CN113189158A - Hydrogen sulfide photoelectrochemical sensor and preparation method thereof - Google Patents
Hydrogen sulfide photoelectrochemical sensor and preparation method thereof Download PDFInfo
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Abstract
The invention relates to a hydrogen sulfide photoelectrochemical sensor and a preparation method thereof. The technical scheme is as follows: firstly, putting a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, and then carrying out air annealing treatment. Then, the melamine is calcined twice, naturally cooled and ground into powder. Finally, dispersing the powder in ethanol and water to obtain a suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, dripping 100-700 mu L of a mixed solution of the suspension and Nafion on the taken-out titanium-containing metal sheet, then performing nitrogen annealing treatment at 400-550 ℃, cooling and washing to obtain a hydrogen sulfide photoelectrochemical sensor, and detecting H2The pH of the solution of S is 2-10, and the test voltage is 0.1-1V. The method is simple and reliable and is used for detecting H2S opens up a new visual field and has great significance for early diagnosis of nervous system diseases and ecological environment detection.
Description
Technical Field
The invention belongs to the technical field of photoelectrochemical sensors, and particularly relates to a hydrogen sulfide photoelectrochemical sensor and a preparation method thereof.
Background
Hydrogen sulfide (H)2S) is a colorless, toxic gas with a unique odor of eggs, when H is present in the environment2When the concentration of S is higher than a certain value, nausea, headache and the like may be caused by light concentration, and the olfactory nerve of a human may be paralyzed and even death may be caused by heavy concentration (g.jgraphene quat dots coated photonic crystal fiber.J.Phys.D. appl.Phys.2020,53,325102.). It is also produced directly in mammalian systems, and is a third endogenous gas signaling molecule found following nitric oxide and carbon monoxide. A number of studies have shown that H2The concentration of S is closely related to many diseases such as alzheimer' S disease, diabetes, liver cirrhosis, breast cancer, etc. (x.y. wang, a biogenic optoelectronic reagent sensor based on the electronic transfer by subcutaneous phthalocyanines. analysis, 2020,145, 3543-3548.). H2S is used as an environmentally harmful gas and an endogenous gas signal molecule, and has great relevance to the safety of an ecosystem and the health of human beings. Therefore, a reliable and accurate H is developed from the viewpoint of both ecological environment and human health safety2The S detection technology has important significance.
At present, several H's have been reported2The analysis methods of S detection, such as colorimetric method, fluorescent method, and chromatography, have been hampered from practical use due to low sensitivity, complicated process, and long analysis time. Also useful for detecting H by electrochemical methods2S, but the method is greatly interfered by the system. The Photoelectrochemistry (PEC) sensor is a novel high-efficiency analysis and detection technology, and has attracted wide attention in the fields of DNA analysis, immunoassay, biomolecule detection and the like.
Therefore, it is necessary to address H2S develops a photoelectrochemical sensor.
Disclosure of Invention
The invention provides a hydrogen sulfide photoelectrochemical sensor with simple method and reliable process and a preparation method thereof for solving the technical problems.
In order to achieve the purpose, the invention adopts the technical scheme that:
a preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the following steps:
firstly, putting a ground and polished titanium-containing metal sheet serving as an anode into electrolyte for anodic oxidation;
then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing;
then, calcining melamine twice, naturally cooling, grinding to powder, and dispersing the powder in ethanol and water to obtain 0.1-3 mg/mL suspension;
and putting the annealed titanium-containing metal sheet into the suspension, performing ultrasonic treatment for 1-2 hours, taking out the suspension, taking 100-700 mu L of mixed solution of the suspension and Nafion, dripping the mixed solution onto the taken titanium-containing metal sheet (the area of the titanium sheet is 9mm multiplied by 9mm), performing nitrogen annealing treatment, naturally cooling, and performing ultrasonic washing to obtain the hydrogen sulfide photoelectrochemical sensor.
Preferably, the volume ratio of the suspension to Nafion is 90-100: 1.
