CN115193458A - Sheet-like BPQDs/ZnIn 2 S 4 Binary heterostructure composite photocatalytic material and preparation method and application thereof - Google Patents

Sheet-like BPQDs/ZnIn 2 S 4 Binary heterostructure composite photocatalytic material and preparation method and application thereof Download PDF

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CN115193458A
CN115193458A CN202210924878.9A CN202210924878A CN115193458A CN 115193458 A CN115193458 A CN 115193458A CN 202210924878 A CN202210924878 A CN 202210924878A CN 115193458 A CN115193458 A CN 115193458A
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bpqds
znin
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black phosphorus
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余愿
任杰
屈彦宁
孙东峰
楚文慧
黄琳茵
强鹏鹏
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Shaanxi University of Science and Technology
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    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • B01J35/39—Photocatalytic properties
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • B01J37/10—Heat treatment in the presence of water, e.g. steam
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    • C01B3/00—Hydrogen; Gaseous mixtures containing hydrogen; Separation of hydrogen from mixtures containing it; Purification of hydrogen
    • C01B3/02—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen
    • C01B3/04—Production of hydrogen or of gaseous mixtures containing a substantial proportion of hydrogen by decomposition of inorganic compounds, e.g. ammonia
    • C01B3/042—Decomposition of water
    • 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
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • 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

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Abstract

The invention belongs to the technical field of photocatalytic materials, and discloses a flaky BPQDs/Znin 2 S 4 A binary heterostructure composite photocatalytic material and a preparation method and application thereof; the preparation method comprises the following steps: uniformly dispersing black phosphorus powder in an NMP solution, carrying out ultrasonic treatment and solid-liquid separation to obtain a liquid component; removing the solvent in the liquid component, and dispersing in the water solvent to obtain a black phosphorus quantum dot suspension; uniformly dispersing indium chloride, thioacetamide and zinc chloride in a solvent A, and carrying out hydrothermal reaction to obtain a precursor; uniformly dispersing the precursor in a solvent B, then adding a black phosphorus quantum dot suspension, stirring for 8-24 h at 50-70 ℃, and drying to obtain flaky BPQDs/ZnIn 2 S 4 A composite photocatalytic material with a binary heterostructure. The inventionThe preparation method has the advantages of low price of the adopted raw materials, no noble metal, high hydrogen production efficiency of the prepared materials, stable use performance and suitability for large-scale application.

Description

Sheet-like BPQDs/ZnIn 2 S 4 Binary heterostructure composite photocatalytic material and preparation method and application thereof
Technical Field
The invention relates to the technical field of catalytic materials, in particular to flaky BPQDs/ZnIn 2 S 4 A binary heterostructure composite photocatalytic material, a preparation method and application thereof.
Background
In recent years, energy consumption is increasingly serious, and in order to meet the requirements of world sustainable development, a plurality of replaceable novel energy sources, such as wind energy, solar energy, hydrogen energy and the like, are urgently required to be searched. Hydrogen energy is favored by people because of its high efficiency and no pollution.
At present, photocatalytic decomposition of water produces hydrogen (H) 2 ) Have been developed as a promising technology for providing clean solar fuels. This work is currently focused on semiconductors with a relatively large forbidden band, such as TiO 2 、C 3 N 4 And the like, and the problems of low light utilization rate and the like caused by the fact that the absorption is only carried out by ultraviolet light, electron holes are easy to recombine, the carrier migration speed is low and the like are solved. Therefore, there is an urgent need to develop a novel photocatalyst having a narrow band gap.
Therefore, the invention provides a sheet-shaped BPQDs/ZnIn 2 S 4 A composite photocatalytic material with a binary heterostructure, a preparation method and application thereof.
Disclosure of Invention
In order to solve the above-mentioned deficiencies in the prior art, the present invention provides a sheet-like BPQDs/ZnIn 2 S 4 A binary heterostructure composite photocatalytic material, a preparation method and application thereof. The invention firstly synthesizes flaky sulfur indium zinc and introduces BPQDs to form a binary heterostructure to accelerate the separation rate of electrons and holes and effectively improve the material at lambda>Hydrogen evolution capacity under visible light of 420 nm.
