CN106996953A - It is a kind of for nano copper hydroxide electrode of glucose detection and preparation method thereof - Google Patents
It is a kind of for nano copper hydroxide electrode of glucose detection and preparation method thereof Download PDFInfo
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Abstract
The present invention relates to inorganic nano material and electrochemical sensor technology field, specifically propose a kind of available for nano copper hydroxide electrode of glucose detection and preparation method thereof.The present invention is for forth generation non-enzymatic glucose detecting electrode generally the problems such as the higher noble metal of cost or nano-carbon material are raw material and snearing method prepares the influence electrodes conduct efficiency of electrode presence and checks stability, to have invented novel electrode on a kind of surface by simple electrochemical oxidation after copper base electrode or material and other conductive material copper facing prepared by growth in situ nano copper hydroxide and preparation method thereof.The electrode prepared in this way is that working electrode can be directly used in glucose detection based on the current-time curvel of electrochemical workstation, and to response time of glucose it is short (<2s), and with higher sensitivity (1000-2000 μ A/cm2/ mM) and the wider detection range of linearity (0.1-10mM), illustrate that the invention has good application potential in the field such as blood sugar test and fermentation process monitoring.
Description
Technical field
The present invention relates to inorganic nano material and electrochemical sensor technology field, and in particular to a kind of nano copper hydroxide
Electrode and preparation method thereof, and utilize the glucose Electrochemical Detection side that the nano copper hydroxide electrode is working electrode
Method.
Background technology
Glucose is the required nutriment of organism metabolism, but concentration of glucose can cause organism serious extremely
Disease, such as diabetes, hypertension, kidney failure, glucose detection is particularly significant in life science and clinical medicine domain.Portugal
The commercial Application of grape sugar is also quite varied, is commonly used for the industrial reducing agent such as process hides, plating, mirror processed of printing and dyeing.Microbial fermentation is given birth to
Fast and accurately detect that judgement and control of the sugared concentration of glucose to fermentation process also have great importance during production.Compared to
Other glucose sensing approach such as colorimetric method, Optical Rotation, chromatography, AAS, Electrochemical Detection have sensitivity it is high,
Analyze speed is fast, selectivity is high, simple operation and other advantages.The key and core of glucose Electrochemical Detection are to prepare efficient work
Make electrode.The development of glucose detection electrode after four generations so far, first three Dai Jun based on glucose oxidase (GOx),
Oxidation using GOx to glucose specificity, by the accessory substance O of reaction2Deng the direct or indirect electricity that is converted into and can be detected
Signal.The problem of it is present be：Enzymatic activity is dependent on environmental factors such as temperature, humidity；Electron transfer process is by the protein of enzyme
Outer layer is limited；Electrode stability is poor, the shelf-life is short, it is high to prepare cost.
More researchers have invested sight the non-enzymatic glucose detecting electrode of forth generation, that is, pass through electrode surface
Nano level catalysis or electron transmission unit direct oxidation glucose, to realize its Concentration Testing.Non-enzymatic glucose detecting electrode
Metal and metallic compound base, compound base, carbon micrometer/nanometer material base three are broadly divided into according to the difference of surface reactive material
Major class.The metal and metallic compound used is more based on the noble metals such as gold, silver, platinum, ruthenium, and CNT, graphene
Cost etc. c-based nanomaterial is equally higher.In addition, the preparation of non-enzymatic glucose detecting electrode at present is mainly using will be above-mentioned
Nano active unit snearing not only influences the electrical efficiency and detection stability of electrode, is also unfavorable for the mode of basic electrode
Large-scale industrial production.
The content of the invention
An object of the present invention is to provide a kind of nano copper hydroxide electrode and preparation method thereof.
Nano copper hydroxide electrode provided by the present invention, by copper-based material and is attached to the copper-based material surface
Nanometer Cu (OH)2Layer is constituted.
Other conductive materials of the copper-based material concretely after copper electrode, copper-plating electrode or copper facing.
Wherein, the plating copper thickness in other conductive materials after the copper-plating electrode or copper facing is more than 500nm.
