CN112756000B - Method for preparing sulfide semiconductor/metal nano particles by sulfur vacancy defects and application thereof - Google Patents
Method for preparing sulfide semiconductor/metal nano particles by sulfur vacancy defects and application thereof Download PDFInfo
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- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 39
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 title claims abstract description 34
- 230000007547 defect Effects 0.000 title claims abstract description 34
- 229910052717 sulfur Inorganic materials 0.000 title claims abstract description 34
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- 238000001782 photodegradation Methods 0.000 claims abstract description 4
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 45
- 239000000243 solution Substances 0.000 claims description 36
- 239000011943 nanocatalyst Substances 0.000 claims description 23
- 238000003756 stirring Methods 0.000 claims description 20
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 19
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- 239000002244 precipitate Substances 0.000 claims description 15
- 229910021617 Indium monochloride Inorganic materials 0.000 claims description 14
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- 238000004729 solvothermal method Methods 0.000 claims description 6
- 238000001291 vacuum drying Methods 0.000 claims description 6
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- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 3
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- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 1
- 239000005977 Ethylene Substances 0.000 description 1
- 229910003771 Gold(I) chloride Inorganic materials 0.000 description 1
- 239000007864 aqueous solution Substances 0.000 description 1
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- FDWREHZXQUYJFJ-UHFFFAOYSA-M gold monochloride Chemical compound [Cl-].[Au+] FDWREHZXQUYJFJ-UHFFFAOYSA-M 0.000 description 1
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- 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
-
- 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
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/52—Gold
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- B01J35/00—Catalysts, in general, characterised by their form or physical properties
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- B01J35/39—Photocatalytic properties
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- 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
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- C01B3/042—Decomposition of water
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Abstract
The invention discloses a method for preparing sulfide semiconductor/metal nano particles by sulfur vacancy defects, which comprises the following steps: (1) Preparing a suspension of a sulfide semiconductor having sulfur vacancies; (2) preparing a metal ion precursor solution; (3) Mixing a suspension of a sulfide semiconductor having sulfur vacancy defects with a metal ion precursor solution; the sulfide semiconductor/metal nano particles prepared by the method are used in the fields of photodegradation, photodecomposition of water and photocatalytic reduction of carbon dioxide, and the photodecomposition of water is preferentially selected; the method can directly reduce the metal ion precursor solution by utilizing the reduction characteristic of defects existing in sulfide, and directly grow metal nano particles on the surface of the semiconductor defect, thereby not only playing a role in passivating the surface defects of the semiconductor, but also enabling the metal nano particles deposited on the surface of the semiconductor to have closer interface contact with the semiconductor.
Description
Technical Field
The invention belongs to the field of photocatalysis, and particularly relates to a method for preparing sulfide semiconductor/metal nano particles by using sulfur vacancy defects and application thereof.
Background
With the rapid development of economy, energy crisis and environmental pollution have become two major social problems facing people. TiO was discovered by Japanese scientists Fujishima and Honda since 1972 2 Since the electrode can decompose water to produce hydrogen under the irradiation of ultraviolet light, the semiconductor photocatalysis technology attracts more and more attention of scientific researchers, has potential application prospect in the fields of environment, energy and the like, and has become the research of countries around the worldThe research hot spot has great research significance.
At present, for a single semiconductor photocatalyst, the recombination of photo-generated electrons and holes is serious, so that the photocatalyst has lower catalytic efficiency, and how to improve the separation efficiency of the photo-generated electrons and the holes in the semiconductor is a key for improving the catalytic efficiency. Deposition of metal nanoparticles on semiconductor surfaces is a very effective method to increase the separation efficiency of photogenerated electrons and holes. Ternary sulfide semiconductor ZnIn 2 S 4 The semiconductor material is a direct band gap semiconductor material, and has a forbidden band width eg=2.06-2.85 eV (-570 nm) and good visible light response. And has low toxicity, environment friendliness and rich crystal structure. Under light irradiation, sulfide semiconductors generate photo-generated electrons and holes. Subsequently, the photo-generated electrons are transferred to the metal nanoparticles, so that the recombination efficiency of the photo-generated electrons and holes is reduced, and the photo-catalytic efficiency is greatly improved. In semiconductor ZnIn 2 S 4 The deposition of metal nanoparticles on a surface is generally carried out in two ways, namely, the preparation of metal nanoparticles by a chemical reduction method in the presence of an organic stabilizer; secondly, metal nano particles are prepared by a photo-deposition method, but the two methods generally need to add an organic stabilizer or introduce strong illumination and a sacrificial agent, the operation process is complicated, and a certain damage effect can be generated on the semiconductor, so that the photo-catalytic performance of the semiconductor is influenced.
