CN114162821A - Schottky junction composite material and preparation method and application thereof - Google Patents

Schottky junction composite material and preparation method and application thereof Download PDF

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CN114162821A
CN114162821A CN202111493886.4A CN202111493886A CN114162821A CN 114162821 A CN114162821 A CN 114162821A CN 202111493886 A CN202111493886 A CN 202111493886A CN 114162821 A CN114162821 A CN 114162821A
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吴静
陈天友
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China University of Geosciences Beijing
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Abstract

The invention relates to the technical field of semiconductor materials, in particular to a Schottky junction composite material and a preparation method and application thereof. The invention provides a Schottky junction composite material, which is prepared from Ti3C2TxA lamellar layer and a carrier supported on the Ti3C2TxAgI microspheres on a sheet layer, wherein, one Ti3C2TxAnd a plurality of AgI microspheres are loaded on the sheet layer. The Schottky junction composite material can be used for photoelectrochemistryThe Schottky junction composite material of the optical sensor can greatly improve the performance of the photoelectrochemical sensor.

Description

Schottky junction composite material and preparation method and application thereof
Technical Field
The invention relates to the technical field of semiconductor materials, in particular to a Schottky junction composite material and a preparation method and application thereof.
Background
Semiconductors have been widely studied as a potential photocatalytic technology. Semiconductor photocatalysis technology can directly utilize solar energy to produce fuel, degrade pollutants and carry out sensing detection on biomolecules, so that the semiconductor photocatalysis technology is concerned. But a single semiconductor has its own drawbacks such as: the rapid recombination of photo-generated electron-hole pairs, poor carrier transport efficiency, low light utilization rate, and the like, thereby limiting the applications thereof. The heterojunction material is an effective means for improving the photoelectrochemical property of the semiconductor, and the semiconductor and the material with excellent conductivity are compounded to form a Schottky junction, so that the photoproduction electron hole pair is effectively separated, the more excellent photochemical property is shown, and the heterojunction material can be used for preparing a high-performance catalyst or a sensor.
Therefore, it is of great significance to research schottky composite materials which can be applied to catalysts or sensors.
Disclosure of Invention
The invention provides a Schottky junction composite material for a photoelectrochemical sensor, which can greatly improve the performance of the photoelectrochemical sensor.
In a first aspect, a Schottky junction composite material is provided, consisting of Ti3C2TxA lamellar layer and a carrier supported on the Ti3C2TxAgI microspheres on a sheet layer, wherein, one Ti3C2TxAnd a plurality of AgI microspheres are loaded on the sheet layer.
In a second aspect, there is provided a method for preparing the schottky junction composite material of the first aspect, comprising the steps of:
(1) to Ti3C2TxThe multi-layered powder is subjected to a dissociation process to reduce Ti that is focused together3C2TxThe number of layers of (a);
(2) ti subjected to dissociation treatment in the step (1)3C2TxAnd containing Ag+After mixing the solutions, ultrasonic treatment is carried out to make Ag+Is adhered to Ti3C2TxOn the surface of the sheet, the dropping solution contains I-To obtain a first mixed solution;
(3) and carrying out ultrasonic treatment and drying treatment on the first mixed solution in sequence to obtain the Schottky junction composite material.
In one embodiment, in said step (1), every 1mg of Ti3C2TxPutting the multilayer powder into 2mL of deionized water, and carrying out ultrasonic treatment to carry out dissociation treatment to obtain a dispersion liquid; in the step (2), Ag is added+Is added dropwise to the dispersion, after which ultrasonic treatment is carried out, and then a solution containing I is added dropwise-To obtain a first mixed solution.
In one embodiment, the dispersion is prepared by mixing 15mgTi3C2TxPutting the multilayer powder into 30mL of deionized water, and performing ultrasonic treatment to obtain the powder; the Ag-containing compound+The solution of (A) is composed of 61.5mg AgNO3Dissolving in 10mL of deionized water to obtain the product; said compound containing I-The solution of (2) was prepared by dissolving 60.1mg KI in 10mL deionized water.
In one embodiment, the duration of the ultrasonic treatment in the step (1) is 1h, and the ultrasonic power is 300W; the duration of the ultrasonic treatment in the step (2) and the ultrasonic treatment in the step (3) is 30min, and the ultrasonic power is 300W; in the step (3), the drying treatment is suction filtration washing and freeze drying; wherein the freeze-drying temperature is-50 ℃, and the freeze-drying time is 12 h.