The nanometer Cu (OH)2Layer be using electrochemical oxidation method on the surface of the copper-based material growth in situ
Nano copper hydroxide (Cu (OH)2) crystal layer.
The nanometer Cu (OH) of described growth in situ2For particle diameter 10-150nm hexahedron crystal grain or diameter 100-
The mixture of 150nm, the individual layer hollow pipe for being about 3-10 μm or both.
Nano copper hydroxide electrode provided by the present invention is prepared by the method comprising the following steps：
In NaOH solution, electrochemical oxidation is carried out by anode of the copper-based material, you can on the copper-based material
Form nanometer Cu (OH)2Layer, so as to obtain the nano copper hydroxide electrode.
In the above method, the concentration of the NaOH solution is 1-5M, concretely 3M.
In the above method, graphite rod or platinum electrode can be used to carry out electrochemical oxidation for negative electrode.
The electrochemical oxidation is carried out under constant current conditions.
The electric current of the electrochemical oxidation is 0.05-2mA, concretely 0.1mA, 0.3mA, 0.5mA or 0.6mA, oxidation
Time is 60-1200s, concretely 300s, 1000s or 1200s.
The above method may also include the operation pre-processed to the copper-based material before electrochemical oxidation.It is described pre-
Processing includes：It is respectively 300nm with particle diameter and 50nm alpha aluminium oxide particle polishing grinding first by the copper-based material, then
The ultrasonic decontamination in ethanol and deionized water respectively, finally dries up the copper-based material nitrogen after cleaning.
The above method may also include the operation of the nano copper hydroxide electrode post processing to obtaining after electrochemical oxidation.
The post processing includes：Use deionized water rinsing electrode surface, nitrogen drying.
Application of the above-mentioned nano copper hydroxide electrode in glucose detection falls within protection scope of the present invention.
The glucose that above-mentioned nano copper hydroxide electrode is working electrode is utilized it is a further object of the present invention to provide a kind of
Electrochemical detection method.
The glucose electrochemical detection method, including：
1) using above-mentioned nano copper hydroxide electrode as working electrode, platinum plate electrode is auxiliary electrode, and Ag/AgCl is reference electricity
Pole forms three-electrode system, and the electric current of the glucose solution of series of standards concentration is detected based on electrochemical workstation, draws electricity
Stream-time graph；
2) relation between current density and concentration of glucose is fitted based on the current versus time curve, obtained
Relation curve between current density and concentration of glucose；
3) current density of unknown concentration sample is detected using the three-electrode system, according to the current density and grape
Relation curve between sugared concentration, calculates the concentration of glucose of unknown sample.
Above method step 1) in, it is (specific containing 10-100mM in the glucose solution of the series of standards concentration
Can be 50mM) NaOH.
Concentration of glucose in the glucose solution of the series of standards concentration is respectively 1,2,3,4,5,6,7,8,9,
10mM。
Step 1) detection in voltage constant be 0.4-0.6V, concretely 0.5V.
The present invention has advantages below compared with prior art：
1) present invention prepares nanometer Cu (OH)2The raw material of electrode only needs Cu and NaOH in theory, and Material Cost is low, and NaOH
Solution can be recycled.
2) nanometer Cu (OH) of the invention2Prepared using the method for electrochemical oxidation, reaction condition is gentle, equipment requirement
Low, energy-conserving and environment-protective, process is simple, prepare rapid, product stability and reappearance is strong.
3) present invention prepares nanometer Cu (OH) in copper-based material surface in situ2Electrode, compared to the snearing method generally used
The electrode of preparation, not only electrical efficiency is high, stability is strong, process is simple, also using the copper-based and other conduction of various patterns
Material prepares electrode, is easy to the various forms of electrodes of large-scale production.