Preferably, the air annealing is to take the titanium-containing metal sheet after the anodic oxidation out of the electrolyte, wash the titanium-containing metal sheet with distilled water, blow-dry the titanium-containing metal sheet with nitrogen, place the titanium-containing metal sheet in a tubular furnace, keep the temperature in the air at 400-500 ℃ for 1-3 hours, cool the titanium-containing metal sheet, take the titanium-containing metal sheet out of the tubular furnace, and ultrasonically clean the titanium-containing metal sheet in distilled water.
Preferably, the two times of calcination are to place the melamine in a muffle furnace at the calcination temperature of 500-600 ℃ for 1-3 hours, naturally cool the melamine, grind the melamine into powder, place the powder in the muffle furnace again at the calcination temperature of 400-600 ℃ for 1-3 hours, naturally cool the melamine, and grind the powder again.
Preferably, the nitrogen annealing is to dry the titanium-containing metal sheet dropwise added with the mixture by using an oven, then place the dried titanium-containing metal sheet into a tube furnace, anneal the titanium-containing metal sheet at 400-550 ℃ for 1-3 hours in a nitrogen atmosphere, take out the titanium-containing metal sheet after natural cooling, and ultrasonically clean the titanium-containing metal sheet in distilled water.
Preferably, the voltage of the anodic oxidation is 5-60V, and the time of the anodic oxidation is 0.5-4 hours.
Preferably, the volume ratio of the ethanol to the water is 2-4: 1.
Preferably, the titanium content of the titanium-containing metal sheet is 50-99.99 wt%.
Preferably, the polishing comprises the steps of firstly carrying out ultrasonic cleaning on the ground titanium-containing metal sheet by using ethanol, acetone and distilled water in sequence, and then carrying out chemical polishing in a solution with the volume ratio of HF to HNO3 to H2O being 1: 2-5: 4-7, wherein the chemical polishing time is 3-10 min; then, the mixture was washed with distilled water and blown dry with nitrogen.
Preferably, the electrolyte is a mixed solution of 0.1-1 wt% of fluorine-containing ions, 1-10 wt% of H2O, 1-10 wt% of CH3OH and 80-99 wt% of ethylene glycol.
Preferably, the fluorine-containing ions are more than one of KF, NaF, NH4F and HF.
The hydrogen sulfide photoelectrochemical sensor prepared by the preparation method of the hydrogen sulfide photoelectrochemical sensor.
By adopting the technical scheme, the invention provides a method for preparing a hydrogen sulfide photoelectrochemical sensor, which takes a titanium dioxide nanotube prepared on a titanium substrate by an anodic oxidation method as a template and prepares g-C by a calcination method3N4Finally, g-C is annealed by nitrogen3N4And C, modifying the titanium dioxide nanotube to obtain the composite material. The performance of the hydrogen sulfide photoelectrochemical sensor is controlled by controlling the volume of the dropwise added mixture and the nitrogen annealing temperature. Studies show that g-C3N4The semiconductor with narrow band gap realizes the enhancement of visible light absorption and improves the photocatalytic performance; the modified C not only improves the electron transport performance of the material and increases the conductivity of the material, but also effectively reduces the recombination rate of electron holes as an electron acceptor, thereby greatly improving the performance of the PEC sensor. The composite material is used for constructing a hydrogen sulfide photoelectrochemical sensor with good performance for detecting H2S opens up a new visual field and has great significance for early diagnosis of nervous system diseases and ecological environment detection.
Compared with the prior art, the invention has the following positive effects:
1. the hydrogen sulfide photoelectrochemical sensor prepared by the invention is prepared on a titanium substrate by an anodic oxidation methodThe prepared self-supporting titanium dioxide nanotube array presents an ordered one-dimensional nano structure, not only provides a directional electron transfer channel, but also can enable reactants and catalytic products to diffuse along the whole tubular depth and permeate to the inner surface and the outer surface of the nanotube, thereby achieving the purpose of large-area transmission. g-C3N4The semiconductor with narrow band gap realizes the enhancement of visible light absorption and improves the photocatalytic performance; the modified C not only improves the electron transmission performance of the material and increases the conductivity of the material, but also effectively reduces the recombination rate of electron holes as an electron acceptor, thereby greatly improving the performance of the PEC sensor in g-C3N4And under the double action of C, the performance of the hydrogen sulfide photoelectrochemical sensor is greatly improved.
