CN109298047A - A method of ascorbic acid is measured using silver nanowires/nanogold combination electrode - Google Patents
A method of ascorbic acid is measured using silver nanowires/nanogold combination electrode Download PDFInfo
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- CN109298047A CN109298047A CN201811240787.3A CN201811240787A CN109298047A CN 109298047 A CN109298047 A CN 109298047A CN 201811240787 A CN201811240787 A CN 201811240787A CN 109298047 A CN109298047 A CN 109298047A
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- ascorbic acid
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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
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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
- G01N27/416—Systems
- G01N27/48—Systems using polarography, i.e. measuring changes in current under a slowly-varying voltage
Abstract
The present invention relates to a kind of using silver nanowires/nanogold combination electrode measurement ascorbic acid method.Use silver nanowires/nanogold combination electrode for working electrode, Ag/AgCl electrode is reference electrode, platinum filament be assist electrode group at three-electrode system, the 0.1mol/L citric acid-sodium citrate buffer for being 6.6 using pH is supporting electrolyte, in the differential pulse voltammetry curve that -0.3V~0.4V potential range record concentration is the ascorbic acid prepare liquid within the scope of 0.55 μm of ol/L~60 μm ol/L, the quantitative analysis of sample is carried out with calibration curve method.It is an object of that present invention to provide a kind of Ascorbic Acid selectivity with higher, higher sensitivity, and are easier the electrochemical methods of operation.
Description
Technical field
The present invention relates to electrochemical sensor fields, and in particular to a kind of flexible silver nanowires/nanogold based on PDMS
Application of the combination electrode in ascorbic acid measurement.
Background technique
Ascorbic acid is widely present in fresh fruit, and in vegetables, human body cannot itself synthesis, it is necessary to by intake acquisition,
There is a serious shortage of when can cause scurvy.Research Methods For Quantitative Estimation of Ascorbic Acid mainly has fluorescence method, high pressure lipuid chromatography (HPLC), height at present
Press capillary electrophoresis, spectrophotometry, microbial method and electrochemical method.And electrochemical method have it is easy to operate, need
Professional, the advantages of can be realized continuous, real-time, automatic detection.And nanogold particle large specific surface area, Ascorbic Acid
With good catalytic activity, the sensitivity and selectivity of electrochemical sensing measurement are improved.Thus the electrochemica biological constructed
Sensor has structure simple compared with traditional detection method, does not need expensive detecting instrument equipment, easy to operate, sensitivity
Height, good selective are widely used in the work of every field.
Summary of the invention
The purpose of the present invention is to provide a kind of Ascorbic Acid selectivity with higher, higher sensitivity, and compare
It is easier to the electrochemical methods of operation.
To achieve the above object, the technical solution adopted by the present invention are as follows: use silver nanowires/nanogold combination electrode for work
Make electrode, Ag/AgCl electrode is reference electrode, platinum filament be assist electrode group at three-electrode system, be 6.6 with pH
0.1mol/L citric acid-sodium citrate buffer is supporting electrolyte, is in -0.3V~0.4V potential range record concentration
The differential pulse voltammetry curve of ascorbic acid prepare liquid within the scope of 0.55 μm of ol/L~60 μm ol/L, is carried out with calibration curve method
The quantitative analysis of sample.
The silver nanowires/nanogold combination electrode includes: that PDMS is substrate, and silver nanowires is conductive layer, nanogold
Particle is electrochemical deposition layer, and the nanogold particle is deposited in silver nanowires.
The present invention utilizes the good flexibility of PDMS, and combines the good electric conductivity of silver nanowires and gold nano grain pair
The selective catalysis of ascorbic acid acts on, and a kind of electrode of the Ascorbic Acid with good electrochemical response is made.Optimization buffering
The parameters such as solution type, pH obtain the electrochemical analysis side of Ascorbic Acid sensitivity with higher, accuracy and precision
Method, and this method is measured applied to actual sample.
Detailed description of the invention
Attached drawing 1 is silver nanowires/nanogold combination electrode surface topography map.
Attached drawing 2 is the response results of Different electrodes Ascorbic Acid.
Attached drawing 3 is the optimization lab diagram of supporting electrolyte solution type.
Attached drawing 4 is the Optimal Curve of pH value.
