CN108519418A - Nanogold-silver-three-dimensional graphene composite material modified electrode and its application in baicalein detection - Google Patents
Nanogold-silver-three-dimensional graphene composite material modified electrode and its application in baicalein detection Download PDFInfo
- Publication number
- CN108519418A CN108519418A CN201810261885.9A CN201810261885A CN108519418A CN 108519418 A CN108519418 A CN 108519418A CN 201810261885 A CN201810261885 A CN 201810261885A CN 108519418 A CN108519418 A CN 108519418A
- Authority
- CN
- China
- Prior art keywords
- silver
- 3dga
- electrode
- composite material
- cile
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
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
- G01N27/333—Ion-selective electrodes or membranes
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)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
- Investigating Or Analyzing Materials By The Use Of Electric Means (AREA)
Abstract
A kind of application the present invention relates to nanometer gold silver three-dimensional graphene composite material modified electrode and its in baicalein detection.The preparation method of the nanometer gold silver three-dimensional graphene composite material (Au Ag 3DGA) includes the following steps：Take suitable gold chloride (HAuCl4), silver nitrate (AgNO3) and after graphene oxide (GO) is added to the water and stirs evenly, suitable triethylene tetramine is added under stiring, it is heated to 170 190 DEG C, after reacting 10 12h, cooled to room temperature, washing are freeze-dried after 10 12h up to the nanometer gold silver three-dimensional graphene composite material (Au Ag 3DGA).
Description
Technical field
The invention belongs to nano material and electrochemical analysis fields, and in particular to a kind of nanogold-silver-three-dimensional grapheme is multiple
Condensation material modified electrode and its application in baicalein detection.
Background technology
Baicalein is a kind of flavone compound of polyphenol hydroxyl, is mainly derived from root and the Bignoniaceae plant of high radix scutellariae
The seed and stem skin of Oroxylum indicum, the leaf of plantago plant greater plantain and the simultaneously Ye Hegen of head grass.Baicalein is swap buffers mouth
One of the active ingredient of liquid is taken, so the assay tool to baicalein has very important significance.Containing about baicalein at present
Quantity measuring method mainly has high performance liquid chromatography (HPLC) and high performance capillary electrophoresis (HPCE) and three kinds of electrochemical means,
Although this two classes detection method results contrast of HPLC and HPCE is accurate, there are troublesome in poeration time-consuming and instruments and consumptive material costliness etc.
Disadvantage.And electrochemical analysis method have many advantages, such as it is easy to operate it is easy, quickly, sensitivity is higher, takes and few has been used for medicine
The analysis of object molecule detects.The present invention provides a kind of nanogold-silver-three-dimensional graphene composite material modified electrode, to radix scutellariae
Plain detection sensitivity is high, and detection limit reaches 0.345nmol/L (3 σ), and stability and favorable reproducibility.
Invention content
The present invention provides a kind of nanogold-silver-three-dimensional graphene composite material modified electrode, it is characterised in that the electrode packet
Basal electrode, nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) coating are included, the basal electrode is ionic liquid
Body decorating carbon paste electrode (CILE).
The present invention provides one kind and being followed successively by CILE basal electrodes, nanogold-silver-three-dimensional graphene composite material from inside to outside
(Au-Ag-3DGA) electrode of coating, i.e. Au-Ag-3DGA/CILE electrodes.
The preparation method of the nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) includes the following steps：It takes
Suitable gold chloride (HAuCl4), silver nitrate (AgNO3) and after graphene oxide (GO) is added to the water and stirs evenly, under stiring
Suitable triethylene tetramine is added, is heated to 170-190 DEG C, after reacting 10-12h, cooled to room temperature, washing, freezing are dry
Up to the nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) after dry 10-12h.Every gram of graphene oxide (GO)
Use 3-4mmol gold chlorides (HAuCl4), gold chloride (HAuCl4) and silver nitrate (AgNO3) molar ratio be 1：1, every milligram of oxygen
Graphite alkene (GO) uses 0.8-1.0mL water, it is preferable to use 0.9mL water, every gram of graphene oxide (GO) use tri- second of 40-60mL
Alkene tetramine is, it is preferable to use 50mL triethylene tetramines.Above-mentioned reaction carries out preferably in autoclave, is preferably heated to 180 DEG C,
Reaction 12 hours；The preferred distilled water of the water or deionized water.