2. The invention utilizes the volume of the dropping mixture and the nitrogen annealing temperature to control the g-C3N4And the modification amount of C to further control the performance of the hydrogen sulfide photoelectrochemical sensor and control TiO by simply controlling the condition of electrochemical anodic oxidation2The morphology of the nanotube is controlled by simple calcination temperature and time3N4The performance of the hydrogen sulfide photoelectric chemical sensor is realized, and the hydrogen sulfide photoelectric chemical sensor has the optimal photoelectric performance.
3. The hydrogen sulfide photoelectrochemical sensor is prepared on the titanium-containing metal sheet, so that the content of hydrogen sulfide can be simply and rapidly tested, and the hydrogen sulfide photoelectrochemical sensor has a good prospect.
Drawings
FIG. 1 is a front photograph of a scanning electron microscope of a hydrogen sulfide photoelectrochemical sensor prepared in example 1 of the present invention;
FIG. 2 is a scanning electron micrograph of the hydrogen sulfide photoelectrochemical sensor of FIG. 1;
FIG. 3 is a Raman spectrum of the hydrogen sulfide photoelectrochemical sensor of FIG. 1;
FIG. 4 is a photocurrent response curve of the hydrogen sulfide photoelectrochemical sensor of FIG. 1;
FIG. 5 is a linear fit curve of the hydrogen sulfide photoelectrochemical sensor of example 1 illustrated in FIG. 1;
FIG. 6 is a graph showing the interference rejection of the hydrogen sulfide photoelectrochemical sensor of example 1 shown in FIG. 1;
fig. 7 is a stability curve of the hydrogen sulfide photoelectrochemical sensor of example 1 illustrated in fig. 1.
Detailed Description
The invention is further described with reference to the following drawings and detailed description, which should not be construed as limiting the invention.
In order to avoid repetition, the polishing process of the titanium-containing metal sheet according to this embodiment is described in the following embodiments, which are not described in detail below:
the titanium content of the titanium-containing metal sheet is 50-99.99 wt%.
Polishing comprises ultrasonic cleaning the polished titanium-containing metal sheet with ethanol, acetone and distilled water, and HF: HNO3︰H2Carrying out chemical polishing in a solution with the volume ratio of O being 1: 2-5: 4-7 for 3-10 min; then, the mixture was washed with distilled water and blown dry with nitrogen.
The electrolyte comprises 0.1-1 wt% of fluorine-containing ions and 1-10 wt% of H2O, 1-10 wt% of CH3And (3) a mixed solution of OH and 80-99 wt% of ethylene glycol.
The air annealing is that the titanium-containing metal sheet after anodic oxidation is taken out from the electrolyte and washed by distilled water, dried by nitrogen and then placed in a tubular furnace, the temperature is kept for 2 hours at the temperature of 450 ℃ in the air, and the titanium-containing metal sheet is taken out after cooling and then ultrasonically cleaned in distilled water.
Sensor measurements H made in all examples2The tests for S were all tested in a three-electrode system by the CHI660 electrochemical workstation. Taking the prepared sample as a working electrode, a platinum sheet as a counter electrode and Ag/AgCl as a reference electrode, performing PEC measurement in a quartz square cell, and adopting a light power density of 100 mW-cm-2As a light source (lambda)>420nm)。
Example 1
A process for preparing the photoelectric chemical sensor of hydrogen sulfide includes such steps as grinding and polishing the Ti-contained metal plate as anode, putting it in electrolyte for anodizingPerforming anodization, wherein the voltage of the anodization is 60V, and the time of the anodization is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 500 mu L of a mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 450 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 2
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 30V, and the time of anodic oxidation is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 500 mu L of a mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 450 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 3
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 5V, and the time of anodic oxidation is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 500 mu L of a mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 450 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 4
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 60V, and the time of anodic oxidation is 2 hours; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, and then placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hoursTaking out, dripping 500 μ L of mixed solution of suspension and Nafion (volume ratio is 100: 1) onto the taken out titanium-containing metal sheet, annealing with nitrogen at 450 deg.C, naturally cooling, ultrasonic washing to obtain hydrogen sulfide photoelectrochemical sensor, and detecting H2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 5
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 60V, and the time of anodic oxidation is 4 hours; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 500 mu L of a mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 450 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 6
