
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims abstract description 10
- 239000011609 ammonium molybdate Substances 0.000 claims abstract description 10
- 229940010552 ammonium molybdate Drugs 0.000 claims abstract description 10
- 235000018660 ammonium molybdate Nutrition 0.000 claims abstract description 10
- ABKQFSYGIHQQLS-UHFFFAOYSA-J sodium tetrachloropalladate Chemical compound [Na+].[Na+].Cl[Pd+2](Cl)(Cl)Cl ABKQFSYGIHQQLS-UHFFFAOYSA-J 0.000 claims abstract description 10
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 21
- 239000008367 deionised water Substances 0.000 claims description 20
- 229910021641 deionized water Inorganic materials 0.000 claims description 20
- 238000001816 cooling Methods 0.000 claims description 17
- 239000000243 solution Substances 0.000 claims description 16
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 15
- 239000002048 multi walled nanotube Substances 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 11
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 11
- 239000012279 sodium borohydride Substances 0.000 claims description 11
- 239000007772 electrode material Substances 0.000 claims description 10
- 239000007864 aqueous solution Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 9
- 239000000725 suspension Substances 0.000 claims description 9
- 238000001035 drying Methods 0.000 claims description 8
- 229910021397 glassy carbon Inorganic materials 0.000 claims description 8
- 238000002156 mixing Methods 0.000 claims description 8
- 229910052799 carbon Inorganic materials 0.000 claims description 5
- 230000001105 regulatory effect Effects 0.000 claims description 5
- 238000001291 vacuum drying Methods 0.000 claims description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 claims description 3
- 238000002425 crystallisation Methods 0.000 claims 1
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- 239000000463 material Substances 0.000 abstract description 15
- 230000035945 sensitivity Effects 0.000 abstract description 7
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- 230000002441 reversible effect Effects 0.000 abstract description 3
- 238000012360 testing method Methods 0.000 description 22
- 230000000052 comparative effect Effects 0.000 description 14
- 230000003647 oxidation Effects 0.000 description 12
- 238000007254 oxidation reaction Methods 0.000 description 12
- 238000000026 X-ray photoelectron spectrum Methods 0.000 description 7
- 238000002484 cyclic voltammetry Methods 0.000 description 7
- 238000005406 washing Methods 0.000 description 6
- 238000004833 X-ray photoelectron spectroscopy Methods 0.000 description 5
- 238000004458 analytical method Methods 0.000 description 5
- 238000011084 recovery Methods 0.000 description 5
- 238000000034 method Methods 0.000 description 4
- 239000002105 nanoparticle Substances 0.000 description 4
- 229910052757 nitrogen Inorganic materials 0.000 description 4
- -1 polytetrafluoroethylene Polymers 0.000 description 4
- 239000013078 crystal Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 229910052760 oxygen Inorganic materials 0.000 description 3
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 3
- 239000004810 polytetrafluoroethylene Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 229910001220 stainless steel Inorganic materials 0.000 description 3
- 239000010935 stainless steel Substances 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 2
- ISWSIDIOOBJBQZ-UHFFFAOYSA-N Phenol Chemical compound OC1=CC=CC=C1 ISWSIDIOOBJBQZ-UHFFFAOYSA-N 0.000 description 2
- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 2
- 230000000844 anti-bacterial effect Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000001903 differential pulse voltammetry Methods 0.000 description 2
- 238000002848 electrochemical method Methods 0.000 description 2
- 239000000686 essence Substances 0.000 description 2
- 238000004817 gas chromatography Methods 0.000 description 2
- 235000012907 honey Nutrition 0.000 description 2
- 230000036039 immunity Effects 0.000 description 2
- 230000002452 interceptive effect Effects 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 238000005498 polishing Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000002798 spectrophotometry method Methods 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 230000002195 synergetic effect Effects 0.000 description 2
- 229910003208 (NH4)6Mo7O24·4H2O Inorganic materials 0.000 description 1
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 1
- 241000238876 Acari Species 0.000 description 1
- 206010011224 Cough Diseases 0.000 description 1
- 206010062717 Increased upper airway secretion Diseases 0.000 description 1
- 244000246386 Mentha pulegium Species 0.000 description 1
- 235000016257 Mentha pulegium Nutrition 0.000 description 1
- 235000004357 Mentha x piperita Nutrition 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 201000005702 Pertussis Diseases 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 description 1
- 229940124326 anaesthetic agent Drugs 0.000 description 1
- 230000003444 anaesthetic effect Effects 0.000 description 1
- 230000002421 anti-septic effect Effects 0.000 description 1
- 230000033228 biological regulation Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000002041 carbon nanotube Substances 0.000 description 1