Attached drawing 5 is the standard curve of various concentration ascorbic acid solution.
Specific embodiment
Below in conjunction with attached drawing and specific embodiment, the present invention is further illustrated.
The present invention is described in detail below by specific embodiment, but is not limited the scope of the invention.Unless otherwise specified, originally
Experimental method used by inventing is conventional method, and experiment equipment used, material, reagent etc. can chemically company be bought.
The preparation of silver nanowires/nanogold combination electrode
Embodiment 1
(1) PDMS substrate makes
Substrate is made using photoetching technique.Electrode drawing is designed using graphics software first, and utilizes photoetching mask-making technology
Drawing is printed into mask plate, secondly in clean silicon chip surface spin coating photoresist, covers the mask plate containing electrode pattern, most
After carry out exposure and imaging, obtain silicon wafer template (silicon chip surface can make 8 electrode templates by lithography).It places it in disposable
In culture dish;Casting quality is than the PDMS mixed solution for 10:1 on it;It places into negative pressure in vacuum desiccator and pumps PDMS
Bubble in mixed solution, used time 2h;It is put into 80 DEG C of constant temperature oven the 1h that is heating and curing after taking-up, and is cut into 8 electrodes
Substrate;The dust that ready-made substrate is removed to surface attachment with 3M adhesive tape (being purchased from Minnesota Mining and Manufacturing Company) processing, is then placed in ultraviolet
2min is cleaned in ozone clean machine, obtains the PDMS substrate with fixed shaped recesses.
(2) PDMS hydrophilic layer is modified
1. preparing the water mixed solution that mass percent is 4%PVA and 7%PVP;2. the PDMS substrate prepared is impregnated
The 20min in PVA and PVP mixed solution places into dry 1.5h in 80 DEG C of vacuum drying oven;3. it is 2. primary to repeat step;④
It is then placed in heat fixation 20min in 100 DEG C of vacuum drying oven.5. it is 2. and 4. primary to repeat step, the PDMS of surface hydrophilic is obtained
Substrate.
(3) prepared by PDMS-AgNWs conductive layer
Dehydrated alcohol and water are mixed in the ratio of 9:1 and are used as solvent, compound concentration is the silver nanowires solution of 5mg/mL,
In the groove for equably spreading over the surface PDMS, place at room temperature drying for one day.
(4) PDMS-AgNWs-AuNPs silver nanowires/nanogold combination electrode preparation
PDMS-AgNWs is immersed into 1mg/ml KAuCl4With 0.5mol/L H2SO4Mixed electrolytic solution in, in -0.2V electricity
Under the conditions of position, the deposition of nanogold particle is carried out on its surface using electrochemical workstation.Reference electrode is Ag/AgCl electrode,
Auxiliary electrode is platinum filament, working electrode PDMS-AgNWs.Obtain PDMS-AgNWs-AuNPs, place at room temperature it is drying for one day,
As silver nanowires/nanogold combination electrode.
Embodiment 2
(1) PDMS substrate makes
Substrate is made using photoetching technique.Electrode drawing is designed using graphics software first, and utilizes photoetching mask-making technology
Drawing is printed into mask plate, secondly in clean silicon chip surface spin coating photoresist, covers the mask plate containing electrode pattern, most
After carry out exposure and imaging, obtain silicon wafer template (silicon chip surface can make 8 electrode templates by lithography).It places it in disposable
In culture dish;Casting quality is than the PDMS mixed solution for 10:1 on it;It places into negative pressure in vacuum desiccator and pumps PDMS
Bubble in mixed solution, used time 2h;It is put into 80 DEG C of constant temperature oven the 1h that is heating and curing after taking-up, and is cut into 8 electrodes
Substrate;The dust that ready-made substrate is removed to surface attachment with 3M adhesive tape (being purchased from Minnesota Mining and Manufacturing Company) processing, is then placed in ultraviolet
2min is cleaned in ozone clean machine, obtains the PDMS substrate with fixed shaped recesses.
(2) PDMS hydrophilic layer is modified
1. preparing the water mixed solution that mass percent is 4%PVA and 7%PVP;2. the PDMS substrate prepared is impregnated
The 20min in PVA and PVP mixed solution places into dry 1.5h in 80 DEG C of vacuum drying oven;3. it is 2. primary to repeat step;④
It is then placed in heat fixation 20min in 100 DEG C of vacuum drying oven.5. it is 2. and 4. primary to repeat step, the PDMS of surface hydrophilic is obtained
Substrate.
