CN113856702A - Cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst and preparation method and application thereof - Google Patents
Cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst and preparation method and application thereof Download PDFInfo
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- CN113856702A CN113856702A CN202111039440.4A CN202111039440A CN113856702A CN 113856702 A CN113856702 A CN 113856702A CN 202111039440 A CN202111039440 A CN 202111039440A CN 113856702 A CN113856702 A CN 113856702A
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- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 title claims abstract description 103
- 229910052980 cadmium sulfide Inorganic materials 0.000 title claims abstract description 103
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- AQMRBJNRFUQADD-UHFFFAOYSA-N copper(I) sulfide Chemical compound [S-2].[Cu+].[Cu+] AQMRBJNRFUQADD-UHFFFAOYSA-N 0.000 title claims abstract description 92
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- IKDUDTNKRLTJSI-UHFFFAOYSA-N hydrazine monohydrate Substances O.NN IKDUDTNKRLTJSI-UHFFFAOYSA-N 0.000 claims description 20
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- YKYOUMDCQGMQQO-UHFFFAOYSA-L cadmium dichloride Chemical compound Cl[Cd]Cl YKYOUMDCQGMQQO-UHFFFAOYSA-L 0.000 claims description 14
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- SJHUQGQHKBUYQV-UHFFFAOYSA-L dichlorocadmium;dihydrate Chemical compound O.O.Cl[Cd]Cl SJHUQGQHKBUYQV-UHFFFAOYSA-L 0.000 description 1
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Classifications
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- B01J35/39—
-
- 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
-
- B01J35/50—
-
- 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
-
- 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 belongs to the field of photocatalysts, and relates to a cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst, a preparation method and application thereof, the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure broad-spectrum (visible and near-infrared) photocatalyst prepared by the invention takes a cadmium sulfide nanorod as a matrix, and a cuprous sulfide nanoshell layer with a near-infrared absorption effect grows in situ on the surface through a cation exchange reaction, on one hand, the cadmium sulfide nanorod of a visible photocatalyst with high catalytic activity and the property that cuprous sulfide has a near-infrared response range are combined, on the other hand, cuprous sulfide and cadmium sulfide are tightly combined to form a heterojunction, which is beneficial to carrier separation and improves the photocatalytic hydrogen production performance, in addition, the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure is prepared through the cation exchange reaction, the synthesis process and equipment are simple, simple operation process, low production cost, high efficiency, short reaction period, good repeatability and wide industrial application prospect.
Description
Technical Field
The invention relates to the technical field of photocatalysts, in particular to a cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure with a broad-spectrum (visible and near-infrared) photocatalytic effect caused by a local surface plasmon resonance effect and a preparation method thereof.
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.
Rapid urbanization and industrialization lead to global shortage of energy resources, and the use of fossil energy causes a large amount of toxic chemical pollutants such as carbon dioxide and sulfur dioxide to be discharged into the environment. Hydrogen energy is a clean energy source that can replace fossil energy. However, hydrogen is currently obtained mainly by reforming methane. Photocatalytic hydrogen production by semiconductors and their composites to convert solar energy into hydrogen fuel is an attractive technology because of the abundance of solar energy and semiconductor materials for photocatalysts on earth. Photocatalysis is a photochemical reaction in the presence of a catalyst, and is the organic combination of photochemistry and the catalyst. Photocatalysis is the initiation or acceleration of specific reduction and oxidation reactions by light irradiation of semiconductors, the essence of which is the conversion of photon energy (solar radiation) into chemical energy. When the semiconductor is impacted by energy photon, the valence band electron is excited to make transition to conduction band, the energy carried by photon is greater than the forbidden band width of semiconductor, the excited electron can cross the forbidden band and enter the conduction band, and the positive charge hole is left in the valence band. The photocatalyst converts light energy existing in nature into energy required by chemical reaction, and is a new energy-saving, high-efficiency, green and environment-friendly technology developed in recent years. However, the research and development of the material as a new functional material also face many limitations, such as low catalytic efficiency, catalyst deactivation, secondary pollution, low sunlight utilization rate, and the like. Based on this, the development and construction of heterostructures have become an important means for obtaining new high-performance photocatalytic materials. For example, as for the traditional titanium dioxide photocatalyst and the derivative photocatalyst thereof, the forbidden bandwidth is wide, the light absorption is limited to the ultraviolet part and part of the visible light region, the ultraviolet region and the visible light region respectively account for about 5% and 48% of the sunlight, and the infrared light which accounts for most of the energy of the sunlight is not fully utilized. In the solar spectrum, near infrared light accounts for 44% of the total energy, so that photocatalysis in the near infrared spectral region (the region of 780-2526 nm) has great research potential. Based on this, the development of near infrared light to obtain new high-performance photocatalytic materials is one of the major points of current work.
