CN113024128B - Tin disulfide-C 3 N 4 Nanosheet array photoanode and preparation method thereof - Google Patents

Tin disulfide-C 3 N 4 Nanosheet array photoanode and preparation method thereof Download PDF

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CN113024128B
CN113024128B CN202110344316.2A CN202110344316A CN113024128B CN 113024128 B CN113024128 B CN 113024128B CN 202110344316 A CN202110344316 A CN 202110344316A CN 113024128 B CN113024128 B CN 113024128B
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tin disulfide
nanosheet
tin
temperature
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CN113024128A (en
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吕慧丹
王子良
刘勇平
庄杨
陈丹杨
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Guilin University of Technology
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    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C17/00—Surface treatment of glass, not in the form of fibres or filaments, by coating
    • C03C17/34—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions
    • C03C17/3411—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials
    • C03C17/3429—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating
    • C03C17/3464—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide
    • C03C17/347—Surface treatment of glass, not in the form of fibres or filaments, by coating with at least two coatings having different compositions with at least two coatings of inorganic materials at least one of the coatings being a non-oxide coating comprising a chalcogenide comprising a sulfide or oxysulfide
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2217/00—Coatings on glass
    • C03C2217/70—Properties of coatings
    • C03C2217/71—Photocatalytic coatings
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/11—Deposition methods from solutions or suspensions
    • C03C2218/111—Deposition methods from solutions or suspensions by dipping, immersion
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/10—Deposition methods
    • C03C2218/15—Deposition methods from the vapour phase
    • C03C2218/152—Deposition methods from the vapour phase by cvd
    • C—CHEMISTRY; METALLURGY
    • C03—GLASS; MINERAL OR SLAG WOOL
    • C03C—CHEMICAL COMPOSITION OF GLASSES, GLAZES OR VITREOUS ENAMELS; SURFACE TREATMENT OF GLASS; SURFACE TREATMENT OF FIBRES OR FILAMENTS MADE FROM GLASS, MINERALS OR SLAGS; JOINING GLASS TO GLASS OR OTHER MATERIALS
    • C03C2218/00—Methods for coating glass
    • C03C2218/30—Aspects of methods for coating glass not covered above
    • C03C2218/32—After-treatment
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
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    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/30—Hydrogen technology
    • Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis

Abstract

The invention provides a tin disulfide-C 3 N 4 The preparation method of the nanosheet array photoanode comprises the following steps: (1) Using sulfur powder as sulfur source and pentahydrateTin chloride is used as a tin source, is placed in a double-temperature-zone tubular furnace, and is used for preparing a tin disulfide nanosheet array through chemical vapor deposition; (2) Sintering at high temperature to obtain light yellow C 3 N 4 Then ultrasonically stripping C in a mixed solution of water and isopropanol 3 N 4 After the completion of the stripping, the supernatant was collected by centrifugation to obtain C 3 N 4 An ultra-thin nanosheet colloidal solution; (3) Soaking tin disulfide nanosheet array in C 3 N 4 Drying the ultrathin nanosheet colloidal solution for different times, and sintering in a tubular furnace under the argon atmosphere to obtain tin disulfide-C 3 N 4 And (3) a nanosheet array photoanode. Tin disulfide-C prepared by the method of the invention 3 N 4 The nano-sheet array photo-anode material has higher conductivity, and meanwhile, the stability and the photoelectric catalytic performance are also obviously improved.

Description

Tin disulfide-C 3 N 4 Nano-sheet array photo-anode and preparation method thereof
Technical Field
The invention belongs to the technical field of photoelectrocatalysis, and particularly relates to tin disulfide-C 3 N 4 Nanosheet array photoanode and also relates to the tin disulfide-C 3 N 4 A preparation method of a nano-sheet array photo-anode.