- 229910021393 carbon nanotube Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 229940112822 chewing gum Drugs 0.000 description 1
- 235000015218 chewing gum Nutrition 0.000 description 1
- 210000004081 cilia Anatomy 0.000 description 1
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- 239000002537 cosmetic Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000001548 drop coating Methods 0.000 description 1
- 238000003487 electrochemical reaction Methods 0.000 description 1
- 230000005518 electrochemistry Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000796 flavoring agent Substances 0.000 description 1
- 235000019634 flavors Nutrition 0.000 description 1
- 235000013305 food Nutrition 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 238000004128 high performance liquid chromatography Methods 0.000 description 1
- 235000001050 hortel pimenta Nutrition 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 238000010348 incorporation Methods 0.000 description 1
- 238000002329 infrared spectrum Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 238000002372 labelling Methods 0.000 description 1
- 239000003446 ligand Substances 0.000 description 1
- 231100000053 low toxicity Toxicity 0.000 description 1
- 238000005259 measurement Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 210000004400 mucous membrane Anatomy 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 208000026435 phlegm Diseases 0.000 description 1
- 230000010287 polarization Effects 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000027756 respiratory electron transport chain Effects 0.000 description 1
- 230000028327 secretion Effects 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- 239000011780 sodium chloride Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 235000013599 spices Nutrition 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 235000020357 syrup Nutrition 0.000 description 1
- 239000006188 syrup Substances 0.000 description 1
- 239000000606 toothpaste Substances 0.000 description 1
- 229940034610 toothpaste Drugs 0.000 description 1
Classifications
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B22—CASTING; POWDER METALLURGY
- B22F—WORKING METALLIC POWDER; MANUFACTURE OF ARTICLES FROM METALLIC POWDER; MAKING METALLIC POWDER; APPARATUS OR DEVICES SPECIALLY ADAPTED FOR METALLIC POWDER
- B22F9/00—Making metallic powder or suspensions thereof
- B22F9/16—Making metallic powder or suspensions thereof using chemical processes
- B22F9/18—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds
- B22F9/24—Making metallic powder or suspensions thereof using chemical processes with reduction of metal compounds starting from liquid metal compounds, e.g. solutions
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- G—PHYSICS
- G01—MEASURING; TESTING
- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
- G01N27/30—Electrodes, e.g. test electrodes; Half-cells
- G01N27/308—Electrodes, e.g. test electrodes; Half-cells at least partially made of carbon
-
- 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
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- Health & Medical Sciences (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Physics & Mathematics (AREA)
- Electrochemistry (AREA)
- Molecular Biology (AREA)
- Analytical Chemistry (AREA)
- Biochemistry (AREA)
- General Health & Medical Sciences (AREA)
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Abstract
The application relates to the technical field of electrochemical sensors, and particularly discloses a palladium nanoparticle-polyacid composite material, an electrochemical sensor, and a preparation method and application thereof. According to the application, ammonium molybdate and pyridine-2, 6-dicarboxylic acid are coordinated to synthesize polyacid, and then the polyacid is reacted with inorganic sodium tetrachloropalladate to obtain the polyacid-based organic-inorganic hybrid material with rapid and reversible multi-electron redox and higher stability. The nanoparticle-polyacid composite material provided by the application has higher affinity to thymol, the electrochemical sensor prepared by the nanoparticle-polyacid composite material can realize rapid detection of thymol, has high sensitivity, the sensitivity reaches 26.3 mu A.mM ‑1, the linear range is 0.065 mM-0.35 mM and 0.35 mM-0.69 mM, the detection limit is 0.856 mu M, and the operation is simple, thereby being beneficial to large-scale popularization and application.
Description
Technical Field
The invention relates to the technical field of electrochemical sensors, in particular to a palladium nanoparticle-polyacid composite material, an electrochemical sensor, and a preparation method and application thereof.
Background
Polyacids have a strong redox nature, and thus the use of polyacids in various fields, especially in electrochemistry, has attracted considerable attention. However, polyacids are very soluble in electrolytes and have low surface areas, resulting in reduced stability and reproducibility of modified electrodes, and thus, there is a need for the synthesis of an organic-inorganic hybrid material based on polyacids to construct electrode modified materials with high stability and good reproducibility.