(3) prepared by PDMS-AgNWs conductive layer
Dehydrated alcohol and water are mixed in the ratio of 9:1 and are used as solvent, compound concentration is the silver nanowires solution of 5mg/mL,
In the groove for equably spreading over the surface PDMS, place at room temperature drying for one day.
(4) PDMS-AgNWs-AuNPs silver nanowires/nanogold combination electrode preparation
PDMS-AgNWs is immersed into 1mg/ml KAuCl4With 0.5mol/L H2SO4Mixed electrolytic solution in, in -0.2V electricity
Under the conditions of position, the deposition of nanogold particle, sedimentation time 200s are carried out on its surface using electrochemical workstation.Reference electrode is
Ag/AgCl electrode, auxiliary electrode are platinum filament, working electrode PDMS-AgNWs.Obtain PDMS-AgNWs-AuNPs, room temperature decentralization
It sets drying for one day spare.PDMS-AgNWs-AuNPs mentioned below, the sedimentation time of gold nano grain are 200s.
Silver nanowires/nanogold combination electrode performance quality depends on silver nanowires and is distributed and takes on flexible substrates surface
The uniformity coefficient of the uniformity coefficient and gold nano grain size and distribution that connect.As shown in Figure 1, silver nanowires is on flexible electrode surface
It is evenly distributed, overlap joint is close;It gold nano grain size and is evenly distributed.Illustrate that the novel electrode is functional.
Embodiment 3
The comparison of Different electrodes
Respectively using PDMS-AgNWs-AuNPs electrode, PDMS-AgNWs, naked gold electrode as working electrode, with Ag/AgCl
Electrode is reference electrode, platinum filament be assist electrode group at three-electrode system, being placed in ascorbic acid concentrations is 1mg/mL, and pH is
In 6.6 0.1mol/L citric acid-sodium citrate electrolyte, ascorbic acid prepare liquid is recorded in -0.3V~0.4V potential range
Differential pulse voltammetry curve, as shown in Fig. 2.Ascorbic acid is big in silver nanowires/nanogold combination electrode surface electric current,
Peak shape is narrow and sharp, this illustrates silver nanowires/nanogold combination electrode than nano-silver thread electrode and commodity gold electrode to Vitamin C
The electrochemical response of acid is more preferable.
Embodiment 4
The optimization of electrolyte solution type
Experimental Research is in four kinds of buffer solutions: citric acid-sodium citrate, tartaric acid-sodium tartrate, Acetic acid-sodium acetate
With sodium dihydrogen phosphate-disodium hydrogen phosphate (concentration 0.1mol/L, and with sodium hydroxide adjust pH value be 6.6) in detect 1mg/mL
The differential pulse voltammetry curve of ascorbic acid solution.It will be by PDMS-AgNWs-AuNPs electrode as working electrode, Ag/AgCl electricity
Extremely reference electrode, platinum filament be assist electrode group at three-electrode system, be placed in ascorbic acid concentrations be 1mg/mL, pH 6.6
0.1mol/L citric acid-sodium citrate electrolyte in, in the difference of -0.3V~0.4V potential range record ascorbic acid prepare liquid
Sectors rushes volt-ampere curve.It is tartaric acid-sodium tartrate, Acetic acid-sodium acetate and phosphorus that three-electrode system, which is equally placed in buffer solution,
In acid dihydride sodium-disodium hydrogen phosphate (0.1mol/L, pH=6.6) electrolyte, as shown in Fig. 3.The result shows that with lemon
In the case that acid-sodium citrate is as buffer solution, the response peak current of ascorbic acid is maximum.