The forbidden band width of the cuprous sulfide is 1.2eV, the cuprous sulfide has a potential near-infrared light catalysis effect, is a well-known semiconductor material which can be excited by near-infrared light, and is widely researched.
Disclosure of Invention
In order to solve the problem that the photocatalyst can only absorb ultraviolet light and visible light in the prior art, the invention aims to provide the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure catalyst which has a wide-spectrum (visible and near-infrared) photocatalytic effect caused by a local plasma resonance effect.
In order to achieve the technical purpose, the invention adopts the following technical scheme:
the invention provides a preparation method of a cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst, which comprises the step of coating a cuprous sulfide nanoshell on a cadmium sulfide nanorod.
The invention adopts a heterostructure formed by compounding the cadmium sulfide nanorod and the cuprous sulfide nanoshell for the first time, and the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure is used as a photocatalyst, so that the heterostructure can be successfully applied to near infrared light catalysis.
In a second aspect of the present invention, there is provided a cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst, comprising:
cadmium sulfide nanorods;
and the cuprous sulfide nanoshells are coated on the outer sides of the cadmium sulfide nanorods.
In a third aspect of the present invention, there is provided an application of the above-mentioned cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst in broad-spectrum photocatalysis, wherein the broad spectrum comprises: visible spectrum and near infrared spectrum.
The fourth aspect of the invention provides an application of the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst in photocatalytic hydrogen production.
The invention has the beneficial effects that:
(1) the cadmium sulfide nanorod/cuprous sulfide nanosheet heterostructure photocatalyst prepared by the method disclosed by the invention is prepared by taking the cadmium sulfide nanorod with visible light response and the cuprous sulfide nanosheet growing on the surface of the cadmium sulfide nanorod as a matrix, and the cuprous sulfide nanosheet with high catalytic activity and near-infrared light catalytic effect grows on the surface of the cadmium sulfide nanorod, so that the property of the excellent visible light catalyst cadmium sulfide is combined, the light absorption range is widened to near-infrared light under the local plasma resonance effect of cuprous sulfide, and the photocatalytic reaction activity of a composite material is improved.
(2) The method adopts cation exchange reaction to prepare the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure, and has the advantages of simple synthesis process and equipment, simple operation process, low production cost, high efficiency, short reaction period, good repeatability and wide industrial application prospect. The prepared cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure has an excellent wide-spectrum (visible and near-infrared) photocatalytic effect in a photocatalytic process, and promotes the wide-spectrum (visible and near-infrared) photocatalytic hydrogen production effect.
(3) The operation method is simple, low in cost, universal and easy for large-scale production.
Drawings
The accompanying drawings, which are incorporated in and constitute a part of this specification, are included to provide a further understanding of the invention, and are incorporated in and constitute a part of this specification, illustrate exemplary embodiments of the invention and together with the description serve to explain the invention and not to limit the invention.
FIG. 1 is a transmission electron microscope image of the hetero-structure of cadmium sulfide nanorod/cuprous sulfide nanoshell prepared in example 2.
FIG. 2 is a graph showing the change of hydrogen production by photolysis of water under simulated sunlight with time of the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure, the cadmium sulfide nanorod, and the cuprous sulfide nanorod prepared in example 2.
Detailed Description
It is to be understood that the following detailed description is exemplary and is intended to provide further explanation of the invention as claimed. 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 invention belongs.
The invention provides a cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure catalyst with a broad-spectrum (visible and near-infrared) photocatalytic effect caused by a local plasma resonance effect.
The invention discloses a cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst, which comprises a rodlike cadmium sulfide nanoshell layer and a rodlike cuprous sulfide nanoshell layer, wherein the rodlike cadmium sulfide nanoshell layer has a diameter size of 50 nm; wherein the cadmium sulfide nano-rods are uniformly wrapped by the cuprous sulfide nano-shell.
Further, the mass ratio of the cadmium sulfide to the cuprous sulfide is 17: 200.
the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst prepared by the method combines the properties of the excellent near-infrared light response cuprous sulfide nanoshell and the visible light response cadmium sulfide nanorod, and under the protection of the cuprous sulfide nanoshell, the catalytic life of the cadmium sulfide nanorod is prolonged, and the other two heterostructure photocatalysts effectively improve the carrier separation efficiency and improve the photocatalytic hydrogen production activity of cadmium sulfide.
