CN114950483A - High-hydrophobic three-dimensional flower-shaped ZnIn2S4/Sn3O4 composite structure material and preparation method and application thereof - Google Patents
High-hydrophobic three-dimensional flower-shaped ZnIn2S4/Sn3O4 composite structure material and preparation method and application thereof Download PDFInfo
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- 239000000463 material Substances 0.000 title claims abstract description 63
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
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- 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
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
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- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- 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
- Y02E60/10—Energy storage using batteries
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- 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
Abstract
The invention discloses a high-hydrophobic three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 Composite structural material, method of preparation and use thereof. The method firstly prepares Sn 3 O 4 Taking the nanoflower as a seed, adding zinc salt, indium salt and sulfur source, and preparing the high-hydrophobic ZnIn through an in-situ hydrothermal method and regulating and controlling experimental conditions 2 S 4 /Sn 3 O 4 The nano composite structure material is used as a photocatalyst for removing toxic and harmful heavy metal Cr (VI) ions in a water body under visible light and catalytically decomposing water to prepare hydrogen under sunlight. In view of the problems in the prior art, the invention providesHighly hydrophobic ZnIn 2 S 4 /Sn 3 O 4 The composite structure material, the preparation method and the application thereof, wherein Sn is prepared firstly 3 O 4 Nano flower is then used as seed, zinc salt, indium salt and sulfur source are added, and ZnIn is prepared through in-situ hydrothermal process and regulating and controlling experiment condition 2 S 4 /Sn 3 O 4 The nano composite structure material is used as a photocatalyst for removing toxic and harmful heavy metal Cr (VI) ions in a water body under visible light and catalytically decomposing water to prepare hydrogen under sunlight.
Description
Technical Field
The invention relates to a high-hydrophobicity three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 A composite structure, a preparation method and application thereof belong to the preparation of nano composite materials and the application in the fields of environmental protection and energy preparation.
Background
With the continuous development and progress of human society, environmental pollution and energy shortage gradually become two major problems affecting human sustainable development, and Qingshan green water and novel efficient renewable energy are the ultimate goals pursued by human beings, so that the development of some novel efficient technologies to solve environmental pollution and energy shortage to achieve the goals is the current research hotspot. The photocatalysis technology is a novel high-efficiency green technology, and can convert solar energy into renewable energy, such as hydrogen energy; the solar water purification device can also utilize sunlight to efficiently treat water pollutants and harmful substances, realizes efficient purification of water, and is a green and environment-friendly technology with the greatest development potential. In the photocatalytic technology, the light absorption performance of the photocatalyst and the separation of the photo-generated electron pair are key factors influencing the photocatalytic efficiency, so that the development of novel high-efficiency photocatalytic materials with low cost and easy recovery is a research focus in the technology.
ZnIn 2 S 4 The classical ternary sulfide has the advantages of narrow band gap, proper band edge position, low toxicity, low cost and the like, is a photocatalytic material with application prospect, and is greatly concerned by people. However, the study found that ZnIn is a single component 2 S 4 Due to the characteristics of the materials, the photoresponse range of the material is limited, and photon-generated carriers are easy to recombine, so that the industrial application of the material is greatly limited. Therefore, for ZnIn 2 S 4 Modification research is an important means for improving the photocatalytic activity of the photocatalyst. At present, the research finds that ZnIn is mixed with the active ingredients 2 S 4 Compounding with other suitable semiconductors to obtain ZnIn 2 S 4 The base composite structure system is the most effective and economic method for enhancing the photocatalytic activity of the material, and is the key direction of the research of the material.