In a third aspect, there is provided an electrode for a photoelectrochemical biosensor, the electrode being a conductive glass modified with the schottky junction composite of the first aspect.
In a fourth aspect, there is provided a method for preparing the electrode of the third aspect, comprising: dispersing the schottky junction composite material in ethanol to obtain a dispersion liquid; and dripping the dispersion liquid on the surface of conductive glass, and airing to obtain the electrode.
In one embodiment, the dispersion is prepared by dispersing every 4mg of the schottky junction composite into 1mL of ethanol; the conductive glass is washed by water, acetone and ethanol and dried at 60 ℃.
In a fifth aspect, there is provided a use of the electrode of the third aspect in detecting Glutathione (GSH) using a photoelectrochemical biosensor, wherein the electrode is used as a photocathode of the photoelectrochemical biosensor.
In one embodiment, in detecting glutathione using the photoelectrochemical biosensor, the concentration of GSH is determined using equation (1):
(I0-I)/I0＝0.0265c+0.9727 (1)
wherein c represents the concentration of GSH, I0Indicating the photo-electric response generated at the cathode without the addition of GSH, and I indicating the photo-electric response generated at the cathode after the addition of GSH, wherein the correlation coefficient R2Is 0.9902.
By combining the embodiments, the Schottky composite material provided by the invention can be applied to a photoelectrochemical sensor, and the performance of the photoelectrochemical sensor can be improved. The photoelectrochemical sensor using the Schottky composite material has stable photoelectric response, high sensitivity to GSH detection and accurate result. The method for preparing the Schottky composite material is an ultrasonic method, the preparation method is simple, easy to operate and high in flux, various Schottky composite materials with different mass ratios can be synthesized by one-time operation, and a large amount of Schottky composite materials can be synthesized.
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FIG. 1 is an experimental schematic diagram of the ultrasonic synthesis method provided by the present invention;
FIG. 2 is a Scanning Electron Microscope (SEM) photograph of an ultrasonically synthesized product provided by the present invention;
FIG. 3 is the photoelectrochemical properties of the products of different mass ratios of the ultrasonic synthesis provided by the present invention;
FIG. 4 is an X-ray diffraction (XRD) pattern of the raw material and the Schottky junction product provided by the present invention;
FIG. 5 is an X-ray photoelectron spectroscopy (XPS) plot of a feedstock and a Schottky junction product provided by the present invention;
FIG. 6 is a UV-VIS absorption spectrum of the material and Schottky junction product provided by the present invention;
FIG. 7 is a fluorescence spectrum of AgI and Schottky junction obtained by the ultrasonic synthesis method provided by the invention;
FIG. 8 is an impedance spectrum of the raw material and Schottky junction product provided by the present invention;
FIG. 9 is a graph showing the photoresponse behavior of Schottky junctions provided by the present invention at different pH's;
FIG. 10 shows the photoelectrochemical properties of a cathode electrode prepared from a Schottky junction according to the present invention when nitrogen is introduced into the electrolyte;
FIG. 11 shows the photoelectrochemical properties of a cathode electrode prepared from a Schottky junction according to the present invention when oxygen is introduced into a saturated nitrogen electrolyte;
FIG. 12 is an electron spin resonance diagram of a DMPO trapping Schottky junction material provided by the present invention generating superoxide radicals under illumination;
FIG. 13 is an electron spin resonance diagram of a DMPO trapping Schottky junction material provided by the present invention generating hydroxyl radicals under illumination;
fig. 14 is a schematic diagram of a photoelectrochemical sensor provided by the present invention for GSH detection;
FIG. 15 is a linear regression equation for detecting GSH by the photoelectrochemical sensor provided by the present invention;
FIG. 16 is a schematic view of the present invention providing anti-interference of a photoelectrochemical sensor;
fig. 17 is a schematic diagram of the stability of the photoelectrochemical sensor provided by the present invention.
Detailed Description
The following description of the embodiments of the present invention is provided for illustrative purposes, and other advantages and effects of the present invention will become apparent to those skilled in the art from the present disclosure.
When numerical ranges are given in the examples, it is understood that both endpoints of each of the numerical ranges and any value therebetween can be selected unless the invention otherwise indicated. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this invention belongs. In addition to the specific methods, devices, and materials used in the examples, any methods, devices, and materials similar or equivalent to those described in the examples may be used in the practice of the invention in addition to the specific methods, devices, and materials used in the examples, in keeping with the knowledge of one skilled in the art and with the description of the invention.
