CN114890455A - Flower-shaped ZnIn 2 S 4 Material and method for producing same - Google Patents
Flower-shaped ZnIn 2 S 4 Material and method for producing same Download PDFInfo
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Abstract
The invention discloses a flower-shaped ZnIn 2 S 4 Material and process for producing the same, Zn (NO) 3 ) 2 ·6H 2 O、In(NO 3 ) 3 Adding the hydrate and TAA into deionized water according to the molar ratio of 1:2:8 to prepare a mixed solution; carrying out hydrothermal reaction on the mixed solution, respectively carrying out suction filtration and washing on the mixed solution by deionized water and methanol, and then carrying out freeze drying and grinding to obtain flower-shaped ZnIn 2 S 4 A material; the invention adopts a hydrothermal method to synthesize flower-shaped ZnIn 2 S 4 The sulfide is simple in preparation process, low in cost, high in material purity, strong in crystallinity and large in specific surface area; organic and inorganic hybridization and modification are realized by participating in dialysis reaction, controlling physical and chemical factors and the like; can be used for preparing single-component tiny crystals and special compound powder with two components or multiple components.
Description
Technical Field
The present invention belongs to a photocatalytic materialIn particular to a flower-shaped ZnIn 2 S 4 Materials and methods for their preparation.
Background
In the modern society, along with the progress and development of the society, the degree of industrialization and artificial intelligence is higher and higher, the requirement on the used materials is higher and higher, and the traditional materials can not meet the use requirement, so that more and more functional materials and composite materials are developed rapidly. The increasing exhaustion of traditional fossil fuels and the serious environmental pollution caused by the combustion of the traditional fossil fuels prompt people to search clean novel energy, and hydrogen energy is paid much attention as high-efficiency clean energy because of wide application prospect. The hydrogen production method of steam reforming methane, which is commonly used in the industry at present, not only consumes huge energy, but also generates a large amount of carbon dioxide gas. The photocatalytic hydrogen production activity mainly depends on the light absorption capacity of a semiconductor photocatalyst, the separation and migration of photon-generated carriers, the surface reaction kinetics and the like.
Ternary metal sulfide semiconductor indium zinc sulfide (ZnIn) 2 S 4 ) Is a direct band gap semiconductor, the band gap of which is about 2.06-2.85 ev (chai b, pen t, zeng p, et al, journal of physical chemistry c, 2011, 115(13): 6149-. In addition, compared with common cadmium sulfide photocatalyst, ZnIn 2 S 4 The photocatalyst has less harm to human bodies and environment, has better light stability than cadmium sulfide, and is a photocatalytic material with wide application prospect. However, ZnIn despite the above advantages 2 S 4 The photocatalyst still has some defects which are mainly represented by low light absorption capacity, low separation efficiency of photon-generated carriers and slow migration process of photon-generated electrons, and the defects cause single ZnIn 2 S 4 The applications in the field of photocatalysis are limited. To increase ZnIn 2 S 4 Photocatalytic performance of (1), researchers are on ZnIn 2 S 4 Numerous attempts to modify have been made. ZnIn is mixed with a solvent 2 S 4 Composite construction of heterojunctions with other narrow bandgap semiconductorsIs one of effective means for improving the photocatalytic performance. By constructing a heterojunction, not only can ZnIn be formed 2 S 4 The light absorption range of the optical crystal is expanded, and due to different energy level structures among the component materials, the separation and migration efficiency of photon-generated carriers can be remarkably promoted, so that the ZnIn can be remarkably improved 2 S 4 The photocatalytic performance of (a).
Conventional ZnIn 2 S 4 The preparation method is a solid phase method and a gas phase method. For example, Lappe et al are used by encapsulating ZnS and In a quartz tube 2 S 3 The solid-state reaction of the powder is carried out at the temperature of 750-850 ℃ to prepare the 3R type ZnIn 2 S 4 Georgobiani et al and Romeo et al synthesized hexagonal phase ZnIn by chemical vapor deposition 2 S 4 . However, these methods have problems such as high temperature, high pressure and long reaction time. To overcome the above disadvantages, ZnIn is being studied 2 S 4 The low temperature preparation method of (1) was studied, for example, Sriram and the like obtained ZnIn at room temperature by a coprecipitation method 2 S 4 Then roasting the precursor at 400-500 ℃ to prepare ZnIn with a cubic spinel structure 2 S 4 A semiconductor material. Lei et al tried the hydrothermal preparation of ZnIn 2 S 4 Ternary sulfide. These studies were carried out for the preparation of ZnIn at low temperatures 2 S 4 Provides experimental basis.