Sn 3 O 4 Sn (Sn) 2+ And Sn 4+ The tin oxide composed of mixed valence state has relatively small band gap and proper band edge position, can realize visible light driven photocatalytic hydrogen evolution and pollutant degradation, and in addition, Sn 3 O 4 The photocatalyst also has oxygen vacancy defect, is stable and nontoxic, and is an excellent photocatalytic material. However, Sn alone 3 O 4 The catalyst also suffers from low solar utilization and photo-generated carrier separation efficiency. Therefore, in order to further improve the photocatalytic activity, the method has a prospect of popularization of industrial application. The invention combines the advantages of two materials, aims to overcome the defects of the two materials, and provides a novel high-hydrophobicity three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 A method for preparing a composite structural material, andthe photocatalyst is used for removing toxic and harmful heavy metal Cr (VI) ions in a water body under visible light and preparing hydrogen by catalytically decomposing water under sunlight, and obtains higher photocatalytic activity. Through literature research, there is no ZnIn reference 2 S 4 /Sn 3 O 4 The reports of composite structure materials are not that the high hydrophobic ZnIn is 2 S 4 /Sn 3 O 4 Report on composite structural materials, therefore, the ZnIn 2 S 4 /Sn 3 O 4 The composite structure is a novel photocatalytic material.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a high-hydrophobicity ZnIn 2 S 4 /Sn 3 O 4 The composite structure material, the preparation method and the application thereof, wherein Sn is prepared firstly 3 O 4 Nano flower is then used as seed, zinc salt, indium salt and sulfur source are added, and ZnIn is prepared through in-situ hydrothermal process and regulating and controlling experiment condition 2 S 4 /Sn 3 O 4 The nano composite structure material is used as a photocatalyst for removing toxic and harmful heavy metal Cr (VI) ions in a water body under visible light and catalytically decomposing water to prepare hydrogen under sunlight.
The invention is realized by the following technical scheme:
high-hydrophobic three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 The preparation method of the composite structure material comprises the following steps:
step 1, weighing SnCl 2 ·2H 2 Adding O and sodium citrate into 40-150 mL of mixed solution of ethanol and deionized water in sequence, stirring until the mixture is completely dissolved, adjusting the pH value by using 0.2-0.5 mol/L NaOH solution, transferring the solution into a hydrothermal reaction kettle, and after the reaction is finished, centrifuging, washing and freeze-drying the precipitate for 12 hours to obtain the nano stannic oxide popcorn;
The invention further adopts the technical improvement scheme that:
SnCl in the step 1 2 ·2H 2 The dosage ratio of O to sodium citrate is 1-15 mmol: 2-40 mmol, and the volume ratio of ethanol to deionized water is 1: 10, the pH value adjusting range is 5-9, the filling ratio of the hydrothermal reaction kettle is 50-70%, the hydrothermal reaction temperature range is 160-180 ℃, and the reaction time is 12-18 h.
The invention further adopts the technical improvement scheme that:
the step 2 comprises nano stannic oxide, deionized water and In (NO) 3 ) 3 .4.5H 2 O, thioacetamide and Zn (NO) 3 ) 2 ·6H 2 The dosage ratio of O is 0.0212-1.5929 g: 50-300 mL, 10-100 mmol: 20-400 mmol: 5-50 mmol, the filling ratio of the hydrothermal reaction kettle is 60-80%, the reaction temperature range is 140-170 ℃, and the reaction time is 4-12 h.
The invention is realized by the following technical scheme:
high-hydrophobic three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 The composite structural material consists of ZnIn 2 S 4 And Sn 3 O 4 A bonding composition in which Sn 3 O 4 The mass ratio of the composite structure sample is 1-10%, and the micro appearance of the composite structure sample is in a three-dimensional flower shape.
The invention further adopts the technical improvement scheme that:
when ZnIn is present 2 S 4 /Sn 3 O 4 When the mass percentage of the tin tetraoxide in the composite structure material is 5%, the contact angle is about 140 degrees, and the composite structure material shows high hydrophobic property.
The invention is realized by the following technical scheme:
high-hydrophobic three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 Application of the composite structure material in catalytic removal of heavy metal Cr (VI) ions under visible light.
