CN115501897B - Nanocomposite, preparation method and application thereof in hydrogen production by visible light catalysis - Google Patents
Nanocomposite, preparation method and application thereof in hydrogen production by visible light catalysis Download PDFInfo
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- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 title claims abstract description 39
- 229910052739 hydrogen Inorganic materials 0.000 title claims abstract description 39
- 239000001257 hydrogen Substances 0.000 title claims abstract description 39
- 239000002114 nanocomposite Substances 0.000 title claims abstract description 32
- 238000004519 manufacturing process Methods 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 claims abstract description 6
- HZAXFHJVJLSVMW-UHFFFAOYSA-N 2-Aminoethan-1-ol Chemical compound NCCO HZAXFHJVJLSVMW-UHFFFAOYSA-N 0.000 claims abstract description 38
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 29
- 238000000034 method Methods 0.000 claims abstract description 21
- 239000006185 dispersion Substances 0.000 claims abstract description 18
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 230000002950 deficient Effects 0.000 claims abstract description 13
- 238000005341 cation exchange Methods 0.000 claims abstract description 9
- 239000000463 material Substances 0.000 claims abstract description 9
- 238000004729 solvothermal method Methods 0.000 claims abstract description 9
- 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
- 150000003751 zinc Chemical class 0.000 claims abstract description 6
- 239000012467 final product Substances 0.000 claims abstract description 5
- 238000002156 mixing Methods 0.000 claims abstract description 5
- 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
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000000243 solution Substances 0.000 claims description 8
- 238000003756 stirring Methods 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 6
- 230000008569 process Effects 0.000 claims description 6
- 238000006243 chemical reaction Methods 0.000 claims description 5
- 238000009210 therapy by ultrasound Methods 0.000 claims description 4
- 230000003197 catalytic effect Effects 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
- 239000010949 copper Substances 0.000 claims 1
- 238000005286 illumination Methods 0.000 claims 1
- 230000035484 reaction time Effects 0.000 claims 1
- 239000011701 zinc Substances 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 17
- 238000007146 photocatalysis Methods 0.000 abstract description 7
- 238000000354 decomposition reaction Methods 0.000 abstract description 5
- 230000031700 light absorption Effects 0.000 abstract description 2
- 230000004298 light response Effects 0.000 abstract description 2
- 229910052984 zinc sulfide Inorganic materials 0.000 description 69
- 230000007547 defect Effects 0.000 description 9
- 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
- 229910052950 sphalerite Inorganic materials 0.000 description 6
- 238000001354 calcination Methods 0.000 description 4
- 229920000877 Melamine resin Polymers 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000010586 diagram 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
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 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
- -1 ethanolamine form ammonium salt Chemical class 0.000 description 2
- 230000006872 improvement Effects 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
- 239000000047 product Substances 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 239000007787 solid 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
- 238000003917 TEM image Methods 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
- 150000001412 amines Chemical class 0.000 description 1
- 125000003118 aryl group Chemical group 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 229910052799 carbon Inorganic materials 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 238000003421 catalytic decomposition reaction Methods 0.000 description 1
- 238000005119 centrifugation Methods 0.000 description 1
- 238000005354 coacervation Methods 0.000 description 1
- 230000001112 coagulating effect 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
- 230000002349 favourable effect Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 238000010438 heat treatment Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001678 irradiating effect Effects 0.000 description 1
- 238000011068 loading method Methods 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 239000000203 mixture Substances 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
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 1
- 239000004810 polytetrafluoroethylene Substances 0.000 description 1
- 239000003755 preservative agent Substances 0.000 description 1
- 230000002335 preservative effect Effects 0.000 description 1
- 230000004043 responsiveness Effects 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000000126 substance Substances 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
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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
- 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 advanced materialsThe technical field of materials and new energy, relates to a method for producing hydrogen by photocatalysis, in particular to a nanocomposite, a preparation method and application thereof in producing hydrogen by visible light catalysis. The preparation method comprises the following steps: treating ethanolamine with light, mixing the treated ethanolamine with water to form a mixed solvent, adding zinc salt, thiourea and PVP into the mixed solvent, performing solvothermal reaction to obtain defective ZnS, preparing defective ZnS and copper salt into ZnS/CuS by cation exchange method, and adding ZnS/CuS into g-C 3 N 4 Is subjected to a dispersion treatment in the dispersion of (a) so that ZnS/CuS and g-C 3 N 4 Compounding to obtain the final product. The nanocomposite provided by the invention has stronger light response and larger visible light absorption intensity and range, so that the performance of photocatalytic decomposition of water to produce hydrogen 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 in particular relates to a nanocomposite, a preparation method and application thereof in producing hydrogen by visible light photocatalysis.
