CN107991371A - Cupric oxide non-enzymatic glucose electrochemical sensor - Google Patents
Cupric oxide non-enzymatic glucose electrochemical sensor Download PDFInfo
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Abstract
A kind of cupric oxide non-enzymatic glucose electrochemical sensor, belongs to detection technique field.The purpose of the present invention is synthesizing transition metal oxide CuO nano materials using easy preparation method, to build the cupric oxide non-enzymatic glucose electrochemical sensor of high sensitivity, wide detection range and low cost.Raspberry shape CuO raw materials of the present invention have copper nitrate, ethanol, P123, HMT, ethylene glycol prepare cupric oxide solid, prepared by cupric oxide solid dispersant liquid drop are applied to and handle working electrode of the spare glassy carbon electrode surface as non-enzymatic glucose sensor early period well, with saturated calomel electrode as reference electrode, platinum electrode is used as to electrode, three-electrode system is formed, so as to build non-enzymatic glucose sensor.The present invention realizes the accurate detection to glucose, and provides basic data and theories integration for its commercial application.CuO/GCE electrodes have excellent selectivity, from the interference of acrylic acid, ascorbic acid etc., are influenced from the chlorion in solution.Therefore, CuO/GCE has the performance of excellent detection glucose.
Description
Technical field
The invention belongs to detection technique field.
Background technology
As the glucose of one of the required compound of major vital, quickly, easily detect its concentration and given birth in social production
Every field living all seems most important, for example, in medical field, with the improvement of living standards, diabetes morbidity connects
Year rises, reliable it is particularly important that sensitively detecting prevention of the blood sugar concentration to diabetes, therefore, a kind of cheap, property of searching
The excellent glucose sensor of energy always is the research hotspot in sensor research field.In addition also contain in some industrial wastewaters
Glucose, such glucose is also usually it needs to be determined that its concentration.
Glucose electrode based on biology enzyme, was developed and perfect, enzyme glucose sensor tends into by more than 50 years
It is ripe.Whether contain enzyme according to the trim on electrode, electrochemical glucose sensor is divided into enzyme glucose sensor and non-
Enzymatic glucose sensor.But due to the unstability of biology enzyme, any generation enzyme glucose sensor is all subject to environmental factor
Restriction, and by glucose oxidase fix modification to electrode surface method it is sufficiently complex, such as electrochemical polymerization, covalently hand over
Connection, gel-sol mass trapping etc..Meanwhile, there be the shortcomings that its repeatability is low the reason for limiting the development of enzyme glucose sensor.
Therefore, function admirable, cheap non-enzymatic glucose sensor starts to obtain the extensive concern of researcher, and obtains
To extensive use.
If a variety of materials of the electrode modification owner of non-enzymatic glucose sensor using metallic element as activated centre, such as
Metal oxide, alloy, composite material based on carbon material etc..The common non-enzymatic glucose sensing based on metal material structure
Device has following several：Pt based sensors, Au based sensors etc., although having had numerous researchers in non-enzymatic glucose sensor
Research field achieve many achievements in research, still, find a kind of more easy electrode material preparation method, and be made
It is always non-enzymatic glucose sensing with high sensitivity, excellent selectivity and linear detection range electrode material as wide as possible
The popular direction of device development.It can be detected numerous among the material of concentration of glucose, precious metals pt, Au and its composite material tool
There is the shortcomings of price is high, is easily poisoned.
The content of the invention
The purpose of the present invention is synthesizing transition metal oxide CuO nano materials using easy preparation method, with structure
Build the cupric oxide non-enzymatic glucose electrochemical sensor of high sensitivity, wide detection range and low cost.
Raspberry shape CuO raw materials of the present invention have copper nitrate, ethanol, P123, HMT, ethylene glycol；Cupric oxide solid
Preparation：
（1）0.2 g P123 are weighed, are placed in 3.8 mL ethanol, by 15 min of its ultrasound, form stable uniform solution；
（2）0.399 g Cu (NO are separately added into solution3)2With 0.045 g HMT, 15 min of ultrasound, stable uniform is formed
Blue-green solution；
（3）46 mL ethylene glycol are added into above-mentioned solution, high density 30 min of ultrasound, form stable, uniform solution, be cooled to
Room temperature；
（4）Obtained solution is moved in 100 mL stainless steel hydrothermal reaction kettles, reacts 24 h in 200 DEG C；
（5）After reaction, question response kettle is cooled to room temperature, and reaction generation solid is centrifuged, sequentially using deionized water and second
Alcohol cleans three times to remove impurity, and dries 12 h in 60 DEG C of vacuum drying chambers, and then product is placed in tubular type Muffle furnace, with
The speed of 3 DEG C/min, which is warming up at 400 DEG C, roasts 2 h, obtains cupric oxide solid.