A process for preparing the photoelectric chemical sensor of hydrogen sulfide includes such steps as grinding and polishing the Ti-contained metal plate as anode, putting it in electrolyte for anodic oxidation, and applying the voltage to anodic oxidation60V, and the time of anodic oxidation is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 500 mu L of a mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 450 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 500 ℃, the time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 7
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 60V, and the time of anodic oxidation is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 500 mu L of a mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 450 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 600 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 8
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 60V, and the time of anodic oxidation is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 500 mu L of a mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 450 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 400 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 9
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 60V, and the time of anodic oxidation is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension, performing ultrasonic treatment for 1-2 hours, taking out the titanium-containing metal sheet, and taking the suspension and NafDripping 500 μ L of mixed solution of ion (volume ratio 100: 1) onto the taken-out titanium-containing metal sheet, annealing with nitrogen at 450 deg.C, naturally cooling, ultrasonically washing to obtain hydrogen sulfide photoelectrochemical sensor, and detecting H2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 600 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 10
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 60V, and the time of anodic oxidation is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 700 mu L of mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 450 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 11
A process for preparing the photoelectric chemical sensor of hydrogen sulfide includes such steps as grinding and polishing the Ti-contained metal plate as anode in electrolyte for anodizing at 60VThe time is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 300 mu L of mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 450 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 12
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 60V, and the time of anodic oxidation is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 500 mu L of mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 400 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 13
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 60V, and the time of anodic oxidation is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension for ultrasonic treatment for 1-2 hours, taking out the suspension, taking 500 mu L of a mixed solution of the suspension and Nafion (volume ratio is 100: 1) to drip on the taken-out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 500 ℃, naturally cooling and ultrasonically washing to obtain a hydrogen sulfide photoelectrochemical sensor, detecting H, and obtaining the hydrogen sulfide photoelectrochemical sensor2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Example 14
A preparation method of a hydrogen sulfide photoelectrochemical sensor comprises the steps of firstly, placing a polished titanium-containing metal sheet as an anode into electrolyte for anodic oxidation, wherein the voltage of anodic oxidation is 60V, and the time of anodic oxidation is 0.5 hour; and then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing to be clean. And then calcining the melamine twice, naturally cooling and grinding the melamine into powder. Finally, dispersing the powder in ethanol and water (volume ratio is 3: 1) to obtain 3mg/mL suspension, placing the annealed titanium-containing metal sheet in the suspension, performing ultrasonic treatment for 1-2 hours, taking out the titanium-containing metal sheet, and taking the suspension and Nafion (volume ratio is 100): 1) dripping 500 mu L of the mixed solution on a taken out titanium-containing metal sheet, then carrying out nitrogen annealing treatment at 550 ℃, obtaining the hydrogen sulfide photoelectrochemical sensor after natural cooling and ultrasonic washing, and detecting H2The pH of the solution with the S content is 2-10, and the test voltage is 0.1-1V.
The two times of calcination are that the melamine is placed in a muffle furnace, the calcination temperature is 550 ℃, the calcination time is 2 hours, the melamine is naturally cooled, ground into powder and then placed in the muffle furnace again, the calcination temperature is 500 ℃, the calcination time is 2 hours, and the melamine is naturally cooled and then ground into powder again.
Table 1 shows photocurrent response data of examples 1 to 14. As can be seen from Table 1, the hydrogen sulfide photoelectrochemical sensors prepared by the method have large photocurrent response, which shows that the separation efficiency of electron-hole pairs is high.