Thymol, also known as thymol, is chemically named 2-isopropyl-5-methylphenol. The thymol has stronger bactericidal effect than phenol and low toxicity, has bactericidal effect on mucous membrane of mouth and throat, can promote movement of tracheal cilia, is beneficial to secretion of tracheal mucous, has easy phlegm eliminating effect, and can be used for treating trachitis, pertussis and the like; can also be used as antiseptic in removing mites, preserving books and anaesthetics; in addition, thymol is food flavor allowed to be used in the regulations of food additive use sanitary standards in China, and is mainly used for preparing essences such as cough syrup, peppermint chewing gum, spice and the like, and can be used as a toothpaste, a perfumed soap and certain cosmetic essence formulas.
Currently, the detection methods of thymol mainly comprise gas chromatography, ultraviolet spectrophotometry and high performance liquid chromatography, wherein the gas chromatography cannot be connected with sample measurement, and the test speed is low; the ultraviolet spectrophotometry has low accuracy, high analysis cost and long analysis time. Because thymol has electrochemically active phenolic hydroxyl groups, the content of thymol can be determined by an electrochemical method at present, but the existing electrochemical sensor for detecting thymol still has the defects of poor selectivity and stability, low sensitivity and the like.
Disclosure of Invention
In view of the above, the application provides a method for preparing a palladium nanoparticle-polyacid composite material, an electrochemical sensor, and a preparation method and application thereof, wherein ammonium molybdate and pyridine-2, 6-dicarboxylic acid are coordinated to synthesize polyacid, and then the polyacid is reacted with inorganic sodium tetrachloropalladate to obtain the polyacid-based organic-inorganic hybrid material with rapid and reversible multi-electron redox and higher stability.
In order to achieve the above purpose, the embodiment of the invention adopts the following technical scheme:
The first aspect of the application provides a preparation method of a palladium nanoparticle-polyacid composite material, which comprises the following steps:
Step one, mixing pyridine-2, 6-dicarboxylic acid, ammonium molybdate and deionized water, regulating the pH value to be 2.5-3.5, reacting for 70-74 h at the temperature of 125-135 ℃, cooling and crystallizing after the reaction is finished, and marking as POM-PDC;
Mixing the polyacid, sodium tetrachloropalladate and deionized water, stirring and reacting for 1-1.5 h at 15-25 ℃, then adding sodium borohydride aqueous solution, stirring and reacting for 2-2.5 h, centrifuging, and drying to obtain the palladium nanoparticle-polyacid composite material, and recording as PdNPs@POM-PDC.
Compared with the prior art, the preparation method of the palladium nanoparticle-polyacid composite material provided by the application has the following advantages:
According to the application, ammonium molybdate (NH 4)6Mo7O24·4H2 O and pyridine-2, 6-dicarboxylic acid are coordinated to synthesize polyacid, then the polyacid is reacted with inorganic substance sodium tetrachloropalladate to obtain an organic-inorganic hybrid material based on polyacid, the polyacid provides an active center, an organic part provides a stable structure, the specific surface area of the polyacid is increased, the polyacid is beneficial to fully contacting with reactants when being applied to the field of sensing, the detection sensitivity is improved, the catalytic activity of the nano-particle palladium and the conductivity of the hybrid material are improved by introducing nano-particle palladium, so that the hybrid material has fast and reversible multi-electron redox and higher stability, the negative charge structure of the hybrid material can accelerate electron transfer speed, and in addition, pdNPs@POM-PDC has extremely high stability and wide application prospect.
Optionally, the mass ratio of the pyridine-2, 6-dicarboxylic acid, ammonium molybdate and deionized water is 0.25-0.27: 1.2 to 1.3: 100-110.
Optionally, in the first step, the conditions for cooling and crystallizing are as follows: cooling to 25-35 ℃ at a cooling rate of 2-4 ℃/h.
Optionally, in the first step, naOH solution with the concentration of 0.8mol/L to 1.2mol/L is adopted to adjust the pH.
Optionally, the mass ratio of the polyacid to the sodium tetrachloropalladate to the deionized water is 4.6-5.4: 126-134: 10000.
Optionally, the mass ratio of the sodium borohydride to the polyacid is 9-11:1.
Optionally, the concentration of the sodium borohydride aqueous solution is 48 mg/mL-52 mg/mL.