The present invention is by glass-carbon electrode successively with 0.3 μm and 0.05 μm of Al2O3Polishing powder sanding and polishing on chamois leather, so
5 min of ultrasound in deionized water and absolute ethyl alcohol successively afterwards, to remove the Al for remaining in electrode surface2O3Polishing powder, then will beat
The electrode N of milled2Drying；Using the GCE after polishing as working electrode, saturated calomel electrode electrode is as reference electrode, platinum
Silk electrode as to electrode in the 1 mM K containing 0.5 mol/L KCl3Fe(CN)6Cyclic voltammetry scan test is carried out in solution
To examine glass-carbon electrode whether to polish qualification；Scanning current potential is -0.1-0.6 V, and sweep speed is 50 mV/s, works as cyclic voltammetric
When the potential difference of oxidation peak and reduction peak is less than 85 mV in curve, glass-carbon electrode can be used for electrode modification, otherwise, beat again
Wear away and wash, untill reaching standard.
The present invention realizes the accurate detection to glucose, and provides basic data and theories integration for its commercial application.
CuO/GCE electrodes have excellent selectivity, from the interference of acrylic acid, ascorbic acid etc., from the chlorine in solution from
Son influences.Therefore, CuO/GCE has the performance of excellent detection glucose.
Brief description of the drawings
Fig. 1 is X-ray diffraction（XRD）Scanning carries out qualitative and crystalline structure to CuO materials；
Fig. 2 is scanning electron microscope（SEM）The features such as the pattern of product prepared by characterization, structure；
Fig. 3 is CuO/GCE and GCE detection glucose cyclic voltammetry curves；
Fig. 4 is CuO/GCE cyclic voltammetry curves in different glucose solution；
Fig. 5 is CuO/GCE cyclic voltammetry curves in various concentrations NaOH solution；
Fig. 6 is CuO/GCE different scanning rates cyclic voltammetry curve and peak current fit standard curve；a）：Difference sweeps fast circulation
Volt-ampere curve, b）：Peak current linear fit（A.0.50 V/s, b.0.40 V/s, c.0.30 V/s, d.0.20 V/s, e.0.10
V/s, f.0.05 V/s, g.0.01 V/s）；
Fig. 7 is CuO/GCE I-t curves and standard curve；a）：CuO/GCE I-t curves, b）：Grading current linear fit；
Fig. 8 is CuO/GCE selectivity tests；
Fig. 9 is X-ray diffraction（XRD）Characterization prepares the crystalline structure and composition of material；
Figure 10 is scanning electron microscope（SEM）The features such as the pattern of product prepared by characterization, structure；
Figure 11 is element composition and content, test result and analysis in CuO；a）：CuO SEM, b）：CuO EDS；
Figure 12 is atomic force microscope（AFM）The feature such as the thickness of CuO materials, 3D structures prepared by characterization；a）：CuO AFM,
b）：CuO AFM profiles；
Figure 13 is CuO/GCE and GCE detection glucose cyclic voltammetry curves；
Figure 14 is CuO/GCE cyclic voltammetry curves in different glucose solution；（A.0.5mM, b.1.0 mM, c.1.5
MM, d.2.0 mM, e.3.0 mM, f.2.5mM）；
Figure 15 is CuO/GCE cyclic voltammetry curves in various concentrations NaOH solution；（A.50 mM, b.75 mM, c.100 mM,
D.150 mM, e.200 mM, f.250 mM）；
Figure 16 is CuO/GCE different scanning rates cyclic voltammetry curve and peak current fit standard curve；a）：Difference sweeps fast circulation
Volt-ampere curve, b）：Peak current linear fit；（A.0.40 V/s, b.0.30 V/s, c.0.20 V/s, d.0.10 V/s, e.
0.05 V/s）；
Figure 17 is CuO/GCE I-t curves and standard curve；a）：CuO/GCE I-t curves, b）：Grading current linear fit；
Figure 18 is CuO/GCE selectivity and mithridatism test chart.
Embodiment
Raspberry shape CuO raw materials of the present invention have copper nitrate, ethanol, P123, HMT, ethylene glycol；Cupric oxide solid
Preparation：
（1）0.2 g P123 are weighed, are placed in 3.8 mL ethanol, by 15 min of its ultrasound, form stable uniform solution；
（2）0.399 g Cu (NO are separately added into solution3)2With 0.045 g HMT, 15 min of ultrasound, stable uniform is formed
Blue-green solution；
（3）46 mL ethylene glycol are added into above-mentioned solution, high density 30 min of ultrasound, form stable, uniform solution, be cooled to
Room temperature；
（4）Obtained solution is moved in 100 mL stainless steel hydrothermal reaction kettles, reacts 24 h in 200 DEG C；
（5）After reaction, question response kettle is cooled to room temperature, and reaction generation solid is centrifuged, sequentially using deionized water and second
Alcohol cleans three times to remove impurity, and dries 12 h in 60 DEG C of vacuum drying chambers, and then product is placed in tubular type Muffle furnace, with
The speed of 3 DEG C/min, which is warming up at 400 DEG C, roasts 2 h, obtains cupric oxide solid.
The present invention is by glass-carbon electrode successively with 0.3 μm and 0.05 μm of Al2O3Polishing powder sanding and polishing on chamois leather, so
5 min of ultrasound in deionized water and absolute ethyl alcohol successively afterwards, to remove the Al for remaining in electrode surface2O3Polishing powder, then will beat
The electrode N of milled2Drying；Using the GCE after polishing as working electrode, saturated calomel electrode electrode is as reference electrode, platinum
Silk electrode as to electrode in the 1 mM K containing 0.5 mol/L KCl3Fe(CN)6Cyclic voltammetry scan test is carried out in solution
To examine glass-carbon electrode whether to polish qualification；Scanning current potential is -0.1-0.6 V, and sweep speed is 50 mV/s, works as cyclic voltammetric
When the potential difference of oxidation peak and reduction peak is less than 85 mV in curve, glass-carbon electrode can be used for electrode modification, otherwise, beat again
Wear away and wash, untill reaching standard.
