CN114460151A - Non-bias enzymatic glucose photoelectrochemical sensing electrode and preparation method thereof - Google Patents
Non-bias enzymatic glucose photoelectrochemical sensing electrode and preparation method thereof Download PDFInfo
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- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3271—Amperometric enzyme electrodes for analytes in body fluids, e.g. glucose in blood
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- G01N—INVESTIGATING OR ANALYSING MATERIALS BY DETERMINING THEIR CHEMICAL OR PHYSICAL PROPERTIES
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- G01N27/26—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means by investigating electrochemical variables; by using electrolysis or electrophoresis
- G01N27/28—Electrolytic cell components
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- G01N27/305—Electrodes, e.g. test electrodes; Half-cells optically transparent or photoresponsive electrodes
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- G01N27/00—Investigating or analysing materials by the use of electric, electrochemical, or magnetic means
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- G01N27/327—Biochemical electrodes, e.g. electrical or mechanical details for in vitro measurements
- G01N27/3275—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction
- G01N27/3278—Sensing specific biomolecules, e.g. nucleic acid strands, based on an electrode surface reaction involving nanosized elements, e.g. nanogaps or nanoparticles
Abstract
The invention belongs to the field of photoelectrochemistry, and discloses a non-bias enzymatic glucose photoelectrochemistry sensing electrode and a preparation method thereof, wherein the non-bias enzymatic glucose photoelectrochemistry sensing electrode sequentially comprises a glucose oxidase layer, a metal nanoparticle layer, an n-type semiconductor thin film layer, a metal thin film layer and a planar insulating substrate along the incident direction of light; the metal thin film layer and the n-type semiconductor thin film layer form ohmic contact; the metal nano particle layer and the n-type semiconductor thin film layer form Schottky contact; an optical resonant cavity is formed among the metal thin film layer, the n-type semiconductor thin film layer and the metal nano particle layer. When a light source irradiates the sensing electrode, the metal nanoparticle layer and the n-type semiconductor thin film layer can generate effective light absorption to respectively generate a hot electron hole pair and a photo-generated electron hole pair; under the action of the Schottky junction, the hot holes and the photoproduction holes are transferred to glucose molecules through the catalytic action of glucolase; the detection of the glucose concentration is realized by monitoring the change of the photocurrent.
Description
Technical Field
The invention belongs to the field of photoelectrochemistry, and relates to a photoelectrochemical sensing electrode for glucose and a preparation method thereof.
Background
Diabetes is a common disease, and detecting the content of glucose in blood and urine is an indispensable means for diagnosing diabetes. The main methods for detecting glucose include spectroscopic methods, mass spectrometry, electrochemical methods and photoelectrochemical methods. Among them, the photoelectrochemical sensing is a detection method developed in recent years. A photoelectrochemical sensor is a device that analyzes a target based on the photoelectrochemical response of a photoelectrode. When effective illumination is introduced, the photoelectrode absorbs photons to form photo-generated electrons and holes, and the photo-generated electrons and the holes participate in chemical generation of a target or other substances in background liquid to cause photocurrent or photovoltage change. The photocurrent or photovoltage exhibits a regular change as the concentration of the target analyte changes. The photoelectrochemical sensor is also considered to be an improved electrochemical sensor, which not only has the characteristics of the traditional electrochemical sensor (such as fast response speed and high sensing sensitivity), but also has attracted extensive attention because the separation of the excitation signal and the detection signal leads to the significant improvement of the device in terms of background noise, minimum detection limit and convenience of operation compared with the traditional electrochemical sensor. However, the current photoelectrochemical sensor has disadvantages of high minimum detection limit, small detectable concentration range, and the need of applying working voltage when detecting glucose (e.g., W.K.Yang, ACS appl.Nano mater, 2020, 3(3), 2723-.
Disclosure of Invention
The invention provides a non-bias enzymatic glucose photoelectrochemical sensing electrode and a preparation method thereof, aiming at solving the problems that a glucose photoelectrochemical sensing system in the prior art needs additional working voltage, has higher minimum detection limit and small detectable concentration range.
