CN110003892B - CdS/ZnS quantum dot prepared by modified sol-gel method and application thereof in photocatalytic hydrogen evolution - Google Patents
CdS/ZnS quantum dot prepared by modified sol-gel method and application thereof in photocatalytic hydrogen evolution Download PDFInfo
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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
- B01J27/04—Sulfides
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- C09K11/56—Luminescent, e.g. electroluminescent, chemiluminescent materials containing inorganic luminescent materials containing sulfur
- C09K11/562—Chalcogenides
- C09K11/565—Chalcogenides with zinc cadmium
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- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
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Abstract
The invention relates to a modified sol-gel method for preparing CdS/ZnS quantum dots and application thereof in photocatalytic hydrogen evolution, in particular to a method for preparing CdS/ZnS quantum dots by taking hydrogel as a special function of gel and application thereof in photocatalytic hydrogen evolution. The method comprises the following steps: dispersing HR to Cd2+/Zn2+In the water solution, the HR/Cd is obtained by stirring the mixture for a period of time at a certain temperature2+And HR/Zn2+;HR/Cd2+And HR/Zn2+Separately adding a certain amount of Na2In the S aqueous solution, stirring gently for a period of time, washing and drying to obtain HR/CdS and HR/ZnS; the method is simple, the preparation cost is low, and no environmental pollution is caused; the CdS/ZnS quantum dots prepared by the method are effectively combined with hydrogel to form a novel miniature hydrogen production reactor, and the novel miniature hydrogen production reactor shows good photocatalytic hydrogen evolution activity and the hydrogel is low in cost; the method provided by the invention can be used for adsorbing Cd in waste liquid2+/Zn2+And ions are vulcanized, so that the metal ions in the waste liquid are removed and reused.
Description
Technical Field
The invention belongs to the technical field of preparation of CdS/ZnS quantum dots and application of the CdS/ZnS quantum dots in photocatalytic hydrogen evolution, and particularly relates to a method for preparing CdS/ZnS quantum dots by taking hydrogel as a special effect of gel and application of the CdS/ZnS quantum dots in photocatalytic hydrogen evolution.
Background
The information in this background section is only for enhancement of understanding of the general background of the invention and is not necessarily to be construed as an admission or any form of suggestion that this information forms the prior art that is already known to a person of ordinary skill in the art.
In recent years, sulfides such as CdS and ZnS have been widely used in photocatalytic hydrogen evolution reactions. A wide variety of topographical structures are prepared, such as solid solutions, nanosheets, nanowires, quantum dots, and the like. Among these structures, quantum dots are considered as very promising structures as photocatalytic hydrogen evolution reactions because quantum dots have advantages of providing a large number of catalytic reaction sites, shortening the carrier transport distance, and improving the separation efficiency of photo-generated electrons and holes. Although significant results are obtained through extensive research by world scientists, the preparation method of the quantum dots is still basically organic phase preparation, the quantum dots of the organic phase are firstly obtained, and then the quantum dots of the organic phase need to be converted into water-soluble phase quantum dots by replacing organic ligand chains, the conversion process is quite complex, and organic pollution is caused. Therefore, the preparation method of the quantum dots is further explored to be a necessary trend and has very high scientific value.
The gel material is a three-dimensional network structure, and the solution can freely shuttle in the network structure, which is very favorable for the growth of crystals, so that the crystals can be stably kept at the formed positions, crystal nuclei are well spatially separated, thereby effectively avoiding agglomeration and minimizing the particle size of the crystals (the characteristics of the sol-gel growth method). In addition, Hydrogel (HR) as a colloid contains a large amount of hydrophilic groups and a special three-dimensional polymeric hinge network structure, can rapidly adsorb a large amount of water swelling and is often used for adsorbing heavy metal ions such as Cd in industrial waste liquid2+,Pb2+,Cu2+,Zn2+And the like by chemical bonding, ionic interaction, physical adsorption, and the like.