Optionally, the sodium borohydride aqueous solution is added dropwise, and the dropping speed is 0.01-0.02 mL/s.
Optionally, the stirring speed is 500 rpm-600 rpm.
Optionally, the drying is vacuum drying, and the temperature is 59-61 ℃.
The second aspect of the application also provides a palladium nanoparticle-polyacid composite material, which is prepared by the preparation method of the palladium nanoparticle-polyacid composite material.
The third aspect of the application also provides an electrochemical sensor, which comprises a glassy carbon electrode (GCE electrode) and an electrode material coated on the surface of the glassy carbon electrode, wherein the electrode material is prepared from the palladium nanoparticle-polyacid composite material and a multi-wall carbon nanotube.
The multi-wall carbon nanotubes (MWCNTs) have large specific surface area, provide a large number of surface adsorption sites for the palladium nanoparticle-polyacid composite material, promote the transmission rate of electrons on the surface of an electrode, and remarkably improve the electrocatalytic activity of the electrochemical sensor through the synergistic effect of the two.
Optionally, the preparation method of the electrochemical sensor comprises the following steps:
Step A, the mass ratio is 0.9-1.1: 0.9 to 1.1:0.9 to 1.1 of multiwall carbon nanotube, palladium nanoparticle-polyacid composite material and N, N-dimethylformamide are ultrasonically mixed to obtain suspension;
And B, uniformly dripping the suspension onto the surface of the GCE electrode, and airing to obtain the multi-wall carbon nano tube-palladium nano particle-polyacid composite material/GCE electrode.
The diameter of the GCE electrode adopted by the application is 3mm, the total length of the outer sleeve is 55-60 mm, and the drop coating amount of the suspension is 6-10 mu L.
The fourth aspect of the application also provides application of the palladium nanoparticle-polyacid composite material in the field of thymol detection.
The fifth aspect of the application also provides the use of the above electrochemical sensor in the field of thymol detection.
The nanoparticle-polyacid composite material provided by the application has higher affinity to thymol, the electrochemical sensor prepared by the nanoparticle-polyacid composite material can realize rapid detection of thymol, has high sensitivity, the sensitivity reaches 26.3 mu A.mM -1, the linear range is 0.065 mM-0.35 mM and 0.35 mM-0.69 mM, the detection limit is 0.856 mu M, and the operation is simple, thereby being beneficial to large-scale popularization and application.
Drawings
In order to more clearly illustrate the technical solutions of the embodiments of the present invention, the drawings that are needed in the embodiments will be briefly described below, and it is obvious that the drawings in the following description are only some embodiments of the present invention, and other drawings may be obtained according to these drawings without inventive effort for a person skilled in the art.
FIG. 1 is an infrared spectrum of POM-PDC provided in test example 1 of the present invention;
FIG. 2 is an XPS spectrum of PdNPs@POM-PDC provided in test example 2 of the invention, wherein, the graph A is an XPS full spectrum of the PdNPs@POM-PDC material, the graph B is an XPS spectrum of a C element in the PdNPs@POM-PDC material, the graph C is an XPS spectrum of an N element in the PdNPs@POM-PDC material, the graph D is an XPS spectrum of a Pd element in the PdNPs@POM-PDC material, the graph E is an XPS spectrum of a Mo element in the PdNPs@POM-PDC material, and the graph F is an XPS spectrum of an O element in the PdNPs@POM-PDC material;
FIG. 3 is a cyclic voltammogram provided in test example 3 of the present invention;
FIG. 4 is an AC impedance chart provided in test example 3 of the present invention;
FIG. 5 is a cyclic voltammogram of thymol provided in test example 4 of the present invention;
FIG. 6 is a cyclic voltammogram of different sweep rates provided by test example 5 of the present invention;
FIG. 7 is a graph showing the oxidation peak current versus sweep rate provided in test example 5 of the present invention;
FIG. 8 is a graph of peak current of oxidation as a function of thymol concentration for test example 6 of the present invention;
FIG. 9 is a graph of the oxidation peak current versus thymol concentration provided in test example 6 of the present invention;
FIG. 10 is a diagram showing the interference immunity provided in test example 7 of the present invention.
Detailed Description
The present invention will be described in further detail with reference to the following examples in order to make the objects, technical solutions and advantages of the present invention more apparent. It should be understood that the specific embodiments described herein are for purposes of illustration only and are not intended to limit the scope of the invention.