The technical scheme is as follows:
a non-biased enzymatic glucose photoelectrochemical sensing electrode having a composite layered structure, comprising: the light-emitting diode comprises a glucose oxidase layer, a metal nanoparticle layer, an n-type semiconductor thin film layer, a metal thin film layer and a planar insulating substrate in sequence along the incident direction of incident light; the metal film layer is used as a back conductive layer and a light reflection layer of the glucose photoelectrochemistry sensing electrode at the same time; part of metal elements in the metal thin film layer are doped into the n-type semiconductor thin film layer, and ohmic contact is formed between the metal thin film layer and the metal thin film layer; an optical resonant cavity is formed among the metal thin film layer, the n-type semiconductor thin film layer and the metal nano particle layer; the n-type semiconductor thin film layer absorbs incident light in a band-to-band manner to generate photo-generated electron-hole pairs; the metal nano particle layer forms in-band absorption on incident light to generate hot electron holes and hot hole pairs; the metal nanoparticle layer and the n-type semiconductor thin film layer form Schottky contact, and partial hot electrons generated by light absorption of the metal nanoparticle layer are injected into the n-type semiconductor thin film layer; the glucose oxidase layer is modified on the surface of the metal nanoparticle layer.
In the scheme, an optical resonant cavity is formed among the metal thin film layer, the n-type semiconductor thin film layer and the metal nano particle layer, so that the light absorption capacity of the n-type semiconductor thin film layer and the metal nano particle layer can be enhanced; the glucose oxidase layer is modified on the surface of the metal nanoparticle layer and is used for identifying and catalyzing glucose molecules; the n-type semiconductor thin film layer is obtained by taking the metal thin film layer as a substrate and depositing through a physical or chemical method. And before the metal nano particle layer is deposited, carrying out heat treatment on the n-type semiconductor thin film layer, wherein in the heat treatment process, part of metal elements in the metal thin film layer are doped into the n-type semiconductor thin film layer, so that the conductivity of the n-type semiconductor thin film layer can be improved, and meanwhile, the n-type semiconductor thin film layer and the metal thin film layer form ohmic contact. When the non-bias enzymatic glucose photoelectrochemical sensing electrode is used, the metal thin film layer is connected with the amperemeter and the counter electrode in sequence through the external lead, and when excitation light irradiates the surface of the working electrode, the current on the amperemeter presents the characteristic of positive correlation with the glucose concentration to be detected, so that the glucose concentration monitoring is realized.
Preferably, the diameter of the nanoparticles in the metal nanoparticle layer is 5-100 nm, the nanoparticles are discontinuously and irregularly distributed in space, and the nanoparticles are made of any one or a mixture of gold, silver, copper and platinum.
Preferably, the n-type semiconductor thin film layer is made of any one or a mixture of more of titanium dioxide, zinc oxide, ferric oxide, tin dioxide and chromium oxide, and the thickness of the n-type semiconductor thin film layer is 50-500 nm.
Preferably, the material of the metal thin film layer is any one or a mixture of more of silver, aluminum, titanium and zinc, and the thickness is 100 nm-50 μm.
Preferably, the thickness of the glucose oxidase layer is 100 nm-1 μm.
Preferably, a platinum electrode is used as a counter electrode of the unbiased enzymatic glucose photoelectrochemical sensing electrode.
Preferably, the incident light is sunlight or simulated sunlight.
Preferably, the unbiased enzymatic glucose photoelectrochemical sensing electrode detects glucose at a concentration ranging from 0.3. mu.M to 100 mM.