The invention further adopts the technical improvement scheme that:
when ZnIn is present 2 S 4 /Sn 3 O 4 When the mass percentage of the tin tetraoxide in the composite structure material is 5%, the composite structure material can completely remove Cr (VI) after being irradiated for 40 min by visible light.
The invention is realized by the following technical scheme:
high-hydrophobic three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 The application of the composite structure material in photocatalytic water decomposition under sunlight to prepare hydrogen.
The invention further adopts the technical improvement scheme that:
when the mass percentage of the stannic oxide in the ZnIn2S4/Sn3O4 composite structure material is 5 percent, the hydrogen production rate by decomposing water under the irradiation of sunlight is 1.783mmol g -1 ·h -1 。
Compared with the prior art, the invention has the following obvious advantages:
the invention provides a novel three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 Composite structure materials and methods for making the novel composite structures are also provided.
Second, ZnIn prepared by the invention 2 S 4 /Sn 3 O 4 The composite structure material shows higher hydrophobic property, and is convenient to recycle from water.
Thirdly, the invention firstly prepares ZnIn 2 S 4 And Sn 3 O 4 Compounding to widen the light absorption range, and obtaining the ZnIn 2 S 4 /Sn 3 O 4 The composite structure material has higher light response capability, and greatly improves the utilization efficiency of solar energy. .
Fourthly, the invention firstly adopts the in-situ method to treat ZnIn 2 S 4 And Sn 3 O 4 Recombination, greatly reducing the contact of intimate interface between the twoRecombination of photoproduction electrons and holes improves photoproduction electron transmission capability, ZnIn 2 S 4 /Sn 3 O 4 The composite structure has better activity of removing toxic and harmful heavy metal Cr (VI) ions in water under visible light and preparing hydrogen by catalytically decomposing water under sunlight, and when Sn is used 3 O 4 The composite structure sample with the mass ratio of 5 percent can completely remove Cr (VI) under the irradiation of visible light for 40 min, and the hydrogen production rate by decomposing water under the irradiation of sunlight can reach 1.783 mmol.h -1 ·g -1 。
Fifthly, the invention synthesizes ZnIn by using a simple preparation process 2 S 4 /Sn 3 O 4 The composite structure material nano composite structure has rich raw material sources, simple and convenient operation process, mild and easily controlled reaction conditions, and has wide application prospect in the aspects of solving the heavy metal ion pollution of water and preparing renewable energy sources.
Drawings
FIG. 1 ZnIn prepared in examples 1, 3 and 4 2 S 4 /Sn 3 O 4 XRD pattern of composite structure material.
FIG. 2 shows Sn obtained in example 3 3 O 4 (a) And ZnIn 2 S 4 /Sn 3 O 4 (b) SEM images of composite structural materials.
FIG. 3 ZnIn prepared in example 3 2 S 4 /Sn 3 O 4 UV-VIS pattern of composite structure material.
FIG. 4 ZnIn prepared in example 3 2 S 4 /Sn 3 O 4 Contact angle test chart of composite structure material
FIG. 5 ZnIn prepared in example 3 2 S 4 /Sn 3 O 4 Graph of Cr (VI) removal effect of composite structure material under visible light through four-cycle experiments
FIG. 6 ZnIn prepared in example 4 2 S 4 /Sn 3 O 4 Transient photocurrent diagrams of composite structural materials.
Detailed Description
The invention will be further described with reference to the drawings and the embodiments, but the scope of the invention is not limited thereto.