Disclosure of Invention
To solve semiconductor ZnIn 2 S 4 The invention uses the principle that the defects rich in the surface of the sulfide semiconductor can directly reduce metal ions, and directly grows the metal nano particles on the surface of the sulfide semiconductor.
The object of the invention is achieved in the following way:
a method for preparing sulfide semiconductor/metal nanoparticles from sulfur vacancy defects, comprising the steps of:
(1) Preparing a suspension of a sulfide semiconductor having sulfur vacancies;
(2) Preparing a metal ion precursor solution;
(3) A suspension of a sulfide semiconductor having sulfur vacancy defects is mixed with a metal ion precursor solution.
Further, the mixing of the suspension of the sulfide semiconductor having sulfur vacancy defects with the metal ion precursor solution refers to adding the metal ion precursor solution to the suspension of the sulfide semiconductor having sulfur vacancy defects and stirring.
Further, the sulfide semiconductor with sulfur vacancy defect is ZnIn 2 S 4 And In 2 S 3 One of which is preferentially selected to be ZnIn 2 S 4 。
Further, the sulfide semiconductor ZnIn with sulfur vacancy defects 2 S 4 Is prepared by the following method: by ZnCl 2 Is zinc source and InCl 3 ZnIn is prepared by a solvothermal method by taking an indium source, thioacetamide as a sulfur source and a mixed solution of ethylene glycol and water as a reaction medium 2 S 4 Nano catalyst: znCl 2 ∙4H 2 O, InCl 3 ∙4H 2 O and TAA are dissolved in a mixed solution of ethylene glycol and water, the ZnCl 2 ∙4H 2 O,InCl 3 ∙4H 2 The molar ratio of O to TAA is 1:2:4, the volume ratio of ethylene glycol to water=1: 5, continuously stirring for 60 minutes, then transferring the mixture into a reaction kettle, preserving heat at 150 ℃ for 12 h, naturally cooling the reaction kettle to room temperature, centrifugally washing the obtained precipitate, and drying the precipitate in a 65 ℃ vacuum drying oven.
Further, the sulfide semiconductor In having sulfur vacancy 2 S 3 Is prepared by the following method: by InCl 3 In is prepared by a solvothermal method by taking indium source, thioacetamide as sulfur source and a mixed solution of ethylene glycol and water as a reaction medium 2 S 3 Nano catalyst: inCl 3 ∙4H 2 O and TAA are dissolved in ethylene glycolAnd water, the InCl 3 ∙4H 2 The molar ratio of O to TAA is 1:2, the volume ratio of ethylene glycol to water=1: 5, stirring for 60 minutes. Then transferred to a reaction kettle and incubated at 150℃for 12 h. And naturally cooling the reaction kettle to room temperature, centrifugally washing the obtained precipitate, and drying the precipitate in a 65 ℃ vacuum drying oven.
Further, the metal ion precursor solution is HAuCl 4 And AgNO 3 Precursor solution, preferably HAuCl 4 Precursor solution.
Further, the HAuCl 4 The precursor solution contains 400 mu L of 1g/mL of HAuCl 4 A solution.
Further, the stirring is preferably 2-8h, preferably 4 h.
Further, the stirring is preferably 4 h for stirring 2-8h in the dark.
The invention also provides application of the sulfide semiconductor/metal nano particle prepared by the sulfur vacancy defect: the sulfide semiconductor/metal nano particles prepared by the method are used in the fields of photodegradation, photodecomposition of water and photocatalytic reduction of carbon dioxide, and the photodecomposition of water is preferentially selected.
In ZnIn 2 S 4 And In 2 S 3 Defects are inevitably generated in the synthesis process of the sulfide nano material, and the semiconductor with the defects has certain reducing capability. The method not only plays a role in passivating the surface defects of the semiconductor, but also can enable the metal nano particles deposited on the surface of the semiconductor to have closer interface contact with the semiconductor. However, to date, znIn is prepared with the aid of this defect 2 S 4 The method of metal nanoparticles has not been reported so far. The metal nano particles are in closer interface contact with the semiconductor, so that the transfer of photo-generated electrons between the metal nano particles and the semiconductor is greatly improved. ZnIn compared with pure semiconductor photocatalytic system 2 S 4 Metal/metalThe catalytic efficiency of the nanoparticle composite system is remarkably improved. The method is simple to operate, does not need external energy input, and can prepare the composite catalyst only by stirring.