4) it is the Electrochemical Detection that working electrode can be directly used for glucose using electrode produced by the present invention, to glucose
Response time it is short (<2s), and with higher sensitivity (1000-2000 μ A/cm2/ mM) and the wider detection range of linearity
(0.1–10mM)。
Brief description of the drawings
Fig. 1 is the original position preparation nanometer Cu (OH) based on copper electrode in present example 12The schematic diagram of electrode, except for
Change outside corresponding anode, it is in situ based on copper-plating electrode and other materials to prepare nanometer Cu (OH)2The process of electrode with etc
Seemingly, negative electrode can select graphite rod or platinum electrode.
Fig. 2 is nanometer Cu (OH) prepared by present example 12The stereoscan photograph of electrode.
Fig. 3 is nanometer Cu (OH) prepared by present example 22The stereoscan photograph of electrode.
Fig. 4 is nanometer Cu (OH) prepared by present example 32The stereoscan photograph of electrode.
Fig. 5 is the nanometer Cu (OH) prepared with present example 12Electrode is working electrode, and Ag/AgCl electrodes are reference electricity
Pole, Pt electrodes are auxiliary electrode, the device of the concentration of glucose of the current versus time curve detection sample based on electrochemical workstation
And process schematic, it is in situ based on copper-plating electrode and other materials to prepare nanometer Cu in addition to corresponding working electrode is replaced
(OH)2Electrode is similar for the detection process of working electrode.
Fig. 6 is the nanometer Cu (OH) prepared with present example 12Electrode is working electrode, is obtained during detection concentration of glucose
The current versus time curve arrived.NaOH containing 50mM in prepare liquid, separated in time is added a certain amount of into prepare liquid respectively
Glucose, make the concentration of glucose in the prepare liquid in each stage, it is known that detecting the change of each stage current density.Fig. 6 (a) Portugals
Grape sugar concentration range be：(Fig. 6 (b) glucose concentration ranges are 1-10mM：0.1-1 mM), detection voltage is 0.5V (vs Ag/
AgCl)。
Between current density and concentration of glucose that Fig. 7 is the Fig. 5 obtained according to Fig. 6 current versus time curve fitting
Relation curve, the current density that can be obtained by the curve and unknown concentration sample detection, the glucose for calculating unknown sample is dense
Degree.Fig. 7 (a) glucose concentration ranges are：(Fig. 7 (b) glucose concentration range is 1-10mM： 0.1–1mM).
Fig. 8 is the nanometer Cu (OH) prepared with present example 12Electrode is working electrode, detects concentration of glucose and adds
Enter the current versus time curve that interfering material is obtained.NaOH containing 50mM in prepare liquid, separated in time, respectively to prepare liquid
It is middle to add a certain amount of vitamin C, dopamine, uric acid, the change of lactose and each stage current density of glucose sugar detection.
Fig. 9 is the percentage block diagram of the current-responsive of the various materials obtained according to Fig. 8 current time-curve.
Embodiment
Below by specific embodiment, the present invention will be described, but the invention is not limited in this.
Experimental method used in following embodiments is conventional method unless otherwise specified；Institute in following embodiments
Reagent, material etc., unless otherwise specified, are commercially obtained.
Embodiment 1
The preparation of nano copper hydroxide electrode
It is respectively 300nm with particle diameter and 50nm Alpha-alumina sanding and polishing by a diameter of 3mm straight type Cu electrodes, and point
Each ultrasonic 1min decontamination not in ethanol and deionized water.It is placed in the NaOH solution that 15mL concentration is 3M, makees after nitrogen drying
It is electrochemically oxidized for anode, using platinum plate electrode as negative electrode, constant electric current is 0.1mA, and oxidization time is 300s.After reaction terminates
With deionized water rinsing, and nitrogen is dried up.Scanned Electronic Speculum characterizes (Fig. 2), and electrode manufactured in the present embodiment is by Cu electrodes and attached
The nanometer Cu (OH) in its surface2Constitute, Cu (OH)2For particle diameter 10-150nm hexahedron crystal grain.