The experiment of removing Cr (VI) ions by visible light is carried out in an GHX-3 type photochemical reaction instrument, a xenon lamp of 250W is used for simulating a solar light source, and lambda is used>The ultraviolet light is filtered out by a 420 nm filter, and the ZnIn prepared by the invention is evaluated 2 S 4 /Sn 3 O 4 The composite structure material has the effect of removing Cr (VI) ions in solution. The method comprises the following specific steps: 50 mL (10 mg/L) of the chromium ion solution was added to the reactor, the initial value thereof was determined, and then 15 mg of ZnIn was added 2 S 4 /Sn 3 O 4 The composite structure material is dark reacted for some time to reach adsorption-desorption balance, illuminated, sampled once every other period, centrifugally separated to obtain supernatant, developed with diphenylcarbazide, and measured in ultraviolet-visible spectrophotometer to obtain absorbance of maximum absorption wavelength (lambda) Cr 543 nm). The removal efficiency of Cr (VI) was calculated from the change in absorbance before and after the light irradiation.
The experiment of hydrogen production by photocatalytic water decomposition is carried out in a top irradiation type photocatalytic reactor, a 300W xenon lamp is used as a solar light source, and the ZnIn prepared by the invention is evaluated 2 S 4 /Sn 3 O 4 The hydrogen production efficiency of the composite structural material. The method comprises the following specific steps: adding 50 mg of photocatalyst into a mixed solution of 40 mL of deionized water and 10 mL of triethanolamine, stirring for 20 min, adding a certain amount of chloroplatinic acid aqueous solution, illuminating for 1h, vacuumizing, maintaining the system temperature at 5 ℃ for photocatalytic hydrogen evolution reaction, collecting gas every 1h, and analyzing by using a gas chromatography GC-7900 to obtain the hydrogen production efficiency.
The first embodiment,
(1) Weighing 1mmol of SnCl 2 ·2H 2 O and 2mmol sodium citrate are sequentially added into 40 mL mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the water is 1: 10), the mixed solution is stirred to be completely dissolved, then 0.2mol/L NaOH solution is used for adjusting the pH value to 5, the mixed solution is transferred into a reaction kettle, the filling degree of the reaction kettle is 50 percent, then the reaction is carried out for 18 hours at 160 ℃, after the reaction is finished, the precipitate is centrifuged, washed and freeze-dried for 12 hours, and the stannic oxide nano-flower can be obtained.
(2) Adding 0.0212g of stannic oxide nanoflower into 50 mL of deionized water under the condition of stirring, continuing stirring and ultrasonic treatment for 10-20 min respectively, repeating the operation twice, and sequentially adding 10 mmol of In (NO) 3 ) 3 .4.5H 2 O, 20 mmol thioacetamide and 5mmol Zn (NO) 3 ) 2 ·6H 2 O, continuously stirring and ultrasonically treating for 10-20 min respectively, repeatedly operating twice, transferring into a reaction kettle with the filling degree of 60%, then reacting at 140 ℃ for 12h, centrifuging after finishing reaction, washing with deionized water for several times, and freeze-drying for 12h to obtain the three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 A composite material. Wherein Sn 3 O 4 The mass ratio of the composite structure is 1%.
ZnIn prepared as per example 1 from FIG. 1 2 S 4 /Sn 3 O 4 XRD pattern of the composite structure sample, it can be seen that the XRD pattern of the sample of example 1 is substantially ZnIn 2 S 4 Spectra are consistent due to Sn 3 O 4 Less content.
Sn was obtained according to example 1 3 O 4 、ZnIn 2 S 4 Sample and ZnIn 2 S 4 /Sn 3 O 4 After the composite structure sample is illuminated for 40 min under visible light, the photocatalytic removal efficiency of Cr (VI) is respectively 8.2%, 65% and 92.1%; the hydrogen production rates under the irradiation of sunlight are respectively 0.080, 0.137 and 0.926 mmol.h -1 ·g -1 It can be seen that the photocatalytic activity of the obtained composite structure sample is higher than that of Sn 3 O 4 The monomer is greatly improved, and especially the photocatalytic hydrogen production activity is improved in a very high proportion.