Background
With the development of society, people face the problems of continuous consumption of fossil energy (petroleum, coal, natural gas and the like) and increasingly serious environmental pollution, so that the development of renewable energy (solar energy, hydrogen energy, water energy, tidal energy, wind energy, biomass energy and the like) arouses great interest. The clean characteristic of solar energy can radically change the problem of environmental pollution caused by fossil energy consumption, so that the photoelectrochemical water decomposition has wide prospect in the aspect of converting the solar energy into clean chemical fuel such as hydrogen and the like.
Tin disulfide, a member of the Transition Metal Dichalcogenides (TMDS), has received much attention because of its low cost, non-toxicity and environmental friendliness, among which the large surface area of the two-dimensional tin disulfide is increasedThe interface contact area is increased, so that the rapid transfer of interface charges and electrochemical reaction are promoted, but the photoelectrocatalysis water decomposition performance and stability of the tin disulfide cannot achieve ideal effects. The formation of a heterojunction is an effective method for improving photocatalytic performance. C 3 N 4 The active material is matched with a tin disulfide energy band and combined to prepare a heterojunction photo-anode, so that the activity of photoelectrocatalysis can be improved. The morphology has a large influence on the performance of the heterojunction, and the nanosheet has a large specific surface area and is beneficial to improving the photocatalytic activity. Based on the technical scheme, the invention provides tin disulfide-C with high photoelectric catalytic activity 3 N 4 And (3) a nanosheet photo-anode material.
Disclosure of Invention
The first purpose of the invention is to provide tin disulfide-C 3 N 4 The preparation method of the nanosheet array photoanode solves the problems of low catalytic activity and poor stability of the existing photoelectric catalyst tin disulfide.
The second purpose of the invention is to provide the tin disulfide-C prepared by the method 3 N 4 And (3) a nanosheet array photoanode.
The first purpose of the invention is realized by the following technical scheme:
tin disulfide-C 3 N 4 The preparation method of the nanosheet array photoanode comprises the following steps:
(1) Placing sulfur powder as a sulfur source, tin tetrachloride pentahydrate as a tin source and conductive glass (FTO) as a substrate in a double-temperature-zone tubular furnace, and preparing a tin disulfide nanosheet array by chemical vapor deposition in an environment of introducing mixed gas of argon and hydrogen;
(2) Urea filled in a crucible is taken as a precursor, and is sintered at high temperature in a muffle furnace to obtain faint yellow C 3 N 4 (ii) a Then preparing C 3 N 4 Ultrasonically stripping in a mixed solution of water and isopropanol, centrifuging and collecting supernatant to obtain C 3 N 4 An ultra-thin nanosheet colloidal solution;
(3) Soaking tin disulfide nanosheet array in C 3 N 4 At different times in the colloidal solution of ultrathin nanosheets, and finallySintering in a tube furnace under argon atmosphere to obtain the tin disulfide-C 3 N 4 And (3) a nanosheet array photoanode.
The method prepares the tin disulfide nanosheet array on FTO by a chemical vapor deposition method, and then adopts a solution stripping method to obtain C 3 N 4 Ultra-thin nanosheets prepared by soaking tin disulfide nanosheet array in C 3 N 4 In the ultrathin nanosheet solution, finally sintering to obtain the tin disulfide-C 3 N 4 And (3) a nanosheet array photoanode. Tin disulfide-C prepared by the method of the invention 3 N 4 The nano-sheet array photo-anode material has higher conductivity, and meanwhile, the stability and the photoelectric catalytic performance are also obviously improved.
The preparation method of the invention can be further improved as follows:
in the step (1), the mass ratio of the sulfur powder to the tin tetrachloride pentahydrate is 0.4-1:0.2-0.5.
In the step (1), the tin disulfide nanosheet array is prepared in a dual-temperature-zone tube furnace by using FTO as a substrate, and the specific operation is as follows: placing the burning boat containing sulfur powder in the upstream central heating zone, wherein the reaction temperature is 200-400 ℃, and placing the burning boat containing tin tetrachloride pentahydrate in the downstream central heating zone, wherein the reaction temperature is 300-500 ℃.
Further, 2 FTO substrates are obliquely placed side by side at a position 8cm away from the right end of the burning boat in the downstream central heating area.
