CN104569096A - Construction method and detection method of cuprous oxide membrane-based enzyme free-oxygen sensitive glucose photo electrochemical sensor - Google Patents
Construction method and detection method of cuprous oxide membrane-based enzyme free-oxygen sensitive glucose photo electrochemical sensor Download PDFInfo
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- CN104569096A CN104569096A CN201510062291.1A CN201510062291A CN104569096A CN 104569096 A CN104569096 A CN 104569096A CN 201510062291 A CN201510062291 A CN 201510062291A CN 104569096 A CN104569096 A CN 104569096A
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Abstract
The invention discloses a construction method of a cuprous oxide membrane-based enzyme free-oxygen sensitive glucose photo electrochemical sensor. The construction method comprises the following steps: with an ITO conductive glass as a working electrode, a platinum wire as a counter electrode and a silver/ silver chloride electrode as a reference electrode, inserting the three electrodes into a sodium hydroxide solution containing 0.05mol/L copper sulfate and 0.1mol/L sodium citrate, and regulating a pH value to be 11; under the conditions that the deposition temperature is 60 DEG C, the deposition potential is -0.4V and the deposition time is 20 minutes, forming a cuprous oxide membrane on the surface of the ITO conductive electrode; and rinsing residual solution on the surface with pure water, drying for 1h at the temperature of 100 DEG C, and forming a stable cuprous oxide membrane-based photocathode. According to the construction method disclosed by the invention, photocurrent detection based on light excitation is low in detection signal background and can have high detection sensitivity and stability without needing expensive instrument and equipment and complex sample treatment.
Description
Technical field
The invention belongs to instrumental analysis field tests, specifically a kind of construction method of the Optical Electro-Chemistry sensor for glucose detection and detection method.
Background technology
In clinical diagnostics, glucose is a kind of important analysis thing, because its high concentration can lead diabetogenic generation.At present, various correlation technique such as: infra-red sepectrometry, fluorescent spectrometry and photocaustic spectroscopy; Surface plasma resonance biosensor; Capacitance detecting method; Electrogenerated chemiluminescence method; Chromatmetry; And capillary electrophoresis has been used to the detection of glucose.These methods need more expensive instrument and equipment and more complicated sample pretreating usually.
Compare above-mentioned analytical technology, enzyme based electrochemical sensor demonstrates high selectivity and high sensitivity, but its poor stability, because glucose oxidase is subject to the impact of the materials such as pH value, humidity, temperature, ionic detergent.In order to address these problems, obtained the concern of analysis science man in recent years based on the non-enzymatic electrochemical sensor of glucose direct oxidation.The existing structure being used for effective enzyme-free glucose sensor based on nano particles such as platinum, gold, copper, platinum-lead, platinum-telluriums at present.But these sensors have the defects such as high cost, poor selectivity and instability, are not suitable for the detection of actual sample.In addition, also have based on the non-enzymatic glucose electrochemical sensor of nano-nickel oxide, cobaltosic oxide, manganese dioxide, ruthenic oxide, iron oxide, cupric oxide and cuprous oxide and report widely.Because above-mentioned material has the features such as low cost, high stability and polyelectron oxidation effect.
Compare electrochemical sensor, Optical Electro-Chemistry sensor has higher sensitivity, because it is combined by the light source be separated and electrochemical workstation, what it was measured is photocurrent, and this photocurrent such as to have at the bottom of signal background at the feature.Recently, bring up seminar and construct the sensitive glucose Optical Electro-Chemistry sensor of a kind of oxygen based on glucose oxidase decorated nanometer cadmium telluride.In order to solve the shortcoming of glucose oxidase self instability, Dong seminar has developed nm of gold/platinum-titania-based non-enzymatic Optical Electro-Chemistry sensor and has detected glucose.But this strategy needs expensive gold/nano platinum particle and tediously long modified electrode step.
Summary of the invention
Goal of the invention: the object of the invention is for the deficiencies in the prior art, provides a kind of and prepares single, environmental friendliness, the cuprous oxide base with low cost construction method without enzyme Optical Electro-Chemistry glucose sensor
Another object of the present invention is to provide a kind of uses above-mentioned cuprous oxide base to carry out the detection method of glucose detection without enzyme Optical Electro-Chemistry glucose sensor.