Disclosure of Invention
The invention aims to provide a flower-shaped ZnIn with low preparation cost and short period 2 S 4 Material and preparation method thereof, and flower-shaped ZnIn prepared from material 2 S 4 The material has good crystallinity, novel appearance and excellent performance.
Flower-shaped ZnIn 2 S 4 The preparation method of the material comprises the following steps:
the method comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 O 2mmol、In(NO 3 ) 3 Dissolving 4mmol of hydrate and 16mmol of TAA in deionized water to prepare a mixed solution of 2-3 mmol/L;
step two: stirring the mixed solution and then carrying out ultrasonic treatment;
step three: adding the mixed solution treated in the second step into a polytetrafluoroethylene lining, and putting the polytetrafluoroethylene lining into an oven to perform hydrothermal reaction for 6 hours at 160 ℃;
step four: after the reaction is finished, respectively filtering the reaction product by deionized water and methanol, freeze-drying and grinding the reaction product to obtain flower-shaped ZnIn 2 S 4 A material.
Further, the stirring in the second step is magnetic stirring at a rotating speed of 200-500 r/min for 10min at room temperature.
Further, the ultrasonic treatment time in the second step is 20-40 min.
Further, the filling ratio of the mixed solution in the third step added into the polytetrafluoroethylene lining is 50-70%.
And further, respectively performing suction filtration and washing on the deionized water and the methanol for 3-6 times in the fourth step.
Compared with the prior art, the invention has at least the following beneficial effects:
(1) the invention adopts a hydrothermal method to synthesize flower-shaped ZnIn 2 S 4 The material has simple preparation process, low cost, high purity, strong crystallinity and rich surface holes and has large specific surface area.
(2) The organic-inorganic hybridization and modification are realized by participating in dialysis reaction, controlling physical and chemical factors and the like. Can be used for preparing single-component tiny crystals and special compound powder with two components or multiple components.
(3) ZnIn prepared by the invention 2 S 4 The material has novel flower shape and appearance and excellent functionality, and is an ideal material for a photocatalytic composite material or a co-catalyst.
Drawings
FIG. 1 shows flower-like ZnIn prepared in example 2 2 S 4 The XRD diffractogram of (1), wherein the abscissa is the angle 2 θ and the ordinate is the intensity.
FIG. 2 shows the flower-like ZnIn of sea urchin prepared in example 2 2 S 4 SEM image of (d).
Detailed description of the preferred embodiment
The invention is further illustrated by the following specific examples.
Example 1:
the method comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 O 2mmol、In(NO 3 ) 3 4mmol of hydrate and 16mmol of TAA (thioacetamide) are dissolved in deionized water according to the molar ratio of 1:2:8 to prepare a mixed solution of 2 mmol/L.
Step two: magnetically stirring the mixed solution at the rotating speed of 300r/min for 10min and then carrying out ultrasonic treatment for 30 min;
step three: adding the mixed solution into a polytetrafluoroethylene lining according to the filling ratio of 60%, and putting the polytetrafluoroethylene lining into an oven to perform hydrothermal reaction for 24 hours at 160 ℃;
step four: after the reaction is finished, respectively filtering and washing the mixture for 4 times by deionized water and methanol, freeze-drying the mixture and grinding the mixture to obtain flower-shaped ZnIn 2 S 4 A material.
Example 2:
the method comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 O 2mmol、In(NO 3 ) 3 4mmol of hydrate and 16mmol of TAA (thioacetamide) are dissolved in deionized water according to the molar ratio of 1:2:8 to prepare a mixed solution of 3 mmol/L.