A sheet of the present inventionLike BPQDs/ZnIn 2 S 4 The binary heterostructure composite photocatalytic material and the preparation method and the application thereof are realized by the following technical scheme:
the first object of the present invention is to provide sheet-like BPQDs/ZnIn 2 S 4 The preparation method of the composite photocatalytic material with the binary heterostructure comprises the following steps:
step 1, uniformly dispersing black phosphorus powder in an NMP solution, and then sequentially carrying out ultrasonic treatment and solid-liquid separation to obtain a liquid component; removing the solvent in the liquid component, and then dispersing in the water solvent to obtain a black phosphorus quantum dot suspension;
step 2, uniformly dispersing indium chloride, thioacetamide and zinc chloride in a solvent A, and then carrying out hydrothermal reaction at the temperature of 150-200 ℃ to obtain a precursor;
step 3, uniformly dispersing the precursor in a solvent B, then adding the black phosphorus quantum dot suspension, carrying out stirring reaction at 50-70 ℃, and drying to obtain the flaky BPQDs/ZnIn 2 S 4 A composite photocatalytic material with a binary heterostructure.
Further, the solvent A is a mixed solution of water and ethanol mixed in any proportion;
the solvent B is water.
Further, the dosage ratio of the black phosphorus powder to the N-methylpyrrolidone (NMP) solution is 1mg to 10mL;
the dosage ratio of the water solvent to the black phosphorus powder is 1mL.
Furthermore, the dosage ratio of the precursor to the black phosphorus quantum dot suspension is 1mg to 3 μ L.
Further, the mass ratio of indium chloride, thioacetamide and zinc chloride is 0.089 to 0.266.
Further, the usage ratio of the indium chloride to the solvent A is 2 to 9mg.
Further, the ultrasonic treatment is carried out by adopting a cell ultrasonic crusher under the ice bath condition, the ultrasonic power is 500-550W, the ultrasonic interval is 2-4 s, and the ultrasonic time is 4-8 h.
Furthermore, the time of the hydrothermal reaction is 20-25 h.
The second purpose of the invention is to provide a sheet-shaped BPQDs/ZnIn prepared by the preparation method 2 S 4 A composite photocatalytic material with a binary heterostructure.
The third object of the present invention is to provide the above sheet-like BPQDs/ZnIn 2 S 4 The application of the composite photocatalytic material with the binary heterostructure in hydrogen production by photolysis of water.
Compared with the prior art, the invention has the following beneficial effects:
dispersing black phosphorus powder in an NMP solution, fully stripping large black phosphorus by ultrasound, removing the NMP solution, and dispersing in an aqueous solvent again to obtain a black phosphorus quantum dot suspension; then adding yellow flaky sulfur indium zinc precursor material prepared by solvothermal reaction by taking zinc chloride, indium chloride and thioacetamide as raw materials, and obtaining flaky BPQDs/ZnIn through stirring reaction 2 S 4 The binary heterostructure composite photocatalytic material greatly improves the lambda-range of the material>The hydrogen evolution rate under the visible light of 420nm opens up a new path for the synthesis of the black phosphorus-based composite photocatalytic material and provides a new reference idea for the photocatalytic hydrogen evolution material.
The invention removes NMP solution for protecting and stripping massive black phosphorus to remove the influence of organic matters, re-disperses the stripped black phosphorus quantum dots in aqueous solvent, then adds sulfur indium zinc, realizes better reaction of the black phosphorus quantum dots and the sulfur indium zinc in the aqueous solvent A, and obtains flaky BPQDs/ZnIn 2 S 4 A composite photocatalytic material with a binary heterostructure.
The catalyst prepared by the invention does not need any noble metal, and the prepared flaky BPQDs/ZnIn 2 S 4 The composite photocatalytic material with the binary heterostructure has good hydrogen evolution performance under visible light and good stability, so that the composite photocatalytic material is suitable for large-scale use.
Drawings
FIG. 1 shows BPQDs/ZnIn provided in example 1 2 S 4 A powder X-ray diffraction pattern of the composite photocatalytic material with the binary heterostructure;
FIG. 2 shows BPQDs/ZnIn provided in example 1 2 S 4 Scanning a scanning image of the composite photocatalytic material with the binary heterostructure;
FIG. 3 shows BPQDs/ZnIn provided in example 1 2 S 4 A transmission diagram of the composite photocatalytic material with the binary heterostructure;
FIG. 4 is a transmission diagram of BPQDs;
FIG. 5 shows BPQDs/ZnIn provided in example 1 2 S 4 A performance diagram of the composite photocatalytic material with the binary heterostructure.