Technical scheme: cuprous oxide film base of the present invention, without the construction method of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, comprises the steps:
(1) ITO electro-conductive glass is cleaned, flushing operation at room temperature drying;
(2) using the ITO electro-conductive glass after step (1) processes as working electrode, platinum filament as to electrode, three electrodes, as contrast electrode, insert containing 0.02 ~ 0.08mol L by silver/silver chloride electrode
-1copper sulphate and 0.05 ~ 0.2mol L
-1in the sodium hydroxide solution of sodium citrate, adjusted to ph is 10 ~ 12;
(3) be 50 ~ 70 DEG C at depositing temperature, sedimentation potential is under the condition of-0.3 ~-0.5V, electro-deposition 15 ~ 30 minutes, forms cuprous oxide film at ITO conductive glass surface;
(4) residual solution on cuprous oxide film pure water rinse surface will prepared in step (3), and under 100 DEG C of conditions dry 1 hour, form stable cuprous oxide film base photocathode.
In the present invention, described ITO electro-conductive glass is of a size of 1 cm x 4 centimetres, and described in step (1), the cleaning method of ITO electro-conductive glass is: by described ITO electro-conductive glass containing 1mol L
-1clean in the cleaning fluid of NaOH and 0.6% hydrogen peroxide.
The purging method of ITO electro-conductive glass described in step (1) is: use acetone and ultrapure water to rinse successively the ITO electro-conductive glass after cleaning.
Preferably, in step (2), by the concentration of NaOH in adjustment solution, the pH value of adjustment solution is 11.
Cuprous oxide film base of the present invention, without the detection method of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, comprises the steps:
(1) using the ITO electro-conductive glass of cuprous oxide film base photocathode that obtains as working electrode, platinum filament as to electrode, three electrodes, as contrast electrode, are inserted 0.05 ~ 0.2molL containing finite concentration glucose by silver/silver chloride electrode
-1sodium hydroxide solution in;
(2) three-electrode system in step (1) is adopted, under the condition of 0.3 ~ 0.8V, to glucose pre-oxidation 4 ~ 12 seconds;
(3) m-electric current test technology when adopting, inclined current potential is-0.1 ~-0.3V, under the irradiation of simulated solar irradiation, carry out photosignal detection.
Testing result shows, and along with the increase of concentration of glucose, photocurrent becomes downtrending, and linear within the scope of finite concentration.
The reaction mechanism mechanism of reaction of the present invention is as follows:
Cu
2O+OH
-+H
2O→Cu(OH)
2+e
-(1)
Cu(OH)
2+OH
-→CuOOH+H
2O+e
-(2)
CuOOH+Glucose→Cu(OH)
2+Glucolactone (3)
Glucolactone+OH
-→Gluconic acid (4)
Cu(OH)
2+H
2O+e
-→Cu
2O+OH
-(5)
O
2+e
-→O
2 -.(6)
The increase of concentration of glucose, causes the decline of dissolved oxygen concentration, and then causes cuprous oxide base photocathode to flow down falling, and detects the concentration of glucose in actual sample based on this principle.
Beneficial effect: (1) cuprous oxide film of the present invention base detects based on the photocurrent under optical excitation without the construction method of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, detection signal background is low, do not need more expensive instrument and equipment and more complicated sample pretreating, higher detection sensitivity and stability can be had; Simultaneously without the need to enzyme modified electrode, there is cost low, easily make, the advantage that efficiency is high; (2) cuprous oxide base of the present invention without enzyme Optical Electro-Chemistry glucose sensor and non-enzymatic precious metal-based electrochemical glucose sensor as: based on the nano particles such as platinum, gold, copper, platinum-lead, platinum-tellurium enzyme-free glucose sensor compared with, it has that cost is low, selectivity good and the feature such as good stability; (3) cuprous oxide base of the present invention has wide (the 0.5-100 μm of ol L of the range of linearity without the display of enzyme Optical Electro-Chemistry glucose sensor experimental result
-1with 0.5-6mmol L
-1), low (the 0.3 μm of ol L of detection limit
-1), the feature such as environmental friendliness.