TABLE 1
The specific embodiment takes the titanium dioxide nanotube as a template to prepare the g-C by a calcination method3N4Finally, g-C is annealed by nitrogen3N4And C, modifying the titanium dioxide nanotube to obtain a composite material, and constructing a hydrogen sulfide photoelectrochemical sensor based on the composite material. Fig. 1 is a front scanning electron micrograph of a hydrogen sulfide photoelectrochemical sensor according to preparation example 1 of the present invention, and fig. 2 is a side scanning electron micrograph of the hydrogen sulfide photoelectrochemical sensor according to example 1 shown in fig. 1. As can be seen from FIGS. 1 and 2, the prepared nanotubes are highly ordered and vertically grown, the average inner diameter of a single nanotube is about 80nm, the wall thickness is about 50nm, the length is 7-8 μm, and the prepared nanotubes have a large number of irregularly-shaped g-C3N4Modified in TiO2NTAs surfaces. To further verify the modification of carbon in the material, we performed a Raman test, which is shown in the Raman plot of FIG. 3 at 1354cm-1And 1592cm-1The two characteristic peaks on the left and right are attributed to the D band and the G band of carbon, indicating that C was successfully modified into the composite. Drawing (A)And 4 is a photocurrent response curve of the hydrogen sulfide photoelectrochemical sensor and the titanium dioxide nanotube array in the embodiment 1 shown in fig. 1. As can be seen from FIG. 4, g-C was modified3N4After reaction with C, TiO2NTAs@C/g-C3N4The photocurrent response is obviously increased, and the dark current is greatly improved, so that the prepared sample can effectively promote the electron transmission rate and improve the visible light excitation e--h+The separation efficiency of (2) and has better conductivity.
FIG. 5 is a linear fit curve of the hydrogen sulfide photoelectrochemical sensor of example 1 illustrated in FIG. 1. The detection range is as follows: 2-800 μ M, sensitivity: 236.36 μ A. mM-1·cm-2The detection limit is as follows: 1.97 μ M (S/N ═ 3). The results of FIG. 5 illustrate H2The S concentration and the photocurrent density have a better linear relationship. Fig. 6 is a graph showing the interference rejection of the hydrogen sulfide photoelectrochemical sensor of example 1 shown in fig. 1. Fig. 7 is a stability curve of the hydrogen sulfide photoelectrochemical sensor of example 1 illustrated in fig. 1. Fig. 6 and 7 can show that the hydrogen sulfide photoelectrochemical sensor proposed by us has higher interference resistance and better stability. The performance of the hydrogen sulfide photoelectrochemical sensor is controlled by controlling the volume of the dropwise added mixture and the nitrogen annealing temperature. Studies show that g-C3N4The semiconductor with narrow band gap realizes the enhancement of visible light absorption and improves the photocatalytic performance; the modified C not only improves the electron transport performance of the material and increases the conductivity of the material, but also effectively reduces the recombination rate of electron holes as an electron acceptor, thereby greatly improving the performance of the PEC sensor. The composite material is used for constructing a hydrogen sulfide photoelectrochemical sensor with good performance for detecting H2S opens up a new visual field and has great significance for early diagnosis of nervous system diseases and ecological environment detection.
Compared with the prior art, the invention has the following positive effects:
1. the hydrogen sulfide photoelectric chemical sensor prepared by the invention is a self-supporting titanium dioxide nanotube array prepared on a titanium substrate by an anodic oxidation method, and presents ordered one-dimensional nanoThe structure not only provides a directional electron transfer channel, but also can lead reactants and catalytic products to diffuse along the whole tubular depth and permeate into the inner surface and the outer surface of the nano tube, thereby achieving the purpose of large-area transmission. g-C3N4The semiconductor with narrow band gap realizes the enhancement of visible light absorption and improves the photocatalytic performance; the modified C not only improves the electron transmission performance of the material and increases the conductivity of the material, but also effectively reduces the recombination rate of electron holes as an electron acceptor, thereby greatly improving the performance of the PEC sensor in g-C3N4And under the double action of C, the performance of the hydrogen sulfide photoelectrochemical sensor is greatly improved.
2. The invention utilizes the volume of the dropping mixture and the nitrogen annealing temperature to control the g-C3N4And the modification amount of C to further control the performance of the hydrogen sulfide photoelectrochemical sensor and control TiO by simply controlling the condition of electrochemical anodic oxidation2The morphology of the nanotube is controlled by simple calcination temperature and time3N4The performance of the hydrogen sulfide photoelectric chemical sensor is realized, and the hydrogen sulfide photoelectric chemical sensor has the optimal photoelectric performance.
3. The hydrogen sulfide photoelectrochemical sensor is prepared on the titanium-containing metal sheet, so that the content of hydrogen sulfide can be simply and rapidly tested, and the hydrogen sulfide photoelectrochemical sensor has a good prospect.