Embodiment 1
A kind of preparation of raspberry shape copper oxide material and structure non-enzymatic glucose sensor, include the preparation of raspberry shape cupric oxide,
The preparation of the raspberry shape cupric oxide：Weigh 0.2 g P123 to be dissolved in 3.8 mL ethanol, 15 min of ultrasound are added to dissolving
0.399 g copper nitrates and 0.045 g HMT ultrasounds obtain stablizing solution to dissolving, and add 46 mL ethylene glycol, high density ultrasound
30 min, fill 200 DEG C of axe at reaction 24 it is small when, obtain precipitation deionization wash three times, ethanol is washed three times, 60 DEG C of vacuum drying chamber
When drying 12 is small, obtains calcining 2 h at 400 DEG C of product, obtain cupric oxide solid.It is prepared by modified glassy carbon electrode：Weigh few
The solid is measured, adds 0.5% Nafion solution and ethanol solution, ultrasonic disperse to ink shape, early period is coated onto by the dispersant liquid drop
The glassy carbon electrode surface handled well, dries in air, CuO/GCE electrodes is obtained, for Electrochemical Detection glucose solution.
Embodiment 2
A kind of preparation of raspberry shape copper oxide material and structure non-enzymatic glucose sensor, include the preparation of raspberry shape cupric oxide,
The preparation of the raspberry shape cupric oxide：Weigh 0.1 g P123 to be dissolved in 3.8 mL ethanol, 15 min of ultrasound are added to dissolving
0.399 g copper nitrates and 0.070 g HMT ultrasounds obtain stablizing solution, add 46mL ethylene glycol, high density ultrasound 30 to dissolving
Min, when filling that reaction 24 is small at 200 DEG C of axe, obtains precipitation deionization and washes three times, ethanol is washed three times, and 60 DEG C of vacuum drying chamber is dry
It is dry 12 it is small when, obtain calcining 2 h at 400 DEG C of product, obtain cupric oxide solid.It is prepared by modified glassy carbon electrode：Weigh a small amount of
The solid, adds 0.5% Nafion solution and ethanol solution, ultrasonic disperse to ink shape, which was coated onto at early period
The glassy carbon electrode surface managed, dries in air, CuO/GCE electrodes is obtained, for Electrochemical Detection glucose solution.
Embodiment 3
A kind of preparation of raspberry shape copper oxide material and structure non-enzymatic glucose sensor, include the preparation of raspberry shape cupric oxide,
The preparation of the raspberry shape cupric oxide：Weigh 0.2 g P123 to be dissolved in 3.8 mL ethanol, 15 min of ultrasound are added to dissolving
0.399 g copper nitrates and 0.045 g HMT ultrasounds obtain stablizing solution to dissolving, and add 46 mL ethylene glycol, high density ultrasound
30 min, fill 200 DEG C of axe at reaction 12 it is small when, obtain precipitation deionization wash three times, ethanol is washed three times, 60 DEG C of vacuum drying chamber
When drying 12 is small, obtains calcining 2 h at 400 DEG C of product, obtain cupric oxide solid.It is prepared by modified glassy carbon electrode：Weigh few
The solid is measured, adds 0.5% Nafion solution and ethanol solution, ultrasonic disperse to ink shape, early period is coated onto by the dispersant liquid drop
The glassy carbon electrode surface handled well, dries in air, CuO/GCE electrodes is obtained, for Electrochemical Detection glucose solution.
Embodiment 4
A kind of preparation of raspberry shape copper oxide material and structure non-enzymatic glucose sensor, include the preparation of raspberry shape cupric oxide,
The preparation of the raspberry shape cupric oxide：Weigh 0.1 g P123 to be dissolved in 3.8 mL ethanol, 15 min of ultrasound are added to dissolving
0.399 g copper nitrates and 0.070 g HMT ultrasounds obtain stablizing solution to dissolving, and add 46 mL ethylene glycol, high density ultrasound
30 min, fill 200 DEG C of axe at reaction 12 it is small when, obtain precipitation deionization wash three times, ethanol is washed three times, 60 DEG C of vacuum drying chamber
When drying 12 is small, obtains calcining 2 h at 400 DEG C of product, obtain cupric oxide solid.It is prepared by modified glassy carbon electrode：Weigh few
The solid is measured, adds 0.5% Nafion solution and ethanol solution, ultrasonic disperse to ink shape, early period is coated onto by the dispersant liquid drop
The glassy carbon electrode surface handled well, dries in air, CuO/GCE electrodes is obtained, for Electrochemical Detection glucose solution.