The present invention provides a kind of electrochemical sensing device, it is characterised in that with the above-mentioned nanogold-silver-three-dimensional graphite of the present invention
Alkene composite material modified electrode is as working electrode, preferably using Au-Ag-3DGA/CILE electrodes as working electrode.
Another embodiment of the present invention provides the above-mentioned nanogold-silver of the present invention-three-dimensional graphene composite material modification electricity
Application of the pole (preferably Au-Ag-3DGA/CILE electrodes) in preparing electrochemical sensing device.
Another embodiment of the present invention provides the above-mentioned nanogold-silver of the present invention-three-dimensional graphene composite material modification electricity
The preparation method of pole (preferably Au-Ag-3DGA/CILE electrodes), it is characterised in that include the following steps：Take appropriate Jin-silver-three-dimensional
Graphene composite material (Au-Ag-3DGA) dispersant liquid drop is applied to the surface Ionic Liquid Modified carbon paste electrode (CILE), naturally dry
Afterwards up to the nanogold-silver-three-dimensional graphene composite material modified electrode (preferably Au-Ag-3DGA/CILE electrodes).Wherein
A concentration of 0.1-0.3mg/mL, preferably 0.2mg/mL of Jin-silver-three-dimensional graphene composite material (Au-Ag-3DGA) dispersion liquid,
The dosage of Jin-silver-three-dimensional graphene composite material (Au-Ag-3DGA) dispersion liquid is advisable with energy even spread electrode surface, ability
The technical staff in domain can reasonably select its dosage according to the property of electrode and coating solution；The ionic liquid is repaiied
Decorations carbon paste electrode (CILE) is prepared by the following method：By suitable graphite powder, N-1- hexyl pyridine hexafluorophosphates HPPF6, liquid
Body paraffin is placed in mortar and grinds uniformly, obtains carbon paste, then inserts in vitreous electricity pole pipe carbon paste and is compacted, interpolation copper wire conduct
Conducting wire obtains Ionic Liquid Modified carbon paste electrode, i.e. CILE basal electrodes；Wherein, graphite powder and HPPF6Mass ratio be 1.5
~2.5:1, preferably 2:1；Every gram of HPPF6Use 500~700 μ L atoleines, preferably 625 μ L；Milling time is 1.5-3.0h；
Glass electrode bore is preferably 4mm.
Another embodiment of the present invention provides above-mentioned nanogold-silver-three-dimensional graphene composite material modified electrode (preferably
Au-Ag-3DGA/CILE electrodes) application in detecting baicalein.It is preferred for detecting the Huang in serum or Shuanghuanglian oral liquid
A kind of reed mentioned in ancient books element.It is 2.0 phosphate buffer solution as supporting electrolyte that pH is used when detecting baicalein.
Solution involved in the present invention is aqueous solution (except having indicated).
Compared with the prior art, the advantages of the present invention are as follows：(1) nanogold-silver-three-dimensional grapheme that prepared by the present invention is multiple
Condensation material modified electrode (preferably Au-Ag-3DGA/CILE electrodes) is high to the detection sensitivity of baicalein, and (detection limit reaches
0.345nmol/L (3 σ)), and stability (RSD2.22%) and favorable reproducibility (RSD4.2%)；(2) contain when detecting in sample
When the substances such as inorganic metal ion, amino acid, glucose, the detection of baicalein is substantially unaffected, and shows that this method can be used for
Detect the baicalein in Shuanghuanglian oral liquid.