At present, the compound formation of schottky by semiconductor and noble metal or graphene is developedThe matrix composite has been extensively studied, and Ti3C2TxThe compounding of materials is relatively less studied. Ti3C2TxIs a new kind of metal two-dimensional layered material, and has strong light absorption capacity, excellent conductivity and abundant surface functional groups. At present, Ti3C2TxMost of the research and application of the method mainly focuses on the electrochemical and photochemical fields, and the field of Photoelectrochemistry (PEC) is still a blank and deserves to be researched. On the one hand, Ti3C2TxCan provide sufficient active sites for semiconductor growth. On the other hand, Ti3C2TxThe contact surface with the semiconductor can form a built-in electric field and is based on Ti3C2TxThe high conductivity of the photo-generated carrier is beneficial to the transfer of the photo-generated carrier, the hole pair of the photo-generated electron can be effectively separated, and the photoelectric effect is improved. Thus, Ti3C2TxAs a two-dimensional support material compounded with a photosensitive material, the composite material can effectively overcome the defects of high compounding efficiency of photoinduced electron hole pairs and short service life of photoinduced electrons, and has certain stability.
Silver iodide (AgI) is a typical p-type semiconductor with a band gap of about 2.7eV, and is a typical photosensitive material due to its wide light absorption range and stable photogenerated current. In addition, due to the fact that AgI is higher at the edge position of a conduction band, the AgI is combined with other semiconductor materials to generate a heterojunction and is used in the field of photocatalysis. However, the application of the photo-generated electron-hole pair is limited due to the rapid recombination of the photo-generated electron-hole pair, and Ti is introduced to solve the problem3C2TxAdjust the photoelectrochemical property, research the photoelectrochemical property and explore the related application.
Through a large number of experimental researches, a Schottky junction composite material is researched, can be applied to a photoelectrochemical sensor, and improves the performance of the photoelectrochemical sensor. In addition, the preparation method of the Schottky junction composite material is simple, convenient and fast, easy to operate and high in flux, various Schottky junction composite materials with different mass ratios can be synthesized by one-time operation, and a large amount of synthesis can be realized.
Next, the scheme provided by the present invention will be specifically described with reference to examples.
Example 1 ultrasonic Synthesis of Schottky junction composite
As shown in FIG. 1, 15mg of Ti was weighed3C2TxPutting the multilayer powder (which can be obtained commercially) into 30mL of deionized water, and performing ultrasonic treatment for 1h to dissociate the powder into a monolayer or less-lamellar dispersed solution; then, 61.5mg AgNO was weighed3Dissolving 60.1mg KI in 10mL deionized water respectively, and firstly, AgNO3The solution is added dropwise with evenly dispersed Ti3C2TxContinuing to perform ultrasonic treatment in the solution for 30min to make Ag+Is uniformly adhered to Ti3C2TxDropwise adding a KI solution into the reaction solution on the surface of the nanosheet, and carrying out ultrasonic treatment for 30 min; and finally, obtaining the synthesized composite material through suction filtration, washing and freeze-drying. The obtained composite material is the Schottky junction composite material. The resulting material was ground using a mortar and 4mg of the schottky junction composite material was weighed and dispersed in 1mL of ethanol for use.
Wherein the power of the ultrasonic wave is 300W.
As shown in a in FIG. 2, Ti3C2TxThe multilayer material is formed by stacking single-layer materials, and the stacking mode can reduce active sites exposed on the surface and is not beneficial to the adsorption of ions. In order to increase the specific surface area of the titanium alloy to increase the active sites, the layered structure is stripped by an ultrasonic method to obtain few-layer or single-layer Ti as shown in b in figure 23C2Tx. The AgI synthesized by the ultrasonic method is agglomerated (as shown in c of fig. 2), which is caused by the absence of attachment sites during the nucleation and growth processes, and such agglomeration causes a great decrease in the light utilization efficiency thereof. Thus introducing Ti3C2TxThen, it provides a good attachment site for AgI growth, and Ti3C2TxThe functional group with electronegativity on the surface can adsorb Ag+This enables easier aggregate growth of AgI on its surface (as shown by d in fig. 2).