For example: patent CN201810616553.8 discloses a quantum dot-Au/C3N4Preparation of hydrogel photocatalyst: a certain amount of Au/C is added3N4Dissolving pore-forming agent and pH regulator in distilled water, and ultrasonic stirring to obtain Au/C3N4Mixing the dispersion solution; dissolving a certain amount of hydrogel matrix and an irradiation sensitizer in deionized water to prepare a high molecular solution; the polymer solution was slowly added to Au/C3N4Mixing the dispersed solution, stirring the solution evenly by ultrasonic, and introducing N2Standing under negative pressure for defoaming, freezing and thawing the obtained dispersion for multiple times, slowly adding a certain amount of quantum dot precursor solution and carboxyl radical scavenger, and introducing N again2Standing under negative pressure to remove bubbles; adding NaOH to the mixed solution to adjust the pH value to be 6-10, filling the mixed solution into a PE (polyethylene) sealing bag, and placing the PE sealing bag in an electron beam with energy of 1-5 MeV, radiation dose of 5-80 kGy and dose rate of 5-20 kGy/pass; washing the irradiated sample with water, drying, crushing, sieving and grading to obtain the quantum dots-Au/C with different granularity3N4Micro-particles of hydrogel photocatalytic material, i.e. quantum dots-Au/C3N4-a hydrogel photocatalyst. However, the inventor finds that: the composite material prepared by the method has the problems that quantum dots are easy to fall off and agglomerate in the process of catalytic hydrogen evolution.
Disclosure of Invention
In order to overcome the problems, the invention provides a modified sol-gel method for preparing CdS/ZnS quantum dots and explores the application of photocatalytic hydrogen evolution of the CdS/ZnS quantum dots. The method can prepare CdS/ZnS quantum dots on the hydrogel, and the quantum dots and the hydrogel form a miniature hydrogen evolution reactor which shows good photocatalytic hydrogen evolution performance.
In order to achieve the technical purpose, the technical scheme adopted by the invention is as follows:
a method for preparing CdS/ZnS quantum dots by a modified sol-gel method comprises the following steps:
dispersing hydrogel HR into Cd2+/Zn2+In the aqueous solution of (2), allowing HR to adsorb Cd in the solution2+/Zn2+Forming HR/Cd2+Or HR/Zn2+;
Mixing HR/Cd2+Or HR/Zn2+Adding to Na2And reacting in an S aqueous solution for a period of time, separating, washing and drying to obtain HR/CdS and HR/ZnS.
Compared with the composite material obtained by mixing the quantum dots with the matrix of the hydrogel and then gelling, the quantum dots prepared by the method can be more firmly grown on the surface of the hydrogel, the interface contact is superior to that of the composite material obtained by mixing the prepared quantum dot material with the hydrogel, the quantum dots can be firmly fixed on the surface of the hydrogel when the photocatalytic reaction is carried out, the composite material cannot fall off or agglomerate, the catalytic efficiency is higher, the recycling of the quantum dots is easy to realize, the quantum dots are prevented from agglomerating into nano particles, and the advantages of the quantum dots are conveniently and fully displayed.
Based on the above discussion, the method and the application explore that the hydrogel is used as a substrate and is combined with a sol-gel growth method to prepare the CdS quantum dots and the ZnS quantum dots, so that the organic pollution is effectively avoided while the quantum dots are obtained, meanwhile, the hydrogel can be used as a micro hydrogen evolution reactor to promote the hydrogen evolution performance of the quantum dots, and the method and the application have high significance and value.
The hydrogel has the advantages of high swelling rate, high mechanical strength, good biocompatibility, biodegradability and the like, but the traditional hydrogel still has the defect of poor mechanical property, so in some embodiments, the hydrogel is cellulose-based hydrogel, the mechanical property of the hydrogel is effectively improved by utilizing the specific interpenetrating network structure of the hydrogel, and the hydrogel is more suitable for being used as a substrate material.
The research finds that: with Cd2+/Zn2+Increase in ion concentration, HR/Cd2+Or HR/Zn2+The loading capacity of medium metal ions is increased, and the catalytic performance of CdS/ZnS quantum dots is enhanced, but when Cd is increased, the catalytic performance of CdS/ZnS quantum dots is improved2+/Zn2+After the ion concentration reaches a certain value, the adsorption of HR on metal ions reaches saturation, and Cd is continuously added2+/Zn2+The improvement of the ion concentration on the catalytic performance of CdS/ZnS quantum dots is not large, therefore, in some embodiments, the HR, Cd2+/Zn2+The mass ratio of the ions is 1-10: 10-50.
Cd, on the other hand2+/Zn2+Ions with Na2S according to the reaction Cd2++S2-The method is carried out according to the CdS ↓molarratio, but in the actual reaction process, part of Cd exists in the hydrogel adsorption process2+/Zn2+Ions cannot adsorb onto the hydrogel, therefore, in some embodiments, the Cd2+/Zn2+Ions and Na2The mass ratio of S is 10-50: 20-80.