Description of the drawings
Fig. 1 is the SEM figures (A, B) and TEM figures (C, D) of nanogold-silver-three-dimensional graphene composite material；
Fig. 2 is nanogold-silver-three-dimensional graphene composite material XRD (A) and Raman (B) phenogram；
Fig. 3 is 1 × 10 in pH 2.0PBS buffer solutions-5Cyclic voltammetric of the mol/L baicaleins on different modifying electrode is bent
Line (A sweeps fast 100mV/s) and AC impedance spectroscopy (B)；Working electrode is respectively (a) CILE, (b) 3DGA/CILE, (c) Au-
Ag-3DGA/CILE (product c)；
Fig. 4 is that DPV curve of the baicalein on Au-Ag-3DGA/CILE electrodes under (A) various concentration (is distinguished from a to j
For：0,1 × 10-9,5.0×10-9,1×10-8,5.0×10-8,1×10-7,5.0×10-7,1×10-6,5.0×10-6,1×10-5mol/L)；(B-D) relationship between oxidation peak current and various concentration baicalein.
Specific implementation mode
For the ease of a further understanding of the present invention, examples provided below has done more detailed description to it.But
It is that these embodiments are only not supposed to be a limitation to the present invention or implementation principle for being better understood from invention, reality of the invention
The mode of applying is not limited to the following contents.
Embodiment 1
Take gold chloride (0.06mmol), silver nitrate (0.06mmol) and graphene oxide (20mg) that distilled water (16mL) is added
In stir evenly after, triethylene tetramine (0.8mL) is added under stiring, is heated to 190 DEG C, after reacting 10h, naturally cools to room
Temperature, washing, freeze-drying 12h after up to the nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA, hereinafter referred to as
Product A).
Embodiment 2
Take gold chloride (0.08mmol), silver nitrate (0.08mmol) and graphene oxide (20mg) that deionized water is added
After being stirred evenly in (20mL), triethylene tetramine (1.2mL) is added under stiring, is heated to 170 DEG C, it is naturally cold after reacting 12h
But to room temperature, after washing, freeze-drying 10h up to the nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA, with
Lower abbreviation product B).
Embodiment 3
Take gold chloride (0.06mmol), silver nitrate (0.06mmol) and graphene oxide (20mg) that distilled water is added
After being stirred evenly in (17.5mL), triethylene tetramine (1.0mL) is added under stiring, is heated to 180 DEG C, it is natural after reacting 12h
Be cooled to room temperature, wash, be freeze-dried after 12h up to the nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA,
Hereinafter referred to as products C).
SEM, TEM, XRD, Raman characterization result of product A-C is consistent, as space is limited, in description of the invention attached drawing 1-2
Only list the corresponding characterization result of products C.
Embodiment 4
It takes after being stirred evenly in graphene oxide (20mg) addition distilled water (17.5mL), triethylene four is added under stiring
Amine (1.0mL) is heated to 180 DEG C, and after reacting 12h, cooled to room temperature, washing is freeze-dried after 12h up to three-dimensional graphite
Alkene composite material (3DGA, hereinafter referred to as product D).
Embodiment 5
(1) 1.5g graphite powders, 1.0g ionic liquids HPPF are taken6It is placed in mortar with 500 μ L atoleines and grinds 1.5h, obtained
To carbon paste, then by carbon paste filling internal diameter to be compacted in the vitreous electricity pole pipe of 4mm, interpolation copper wire obtains CILE as conducting wire；
(2) it takes aqueous solution (0.1mg/mL) drop coating of 8-10 μ L products A in the surfaces CILE, is just repaiied after natural drying
Adorn electrode A u-Ag-3DGA/CILE (hereinafter referred to as product a).
Embodiment 6
(1) 2.5g graphite powders, 1.0g ionic liquids HPPF are taken6It is placed in mortar with 700 μ L atoleines and grinds 3h, obtained
Carbon paste, then by carbon paste filling internal diameter to be compacted in the vitreous electricity pole pipe of 4mm, interpolation copper wire obtains CILE as conducting wire；
(2) it takes aqueous solution (0.3mg/mL) drop coating of 8-10 μ L products B in the surfaces CILE, is just repaiied after natural drying
Adorn electrode A u-Ag-3DGA/CILE (hereinafter referred to as product b).
