CN115501897A - Nano composite material, preparation method and application thereof in hydrogen production by visible light catalysis - Google Patents
Nano composite material, preparation method and application thereof in hydrogen production by visible light catalysis Download PDFInfo
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- CN115501897A CN115501897A CN202211121451.1A CN202211121451A CN115501897A CN 115501897 A CN115501897 A CN 115501897A CN 202211121451 A CN202211121451 A CN 202211121451A CN 115501897 A CN115501897 A CN 115501897A
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- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- 239000001257 hydrogen Substances 0.000 title claims abstract description 39
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 38
- 238000004519 manufacturing process Methods 0.000 title claims abstract description 35
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 34
- 239000000463 material Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 12
- 238000006555 catalytic reaction Methods 0.000 title abstract description 7
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 44
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 28
- 238000000034 method Methods 0.000 claims abstract description 17
- 230000001699 photocatalysis Effects 0.000 claims abstract description 16
- 230000007547 defect Effects 0.000 claims abstract description 15
- 239000006185 dispersion Substances 0.000 claims abstract description 14
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 238000004729 solvothermal method Methods 0.000 claims abstract description 10
- 238000005341 cation exchange Methods 0.000 claims abstract description 8
- 150000001879 copper Chemical class 0.000 claims abstract description 8
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000007788 liquid Substances 0.000 claims abstract description 6
- 238000002156 mixing Methods 0.000 claims abstract description 6
- 150000003751 zinc Chemical class 0.000 claims abstract description 6
- 238000013329 compounding Methods 0.000 claims abstract description 4
- WHNWPMSKXPGLAX-UHFFFAOYSA-N N-Vinyl-2-pyrrolidone Chemical compound C=CN1CCCC1=O WHNWPMSKXPGLAX-UHFFFAOYSA-N 0.000 claims abstract 3
- 239000000243 solution Substances 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 230000002950 deficient Effects 0.000 claims description 7
- 238000006243 chemical reaction Methods 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 4
- 238000009210 therapy by ultrasound Methods 0.000 claims description 3
- 239000002131 composite material Substances 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 150000003839 salts Chemical class 0.000 claims 2
- 125000002091 cationic group Chemical group 0.000 claims 1
- 239000010949 copper Substances 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 238000007146 photocatalysis Methods 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract 1
- 229910052984 zinc sulfide Inorganic materials 0.000 description 71
- 239000001267 polyvinylpyrrolidone Substances 0.000 description 7
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 description 7
- 229920000036 polyvinylpyrrolidone Polymers 0.000 description 7
- 238000002441 X-ray diffraction Methods 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- 238000001354 calcination Methods 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000013507 mapping Methods 0.000 description 3
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 description 3
- 239000002105 nanoparticle Substances 0.000 description 3
- 239000000843 powder Substances 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 238000005406 washing Methods 0.000 description 3
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 150000001768 cations Chemical class 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 239000012153 distilled water Substances 0.000 description 2
- 239000012535 impurity Substances 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 239000007787 solid Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 238000001132 ultrasonic dispersion Methods 0.000 description 2
- JIAARYAFYJHUJI-UHFFFAOYSA-L zinc dichloride Chemical compound [Cl-].[Cl-].[Zn+2] JIAARYAFYJHUJI-UHFFFAOYSA-L 0.000 description 2
- ONDPHDOFVYQSGI-UHFFFAOYSA-N zinc nitrate Chemical compound [Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O ONDPHDOFVYQSGI-UHFFFAOYSA-N 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 1
- 239000004809 Teflon Substances 0.000 description 1
- 229920006362 Teflon® Polymers 0.000 description 1
- PTFCDOFLOPIGGS-UHFFFAOYSA-N Zinc dication Chemical compound [Zn+2] PTFCDOFLOPIGGS-UHFFFAOYSA-N 0.000 description 1
- 239000005083 Zinc sulfide Substances 0.000 description 1
- 150000003863 ammonium salts Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 239000007795 chemical reaction product Substances 0.000 description 1
- 230000001112 coagulating effect Effects 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 229910001431 copper ion Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 230000000694 effects Effects 0.000 description 1
- 239000003995 emulsifying agent Substances 0.000 description 1
- 235000019441 ethanol Nutrition 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000012467 final product Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000004570 mortar (masonry) Substances 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 230000035699 permeability Effects 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 238000011160 research Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 238000000527 sonication Methods 0.000 description 1