Example II,
(1) Weighing 3mmol SnCl 2 ·2H 2 O and 7.5 mmol sodium citrate are sequentially added into 70 mL mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the water is 1: 10), the mixture is stirred to be completely dissolved, then 0.3 mol/L NaOH solution is used for adjusting the pH value to 6, the mixture is transferred into a reaction kettle, the filling degree of the reaction kettle is 70 percent, then the mixture reacts for 16 hours at the temperature of 170 ℃, and after the reaction is finished, the precipitate is centrifuged, washed and freeze-dried 12h, obtaining the stannic oxide nanoflower.
(2) Adding 0.1963 g of stannic oxide nanoflower into 100 mL of deionized water under stirring, continuing stirring and ultrasonic treating for 10-20 min respectively, repeating the operation twice, and sequentially adding 30 mmol of In (NO) 3 ) 3 .4.5H 2 O, 80 mmol thioacetamide and 15mmol Zn (NO) 3 ) 2 ·6H 2 O, continuously stirring and ultrasonically treating for 10-20 min respectively, repeatedly operating twice, transferring into a reaction kettle with the filling degree of 60%, then reacting for 10 h at 150 ℃, centrifuging after finishing reaction, washing with deionized water for several times, and freeze-drying for 12h to obtain the three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 A composite material. Wherein Sn 3 O 4 The mass ratio of the composite structure is 3%.
ZnIn prepared as in example 2 2 S 4 /Sn 3 O 4 After the composite structure sample is illuminated for 40 min under visible light, the photocatalytic removal efficiency of Cr (VI) is 95.3 percent; the hydrogen production rate under the irradiation of sunlight is 1.137 mmol.h -1 ·g -1 。
Example III,
(1) Weighing 5mmol of SnCl 2 ·2H 2 O and 15mmol sodium citrate are sequentially added into 80 mL mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the water is 1: 10), the mixed solution is stirred to be completely dissolved, then 0.4 mol/L NaOH solution is used for adjusting the pH value to 7, the mixed solution is transferred into a reaction kettle, the filling degree of the reaction kettle is 60 percent, then the reaction kettle reacts for 12 hours at 180 ℃, after the reaction is finished, the precipitate is centrifuged, washed and freeze-dried for 12 hours, and the stannic oxide nanoflower can be obtained.
(2) Adding 0.5569g of stannic oxide nanoflower into 150 mL of deionized water under stirring, continuing stirring and ultrasonic treating for 10-20 min respectively, repeating the operation twice, and sequentially adding 50 mmol of In (NO) 3 ) 3 .4.5H 2 O, 125 mmol thioacetamide and 25 mmol Zn (NO) 3 ) 2 ·6H 2 O, continuously stirring and ultrasonically treating for 10-20 min respectively, repeatedly operating twice, transferring into a reaction kettle with the filling degree of 60%, and then reacting at 170 ℃ for 4 hAfter the reaction is finished, centrifuging, washing for a plurality of times by deionized water, and freeze-drying for 12 hours to obtain the three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 A composite material. Wherein Sn 3 O 4 The mass ratio of the composite structure is 5%.
ZnIn prepared as per example 3 from FIG. 1 2 S 4 /Sn 3 O 4 XRD pattern of the composite structure sample, it can be seen that the XRD pattern of the example 3 sample is essentially ZnIn 2 S 4 Spectra were consistent, however ZnIn compared to example 1 2 S 4 The intensity of the characteristic peak of the graph is reduced due to Sn 3 O 4 The amount is increased.
Sn prepared according to example 3 in FIG. 2 of the present invention 3 O 4 And ZnIn 2 S 4 /Sn 3 O 4 SEM image of composite structure sample, from which Sn can be seen 3 O 4 Is a three-dimensional flower-like structure composed of nanosheets, ZnIn 2 S 4 /Sn 3 O 4 The composite structure sample is also in a three-dimensional flower-like structure, but the flower-like appearances of the composite structure sample and the three-dimensional flower-like structure sample are obviously different, and only a small amount of Sn is seen 3 O 4 Flake structure due to Sn 3 O 4 The content is less, which fully indicates that the two are successfully compounded.