Background
The disclosure of this background section is only intended to increase the 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 already known to those of ordinary skill in the art.
ZnS is used as a harmless and nontoxic semiconductor nanomaterial and can be used for producing hydrogen by photocatalysis. However, znS has a wide forbidden bandwidth (3.7 eV) so that it can only use ultraviolet light (< 400 nm) which is only 5% of the solar energy reaching the earth's surface and cannot respond to visible light. Meanwhile, the forbidden bandwidth of ZnS is wider, so that the pure ZnS is unfavorable for photoresponse, and the performance of ZnS in photocatalytic hydrogen production is poor.
Disclosure of Invention
In order to solve the defects in the prior art, the invention aims to provide the nanocomposite, the preparation method and the application thereof in hydrogen production by visible light catalysis, and compared with ZnS, the nanocomposite provided by the invention has stronger light response and larger visible light absorption intensity and range, so that the performance of decomposing water into hydrogen by photocatalysis can be obviously improved.
In order to achieve the above purpose, the technical scheme of the invention is as follows:
in one aspect, a method of preparing a nanocomposite comprises reacting ethanolTreating amine with light, mixing the treated ethanolamine with water to form a mixed solvent, adding zinc salt, thiourea and polyvinylpyrrolidone (PVP) into the mixed solvent, performing solvothermal reaction to obtain defective ZnS, preparing defective ZnS and copper salt into ZnS/CuS by cation exchange method, and adding ZnS/CuS into g-C 3 N 4 Is subjected to a dispersion treatment in the dispersion of (a) so that ZnS/CuS and g-C 3 N 4 Compounding to obtain the final product.
The invention makes the ethanolamine form ammonium salt with positive ion through light treatment, so that the ZnS has unique defect. And then the ZnS/CuS heterojunction is obtained through ion exchange, so that electrons and holes are not easy to combine, the width of a base band is reduced, and the photoresponsivity is facilitated. Then through loading g-C 3 N 4 The forbidden bandwidth is reduced, so that the visible light is better absorbed, and the performance of photocatalytic decomposition of the water to produce hydrogen is obviously improved.
In another aspect, a nanocomposite obtained by the above preparation method.
In a third aspect, the application of the nanocomposite in photocatalytic hydrogen production or in visible light catalytic hydrogen production is provided.
The beneficial effects of the invention are as follows:
1. the invention makes the ZnS prepared generate unique defects by carrying out light treatment on the ethanolamine, thereby increasing the photocatalytic hydrogen production performance of the finally formed nanocomposite.
2. The PVP is added into the solvothermal reaction system, so that the PVP has a coacervation effect, can be adsorbed on the surfaces of the nano particles to form protection, prevents the nano particles from coagulating, and can promote the growth of the nano particles, thereby cooperating with the photo-treated ethanolamine, and generating unique defects in the ZnS.
3. According to the invention, znS and CuS are combined to generate the ZnS/CuS heterojunction by a cation exchange method, so that the increase of light responsiveness is facilitated, and the reservation of unique defects generated by ZnS is ensured, thereby increasing the photocatalytic hydrogen production performance of the finally formed nanocomposite.
4. The invention loads ZnS/CuS with defects into g-C 3 N 4 The Z-shaped photocatalysis mechanism is formed between the two, which is favorable for separating electrons and holes, reduces the forbidden bandwidth of the composite material, can better absorb visible light, and realizes the remarkable improvement of the performance of photocatalytic decomposition of water to produce hydrogen.