Embodiment 5
A kind of preparation of raspberry shape copper oxide material and structure non-enzymatic glucose sensor, include the preparation of raspberry shape cupric oxide,
The preparation of the raspberry shape cupric oxide：Weigh 0.2 g P123 to be dissolved in 3.8 mL ethanol, 15 min of ultrasound are added to dissolving
0.399 g copper nitrates and 0.045 g HMT ultrasounds obtain stablizing solution to dissolving, and add 46 mL ethylene glycol, high density ultrasound
30 min, fill 200 DEG C of axe at reaction 24 it is small when, obtain precipitation deionization wash three times, ethanol is washed three times, 60 DEG C of vacuum drying chamber
When drying 12 is small, obtains calcining 1 h at 450 DEG C of product, obtain cupric oxide solid.It is prepared by modified glassy carbon electrode：Weigh few
The solid is measured, adds 0.5% Nafion solution and ethanol solution, ultrasonic disperse to ink shape, early period is coated onto by the dispersant liquid drop
The glassy carbon electrode surface handled well, dries in air, CuO/GCE electrodes is obtained, for Electrochemical Detection glucose solution.
Embodiment 6
CuO/GCE in embodiment 1-5 is used for Electrochemical Detection respectively, electrochemical property test is tested in electrochemical workstation is
Carried out on system, CuO/GCE is working electrode, and saturated calomel electrode is reference electrode, and platinum electrode forms three electricity for auxiliary electrode
Polar body system.Electrolyte is the sodium hydroxide solution of 0.1 M.Electrochemical operation instrument purchases Shanghai Chen Hua company.
The present invention is utilized respectively microwave assisting method and is prepared for CuO materials with solvent-thermal process method, is introduced in preparation process
Template P123, is played a role using its formation of unique structural property in the synthesis process to the microstructure of CuO.
Then the CuO materials prepared modify glassy carbon electrode surface respectively, obtain CuO/GCE working electrodes, and for building non-enzymatic
Glucose sensor, carries out Electrochemical Detection to concentration of glucose, analyzes the electrochemistry of the non-enzymatic glucose sensor of its structure
Performance.
First, auxiliary law CuO non-enzymatic glucose sensors chemical property
Prepare CuO characterization results and analysis
Pass through X-ray diffraction（XRD）Scanning carries out qualitative and crystalline structure to CuO materials and analyzes, the CuO XRD test knots of preparation
The results are shown in Figure 1 for fruit.
It can be seen from the figure that CuO has several principal character peaks, 2 θ=32.342 °, 35.316 °, 38.580 °,
48.663 °, 51.202 °, 53.306 °, 58.093 °, 61.430 °, 65.565 °, 67.668 °, 72.238 °, 74.850 ° it is right respectively
That has answered the CuO in CuO standard cards #72-0629 goes out peak position, and correspond to CuO's（110）、（002）、（111）、（11-
2）、（20-2）、（112）、（021）、（202）、（11-3）、（31-1）、（220）With（22-2）Crystal face, can from XRD spectrum
Go out, CuO characteristic peaks are obvious, and intensity is big, occur almost without other miscellaneous peaks, illustrate CuO samples almost without impurity, and crystallinity
It is good, it was demonstrated that to successfully synthesize CuO materials.
CuO SEM are characterized
Pass through scanning electron microscope（SEM）The features such as the pattern of product prepared by characterization, structure.Test result and analysis are as schemed
Shown in 2.
It can be seen from the figure that the CuO of gained is the bulk material of surfacing after roasting, block structure is smooth, structure
Substantially, by being contrasted with scale, it can be seen that the size of block structure is 500nm or so, and product structure is uniform, in this scanning
The block structure of this surfacing is substantially in region.
CuO non-enzymatic glucose sensor chemical properties
It is prepared by CuO/GCE
Pretreated glass-carbon electrode is spare.CuO materials are added in the mixed solution of Nafion and absolute ethyl alcohol, ultrasound
The black suspension solution of stable uniform is dispersed to, takes the 10 μ L dispersant liquid drops to be applied to and handles spare glass-carbon electrode table early period well
Face, in N2Dried under protection, up to CuO modified electrodes（CuO/GCE）And as the working electrode of non-enzymatic glucose sensor, satisfy
With calomel electrode as reference electrode, platinum electrode is used as to electrode, forms three-electrode system.Build non-enzymatic glucose sensing
Device.
CuO/GCE is compared with GCE cyclic voltammetry curves
By cupric oxide modified electrode（CuO/GCE）With bare electrode（GCE）Compare, CuO/GCE and GCE are placed in NaOH concentration respectively
For 100 mM, concentration of glucose is in the bottom liquid of 2 mM, carries out cyclic voltammetric（C-V）Scanning, scanning voltage scope is -0.2-
0.8 V, sweep speed are 50 mV/s, and the results are shown in Figure 3.
Response current of the glucose on naked GCE surfaces is extremely weak, left in 0.45 V after suitable CuO is modified on GCE surfaces
It is right obvious oxidation peak current occur.And other electric currents all accordingly strengthen, illustrate that CuO lives glucose with electrochemical catalysis
Property, CuO modification GCE electrodes after, oxidation peak current is remarkably reinforced, this is attributed to the fact that the excellent electro-chemical activities of CuO, and sheet
The good electric conductivity and catalytic activity that improve electrode of CuO materials, electron transmission speed is accelerated, it is possible thereby to prove
CuO modification GCE electrodes have the ability of detection glucose.