Example 2 basic Property characterization of Schottky junction composites
Under the ultrasonic condition, 5 kinds of Schottky junction composite materials with different mass ratios, which are respectively 5% -Ti, are synthesized in one step3C2Tx/AgI (i.e. Ti)3C2TxIn the mass ratio of 5 percent AgI) and 10 percent to Ti3C2Tx/AgI (i.e. Ti)3C2TxIn a mass ratio of AgI of 10%), 15% -Ti3C2Tx/AgI (i.e. Ti)3C2Tx20% -Ti of which the mass ratio of AgI is 15%)3C2Tx/AgI (i.e. Ti)3C2TxIn a mass ratio of AgI of 20%), 25% -Ti3C2Tx/AgI (i.e. Ti)3C2TxMass ratio of AgI of 25%), high-throughput synthesis was achieved. Schottky junction composite material and Ti with different mass ratios for the 5 kinds of materials3C2TxAnd AgI characterize the photoelectrochemical response. Specifically, as shown in the photoelectric response diagram in fig. 3, the 5 kinds of schottky junction composite materials with different mass ratios obtained by ultrasonic synthesis are compared with the photoelectric response of the raw materials thereof at Ti3C2TxThe photoelectric response is relatively optimal when the mass ratio is 15%. Selecting 15% -Ti3C2TxThe structure of the/AgI is characterized, and an XRD pattern shows that the compound not only has a characteristic peak of AgI, but also increases a peak of Ag (shown in figure 4). The appearance of the simple substance Ag indicates that part of Ag exists in the synthesis process+The Ag simple substance in the compound can not only play a role in improving charge transmission efficiency, but also can improve photoelectric performance through a local surface plasmon resonance effect. To further explore the change of valence state during the synthesis, XPS characterization was performed on the materials before and after the synthesis, as shown in FIG. 5, wherein a in FIG. 5 and d in FIG. 5 show the Schottky junction composite material, Ti3C2TxThe complete spectrum with AgI proves the successful preparation of the material; b in FIG. 5 is a high-resolution map of C1s, and it can be seen by comparison that a vigorous reaction occurs during the synthesis process resulting in the cleavage of Ti-C bonds; in FIG. 5C is a high-resolution map of Ti 2p, can be divided into 6 peaks, and is Ti (IV) 2p1/2、Ti(Ⅲ)2p1/2、Ti(Ⅱ)2p1/2、Ti(Ⅳ)2p3/2、Ti(Ⅱ)2p3/2And Ti (III) 2p3/2Corresponding to 464.9eV, 462.7eV, 460.8eV, 458.9eV, 456.2eV and 454.6eV, respectively, the low valence Ti has stronger reduction activity and can be used as an electron donor to induce a reduction reaction. After AgI is introduced to synthesize the Schottky junction, 454.6eV and 456.2eV peaks corresponding to low-valence Ti disappear, which shows that in the synthesis process, due to the consumption of low-valence Ti electrons, a strong redox reaction occurs, and this corresponds to the appearance of an Ag characteristic peak in an XRD (X-ray diffraction) diagram; in addition, with Ti3C2TxIn contrast, Ti3C2TxTi (IV) 2p on AgI1/2And Ti (IV) 2p3/2The peak is positively shifted, while the Ag 3d and I3 d peaks are negatively shifted (as shown by c, e and f in FIG. 5), and the surface charge distribution is negatively correlated with the binding energy, so the XPS results also demonstrate the mode of carrier transport in the Schottky junction, i.e., Ti3C2TxAnd the electrons are transferred to AgI, so that the function of hole capture is realized. As shown in FIG. 6, the absorption boundary of the obtained Schottky junction composite material is expanded relative to AgI in the ultraviolet absorption spectrum, which indicates that Ti3C2TxThe introduction of (2) improves the light utilization efficiency. Fluorescence spectroscopy (PL) can provide useful information for the photo-induced electron-hole separation efficiency and carrier transport of heterojunction materials, and generally the electrical potential is converted into fluorescence emission after recombination of excited electrons and holes, so the lower the PL signal, the higher the electron-hole separation efficiency and the higher the conductivity. As shown in FIG. 7, the semiconductor AgI has a higher PL peak intensity than the Schottky junction composite, which indicates that Ti is present3C2TxThe introduction of (b) facilitates efficient separation of photo-induced carriers. The impedance plot (as shown in fig. 8) further demonstrates the better conductivity of the schottky junction composite relative to the AgI semiconductor.