- 229910052950 sphalerite Inorganic materials 0.000 description 1
- 235000005074 zinc chloride Nutrition 0.000 description 1
- 239000011592 zinc chloride Substances 0.000 description 1
- NWONKYPBYAMBJT-UHFFFAOYSA-L zinc sulfate Chemical compound [Zn+2].[O-]S([O-])(=O)=O NWONKYPBYAMBJT-UHFFFAOYSA-L 0.000 description 1
- 229910000368 zinc sulfate Inorganic materials 0.000 description 1
- 229960001763 zinc sulfate Drugs 0.000 description 1
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 1
Images
Classifications
-
- 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
- B01J27/24—Nitrogen compounds
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- 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
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B2203/00—Integrated processes for the production of hydrogen or synthesis gas
- C01B2203/10—Catalysts for performing the hydrogen forming reactions
- C01B2203/1041—Composition of the catalyst
- C01B2203/1076—Copper or zinc-based catalysts
-
- 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 technical field of advanced materials and new energy, relates to a method for producing hydrogen by photocatalysis, and particularly relates to a nano composite material, a preparation method and application thereof in visible light catalysis hydrogen production. The preparation method comprises the following steps: performing photo-treatment on ethanolamine, mixing the photo-treated ethanolamine with water to form a mixed solvent, adding zinc salt, thiourea and PVP into the mixed solvent, performing solvothermal reaction to obtain ZnS with defects, preparing ZnS/CuS from the ZnS with defects and copper salt by adopting a cation exchange method, and adding the ZnS/CuS to g-C 3 N 4 Is subjected to dispersion treatment in the dispersion liquid to ensure that ZnS/CuS and g-C are mixed 3 N 4 And (5) compounding to obtain the product. The nano composite material provided by the invention has stronger photoresponse and larger visible light absorption intensity and range, becauseAnd the performance of hydrogen production by photocatalytic water decomposition can be obviously improved.
Description
Technical Field
The invention belongs to the technical field of advanced materials and new energy, relates to a method for producing hydrogen by photocatalysis, and particularly relates to a nano composite material, a preparation method and application thereof in hydrogen production by visible light catalysis.
Background
The information disclosed 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.
ZnS is used as a harmless and nontoxic semiconductor nano material and can be used for photocatalytic hydrogen production. However, the wide band gap of ZnS (3.7 eV) renders it only capable of using ultraviolet light (< 400 nm) which is only 5% of the solar energy reaching the surface of the earth and is not responsive to visible light. Meanwhile, the forbidden bandwidth of ZnS is wide, so that pure ZnS is not beneficial to photoresponse, and the performance of ZnS in photocatalytic hydrogen production is poor.
Disclosure of Invention
In order to solve the defects of the prior art, the invention aims to provide the nano composite material, the preparation method and the application thereof in hydrogen production by visible light catalysis.
In order to realize the purpose, the technical scheme of the invention is as follows:
on one hand, a method for preparing a nanocomposite includes photo-treating ethanolamine, mixing the photo-treated ethanolamine with water to form a mixed solvent, adding zinc salt, thiourea and polyvinylpyrrolidone (PVP) to the mixed solvent, performing a solvothermal reaction to obtain defective ZnS, preparing the defective ZnS and a copper salt into ZnS/CuS by a cation exchange method, adding the ZnS/CuS to g-C 3 N 4 Is subjected to dispersion treatment so that ZnS/CuS and g-C are dispersed in 3 N 4 Compounding to obtain the product.
According to the invention, the ethanolamine is subjected to light treatment, so that ammonium salt with positive ions is formed in the ethanolamine, and the generated ZnS has unique defects. And then the ZnS/CuS heterojunction is obtained through ion exchange, so that electrons and holes are not easy to recombine, the width of a base band is reduced, and the photoresponse is facilitated. Then passing through a load g-C 3 N 4 The forbidden band width is reduced, so that visible light is better absorbed, and the performance of hydrogen production by photocatalytic water decomposition is obviously improved.
In another aspect, a nanocomposite is obtained by the above-described method of preparation.
In a third aspect, the application of the nano composite material in hydrogen production by photocatalysis or hydrogen production by visible light catalysis.
The invention has the beneficial effects that:
1. according to the invention, the ethanolamine is subjected to photo-treatment, so that the prepared ZnS has unique defects, and the photocatalytic hydrogen production performance of the finally formed nano composite material is improved.
2. The PVP is added into the solvothermal reaction system, so that the PVP has a condensation effect, can be adsorbed on the surface of the nano-particles to form protection, prevents the nano-particles from coagulating, and can promote the growth of the nano-particles, so that the prepared ZnS has a unique defect in cooperation with the ethanolamine subjected to the photo-treatment.