Detailed Description
The technical solution in the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings in the embodiments of the present invention.
Example 1
This example provides a sheet of BPQDs/ZnIn 2 S 4 The binary heterostructure composite photocatalytic material is prepared by the following steps:
step 1, uniformly dispersing black phosphorus powder in an N-methylpyrrolidone (NMP) solution, and then sequentially carrying out ultrasonic treatment and solid-liquid separation to obtain a liquid component; removing the solvent in the liquid component, and then dispersing in the water solvent to obtain a black phosphorus quantum dot suspension;
the present invention is not limited to a specific dispersion mode of the black phosphorus powder in the NMP solution, as long as a uniform suspension can be formed. Optionally, in the present invention, an ultrasonic method is adopted for dispersion, and 5mg of black phosphorus powder is weighed and added into 10ml of nmp solution, and ultrasonic power of 200W is used for 1 hour, so as to obtain a uniformly dispersed suspension of black phosphorus powder.
The invention does not limit the specific technological parameters of ultrasonic treatment, as long as the large black phosphorus can be fully stripped. Optionally, in this embodiment, a cell ultrasonic crusher is used, and ultrasonic processing is performed for 6 hours at an ultrasonic interval of 3s (ultrasonic 3s, stop 3s, and ultrasonic 3s again) with an ultrasonic power of 540W in an ice bath, so as to sufficiently strip the large black phosphorus.
The invention is not limited to a specific manner of solid-liquid separation as long as large-sized residues in the suspension can be removed. Optionally, the invention adopts a centrifugal mode, firstly centrifuges for 30min at the speed of 4000r/min, and then centrifuges for 30min at the speed of 7000r/min to remove large residues, and the obtained supernatant is the required liquid component.
The present invention is not limited to a specific manner of removing the solvent NMP in the liquid component as long as the solvent NMP in the liquid component can be removed. Optionally, the method adopts a rotary evaporator, and performs rotary evaporation for 30min at the temperature of 140 ℃ to fully evaporate the NMP solvent, so that the obtained dark yellow viscous substance is the black phosphorus quantum dot.
In order to obtain a clean black phosphorus quantum dot suspension, the black phosphorus quantum dot suspension is further added with water to be subjected to rotary evaporation and water washing twice to remove the residual NMP solvent before being dispersed in a water solvent, and then is dispersed in 1mL of deionized water to obtain the black phosphorus quantum dot suspension.
Step 2, uniformly dispersing indium chloride, thioacetamide and zinc chloride in a solvent A, and then carrying out hydrothermal reaction at the temperature of 150-200 ℃ to obtain a precursor;
it should be noted that the invention is not limited to the specific components and the amount of the solvent A, as long as the indium chloride can react with the zinc source and thioacetamide during the hydrothermal treatment to obtain ZnIn 2 S 4 And (4) finishing. In this example, optionally, a mixed solution of water and ethanol in equal volume is used as the solvent a, and 30ml of the mixed solution of water and ethanol is measured to disperse 0.177g of indium chloride, 0.18g of thioacetamide and 0.54g of zinc chloride, so as to obtain a mixed solution.
The invention does not limit the specific dispersion mode of indium chloride, thioacetamide and zinc chloride in the solvent A, as long as the indium chloride, thioacetamide and zinc chloride can be uniformly dispersed in the solvent A to obtain a uniform solution. In this example, the dispersion was carried out by stirring, and the dispersion was made uniform by stirring at a rate of 500r/min for 30min.
The invention does not limit the specific reaction temperature and reaction time of the hydrothermal treatment, and the reaction time can be flexibly adjusted according to the reaction temperature of the time as long as the precursor (yellow sulfur indium zinc powder) can be obtained. However, the reaction temperature of the hydrothermal treatment is preferably not more than 150 to 200 ℃ to ensure that yellow S-in-Zn powder can be obtained. In the present example, alternatively, the reaction is carried out at 180 ℃ for 24h, then the solid product is obtained by centrifugation, the solid product is washed with water and ethanol for multiple times to remove surface impurities, and then dried to remove the surface solvent of the solid product, so as to obtain yellow sulfur indium zinc powder.