Concentration of glucose influences CuO/GCE
In order to study applicability of the GCE electrodes of CuO modifications in non-enzymatic glucose sensor, CuO/GCE is in 100 mM for research
The cyclic voltammetry curve of different glucose is detected in NaOH solution, C-V sweep speeds are 50 mV/s, and detection glucose is dense
Spend for 0.5-3.0mM, as shown in Figure 4.
With the increase of concentration of glucose, the sweep current of CuO/GCE also increases therewith, and concentration is bigger, sweep current
It is bigger, therefore CuO/GCE has good electrochemical properties to the glucose of various concentrations.Increase to 3mM in concentration of glucose
When, due to consumption and the upper limit of detection beyond CuO/GCE of electrode surface CuO, it is 2.5mM electric currents to occur than concentration of glucose
The phenomenon to diminish.
NaOH concentration influences CuO/GCE
Concentration of glucose is detected in alkaline conditions, and under the conditions of same potential, identical concentration of glucose, high concentration NaOH is molten
Liquid can provide more hydroxyl radical free radicals, and therefore, changing for NaOH concentration can produce glucose detection certain influence.
Cyclic voltammetry curves of the CuO/GCE in the NaOH solution of various concentrations to 2 mM glucose detections is as shown in figure 5, C-V's sweeps
It is 50 mV/s to retouch speed, and NaOH concentration is 50-200 mM.
With the increase of NaOH concentration, response current gradually increases.
Sweep speed influences CuO/GCE
CuO/GCE in 100 mM NaOH solutions, detectable concentration be 2 mM glucose, modulation sweep speed for 0.01 V/s,
0.05 V/s, 0.10 V/s, 0.20 V/s, 0.30 V/s, 0.40 V/s, 0.50 V/s, its cyclic voltammetry curve and analysis are such as
Shown in Fig. 6.
With the increase of sweep speed, response current changes, and to peak current fit standard curve, gained equation is such as
Shown in formula 4-1.
（4-1）
Wherein, y represents current density, and x represents sweep speed, it is seen then that peak current is directly proportional to sweep speed, coefficient R2=
0.99416, peak current is linearly related with sweep speed, and it is one typical to the electrocatalytic oxidation of glucose to show CuO/GCE
Adsorption controls the electrochemical behavior of process.
Current-vs-time method detects CuO/GCE
Detected first by cyclic voltammetric and determine its redox peaks appearance voltage, and select it to be detected as current-vs-time method
Initial potential, it is 0.55 V to obtain the spike potential that goes out of CuO/GCE by detection, under 0.55 V voltages, in 100 mM NaOH
Glucose is continuously added in solution and carries out current-vs-time method test（I-t）, test and analysis result are as shown in Figure 7.
In the system, Electrochemical Detection, CuO/GCE successfully are realized to 2.0 mM glucose solutions to 520 nM of concentration
Linear response up to 1.5 mM（R2=0.99145）, and fast response time, is adding glucose immediate current, that is, become
Change, electric current has been stablized in several seconds, and CuO/GCE sensitivity is 2491.362 μ Acm-2·mM-1, test limit as low as 83nM（S/
N=3）.Block structure smooth CuO prepared by microwave assisting method has larger specific surface area, when electrochemical reaction
More electronics can be provided, therefore, material has more excellent electrochemical properties, shows that CuO/GCE realizes glucose
Good Electrochemical Detection.
CuO/GCE selectivity, mithridatism detection
Be sequentially added into the mixed solution of 100 mM NaOH and 2 mM glucose 0.1 mM acrylic acid, 0.1 mM uric acid,
0.1 mM ascorbic acid, 200 mM NaCl, CuO/GCE still realize glucose accurate detection, in detection process,
The presence of other impurities does not change the size of response current, illustrates that CuO/GCE has good selectivity.Containing chlorion
Glucose alkaline solution in, chlorion in solution to CuO/GCE electrodes when detecting glucose almost without impacting,
Size of current does not change, and illustrates that chlorion does not damage the electrode, therefore CuO/GCE has certain mithridatism,
As shown in Figure 8.
2nd, the characterization result of synthetic method CuO and analysis
CuO XRD characterizations
Pass through X-ray diffraction（XRD）Characterization prepares the crystalline structure and composition of material, and solvent-thermal process method prepares CuO XRD and surveys
Test result and analysis are as shown in Figure 9.
CuO has several principal character peaks, 2 θ=32.342 °, 35.316 °, 38.580 °, 48.663 °, 51.202 °,
53.306 °, 58.093 °, 61.430 °, 65.565 °, 67.668 °, 72.238 °, 74.850 ° have corresponded to CuO's respectively（110）、
（002）、（111）、（200）、（20-2）、（112）、（021）、（202）、（11-3）、（31-1）、（220）With（22-2）Crystal face, from
As can be seen that CuO characteristic peaks are obvious in XRD spectrum, occur almost without other miscellaneous peaks, illustrate CuO samples almost without impurity, and
Good crystallinity, i.e. this Success in Experiment have synthesized CuO materials.
CuO SEM are characterized
Pass through scanning electron microscope（SEM）The features such as the pattern of product prepared by characterization, structure.Test result and analysis are as schemed
Shown in 10.