3. According to the invention, the ZnS and CuS are combined to generate a ZnS/CuS heterojunction through a cation exchange method, so that the increase of photoresponsiveness can be facilitated, the reservation of unique defects generated by ZnS is ensured, and the photocatalytic hydrogen production performance of the finally formed nano composite material is improved.
4. The invention loads the defective ZnS/CuS with g-C 3 N 4 And a Z-shaped photocatalytic mechanism is formed between the two, so that the separation of electrons and holes is facilitated, the forbidden bandwidth of the composite material is reduced, visible light can be better absorbed, and the performance of photocatalytic water decomposition for hydrogen production is remarkably improved.
Experiments show that the ZnS with the unique defect prepared by the invention has higher hydrogen production performance for photocatalytic water decomposition, the hydrogen production is about 2.5 times of that of the common ZnS, and the ZnS/CuS formed by using the ZnS with the unique defect and the final nano composite material have higher hydrogen production. In addition, researches show that the final nano composite material prepared by the invention can realize hydrogen production by water decomposition under the catalysis of visible light.
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 included to illustrate an exemplary embodiment of the invention and not to limit the invention.
FIG. 1 shows ZnS, znS/CuS and CuS/ZnS/g-C prepared in example 1 of the present invention 3 N 4 X-ray diffraction Pattern (XRD) of the nanocomposite, a is XRD of ZnS, b is XRD of ZnS/CuS, and C is CuS/ZnS/g-C 3 N 4 XRD of the nanocomposite;
FIG. 2 shows ZnS/CuS and CuS/ZnS/g-C prepared in example 1 of the present invention 3 N 4 Scanning Electron Microscope (SEM) of the nano composite material, a and b are SEM of ZnS/CuS, C and d are CuS/ZnS/g-C 3 N 4 SEM of (2);
FIG. 3 is a Transmission Electron Micrograph (TEM) of ZnS prepared in example 1 of the present invention;
FIG. 4 shows CuS/ZnS/g-C prepared in example 1 of the present invention 3 N 4 XPS mapping of the nanocomposite, a is the XPS mapping of C1s, b is the XPS mapping of N1 s;
FIG. 5 shows ZnS, znS/CuS and CuS/ZnS/g-C prepared in example 1 of the present invention 3 N 4 The hydrogen yield histogram of hydrogen prepared by decomposing water by the nano composite material under ultraviolet-visible light;
FIG. 6 shows ZnS, znS/CuS and CuS/ZnS/g-C prepared in example 1 of the present invention 3 N 4 The hydrogen yield histogram of hydrogen produced by decomposing water with the nanocomposite under visible light.
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.
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 exemplary embodiments according to the invention. 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.
In view of the poor performance of ZnS in photocatalytic hydrogen production at present, the invention provides a nano composite material, a preparation method and application thereof in visible light catalytic hydrogen production.
In a typical embodiment of the present invention, there is provided a method for preparing a nanocomposite, comprising the steps of photo-treating ethanolamine, mixing the photo-treated ethanolamine with water to form a mixed solvent, adding zinc salt, thiourea and PVP to the mixed solvent, then performing a solvothermal reaction to obtain ZnS having defects, preparing ZnS/CuS from the ZnS having defects and a copper salt using a cation exchange method, adding ZnS/CuS to g-C 3 N 4 Is subjected to dispersion treatment so that ZnS/CuS and g-C are dispersed in 3 N 4 And (5) compounding to obtain the product.
The ethanolamine is added as an emulsifier and simultaneously promotes the ZnS to carry out crystal growth.
The zinc salt in the invention refers to a compound with zinc ion as cation, such as zinc nitrate, zinc chloride, zinc sulfate and the like.
The copper salt in the present invention refers to a compound in which the cation is copper ion, such as copper nitrate, copper chloride, copper sulfate, etc.
In some examples of this embodiment, the ethanolamine is subjected to a light treatment process comprising: the ethanolamine is left to stand under the light until the solution turns yellow.
In some examples of this embodiment, the zinc salt, thiourea, PVP and ethanolamine are added in a ratio of 7 to 8.
In some examples of this embodiment, the volume ratio of ethanolamine to water is from 0.9 to 1.1.
In some examples of this embodiment, the volume of water during the solvothermal reaction is 25 to 35% of the volume of the reaction vessel. The nano composite material prepared under the condition has better photocatalytic performance.
In some examples of this embodiment, the solvothermal reaction is carried out at a temperature of 170 to 190 ℃ for a period of 3 to 5 hours.
In some examples of this embodiment, the solvothermal reaction product is washed with distilled water and absolute ethanol and dried.