Experiments show that ZnS with unique defects prepared by the invention has higher hydrogen production performance of photocatalytic water splitting, the hydrogen production amount is about 2.5 times of that of common ZnS, and ZnS/CuS formed by utilizing the ZnS with the unique defects and the final nanocomposite have higher hydrogen production amount. In addition, research shows that the final nanocomposite prepared by the invention can realize the catalytic decomposition of water to produce hydrogen under the condition of visible light.
Drawings
The accompanying drawings, which are included to provide a further understanding of the invention and are incorporated in and constitute a part of this specification, illustrate embodiments of the invention and together with the description serve to explain 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 nanocomposite material, a being XRD of ZnS, b being XRD of ZnS/CuS, C being 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 nanocomposite, a, b are SEM of ZnS/CuS, C, d are CuS/ZnS/g-C 3 N 4 SEM of (2);
FIG. 3 is a Transmission Electron Microscope (TEM) of ZnS prepared in example 1 of the present invention;
FIG. 4 is a CuS/ZnS/g-C prepared in example 1 of the present invention 3 N 4 XPS diagram of the nanocomposite, a is XPS diagram of C1s, b is XPS diagram of N1 s;
FIG. 5 is a sample of ZnS, znS/CuS and CuS/ZnS/g-C prepared in example 1 of the present invention 3 N 4 Decomposing water by the nanocomposite under ultraviolet-visible light to prepare a hydrogen yield histogram of hydrogen;
FIG. 6 is a graph showing ZnS, znS/CuS and CuS/ZnS/g-C prepared in example 1 of the present invention 3 N 4 The nanocomposite is a hydrogen yield histogram of hydrogen produced by decomposing water under visible light.
Detailed Description
It should be noted that the following detailed description is exemplary and is intended to provide further explanation of the invention. 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 present invention. As used herein, the singular is also intended to include the plural unless the context clearly indicates otherwise, and furthermore, it is to be understood that the terms "comprises" and/or "comprising" when used in this specification are taken to specify the presence of stated features, steps, operations, devices, components, and/or combinations thereof.
In view of the poor performance of ZnS in carrying out photocatalytic hydrogen production at present, the invention provides a nanocomposite, a preparation method and application of the nanocomposite in producing hydrogen by visible light catalysis.
In one exemplary embodiment of the present invention, a method for preparing a nanocomposite is provided, wherein ethanolamine is subjected to light treatment, the light-treated ethanolamine is mixed with water to form a mixed solvent, zinc salt, thiourea and PVP are added into the mixed solvent, then solvothermal reaction is performed to obtain defective ZnS, the defective ZnS and copper salt are prepared into ZnS/CuS by a cation exchange method, and the ZnS/CuS is added into g-C 3 N 4 Is subjected to a dispersion treatment in the dispersion of (a) so that ZnS/CuS and g-C 3 N 4 Compounding to obtain the final product.
The invention adds ethanolamine as emulsifier and promotes ZnS to carry out crystal growth.
The zinc salt refers to a compound of which the cations are zinc ions, such as zinc nitrate, zinc chloride, zinc sulfate and the like.
The copper salt refers to a compound of which the cation is copper ion, such as copper nitrate, copper chloride, copper sulfate and the like.
In some examples of this embodiment, the ethanolamine is light treated as follows: the ethanolamine is placed under light to treat until the solution turns yellow.
In some examples of this embodiment, the ratio of zinc salt, thiourea, PVP and ethanolamine is added in the range of 7 to 8:10:450 to 550:9 to 11, mol:mol:g:L.
In some examples of this embodiment, the volume ratio of ethanolamine to water is from 0.9 to 1.1:3.
In some examples of this embodiment, the volume of water during the solvothermal reaction is 25 to 35% of the reaction vessel volume. The nano composite material prepared by the method has better photocatalysis performance.