Glucose sensing approach
The nanometer Cu (OH) prepared with this example2Electrode is working electrode, and platinum plate electrode is auxiliary electrode, and Ag/AgCl is
Reference electrode, current versus time curve is determined based on above-mentioned three-electrode system using electrochemical workstation.In hydroxide containing 50mM
A certain amount of glucose is gradually added in the prepare liquid of sodium, it is respectively 1,2,3,4,5,6,7,8,9,10mM to make concentration of glucose
(concentration of glucose in illustration is 0.1,0.2,0.3,0.4,0.5,0.6,0.7,0.8,0.9,1.0mM), detects voltage constant
For 0.5V, as a result as shown in Figure 6.The current versus time curve obtained based on this example is between current-responsive and concentration of glucose
Relation carry out linear fit, as a result as shown in Figure 7.(it is 0.1- in illustration in the range of concentration of glucose is 1-10mM
1mM), the linear relationship between concentration of glucose and response current is y=1.0772x+1.1062 (x is current density), linearly
Spend for 0.9967；In the range of concentration of glucose is 0.1-1mM, the linear relationship between concentration of glucose and response current
For y=1.3294x+0.3940 (x is current density), the linearity is 0.9993；Response time<2s, sensitivity is 1320 μ A/
cm2/mM。
The nanometer Cu (OH) prepared with this example2Electrode is working electrode, and platinum plate electrode is auxiliary electrode, and Ag/AgCl is
Reference electrode, the interference of Common materials in blood is determined based on above-mentioned three-electrode system, in solution using electrochemical workstation
In be gradually added vitamin c, dopamine, uric acid, lactose, glucose is detected to current-responsive.As a result as shown in figure 8, root
It is as shown in Figure 9 that block diagram is made according to current-responsive.The concentration of vitamin c in blood is amplified after 100 times, current-responsive
Only percent 10 or so.By result it can be seen that nanometer Cu (OH) prepared by the present invention2The selectivity of electrode pair glucose
Very well.
The nanometer Cu (OH) prepared with this example2Electrode is working electrode, and platinum plate electrode is auxiliary electrode, and Ag/AgCl is
Reference electrode, concentration of glucose, measurement result such as following table are determined based on above-mentioned three-electrode system using electrochemical workstation.
| Concentration of glucose (actual value)/mM | Concentration of glucose (calculated value)/mM | Error % |
| 1.5 | 1.5496 | 3.3041 |
| 3.5 | 3.4347 | -1.8652 |
| 5.5 | 5.3010 | -3.6177 |
From the above results, the nanometer Cu (OH) of the present invention is utilized2Electrode is that working electrode determines concentration of glucose
As a result accurate, error is small.
Embodiment 2
The preparation of nano copper hydroxide electrode
It is respectively 300nm with particle diameter and 50nm Alpha-alumina sanding and polishing by a diameter of 3mm straight type Cu electrodes, and point
Each ultrasonic 1min decontamination not in ethanol and deionized water.It is placed in the NaOH solution that 15mL concentration is 1M, makees after nitrogen drying
It is electrochemically oxidized for anode, using platinum plate electrode as negative electrode, constant electric current is 0.3mA, and oxidization time is 300s.After reaction terminates
With deionized water rinsing, and nitrogen is dried up.Scanned Electronic Speculum characterizes (Fig. 3), and electrode manufactured in the present embodiment is by Cu electrodes and attached
The nanometer Cu (OH) in its surface2Constitute, Cu (OH)2For particle diameter 10-150nm hexahedron crystal grain and diameter 100-
150nm, be about 3-10 μm individual layer hollow pipe mixture.