Step two: magnetically stirring the mixed solution at the rotating speed of 450r/min for 10min and then carrying out ultrasonic treatment for 40 min;
step three: adding the mixed solution into a polytetrafluoroethylene lining according to the filling ratio of 50%, and putting the polytetrafluoroethylene lining into an oven to perform hydrothermal reaction for 20 hours at 180 ℃;
step four: after the reaction is finished, respectively filtering and washing for 6 times by deionized water and methanol, freeze-drying and grinding to obtain flower-shaped ZnIn 2 S 4 A material.
It can be seen from FIG. 1 that the sample prepared in example 2 corresponds to the XRD pattern of the standard card, and the diffraction peak corresponds to the hexagonal phase ZIS of the standard powder diffraction card NO. 01-072-0773. And ZnS, In was not detected 2 S 3 And other impurities diffraction peaks, which proves that ZnIn is prepared 2 S 4 Instead of ZnS, In 2 S 3 The product mixture of (1).
As can be seen from FIG. 2, the material prepared in example 2 has a novel morphology and is flower-shaped.
Example 3:
the method comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 O 2mmol、In(NO 3 ) 3 4mmol of hydrate and 16mmol of TAA (thioacetamide) are dissolved in deionized water according to the molar ratio of 1:2:8 to prepare a mixed solution of 3 mmol/L.
Step two: magnetically stirring the mixed solution at the rotating speed of 500r/min for 10min and then carrying out ultrasonic treatment for 40 min;
step three: adding the mixed solution into a polytetrafluoroethylene lining according to the filling ratio of 55%, and putting the polytetrafluoroethylene lining into an oven for hydrothermal reaction at 180 ℃ for 18 h;
step four: after the reaction is finished, respectively filtering and washing the mixture for 5 times by deionized water and methanol, freeze-drying the mixture and grinding the mixture to obtain flower-shaped ZnIn 2 S 4 A material.
Example 4:
the method comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 O 2mmol、In(NO 3 ) 3 4mmol of hydrate and 16mmol of TAA (thioacetamide) are dissolved in deionized water according to the molar ratio of 1:2:8 to prepare a mixed solution of 2 mmol/L.
Step two: magnetically stirring the mixed solution at the rotating speed of 500r/min for 10min and then carrying out ultrasonic treatment for 40 min;
step three: adding the mixed solution into a polytetrafluoroethylene lining according to the filling ratio of 60%, and putting the polytetrafluoroethylene lining into an oven to perform hydrothermal reaction for 6 hours at 160 ℃;
step four: after the reaction is finished, respectively filtering and washing the mixture for 5 times by deionized water and methanol, freeze-drying the mixture and grinding the mixture to obtain flower-shaped ZnIn 2 S 4 Material
Example 5:
the method comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 O 2mmol、In(NO 3 ) 3 4mmol of hydrate and 16mmol of TAA (thioacetamide) are dissolved in deionized water according to the molar ratio of 1:2:8 to prepare a mixed solution of 3 mmol/L.
Step two: magnetically stirring the mixed solution at the rotating speed of 500r/min for 10min and then carrying out ultrasonic treatment for 30 min;
step three: adding the mixed solution into a polytetrafluoroethylene lining according to the filling ratio of 70%, and putting the polytetrafluoroethylene lining into an oven to perform hydrothermal reaction for 6 hours at 200 ℃;
step four: after the reaction is finished, respectively filtering and washing for 6 times by deionized water and methanol, freeze-drying and grinding to obtain flower-shaped ZnIn 2 S 4 A material.
Example 6:
the method comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 O 2mmol、In(NO 3 ) 3 4mmol of hydrate and 16mmol of TAA (thioacetamide) are dissolved in deionized water according to the molar ratio of 1:2:8 to prepare a mixed solution of 2 mmol/L.
Step two: magnetically stirring the mixed solution at the rotating speed of 500r/min for 10min and then carrying out ultrasonic treatment for 40 min;
step three: adding the mixed solution into a polytetrafluoroethylene lining according to the filling ratio of 60%, and putting the polytetrafluoroethylene lining into an oven to perform hydrothermal reaction for 10 hours at 185 ℃;
step four: after the reaction is finished, respectively filtering and washing the mixture for 5 times by deionized water and methanol, freeze-drying the mixture and grinding the mixture to obtain flower-shaped ZnIn 2 S 4 Material
Example 7:
the method comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 O 2mmol、In(NO 3 ) 3 4mmol of hydrate and 16mmol of TAA (thioacetamide) are dissolved in deionized water according to the molar ratio of 1:2:8 to prepare a mixed solution of 3 mmol/L.