Embodiment 7
(1) 1.6g graphite powders, 0.8g ionic liquids HPPF are taken6It is placed in mortar with 500 μ L atoleines and grinds 2.0h, obtained
To carbon paste, then by carbon paste filling internal diameter to be compacted in the vitreous electricity pole pipe of 4mm, interpolation copper wire obtains CILE as conducting wire；
(2) it takes aqueous solution (0.2mg/mL) drop coating of 8-10 μ L products Cs in the surfaces CILE, is just repaiied after natural drying
Adorn electrode A u-Ag-3DGA/CILE (hereinafter referred to as product c).
Embodiment 8
(1) 1.6g graphite powders, 0.8g ionic liquids HPPF are taken6It is placed in mortar with 500 μ L atoleines and grinds 2.0h, obtained
To carbon paste, then by carbon paste filling internal diameter to be compacted in the vitreous electricity pole pipe of 4mm, interpolation copper wire obtains CILE as conducting wire；
(2) it takes aqueous solution (0.2mg/mL) drop coating of 8-10 μ L products D in the surfaces CILE, is just repaiied after natural drying
Adorn electrode 3DGA/CILE (hereinafter referred to as product d).
Electrochemical behavior research of 9 baicalein of embodiment on CILE, product c-d
In the PBS buffer solutions of 0.1mol/LpH 2.0,1.0 × 10 have been investigated using cyclic voltammetry-5The Huang of mol/L
Electrochemical behavior of a kind of reed mentioned in ancient books element on Different electrodes (CILE, product c-d), the results are shown in Figure 3.CILE (on curve a), radix scutellariae
There are a pair of of redox peaks in 0.436V and 0.420V in element, and Ipa and Ipc are respectively 1.574 μ A and 0.964 μ A, illustrate radix scutellariae
Its Direct Electrochemistry may be implemented on the surfaces CILE in element.Curve b is baicalein in 3DGA/CILE (the electrochemical scholarship and moral conduct on product d)
For curve, Epa and Epc are located at 0.436V and 0.431V, and Ipa and Ipc are respectively 2.198 μ A and 2.060 μ A, are on CILE
1.40 times of peak current and 2.14 times, illustrates that the presence of 3DGA has the electron transmission conducive to electrode interface, baicalein can be improved
Electrochemical signals.Curve c is baicalein in Au-Ag-3DGA/CILE (the electrochemical behavior curve on product c), Epa and Epc
It is located at 0.443V and 0.425V, Ipa and Ipc are respectively 6.668 μ A and 4.282 μ A, and value is respectively 3DGA/CILE's
3.03 times and 2.08 times, be 4.24 times and 4.44 times of CILE, shows that the presence of Au-Ag-3DGA significantly improves baicalein and exists
The electron transport rate on modified electrode surface, improves electrode performance, this may be high surface area, the height due to Au-Ag-3DGA
The advantageous effect that electric conductivity and synergistic effect generate jointly.
10 range of linearity of embodiment is limited with detection
In the PBS buffer solutions of pH 2.0, baicalein oxidation peak has been investigated using DPV methods (sweeping fast 0.05-0.90V/s)
Relationship between electric current and its concentration, Fig. 4 A are the stacking chart of part representativeness DPV curves.The result shows that the DPV oxygen of baicalein
Change peak current 1 × 10-9~1 × 10-8Mol/L (Fig. 4 B), 1 × 10-8~1 × 10-7Mol/L (Fig. 4 C) and 1 × 10-7~1 ×
10-5It is in good linear relationship respectively in three concentration ranges of mol/L (Fig. 4 D), linear regression respectively is：Ipa(μA)
=177.66C (μm ol/L)+0.684 (n=7, γ=0.995), Ipa (μ A)=47.47C (μm ol/L)+2.14 (n=6, γ
=0.993), Ipa (μ A)=2.81C (μm ol/L)+6.99 (n=11, γ=0.995), detection are limited to 0.345nmol/L (3
σ)。
11 selectivity of embodiment
Experiment uses DPV methods (in the PBS buffer solutions of pH 2.0, sweeping fast 0.05-0.90V/s) inorganic gold common to part
Belong to the coexisting substances pair 1.0 × 10 such as ion, amino acid-5The influence that mol/L baicaleins measure is investigated, experimental result such as table
Shown in 1.Find out that the presence of Common materials has not significant impact the measurement of baicalein by the data in table, illustrates Au-Ag-
(product c) has selectivity well to 3DGA/CILE to the measurement of baicalein.