Example 3 photoelectrochemical Properties and mechanistic characterization of Schottky junction composites
Firstly, preparing conductive glass (specifically ITO conductive glass) modified by Schottky junction composite material. Repeatedly ultrasonically washing the conductive glass for several times for 15min each time by using deionized water, acetone and ethanol, and then drying at 60 ℃; taking 25 μ L of dispersed solution of Schottky junction composite material (i.e. 4mg of Schottky junction composite material (specifically 15% -Ti as above)3C2TxAgI) is dispersed by 1mL, the obtained dispersion solution) is dropped on the surface of the conductive glass, and the glassy carbon electrode (15% -Ti) modified by the Schottky junction composite material is obtained by natural airing3C2Tx/AgI/ITO)。
Utilizing the prepared 15% -Ti3C2Txthe/AgI/ITO electrode characterizes the photoelectrochemical property of the Schottky junction composite material obtained by ultrasonic synthesis. As shown in fig. 9, under different pH conditions, the photoelectric response increases with the increase of the hydrogen ion concentration, and the hydrogen ion concentration has a certain effect on the photocurrent intensity, probably because the presence of the hydrogen ion can further react with active oxygen, consume the excited-state electrons of the schottky junction composite material, and promote the separation of electron holes. In order to prove that the photo-generated electrons of the Schottky junction composite material are captured by oxygen in electrolyte to generate active oxygen, the sensitivity of a photoelectric cathode modified by the Schottky junction composite material to dissolved oxygen is researched. As shown in fig. 10 and 11, the electrolyte solution filled with saturated air is deoxygenated by introducing nitrogen, and then the electrolyte solution filled with saturated nitrogen is oxygenated, and the sensitivity of the electrode to dissolved oxygen is examined, and as can be seen from fig. 11 and 10, the photocurrent gradually decreases with the filling of nitrogen and reaches a minimum value when oxygen is completely removed, and when oxygen is filled with the electrolyte solution containing saturated nitrogen, the photocurrent gradually increases with the increase of oxygen concentration and reaches a maximum value when saturated, which indicates that dissolved oxygen plays a major role in the electron transfer process.
Electron spin resonance spectroscopy (ESR) further demonstrates that oxygen traps the reactive oxygen species generated by electrons. The superoxide anion was trapped by 5, 5-dimethyl-L-pyroline N-oxide (DMPO) in methanol solution, as shown in FIG. 12, with no ESR signal in the dark, but with a significant quadruple-peak signal of DMPO-trapped superoxide anion after light. The hydroxyl radical was also captured by DMPO, and as can be seen from fig. 13, the signal of the hydroxyl radical gradually increased with the increase of the light irradiation time, while the signal of the superoxide anion radical did not change much with time, so it is presumed that the formation of a part of the hydroxyl radical was related to the redox product of the superoxide anion. From this we can deduce the possible reaction under light excitation:
Ti3C2Tx/AgI+hν→AgI(e-+h+)
AgI(h+)→Ti3C2Tx(h+)
O2+e-→·O2 -
·O2 -+2H++e-→H2O2
H2O2+e-→·OH+OH-
example 4 construction of a sensor for GSH detection based on the photoelectrochemical Properties of the Schottky junction composite
GSH is the most prevalent non-protein thiol in biological systems, and is commonly found in every cell in an organism, and can capture reactive oxygen radicals in the body to play an antioxidant role. Abnormal GSH levels are associated with a number of diseases, including cancer, liver damage, aids, and diseases caused by aging. Therefore, the detection of GSH has important significance for biochemical analysis, pathological detection, clinical test and organism aging research.
The present invention utilizes Ti prepared in the above examples3C2Txthe/AgI electrode extends the detection of GSH to the cathode. Specifically, Ti prepared in the above examples3C2Txthe/AgI electrode was used as the photocathode of a photoelectrochemical biosensor, which was then used to detect GSH. Wherein, under illumination, photo-generated electrons generated by the cathode are captured by dissolved oxygen in the electrolyte to generate superoxide anions, and further electrons are consumed to generate H2O2And hydroxyl radical to improve photoelectric response, and GSH has antioxidant capacity to compete with cathode for oxygen and consume superoxide anionTherefore, the photoelectric response is reduced after the GSH is added, and the reduced photo-generated current intensity is in direct proportion to the concentration of the GSH. Fig. 14 shows a graph of the change in photoelectric response with increasing GSH concentration. As shown in FIG. 15, Ti3C2TxThe standard curve of the/AgI electrode for detecting the GSH is that the photoelectric response is reduced and the photoelectric response is linearly related with the increase of the concentration of the GSH, the linear equation is 0.0265x +0.9727, and the correlation coefficient is 0.9902. The selectivity of the sensor was also tested, and glucose, ascorbic acid, hydrogen peroxide and glutathione were added to the electrolyte, respectively, and the sensor was found to respond significantly only to GSH (as shown in fig. 16). The stability of the sensor was also tested, and as shown in fig. 17, the photoelectric response of the sensor was stable by repeatedly switching the light source on and off within 400 s.