Research finds that; the hydrogel has good adsorption performance on metal ions, and the mixing efficiency and the contact probability of the hydrogel and the metal ions can be effectively improved by adding stirring treatment, so that the adsorption rate of the metal ions on the hydrogel is improved, and therefore, in some embodiments, Cd in an HR adsorption solution2+/Zn2+The specific conditions are as follows: stirring for 10-120 min at 10-30 ℃.
In Cd2++S2-In the reaction of CdS ↓, the increase of the temperature can promote the chemical equilibrium to move right, increase the production of CdS, and the stirring treatment can make Cd move right2+、S2Mixing well, increasing the probability of contact. Thus, in some embodiments, Na2In the S aqueous solution, the reaction condition is that the stirring is carried out for 10-30 min at 10-30 ℃.
The invention also provides the CdS/ZnS quantum dot prepared by any one of the methods.
The invention also provides a photocatalytic hydrogen evolution catalyst, which comprises: the CdS/ZnS quantum dot is described above.
The invention also provides a photocatalytic hydrogen evolution electrode, comprising: the photocatalytic hydrogen evolution catalyst.
The invention also provides a photocatalytic hydrogen evolution device, comprising: the photocatalytic hydrogen evolution electrode.
The invention also provides application of the CdS/ZnS quantum dot in the field of environmental protection.
The invention has the beneficial effects that:
(1) the CdS/ZnS quantum dot preparation method provided by the invention is simple, low in preparation cost and free of environmental pollution.
(2) The CdS/ZnS quantum dots prepared by the method are effectively combined with hydrogel to form a novel miniature hydrogen production reactor, and the novel miniature hydrogen production reactor shows good photocatalytic hydrogen evolution activity and is low in hydrogel cost.
(3) The method provided by the invention can be used for adsorbing Cd in waste liquid2+/Zn2+And ions are vulcanized, so that the metal ions in the waste liquid are removed and reused.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this application, illustrate embodiments of the application and, together with the description, serve to explain the application and are not intended to limit the application.
FIG. 1 is a transmission electron micrograph of HR/CdS and HR/ZnS prepared according to example 1 of the present invention, wherein a is HR/CdS and b is HR/ZnS.
FIG. 2 is an XRD pattern of HR/CdS, HR/ZnS prepared according to example 1 of the present invention.
FIG. 3 is a graph of the photocatalytic performance of HR/CdS and HR/ZnS 16h prepared in example 1 of the present invention.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the disclosure. Unless defined otherwise, all technical and scientific terms used herein have the same meaning as commonly understood by one of ordinary skill in the art to which this application belongs.
It is noted that the terminology used herein is for the purpose of describing particular embodiments only and is not intended to be limiting of example embodiments according to the present application. As used herein, the singular forms "a", "an" and "the" are intended to include the plural forms as well, and it should be understood that when the terms "comprises" and/or "comprising" are used in this specification, they specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof, unless the context clearly indicates otherwise.
The examples do not specify particular techniques or conditions, and are performed according to the techniques or conditions described in the literature in the art or according to the product specifications. The reagents or instruments used are not indicated by the manufacturer, and are all conventional products commercially available.
As introduced in the background art, the method aims at the problems that the existing preparation method of the quantum dots is basically organic phase preparation, the conversion process is complex and organic pollution is easily caused. Therefore, the invention provides a preparation method for preparing CdS/ZnS quantum dots by a modified sol-gel method.
The first purpose of the invention is to provide a preparation method of CdS/ZnS quantum dots.
The second purpose of the invention is to provide the HR/CdS and HR/ZnS quantum dot photocatalyst obtained by the method.
The third purpose of the invention is to provide the HR/CdS and HR/ZnS quantum dot photocatalyst and the application of the preparation method thereof.
The method specifically comprises the following steps:
(1) dispersing HR to Cd2+/Zn2+In the water solution, the HR/Cd is obtained by stirring the mixture for a period of time at a certain temperature2+And HR/Zn2+;
(2)HR/Cd2+And HR/Zn2+Separately adding a certain amount of Na2In the S aqueous solution, stirring gently for a period of time, washing and drying to obtain HR/CdS and HR/ZnS;
as a further technical scheme, the hydrogel in the step (1) is cellulose-based hydrogel.