Embodiment 5
The Optimal Curve of pH value
Citric acid-of the Experimental Research in pH=6.0, pH=6.2, pH=6.4, pH=6.6, pH=6.8, pH=7.0
Sodium citrate buffer (concentration 0.1mol/L, and adjust pH value with sodium hydroxide and detect 1mg/mL Vitamin C to be 6.6) middle
The differential pulse voltammetry curve of acid solution.Using PDMS-AgNWs-AuNPs electrode as working electrode, Ag/AgCl electrode is reference
Electrode, platinum filament be assist electrode group at three-electrode system, be placed in ascorbic acid concentrations be 1mg/mL, pH be 6.0 0.1mol/
In L citric acid-sodium citrate electrolyte, in -0.3V~0.4V potential range record ascorbic acid prepare liquid differential pulse volt
Pacify curve.Three-electrode system is equally placed in citric acid-lemon of pH=6.2, pH=6.4, pH=6.6, pH=6.8, pH=7.0
In lemon acid sodium electrolyte, as shown in Fig. 4.The result shows that using the citric acid-sodium citrate of pH=6.6 as buffer solution
In the case where, the response peak current of ascorbic acid is maximum.
Embodiment 6
Sample: Ascorbyl C pill;
Source: Northeast Pharmaceutical Group Shenyang First Pharmaceutical Co., Ltd.
Measuring method: use three-electrode system: homemade silver nanowires/nanogold combination electrode is working electrode, Ag/
AgCl electrode is reference electrode, and platinum filament is auxiliary electrode, the 0.1mol/L citric acid-sodium citrate buffer for being 6.6 with pH
For supporting electrolyte, electric mearsurement measurement is carried out using differential pulse voltammetry, records ascorbic acid in the section of -0.3~0.4V
Interior differential pulse voltammetry curve, as shown in figure 5, carrying out quantitative analysis using calibration curve method.
Experiment is measured in parallel 10 times, and obtaining oxidation peak to peak current average value is 2.3625 × 10-4A substitutes into linear regression side
Journey y=1.76356 × 10-4+2.45546×10-6The average content that x calculates every ball ascorbic acid in Ascorbyl C pill is
107.4 milligram.The relative error of sign value (100 milligrams/ball) and measured value: 7.4%;The relative standard of 10 parallel determinations is inclined
Poor RSD value is 3.77%.
The present invention utilizes the good flexibility of PDMS, and combines the good electric conductivity of silver nanowires and gold nano grain pair
The selective catalysis of ascorbic acid acts on, and a kind of electrode of the Ascorbic Acid with good electrochemical response is made.Optimization buffering
The parameters such as solution type, pH obtain the electrochemical analysis side of Ascorbic Acid sensitivity with higher, accuracy and precision
Method, and this method is measured applied to actual sample.
Claims (2)
1. a kind of using silver nanowires/nanogold combination electrode measurement ascorbic acid method, which is characterized in that use silver nanoparticle
Line/nanogold combination electrode be working electrode, Ag/AgCl electrode be reference electrode, platinum filament be auxiliary electrode group at three electrodes
System, the 0.1mol/L citric acid-sodium citrate buffer for being 6.6 using pH is supporting electrolyte, in -0.3V~0.4V current potential
Range records the differential pulse voltammetry curve that concentration is the ascorbic acid prepare liquid within the scope of 0.55 μm of ol/L~60 μm ol/L, uses
The quantitative analysis of calibration curve method progress sample.
2. it is as described in claim 1 a kind of using silver nanowires/nanogold combination electrode measurement ascorbic acid method, it is special
Sign is that the silver nanowires/nanogold combination electrode includes: that PDMS is substrate, and silver nanowires is conductive layer, nanogold
Grain is electrochemical deposition layer, and the nanogold particle is deposited in silver nanowires.
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Cited By (2)
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CN110376265A (en) * | 2019-08-15 | 2019-10-25 | 蚌埠学院 | A method of detection ascorbic acid |
CN111999357A (en) * | 2020-07-31 | 2020-11-27 | 惠州市钰芯电子材料有限公司 | Preparation method of nano silver wire array sensor and application of nano silver wire array sensor in ascorbic acid biomolecule determination |
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Cited By (2)
Publication number | Priority date | Publication date | Assignee | Title |
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CN110376265A (en) * | 2019-08-15 | 2019-10-25 | 蚌埠学院 | A method of detection ascorbic acid |
CN111999357A (en) * | 2020-07-31 | 2020-11-27 | 惠州市钰芯电子材料有限公司 | Preparation method of nano silver wire array sensor and application of nano silver wire array sensor in ascorbic acid biomolecule determination |
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Application publication date: 20190201 |