In the scheme of the invention, the metal nanoparticles in the metal nanoparticle layer have large specific surface area, large absorption cross section, tunable local surface plasmon resonance and excellent catalytic effect. The metal nanoparticle layer, the n-type semiconductor thin film layer and the metal thin film layer form an optical resonant cavity, so that the respective light absorption capacities of the n-type semiconductor thin film layer and the metal nanoparticle layer can be obviously enhanced, and the utilization rate of the sensing electrode to the broad-spectrum excitation light source is improved. The metal nanoparticle layer and the n-type semiconductor thin film layer form Schottky contact, so that on one hand, separation of photogenerated electron hole pairs in the n-type semiconductor thin film layer can be promoted, and collection of hot electrons and hot holes generated in the metal nanoparticle layer can be promoted (namely hot electrons are injected into the n-type semiconductor thin film layer, and the hot holes are transferred into glucose oxidase). The metal thin film layer is used as a back conductive layer of the sensing electrode and also used as a doping source of the n-type semiconductor thin film layer, so that the conductivity of the n-type semiconductor thin film layer can be remarkably improved, and the light absorption band gap of the n-type semiconductor thin film layer is reduced. The glucose oxidase layer has a large specific surface area due to inheriting the microscopic morphology of the metal nanoparticle layer, has a specific recognition function on glucose molecules, and can quickly transfer holes on the surface of the sensing electrode, so that the holes on the surface of the sensing electrode can be ensured to quickly and efficiently participate in the oxidation reaction of the glucose molecules. When a broad-spectrum light source is introduced to irradiate the sensing electrode, the metal nanoparticle layer and the n-type semiconductor thin film layer can generate effective light absorption to respectively generate a hot electron hole pair and a photo-generated electron hole pair. Under the action of the Schottky junction, hot holes and photo-generated holes are transferred to glucose molecules (namely participate in the oxidation reaction of the glucose molecules) through the catalytic action of glucolase, hot electrons are injected into the n-type semiconductor thin film layer, and the hot electrons and photo-generated electrons in the n-type semiconductor thin film layer flow to the counter electrode through the metal thin film layer to participate in the corresponding reduction reaction. A macroscopic photocurrent is observable between the sensing and counter electrodes and increases as the glucose concentration increases. The detection of the glucose concentration is realized by monitoring the change of the photocurrent.
Based on the characteristics, the sensing electrode provided by the scheme of the invention can work under zero bias and realize selective detection on glucose with the concentration range of 0.3 mu M-100 mM only under the excitation of sunlight, the lowest detection limit is as low as 0.3 mu M, and the highest sensing sensitivity is 3.75 mu A mu M-1cm-2。
The application also discloses a preparation method of the unbiased enzymatic glucose photoelectrochemical sensing electrode, which comprises the following steps:
1) after chemically cleaning a plane insulating substrate, depositing a metal film layer with the thickness of 100 nm-50 mu m on the surface of the plane insulating substrate by a physical method;
2) depositing a 50-500 nm n-type semiconductor thin film layer on the surface of the metal thin film layer by a physical method;
3) heat-treating for 2-3 hours in an air atmosphere at 400-600 ℃;
4) growing a metal nano particle layer on the surface of the n-type semiconductor thin film layer by adopting an electrochemical deposition method;
5) performing oxygen plasma treatment on the metal nanoparticle layer to enhance the hydrophilicity of the composite structure of the n-type semiconductor thin film layer and the metal nanoparticle layer;
6) modifying glucose oxidase on the surface of the metal nanoparticle layer by a spin coating method or a soaking method to form a glucose oxidase layer;
7) and naturally drying to obtain a multilayer structure of the metal thin film layer/the n-type semiconductor thin film layer/the metal nanoparticle layer/the glucose oxidase layer.
8) And (4) leading out a lead end on the metal film layer in the multilayer structure prepared in the step 7), thus obtaining the glucose photoelectrochemical sensing electrode.
Drawings
FIG. 1: a schematic structure diagram of a non-bias enzymatic glucose photoelectrochemical sensing electrode;
wherein: 11 is a plane insulating substrate, 12 is a metal film layer, 13 is an n-type semiconductor film layer, 14 is a gold nanoparticle layer, 15 is a glucose oxidase layer, and 16 is a lead end of a sensing electrode.
FIG. 2: a working principle diagram of a glucose sensing system based on a non-bias enzymatic glucose photoelectrochemical sensing electrode;
wherein: 21 is a non-bias enzymatic glucose photoelectrochemical sensing electrode, 22 is a counter electrode, 23 is a detection cell, and 24 is illumination.
FIG. 3: a photocurrent response condition graph of a non-bias enzymatic glucose photoelectrochemical sensing electrode to low glucose concentration of 0-1 mu M;
FIG. 4: a graph of the photocurrent response of a non-bias enzymatic glucose photoelectrochemical sensing electrode to a high glucose concentration of 1 mu M-100 mM;
FIG. 5: a linear fitting curve of the photocurrent response and the low glucose concentration of 0.3-1 mu M of the prepared unbiased enzymatic glucose photoelectrochemical sensing electrode;
FIG. 6: the linear fitting curve of the photocurrent response and the high glucose concentration of the prepared unbiased enzymatic glucose photoelectrochemical sensing electrode is 1 mu M-100 mM;
FIG. 7: a stability test chart of the prepared unbiased enzymatic glucose photoelectrochemical sensing electrode;
FIG. 8: the anti-interference test chart of the prepared non-bias enzymatic glucose photoelectrochemical sensing electrode;
FIG. 9: the prepared non-bias enzymatic glucose photoelectrochemical sensing electrode is used for generating a photocurrent percentage diagram of four typical interference substances;
FIG. 10: a cross-sectional electron microscope image of the prepared unbiased enzymatic glucose photoelectrochemical sensing electrode;
wherein: 101 is a silicon dioxide substrate, 102 is an aluminum thin film layer, 103 is a titanium dioxide thin film layer, and 104 is a composite structure of a gold nanoparticle layer and a glucose oxidase layer.