Step 3, uniformly dispersing the precursor in a solvent B, then adding the black phosphorus quantum dot suspension, carrying out stirring reaction at 60 ℃, and drying to obtain the flaky BPQDs/ZnIn 2 S 4 A binary heterostructure composite photocatalytic material;
it should be noted that the invention does not limit the specific components and dosage of the solvent B, as long as the solvent B and the black phosphorus quantum dots can react in the subsequent stirring treatment process to obtain flaky BPQDs/ZnIn 2 S 4 The composite photocatalytic material with the binary heterostructure is prepared. In this example, deionized water was optionally used as solvent B, and 20mL of deionized water was weighed out for dispersing 100mg of the precursor (yellow sulfur indium zinc powder).
The present invention does not limit the specific dispersion manner of the precursor in the solvent B as long as ZnIn can be made 2 S 4 The material is uniformly dispersed in the solvent B to obtain a uniform solution. In this embodiment, the dispersion is performed by using an ultrasonic method, the ultrasonic power is 200W, and the ultrasonic time is 30min.
The invention does not limit the specific stirring speed of the stirring reaction in the step 3, as long as the precursor and the black phosphorus quantum dots can be ensured to be fully contacted under the stirring action, so as to obtain the material with uniform component structure. In this embodiment, optionally, after 200. Mu.L of the black phosphorus quantum dot suspension is added, stirring is carried out at a speed of 600r/min for 12h.
The present invention is not limited to a specific method of drying as long as the solvent in the material can be removed. In this embodiment, optionally, a vacuum drying oven at 60 ℃ is used for drying for 12 hours.
Example 2
This example provides a sheet of BPQDs/ZnIn 2 S 4 The binary heterostructure composite photocatalytic material and the preparation method thereof are different from the embodiment 1 only in that:
in step 2 of this example, 0.089g of indium chloride, 0.18g of thioacetamide, and 0.54g of zinc chloride were placed in a 50ml polytetrafluoroethylene liner, and a mixed solution of 30ml of a mixture of water and ethanol in equal volume was added thereto and stirred for 30 minutes to disperse the mixture uniformly, thereby obtaining a mixed solution.
Example 3
This example provides a sheet of BPQDs/ZnIn 2 S 4 The composite photocatalytic material with the binary heterostructure and the preparation method thereof are only different from the preparation method of the embodiment 1 that:
in step 2 of this example, 0.266g of indium chloride, 0.18g of thioacetamide, and 0.54g of zinc chloride were placed in a 50ml polytetrafluoroethylene liner, and a mixed solution of 30ml of a mixture of water and ethanol in equal volume was added thereto and stirred for 30 minutes to disperse the mixture uniformly, thereby obtaining a mixed solution.
Example 4
This example provides a sheet of BPQDs/ZnIn 2 S 4 The binary heterostructure composite photocatalytic material and the preparation method thereof are different from the embodiment 1 only in that:
in step 2, the hydrothermal reaction temperature is 160 ℃.
Example 5
This example provides a sheet form of BPQDs/ZnIn 2 S 4 The binary heterostructure composite photocatalytic material and the preparation method thereof are different from the embodiment 1 only in that:
in step 2, the hydrothermal reaction temperature is 200 ℃.
Example 6
This example provides a sheet form of BPQDs/ZnIn 2 S 4 The binary heterostructure composite photocatalytic material and the preparation method thereof are different from the embodiment 1 only in that:
in this example, the amount of the black phosphorus quantum dots is 100 μ L.
Example 7
This example provides a sheet of BPQDs/ZnIn 2 S 4 The binary heterostructure composite photocatalytic material and the preparation method thereof are different from the embodiment 1 only in that:
in this example, the amount of black phosphorus quantum dots was 300. Mu.L.
Example 8
This example provides a sheet of BPQDs/ZnIn 2 S 4 The composite photocatalytic material with the binary heterostructure and the preparation method thereof are only different from the preparation method of the embodiment 1 that:
in step 1 of this embodiment:
the dosage ratio of the black phosphorus powder to the NMP solution is 1mg;
the dosage ratio of the hydrosolvent to the black phosphorus powder is 1mL;
the ultrasonic power of ultrasonic treatment is 500W, the ultrasonic interval is 2s, and the ultrasonic time is 8h;
the centrifugal mode of solid-liquid separation is as follows: the mixture was centrifuged at 3000r/min for 30min and then at 6000r/min for 30min.
