CN113769762A - Ultrathin ZnIn2S4Nano-sheet photocatalyst material and preparation method and application thereof - Google Patents
Ultrathin ZnIn2S4Nano-sheet photocatalyst material and preparation method and application thereof Download PDFInfo
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- 238000002360 preparation method Methods 0.000 title claims abstract description 30
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- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
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Abstract
The invention relates to an ultrathin ZnIn2S4The preparation method comprises the steps of carrying out low-temperature reflux and ultrasonic stripping to obtain ultrathin ZnIn2S4Nanosheets. The ultrathin nanosheet photocatalyst material provided by the invention can effectively increase reactive sites, shorten the migration distance of photo-generated electrons and holes and improve the photocatalytic sterilization efficiency. The material also has good visible light absorption performance, and can kill escherichia coli, staphylococcus aureus and drug-resistant staphylococcus aureus 100% within 5-20 minutes under the irradiation of visible light. The preparation method of the photocatalyst of the invention does not need to prepareThe method has the advantages of special equipment, simple process, strong controllability, easy realization of large-scale production and practical value.
Description
Technical Field
The invention relates to the technical field of photocatalyst materials, in particular to a photocatalystUltra-thin ZnIn2S4A nano-sheet photocatalyst material, a preparation method and application thereof.
Background
The 2019 outbreak of coronavirus disease (COVID-19) re-warns us that pathogenic microorganisms such as pathogenic bacteria (e.g. escherichia coli, staphylococcus aureus and pseudomonas aeruginosa) and viruses (e.g. swine flu H1N1 and human coronavirus) pose serious threats to public health. Traditional disinfection methods, such as ozone, uv irradiation, chlorination, antimicrobial agents, etc., consume a lot of energy and have many side effects (toxic by-products, antibiotic resistance, etc.), which are disadvantageous from a long-term sustainability point of view.
In contrast, photocatalytic disinfection technology is considered a promising alternative to traditional disinfection technologies due to its greenness, safety and long-term effectiveness. Photocatalytic disinfection is generally characterized in that a plurality of Reactive Oxygen Species (ROS) (which are lethal to microorganisms) are generated in the semiconductor material under the irradiation of light·O2 -、·OH and1O2etc.). These reactive oxygen species, upon contact with the bacteria, first destroy the cell wall layer, causing leakage of small molecules that allow ROS to further penetrate into the cell interior, destroying internal components, and thereby completely inactivating the bacteria.
The photocatalytic disinfection phenomenon is reported as early as the 19 th century and the 80 th year, but because most semiconductor photocatalysts have wider band gaps, sterilization can be realized only under ultraviolet light, which greatly limits the practical utility of the photocatalytic disinfection technology, because the ultraviolet light only accounts for less than 5% of the solar illumination and can be ignored for indoor illumination. Thus, ideal semiconductors for practical disinfection applications are those sensitive to visible light. In addition to visible light response, these semiconductors are composed of elements abundant on earth, are inexpensive, and have good biosafety. Therefore, there is a strong need to develop new semiconductor photocatalysts that can meet all these criteria.
Metal sulfides have proven to be viable due to their proper Conduction Band (CB) position, relatively narrow band gap, and relatively good chemical stabilityTo respond to visible light. In particular ternary chalcogenides ZnIn2S4It is considered by researchers to be a new star that rises by virtue of its optical properties and visible light responsiveness. ZnIn in contrast to other ternary metal chalcogenides2S4The preparation process is simple, and has the advantages of CdS, CuS, ZnS and other traditional metal sulfides, but the toxicity is lower than that of CdS, and the band gap is narrower than that of ZnS. See ACS Applied Materials Interfaces, 2015, 7 th, 16440-. The unique property endows ZnIn2S4Great potential in photocatalytic applications, such as hydrogen production by water splitting, pollutant degradation, selective organic matter conversion, and the like. However, for ordinary ZnIn2S4There are still some significant problems to be solved, which limit the performance in practical applications. For example, the photoactivity of a catalyst depends on its ability to generate photogenerated electron-hole pairs, however, low separation efficiency and poor electron transport ability inhibit efficient separation of photogenerated electron-hole pairs, resulting in a common bulk ZnIn2S4Are poor in photocatalytic activity, and therefore an effective strategy is needed to raise ZnIn2S4The photocatalytic performance of (a).