Step two: magnetically stirring the mixed solution at the rotating speed of 200r/min for 10min and then carrying out ultrasonic treatment for 20 min;
step three: adding the mixed solution into a polytetrafluoroethylene lining according to the filling ratio of 70%, and putting the polytetrafluoroethylene lining into an oven to perform hydrothermal reaction for 10 hours at 180 ℃;
step four: after the reaction is finished, respectively filtering and washing for 6 times by deionized water and methanol, freeze-drying and grinding to obtain flower-shaped ZnIn 2 S 4 A material.
The above-described embodiments are provided to better explain the principles of the present invention and not to limit the present invention by any means, such as by making modifications, equivalents, and improvements within the spirit and scope of the present invention as defined by the appended claims.
Claims (6)
1. Flower-shaped ZnIn 2 S 4 The preparation method of the material is characterized by comprising the following steps:
the method comprises the following steps: adding Zn (NO) 3 ) 2 ·6H 2 O 2mmol、In(NO 3 ) 3 Dissolving 4mmol of hydrate and 16mmol of TAA in deionized water to prepare a mixed solution of 2-3 mmol/L;
step two: stirring the mixed solution and then carrying out ultrasonic treatment;
step three: adding the mixed solution treated in the second step into a polytetrafluoroethylene lining, and putting the polytetrafluoroethylene lining into an oven to perform hydrothermal reaction for 6-24 hours at 160-200 ℃;
step four: after the reaction is finished, respectively filtering the reaction product by deionized water and methanol, freeze-drying and grinding the reaction product to obtain flower-shaped ZnIn 2 S 4 A material.
2. Flower-like ZnIn according to claim 1 2 S 4 The preparation method of the material is characterized by comprising the following steps: and the stirring in the second step is magnetic stirring at the rotating speed of 200-500 r/min for 10min at room temperature.
3. Flower-like ZnIn according to claim 1 2 S 4 The preparation method of the material is characterized by comprising the following steps: and the ultrasonic treatment time in the second step is 20-40 min.
4. Flower-like ZnIn according to claim 1 2 S 4 The preparation method of the material is characterized by comprising the following steps: and adding the mixed solution in the third step into a polytetrafluoroethylene lining, wherein the filling ratio of the mixed solution in the third step is 50-70%.
5. Flower-like ZnIn according to claim 1 2 S 4 The preparation method of the material is characterized by comprising the following steps: and step four, respectively carrying out suction filtration and washing on deionized water and methanol for 3-6 times.
6. Flower-like ZnIn produced by the production method according to any one of claims 1 to 5 2 S 4 A material.
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Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403066A (en) * | 2022-09-27 | 2022-11-29 | 陕西科技大学 | Spherical ZnIn assembled by nanosheets 2 S 4 Material and method for the production thereof |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107737597A (en) * | 2017-10-11 | 2018-02-27 | 肇庆市华师大光电产业研究院 | A kind of titanium doped indium sulfide zinc flower-like microsphere and its preparation method and application |
| CN110961121A (en) * | 2019-11-26 | 2020-04-07 | 江苏大学 | Z-type photocatalyst, preparation method and application |
| CN112960688A (en) * | 2021-02-04 | 2021-06-15 | 河南大学 | ZnIn2S4Sodium ion battery negative electrode material and preparation method thereof |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN107737597A (en) * | 2017-10-11 | 2018-02-27 | 肇庆市华师大光电产业研究院 | A kind of titanium doped indium sulfide zinc flower-like microsphere and its preparation method and application |
| CN110961121A (en) * | 2019-11-26 | 2020-04-07 | 江苏大学 | Z-type photocatalyst, preparation method and application |
| CN112960688A (en) * | 2021-02-04 | 2021-06-15 | 河南大学 | ZnIn2S4Sodium ion battery negative electrode material and preparation method thereof |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115403066A (en) * | 2022-09-27 | 2022-11-29 | 陕西科技大学 | Spherical ZnIn assembled by nanosheets 2 S 4 Material and method for the production thereof |
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