As a further technical scheme, the water temperature in the step (1) is controlled to be 10-30 ℃.
As a further technical scheme, in the step (1), HR and Cd2+/Zn2+The feeding proportion of the ions is (1-10) mg and (10-50) mg.
As a further technical scheme, in the step (1), the stirring time is 10-120 min.
As a further technical scheme, in the step (2), Na is added2The S aqueous solution further comprises a stirring step, wherein the stirring time is 10-30 min, and the stirring temperature is controlled to be 10-30 ℃.
As a further technical scheme, in the step (2), Na is introduced2Na in S aqueous solution2The amount of S is 20-80 mg.
Finally, the invention discloses the application of the CdS/ZnS quantum dot and the preparation method thereof in the field of environmental protection.
The principle of the invention for preparing CdS/ZnS quantum dots is as follows: the Hydrogel (HR) adsorbs the metal ions, Cd, in solution2+/Zn2+Cd by chemical bond or ionic interaction, physical adsorption, or the like2+/Zn2+Is fixed at the corresponding position to realize the effective separation of space when HR/Cd is used2+And HR/Zn2+Adding to Na2After the aqueous solution of S is treated, the hydrogel is used as a gel, and the characteristics of crystal growth by a composite sol-gel method can ensure that the formed CdS/ZnS crystal is stably kept at a formed position, crystal nuclei are well spatially separated, thereby effectively avoiding agglomeration, minimizing the grain size of the crystal and further obtaining the CdS/ZnS quantum dot. The method provides a new approach for the preparation and application of the quantum dots.
The scheme of the application is described by specific examples below.
In the following examples, hydrogels were prepared as follows: weighing 0.25g of corncob cellulose, adding the corncob cellulose into a three-mouth flask, adding 15mL of distilled water, placing the three-mouth flask on an intelligent magnetic stirrer, heating to 85 ℃, stirring for 60min, introducing nitrogen during heating, adding 50 mu L of tetramethylethylenediamine and 0.05g of ammonium persulfate after the cellulose is completely dissolved, continuing stirring for 10min, pouring acrylic acid and N.N-methylene bisacrylamide with adjusted neutralization degrees into the three-mouth flask, continuing heating and stirring, observing the temperature and the liquid in the flask, recording the temperature when flocculation begins, taking the three-mouth flask down, cooling, taking out the hydrogel in the flask into a small beaker, adding 200mL of anhydrous ethanol, standing for 24h, washing with deionized water hydrogel, then placing the washed hydrogel into an electric heating air blowing drying oven, drying for 24h at 60 ℃, cutting the hydrogel into 2X 2mm small blocks after drying is completed, bagging for later use.
Example 1
A preparation method of CdS/ZnS quantum dots comprises the following steps:
(1) dispersing 10mg HR into50mL of 800mg/L Cd2+/Zn2+Slightly stirring in water solution at 25 deg.C for 90min, separating to obtain HR/Cd2+And HR/Zn2+;
(2)HR/Cd2+And HR/Zn2+Separately, 100mL of 800mg/L Na was added2In the S water solution, stirring gently for 30min, separating, washing and drying to obtain HR/CdS and HR/ZnS;
example 2
A preparation method of CdS/ZnS quantum dots comprises the following steps:
(1) dispersing 5mg HR to 40mL of 800mg/L Cd2+/Zn2+Slightly stirring in water solution at 20 deg.C for 60min, and separating to obtain HR/Cd2+And HR/Zn2+;
(2)HR/Cd2+And HR/Zn2+Respectively added to 80mL of 800mg/L Na2In the S water solution, stirring gently for 20min, separating, washing and drying to obtain HR/CdS and HR/ZnS;
example 3
A preparation method of CdS/ZnS quantum dots comprises the following steps:
(1) dispersing 8mg HR to 30mL of 800mg/L Cd2+/Zn2+Gently stirring in water solution at 15 deg.C for 120min, and separating to obtain HR/Cd2+And HR/Zn2+;
(2)HR/Cd2+And HR/Zn2+Separately, 20mL of 800mg/L Na was added2In the S water solution, stirring gently for 10min, separating, washing and drying to obtain HR/CdS and HR/ZnS;
example 4
A preparation method of CdS/ZnS quantum dots comprises the following steps:
(1) dispersing 3mg HR to 15mL of 800mg/L Cd2+/Zn2+Slightly stirring in water solution at 30 deg.C for 70min, and separating to obtain HR/Cd2+And HR/Zn2+;
(2)HR/Cd2+And HR/Zn2+Separately, 60mL of 800mg/L Na was added2Stirring the solution in the S water solution for 25min, separating, washing and dryingDrying to obtain HR/CdS and HR/ZnS;
and (3) performance testing:
(1) the XRD test was performed on the final product obtained in step (2) of examples 1 to 4, and the test results of example 1 were taken as an example, and the results are shown in fig. 2, which shows that: CdS/ZnS was successfully synthesized.