Drawings
FIGS. 1 (a) and 1 (b) show ZnIn prepared 2 S 4 FIG. 1 (c) is a scanning electron microscope image of a nanocatalyst, in which ZnIn is prepared in example 1 2 S 4 Element surface scanning of Au composite catalyst;
FIG. 2 shows the ZnIn preparation 2 S 4 TEM and HRTEM images of nanocatalysts;
FIG. 3 shows the ZnIn preparation 2 S 4 TEM and HRTEM images of Au composite catalyst;
FIG. 4 shows the ZnIn preparation 2 S 4 And ZnIn 2 S 4 A graph showing the change of the hydrogen content of the photocatalytic reduction product of the Au composite catalyst over time;
FIG. 5 shows the ZnIn preparation 2 S 4 TEM and HRTEM pictures of Au composite catalyst;
FIG. 6 (a) shows the In prepared 2 S 3 Scanning electron microscope image of the nanocatalyst, FIG. 6 (b) is an In prepared 2 S 3 Scanning electron microscope image of Ag composite catalyst; 6 (c) is In 2 S 3 Scanning electron microscopy of Au complex catalyst.
Detailed Description
For better illustrating the present invention, the technical scheme of the present invention is convenient to understand, and the present invention is further described in detail below.
The sulfide semiconductor ZnIn with sulfur vacancy defect 2 S 4 Is prepared by the following method: by ZnCl 2 Is zinc source and InCl 3 ZnIn is prepared by a solvothermal method by taking an indium source, thioacetamide (TAA) as a sulfur source and a mixed solution of ethylene glycol and water as a reaction medium 2 S 4 Nano catalyst: znCl 2 ∙4H 2 O, InCl 3 ∙4H 2 O and TAA are dissolved in a mixed solution of ethylene glycol and water, the ZnCl 2 ∙4H 2 O,InCl 3 ∙4H 2 The molar ratio of O to TAA is 1:2:4, stirring for 60 minutes. Then transferred to a reaction kettle and incubated at 150℃for 12 h. And naturally cooling the reaction kettle to room temperature, centrifugally washing the obtained precipitate, and drying the precipitate in a 65 ℃ vacuum drying oven.
ZnIn prepared 2 S 4 Scanning electron microscope images of the nanocatalyst are shown in fig. 1 (a) and 1 (b), and it can be seen that the ZnIn is prepared 2 S 4 The shape of the nano catalyst is microsphere composed of nano sheets.
FIG. 2 shows ZnIn prepared in example 1 2 S 4 TEM and HRTEM pictures of the nanocatalysts, from which microsphere morphology consisting of nanoplatelets can also be seen.
40 mg of ZnIn 2 S 4 Dispersing the nano catalyst in 50 mL water, and performing ultrasonic treatment for 15 minutes to obtain ZnIn 2 S 4 And (3) suspending liquid.
1g of AuCl 3 Dissolving in 100 mL HCl aqueous solution to obtain HAuCl 4 Solution, then 400. Mu.L of HAuCl is taken 4 The solution was diluted to 50 mL with water to prepare an Au metal ion precursor solution.
To ZnIn 2 S 4 Adding a solution of a metal ion precursor into the suspension liquid system, and stirring in the dark to prepare ZnIn 2 S 4 Metal nanoparticle composite nanocatalyst: 50 mL of metal ion precursor solution, wherein the metal ion precursor contains 400 mu L1 g/mL of HAuCl 4 Slowly adding the solution into the ZnIn dropwise 2 S 4 In the suspension, stirring is continued for 2 to 8h, preferably 4 to h. The resulting precipitate was washed by centrifugation and dried in a 65 ℃ vacuum oven.
ZnIn prepared 2 S 4 The elemental surface scan of the Au composite catalyst is shown in the attached figure 1 (c). From the figure it can be seen that the presence of the elemental Au signal indicates that the Au nanoparticles have been successfully deposited in ZnIn 2 S 4 And (3) upper part.