Chinese patent document CN111437834A discloses a ZnIn based on sulfur indium zinc2S4The method for constructing the nanosheet in-situ heterojunction is characterized in that zinc acetate dihydrate and indium chloride tetrahydrate are used as raw materials, thioacetamide is used as a sulfur source, deionized water and ethanol are used as solvents, and ultrathin and uniform ZnIn is prepared2S4Nanosheet and In-situ construction of heterojunction In ammonia solution2O3@ZnIn2S4、In(OH)3@ZnIn2S4. ZnIn prepared by the invention2S4The nanosheet in-situ heterojunction can effectively inhibit the recombination of photo-generated electron-hole pairs and can be used for photocatalysis of CO2Excellent performance is shown on reduction. The preparation method has the advantages of simple preparation process, short period, low cost, large-scale industrial production and good economic benefit and environmental benefit. Chinese patent document CN110961123A discloses an all-solid direct Z-type ZnIn prepared by a hydrothermal method2S4-MoSe2A high-efficiency photocatalyst belongs to the technical field of semiconductor photocatalysis. Firstly, ZnIn is prepared by a hydrothermal method2S4Then, the obtained product is mixed with commercially available Na2MoO4·2H2The O is jointly dispersed into the aqueous solution to obtain ZnIn2S4With Na2MoO4The mixed dispersion of (4); then adding Se powder solution dissolved in hydrazine hydrate into the mixed dispersion liquid, uniformly mixing, transferring into a reaction kettle, carrying out hydrothermal reaction for 4-6 hours at the temperature of 220-260 ℃, centrifuging, washing, and drying the product to obtain the all-solid-state direct Z-type ZnIn2S4-MoSe2High-efficiency photocatalyst. The photocatalyst shows excellent hydrogen production performance by photolysis of water, and under the irradiation of visible light, the photocatalytic hydrogen production efficiency is up to 50000-55000 mu mol-g-1·h-1. But with respect to the present invention an ultra-thin ZnIn2S4The nano-sheet photocatalyst material, and a preparation method and application thereof are not reported at present.
Disclosure of Invention
The first purpose of the invention is to provide an ultra-thin ZnIn against the defects in the prior art2S4A nano-sheet photocatalyst material.
It is a second object of the present invention to provide the ultra-thin ZnIn2S4A preparation method of a nano-sheet photocatalyst material.
It is a third object of the present invention to provide the ultra-thin ZnIn2S4Application of nano-sheet photocatalyst material.
To achieve the first object, the present invention provides an ultra-thin ZnIn2S4Nano sheet photocatalyst material, said ultrathin ZnIn2S4The thickness of the nano-sheet photocatalyst material is 4-5nm, and the nano-sheet photocatalyst material is a double-layer ZnIn2S4Nanosheets.
To achieve the second object, the present invention provides the ultra-thin ZnIn2S4The preparation method of the nanosheet photocatalyst material comprises the following steps:
low-temperature reflux: dissolving a zinc source and an indium source in deionized water, stirring at room temperature, adding a sulfur source, and then putting into an oil bath pot for heating and vigorously stirring.
Ultrasonic stripping: centrifuging the obtained suspension, collecting the precipitate, washing twice with deionized water, dispersing into deionized water again, centrifuging after ultrasonic treatment, and taking supernatant as a final product.
Preferably, in the preparation method of the photocatalyst material, the indium source is indium nitrate, the zinc source is zinc acetate, and the sulfur source is thioacetamide.
More preferably, in the preparation method of the photocatalyst material, the molar ratio of the indium nitrate to the zinc acetate is 1:2, and the thioacetamide is at least 1/3-2/3 in excess.
Preferably, the preparation method of the photocatalyst material is carried out in an oil bath kettle, and the reaction temperature is 80-100 ℃.
Preferably, in the preparation method of the photocatalyst material, ultrasonic peeling is carried out in an ultrasonic machine, the ultrasonic power is 250W, and the ultrasonic time is 0.5-5 h.
Preferably, in the preparation method of the photocatalyst material, product screening is performed in a centrifuge, the rotation speed of the centrifuge is 3000-.
To achieve the third object, the present invention provides the above ultra-thin ZnIn2S4The application of the nanosheet photocatalyst material in photocatalytic sterilization is characterized in that bacteria capable of being killed in the application are escherichia coli, staphylococcus aureus or drug-resistant staphylococcus aureus.
The invention has the advantages that:
1. the invention provides an ultrathin ZnIn2S4The preparation method of the nanosheet can effectively increase the reactive sites, shorten the migration distance of photo-generated electrons and holes and improve the photocatalytic sterilization efficiency.
2. The material also has good visible light absorption performance, and can kill escherichia coli, staphylococcus aureus and drug-resistant staphylococcus aureus 100% within 5-20 minutes under the irradiation of visible light.
3. The preparation method of the photocatalyst does not need special equipment, has simple process and strong controllability, can easily realize large-scale production and has practical value.