In step 2 of this embodiment:
the mass ratio of indium chloride, thioacetamide and zinc chloride is 0.089;
taking a mixed solution of water and ethanol mixed according to a volume ratio of 1:2 as a solvent A;
the dosage ratio of the indium chloride to the solvent A is 2mg;
the reaction temperature of the hydrothermal reaction is 200 ℃, and the reaction time is 20h.
In step 3 of this embodiment:
the dosage ratio of the precursor to the solvent B is 45mg;
the stirring reaction temperature is 50 ℃, the stirring speed is 500r/min, and the stirring time is 24h.
The drying temperature is 70 ℃, and the drying time is 8h.
Example 9
This example provides a sheet of BPQDs/ZnIn 2 S 4 The binary heterostructure composite photocatalytic material and the preparation method thereof are different from the embodiment 1 only in that:
in step 1 of this embodiment:
the dosage ratio of the black phosphorus powder to the NMP solution is 1mg;
the dosage ratio of the water solvent to the black phosphorus powder is 1mL;
the ultrasonic power of ultrasonic treatment is 550W, the ultrasonic interval is 4s, and the ultrasonic time is 4h;
the centrifugal mode of solid-liquid separation is as follows: firstly centrifuging at 5000r/min for 40min, and then centrifuging at 8000r/min for 20min.
In step 2 of this embodiment:
the mass ratio of indium chloride, thioacetamide and zinc chloride is 0.266;
taking a mixed solution of water and ethanol mixed according to a volume ratio of 2:1 as a solvent A;
the dosage ratio of indium chloride to the solvent A is 9mg;
the reaction temperature of the hydrothermal reaction is 150 ℃, and the reaction time is 25h.
In step 3 of this embodiment:
the dosage ratio of the precursor to the black phosphorus quantum dot suspension is 55mg;
the stirring reaction temperature is 70 ℃, the stirring speed is 700r/min, and the stirring time is 8h.
The drying temperature is 60 ℃, and the drying time is 16h.
Test section
(I) XRD test
The invention relates to sheet-like BPQDs/ZnIn prepared in example 1 2 S 4 The composite photocatalytic material with a binary heterostructure is taken as an example, XRD test is carried out on the composite photocatalytic material, and the test result is shown in figure 1.
As can be seen from FIG. 1, the sheet-like BPQDs/ZnIn prepared in example 1 of the present invention 2 S 4 The XRD peak positions of the composite photocatalytic material with the binary heterostructure appear at 21.58, 27.69, 47.17, 55.58, 77.19 degrees, which correspond to (006), (102), (110), (022) and (212) planes (PDF # 065-2023), and no peak appears due to too low content of phosphorus, which indicates that the flaky BPQDs/ZnIn prepared by the invention successfully 2 S 4 A catalyst.
(II) SEM test
The invention is prepared as in example 1Sheet-like BPQDs/ZnIn of 2 S 4 The composite photocatalytic material with the binary heterostructure is taken as an example, SEM test is performed on the composite photocatalytic material, and the test result is shown in fig. 2.
As can be seen from FIG. 2, the sheet-like BPQDs/ZnIn prepared in example 1 of the present invention 2 S 4 The composite photocatalytic material with the binary heterostructure is in a flower-flake structure.
(III) TEM test
The invention uses the sheet-like BPQDs/ZnIn prepared in example 1 2 S 4 For example, the binary heterostructure composite photocatalytic material is subjected to TEM test, and the test results are respectively shown in fig. 3.
FIG. 4 is a TEM test result of BPQDs, and it can be seen that BPQDs prepared by the present invention have a diameter of about 3-5nm.
As can be seen from FIG. 3, the sheet-like BPQDs/ZnIn prepared in example 1 2 S 4 BPQDs (such as white circles) in the composite photocatalytic material with the binary heterostructure uniformly grow on ZnIn 2 S 4 A surface.
(IV) photocatalytic hydrogen evolution Performance test
The invention is directed to the flaky BPQDs/ZnIn prepared in examples 1, 6 and 7 2 S 4 The photocatalytic hydrogen evolution of the composite photocatalytic material with the binary heterostructure is detected, and the result is shown in figure 5.