ZnIn prepared according to example 3 in FIG. 3 of the present invention 2 S 4 /Sn 3 O 4 The UV-VIS diagram of the composite structure sample shows that Sn is added 3 O 4 And ZnIn 2 S 4 After recombination, the visible light absorption properties of the sample are relative to Sn 3 O 4 Obviously improved and has better visible light response capability.
ZnIn prepared according to example 3 in FIG. 4 of the present invention 2 S 4 /Sn 3 O 4 Contact angle test chart of composite structure sample, from which Sn can be seen 3 O 4 And ZnIn 2 S 4 After compounding, the contact angle of the compound sample is about 140 degrees and far greater than 90 degrees, which indicates that the sample has higher hydrophobic property, thereby being beneficial to recycling in the using processThe application is as follows.
ZnIn prepared as in example 3 2 S 4 /Sn 3 O 4 After the composite structure sample is illuminated for 40 min under visible light, the photocatalytic removal efficiency of Cr (VI) ions is 100 percent; the hydrogen production rate under the irradiation of sunlight is 1.783 mmol.h -1 ·g -1 。
ZnIn prepared according to example 3 in FIG. 5 of the present invention 2 S 4 /Sn 3 O 4 The efficiency of the composite structure samples in visible light after four cycles of Cr (VI) removal, as can be seen from the graph, ZnIn obtained in example 3 2 S 4 /Sn 3 O 4 The composite structure sample can still keep higher activity after four cycles, which shows that the composite structure sample has higher use cycle performance and great industrial application prospect.
Example four,
(1) Weighing 15mmol of SnCl 2 ·2H 2 And adding O and 40 mmol of sodium citrate into 150 mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the water is 1: 10) in sequence, stirring to completely dissolve, adjusting the pH to 8 by using 0.5mol/L NaOH solution, transferring into a reaction kettle, controlling the filling degree of the reaction kettle to be 50%, reacting at 160 ℃ for 15h, and after the reaction is finished, centrifuging, washing and freeze-drying the precipitate for 12h to obtain the nano stannic oxide popcorn (2.1 g).
(2) Adding 1.5929g of stannic oxide nanoflower into 300 mL of deionized water under stirring, continuing stirring and ultrasonic treating for 10-20 min respectively, repeating the operation twice, and sequentially adding 100 mmol of In (NO) 3 ) 3 .4.5H 2 O, 400 mmol thioacetamide and 50 mmol Zn (NO) 3 ) 2 ·6H 2 O, continuously stirring and ultrasonically treating for 10-20 min respectively, repeatedly operating twice, transferring into a reaction kettle with the filling degree of 70%, then reacting at 160 ℃ for 8h, centrifuging after finishing reaction, washing with deionized water for several times, and freeze-drying for 12h to obtain the three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 A composite material. Wherein Sn 3 O 4 The mass ratio of the composite structure is 7%.
From FIG. 1ZnIn prepared as in example 2 2 S 4 /Sn 3 O 4 XRD pattern of the composite structure sample, it can be seen that the XRD pattern of the sample of example 1 is substantially ZnIn 2 S 4 Spectra were consistent, however ZnIn compared to examples 1 and 3 2 S 4 The intensity of the characteristic peak of the plot continues to decrease due to Sn 3 O 4 The amount is increased.
FIG. 4 of the drawings shows ZnIn prepared according to example 4 2 S 4 /Sn 3 O 4 Transient photoelectricity graphs of the composite structure sample and two monomers can be seen, and Sn is used 3 O 4 And ZnIn 2 S 4 After the compound, the photocurrent generated by the compound structure sample under the illumination condition is obviously enhanced, which shows that the compound of the two can promote the separation of photo-generated charges and the photocatalytic activity.