Example 1
The embodiment of the invention provides a preparation method of a palladium nanoparticle-polyacid composite material, which comprises the following steps:
Step one, uniformly mixing 26.3mg of pyridine-2, 6-dicarboxylic acid, 123mg of ammonium molybdate and 10g of deionized water, regulating the pH to 3 by adopting a NaOH solution with the concentration of 1mol/L, transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 25mL, reacting for 72 hours at the temperature of 130 ℃, cooling to 30 ℃ at the cooling rate of 3 ℃/h after the reaction is finished, cooling and crystallizing to obtain colorless blocky crystals, filtering, washing by deionized water, drying at the temperature of 30 ℃ to obtain polyacid, and marking as POM-PDC;
Step two, dissolving 5mg of the POM-PDC and 130mg of sodium tetrachloropalladate in 10mL of deionized water, stirring and reacting for 1h at 20 ℃, then dropwise adding 1mL of sodium borohydride aqueous solution with the concentration of 50mg/mL for 75s, continuing stirring and reacting for 2h after the dropwise adding is finished, centrifuging, washing with deionized water for 3 times, and vacuum drying at 60 ℃ to obtain the palladium nanoparticle-polyacid composite material, and marking as PdNPs@POM-PDC.
Example 2
The embodiment of the invention provides a preparation method of a palladium nanoparticle-polyacid composite material, which comprises the following steps:
Step one, uniformly mixing 25mg of pyridine-2, 6-dicarboxylic acid, 120mg of ammonium molybdate and 10.5g of deionized water, regulating the pH to 3.5 by adopting a NaOH solution with the concentration of 0.8mol/L, transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 25mL, reacting for 74 hours at the temperature of 125 ℃, cooling to 25 ℃ at the cooling rate of 4 ℃/h after the reaction is finished, cooling and crystallizing to obtain colorless blocky crystals, filtering, washing with deionized water, drying at the temperature of 30 ℃, and obtaining polyacid, which is marked as POM-PDC;
step two, dissolving 4.6mg of the POM-PDC and 126mg of sodium tetrachloropalladate in 10mL of deionized water, stirring and reacting for 1.5h at 15 ℃, then dropwise adding 0.9mL of sodium borohydride aqueous solution with the concentration of 48mg/mL for 90s, continuing stirring and reacting for 2.5h after the dropwise adding is finished, centrifuging, washing with deionized water for 3 times, and vacuum drying at 59 ℃ to obtain the palladium nanoparticle-polyacid composite material, and marking as PdNPs@POM-PDC.
Example 3
The embodiment of the invention provides a preparation method of a palladium nanoparticle-polyacid composite material, which comprises the following steps:
Step one, uniformly mixing 27mg of pyridine-2, 6-dicarboxylic acid, 130mg of ammonium molybdate and 11g of deionized water, regulating the pH to 2.5 by adopting a NaOH solution with the concentration of 1.2mol/L, transferring the obtained solution into a stainless steel reaction kettle with a polytetrafluoroethylene lining of 25mL, reacting for 72 hours at the temperature of 135 ℃, cooling to 30 ℃ at the cooling rate of 2 ℃/h after the reaction is finished, cooling and crystallizing to obtain colorless blocky crystals, filtering, washing by deionized water, drying at the temperature of 30 ℃ to obtain polyacid, and marking as POM-PDC;
And secondly, dissolving 5.4mg of the POM-PDC and 134mg of sodium tetrachloropalladate in 10mL of deionized water, stirring and reacting for 1.2h at 25 ℃, then dropwise adding 1.1mL of sodium borohydride aqueous solution with the concentration of 52mg/mL for 60s, continuing stirring and reacting for 2h after the dropwise adding is finished, centrifuging, washing with deionized water for 3 times, and vacuum drying at 59 ℃ to obtain the palladium nanoparticle-polyacid composite material, and marking as PdNPs@POM-PDC.
Example 4
The embodiment provides an electrochemical sensor for detecting thymol, which comprises a GCE electrode and an electrode material coated on the surface of the GCE electrode, wherein the electrode material is prepared from PdNPs@POM-PDC and MWCNTs prepared in the embodiment 1.