Further, the two temperature zones are heated to the set temperature for 45min at the same time, and the temperature is kept for 10-30min.
Further, argon is introduced in the temperature rising process, the gas flow is 80s.c.c.m, the argon flow is reduced to 60s.c.c.m in the heat preservation process, and hydrogen is introduced, and the gas flow is 20s.c.c.m; and (4) closing the hydrogen gas path after the heat preservation time is over, changing the flow of the argon gas to be 80s.c.c.m again, and taking out the sample after the temperature of the tube furnace is reduced to the room temperature to obtain the tin disulfide nanosheet.
And (2) carrying out ultrasonic cleaning in acetone, deionized water and ethanol before the FTO is used in the step (1), wherein the ultrasonic cleaning time is 30min each time.
In the step (1), the argon gas has a purity of 99.99 percent, and the hydrogen gas has a purity of 99.99 percent.
The volume ratio of water to propanol in the step (2) is 2.
Further, C 3 N 4 The mass-to-volume ratio of the mixed solution with water and propanol was 6.
The step (3) is specifically operated as follows: array of tin disulfide nanosheets obtained in (1) in C 3 N 4 Soaking the ultrathin nanosheet colloid solution for 2-5h, continuously stirring in the soaking process, and then sintering in a tubular furnace filled with argon at 350-550 ℃ for 1-3h, wherein the flow of the argon is 80s.c.c.m in the sintering process.
The second purpose of the invention is realized by the following technical scheme:
tin disulfide-C 3 N 4 The nano-sheet array photo-anode is prepared by the method.
Compared with the prior art, the invention has the following beneficial effects:
(1) Tin disulfide-C of the invention 3 N 4 The preparation method of the nanosheet array photoanode obtains the tin disulfide-C on the FTO substrate 3 N 4 The nano-sheet array photo-anode material has good conductivity, high photoelectrocatalysis activity and obviously improved stability at 0.5mol/LNa 2 SO 4 Photocurrent density in solution and at 1.23V (vs Ag/AgCl) was 8.7mA cm -2 And simultaneously shows better stability in a time current curve test.
(2) The preparation method is simple, low in cost and easy to control reaction conditions. Provides a good method for preparing the photo-anode material with high photoelectric catalytic activity, and is beneficial to the progress and development of the photoelectric catalytic decomposition technology.
Drawings
FIG. 1 shows tin disulfide-C obtained in example 2 of the present invention 3 N 4 And (3) XRD spectrum of the nano-sheet array photo-anode material.
FIG. 2 shows tin disulfide-C obtained in example 2 of the present invention 3 N 4 SEM image of nano-sheet array photo-anode material.
FIG. 3 shows tin disulfide-C obtained in example 2 of the present invention 3 N 4 EDS spectrogram of the nano-sheet array photo-anode.
FIG. 4 shows tin disulfide-C obtained in examples 1 to 3 of the present invention 3 N 4 LSV curve diagram of photoelectrocatalysis performance of the nanosheet array photoanode.
FIG. 5 shows tin disulfide-C obtained in examples 1 to 3 of the present invention 3 N 4 Time-current (i-t) curve diagram of nano-sheet array photoanode.
Detailed Description
The present invention is further described below in conjunction with specific examples to better understand and implement the technical solutions of the present invention for those skilled in the art.
Example 1
Tin disulfide-C 3 N 4 The preparation method of the nanosheet array photoanode comprises the following steps:
(1) And (3) respectively ultrasonically treating FTO (1 cm multiplied by 2.5 cm) in acetone, alcohol and ethanol solution for 30min to remove surface pollutants, and drying for later use. In a double-temperature-zone tube furnace, a burning boat containing 0.68g of sulfur powder is placed in an upstream central heating zone, the reaction temperature is 250 ℃, a burning boat containing 0.34g of stannic chloride pentahydrate is placed in a downstream central heating zone, the reaction temperature is 450 ℃, and 2 FTO substrates are obliquely placed side by side at a position 8cm away from the right end of the burning boat in the downstream central heating zone. The two temperature zones are heated up to the set temperature for 45min at the same time, and the temperature is kept for 17min. Argon is introduced in the temperature rising process, the gas flow is 80s.c.c.m, the argon flow is reduced to 60s.c.m in the heat preservation process, and hydrogen is introduced, and the gas flow is 20s.c.m. And (4) closing the hydrogen gas path after the heat preservation time is over, changing the flow of the argon gas to 80s.c.c.m again, and taking out the sample after the temperature of the isopipe furnace is reduced to the room temperature to obtain the tin disulfide nanosheet.