1 interfering substance pair 1.0 × 10 of table-5The influence of mol/L baicaleins detection
The measurement of 12 Shuanghuanglian oral liquid sample of embodiment
To examine the actual application ability of this method, by this method for radix scutellariae cellulose content in drug Shuanghuanglian oral liquid
It measures.Low concentration determination experiment step method is as follows：Shuanghuanglian oral liquid is diluted 50,000 times with the PBS buffer solutions of pH 2.0,
Establishing criteria addition method is measured the concentration of baicalein that the results are shown in Table 2, the rate of recovery 97.0%~106.0% it
Between.High concentration determination experiment step method is as follows：Shuanghuanglian oral liquid is diluted 10,000 times with the PBS buffer solutions of pH 2.0,
Then establishing criteria addition method is measured the concentration of baicalein that the results are shown in Table 3, and the rate of recovery is 95.3%~104.5%
Between.The relative standard deviation of sample detection is respectively less than 5%, illustrates that this method has preferable survey to the actual sample of baicalein
Determine result.
The content of baicalein and the rate of recovery (n=3) in swap buffers between 2 low concentration region of table
The content of baicalein and the rate of recovery (n=3) in swap buffers between 3 high concentration region of table
The stability and reproducibility of 13 electrode of embodiment
By Au-Ag-3DGA/CILE 1 × 10-5After continuous scanning 30 is enclosed in mol/L baicalein solution, peak current is reduced to just
The 97.8% of beginning electric current, continuous scanning 70 enclose after, peak current is reduced to the 95.6% of initial current, illustrate the modified electrode have compared with
Good stability.To 1 × 10-5The baicalein parallel determination of mol/L 10 times, RSD values are 2.22%, are utilized respectively product a-c pairs 1
×10-5The baicalein solution of mol/L is measured, RSD 4.2%, illustrates that electrode has good stability and reproducibility.
Claims (10)
1. a kind of nanogold-silver-three-dimensional graphene composite material modified electrode, it is characterised in that the electrode include basal electrode,
Nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) coating, the basal electrode are Ionic Liquid Modified carbon paste electricity
Pole (CILE).
2. one kind being followed successively by CILE basal electrodes, nanogold-silver-three-dimensional graphene composite material (Au-Ag-3DGA) from inside to outside
The electrode of coating, i.e. Au-Ag-3DGA/CILE electrodes.
3. claim 1-2 any one of them electrodes, it is characterised in that the nanogold-silver-three-dimensional graphene composite material
(Au-Ag-3DGA) preparation method includes the following steps：Take suitable gold chloride (HAuCl4), silver nitrate (AgNO3) and oxidation
Graphene (GO) is added to the water stir evenly after, suitable triethylene tetramine is added under stiring, is heated to 170-190 DEG C, instead
After answering 10-12h, cooled to room temperature washes, is multiple up to the nanogold-silver-three-dimensional grapheme after freeze-drying 10-12h
Condensation material (Au-Ag-3DGA).
4. the electrode described in claim 3, it is characterised in that every gram of graphene oxide (GO) uses 3-4mmol gold chlorides
(HAuCl4), gold chloride (HAuCl4) and silver nitrate (AgNO3) molar ratio be 1：1, every milligram of graphene oxide (GO) uses
0.8-1.0mL water, every gram of graphene oxide (GO) use 40-60mL triethylene tetramines.
5. claim 3-4 any one of them electrodes, it is characterised in that reaction carries out preferably in autoclave, preferably adds
Heat is reacted 12 hours to 180 DEG C；The preferred distilled water of the water or deionized water.