Accompanying drawing explanation
Fig. 1 is cuprous oxide film base of the present invention without the electrode reaction schematic diagram of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen;
Fig. 2 is low resolution (A) and high-resolution (B) the Electronic Speculum figure of the cuprous oxide film that the embodiment of the present invention 1 obtains;
Fig. 3 is X-ray diffraction (A) and UV-Vis diffuse reflection spectroscopy (B) figure of the cuprous oxide film that the embodiment of the present invention 1 obtains;
Fig. 4 is high-resolution x-ray photoelectron spectroscopy Cu 2p (A) and the O 1s (B) of the cuprous oxide film that the embodiment of the present invention 1 obtains;
Fig. 5 photocurrent curve (A) that to be cuprous oxide film base of the present invention change with concentration of glucose without the glucose Optical Electro-Chemistry sensor that enzyme-oxygen is sensitive and its quantitation curves (B);
Fig. 6 is the impact that the dopamine, ascorbic acid, uric acid, sodium chloride and composition thereof that may exist in actual sample detects without the glucose Optical Electro-Chemistry sensor that enzyme-oxygen is sensitive invention cuprous oxide film base.
Embodiment
Below by accompanying drawing, technical solution of the present invention is described in detail, but protection scope of the present invention is not limited to described embodiment.
Embodiment 1: a kind of cuprous oxide film base, without the construction method of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, comprises the steps:
(1) ITO electro-conductive glass is cut into 1 cm x 4 cm size, containing 1mol L
-1clean in the cleaning fluid of NaOH and 0.6% hydrogen peroxide, after cleaning, use acetone and ultrapure water carry out flushing and at room temperature dry successively;
(2) using the ITO electro-conductive glass after step (1) processes as working electrode, platinum filament as to electrode, three electrodes, as contrast electrode, insert containing 0.05mol L by silver/silver chloride electrode
-1copper sulphate and 0.1mol L
-1in the sodium hydroxide solution of sodium citrate, in adjustment solution, the concentration of NaOH, makes solution ph be 11;
(3) be 50 DEG C ~ 70 DEG C at depositing temperature, sedimentation potential is under the condition of-0.3V ~-0.5V, electro-deposition 20 minutes, forms cuprous oxide film at ITO conductive glass surface;
(4) residual solution on cuprous oxide film water rinse surface will prepared in step (3), and under 100 DEG C of conditions dry 1 hour, form stable cuprous oxide film base photocathode.
Fig. 2 is low resolution (A) and high-resolution (B) the Electronic Speculum figure of cuprous oxide in the present embodiment, can find out that ITO electro-conductive glass forms uniform film from figure (A), uniform membraneous material contributes to the catalytic oxidation performance improving glucose, can ensure the stability of photocathode; Can clearly find out from figure (B), the cube cuprous oxide of rule is of a size of 800nm.
Fig. 3 is X-ray diffraction (A) and UV-Vis diffuse reflection spectroscopy (B) figure of cuprous oxide in the present embodiment, can find out that cuprous oxide mainly grows along < 111 > crystal face from figure (A), all diffraction peaks can index be (JCPDS card no.78-2076), there is not impurity diffraction peak, show to have prepared high-purity cuprous oxide crystal; Can find out that cuprous oxide has good absorption within the scope of 200-800nm from figure (B), it contributes to improving electricity conversion thus improves Optical Electro-Chemistry detection sensitivity, its maximum absorption wavelength is 568nm, corresponding band gap magnitude is 2.18eV, again proves successfully to have synthesized cuprous oxide.
Fig. 4 is high-resolution x-ray photoelectron spectroscopy (A) Cu 2p and (B) O 1s of cuprous oxide in the present embodiment.Can see that copper relevant peaks type becomes symmetrical structure from figure (A), and combination corresponding to Cu 2p3/2 peak position can be 932.6eV, it can be summed up as 1 valency copper in cuprous oxide, the combination of O 1s can be 530.4eV on year-on-year basis, it can be summed up as the oxygen condition in cuprous oxide, successfully demonstrates again the structure of cupric oxide.
Carried out the detection method of glucose detection by described cuprous oxide film base without the glucose Optical Electro-Chemistry sensor that enzyme-oxygen is sensitive, comprise the steps:
(1) using the ITO electro-conductive glass that forms stable cuprous oxide film base photocathode as working electrode, platinum filament as to electrode, three electrodes, as contrast electrode, are inserted the 0.1molL containing finite concentration glucose by silver/silver chloride electrode
-1sodium hydroxide solution in;
(2) three-electrode system in step (1) is adopted, under the condition of 0.6V, to glucose pre-oxidation 8 seconds;
(3) m-electric current test technology when adopting, inclined current potential is-0.2V, under the irradiation of simulated solar irradiation, carry out photosignal detection.