Glucose sensing approach
The nanometer Cu (OH) prepared with this example2Electrode is the examination of glucose concentration method and the phase of example 1 of working electrode
Together.As a result show：In the range of concentration of glucose is 1-10mM, the linear relationship between concentration of glucose and response current is
Y=1.1327x+1.2043, the linearity is 0.9955；In the range of concentration of glucose is 0.1-1mM, concentration of glucose and sound
Linear relationship between induced current is y=1.3794x+0.3540, and the linearity is 0.9993；Response time<2s, sensitivity is
1370μA/cm2/mM。
Embodiment 3
The preparation of nano copper hydroxide electrode
It is respectively 300nm with particle diameter and 50nm Alpha-alumina sanding and polishing by a diameter of 3mm straight type Cu electrodes, and point
Each ultrasonic 1min decontamination not in ethanol and deionized water.It is placed in the NaOH solution that 15mL concentration is 5M, makees after nitrogen drying
It is electrochemically oxidized for anode, using platinum plate electrode as negative electrode, constant electric current is 0.5mA, and oxidization time is 300s.After reaction terminates
With deionized water rinsing, and nitrogen is dried up.Scanned Electronic Speculum characterizes (Fig. 4), and electrode manufactured in the present embodiment is by Cu electrodes and attached
The nanometer Cu (OH) in its surface2Constitute, Cu (OH)2For diameter 100-150nm, it is about 3-10 μm of individual layer hollow Nano
Pipe.
Glucose sensing approach
The nanometer Cu (OH) prepared with this example2Electrode is the examination of glucose concentration method and the phase of example 1 of working electrode
Together.As a result show：In the range of concentration of glucose is 1-10mM, the linear relationship between concentration of glucose and response current is
Y=1.0032x+1.6062, the linearity is 0.9938；In the range of concentration of glucose is 0.1-1mM, concentration of glucose and sound
Linear relationship between induced current is y=1.2775x+0.3824, and the linearity is 0.9945；Response time<2s, sensitivity is
1270μA/cm2/mM。
Embodiment 4
The preparation of nano copper hydroxide electrode
The copper platinum (thickness about 1mm) that copper content is more than 99.9% is cut into 1cm × 2cm rectangle, is with particle diameter respectively
300nm and 50nm Alpha-alumina sanding and polishing, and each ultrasonic 1min decontamination in ethanol and deionized water respectively.Nitrogen blows
It is placed in after dry in the NaOH solution that 15mL concentration is 3M, the depth for controlling immersed in liquid level is 1cm, as anode by electrochemistry oxygen
Change, using platinum plate electrode as negative electrode, constant electric current is 0.5mA, and oxidization time is 1000s.Reaction uses deionized water rinsing after terminating,
And nitrogen is dried up.Scanned Electronic Speculum is characterized, and the microscopic appearance that copper platinum is oxidized region is substantially identical with example 3 (Fig. 4).This implementation
Electrode prepared by example is by copper platinum and is attached to the nanometer Cu (OH) in oxidized region2Constitute, Cu (OH)2For diameter 100-150nm,
It is about 3-10 μm of individual layer hollow nanotube.
Glucose sensing approach
The nanometer Cu (OH) prepared with this example2Electrode is working electrode, and the depth for invading prepare liquid is still 1cm, i.e. quilt
Oxide regions, involved other examination of glucose concentration methods are identical with example 1.As a result show：It is 1- in concentration of glucose
In the range of 10mM, the linear relationship between concentration of glucose and response current is y=1.1345x+ 1.5728, and the linearity is
0.9983；In the range of concentration of glucose is 0.1-1mM, the linear relationship between concentration of glucose and response current is y=
1.3657x+0.3720, the linearity is 0.9993；Response time<2s, sensitivity is 1360 μ A/cm2/mM。
Embodiment 5
The preparation of nano copper hydroxide electrode
It is respectively 300nm with particle diameter and 50nm Alpha-alumina sanding and polishing by a diameter of 3mm straight type gold electrode, and point
Each ultrasonic 1min decontamination not in ethanol and deionized water.It is placed in after nitrogen drying as negative electrode in 25mL electroplate liquids, copper rod is
1min is electroplated under anode, 1mA constant current conditions, with deionized water rinsing, and nitrogen is dried up.Electroplate liquid is water-soluble for 25% copper sulphate
Liquid, wherein containing 5% sulfuric acid and micro polyethylene glycol and dodecyl sodium sulfate, can also take other manner copper facing, it is desirable to
Plate copper thickness and be more than 500nm.Gold electrode after copper facing is placed in the NaOH solution that 15mL concentration is 5M, electrochemical as anode
Oxidation is learned, using platinum plate electrode as negative electrode, constant electric current is 0.1mA, and oxidization time is 300s.Reaction is rushed after terminating with deionized water
Wash, and nitrogen is dried up.Scanned Electronic Speculum is characterized, the microscopic appearance of electrode surface manufactured in the present embodiment substantially with example 1 (Fig. 2)
It is identical.Electrode manufactured in the present embodiment is by gold electrode and is attached to the nanometer Cu (OH) on its surface2Constitute, Cu (OH)2For particle diameter
10-150nm hexahedron crystal grain.