A preparation method of a cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure comprises the following specific steps:
step 1: synthesizing cadmium sulfide nano-rods by a hydrothermal method. Dissolving 2.3 g of cadmium chloride and 2.3 g of thiourea in 30 ml of ethylenediamine, uniformly stirring, pouring into a reaction kettle, carrying out hydrothermal reaction for 48 hours at 180 ℃, alternately washing the obtained yellow precipitate with absolute ethyl alcohol and deionized water, and drying in the air to obtain the cadmium sulfide nanorod.
It should be noted that the present step is a process for preparing cadmium sulfide nanorods by using a hydrothermal method, and the present invention provides only a specific exemplary method to facilitate the understanding of the present invention, and obviously, the purpose of achieving the present step is not limited to the method provided by the present step, for example, cadmium sulfide can be prepared by using other methods, or a commercially available cadmium sulfide product meeting the above requirements can be used.
Step 2: slowly dripping concentrated hydrochloric acid into the hydrazine hydrate solution under stirring at low temperature until the pH value of the mixed solution is equal to 7 for standby.
The hydrazine hydrate solution and the concentrated hydrochloric acid are mixed and react to release a large amount of heat, and an ice-water mixture water bath method or circulating water cooling is adopted to manufacture a low-temperature environment. Guarantee
And step 3: 100 mg of cadmium sulfide nanorods were immersed in 10 ml of a hydrazine hydrate/hydrochloric acid mixed solution (pH ≈ 7) and uniformly stirred to obtain a first mixed solution.
And 4, step 4: a certain amount of cuprous sulfide is dissolved in 10 ml of hydrazine hydrate/hydrochloric acid mixed solution, and the second mixed solution is obtained after the cuprous sulfide is fully stirred and dissolved.
And 5: and (4) adding the second mixed solution obtained in the step (4) into the first mixed solution, and uniformly stirring to obtain a third mixed solution.
Step 6: and filtering the third mixed solution to obtain a precipitate, washing the obtained precipitate with deionized water and absolute ethyl alcohol, and drying the washed precipitate to obtain the prepared cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure.
The method adopts cation exchange reaction to prepare the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure, and has the advantages of simple synthesis process and equipment, simple operation process, low production cost, high efficiency, good repeatability and wide industrial application prospect. The prepared cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure has excellent wide-spectrum (visible and near-infrared) photocatalytic effect in the photocatalytic hydrogen production process, and promotes the wide-spectrum (visible and near-infrared) photocatalytic hydrogen production effect.
And 4, the dosage of the cuprous sulfide in the step 4 is 0-138 mg.
Preferably, the amount of cuprous sulfide used in step 4 is 10 mg.
And (5) stirring by adopting magnetic stirring for 5-30 minutes.
Preferably, the washed precipitate is dried in step 6 at 60 ℃ for 12 hours.
The invention discloses an application of the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure and a preparation method thereof in the field of photocatalysis, in particular to application in photocatalytic decomposition of water; because the composite catalytic agent provided by the invention has a noble metal-free promoter, the composite catalytic agent has high-efficiency water photolysis capacity.
The invention is further described below with reference to the accompanying drawings 1 to 2 and examples for the purpose of facilitating understanding by those skilled in the art:
the raw materials used in the following examples 1 to 5 were a mixed solution of hydrochloric acid and hydrazine hydrate, cadmium chloride dihydrate, thiourea, ethylenediamine, absolute ethanol, and deionized water, and the used equipment was a beaker for mixing, a magnetic stirrer, a hydrothermal reaction vessel, a transmission electron mirror, and a gas chromatography photocatalytic activity evaluation system. When preparing the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure, firstly, slowly dropwise adding concentrated hydrochloric acid (the amount concentration of a hydrogen chloride substance is 12 mol/L) into a hydrazine hydrate aqueous solution (the amount concentration of a hydrazine hydrate substance is 16.5 mol/L) under low-temperature stirring until the pH value of the mixed solution is about 7 to obtain a hydrazine hydrate/hydrochloric acid mixed solution. And then immersing the cadmium sulfide nanorod into a hydrazine hydrate/hydrochloric acid mixed solution and uniformly stirring to obtain a first mixed solution. And dissolving cuprous sulfide in a hydrazine hydrate/hydrochloric acid mixed solution, and fully stirring and dissolving to obtain a second mixed solution. And pouring the second mixed solution into the first mixed solution under the stirring state to obtain a third mixed solution. And filtering the third mixed solution to obtain a precipitate, washing the precipitate and drying in vacuum to obtain the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure. And after the prepared cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure is taken out, the heterostructure is observed and analyzed through a transmission electron microscope and a photocatalytic effect testing system.