In some examples of this embodiment, the solvothermal reaction is carried out at a temperature of 170 to 190 ℃ for a time of 3 to 5 hours.
In some examples of this embodiment, the solvothermal material is washed with distilled water and absolute ethanol and dried.
In some examples of this embodiment, the process of making defective ZnS and copper salts into ZnS/CuS using cation exchange method is: the defective ZnS and copper salt were added to water for continuous mixing and dispersion. More specifically, ultrasonic dispersion is first performed, followed by stirring. The ultrasonic dispersion time is 25-35 min. Stirring time is 5-7 h.
In some examples of this embodiment, g-C 3 N 4 The preparation process of the dispersion liquid of (2) comprises the following steps: will g-C 3 N 4 Adding into a mixed solution of ethanol and water, and performing ultrasonic treatment. The purpose of the ultrasonic treatment is to make g-C in large blocks 3 N 4 Layering and dispersing uniformly to form a fold shape. The ultrasonic treatment time is 25-35 min.
In some examples of this embodiment, znS/CuS was added to g-C 3 N 4 The dispersion treatment process in the dispersion liquid of (2) comprises the following steps: znS/CuS was added to g-C 3 N 4 Continuously stirring the dispersion liquid of (2). 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 of (2) comprises the following steps: calcining melamine to obtain the product. The calcination temperature is 450-550 ℃ and the calcination time is 3-4 h. This condition enables the melamine to be fully 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 (2) is 18-20:1.
In another embodiment of the present invention, there is provided a nanocomposite obtained by the above-described preparation method.
The third embodiment of the invention provides an application of the nanocomposite in photocatalytic hydrogen production or in visible light catalytic hydrogen production.
In some examples of this embodiment, the nanocomposite is added to water for light treatment.
In order to enable those skilled in the art to more clearly understand the technical scheme of the present invention, the technical scheme of the present invention will be described in detail with reference to specific embodiments.
Example 1
(1) Adding melamine into a crucible, covering the crucible with a cover, placing the crucible in a temperature programming muffle furnace, heating to 500 ℃ at a rate of 5 ℃ per minute, keeping for 3 hours for calcination, and obtaining a sample g-C after the muffle furnace is naturally cooled 3 N 4 The sample was taken out, ground into powder in a mortar, and then the powder sample was collected for use. Prepared g-C 3 N 4 As a pale yellow solid, g-C employed in the following step 3 N 4 All are powder.
(2) 100mL of ethanolamine is put into a 250mL beaker, then a preservative film is used for sealing, a small opening is inserted into a needle tube to ensure the air permeability of the beaker, and natural oxidation is carried out in the sun until the solution turns yellow slightly, thus 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 the 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 was added to the above stirred solution and stirring was continued for 30min to mix the solution uniformly. Subsequently, the obtained solution was poured into a 100mL polytetrafluoroethylene reaction kettle, and put into an oven to be thermally reacted at 180℃for 4 hours. After the reaction kettle is naturally cooled, the obtained substance is centrifuged, and is washed with distilled water and absolute ethyl alcohol for 3 times, so as to remove soluble impurities and improve the dispersibility of solids. And putting the obtained sample into an oven for drying at 70 ℃ after centrifugation. 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 the sample has a hexagonal wurtzite structure and no impurity peak is generated. SEM image (fig. 2 a) shows that ZnS is spherical structure and has a size of 200nm, a smooth and flat surface and complete crystal face. The TEM image of fig. 3 shows that the prepared ZnS has a curved interface, i.e., it shows that ZnS prepared by photo-treating ethanolamine has a more unique defect, and the structure is different from that of general zinc sulfide.
(4) 0.4628g of ZnS and 0.0604g of copper nitrate trihydrate were added to a glass beaker with 40mL of deionized water and dispersed ultrasonically in an ultrasonic machine for 30min, followed by stirring for 6h. Subsequently, the resulting solution was centrifuged, and the product was dried in an oven at 70 ℃ for 12 hours after multiple washes with absolute ethanol to obtain CuS/ZnS.