Drawings
Figure 1 XRD patterns of example 1 and comparative examples 1 and 2.
FIG. 2 atomic force microscope picture of example 1.
FIG. 3 SEM photograph of example 1.
FIG. 4 is a scanning electron micrograph of comparative example 1.
FIG. 5 is a scanning electron micrograph of comparative example 2.
FIG. 6 of example 1 and comparative examples 1 and 2·O2 -Free radical EPR profile.
FIG. 7 of example 1 and comparative examples 1 and 2·EPR spectrum of OH free radical.
FIG. 8 of example 1 and comparative examples 1 and 21O2Free radical EPR spectrum of (a).
FIG. 9 is a graph showing the effect of photo-catalytically killing Escherichia coli, Staphylococcus aureus and drug-resistant Staphylococcus aureus in example 1 and comparative examples 1 and 2.
Detailed Description
The following detailed description of the present invention will be made with reference to the accompanying drawings.
EXAMPLE 1 ZnIn of the invention2S4Preparation of nanosheet (I)
0.3293g of zinc acetate dihydrate and 0.6635g of anhydrous indium chloride are dissolved in 250mL of deionized water, stirred at room temperature for 30min, 0.6010g of thioacetamide are added, and then the mixture is put into an oil bath kettle and heated to 95 ℃, and stirred vigorously for 5 h. Centrifuging the obtained suspension, collecting precipitate, washing twice with deionized water, dispersing into 200mL deionized water again, performing ultrasonic treatment for 30min, centrifuging at 6000rpm for 5min, and collecting supernatant as final product. The samples were irregular flakes with a lateral dimension of about 1 μm and a thickness of about 4-5nm, see FIGS. 2 and 3.
Example 2 ultra-thin ZnIn of the invention2S4Preparation of nanosheet (II)
0.3293g of zinc acetate dihydrate and 0.6635g of anhydrous indium chloride are dissolved in 250mL of deionized water, stirred at room temperature for 30min, 0.7513g of thioacetamide is added, and then the mixture is put into an oil bath kettle, heated to 80 ℃, and stirred vigorously for 8 h. Centrifuging the obtained suspension, collecting precipitate, washing with deionized water five times, dispersing into 200mL deionized water again, performing ultrasonic treatment for 5h, centrifuging at 6000rpm for 10min, and taking supernatant as a final product.
Example 3 ultra-thin MgIn of the invention2S4Preparation of nanosheet (III)
0.3293g of zinc acetate dihydrate and 0.6635g of anhydrous indium chloride are dissolved in 250mL of deionized water, stirred at room temperature for 30min, 0.6010g of thioacetamide is added, and then the mixture is put into an oil bath kettle, heated to 120 ℃, and stirred vigorously for 3 h. Centrifuging the obtained suspension, collecting precipitate, washing with deionized water for three times, dispersing into 200mL of deionized water again, performing ultrasonic treatment for 30min, centrifuging at 3000rpm for 30min, and collecting supernatant as final product.
Comparative example 1 particulate ZnIn2S4Preparation method of (1)
0.3293g of zinc acetate dihydrate, 0.6635g of anhydrous indium chloride and 0.6010g of thioacetamide are ultrasonically dissolved in 250mL of deionized water, the mixture is placed in an oven and heated for 2 hours at 80 ℃, and precipitates are collected by centrifugation and are left for use after being dried. The samples were irregular particles of 1 μm size, see FIG. 4.
Comparative example 2 ZnIn2S4Preparation method of nanosheet (less sulfur)
Preparation of ZnIn by changing reactant ratio2S4Dissolving 0.3293g of zinc acetate dihydrate and 0.6635g of anhydrous indium chloride in 250mL of deionized water, stirring at room temperature for 30min, adding 0.4508g of thioacetamide, then placing the mixture into an oil bath pan, heating to 95 ℃, and stirring vigorously for 5 h. Centrifuging the obtained suspension, collecting precipitate, washing twice with deionized water, dispersing into 200mL deionized water again, performing ultrasonic treatment for 30min, centrifuging at 6000rpm for 5min, and collecting supernatant as final product. The samples were unpeeled nanosheets, see fig. 5.
Comparative example 3 ZnIn2S4Preparation of nanomaterials
The reaction procedure was the same as in example 1, except thatControlling the ultrasonic time to be 10min in the reaction process to prepare the product ZnIn2S4And (3) nano materials.
Comparative example 4 ZnIn2S4Preparation of nanomaterials
The reaction steps are the same as those in example 1, the rotating speed of a centrifugal machine in the reaction process is regulated to 2000rpm, and the product ZnIn is prepared2S4And (3) nano materials.