(2) Sintering to obtain light yellow C 3 N 4 Taking 90mgC 3 N 4 And putting into a brown glass bottle with a cover. Sequentially adding 10ml of deionized water and 5ml of isopropanol, stirring uniformly and then carrying out ultrasonic treatment for 24h. Centrifuging the obtained solution in a centrifuge at 3000r/min for 10min, and collecting supernatant to obtain C 3 N 4 And (3) an ultrathin nanosheet colloidal solution.
(3) Take 15mlC 3 N 4 And transferring the ultrathin nanosheet colloidal solution into a 25ml beaker, fixing the tin disulfide nanosheet on the wall of the beaker by using a clamp, stirring and soaking for 4 hours, taking out the sample, and drying the sample in an oven at 60 ℃ for 3 hours. And then transferring the sample into a tube furnace to be sintered in argon atmosphere, heating up to 350 ℃ at the heating rate of 2 ℃/min, preserving the heat for 1h, cooling to room temperature, and taking out to obtain the tin disulfide-C 3 N 4 And (3) a nanosheet array photoanode.
Example 2
Tin disulfide-C 3 N 4 The preparation method of the nanosheet array photoanode comprises the following steps:
(1) And (3) respectively performing ultrasonic treatment on FTO (1 cm multiplied by 2.5 cm) in acetone, alcohol and ethanol solution for 30min to remove surface pollutants, and drying for later use. In a double-temperature-zone tube furnace, a burning boat containing 0.4g of sulfur powder is placed in an upstream central heating zone, the reaction temperature is 200 ℃, a burning boat containing 0.2g of stannic chloride pentahydrate is placed in a downstream central heating zone, the reaction temperature is 300 ℃, and 2 FTO substrates are obliquely placed side by side at a position 8cm away from the right end of the burning boat in the downstream central heating zone. The two temperature zones are heated to the set temperature for 45min at the same time, and the temperature is kept for 30min. Argon is introduced in the temperature rising process, the gas flow is 80s.c.c.m, the argon flow is reduced to 60s.c.m in the heat preservation process, and hydrogen is introduced, and the gas flow is 20s.c.m. And (4) closing the hydrogen gas path after the heat preservation time is over, changing the flow of the argon gas to be 80s.c.c.m again, and taking out the sample after the temperature of the tube furnace is reduced to the room temperature to obtain the tin disulfide nanosheet.
(2) Preparing light yellow C by adopting a sintering method 3 N 4 Take 90mgC 3 N 4 And putting into a brown glass bottle with a cover. Sequentially adding 10ml of deionized water and 5ml of isopropanol, stirring uniformly and then carrying out ultrasonic treatment for 24h. Centrifuging the obtained solution in a centrifuge at 3000r/min for 10min, and collecting supernatant to obtain C 3 N 4 And (3) an ultrathin nanosheet colloidal solution.
(3) Taking 15ml C 3 N 4 Transferring the ultrathin nanosheet colloidal solution into a 25ml beaker, fixing the tin disulfide nanosheet on the wall of the beaker by using a clamp, stirring and soaking for 2 hours, taking out a sample, and drying the sample in an oven at 60 DEG CAnd 3h. And then transferring the sample into a tube furnace to be sintered in argon atmosphere at the heating rate of 2 ℃/min, heating to 400 ℃, keeping the temperature for 2h, cooling to room temperature, and taking out to obtain the tin disulfide-C 3 N 4 And (3) a nanosheet array photoanode.