The preparation method of the electrochemical sensor comprises the following steps:
Step A, respectively ultrasonically cleaning a glassy carbon electrode by using water and ethanol, and polishing on flannelette by sequentially using alumina polishing powder with particle diameters of 1.0 mu m, 0.3 mu m and 0.05 mu m; carrying out cyclic voltammetry test on the polished electrode in 0.1mol/L KCl solution containing 5mmol/L K 3[Fe(CN)6 until the potential difference is less than 90mV, and finally drying by adopting nitrogen;
Step B, respectively adding 1mg of MWCNTs and 1mg of PdNPs@POM-PDC into 1mL of N, N-dimethylformamide, and carrying out ultrasonic mixing to obtain a suspension;
step C, uniformly dripping the suspension onto the surface of the GCE electrode, and airing to obtain the PdNPs@POM-PDC-MWCNTs/GCE electrode; wherein the amount of the dripping is 6 mu L.
The diameter of the glassy carbon electrode is 3mm, and the total length of the outer sleeve is 60mm.
In order to better illustrate the technical solutions of the present invention, the following is further compared with examples of the present invention.
Comparative example 1
This comparative example provides an electrochemical sensor for detecting thymol, which is a GCE electrode.
Comparative example 2
This comparative example provides an electrochemical sensor for detecting thymol comprising a GCE electrode, an electrode material coated on the surface of the GCE electrode, wherein the electrode material is pdnps@pom-PDC prepared in example 1.
The step B of the preparation process of the electrochemical sensor is as follows: 1mg of PdNPs@POM-PDC is added into 1mL of N, N-dimethylformamide, and the mixture is ultrasonically mixed to obtain a suspension; the remaining steps are the same as those of embodiment 4, and will not be described again.
Comparative example 3
This comparative example provides an electrochemical sensor for detecting thymol comprising a GCE electrode, an electrode material coated on the surface of the GCE electrode, said electrode material being POM-PDC prepared in example 1.
The step B of the preparation process of the electrochemical sensor is as follows: 1mg of POM-PDC was added to 1mL of N, N-dimethylformamide, and the mixture was ultrasonically mixed to obtain a suspension; the remaining steps are the same as those of embodiment 4, and will not be described again.
In order to better illustrate the characteristics of the electrochemical sensors provided in the examples of the present invention, the electrochemical sensors prepared in example 4 and comparative examples 1 to 3 were subjected to performance test.
Test example 1
The POM-PDC prepared in example 1 was subjected to infrared analysis, and the results are shown in FIG. 1. As can be seen from fig. 1, the strong peaks appearing at 952cm -1、902cm-1、843cm-1、725cm-1 are respectively assigned to the upsilon (mo=o t)、υ(Mo-Ob -Mo) and upsilon (Mo-Oc-Mo) vibrational peaks of the octanuclear molybdenum cluster; the absorption peak at 1600-1100 cm -1 corresponds to the stretching vibration of C= O, C = N, C =C double bond and the stretching vibration of C-O, C-N, C-C single bond in the ligand, so that the product prepared by the application is the polyacid POM-PDC.
The polyacids prepared in examples 2 to 3 were substantially the same as the infrared detection results of example 1, and it was found that the products prepared in examples 2 to 3 were polyacids POM-PDC.
Test example 2
The PdNPs@POM-PDC prepared in example 1 were subjected to X-ray photoelectron spectroscopy XPS analysis, and the results are shown in FIG. 2. As can be seen from fig. 2, graphs a-F show XPS spectra of C, N, O, pd and Mo, demonstrating the presence of these corresponding elements; wherein XPS analysis of C1 s, N1 s and O1 s spectra show single peaks at 284.8eV, 399.0eV and 531.1 eV; two main peaks of Pd 3d (3 d 3/2,3d5/2) appear at 341.1eV and 335.7eV, demonstrating the successful incorporation of PdNPs into the composite; the Mo 3d 3/2 and 3d 5/2 peaks observed at 236.3eV and 233.2eV in fig. E indicate the presence of Mo 6+ ions in the polymolybdate; the above results all indicate that the polyacid POM-PDC is effectively compounded with PdNPs.
XPS test results of the palladium nanoparticle-polyacid composite materials prepared in examples 2 to 3 are basically consistent with those of example 1, thereby demonstrating that POM-PDC is effectively compounded with PdNPs.