Testing result shows, and along with the increase of concentration of glucose, photocurrent becomes downtrending, and linear within the scope of finite concentration.
Fig. 5 be along with concentration of glucose change photocurrent curve (A) and its quantitation curves (B).The range of linearity that can obtain this sensor from figure is 0.5-100 μm of ol L
-1with 0.5-6mmol L
-1, detection limit low is 0.3 μm of ol L
-1.
In order to illustrate that this sensor has good selectivity, add respectively in test fluid isocyatic ascorbic acid, dopamine, uric acid, sodium chloride with and composition thereof, control test is carried out according to above-mentioned steps.
Fig. 6 is the impact that the dopamine, ascorbic acid, uric acid, sodium chloride and composition thereof that may exist in actual sample detects glucose Optical Electro-Chemistry.Experiment proves, equimultiple concentration (0.1mol L
-1) dopamine, ascorbic acid, uric acid, sodium chloride and composition thereof do not disturb this sensor to the detection of glucose, show that the method has fabulous selectivity.
Embodiment 2: a kind of cuprous oxide film base, without the construction method of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, comprises the steps:
(1) ITO electro-conductive glass is cut into 1 cm x 4 cm size, containing 1mol L
-1clean in the cleaning fluid of NaOH and 0.6% hydrogen peroxide, after cleaning, use acetone and ultrapure water carry out flushing and at room temperature dry successively;
(2) using the ITO electro-conductive glass after step (1) processes as working electrode, platinum filament as to electrode, three electrodes, as contrast electrode, insert containing 0.02mol L by silver/silver chloride electrode
-1copper sulphate and 0.05mol L
-1in the sodium hydroxide solution of sodium citrate, in adjustment solution, the concentration of NaOH, makes solution ph be 10;
(3) be 50 DEG C at depositing temperature, sedimentation potential is under the condition of-0.3V, electro-deposition 15 minutes, forms cuprous oxide film at ITO conductive glass surface;
(4) residual solution on cuprous oxide film water rinse surface will prepared in step (3), and under 100 DEG C of conditions dry 1 hour, form stable cuprous oxide film base photocathode.
Carried out the detection method of glucose detection by described cuprous oxide film base without the glucose Optical Electro-Chemistry sensor that enzyme-oxygen is sensitive, comprise the steps:
(1) using the ITO electro-conductive glass that forms stable cuprous oxide film base photocathode as working electrode, platinum filament as to electrode, three electrodes, as contrast electrode, are inserted the 0.05mol L containing finite concentration glucose by silver/silver chloride electrode
-1sodium hydroxide solution in;
(2) three-electrode system in step (1) is adopted, under the condition of 0.3V, to glucose pre-oxidation 4 seconds;
(3) m-electric current test technology when adopting, inclined current potential is-0.1V, under the irradiation of simulated solar irradiation, carry out photosignal detection.
Testing result shows, and along with the increase of concentration of glucose, photocurrent becomes downtrending, and linear within the scope of finite concentration.In order to illustrate that this sensor has good selectivity, add respectively in test fluid isocyatic ascorbic acid, dopamine, uric acid, sodium chloride with and composition thereof, control test is carried out according to above-mentioned steps, and experiment proves equimultiple concentration (0.1mol L
-1) dopamine, ascorbic acid, uric acid, sodium chloride and composition thereof do not disturb this sensor to the detection of glucose, show that the method has fabulous selectivity.
Embodiment 3: a kind of cuprous oxide film base, without the construction method of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, comprises the steps:
(1) ITO electro-conductive glass is cut into 1 cm x 4 cm size, containing 1mol L
-1clean in the cleaning fluid of NaOH and 0.6% hydrogen peroxide, after cleaning, use acetone and ultrapure water carry out flushing and at room temperature dry successively;
(2) using the ITO electro-conductive glass after step (1) processes as working electrode, platinum filament as to electrode, three electrodes, as contrast electrode, insert containing 0.08mol L by silver/silver chloride electrode
-1copper sulphate and 0.2mol L
-1in the sodium hydroxide solution of sodium citrate, in adjustment solution, the concentration of NaOH, makes solution pH value be 12;
(3) be 70 DEG C at depositing temperature, sedimentation potential is under the condition of 0.5V, electro-deposition 30 minutes, forms cuprous oxide film at ITO conductive glass surface;
(4) residual solution on cuprous oxide film water rinse surface will prepared in step (3), and under 100 DEG C of conditions dry 1 hour, form stable cuprous oxide film base photocathode.