Example 3
Tin disulfide-C 3 N 4 The preparation method of the nanosheet array photoanode comprises the following steps:
(1) And (3) respectively performing ultrasonic treatment on FTO (1 cm multiplied by 2.5 cm) in acetone, alcohol and ethanol solution for 30min to remove surface pollutants, and drying for later use. In a double-temperature-zone tube furnace, a burning boat containing 1.0g of sulfur powder is placed in an upstream central heating zone, the reaction temperature is 400 ℃, a burning boat containing 0.5g of stannic chloride pentahydrate is placed in a downstream central heating zone, the reaction temperature is 500 ℃, the position 8cm away from the right end of the burning boat in the downstream central heating zone is obliquely placed side by side with 2 FTO substrates. The two temperature zones are heated up to the set temperature for 45min and then are kept warm for 10min. Argon is introduced in the temperature rising process, the gas flow is 80s.c.c.m, the argon flow is reduced to 60s.c.m in the heat preservation process, and hydrogen is introduced, and the gas flow is 20s.c.m. And (4) closing the hydrogen gas path after the heat preservation time is over, changing the flow of the argon gas to 80s.c.c.m again, and taking out the sample after the temperature of the isopipe furnace is reduced to the room temperature to obtain the tin disulfide nanosheet.
(2) Sintering to obtain light yellow C 3 N 4 Taking 90mgC 3 N 4 And putting into a brown glass bottle with a cover. Sequentially adding 10ml of deionized water and 5ml of isopropanol, stirring uniformly and then carrying out ultrasonic treatment for 24h. Centrifuging the obtained solution in a centrifuge at 3000r/min for 10min, and collecting supernatant to obtain C 3 N 4 And (3) an ultrathin nanosheet colloidal solution.
(3) Taking 15ml C 3 N 4 And transferring the ultrathin nanosheet colloidal solution into a 25ml beaker, fixing the tin disulfide nanosheet on the wall of the beaker by using a clamp, stirring and soaking for 5 hours, taking out the sample, and drying the sample in an oven at 60 ℃ for 3 hours. And then transferring the sample into a tube furnace to be sintered in argon atmosphere, heating up to 550 ℃, keeping the temperature for 3h, cooling to room temperature, and taking out to obtain the tin disulfide-C 3 N 4 Nano-sheet array photo-anode。
Example 4
(1) And (3) respectively ultrasonically treating FTO (1 cm multiplied by 2.5 cm) in acetone, alcohol and ethanol solution for 30min to remove surface pollutants, and drying for later use. In a double-temperature-zone tube furnace, a burning boat containing 0.8g of sulfur powder is placed in an upstream central heating zone, the reaction temperature is 300 ℃, a burning boat containing 0.25g of stannic chloride pentahydrate is placed in a downstream central heating zone, the reaction temperature is 400 ℃, and 2 FTO substrates are obliquely placed side by side at a position 8cm away from the right end of the burning boat in the downstream central heating zone. The two temperature zones are heated to the set temperature for 45min at the same time, and the temperature is kept for 20min. Argon is introduced in the temperature rising process, the gas flow is 80s.c.c.m, the argon flow is reduced to 60s.c.m in the heat preservation process, and hydrogen is introduced, and the gas flow is 20s.c.m. And (4) closing the hydrogen gas path after the heat preservation time is over, changing the flow of the argon gas to be 80s.c.c.m again, and taking out the sample after the temperature of the tube furnace is reduced to the room temperature to obtain the tin disulfide nanosheet.
(2) Preparing light yellow C by adopting a sintering method 3 N 4 Taking 90mgC 3 N 4 And putting into a brown glass bottle with a cover. Sequentially adding 10ml of deionized water and 5ml of isopropanol, stirring uniformly and then carrying out ultrasonic treatment for 24h. Centrifuging the obtained solution in a centrifuge at 3000r/min for 10min, and collecting supernatant to obtain C 3 N 4 And (3) an ultrathin nanosheet colloidal solution.