Example 1
Firstly, dissolving 2.3 g of cadmium chloride and 2.3 g of thiourea in 30 ml of ethylenediamine, uniformly stirring, pouring into a reaction kettle, carrying out hydrothermal reaction for 48 hours at 180 ℃, alternately washing obtained yellow precipitate with absolute ethyl alcohol and deionized water, and drying in the air to obtain the cadmium sulfide nanorod.
Cadmium sulfide nanorods prepared in example 1 above.
Example 2
Firstly, dissolving 2.3 g of cadmium chloride and 2.3 g of thiourea in 30 ml of ethylenediamine, uniformly stirring, pouring into a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 48 hours, washing the obtained yellow precipitate with absolute ethyl alcohol and deionized water, and drying to obtain the cadmium sulfide nanorod. 100 mg of cadmium sulfide nanorods were immersed in 10 ml of a hydrazine hydrate/hydrochloric acid mixed solution (pH ≈ 7) and uniformly stirred to obtain a first mixed solution. Then, 10 mg of cuprous sulfide was dissolved in 10 ml of a hydrazine hydrate/hydrochloric acid mixed solution, and dissolved by stirring sufficiently to obtain a second mixed solution. The second mixed solution was poured into the first mixed solution under stirring to obtain a third mixed solution, and the third mixed solution was stirred for 10 minutes. And then filtering the third mixed solution to obtain a precipitate, washing the obtained precipitate with deionized water, then carrying out vacuum drying on the washed precipitate for 12 hours at the temperature of 60 ℃, and finally taking out the prepared cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure.
The cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure prepared in example 2 above. Compared with the cadmium sulfide nanorod with a single structure, the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure has higher hydrogen production efficiency under illumination, and the utilization rate of sunlight is effectively improved by utilizing near infrared light response caused by the local plasma resonance effect of the cuprous sulfide nanoshell.
Example 3
Firstly, dissolving 2.3 g of cadmium chloride and 2.3 g of thiourea in 30 ml of ethylenediamine, uniformly stirring, pouring into a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 48 hours, washing the obtained yellow precipitate with absolute ethyl alcohol and deionized water, and drying to obtain the cadmium sulfide nanorod. 100 mg of cadmium sulfide nanorods were immersed in 10 ml of a hydrazine hydrate/hydrochloric acid mixed solution (pH ≈ 7) and uniformly stirred to obtain a first mixed solution. Then, 15 mg of cuprous sulfide was dissolved in 10 ml of a hydrazine hydrate/hydrochloric acid mixed solution to be sufficiently stirred and dissolved to obtain a second mixed solution. The second mixed solution was poured into the first mixed solution under stirring to obtain a third mixed solution, and the third mixed solution was stirred for 10 minutes. And then filtering the third mixed solution to obtain a precipitate, washing the obtained precipitate with deionized water, then carrying out vacuum drying on the washed precipitate for 12 hours at the temperature of 60 ℃, and finally taking out the prepared cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure.
The cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure prepared in example 3 above.
Example 4
Firstly, dissolving 2.3 g of cadmium chloride and 2.3 g of thiourea in 30 ml of ethylenediamine, uniformly stirring, pouring into a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 48 hours, washing the obtained yellow precipitate with absolute ethyl alcohol and deionized water, and drying to obtain the cadmium sulfide nanorod. 100 mg of cadmium sulfide nanorods were immersed in 10 ml of a hydrazine hydrate/hydrochloric acid mixed solution (pH ≈ 7) and uniformly stirred to obtain a first mixed solution. Then, 20 mg of cuprous sulfide was dissolved in 10 ml of a hydrazine hydrate/hydrochloric acid mixed solution to be sufficiently stirred and dissolved to obtain a second mixed solution. The second mixed solution was poured into the first mixed solution under stirring to obtain a third mixed solution, and the third mixed solution was stirred for 10 minutes. And then filtering the third mixed solution to obtain a precipitate, washing the obtained precipitate with deionized water, then carrying out vacuum drying on the washed precipitate for 12 hours at the temperature of 60 ℃, and finally taking out the prepared cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure.
The cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure prepared in example 4 above.