Example 4 topography Observation
The morphology of the product was observed using a Hitachi S4800 scanning electron microscope. The SEM of example 1 is shown in FIG. 3, and the SEM of the products of examples 2 and 3 is similar to that of example 1, showing that ZnIn is prepared2S4Nanosheets, evaluated, ZnIn of example 12S4The thickness of the nano-sheet is 4-5nm, and the nano-sheet is a double-layer ZnIn2S4Nanosheets having a transverse dimension of 1 μm and a specific surface area of 42.1m2G, ZnIn of examples 2-52S4The thickness of the nano-sheet is 4-5nm, and the nano-sheet is a double-layer ZnIn2S4The nano sheet has transverse size of 0.8-1.2 μm and specific surface area of 40-45m2The range of/g.
FIG. 4 is a scanning electron microscope picture of comparative example 1, showing that bulk ZnIn is obtained by the preparation2S4A material.
FIG. 5 is a scanning microscope photograph of the product prepared in comparative example 2, showing that the sample is difficult to peel off and an ultra-thin ZnIn cannot be obtained when the amount of the sulfur source added is small2S4Nanosheets.
The product of comparative example 3 was also similar to comparative example 2, and the sample was difficult to peel.
The product of comparative example 4 was observed by scanning electron microscope to obtain ZnIn2S4Nanosheets, but with greater thickness, more like granules.
EXAMPLE 5 characterization of free radical Generation
The free radicals generated by the samples were characterized using a Bruker ESR5000 electron paramagnetic resonance spectrometer. Referring to FIGS. 6, 7, and 8, the ultra-thin nano-flake ZnIn prepared when an excessive sulfur source is added2S4Generated superoxide radical, hydroxyl radicalThe signals of free radicals and singlet oxygen are obviously stronger than those of granular ZnIn2S4And samples with less sulfur source added.
EXAMPLE 6 Performance test for photocatalytic killing of Escherichia coli
ZnIn obtained by the above preparation method2S4A photocatalytic material is used for testing the performance of killing escherichia coli through photocatalysis, a 23.3mg sample is dissolved in physiological saline, 1.7mL of suspension bacterial liquid with the concentration of 0.5 McLee unit of escherichia coli is added to be mixed and stirred uniformly, stirring is carried out for 30min under a dark condition, then a 300W xenon lamp with a 400nm filter is turned on to illuminate, 100 mu L of solution is extracted for 0min and 30min under the dark condition and 5min, 10min, 20min, 30min, 60min, 90min and 120min after the lamp is turned on, the solution is diluted by 1000 times, then 100 mu L of diluted mixed solution is uniformly mixed with 300 mu L of physiological saline, and the mixed solution is coated on a sheep blood agar plate. After being cultured in an incubator overnight, the culture medium is taken out and observed for counting.
Example 7 photocatalytic killing of Staphylococcus aureus Performance test
For ZnIn2S4A photocatalytic material is used for testing the performance of killing staphylococcus aureus in a photocatalytic manner, a 23.3mg sample is dissolved in physiological saline, 1.7mL of suspension bacterial liquid with the concentration of the staphylococcus aureus being 0.5 McLee unit is added and mixed evenly, the mixture is stirred for 30min under the dark condition, then a 300W xenon lamp provided with a 400nm filter is turned on for illumination, 0min and 30min under the dark condition and 100 mu L of solution obtained after 5min, 10min, 20min, 30min, 60min, 90min and 120min after the lamp is turned on are extracted, the solution is diluted by 1000 times, then 100 mu L of diluted mixed solution and 300 mu L of physiological saline are uniformly mixed, and the mixed solution is coated on a sheep blood agar plate. After being cultured in an incubator overnight, the culture medium is taken out and observed for counting.
Example 8 photocatalytic killing of drug-resistant Staphylococcus aureus Performance test
A performance test of photocatalytic killing of drug-resistant staphylococcus aureus is carried out on a photocatalytic material, 23.3mg of a sample is dissolved in physiological saline, 1.7mL of suspension liquid with the concentration of the drug-resistant staphylococcus aureus being 0.5 McLee unit is added and uniformly mixed and stirred, the mixture is stirred for 30min under a dark condition, then a 300W xenon lamp with a 400nm filter is turned on for illumination, 0min and 30min under the dark condition and 100 mu L of solution obtained after 5min, 10min, 20min, 30min, 60min, 90min and 120min after the lamp is turned on are extracted, the solution is diluted by 1000 times, then 100 mu L of diluted mixed solution and 300 mu L of physiological saline are uniformly mixed and then are coated on a sheep blood agar plate. After being cultured in an incubator overnight, the culture medium is taken out and observed for counting.