(3) Taking 15ml C 3 N 4 And transferring the ultrathin nanosheet colloidal solution into a 25ml beaker, fixing the tin disulfide nanosheet on the wall of the beaker by using a clamp, stirring and soaking for 3 hours, taking out the sample, and drying the sample in an oven at 60 ℃ for 3 hours. And then transferring the sample into a tube furnace to be sintered in argon atmosphere, heating up to 450 ℃ at the heating rate of 2 ℃/min, preserving the heat for 1h, cooling to room temperature, and taking out to obtain the tin disulfide-C 3 N 4 And (3) a nanosheet array photoanode.
Photoelectrochemical property test: directly mixing the tin disulfide-C prepared in the example 3 N 4 The nanosheet array material is used as a working electrode (the test area is 1 cm) 2 ) The platinum sheet electrode is an auxiliary electrode, and the Ag/AgCl electrode is a reference electrode. 0.5mol/LNa at room temperature 2 SO 4 Photoelectrochemical property in electrolyteCan be tested.
As shown in fig. 1, an XRD pattern of the photoanode material prepared in example 2 is shown. For tin disulfide-C 3 N 4 Nanosheet array photoanode due to SnS 2 Nanosheet surface-supported C 3 N 4 The content is less, and the figure shows that C is caused 3 N 4 Characteristic peak of (2) and SnS 2 The characteristic peak positions of the nano-sheets are coincident, so that further tin disulfide-C is needed 3 N 4 And carrying out structural characterization on the nanosheet array photoanode. In addition, the main diffraction peaks of tin disulfide appear at 2 theta =14.92 °,28.12 °,32.05 °,41.78 °,49.86 ° and 52.36 °, which are well matched with standard cards (JCPDS No. 23-0677).
As shown in fig. 2, is an SEM image of the photoanode material prepared in example 2. From the figure, it can be clearly seen that C 3 N 4 Presence of nanosheets, C prepared by ultrasonic exfoliation 3 N 4 The volume of the nano-sheet is far less than that of SnS 2 Nanosheets, some C 3 N 4 Loaded in SnS 2 SnS on nanosheet surface, even in partial region 2 Nanosheet quilt C 3 N 4 Complete coverage indicates that the two are well bonded, which reduces interfacial transport resistance and facilitates electron transport.
As shown in fig. 3, which is an EDS spectrum of the photo-anode material prepared in example 2, it can be seen that the material only contains four elements, i.e., C, N, S, and Sn, and no other impurities are introduced.
As shown in fig. 4, which is a plot of LSV of the photoanode materials prepared in examples 1-3. It can be seen from the figure that as the soaking time increases, the tin disulfide surface is loaded with C 3 N 4 The content also gradually increases, and the tin disulfide-C 3 N 4 The photoelectrocatalysis performance of the nanosheet array photoanode shows a trend of being improved first and then gradually descending, and meanwhile, the tin disulfide nanosheet has the most excellent photoelectrocatalysis performance when the soaking time in the supernatant is 8 hours.
As shown in FIG. 5, a time-current (i-t) graph is shown for the photoanode materials prepared in examples 1-3. It can be seen from the figure that the same principle is followed as in figure 4, with the disulfideTin surface-supported C 3 N 4 Increase in the content of tin disulfide-C compared with tin disulfide 3 N 4 The stability of the nano-sheet array photo-anode shows a trend of gradually increasing and then gradually decreasing.
The above embodiments are described in detail for different implementations of the present invention, but the implementation manner of the present invention is not limited thereto, and those skilled in the art can achieve the object of the present invention based on the disclosure of the present invention, and any modifications and variations based on the concept of the present invention fall within the protection scope of the present invention, and the specific protection scope is subject to the claims.