FIG. 3 shows the ZnIn preparation 2 S 4 TEM and HRTEM pictures of Au composite catalyst, from whichThe generation of Au nanoparticles can be clearly seen, and ZnIn is seen from HRTEM images 2 S 4 Has better interface contact with Au.
The application of sulfide semiconductor/metal nano-particles prepared by the sulfur vacancy defect comprises the following steps: the method is used in the fields of photodegradation, photodecomposition of water and photocatalytic reduction of carbon dioxide, and the photodecomposition of water is preferentially selected.
The experimental process and the result of the photolysis of water are as follows: preparing 100 mL solution of 90 mL water and 10 mL triethanolamine, and weighing 40 mg ZnIn prepared above 2 S 4 Nanocatalyst and ZnIn 2 S 4 And (3) putting the metal nanoparticle composite nano catalyst into the water and the triethanolamine, and uniformly dispersing the catalyst in the solution by ultrasonic treatment for half an hour. First, ar was introduced into the reaction system under a dark condition for about half an hour to exclude air from the system. The reduction products were then checked by gas chromatography at intervals of 1. 1 h under xenon lamp irradiation, and the results of the photolytic water test are shown in fig. 4. It can be seen from this that by ZnIn 2 S 4 Construction of Au composite catalytic system, effective separation of photo-generated electrons and holes and separation of ZnIn 2 S 4 Compared with the prior art, the photocatalysis efficiency is remarkably improved.
The preparation method of the silver metal ion precursor solution comprises the following steps: first, 0.0849 g AgNO 3 Dissolving in 250 mL water to prepare 2mmol/L AgNO 3 The solution was then diluted to 50. 50 mL with water to 2.5. 2.5 mL to give an Ag metal ion precursor solution.
To ZnIn 2 S 4 Adding silver metal ion precursor solution into the suspension liquid system, and stirring in the dark to prepare ZnIn 2 S 4 Metal nanoparticle composite nanocatalyst: 50 mL of silver metal ion precursor solution containing 2.5 mL of 2mmol/L AgNO 3 Slowly adding the solution into the ZnIn dropwise 2 S 4 The suspension is stirred for 2-8 hours, preferably 4 h. The resulting precipitate was washed by centrifugation and dried in a 65 ℃ vacuum oven.
FIG. 5 shows the ZnIn preparation 2 S 4 TEM and HRTEM pictures of the Ag composite catalyst, from which the generation of Ag nanoparticles can be clearly seen, and ZnIn can be seen from the HRTEM pictures 2 S 4 Has better interface contact with Ag.
The sulfide semiconductor In having sulfur vacancy defect 2 S 3 Is prepared by the following method: by InCl 3 In is prepared by a solvothermal method by taking an indium source, thioacetamide TAA as a sulfur source and a mixed solution of ethylene glycol and water as a reaction medium 2 S 3 Nano catalyst: inCl 3 ∙4H 2 O and TAA are dissolved in a mixed solution of ethylene glycol and water in a volume ratio=1: 5, stirring for 60 minutes. Then transferred to a reaction kettle and incubated at 150℃for 12 h. And naturally cooling the reaction kettle to room temperature, centrifugally washing the obtained precipitate, and drying the precipitate in a 65 ℃ vacuum drying oven.
In prepared 2 S 3 The scanning electron microscope of the nanocatalyst is shown In FIG. 6 (a), and it can be seen that In was prepared 2 S 3 The shape of the nano catalyst is microsphere composed of nano sheets.
40 mg In 2 S 3 Dispersing the nano catalyst In 50 mL water, and performing ultrasonic treatment for 15 minutes to obtain In 2 S 3 And (3) suspending liquid.
To In 2 S 3 Adding silver metal ion precursor solution into the suspension system, stirring In the dark to obtain In 2 S 3 Metal nanoparticle composite nanocatalyst: 50 mL of silver metal ion precursor solution, the silver metal ion precursor contains 2.5 mL 2mmol/L AgNO 3 The solution was slowly added dropwise to the above In 2 S 3 In the suspension, stirring is continued for 2 to 8h, preferably 4 to h. The resulting precipitate was washed by centrifugation and dried in a 65 ℃ vacuum oven.
In prepared 2 S 3 The scanning electron microscope image of the Ag composite catalyst is shown In FIG. 6 (b), from which it is apparent that the Ag nanoparticles are In 2 S 3 And (3) generating on the semiconductor.