Detailed Description
In order to more clearly illustrate the technical solution, the following is further described with reference to the accompanying drawings and embodiments.
Example 1
A non-biased enzymatic glucose photoelectrochemical sensing electrode, as shown in figure 1: the glucose photoelectrochemistry sensing electrode is of a composite structure and sequentially comprises a glucose oxidase layer 15, a metal nanoparticle layer 14, an n-type semiconductor thin film layer 13, a metal thin film layer 12, a planar insulating substrate 11 and a lead terminal 16 led out from the metal thin film layer along a light incidence direction. The metal nanoparticle layer 14 and the n-type semiconductor thin film layer 13 form schottky contact, so that part of hot electrons in the metal nanoparticle layer 14 can be collected by the n-type semiconductor thin film layer 13, and the separation efficiency of photo-generated electron-hole pairs in the n-type semiconductor thin film layer 13 can be improved; the metal thin film layer 12, the n-type semiconductor thin film layer 13 and the metal nanoparticle layer 14 form an optical resonant cavity (wherein the n-type semiconductor thin film layer 13 is a cavity), so that the light absorption capability of the n-type semiconductor thin film layer 13 and the metal nanoparticle layer 14 can be remarkably enhanced (wherein the light absorption of the n-type semiconductor thin film layer is interband absorption to generate a photo-generated electron hole pair, the light absorption of the metal nanoparticle layer is intraband absorption to generate a hot electron hole pair and a hot hole pair); the n-type semiconductor thin film layer and the metal thin film layer 12 form ohmic contact, so that electrons in the n-type semiconductor thin film layer 13 can be transported to a counter electrode through the metal thin film layer 12; in the heat treatment process, the metal thin film layer 12 has a doping effect on the n-type semiconductor thin film layer 13, so that the conductivity of the n-type semiconductor thin film layer 13 is increased and the light absorption band gap is reduced, and the absorption spectrum range of the n-type semiconductor thin film layer 13 and the separation efficiency of photo-generated electron-hole pairs are improved; the glucose oxidase 15 has the microscopic morphology characteristics of the metal nanoparticle layer 14, has a large specific surface area, has specific recognition and enzymolysis reaction functions on glucose molecules, and can quickly transfer holes on the surface of the sensing electrode into a solution (namely participate in the oxidation reaction of the glucose molecules).
As shown in fig. 2: the glucose photoelectrochemistry sensing electrode 21 is connected with a counter electrode 22 (such as a platinum mesh electrode) through a lead terminal 16, and an ammeter is arranged between the sensing electrode 21 and the counter electrode 22; after injection of 0.1M phosphate buffer solution containing different concentrations of glucose into the cell 23, the sensing electrode 21 was given simulated solar illumination 24, which produced a significant photocurrent response at zero bias (note: the corresponding photocurrent response was greater at forward bias).