(5) 0.015g of g-C is weighed 3 N 4 Into a beaker containing 20mL of absolute ethanol and 20mL of deionized water, and ultrasonically dispersed in an ultrasonic machine for 30min, then 0.285g of ZnS/CuS was added, and the mixture was stirred on a magnetic stirrer for 6h, and then the resulting solution was centrifugally washed 3 times and dried in an oven at 70℃for 12h. Obtaining a sample CuS/ZnS/g-C 3 N 4 . From the SEM images (FIGS. 2b and 2 d) g-C can be seen 3 N 4 As can be seen from FIG. 2C, g-C is carried in spherical ZnS/CuS 3 N 4 Is attached to the spherical ZnS/CuS in a lump. In FIG. 4a, two integral peaks are observed, containing a C-C single bond and containing SP 2 The presence of C-NH, N- (C) 3 and C-N-C groups can be confirmed by observation in fig. 4b, of a hybridized carbon containing N-c=n of an N aromatic ring.
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 Adding into water, and irradiating with ultravioletThe water decomposition to produce hydrogen is carried out under visible light conditions, the results are shown in figure 5. Under ultraviolet-visible light, the hydrogen yield of defective ZnS is 3128 mu mol/g.h, about 2.5 times that of common ZnS, and the hydrogen yield of CuS/ZnS prepared by cation exchange method is 5221 mu mol/g.h, loaded with g-C 3 N 4 Then the hydrogen yield is further improved 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 Adding the catalyst into water, and carrying out water decomposition to prepare hydrogen under the condition of visible light, wherein the result is shown in fig. 6, and shows that: the hydrogen yield of ZnS is 0, and after cation exchange, the hydrogen yield of CuS/ZnS realizes 0 breakthrough, the yield is 1784 mu mol/g.h, and g-C is loaded 3 N 4 The hydrogen yield was further increased to 2266. Mu. Mol/g.h.
The above description is only of the preferred embodiments of the present invention and is not intended to limit the present invention, but various modifications and variations can be made to the present invention by those skilled in the art. Any modification, equivalent replacement, improvement, etc. made within the spirit and principle of the present invention should be included in the protection scope of the present invention.
Claims (7)
1. A process for preparing the nano-class composite material used for preparing hydrogen by visible light catalysis 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, preparing ZnS/CuS from defective ZnS and Cu salt by cation exchange method, and adding ZnS/CuS to g-C 3 N 4 Is subjected to a dispersion treatment in the dispersion of (a) so that ZnS/CuS and g-C 3 N 4 Compounding to obtain the final product;
wherein, the process of carrying out light treatment on the ethanolamine comprises the following steps: the ethanolamine is placed under illumination for treatment until the solution turns yellow; the addition ratio of zinc salt, thiourea, PVP and ethanolamine is 7-8:10:450-550:9-11, mol is mol g is L; in the solvothermal reaction, the reaction temperature is 170-190 ℃ and the reaction time is 3-5 h.
2. The method of claim 1, wherein the volume of water in the solvothermal reaction process is 25-35% of the volume of the reaction vessel.
3. The method for preparing nanocomposite material according to claim 1, wherein the process of preparing ZnS/CuS from defective ZnS and copper salt by cation exchange method comprises: the defective ZnS and copper salt were added to water for continuous mixing and dispersion.
4. The method of preparing a nanocomposite material according to claim 1, wherein g-C 3 N 4 The preparation process of the dispersion liquid of (2) comprises the following steps: will g-C 3 N 4 Adding into a mixed solution of ethanol and water, and performing ultrasonic treatment.
5. The method of preparing nanocomposite material according to claim 1, wherein ZnS/CuS is added to g-C 3 N 4 The dispersion treatment process in the dispersion liquid of (2) comprises the following steps: znS/CuS was added to g-C 3 N 4 Continuously stirring the dispersion liquid of (2).
6. A nanocomposite material characterized by being obtained by the production method according to any one of claims 1 to 5.
7. Use of the nanocomposite of claim 6 in the visible light catalytic production of hydrogen.
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