To In 2 S 3 Adding a solution of a metal ion precursor into the suspension liquid system, and stirring In the dark to prepare In 2 S 3 Metal nanoparticle composite nanocatalyst: 50 mL of metal ion precursor solution containing 400 [ mu ] L of 1g/mL of HAuCl 4 Slowly adding In dropwise 2 S 3 In the suspension, stirring is continued for 2 to 8h, preferably 4 to h. The resulting precipitate was washed by centrifugation and dried in a 65 ℃ vacuum oven.
In prepared 2 S 3 A scanning electron microscope image of the Au composite catalyst is shown In FIG. 6 (c), from which it is evident that the Au nanoparticles are In 2 S 3 And (3) generating on the semiconductor.
The foregoing is merely a preferred embodiment of the present invention, and it should be noted that it will be apparent to those skilled in the art that several changes and modifications can be made without departing from the general inventive concept, and these should also be regarded as the scope of the invention.
Claims (3)
1. A method for preparing sulfide semiconductor/metal nano-particles by using sulfur vacancy defects, which is characterized by comprising the following steps: the method comprises the following steps:
(1) Preparing a suspension of a sulfide semiconductor nanocatalyst having a sulfur vacancy defect;
(2) Preparing a metal ion precursor solution;
(3) Mixing a suspension of a sulfide semiconductor having sulfur vacancy defects with a metal ion precursor solution;
directly growing metal nano particles on the surface of the sulfide semiconductor by utilizing the principle that the defects rich in the surface of the sulfide semiconductor can directly reduce metal ions, wherein a reducing agent is not added in the method;
mixing the suspension liquid of the sulfide semiconductor with the sulfur vacancy defects with a metal ion precursor solution, namely adding the metal ion precursor solution into the suspension liquid of the sulfide semiconductor with the sulfur vacancy defects, and stirring; stirring in the dark for 2-8 h;
the sulfide semiconductor with sulfur vacancy defect is ZnIn 2 S 4 And In 2 S 3 One of them;
the metal ion precursor solution is HAuCl 4 Or AgNO 3 A precursor solution;
the sulfide semiconductor ZnIn with sulfur vacancy defect 2 S 4 Is prepared by the following method: by ZnCl 2 Is zinc source and InCl 3 ZnIn is prepared by a solvothermal method by taking an indium source, thioacetamide as a sulfur source and a mixed solution of ethylene glycol and water as a reaction medium 2 S 4 Nano catalyst: znCl 2 ∙4H 2 O、InCl 3 ∙4H 2 O and thioacetamide are dissolved in a mixed solution of ethylene glycol and water, the ZnCl 2 ∙4H 2 O、InCl 3 ∙4H 2 The molar ratio of O to thioacetamide is 1:2:4, the volume ratio of ethylene glycol to water=1: 5, continuously stirring for 60 minutes, then transferring to a reaction kettle, preserving heat at 150 ℃ for 12 h, naturally cooling the reaction kettle to room temperature, centrifugally washing the obtained precipitate, and drying in a 65 ℃ vacuum drying oven;
the sulfide semiconductor In having sulfur vacancy defect 2 S 3 Is prepared by the following method: by InCl 3 In is prepared by a solvothermal method by taking indium source, thioacetamide as sulfur source and a mixed solution of ethylene glycol and water as a reaction medium 2 S 3 Nano catalyst: inCl 3 ∙4H 2 O and thioacetamide are dissolved in a mixed solution of ethylene glycol and water, said InCl 3 ∙4H 2 The molar ratio of O to thioacetamide is 1:2, the volume ratio of ethylene glycol to water=1: 5, continuously stirring for 60 minutes, then transferring the mixture into a reaction kettle, preserving heat at 150 ℃ for 12 h, naturally cooling the reaction kettle to room temperature, centrifugally washing the obtained precipitate, and drying the precipitate in a 65 ℃ vacuum drying oven.
2. The method for preparing sulfide semiconductor/metal nanoparticles with sulfur vacancy defects as set forth in claim 1, wherein: by a means ofThe HAuCl 4 The precursor solution is 400 mu L1 g/mL HAuCl 4 A solution.
3. An application of sulfide semiconductor/metal nano particles prepared by sulfur vacancy defects is characterized in that: sulfide semiconductor/metal nanoparticles prepared by the method according to any one of claims 1 to 2 are used in the fields of photodegradation, photolysis of water, and photocatalytic reduction of carbon dioxide.
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