It can be seen from the figure that the CuO of gained is that surface has raised bulk material after roasting, block structure upper process is bright
It is aobvious, by being contrasted with scale, it can be seen that the raised size in block structure is about 100 nm, this surface bulge shape structure tool
There is larger specific surface area, product structure is uniform, and this surface bulge structure is substantially in this scanning area.
CuO EDS are characterized
By the element composition and content in the prepared CuO of energy disperse spectroscopy characterization, test result and analysis are as shown in figure 11.
It can be seen from the figure that Cu and O elements are comprised only in CuO, and without the appearance of other impurity peaks, the weight of O and Cu
Percentage（Wt %）For 21.37%, 78.63%, atomicity percentage（At %）For 51.91%, 48.09%, it may be determined that at this
In scanning electron microscope region, copper is comprised only.
CuO AFM are characterized
Pass through atomic force microscope（AFM）The feature such as the thickness of CuO materials, 3D structures prepared by characterization.Test result and analysis
As shown in figure 12.
As can be seen from Figure, the CuO materials synthesized by the experiment are bulge-structure, the material in this scanning range
Projection thickness be 107.8 nm, which significantly increases the specific surface area of CuO materials, can be provided in reaction more
Contact area, there is provided more avtive spots.
Synthetic method CuO non-enzymatic glucose sensor chemical properties
The preparation of CuO/GCE
Glass-carbon electrode processing early period is spare.The Nafion of 25 μ L 0.5% is taken to be dissolved in 475 μ L absolute ethyl alcohols, then to the solution
0.0115 g CuO materials of middle addition, after ultrasonic disperse, take the 10 μ L dispersant liquid drops to be applied to the glassy carbon electrode surface after polishing,
N2In dry, it is dry after up to CuO modified electrodes（CuO/GCE）And as the working electrode of non-enzymatic glucose sensor, saturation
As reference electrode, platinum electrode is used as to electrode calomel electrode, forms three-electrode system.
CuO/GCE is compared with GCE
By CuO/GCE compared with GCE, it is 100 mM that CuO/GCE and GCE are placed in NaOH concentration respectively, concentration of glucose 2
In the bottom liquid of mM, cyclic voltammetric is carried out（C-V）Scanning, scanning voltage scope is -0.2-0.8 V, and sweep speed is 50 mV/s,
As a result it is as shown in figure 13.
Response current of the glucose on naked GCE surfaces is extremely weak, left in 0.45 V after suitable CuO is modified on GCE surfaces
It is right obvious oxidation peak current occur, and other electric currents all accordingly strengthen, and illustrate that CuO lives glucose with electrochemical catalysis
Property[91], CuO modification GCE electrodes after, oxidation peak current is remarkably reinforced, this is attributed to the fact that the specific surface area of CuO super larges, makes its tool
There is more preferable electro-chemical activity, improve the electric conductivity and catalytic activity of electrode, accelerate electron transmission speed, it was demonstrated that CuO is repaiied
Adorn the ability that GCE electrodes have detection glucose.
Concentration of glucose influences CuO/GCE
In order to study the GCE electrodes of CuO modifications in the applicability of non-enzymatic glucose sensor, this experimental study CuO/GCE is 100
The cyclic voltammetry curve of different glucose is detected in mM NaOH solutions, C-V sweep speeds are 50 mV/s, detect glucose
Concentration is 0.5-3.0mM, as a result as shown in figure 14.
With the increase of concentration of glucose, the sweep current of CuO/GCE also increases therewith, and concentration is bigger, sweep current
Bigger, still, when concentration of glucose is 3.0 mM, electric current diminishes this is because the concentration of glucose exceeds the sensor
Linear detection range the reason for.Therefore CuO/GCE has good electrochemical properties to the glucose of various concentrations.
NaOH concentration influences CuO/GCE
Concentration of glucose is detected in alkaline conditions, and under the conditions of same potential, identical concentration of glucose, high concentration NaOH is molten
Liquid can provide more hydroxyl radical free radicals, and therefore, changing for NaOH concentration can produce glucose detection certain influence.
CuO/GCE is as shown in figure 15 to the cyclic voltammetry curve of 2 mM glucose detections in the NaOH solution of various concentrations, and C-V's sweeps
It is 50 mV/s to retouch speed, and NaOH concentration is 50-250 mM.
As can be seen from Figure 14, as the increase of NaOH concentration, response current gradually increase；When NaOH concentration increases to
200 mM and 250 mM, response current incrementss very little, this is related with GCE surfaces, the load capacity of CuO.
Sweep speed influences CuO/GCE
CuO/GCE in 100 mM NaOH solutions, detectable concentration be 2 mM glucose, modulation sweep speed for 0.05 V/s,
0.10 V/s, 0.20 V/s, 0.30 V/s, 0.40 V/s, its cyclic voltammetry curve and analysis are as shown in figure 16.
With the increase of sweep speed, response current changes, and to peak current fit standard curve, gained equation is such as
Shown in formula 4-2.
（4-2）
Wherein, y represents current density, and x represents sweep speed, it is seen then that peak current is directly proportional to sweep speed, coefficient R2=
0.99399, it is the electrochemical scholarship and moral conduct of a typical adsorption control process to the electrocatalytic oxidation of glucose to show CuO/GCE
For.