Example 5
Firstly, dissolving 2.3 g of cadmium chloride and 2.3 g of thiourea in 30 ml of ethylenediamine, uniformly stirring, pouring into a reaction kettle, carrying out hydrothermal reaction at 180 ℃ for 48 hours, washing the obtained yellow precipitate with absolute ethyl alcohol and deionized water, and drying to obtain the cadmium sulfide nanorod. 100 mg of cadmium sulfide nanorods were immersed in 10 ml of a hydrazine hydrate/hydrochloric acid mixed solution (pH ≈ 7) and uniformly stirred to obtain a first mixed solution. Then 138 mg of cuprous sulfide was dissolved in 10 ml of hydrazine hydrate/hydrochloric acid mixed solution to be sufficiently stirred and dissolved to obtain a second mixed solution. The second mixed solution was poured into the first mixed solution under stirring to obtain a third mixed solution, and the third mixed solution was stirred for 10 minutes. And then filtering the third mixed solution to obtain a precipitate, washing the obtained precipitate with deionized water, then carrying out vacuum drying on the washed precipitate for 12 hours at the temperature of 60 ℃, and finally taking out the prepared cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure.
The cuprous sulfide nanorod nanostructures prepared in example 5 above.
Examples of the experiments
The obtained cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst sample is observed by a transmission electron microscope, and the result is shown in fig. 1, wherein a cuprous sulfide nanoshell layer grows in situ on the cadmium sulfide nanorod.
The cadmium sulfide nanorod, the cuprous sulfide nanorod, and the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure prepared in the above example 2 were subjected to photocatalytic decomposition hydrogen production experiments under illumination and magnetic stirring conditions. The cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure obtained through the cation exchange reaction, the cuprous sulfide nanorod and the cadmium sulfide nanorod obtained without further treatment after the hydrothermal reaction are subjected to a photocatalytic decomposition water hydrogen production experiment, and the change of the hydrogen production amount along with time is shown in figure 2.
From FIG. 2, it can be seen that the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure (example 2) has the best hydrogen production performance compared to the cadmium sulfide nanorod and cuprous sulfide nanorod with a single structure, the hydrogen production in 8 hours is 640.95 micromoles per gram per hour, which is 8 times that of the pure cadmium sulfide nanorod, and the catalytic ability of the pure cadmium sulfide nanorod (74 micromoles per gram per hour) is always maintained at a very weak level. A hydrogen production amount of the cuprous sulfide is found to be 0 through a cuprous sulfide nanorod photocatalytic hydrogen production experiment.
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.
Claims (10)
1. A preparation method of a cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst is characterized in that a cuprous sulfide nanoshell layer is coated on a cadmium sulfide nanorod to obtain the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst.
2. The method for preparing the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst of claim 1, wherein the coating employs a cation exchange reaction.
3. The preparation method of the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst of claim 1, wherein the coating comprises the specific steps of:
immersing cadmium sulfide nanorods into a hydrazine hydrate/hydrochloric acid mixed solution, and uniformly mixing to obtain a first mixed solution;
dissolving cuprous sulfide in a hydrazine hydrate/hydrochloric acid mixed solution to obtain a second mixed solution;
and adding the second mixed solution into the first mixed solution, uniformly mixing to obtain a third mixed solution, carrying out solid-liquid separation, collecting the precipitate, washing and drying to obtain the catalyst.
4. The preparation method of the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst according to claim 1, wherein the mass ratio of cadmium sulfide to cuprous sulfide is 100: 0-138, the amount of cuprous sulfide is not zero, and preferably the mass ratio of cadmium sulfide to cuprous sulfide is 10: 1.
5. The method for preparing the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst of claim 1, wherein the cadmium sulfide nanorod is prepared by a hydrothermal method.
6. The preparation method of the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst of claim 5, wherein the specific conditions of the hydrothermal reaction are as follows: and (3) reacting the cadmium chloride and the thiourea in an ethylenediamine solution at 180-190 ℃ for 48-56 hours.
7. A cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst, comprising:
cadmium sulfide nanorods;
and the cuprous sulfide nanoshells are coated on the outer sides of the cadmium sulfide nanorods.
8. The cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst of claim 7, wherein the ratio of cadmium sulfide to cuprous sulfide is 17: 200 of a carrier;
or the diameter size of the cadmium sulfide nanorod is 48-52 nm.
9. The use of the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst of claim 7 or 8, in a broad spectrum photocatalytic application, wherein the broad spectrum comprises: visible spectrum and near infrared spectrum.
10. The use of the cadmium sulfide nanorod/cuprous sulfide nanoshell heterostructure photocatalyst of claim 7 or 8 in photocatalytic hydrogen production.
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