As can be seen from FIG. 5, the sheet-like BPQDs/ZnIn of example 1, example 6 and example 7 2 S 4 Composite photocatalytic material with binary heterostructure in lambda>The catalyst shows better hydrogen evolution rate under the visible light of 420nm, and the hydrogen evolution rate of the example 1 can reach 1.41mmol/g/h, which shows that the catalyst prepared in the example 1 of the invention has better catalytic performance.
The apparatus used in the above-described hydrogen production reaction of the present invention is a closed gas circulation system of gas chromatography (GC-2014, SHIMADZU) of Shimadzu and of Labsolar-6A, perfect. And the specific test method is as follows:
first, a mixed solution of 30mg of a catalyst and 10ml of Triethanolamine (TEOA) used as a sacrificial agent for trapping a cavity in a reaction and 90ml of deionized water was charged into a photocatalytic reactor, and quartz glass was covered. The reaction temperature of the whole system is set to be 5 ℃ through a cooling circulating water system, then the system is vacuumized, after about 30 minutes, no bubble exists in the reactor, pressure maintaining treatment is carried out for 10 minutes, after the air pressure is stable, illumination reaction is carried out on the gas by a 300W xenon lamp (PLS-SXE 300D, beijing Perfectlight), generated gas is collected once every half hour, nitrogen is used as carrier gas, the reaction time is 3 hours, then quantitative test is carried out on the gas by gas chromatography, and therefore the whole photocatalytic hydrogen production reaction is achieved.
It is to be understood that the above-described embodiments are only some of the embodiments of the present invention, and not all of the embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present invention.

Claims (10)

1. Sheet-like BPQDs/ZnIn 2 S 4 The preparation method of the composite photocatalytic material with the binary heterostructure is characterized by comprising the following steps:
step 1, uniformly dispersing black phosphorus powder in an N-methyl pyrrolidone solution, and then sequentially carrying out ultrasonic treatment and solid-liquid separation to obtain a liquid component; removing the solvent in the liquid component, and then dispersing in the water solvent to obtain a black phosphorus quantum dot suspension;
step 2, uniformly dispersing indium chloride, thioacetamide and zinc chloride in a solvent A, and then carrying out hydrothermal reaction at the temperature of 150-200 ℃ to obtain a precursor;
step 3, uniformly dispersing the precursor in a solvent B, then adding the black phosphorus quantum dot suspension, carrying out stirring reaction at 50-70 ℃, and drying to obtain the flaky BPQDs/ZnIn 2 S 4 A composite photocatalytic material with a binary heterostructure.
2. The production method according to claim 1, wherein the solvent a is a mixed solution of water and ethanol in an arbitrary ratio;
the solvent B is water.
3. The preparation method according to claim 1, wherein the dosage ratio of the black phosphorus powder to the N-methylpyrrolidone solution is 1mg to 10mL;
the dosage ratio of the water solvent to the black phosphorus powder is 1mL.
4. The preparation method according to claim 1, wherein the dosage ratio of the precursor to the solvent B is 45 to 55mg;
the dosage ratio of the black phosphorus quantum dot suspension to the precursor is 1-3 mu L to 1mg.
5. The preparation method according to claim 1, wherein the mass ratio of indium chloride, thioacetamide and zinc chloride is 0.089 to 0.266;
the dosage ratio of the solvent A to the indium chloride is 1mL.
6. The preparation method of claim 1, wherein the ultrasonic treatment is performed by using a cell ultrasonic crusher under ice bath conditions, the ultrasonic power is 500-550W, the ultrasonic interval is 2-4 s, and the ultrasonic time is 4-8 h.
7. The method according to claim 1, wherein the hydrothermal reaction is carried out for 20 to 25 hours.
8. The method according to claim 1, wherein the stirring speed of the stirring treatment is 500 to 700r/min, and the stirring time is 8 to 24 hours.
9. A sheet-like BPQDs/ZnIn prepared by the preparation method according to any one of claims 1 to 8 2 S 4 A composite photocatalytic material with a binary heterostructure.
10. The sheet-like BPQDs/ZnIn of claim 9 2 S 4 The application of the composite photocatalytic material with the binary heterostructure in hydrogen production by photolysis of water.
CN202210924878.9A 2022-08-02 2022-08-02 Sheet-like BPQDs/ZnIn 2 S 4 Binary heterostructure composite photocatalytic material and preparation method and application thereof Pending CN115193458A (en)

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