6. a kind of electrochemical sensing device, it is characterised in that with claim 1-5 any one of them nanogold-silver-three-dimensional stone
Black alkene composite material modified electrode is as working electrode, preferably using Au-Ag-3DGA/CILE electrodes as working electrode.
7. claim 1-5 any one of them nanogold-silver-three-dimensional graphene composite material modified electrode (preferably Au-Ag-
3DGA/CILE electrodes) application in preparing electrochemical sensing device.
8. claim 1-5 any one of them nanogold-silver-three-dimensional graphene composite material modified electrode (preferably Au-Ag-
3DGA/CILE electrodes) preparation method, it is characterised in that include the following steps：Take appropriate Jin-silver-three-dimensional grapheme composite wood
Material (Au-Ag-3DGA) dispersant liquid drop is applied to the surface Ionic Liquid Modified carbon paste electrode (CILE), is received after natural drying up to described
Meter Jin-silver-three-dimensional graphene composite material modified electrode (preferably Au-Ag-3DGA/CILE electrodes).Wherein Jin-silver-three-dimensional stone
A concentration of 0.1-0.3mg/mL, preferably 0.2mg/mL of black alkene composite material (Au-Ag-3DGA) dispersion liquid；The ionic liquid
Decorating carbon paste electrode (CILE) is prepared by the following method：By suitable graphite powder, N- hexyl pyridine hexafluorophosphates (HPPF6)、
Atoleine is placed in mortar and grinds uniformly, obtains carbon paste, then inserts in vitreous electricity pole pipe carbon paste and be compacted, interpolation copper wire is made
For conducting wire, Ionic Liquid Modified carbon paste electrode, i.e. CILE basal electrodes are obtained；Wherein, graphite powder and HPPF6Mass ratio be
1.5~2.5:1, preferably 2:1；Every gram of HPPF6Use 500~700 μ L atoleines, preferably 625 μ L；Milling time is 1.5-
3.0h；Glass electrode bore is preferably 4mm.
9. claim 1-5 any one of them nanogold-silver-three-dimensional graphene composite material modified electrode (preferably Au-Ag-
3DGA/CILE electrodes) application in detecting baicalein.
10. the application described in claim 9, it is characterised in that be preferred for detecting the radix scutellariae cellulose content in Shuanghuanglian oral liquid.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810261885.9A CN108519418B (en) | 2018-03-28 | 2018-03-28 | Nano-gold-silver-three-dimensional graphene composite material modified electrode and application thereof in baicalein detection |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201810261885.9A CN108519418B (en) | 2018-03-28 | 2018-03-28 | Nano-gold-silver-three-dimensional graphene composite material modified electrode and application thereof in baicalein detection |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN108519418A true CN108519418A (en) | 2018-09-11 |
| CN108519418B CN108519418B (en) | 2020-04-14 |
Family
ID=63434412
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201810261885.9A Active CN108519418B (en) | 2018-03-28 | 2018-03-28 | Nano-gold-silver-three-dimensional graphene composite material modified electrode and application thereof in baicalein detection |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN108519418B (en) |
Cited By (5)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109239161A (en) * | 2018-11-21 | 2019-01-18 | 海南师范大学 | A kind of preparation method of biomass porous carbon composite and its application study in electrochemical sensor |
| CN109307700A (en) * | 2018-10-19 | 2019-02-05 | 海南师范大学 | A kind of method of cobalt-based metal-organic framework material/three-dimensional grapheme nanocomposite modified electrode measurement rutin |
| CN111141798A (en) * | 2019-12-31 | 2020-05-12 | 青岛科技大学 | Preparation method of multi-walled carbon nanotube-banana peel-based biomass carbon electrochemical sensor and application of baicalein detection |
| CN111337555A (en) * | 2020-03-24 | 2020-06-26 | 泉州师范学院 | Method for preparing reduced graphene oxide-nanogold composite material by using perilla extract and application of reduced graphene oxide-nanogold composite material in electrochemical sensor |