Test example 3
The electrochemical sensors prepared in example 4 and comparative examples 1 to 3 were placed in 5mmol/L of a solution of [ Fe (CN) 6]3-, respectively, and their electrochemical properties were studied by cyclic voltammetry, and the results are shown in FIG. 3. As can be seen from fig. 3, all the electrode-modified electrodes exhibited a pair of redox peaks, which were in accordance with the electrochemical reaction process of [ Fe (CN) 6]3-, but their oxidation peak currents were different, the trends were as follows: example 1> comparative example 2> comparative example 3, since the electrical conductivity of the polyacid is poor, the electrical conductivity of the material can be improved after the palladium nanoparticle is added; when MWCNTs are added, the electrical conductivity of the composite is further improved.
Electrochemical sensors prepared in example 4 and comparative examples 1 to 3 were respectively placed in 0.1M KCl solution containing 5mM potassium ferricyanide-potassium ferrocyanide for electrochemical characterization, and as shown in fig. 4, the numerical value of the diameter of the semicircle in each curve in fig. 4 is the polarization resistance of the electrode surface, and the trend of the resistance value is calculated as follows: example 1 < comparative example 2 < comparative example 3. From this, it can be seen that the resistance of the composite material is reduced after the carbon nanotubes are added, which is consistent with the results of fig. 3, indicating that the composite material-modified electrode has excellent electrochemical properties.
Test example 4
Electrochemical sensors prepared in example 4 and comparative examples 1 to 3 were each placed in a 0.1M PBS solution containing 0.4mM thymol, and their electrochemical properties were studied by cyclic voltammetry, and the results are shown in fig. 5. As can be seen from fig. 5, the electrochemical sensor prepared in example 4 has excellent electrochemical properties through the synergistic effect of the palladium nanoparticle, the polyacid and the MWCNTs.
Test example 5 reaction mechanism
The electrochemical sensor prepared in example 4 was placed in 0.1M PBS containing 0.4mM thymol, and cyclic voltammetry was studied at a sweep rate in the range of 10mV/s to 200mV/s, and the results are shown in FIG. 6. It can be seen from FIG. 6 that the oxidation peak current increased with increasing sweep rate. The oxidation peak current is plotted against the square root of the sweep rate, and as shown in FIG. 7, it can be seen that there is a good linear relationship between the oxidation peak current and the square root of the sweep rate. Thus, thymol is demonstrated to be a diffusion controlling process on PdNPs@POM-PDC-MWCNTs/GCE.
Test example 6 quantitative analysis of thymol
The change in peak current of oxidation with concentration was studied using Differential Pulse Voltammetry (DPV). The experimental conditions are as follows: the electrochemical sensor prepared in example 4 was placed in 0.1M PBS containing 0.4mM thymol, at pH 6, and the results are shown in FIGS. 8-9.
As can be seen from FIG. 8, the oxidation peak current increased with the increase in concentration in the range of 0.065mM to 0.69 mM. The linear relationship between the oxidation peak current change and thymol concentration was obtained by DPV, and the result is shown in fig. 9, and as can be seen from fig. 9, there is a two-stage linear relationship in the range of 0.065mM to 0.35mM, and the linear equation is i=54.9c-0.782 (R 2 =0.997); in the range of 0.35mM to 0.69mM, the linear equation is i=26.3c+9.47 (R 2 =0.993). The sensitivity was calculated to be 54.9. Mu.A.mM -1 in the range of 0.065 mM-0.35 mM and 26.3. Mu.A.mM -1 in the range of 0.35 mM-0.69 mM, respectively; the detection limit was 0.856 μm (S/n=3).
Test example 7 interference immunity reproducibility
The electrochemical sensors prepared in example 4 were placed in systems to which different interfering substances were added, respectively, and their interference resistance was studied, and the results are shown in fig. 10. As can be seen from fig. 10, the oxidation peak currents of different interfering substances in the 0.1M PBS solution are substantially uniform, and the oxidation peak currents are increased with the increase of the thymol concentration, so that the electrochemical sensor prepared by the present application has excellent interference resistance. In FIG. 10, 1 is 0.4mM thymol; 2 is 0.4mM thymol and 0.4mM FeCl 3·6H2 O;3 is 0.4mM thymol and 0.4mM H 2O2; 4 is 0.4mM thymol with 0.4mM KNO 3; 5 is 0.4mM thymol with 0.4mM NaCl;6 is 0.4mM thymol and 0.4mM p-nitrophenol; 7 is 0.6mM thymol.