Glucose sensing approach
The nanometer Cu (OH) prepared with this example2Electrode is the examination of glucose concentration method and the phase of example 1 of working electrode
Together.As a result show：In the range of concentration of glucose is 1-10mM, the linear relationship between concentration of glucose and response current is
Y=1.6010x+0.9042, the linearity is 0.9984；In the range of concentration of glucose is 0.1-1mM, concentration of glucose and sound
Linear relationship between induced current is y=1.7235x+0.2940, and the linearity is 0.9976；Response time<2s, sensitivity is
1720μA/cm2/mM。
Embodiment 6
The preparation of nano copper hydroxide electrode
By each ultrasonic 1min decontamination in ethanol and deionized water respectively of a diameter of 5mm graphite rod.Nitrogen drying is rearmounted
As negative electrode in 25mL electroplate liquids, the depth for controlling immersed in liquid level is 1cm, and copper rod is plating under anode, 1mA constant current conditions
2min, with deionized water rinsing, and nitrogen is dried up.Electroplate liquid composition is same as Example 5, can also take other manner copper facing,
It is required that plating copper thickness is more than 500nm.Graphite rod after copper facing is placed in the NaOH solution that 30mL concentration is 5M, is used as anode quilt
Electrochemical oxidation, using graphite rod as negative electrode, constant electric current is 0.6mA, and oxidization time is 1200s.Reaction uses deionization after terminating
Water is rinsed, and nitrogen is dried up.Scanned Electronic Speculum is characterized, graphite rod copper facing and be oxidized the microscopic appearance in region substantially with example 3
(Fig. 4) is identical.Electrode manufactured in the present embodiment is by graphite rod and is attached to the nanometer Cu (OH) in oxidized region2Constitute, Cu
(OH)2For diameter 100-150nm, it is about 3-10 μm of individual layer hollow nanotube..
Glucose sensing approach
The nanometer Cu (OH) prepared with this example2Electrode is the examination of glucose concentration method and the phase of example 1 of working electrode
Together.As a result show：In the range of concentration of glucose is 1-10mM, the linear relationship between concentration of glucose and response current is
Y=0.8234x+1.7735, the linearity is 0.9987；In the range of concentration of glucose is 0.1-1mM, concentration of glucose and sound
Linear relationship between induced current is y=1.0371x+0.4240, and the linearity is 0.9963；Response time<2s, sensitivity is
1000μA/cm2/mM。
Claims (10)
1. a kind of nano copper hydroxide electrode, by copper-based material and the nanometer Cu (OH) on the copper-based material surface is attached to2Layer
Constitute.
2. nano copper hydroxide electrode according to claim 1, it is characterised in that：The copper-based material is copper electrode, plating
Other conductive materials after copper electrode or copper facing；Copper facing in other conductive materials after wherein described copper-plating electrode or copper facing is thick
Degree is more than 500nm.
3. nano copper hydroxide electrode according to claim 1 or 2, it is characterised in that：The nanometer Cu (OH)2Layer is profit
With the nano copper hydroxide (Cu (OH) of method growth in situ on the surface of the copper-based material of electrochemical oxidation2) crystal
Layer.
4. nano copper hydroxide electrode according to claim 3, it is characterised in that：The nanometer Cu of described growth in situ
(OH)2For particle diameter 10-150nm hexahedron crystal grain or diameter 100-150nm, it is about 3-10 μm of individual layer hollow pipe or two
The mixture of person.