FIG. 9 shows ZnIn in example 12S4Nanosheets and ZnIn in comparative examples 1 and 22S4The sample photocatalysis kills the Escherichia coli, the staphylococcus aureus and the drug-resistant staphylococcus aureus. As can be seen, ZnIn2S4Nanosheet and particulate ZnIn2S4The inhibition effect on escherichia coli is strongest, staphylococcus aureus is the second, and drug-resistant staphylococcus aureus is the last. The results of the photocatalytic sterilization performance test of the other examples and comparative examples are shown in table 1. With particulate ZnIn2S4In contrast, ZnIn2S4The nano-sheet has higher sterilization efficiency, the photoactivity of the catalyst depends on the capability of the catalyst to generate photo-generated electron-hole pairs, and the common blocky ZnIn2S4The low separation efficiency and poor electron transport capacity inhibit the effective separation of the photoproduction electron-hole pairs, resulting in poor photocatalytic activity, and thus an effective strategy is required to promote ZnIn2S4The photocatalytic performance of (a).
TABLE 1 percentage of viable bacteria (%) -at 30min time point for the products of examples 2-3 and comparative examples 3-4
The above description is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, several modifications and additions can be made without departing from the method of the present invention, and these modifications and additions should also be regarded as the protection scope of the present invention.
Claims (8)
1. Ultrathin ZnIn2S4Nano sheet photocatalyst materialThe material is characterized in that the thickness of the nanosheet photocatalyst material is 4-5nm, and the nanosheet photocatalyst material is a double-layer ZnIn2S4Nanosheets.
2. The ultra-thin ZnIn of claim 12S4The nano-sheet photocatalyst material is characterized in that the preparation method of the photocatalyst material comprises the following steps:
low-temperature reflux: dissolving a zinc source and an indium source in deionized water, stirring at room temperature, adding a sulfur source, and then putting into an oil bath pot for heating and vigorously stirring.
Ultrasonic stripping: centrifuging the obtained suspension, collecting the precipitate, washing twice with deionized water, dispersing into deionized water again, centrifuging after ultrasonic treatment, and taking supernatant as a final product.
3. The photocatalyst material according to claim 2, wherein the indium source is indium nitrate, the zinc source is zinc acetate, and the sulfur source is thioacetamide.
4. The photocatalyst material as set forth in claim 3, wherein the molar ratio of indium nitrate to zinc acetate is 1:2, and the thioacetamide is in excess of 1/3-2/3.
5. The photocatalytic material as set forth in claim 2, wherein the photocatalytic material is produced in an oil bath at a reaction temperature of 80 to 100 ℃.
6. The photocatalyst material as set forth in claim 2, wherein the photocatalyst material is prepared by a method in which ultrasonic exfoliation is carried out in an ultrasonic machine, the ultrasonic power is 250W, and the ultrasonic time is 0.5 to 5 hours.
7. The photocatalyst material as set forth in claim 2, wherein in the preparation method of the photocatalyst material, product screening is performed in a centrifuge, the rotation speed of the centrifuge is 3000-6000rpm, and the centrifugation time is 5-30 min.
8. The ultra-thin ZnIn of claims 1-72S4The application of the nanosheet photocatalyst material in photocatalytic sterilization is characterized in that bacteria capable of being killed in the application are escherichia coli, staphylococcus aureus or drug-resistant staphylococcus aureus.
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115400792A (en) * | 2022-09-29 | 2022-11-29 | 南京师范大学 | Modified PDI photocatalyst and preparation method and application thereof |
| CN115739131A (en) * | 2022-10-17 | 2023-03-07 | 河南师范大学 | Ultrathin BiOCl @ Bi 2 S 3 @Cu 2 S heterojunction nanosheet and preparation method and application thereof |
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| Publication number | Priority date | Publication date | Assignee | Title |
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| CN115400792A (en) * | 2022-09-29 | 2022-11-29 | 南京师范大学 | Modified PDI photocatalyst and preparation method and application thereof |
| CN115400792B (en) * | 2022-09-29 | 2024-04-26 | 南京师范大学 | Modified PDI photocatalyst and preparation method and application thereof |
| CN115739131A (en) * | 2022-10-17 | 2023-03-07 | 河南师范大学 | Ultrathin BiOCl @ Bi 2 S 3 @Cu 2 S heterojunction nanosheet and preparation method and application thereof |
| CN115739131B (en) * | 2022-10-17 | 2023-11-14 | 河南师范大学 | Ultrathin BiOCl@Bi 2 S 3 @Cu 2 S heterojunction nano-sheet and preparation method and application thereof |
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