| CN115070028A (en) * | 2022-05-12 | 2022-09-20 | 北京农学院 | Method for rapidly detecting pesticide and veterinary drug residues by gold-based nano material electrochemical sensor |
Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104986808A (en) * | 2015-06-26 | 2015-10-21 | 江苏大学 | Preparation method and application of cobaltosic oxide/graphene aerogel composite material |
| CN105688763A (en) * | 2016-04-08 | 2016-06-22 | 江苏大学 | Method for preparing platinum nano particle supported nitrogen-doped three-dimensional graphene aerogel via one-step method |
| CN106159199A (en) * | 2015-04-28 | 2016-11-23 | 扈胜禄 | A kind of 3D Graphene electrodes for highly dense accumulator, prepare and apply |
| CN106328947A (en) * | 2016-10-12 | 2017-01-11 | 北京化工大学 | Graphene aerogel loaded two-phase transition metal sulfide as well as preparation method and application thereof |
| CN107219281A (en) * | 2017-03-13 | 2017-09-29 | 海南师范大学 | A kind of preparation and application of platinum three-dimensional grapheme airsetting matrix enzyme sensor part |
| CN107808779A (en) * | 2016-09-08 | 2018-03-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | CNT/three-dimensional graphene composite material, its preparation method and application |
-
2018
- 2018-03-28 CN CN201810261885.9A patent/CN108519418B/en active Active
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106159199A (en) * | 2015-04-28 | 2016-11-23 | 扈胜禄 | A kind of 3D Graphene electrodes for highly dense accumulator, prepare and apply |
| CN104986808A (en) * | 2015-06-26 | 2015-10-21 | 江苏大学 | Preparation method and application of cobaltosic oxide/graphene aerogel composite material |
| CN105688763A (en) * | 2016-04-08 | 2016-06-22 | 江苏大学 | Method for preparing platinum nano particle supported nitrogen-doped three-dimensional graphene aerogel via one-step method |
| CN107808779A (en) * | 2016-09-08 | 2018-03-16 | 中国科学院苏州纳米技术与纳米仿生研究所 | CNT/three-dimensional graphene composite material, its preparation method and application |
| CN106328947A (en) * | 2016-10-12 | 2017-01-11 | 北京化工大学 | Graphene aerogel loaded two-phase transition metal sulfide as well as preparation method and application thereof |
| CN107219281A (en) * | 2017-03-13 | 2017-09-29 | 海南师范大学 | A kind of preparation and application of platinum three-dimensional grapheme airsetting matrix enzyme sensor part |
Non-Patent Citations (4)
| Title |
|---|
| CUI"E ZOU等: "Rutin detection using highly electrochemical sensing amplified by an Au–Ag nanoring decorated N-doped graphene nanosheet", 《RSC ADV.》 * |
| KAMILA ŻELECHOWSKA等: "Graphene hydrogels with embedded metal nanoparticles as efficient catalysts in 4-nitrophenol reduction and methylene blue decolorization", 《POL. J. CHEM. TECH.》 * |
| TAO WU等: "Graphene oxide supported Au–Ag alloy nanoparticles with different shapes and their high catalytic activities", 《NANOTECHNOLOGY》 * |
| 闫丽君: "石墨烯复合材料的电化学传感器的制备与应用研究", 《中国优秀硕士学位论文全文数据库 工程科技I辑》 * |
Cited By (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN109307700A (en) * | 2018-10-19 | 2019-02-05 | 海南师范大学 | A kind of method of cobalt-based metal-organic framework material/three-dimensional grapheme nanocomposite modified electrode measurement rutin |
| CN109239161A (en) * | 2018-11-21 | 2019-01-18 | 海南师范大学 | A kind of preparation method of biomass porous carbon composite and its application study in electrochemical sensor |
| CN109239161B (en) * | 2018-11-21 | 2020-01-24 | 海南师范大学 | Preparation method of biomass porous carbon composite material and application research of biomass porous carbon composite material in electrochemical sensor |
| CN111141798A (en) * | 2019-12-31 | 2020-05-12 | 青岛科技大学 | Preparation method of multi-walled carbon nanotube-banana peel-based biomass carbon electrochemical sensor and application of baicalein detection |
| CN111337555A (en) * | 2020-03-24 | 2020-06-26 | 泉州师范学院 | Method for preparing reduced graphene oxide-nanogold composite material by using perilla extract and application of reduced graphene oxide-nanogold composite material in electrochemical sensor |