ZnIn prepared as in example 4 2 S 4 /Sn 3 O 4 After the composite structure sample is illuminated for 40 min under visible light, the photocatalytic removal efficiency of Cr (VI) is 97.3 percent; the hydrogen production rate under the irradiation of sunlight is 1.315 mmol.h -1 ·g -1 。
Examples V,
(1) Weighing 10 mmol of SnCl 2 ·2H 2 O and 25 mmol of sodium citrate are sequentially added into 150 mL of mixed solution of ethanol and deionized water (the volume ratio of the ethanol to the water is 1: 10), the mixed solution is stirred to be completely dissolved, then 0.5mol/L of NaOH solution is used for adjusting the pH value to 9, the mixed solution is transferred into a reaction kettle, the filling degree of the reaction kettle is 60 percent, then the reaction is carried out for 16h at 160 ℃, after the reaction is finished, the precipitate is centrifuged, washed and freeze-dried for 12h, and the nano-stannic oxide can be obtained.
(2) Adding 1.1757g of stannic oxide nanoflower into 200 mL of deionized water under stirring, continuing stirring and ultrasonic treating for 10-20 min respectively, repeating the operation twice, and sequentially adding 50 mmol of In (NO) 3 ) 3 .4.5H 2 O, 150 mmol thioacetamide and 25 mmol Zn (NO) 3 ) 2 ·6H 2 O, continuously stirring and ultrasonically treating for 10-20 min respectively, repeatedly operating twice, transferring into a reaction kettle with the filling degree of 80%, and carrying out ultrasonic treatmentReacting at 140 ℃ for 12h, centrifuging after the reaction is finished, washing for a plurality of times by deionized water, and freeze-drying for 12h to obtain three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 A composite material. Wherein Sn 3 O 4 The mass ratio of the composite structure is 10%.
ZnIn prepared as in example 5 2 S 4 /Sn 3 O 4 After the composite structure sample is illuminated for 40 min under visible light, the photocatalytic removal efficiency of Cr (VI) is 90.3 percent; the hydrogen production rate under the irradiation of sunlight is 1.223 mmol.h -1 ·g -1 。
The method has the advantages of rich sources of the used raw materials, simple and convenient operation process, mild and easily-controlled reaction conditions, and capability of preparing the three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 The composite structural material has high hydrophobic property and is convenient to recycle. Experiments of removing toxic and harmful heavy metal Cr (VI) ions in water under visible light and preparing hydrogen by catalytically decomposing water under sunlight show that the three-dimensional flower-shaped ZnIn prepared by the invention 2 S 4 /Sn 3 O 4 The composite structure has better photocatalytic activity on Cr (VI) ions and decomposed water, when Sn 3 O 4 ZnIn with the mass ratio of 5 percent 2 S 4 /Sn 3 O 4 The composite structure sample has the highest photocatalytic activity, and can completely remove Cr (VI) after being irradiated for 40 min by visible light; the hydrogen production rate by decomposing water under the irradiation of sunlight can reach 1.783 mmol.h -1 ·g -1 The photocatalytic activity is greatly improved compared with that of two monomers, and the photocatalytic activity has higher recycling stability. The composite structure material obtained by the invention has important and wide application prospect in the aspects of environmental water pollution treatment and energy crisis.
Claims (9)
1. High-hydrophobicity three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 The preparation method of the composite structure material is characterized by comprising the following steps:
step 1, weighing SnCl 2 ·2H 2 O and sodium citrate are added into 40-150 mL of ethanol and deionized water in sequenceStirring the mixed solution until the mixed solution is completely dissolved, adjusting the pH value by using 0.2-0.5 mol/L NaOH solution, transferring the mixed solution into a hydrothermal reaction kettle, and centrifuging, washing and freeze-drying the precipitate for 12 hours after the reaction is finished to obtain the stannic oxide nanoflower;
step 2, adding the stannic oxide nanoflowers into deionized water under the stirring condition, continuing stirring and ultrasonic treatment for 10-20 min respectively, repeating the operation twice, and sequentially adding In (NO) 3 ) 3 .4.5H 2 O, thioacetamide and Zn (NO) 3 ) 2 ·6H 2 O, continuously stirring and ultrasonically treating for 10-20 min respectively, repeatedly operating twice, transferring into a reverse hydrothermal reaction kettle, centrifuging, washing with deionized water for several times after the reaction is finished, and freeze-drying for 12h to obtain three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 A composite structural material.