Current-vs-time method detects CuO/GCE
Detected by cyclic voltammetric and determine its redox peaks appearance voltage, and select it as the first of current-vs-time method detection
Beginning current potential, the spike potential that goes out that CuO/GCE is obtained by detection is 0.58V, under the initial voltage of 0.58 V, in 100 mM
Glucose is added in NaOH solution and carries out current-vs-time method test（I-t）, test and analysis result are as shown in figure 17.
In the system, Electrochemical Detection, CuO/GCE successfully are realized to 6.5 mM glucose solutions to 179 nM of concentration
Linear response up to 3.5 mM（R2=0.9935）, and fast response time, is adding glucose immediate current, that is, become
Change, electric current has been stablized in 2 s, and sensitivity is 2810.01 μ Acm-2·mM-1, test limit as low as 59nM（S/N=3）.Therefore,
The raspberry shape CuO materials have more excellent electrochemical properties, show that CuO/GCE realizes glucose good electrochemistry
Detection.
CuO/GCE selectivity, mithridatism
Be sequentially added into the mixed solution of 100 mM NaOH and 2 mM glucose 0.1 mM acrylic acid, 0.1 mM uric acid,
0.1 mM ascorbic acid, 200 mM NaCl, CuO/GCE still realize glucose accurate detection, in detection process,
The presence of other impurities does not change the size of response current, illustrates that CuO/GCE has the good property selected.Containing chlorion
Glucose alkaline solution in, chlorion in solution to CuO/GCE electrodes when detecting glucose almost without impacting,
Size of current does not change, and illustrates chlorion not to the damaging property of electrode, therefore CuO/GCE has necessarily antitoxin
Property, as shown in figure 18.
（1）Using auxiliary law and the method for roasting, under the conditions of existing for template P123, it is smooth surface has been synthesized
Block structure CuO materials.Prove that synthesized material is CuO materials by characterizing, product purity is high, and better crystallinity degree, does not have
Other impurities produce.And prove the bulk material that synthesized CuO materials are regular uniform.
（2）Using CuO materials modification to glassy carbon electrode surface, CuO/GCE electrodes are obtained, and it is non-for building electrochemistry
Enzymatic glucose sensor, in alkaline conditions, carries out cyclic voltammetry scan, and CuO/GCE electrodes can be used for examination of glucose concentration,
And when detecting concentration of glucose, electrochemistry is controlled for typical adsorption in the electrochemical reaction that electrode surface is carried out
Behavior.The sensitivity of the non-enzymatic glucose sensor can reach 2491.236 μ Acm-2·mM-1, detection range 520nM
To 2mM, Monitoring lower-cut 83nM（S/N=3）, and be swift in response, it is good to show that CuO/GCE has when detecting glucose solution
Property.CuO/GCE when detecting concentration of glucose from the interference of acrylic acid, uric acid, ascorbic acid, be not subject to Chlorine in Solution from
The influence of sub- concentration, illustrates that CuO/GCE has good selectivity and mithridatism.
（3）Since auxiliary law is when synthesizing CuO, the control to synthetic pattern is not especially desirable, synthesized CuO
Block microstructure specific surface area is small, and active sites points are less, and electrochemical properties are weak, causes microwave method synthesis CuO structures
The detection range of non-enzymatic glucose sensor is narrow, and sensitivity is not high.Therefore seek thermal synthesis method and prepare CuO materials, optimize CuO materials
The chemical property of material, realizes the Sensitive Detection to glucose.
（4）Using thermal synthesis method and the method for roasting, under the conditions of existing for template P123, surface has been synthesized with micro-
Small protrusion, the CuO particulates of raspberry shape, prove that synthesized material is exactly CuO materials by characterizing, do not contain other materials, pure
Degree is high, better crystallinity degree, and proves that synthesized CuO materials have the structure of surface bulge, and even structure, raised size are
100 nm or so.
（5）By CuO materials modification made from hot method to glassy carbon electrode surface, obtain CuO/GCE electrodes and be used to build non-enzymatic
Glucose sensor, in alkaline solution, carries out Electrochemical Detection to glucose, realizes the detection to concentration of glucose, and
And the electrochemical reaction occurred when electrode surface carries out electrocatalytic oxidation to glucose is that typical adsorption controls electricity
Chemical behavior, reaction rate are unrelated with the concentration of glucose in solution.By the measurement of current-vs-time method, hot method CuO/ is obtained
The detection range of GCE electrodes is 179nM to 6.5mM, and detection sensitivity is 2810.01 μ Acm-2·mM-1, Monitoring lower-cut is as low as
59nM（S/N=3）, CuO/GCE realizes the detection to the wide detection range of high sensitivity of glucose and the reaction time exists substantially
2 s or so are completed.This presence for being mainly attributed to prepare the template P123, P123 that are introduced in raw material causes the CuO synthesized
The microscopic appearance of material has the raspberry shape of protrusion for surface, and such pattern significantly increases the specific surface area of CuO, right
More avtive spots can be provided during the electrocatalysis oxidation reaction of glucose and participate in reaction.CuO/GCE electrodes have excellent at the same time
Good selectivity, from the interference of acrylic acid, ascorbic acid etc., influences from the chlorion in solution.Therefore, CuO/
GCE has the performance of excellent detection glucose.