By combining the embodiments, the Schottky composite material provided by the invention can be applied to a photoelectrochemical sensor, and the performance of the photoelectrochemical sensor can be improved. The photoelectrochemical sensor using the Schottky composite material has stable photoelectric response, high sensitivity to GSH detection and accurate result. The method for preparing the Schottky composite material is an ultrasonic method, the preparation method is simple, easy to operate and high in flux, various Schottky composite materials with different mass ratios can be synthesized by one-time operation, and a large amount of Schottky composite materials can be synthesized.
The foregoing embodiments are merely illustrative of the principles and utilities of the present invention and are not intended to limit the invention. Any person skilled in the art can modify or change the above-mentioned embodiments without departing from the spirit and scope of the present invention. Accordingly, it is intended that all equivalent modifications or changes which can be made by those skilled in the art without departing from the spirit and technical spirit of the present invention be covered by the claims of the present invention.

Claims (10)

1. The Schottky junction composite material is characterized by comprising Ti3C2TxA lamellar layer and a carrier supported on the Ti3C2TxAgI microspheres on a sheet layer, wherein, one Ti3C2TxOn the sheet layerA plurality of AgI microspheres are loaded.
2. The method of preparing a schottky junction composite as claimed in claim 1, comprising the steps of:
(1) to Ti3C2TxThe multi-layered powder is subjected to a dissociation process to reduce Ti that is focused together3C2TxThe number of layers of (a);
(2) ti subjected to dissociation treatment in the step (1)3C2TxAnd containing Ag+After mixing the solutions, ultrasonic treatment is carried out to make Ag+Is adhered to Ti3C2TxOn the surface of the sheet, the dropping solution contains I-To obtain a first mixed solution;
(3) and carrying out ultrasonic treatment and drying treatment on the first mixed solution in sequence to obtain the Schottky junction composite material.
3. The method of claim 2,
in said step (1), every 1mg of Ti3C2TxPutting the multilayer powder into 2mL of deionized water, and carrying out ultrasonic treatment to carry out dissociation treatment to obtain a dispersion liquid;
in the step (2), Ag is added+Is added dropwise to the dispersion, after which ultrasonic treatment is carried out, and then a solution containing I is added dropwise-To obtain a first mixed solution.
4. The method according to claim 3, wherein the dispersion is prepared by mixing 15mg Ti3C2TxPutting the multilayer powder into 30mL of deionized water, and performing ultrasonic treatment to obtain the powder; the Ag-containing compound+The solution of (A) is composed of 61.5mg AgNO3Dissolving in 10mL of deionized water to obtain the product; said compound containing I-The solution of (2) was prepared by dissolving 60.1mg KI in 10mL deionized water.
5. The method of claim 2,
the duration time of the ultrasonic treatment in the step (1) is 1h, and the ultrasonic power is 300W;
the duration of the ultrasonic treatment in the step (2) and the ultrasonic treatment in the step (3) is 30min, and the ultrasonic power is 300W;
in the step (3), the drying treatment is suction filtration washing and freeze drying; wherein the freeze-drying temperature is-50 ℃, and the freeze-drying time is 12 h.
6. An electrode for a photoelectrochemical biosensor, wherein said electrode is a conductive glass modified with the schottky junction composite of claim 1.
7. The method of preparing an electrode according to claim 6, comprising:
dispersing the schottky junction composite material of claim 1 in ethanol to obtain a dispersion;
and dripping the dispersion liquid on the surface of conductive glass, and airing to obtain the electrode.
8. The method of claim 7, wherein the dispersion is prepared by dispersing every 4mg of the schottky junction composite in 1mL of ethanol; the conductive glass is washed by water, acetone and ethanol and dried at 60 ℃.
9. Use of an electrode according to claim 6 for the detection of Glutathione (GSH) using a photoelectrochemical biosensor, wherein the electrode is used as a photocathode of the photoelectrochemical biosensor.
10. Use according to claim 9, wherein in detecting GSH using the photoelectrochemical biosensor, the concentration of GSH is determined using equation (1):
(I0-I)/I0＝0.0265c+0.9727 (1)
wherein c representsConcentration of GSH, I0Indicating the photo-electric response generated at the cathode without the addition of GSH, and I indicating the photo-electric response generated at the cathode after the addition of GSH, wherein the correlation coefficient R2Is 0.9902.
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