2. Three-dimensional flower-like ZnIn of highly hydrophobic type according to claim 1 2 S 4 /Sn 3 O 4 The preparation method of the composite structure material is characterized by comprising the following steps: SnCl in the step 1 2 ·2H 2 The dosage ratio of O to sodium citrate is 1-15 mmol: 2-40 mmol, and the volume ratio of ethanol to deionized water is 1: 10, the pH value adjusting range is 5-9, the filling ratio of the hydrothermal reaction kettle is 50-70%, the hydrothermal reaction temperature range is 160-180 ℃, and the reaction time is 12-18 h.
3. Three-dimensional flower-like ZnIn of highly hydrophobic type according to claim 1 2 S 4 /Sn 3 O 4 The preparation method of the composite structure material is characterized by comprising the following steps: the step 2 comprises nano stannic oxide, deionized water and In (NO) 3 ) 3 .4.5H 2 O, thioacetamide and Zn (NO) 3 ) 2 ·6H 2 The dosage ratio of O is 0.0212-1.5929 g: 50-300 mL, 10-100 mmol: 20-400 mmol: 5-50 mmol, the filling ratio of the hydrothermal reaction kettle is 60-80%, the reaction temperature range is 140-170 ℃, and the reaction time is 4-12 h.
4. High-hydrophobicity three-dimensional flower-shaped ZnIn 2 S 4 /Sn 3 O 4 Composite structural material, characterized in that it is prepared by the preparation method of any one of claims 1 to 3, and is made of ZnIn 2 S 4 And Sn 3 O 4 A bonding composition in which Sn 3 O 4 The mass ratio of the composite structure sample is 1-10%, and the micro appearance of the composite structure sample is in a three-dimensional flower shape.
5. Three-dimensional flower-like ZnIn of highly hydrophobic type according to claim 4 2 S 4 /Sn 3 O 4 Composite structural material characterized in that: when ZnIn is present 2 S 4 /Sn 3 O 4 When the mass percentage of the tin tetraoxide in the composite structure material is 5%, the contact angle is about 140 degrees, and the composite structure material shows high hydrophobic property.
6. The highly hydrophobic three-dimensional flower-like ZnIn of claim 4 or 5 2 S 4 /Sn 3 O 4 Application of the composite structure material in catalytic removal of heavy metal Cr (VI) ions under visible light.
7. The highly hydrophobic three-dimensional flower-like ZnIn of claim 6 2 S 4 /Sn 3 O 4 The application of the composite structure material in the catalytic removal of heavy metal Cr (VI) ions under visible light is characterized in that: when ZnIn is present 2 S 4 /Sn 3 O 4 When the mass percentage of the tin tetraoxide in the composite structure material is 5%, the composite structure material can completely remove Cr (VI) after being irradiated for 40 min by visible light.
8. The highly hydrophobic three-dimensional flower-like ZnIn of claim 4 or 5 2 S 4 /Sn 3 O 4 The application of the composite structure material in photocatalytic water decomposition under sunlight to prepare hydrogen.
9. The highly hydrophobic three-dimensional flower-like ZnIn of claim 8 2 S 4 /Sn 3 O 4 Composite structural materials in sunlightThe application of photocatalytic water splitting hydrogen production is characterized in that: when ZnIn is present 2 S 4 /Sn 3 O 4 When the mass percentage of the stannic oxide in the composite structure material is 5 percent, the hydrogen production rate by decomposing water under the irradiation of sunlight is 1.783 mmol/g -1 ·h -1 。
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