In some examples of this embodiment, the process of making ZnS/CuS from defective ZnS and copper salts using cation exchange method is: adding ZnS with defects and copper salt into water, and continuously mixing and dispersing. More specifically, ultrasonic dispersion is performed first, and then stirring is performed. The time of ultrasonic dispersion is 25-35 min. The stirring time is 5-7 h.
In some examples of this embodiment, g-C 3 N 4 The preparation process of the dispersion liquid comprises the following steps: g to C 3 N 4 Adding into mixed solution of ethanol and water, and performing ultrasonic treatment. The purpose of the sonication was to get large chunks of g-C 3 N 4 The layers are layered and uniformly dispersed, so that the corrugated paper is formed. The ultrasonic treatment time is 25-35 min.
In some examples of this embodiment, znS/CuS is added to g-C 3 N 4 The process of performing dispersion treatment in the dispersion liquid of (1) is as follows: addition of ZnS/CuS to g-C 3 N 4 The dispersion of (3) is continuously stirred. The stirring time is 5-7 h. Can make g-C 3 N 4 Can be dispersed and fully loaded on ZnS/CuS.
In some examples of this embodiment, g-C 3 N 4 The preparation method comprises the following steps: the melamine is obtained by calcining. The calcining temperature is 450-550 ℃, and the calcining time is 3-4 h. This condition enables the melamine to be sufficiently calcined without other functional groups.
In some examples of this embodiment, znS/CuS is combined with g-C 3 N 4 The mass ratio of (A) to (B) is 18 to 20.
In another embodiment of the present invention, there is provided a nanocomposite obtained by the above-mentioned production method.
In a third embodiment of the present invention, an application of the above nanocomposite in photocatalytic hydrogen production or visible light-catalyzed hydrogen production is provided.
In some examples of this embodiment, the nanocomposite is added to water for light treatment.
In order to make the technical solutions of the present invention more clearly understood by those skilled in the art, the technical solutions of the present invention will be described in detail below with reference to specific embodiments.
Example 1
(1) Adding melamine into a crucible, covering the crucible with a cover, putting the crucible in a temperature programming muffle furnace, raising the temperature to 500 ℃ at a rate of 5 ℃ per minute, keeping the temperature for 3 hours for calcination, and obtaining a sample which is g-C after the muffle furnace is naturally cooled 3 N 4 And taking out the sample, putting the sample into a mortar, grinding the sample into powder, and collecting the powder sample for later use. g-C prepared 3 N 4 As a pale yellow solid, g-C used in the following steps 3 N 4 All are powder.
(2) And (3) putting 100mL of ethanolamine into a 250mL beaker, sealing the beaker by using a preservative film, inserting a small opening by using a needle tube to ensure the air permeability of the beaker, and performing natural oxidation in the sun until the solution turns slightly yellow, namely that the light treatment is successful.
(3) 2.23g of zinc nitrate hexahydrate and 0.76g of thiourea were added to 30mL of deionized water and 10mL of ethanolamine obtained in step (2) at room temperature, and stirred with a magnetic stirrer until the zinc nitrate hexahydrate was completely dissolved. Then 0.5g PVP is added to the stirred solution and stirring is continued for 30min to mix the solution evenly. Subsequently, the resulting solution was poured into a 100mL Teflon reaction vessel and placed in an oven for thermal reaction at 180 ℃ for 4 hours. And after the reaction kettle is naturally cooled, centrifuging the obtained substance, and washing the substance for 3 times by using distilled water and absolute ethyl alcohol to remove soluble impurities and improve the solid dispersibility. And (4) placing the sample obtained after centrifugation into an oven to be dried at 70 ℃. And finally collecting the final product. The XRD pattern of the obtained sample is shown in FIG. 1a, and it can be seen from the figure that it is a hexagonal wurtzite structure, and no impurity peak is generated. SEM picture (figure 2 a) shows that ZnS is spherical structure and the size is 200nm, the surface is flat and smooth, and the crystal face is complete. The TEM image of fig. 3 shows that the prepared ZnS has a curved interface, i.e., shows that ZnS prepared by photo-treating ethanolamine has a unique defect, which is different from that of general zinc sulfide.
(4) 0.4628g of ZnS and 0.0604g of copper nitrate trihydrate were added in a glass beaker containing 40mL of deionized water, and ultrasonically dispersed in an ultrasonic machine for 30min, followed by stirring for 6h. Subsequently, the resulting solution was centrifuged, subjected to multiple washings with anhydrous ethanol, and the product was dried in an oven at 70 ℃ for 12 hours to obtain CuS/ZnS.