5. preparing the method for the nano copper hydroxide electrode any one of claim 1-4, comprise the steps：In NaOH
In solution, electrochemical oxidation is carried out by anode of the copper-based material, you can nanometer Cu (OH) is formed on the copper-based material2
Layer, so as to obtain the nano copper hydroxide electrode.
6. method according to claim 5, it is characterised in that：The concentration of the NaOH solution is 1-5M；
Graphite rod or platinum electrode can be used to carry out electrochemical oxidation for negative electrode；
The electrochemical oxidation is carried out under constant current conditions.
7. method according to claim 6, it is characterised in that：The electric current of the electrochemical oxidation is 0.05-2mA, oxidation
Time is 60-1200s.
8. application of the nano copper hydroxide electrode in glucose detection any one of claim 1-4.
9. a kind of glucose electrochemical detection method, comprises the steps：
1) using the nano copper hydroxide electrode any one of claim 1-4 as working electrode, platinum plate electrode is auxiliary electricity
Pole, Ag/AgCl is reference electrode formation three-electrode system, and the glucose of series of standards concentration is detected based on electrochemical workstation
The electric current of solution, draws current versus time curve；
2) relation between current density and concentration of glucose is fitted based on the current versus time curve, obtains electric current
Relation curve between density and concentration of glucose；
3) current density of unknown concentration sample is detected using the three-electrode system, it is dense according to the current density and glucose
Relation curve between degree, calculates the concentration of glucose of unknown sample.
10. method according to claim 9, it is characterised in that：Methods described step 1) in, the series of standards concentration
Glucose solution in the NaOH containing 10-100mM；
Concentration of glucose in the glucose solution of the series of standards concentration is respectively 1,2,3,4,5,6,7,8,9,10mM；
Step 1) detection in voltage constant be 0.4-0.6V.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111796014A (en) * | 2020-06-28 | 2020-10-20 | 华南理工大学 | Cerium dioxide modified copper hydroxide composite electrode and application thereof in glucose sensor |
| CN115656288A (en) * | 2022-10-20 | 2023-01-31 | 嘉庚创新实验室 | Foamy copper with surface coated with nano copper and application of foamy copper as enzyme-free glucose detection sensor |
Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN106226382A (en) * | 2016-08-08 | 2016-12-14 | 北京科技大学 | Nano porous copper/Cu (OH)2nano-wire array sensor electrode material and preparation method thereof |
| US20170168007A1 (en) * | 2012-09-06 | 2017-06-15 | Amrita Vishwa Vidyapeetham | Non-enzymatic glucose sensor |
-
2017
- 2017-04-18 CN CN201710251780.0A patent/CN106996953A/en active Pending
Patent Citations (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20170168007A1 (en) * | 2012-09-06 | 2017-06-15 | Amrita Vishwa Vidyapeetham | Non-enzymatic glucose sensor |
| CN106226382A (en) * | 2016-08-08 | 2016-12-14 | 北京科技大学 | Nano porous copper/Cu (OH)2nano-wire array sensor electrode material and preparation method thereof |
Non-Patent Citations (2)
| Title |
|---|
| LILI BIE等: "Hierarchical Cu/Cu(OH)2 nanorod arrays grown on Cu foam as a high-performance 3D self-supported electrode for enzyme-free glucose sensing", 《RSC ADVANCES》 * |
| SHENGHAI ZHOU 等: "Direct growth of vertically aligned arrays of Cu(OH)2 nanotubes for the electrochemical sensing of glucose", 《SENSORS AND ACTUATORS B:CHEMICAL》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111796014A (en) * | 2020-06-28 | 2020-10-20 | 华南理工大学 | Cerium dioxide modified copper hydroxide composite electrode and application thereof in glucose sensor |
| CN111796014B (en) * | 2020-06-28 | 2021-07-16 | 华南理工大学 | Cerium dioxide modified copper hydroxide composite electrode and application thereof in glucose sensor |
| CN115656288A (en) * | 2022-10-20 | 2023-01-31 | 嘉庚创新实验室 | Foamy copper with surface coated with nano copper and application of foamy copper as enzyme-free glucose detection sensor |
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