As shown in FIGS. 3 and 4, the dark current between the sensing electrode and the counter current was 50nACm in the background solution without glucose (i.e., 0.1M phosphate buffer solution) and the background solution with different concentrations of glucose added-2Accessory fluctuations; after the simulated solar illumination is introduced, the photocurrent density is increased from 13 mu Acm as the glucose concentration is increased from 0 to 100mM-2Gradually increased to 23 μ Acm-2(much larger than dark current), and the dark current is only 10-50 nACm-2. It should be noted that when the concentration of glucose added to the background solution is 0.1 μ M, the corresponding photocurrent density is almost the same as the corresponding value of the background solution without glucose, and when the concentration of glucose is increased to 0.3 μ M, the corresponding photocurrent density is obviously different from the corresponding value of the background solution without glucose, which indicates that the lower limit of glucose detection of the sensing electrode is 0.3 μ M. Performing linear fitting on the photoresponse current and the glucose concentration to obtain two linear ranges, wherein one concentration range is 0.3-1 mu M, and the corresponding sensing sensitivity is 3.75 mu A mu M-1cm-2(see FIG. 5), another concentration range is 0.001-100 mM, corresponding to a sensing sensitivity of 1.63 XlgCmu AmM-1cm2(where C is the glucose concentration, as shown in FIG. 6). And further testing the stability and the anti-interference performance of the glucose photoelectrochemistry sensing electrode. As shown in fig. 7, the photoresponse current density generated by the sensing electrode in the background solution containing 10mM glucose did not decay significantly over the 30 minute test period under the simulated on/off solar illumination. As shown in fig. 8 and 9, 1mL of 0.1M glucose, uric acid, ascorbic acid, sucrose and sodium chloride were added dropwise to 60mL of 0.1M phosphate background solution, and the photocurrent variation generated by adding glucose to the background solution was much larger than that of the other four substances (i.e., the photocurrent variation generated by adding uric acid and ascorbic acid was 10% of that of adding glucose, and the photocurrent variation generated by adding sucrose and sodium chloride was only 1% of that of adding glucose). The comparison with four typical interference substances, namely uric acid, ascorbic acid, sucrose and sodium chloride, proves that the sensing electrode has good anti-interference and selectivity on glucose detection.
The data fully show that the glucose photoelectrochemistry sensing electrode prepared by the technical scheme can realize effective detection on glucose in the concentration range of 0.3 mu M-100 mM under zero bias, and has good stability, anti-interference performance and selectivity.
Example two
A method for preparing non-bias enzymatic glucose photoelectrochemical sensing electrode uses planar silicon dioxide (SiO)2) Is a substrate comprising:
1) after chemically cleaning a substrate, depositing a layer of aluminum (Al) film with the thickness of 150nm on the surface of the substrate through direct current magnetron sputtering;
2) by radio frequency sputtering a layer of titanium dioxide (TiO) 180nm thick2) A film;
3) heat treatment is carried out for 2 hours at 500 ℃ in air atmosphere;
4) obtaining a layer of gold nanoparticles (Au NPs) by adopting a photo-assisted electrochemical deposition method;
5) performing oxygen plasma treatment to increase the hydrophilicity of the composite structure of the titanium dioxide thin film layer and the gold nanoparticle layer;
6) modifying a glucose oxidase (GOx) layer on the surface of the titanium dioxide thin film layer and gold nanoparticle layer composite structure by adopting a spin coating method;
7) naturally drying to obtain SiO2/Al/TiO2Au NPs/GOx laminated structure;
8) and leading out a copper wire (as a lead terminal) on the aluminum film layer to obtain the glucose photoelectrochemical sensing electrode.
Fig. 10 is a cross-sectional microscopic morphology of the prepared glucose photoelectrochemical sensing electrode, and it can be clearly seen that an interface between a silicon dioxide substrate 101 and an aluminum thin film layer 102 and an interface between the aluminum thin film layer and a titanium dioxide thin film layer 103 are provided, 104 is a composite structure of a gold nanoparticle layer and a glucose oxidase layer, the gold nanoparticle layer and the glucose oxidase layer are nested together, the gold nanoparticle layer is completely wrapped by the glucose oxidase layer, and no clear boundary exists between the gold nanoparticle layer and the glucose oxidase layer. In addition, in the composite structure of the gold nanoparticle layer and the glucose oxidase layer, the morphology of the nanoparticles can be seen, and the surface is in a non-planar rough state. This demonstrates that the aluminum thin film layer and the titanium dioxide thin film layer maintain the planar morphology of the silicon dioxide substrate, the gold nanoparticle layer is a discontinuous thin film layer, and the gaps of the gold nanoparticles are filled with glucose oxidase, while the glucose oxidase layer exhibits a rough, undulating surface morphology due to the discontinuity of the gold nanoparticle layer.
Placing the prepared glucose photoelectrochemistry sensing electrode and a counter electrode in a transparent detection pool, connecting the sensing electrode and the counter electrode through an external lead, and introducing an ammeter between the two electrodes; background liquid (such as phosphate buffer solution) containing glucose with different concentrations is injected into the detection cell, and simulated solar illumination is given to the sensing electrode, so that the glucose can be detected under zero bias in a selective, low detection limit and wide concentration range.