(2) The transmission electron microscope test is performed on the final product obtained in the step (2) of the embodiments 1 to 4, and the test result of the embodiment 1 is taken as an example, and the result is shown in fig. 1, which shows that: the successfully synthesized CdS/ZnS are quantum dots and are uniformly dispersed on the HR.
(3) The HR/CdS and HR/ZnS photocatalysts prepared in example 1 were subjected to a hydrogen evolution reaction test. The test method comprises the following steps: respectively dispersing HR/CdS and HR/ZnS into a sodium sulfide and sodium sulfite solution, placing the solution into a hydrogen production reactor, placing a 350W xenon lamp at the position 5cm above the solution, sampling 1mL of gas every 1H, and analyzing H by mass spectrometry and gas chromatography2And (4) content. The results are shown in fig. 3, where it can be seen that: HR/CdS, HR/ZnS showed good hydrogen evolution performance.
It should be noted that the above-mentioned embodiments are only preferred embodiments of the present invention, and the present invention is not limited thereto, and although the present invention has been described in detail with reference to the foregoing embodiments, it will be apparent to those skilled in the art that modifications and equivalents can be made in the technical solutions described in the foregoing embodiments, or equivalents thereof. Any modification, equivalent replacement, or improvement made within the spirit and principle of the present invention should be included in the protection scope of the present invention. Although the embodiments of the present invention have been described with reference to the accompanying drawings, it is not intended to limit the scope of the present invention, and it should be understood by those skilled in the art that various modifications and variations can be made without inventive efforts by those skilled in the art based on the technical solution of the present invention.
Claims (9)
1. A method for preparing CdS or ZnS quantum dots by a modified sol-gel method is characterized by comprising the following steps:
dispersing hydrogel HR into Cd2+Or Zn2+In the aqueous solution of (2), allowing HR to adsorb Cd in the solution2+Or Zn2+Form HR-Cd2+Or HR-Zn2+;
Mixing HR-Cd2+Or HR-Zn2+Adding to Na2Reacting in S water solution for a period of time, separating, washing and drying to obtain HR-CdS and HR-ZnS;
the hydrogel is a cellulose-based hydrogel;
the preparation method of the hydrogel comprises the following steps: weighing corncob cellulose, adding distilled water, heating, introducing nitrogen in the heating process, adding tetramethylethylenediamine and ammonium persulfate after the cellulose is completely dissolved, continuing stirring, pouring acrylic acid and N.N-methylene bisacrylamide with the adjusted neutralization degree, continuing heating and stirring, observing the temperature and liquid in a flask, recording the temperature when flocculation begins, cooling at normal temperature, cooling, taking out hydrogel in the flask, adding absolute ethyl alcohol, standing, washing with deionized water, drying the washed hydrogel, and obtaining the corn cob cellulose hydrogel after drying.
2. The method of claim 1, wherein the HR, Cd2+Or Zn2+Ions and Na2The mass ratio of S is 1-10: 10-50: 20-80.
3. The method of claim 1, wherein the HR adsorbs Cd from the solution2+Or Zn2+The specific conditions are as follows: stirring for 10-120 min at 10-30 ℃.
4. The method of claim 1, wherein Na2In the S aqueous solution, the reaction condition is that the stirring is carried out for 10-30 min at 10-30 ℃.
5. CdS or ZnS quantum dots prepared according to the method of any one of claims 1 to 4.
6. A photocatalytic hydrogen evolution catalyst, comprising: the CdS or ZnS quantum dot of claim 5.
7. A photocatalytic hydrogen evolution electrode, comprising: the photocatalytic hydrogen evolution catalyst as set forth in claim 6.
8. A photocatalytic hydrogen evolution apparatus, comprising: the photocatalytic hydrogen evolution electrode of claim 7.
9. The use of CdS or ZnS quantum dots as defined in claim 5 in the environmental protection field.
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