Therefore, the invention opens up a new route of the hydrogen sulfide photoelectrochemical sensor, has simple method and reliable process, realizes the rapid and accurate measurement of the hydrogen sulfide content, and aims to detect H2S opens up a new visual field and has great application prospect and economic value in early diagnosis of nervous system diseases and ecological environment detection.
Claims (10)
1. A preparation method of a hydrogen sulfide photoelectrochemical sensor is characterized by comprising the following steps:
firstly, putting a ground and polished titanium-containing metal sheet serving as an anode into electrolyte for anodic oxidation;
then washing and drying the titanium-containing metal sheet after anodic oxidation, then carrying out air annealing treatment, naturally cooling, and then ultrasonically washing;
then, calcining melamine twice, naturally cooling, grinding to powder, and dispersing the powder in ethanol and water to obtain 0.1-3 mg/mL suspension;
and putting the annealed titanium-containing metal sheet into the suspension, performing ultrasonic treatment for 1-2 hours, taking out the titanium-containing metal sheet, taking 100-700 mu L of mixed solution of the suspension and Nafion, dripping the mixed solution onto the taken out titanium-containing metal sheet, performing nitrogen annealing treatment, naturally cooling, and performing ultrasonic washing to obtain the hydrogen sulfide photoelectrochemical sensor.
2. The method for preparing the hydrogen sulfide photoelectrochemical sensor according to claim 1, wherein a volume ratio of the suspension to Nafion is 90-100: 1.
3. The preparation method of the hydrogen sulfide photoelectrochemical sensor according to claim 1, wherein the air annealing comprises the steps of taking the titanium-containing metal sheet after anodic oxidation out of the electrolyte, washing with distilled water, drying with nitrogen, placing in a tube furnace, keeping the temperature in the air at 400-500 ℃ for 1-3 hours, cooling, taking out, and performing ultrasonic cleaning in distilled water.
4. The preparation method of the hydrogen sulfide photoelectrochemical sensor according to claim 1, wherein the two times of calcination are to place the melamine in a muffle furnace at a calcination temperature of 500-600 ℃ for 1-3 hours, to naturally cool the melamine, to grind the melamine into powder, to place the melamine in the muffle furnace again at a calcination temperature of 400-600 ℃ for 1-3 hours, and to naturally cool the melamine, to grind the melamine into powder again.
5. The method for preparing the hydrogen sulfide photoelectrochemical sensor according to claim 1, wherein the nitrogen annealing is carried out by drying the titanium-containing metal sheet to which the mixture is added in an oven, placing the dried titanium-containing metal sheet in a tube furnace, annealing the titanium-containing metal sheet at 400-550 ℃ for 1-3 hours in a nitrogen atmosphere, taking out the titanium-containing metal sheet after natural cooling, and carrying out ultrasonic cleaning in distilled water.
6. The method for preparing a hydrogen sulfide photoelectrochemical sensor according to claim 1, wherein a voltage of the anodic oxidation is 5 to 60V, and a time of the anodic oxidation is 0.5 to 4 hours.
7. The method for preparing the hydrogen sulfide photoelectrochemical sensor according to claim 1, wherein a volume ratio of the ethanol to the water is 2-4: 1.
8. The method of claim 1, wherein the polishing comprises sequentially ultrasonic cleaning the polished titanium-containing metal sheet with ethanol, acetone and distilled water, and HF: HNO3︰H2Carrying out chemical polishing in a solution with the volume ratio of O being 1: 2-5: 4-7 for 3-10 min; then, the mixture was washed with distilled water and blown dry with nitrogen.
9. The method for preparing a hydrogen sulfide photoelectrochemical sensor according to claim 1, wherein the electrolyte comprises 0.1 to 1 wt% of fluorine-containing ions and 1 to 10 wt% of H2O, 1-10 wt% of CH3And (3) a mixed solution of OH and 80-99 wt% of ethylene glycol.
10. The hydrogen sulfide photoelectrochemical sensor manufactured by the method for manufacturing a hydrogen sulfide photoelectrochemical sensor according to any one of claims 1 to 9.
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