The electrochemical sensor prepared in example 4 was used for the determination of 0.4mM thymol, 5 times with a Relative Standard Deviation (RSD) of 1.42%. Four identical electrochemical sensors were prepared using the procedure of example 4, each for the determination of 0.4mM thymol, with an RSD of 2.71%. Therefore, the electrochemical sensor provided by the application has excellent reproducibility.
Test example 8 actual sample test
The electrochemical sensor prepared in example 4 was used to detect the powder of thymol and honey in the market, and the standard recovery rate of the actual sample was determined by standard recovery experiment. The result is shown in table 1, the recovery rate of the pediatric thymol powder is 93.9% -100.1%, the recovery rate of the honey is 95.8% -97.5%, and the RSD in the actual sample is 1.30% -2.43%, which indicates that the sensor prepared by the application can detect the actual sample.
TABLE 1 actual sample labelling recovery
Electrochemical sensors prepared with the palladium nanoparticle-polyacid composite materials provided in examples 2-3 were used for detection of thymol, and the technical effects were substantially equivalent to those of example 4.
The foregoing description of the preferred embodiments of the invention is not intended to be limiting, but rather is intended to cover all modifications, equivalents, or alternatives falling within the spirit and principles of the invention.
Claims (6)
1. The application of the electrochemical sensor in the field of thymol detection is characterized in that the electrochemical sensor comprises a glassy carbon electrode and an electrode material coated on the surface of the glassy carbon electrode, wherein the electrode material is prepared from a palladium nanoparticle-polyacid composite material and a multi-wall carbon nanotube;
The preparation method of the palladium nanoparticle-polyacid composite material comprises the following steps:
Step one, mixing pyridine-2, 6-dicarboxylic acid, ammonium molybdate and deionized water, regulating the pH value to be 2.5-3.5, reacting for 70-74 h at the temperature of 125-135 ℃, and cooling for crystallization to obtain polyacid after the reaction is finished;
And step two, mixing the polyacid, sodium tetrachloropalladate and deionized water, stirring and reacting for 1 to 1.5 hours at 15 to 25 ℃, then adding sodium borohydride aqueous solution, stirring and reacting for 2 to 2.5 hours, centrifuging, and drying to obtain the palladium nanoparticle-polyacid composite material.
2. Use of the electrochemical sensor according to claim 1 in the field of thymol detection, characterized in that: the mass ratio of the pyridine-2, 6-dicarboxylic acid, ammonium molybdate and deionized water is 0.25-0.27: 1.2 to 1.3: 100-110.
3. Use of the electrochemical sensor according to claim 1 in the field of thymol detection, characterized in that: in the first step, the conditions for cooling and crystallizing are as follows: cooling to 25-35 ℃ at a cooling rate of 2-4 ℃/h; and/or
In the first step, naOH solution with the concentration of 0.8mol/L to 1.2mol/L is adopted to adjust the pH.
4. Use of the electrochemical sensor according to claim 1 in the field of thymol detection, characterized in that: the mass ratio of the polyacid to the sodium tetrachloropalladate to the deionized water is 4.6-5.4: 126-134: 10000; and/or
The mass ratio of the sodium borohydride to the polyacid is 9-11:1.
5. Use of the electrochemical sensor according to claim 1 in the field of thymol detection, characterized in that: the concentration of the sodium borohydride aqueous solution is 48 mg/mL-52 mg/mL; and/or
The sodium borohydride aqueous solution is added dropwise, and the dropping speed is 0.01-0.02 mL/s; and/or
The stirring speed is 500 rpm-600 rpm; and/or
The drying is vacuum drying, and the temperature is 59-61 ℃.
6. Use of the electrochemical sensor according to claim 1 in the field of thymol detection, characterized in that: the preparation method of the electrochemical sensor comprises the following steps:
Step A, the mass ratio is 0.9-1.1: 0.9 to 1.1:0.9 to 1.1 of multiwall carbon nanotube, palladium nanoparticle-polyacid composite material and N, N-dimethylformamide are ultrasonically mixed to obtain suspension;
and B, uniformly dripping the suspension on the surface of the glassy carbon electrode, airing, and obtaining the multi-wall carbon nano tube-palladium nano particle-polyacid composite material/glassy carbon electrode.
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| CN109470749A (en) * | 2018-11-21 | 2019-03-15 | 河北工业职业技术学院 | A kind of hybrid inorganic-organic compound based on polyacid, electrochemical sensor and its preparation method and application |
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