| CN115070028A (en) * | 2022-05-12 | 2022-09-20 | 北京农学院 | Method for rapidly detecting pesticide and veterinary drug residues by gold-based nano material electrochemical sensor |
Also Published As
| Publication number | Publication date |
|---|---|
| CN108519418B (en) | 2020-04-14 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN108519418A (en) | Nanogold-silver-three-dimensional graphene composite material modified electrode and its application in baicalein detection | |
| Ensafi et al. | Voltammetric determination of isoproterenol using multiwall carbon nanotubes‐ionic liquid paste electrode | |
| Chokkareddy et al. | An amino functionalized magnetite nanoparticle and ionic liquid based electrochemical sensor for the detection of acetaminophen | |
| Deng et al. | Simultaneous determination of ascorbic acid and rutin in pharmaceutical preparations with electrochemical method based on multi-walled carbon nanotubes–chitosan composite film modified electrode | |
| CN108445057A (en) | A kind of preparation and analysis method for detecting the electrochemical sensor of heavy metal ion | |
| CN105842321B (en) | The preparation method of the non-enzymatic glucose electrochemical sensor of cupric oxide nano pin/nitrogen-doped graphene composite | |
| Dang et al. | Selective electrochemical detection of hydroquinone and catechol at a one-step synthesised pine needle-like nano-CePO 4 modified carbon paste electrode | |
| CN112578011A (en) | Sensor and detection method for detecting dopamine and uric acid | |
| CN112051312B (en) | Electrochemical sensing detection method for paraquat in food and modified electrode thereof | |
| CN109164150A (en) | A kind of preparation of gold nanometer cage modified electrode and the method for detecting rutin content | |
| Meng et al. | A molecularly imprinted electrochemical sensor based on gold nanoparticles and multiwalled carbon nanotube–chitosan for the detection of tryptamine | |
| CN109085225A (en) | A kind of preparation method of the protein electrochemistry trace sensor of step sedimentation modification carbon electrode | |
| CN109521072A (en) | Detect heteroauxin and salicylic method and its electrochemical sensor used | |
| Kumar et al. | Electrochemical determination of guanine and uric acid using NdFeO3 Nps modified graphite paste electrode | |
| CN105466989B (en) | The electrochemical detection method of lead in a kind of soy sauce | |
| Xie et al. | Mesopores cellular foam-based electrochemical sensor for sensitive determination of ractopamine | |
| Song et al. | Electrochemical reduction of tartrazine at multi-walled carbon nanotube-modified pyrolytic graphite electrode | |
| CN110031526A (en) | One kind being based on K2Fe4O7The dopamine of electrode is without enzyme sensor, preparation method and applications | |
| CN107255664B (en) | A kind of photic electrochemical sensor preparation method and application of SnSe/SWNT modified electrode detecting chloramphenicol | |
| Liu et al. | A highly sensitive sensor for synephrine detection based on multi-walled carbon nanotubes modified glass carbon electrodes | |
| Suchacz et al. | Voltammetric quantitation of acetaminophen in tablets using solid graphite electrodes | |
| CN113295749B (en) | Nitrogen-doped graphene/ionic liquid composite material modified glassy carbon electrode, preparation method thereof and epinephrine quantitative detection method | |
| CN105929000B (en) | The three-dimensional nitrogenous graphene/MoS of Nafion functionalization2The preparation of paste electrode and simultaneously Analyze 5-HT and dopamine | |
| Abd-Rabboh et al. | Effective screen-printed potentiometric devices modified with carbon nanotubes for the detection of chlorogenic acid: application to food quality monitoring | |
| Wang et al. | Sensitive Electrochemical Determination of Hyperin Based on Electrochemically Activated ZrO2 Nanoparticles-Modified Carbon Paste Electrode |
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 |