Claims (2)
- A kind of 1. cupric oxide non-enzymatic glucose electrochemical sensor, it is characterised in that：The raspberry shape CuO raw materials have nitric acid Copper, ethanol, P123, HMT, ethylene glycol；The preparation of cupric oxide solid：（1）0.2 g P123 are weighed, are placed in 3.8 mL ethanol, by 15 min of its ultrasound, form stable uniform solution；（2）0.399 g Cu (NO are separately added into solution3)2With 0.045 g HMT, 15 min of ultrasound, form stable uniform Blue-green solution；（3）46 mL ethylene glycol are added into above-mentioned solution, high density 30 min of ultrasound, form stable, uniform solution, be cooled to Room temperature；（4）Obtained solution is moved in 100 mL stainless steel hydrothermal reaction kettles, reacts 24 h in 200 DEG C；（5）After reaction, question response kettle is cooled to room temperature, and reaction generation solid is centrifuged, sequentially using deionized water and second Alcohol cleans three times to remove impurity, and dries 12 h in 60 DEG C of vacuum drying chambers, and then product is placed in tubular type Muffle furnace, with The speed of 3 DEG C/min, which is warming up at 400 DEG C, roasts 2 h, obtains cupric oxide solid.
- 2. cupric oxide non-enzymatic glucose electrochemical sensor according to claim 1, it is characterised in that：By glass-carbon electrode according to Secondary 0.3 μm and 0.05 μm of Al2O3Polishing powder sanding and polishing on chamois leather, then successively in deionized water and absolute ethyl alcohol Middle ultrasonic 5 min, to remove the Al for remaining in electrode surface2O3Polishing powder, then the electrode N that will have been polished2Drying；With polishing GCE afterwards is as working electrode, and for saturated calomel electrode electrode as reference electrode, platinum electrode is used as is containing 0.5 to electrode The 1 mM K of mol/L KCl3Fe(CN)6Cyclic voltammetry scan test is carried out in solution to examine glass-carbon electrode whether to polish qualification； Scanning current potential is -0.1-0.6 V, and sweep speed is 50 mV/s, when oxidation peak in cyclic voltammetry curve and the potential difference of reduction peak During less than 85 mV, glass-carbon electrode can be used for electrode modification, otherwise, polishing washing again, untill reaching standard.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
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Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110172417A1 (en) * | 2008-07-09 | 2011-07-14 | Postech Academy-Industry Foundation | Heterogeneous Copper Nanocatalyst and Manufacturing Methods Thereof |
| CN103050702A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery |
| CN106865627A (en) * | 2017-02-28 | 2017-06-20 | 四川理工学院 | Ultra-thin Ni Co layer structure hydroxide and its preparation method and application |
| CN106896151A (en) * | 2017-03-01 | 2017-06-27 | 西南交通大学 | A kind of preparation method for detecting the cupric oxide chemically modified electrode of glucose |
-
2017
- 2017-11-10 CN CN201711102154.1A patent/CN107991371B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20110172417A1 (en) * | 2008-07-09 | 2011-07-14 | Postech Academy-Industry Foundation | Heterogeneous Copper Nanocatalyst and Manufacturing Methods Thereof |
| CN103050702A (en) * | 2011-10-17 | 2013-04-17 | 中国科学院大连化学物理研究所 | Application of carbon material containing in-situ doped component with catalytic activity to lithium-air battery |
| CN106865627A (en) * | 2017-02-28 | 2017-06-20 | 四川理工学院 | Ultra-thin Ni Co layer structure hydroxide and its preparation method and application |
| CN106896151A (en) * | 2017-03-01 | 2017-06-27 | 西南交通大学 | A kind of preparation method for detecting the cupric oxide chemically modified electrode of glucose |
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|---|---|---|---|---|
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| CN110550649A (en) * | 2019-08-23 | 2019-12-10 | 安徽大学 | Porous copper oxide nanobelt assembled film, electrode plate, preparation method and application thereof |
| CN113130950B (en) * | 2019-12-30 | 2022-07-12 | 大连大学 | Method for constructing maltose fuel cell by electrocatalytic oxidation of maltose solution by CuO/nickel foam electrode |
| CN113130950A (en) * | 2019-12-30 | 2021-07-16 | 大连大学 | Method for constructing maltose fuel cell by electrocatalytic oxidation of maltose solution by CuO/nickel foam electrode |
| CN112858405A (en) * | 2021-01-14 | 2021-05-28 | 东北大学 | Cu for non-enzymatic blood sugar detection2Preparation method of O yolk shell nanospheres |
| CN114002305A (en) * | 2021-11-02 | 2022-02-01 | 怀化学院 | Electrochemical sensor based on nano-matrix supported bimetallic catalyst and manufacturing method and application thereof |
| CN114660147A (en) * | 2022-03-29 | 2022-06-24 | 重庆医科大学 | Based on Fe doped NiMoO4Non-enzymatic glucose electrochemical sensor and preparation method and application thereof |
| CN114660147B (en) * | 2022-03-29 | 2023-09-15 | 重庆医科大学 | Based on Fe doped NiMoO 4 Non-enzymatic glucose electrochemical sensor and preparation method and application thereof |
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