Claims (10)
1. A non-biased enzymatic glucose photoelectrochemical sensing electrode having a composite layered structure, comprising: the light-emitting diode comprises a glucose oxidase layer, a metal nanoparticle layer, an n-type semiconductor thin film layer, a metal thin film layer and a planar insulating substrate in sequence along the incident direction of incident light; the metal film layer is used as a back conductive layer and a light reflection layer of the glucose photoelectrochemistry sensing electrode at the same time; part of metal elements in the metal thin film layer are doped into the n-type semiconductor thin film layer, and ohmic contact is formed; an optical resonant cavity is formed among the metal thin film layer, the n-type semiconductor thin film layer and the metal nano particle layer; the n-type semiconductor thin film layer absorbs incident light in a band-to-band manner to generate photo-generated electron-hole pairs; the metal nano particle layer forms in-band absorption on incident light to generate hot electron holes and hot hole pairs; the metal nanoparticle layer and the n-type semiconductor thin film layer form Schottky contact, and partial hot electrons generated by light absorption of the metal nanoparticle layer are injected into the n-type semiconductor thin film layer; the glucose oxidase layer is modified on the surface of the metal nanoparticle layer.
2. The unbiased enzymatic glucose photoelectrochemical sensing electrode of claim 1, wherein: the diameter of the nano particles in the metal nano particle layer is 5-100 nm, the nano particles are discontinuously and irregularly distributed in space, and the nano particles are made of any one or a mixture of gold, silver, copper and platinum.
3. The unbiased enzymatic glucose photoelectrochemical sensing electrode of claim 1, wherein: the n-type semiconductor thin film layer is made of any one or a mixture of more of titanium dioxide, zinc oxide, ferric oxide, tin dioxide and chromium oxide, and the thickness of the n-type semiconductor thin film layer is 50-500 nm.
4. The unbiased enzymatic glucose photoelectrochemical sensing electrode of claim 1, wherein: the metal film layer is made of any one or a mixture of more of silver, aluminum, titanium and zinc, and the thickness of the metal film layer is 100 nm-50 mu m.
5. The unbiased enzymatic glucose photoelectrochemical sensing electrode of claim 1, wherein: the thickness of the glucose oxidase layer is 100 nm-1 mu m.
6. The unbiased enzymatic glucose photoelectrochemical sensing electrode of claim 1, wherein: the incident light is sunlight or simulated sunlight.
7. The unbiased enzymatic glucose photoelectric electrochemical sensing electrode according to claim 1, characterized in that: the metal thin film layer is connected with an ammeter and a counter electrode in sequence through an external lead.
8. The unbiased enzymatic glucose photoelectrochemical sensing electrode of claim 7, wherein: the counter electrode is a platinum electrode.
9. A preparation method of a non-bias enzymatic glucose photoelectrochemical sensing electrode is characterized by comprising the following steps: 1) after chemically cleaning a planar insulating substrate, depositing a metal film layer of 100 nm-50 microns on the surface of the planar insulating substrate by a physical method;
2) depositing a 50-500 nm n-type semiconductor thin film layer on the surface of the metal thin film layer by a physical method;
3) heat-treating for 2-3 hours in an air atmosphere at 400-600 ℃;
4) growing a metal nano particle layer on the surface of the n-type semiconductor thin film layer by adopting an electrochemical deposition method;
5) performing oxygen plasma treatment on the metal nanoparticle layer to enhance the hydrophilicity of the composite structure of the n-type semiconductor thin film layer and the metal nanoparticle layer;
6) modifying glucose oxidase on the surface of the metal nanoparticle layer by a spin coating method or a soaking method to form a glucose oxidase layer;
7) naturally drying to obtain a multilayer structure of a metal thin film layer/an n-type semiconductor thin film layer/a metal nanoparticle layer/a glucose oxidase layer;
8) and 7) leading out a lead end on the metal film layer in the multilayer structure prepared in the step 7), thus preparing the glucose photoelectrochemical sensing electrode.
10. The method for preparing an unbiased enzymatic glucose photoelectric chemical sensing electrode as set forth in claim 9, wherein: the planar insulating substrate is a silicon dioxide substrate, the metal thin film layer is an aluminum thin film layer, the n-type semiconductor thin film layer is a titanium dioxide thin film layer, and the metal nanoparticle layer is a gold nanoparticle layer.
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