Claims (10)

1. Tin disulfide-C 3 N 4 The preparation method of the nano-sheet array photo-anode is characterized by comprising the following steps:
(1) Placing sulfur powder as a sulfur source, tin tetrachloride pentahydrate as a tin source and FTO (fluorine-doped tin oxide) conductive glass as a substrate in a double-temperature-zone tubular furnace, and preparing a tin disulfide nanosheet array by chemical vapor deposition in an environment of introducing mixed gas of argon and hydrogen;
(2) Urea filled in a crucible is taken as a precursor, and is sintered at high temperature in a muffle furnace to obtain light yellow C 3 N 4 (ii) a Then preparing C 3 N 4 Ultrasonically stripping in a mixed solution of water and isopropanol, centrifuging and collecting supernatant to obtain C 3 N 4 An ultra-thin nanosheet colloidal solution;
(3) Soaking tin disulfide nanosheet array in C 3 N 4 Drying the ultrathin nanosheet colloidal solution for different times, and sintering in a tubular furnace under the argon atmosphere to obtain tin disulfide-C 3 N 4 And (3) a nanosheet array photoanode.
2. Tin disulfide-C according to claim 1 3 N 4 The preparation method of the nanosheet array photoanode is characterized in that the mass ratio of the sulfur powder to the tin tetrachloride pentahydrate in the step (1) is 0.4-1:0.2-0.5.
3. Tin disulfide-C according to claim 1 3 N 4 The preparation method of the nano-sheet array photo-anode is characterized in that in the step (1), the tin disulfide nano-sheet array is prepared in a two-temperature-zone tube furnace by taking FTO as a substrate, and the specific operation is as follows: placing the burning boat containing sulfur powder in the upstream central heating zone, wherein the reaction temperature is 200-400 ℃, and placing the burning boat containing tin tetrachloride pentahydrate in the downstream central heating zone, wherein the reaction temperature is 300-500 ℃.
4. Tin disulfide-C according to claim 3 3 N 4 The preparation method of the nano-sheet array photo-anode is characterized in that 2 FTO substrate rows are obliquely arranged at a position 8cm away from the right end of a downstream central heating zone burning boat.
5. Tin disulfide-C according to claim 3 3 N 4 The preparation method of the nano-sheet array photo-anode is characterized in that two temperature zones are heated to a set temperature for 45min at the same time, and the temperature is kept for 10-30min.
6. Tin disulfide-C according to claim 3 3 N 4 The preparation method of the nanosheet array photoanode is characterized in that argon is introduced in the heating process, the gas flow is 80s.c.c.m, the argon flow is reduced to 60s.c.m in the heat preservation process, hydrogen is introduced, the gas flow is 20 s.c.m, the hydrogen gas path is closed after the heat preservation time is over, the argon flow is changed to 80s.c.m again, and a sample is taken out after the temperature of a tubular furnace is reduced to the room temperature, so that the tin disulfide nanosheet is obtained.
7. Tin disulfide-C according to any one of claims 1 to 6 3 N 4 The preparation method of the nano-sheet array photoanode is characterized in that ultrasonic cleaning is carried out in acetone, deionized water and ethanol before FTO is used in the step (1), and the ultrasonic cleaning time is 30min each time; in the step (1), the argon gas has a purity of 99.99 percent, and the hydrogen gas has a purity of 99.99 percent.
8. Tin disulfide-C according to claim 7 3 N 4 The preparation method of the nano-sheet array photo-anode is characterized in that the volume ratio of water to propanol in the step (2) is 2; c 3 N 4 The mass-to-volume ratio of the mixed solution with water and propanol was 6.
9. Tin disulfide-C according to claim 1 3 N 4 The preparation method of the nanosheet array photoanode comprises the following specific operations in step (3): and (2) soaking the tin disulfide nanosheet array obtained in the step (1) in an ultrathin nanosheet colloidal solution for 2-5h, continuously stirring in the soaking process, and then sintering in a tubular furnace filled with argon at 350-550 ℃ for 1-3h, wherein the flow of the argon in the sintering process is 80s.c.c.m.
10. Tin disulfide-C 3 N 4 A nanosheet array photoanode, prepared by the method of any one of claims 1 to 9.
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