Carried out the detection method of glucose detection by described cuprous oxide film base without the glucose Optical Electro-Chemistry sensor that enzyme-oxygen is sensitive, comprise the steps:
(1) using the ITO electro-conductive glass that forms stable cuprous oxide film base photocathode as working electrode, platinum filament as to electrode, three electrodes, as contrast electrode, are inserted the 0.2molL containing finite concentration glucose by silver/silver chloride electrode
-1sodium hydroxide solution in;
(2) three-electrode system in step (1) is adopted, under the condition of 0.8V, to glucose pre-oxidation 12 seconds;
(3) m-electric current test technology when adopting, inclined current potential is-0.3V, under the irradiation of simulated solar irradiation, carry out photosignal detection.
Testing result shows, and along with the increase of concentration of glucose, photocurrent becomes downtrending, and linear within the scope of finite concentration.In order to illustrate that this sensor has good selectivity, add respectively in test fluid isocyatic ascorbic acid, dopamine, uric acid, sodium chloride with and composition thereof, control test is carried out according to above-mentioned steps, and experiment proves equimultiple concentration (0.1mol L
-1) dopamine, ascorbic acid, uric acid, sodium chloride and composition thereof do not disturb this sensor to the detection of glucose, show that the method has fabulous selectivity.
As mentioned above, although represented with reference to specific preferred embodiment and described the present invention, it shall not be construed as the restriction to the present invention self.Under the spirit and scope of the present invention prerequisite not departing from claims definition, various change can be made in the form and details to it.
Claims (5)
1. cuprous oxide film base is without a construction method for the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, it is characterized in that comprising the steps:
(1) ITO electro-conductive glass is cleaned, flushing operation at room temperature drying;
(2) using the ITO electro-conductive glass after step (1) processes as working electrode, platinum filament as to electrode, three electrodes, as contrast electrode, insert containing 0.02 ~ 0.08mol L by silver/silver chloride electrode
-1copper sulphate and 0.05 ~ 0.2mol L
-1in the sodium hydroxide solution of sodium citrate, adjusted to ph is 10 ~ 12;
(3) be 50 ~ 70 DEG C at depositing temperature, sedimentation potential is under the condition of-0.3 ~-0.5V, deposits 15 ~ 30 minutes, forms cuprous oxide film at ITO conductive glass surface;
(4) residual solution on cuprous oxide film pure water rinse surface will prepared in step (3), and under 100 DEG C of conditions dry 1 hour, form stable cuprous oxide film base photocathode.
2. cuprous oxide film base according to claim 1 is without the construction method of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, it is characterized in that, described ITO electro-conductive glass is of a size of 1 cm x 4 centimetres, and described in step (1), the cleaning method of ITO electro-conductive glass is: by described ITO electro-conductive glass containing 1mol L
-1clean in the cleaning fluid of NaOH and 0.6% hydrogen peroxide.
3. cuprous oxide film base according to claim 2 is without the construction method of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, it is characterized in that, the purging method of ITO electro-conductive glass described in step (1) is: use acetone and ultrapure water to rinse successively the ITO electro-conductive glass after cleaning.
4. cuprous oxide film base according to claim 1 is without the construction method of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, it is characterized in that, in step (2), by the concentration of NaOH in adjustment solution, and the pH value of adjustment solution.
5. cuprous oxide film base according to claim 1 is without the detection method of the sensitive glucose Optical Electro-Chemistry sensor of enzyme-oxygen, it is characterized in that comprising the steps:
(1) using the ITO electro-conductive glass of cuprous oxide film base photocathode that obtains as working electrode, platinum filament as to electrode, three electrodes, as contrast electrode, are inserted 0.05 ~ 0.2molL containing finite concentration glucose by silver/silver chloride electrode
-1sodium hydroxide solution in;
(2) three-electrode system in step (1) is adopted, under the condition of 0.3 ~ 0.8V, to glucose pre-oxidation 4 ~ 12 seconds;
(3) m-electric current test technology when adopting, inclined current potential is-0.1 ~-0.3V, under the irradiation of simulated solar irradiation, carry out photosignal detection.
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