(5) 0.015g of g-C are weighed 3 N 4 Adding into a beaker containing 20mL of absolute ethyl alcohol and 20mL of deionized water, ultrasonically dispersing in an ultrasonic machine for 30min, then adding 0.285g of ZnS/CuS, placing on a magnetic stirrer for stirring for 6h, then centrifugally washing the obtained solution for 3 times, and drying in an oven at 70 ℃ for 12h. Obtaining a sample CuS/ZnS/g-C 3 N 4 . From the SEM pictures (FIGS. 2b and 2 d) it can be seen that g-C 3 N 4 ZnS/CuS loaded in spheres, g-C as can be seen in FIG. 2C 3 N 4 Attached in bulk on spherical ZnS/CuS. In FIG. 4a, two integral peaks are observed, containing a single C-C bond and containing SP 2 N-C = N of the N-containing aromatic ring of the hybrid carbon, in fig. 4b, the presence of C-NH, N- (C) 3 and C-N-C groups can be confirmed by observation.
The ZnS prepared in step (3), cuS/ZnS prepared in step (4) and CuS/ZnS/g-C prepared in step (5) of this example were mixed 3 N 4 The hydrogen is added into water and decomposed under the condition of ultraviolet-visible light to prepare hydrogen, and the result is shown in figure 5. Under ultraviolet-visible light, the hydrogen production amount of ZnS having defects therein is 3128. Mu. Mol/g.h, which is about 2.5 times that of ordinary ZnS, and CuS/ZnS produced by cation exchange method having a hydrogen production amount of 5221. Mu. Mol/g.h, loaded with g-C 3 N 4 Then, the hydrogen production was further increased to 6206. Mu. Mol/g.h.
ZnS prepared in step (3), cuS/ZnS prepared in step (4) and CuS/ZnS/g-C prepared in step (5) of this example 3 N 4 The hydrogen is produced by adding the water into water and decomposing the water under visible light conditions, and the result is shown in figure 6, which shows that: the hydrogen yield of ZnS is 0, and after cation exchange, the hydrogen yield of CuS/ZnS realizes the breakthrough of 0, the yield is 1784 mu mol/g.h, and g-C is loaded 3 N 4 Then, the hydrogen yield was further increased to 2266. Mu. Mol/g.h.
The above description is only a preferred embodiment of the present invention and is not intended to limit the present invention, and various modifications and changes may be made by those skilled in the art. 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 process for preparing nano-class composite material includes such steps as photo-treating ethanolamine, mixing it with water to obtain mixed solvent, adding Zn salt, thiourea and PVP to the mixed solvent, solvothermal reaction to obtain defective ZnS, cationic exchange to obtain ZnS/CuS from defective ZnS and Cu salt, adding ZnS/CuS to g-C 3 N 4 Is subjected to dispersion treatment in the dispersion liquid to ensure that ZnS/CuS and g-C are mixed 3 N 4 Compounding to obtain the product.
2. The method for preparing a nanocomposite as claimed in claim 1, wherein the step of subjecting the ethanolamine to light treatment comprises: the ethanolamine is left to stand under the light until the solution turns yellow.
3. The preparation method of the nanocomposite material according to claim 1, wherein the addition ratio of the zinc salt, thiourea, PVP and ethanolamine is 7-8.
4. The process for preparing a nanocomposite as claimed in claim 1, wherein the volume of water in the solvothermal reaction is 25 to 35% of the volume of the reaction vessel.
5. The process for preparing a nanocomposite as claimed in claim 1, wherein the reaction temperature in the solvothermal reaction is from 170 to 190 ℃ and the reaction time is from 3 to 5 hours.
6. The method for preparing a nanocomposite as claimed in claim 1, wherein the step of preparing ZnS/CuS from defective ZnS and copper salt using a cation exchange method comprises: adding ZnS and copper salt with defects into water and continuously mixing and dispersing.
7. The process for preparing a nanocomposite as claimed in claim 1, wherein g-C is 3 N 4 The preparation process of the dispersion liquid comprises the following steps: g to C 3 N 4 Adding into mixed solution of ethanol and water, and performing ultrasonic treatment.
8. The method for preparing a nanocomposite as claimed in claim 1, wherein ZnS/CuS is added to g-C 3 N 4 The process of performing dispersion treatment in the dispersion liquid of (1) is as follows: addition of ZnS/CuS to g-C 3 N 4 The dispersion of (2) was continuously stirred.
9. A nanocomposite obtained by the production method according to any one of claims 1 to 8.
10. Use of the nanocomposite material of claim 9 in photocatalytic hydrogen production or in visible light-catalyzed hydrogen production.
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