CN116809107A - ZnWO (zinc-oxygen) device 4 /g-C 3 N 4 Heterostructure nanofiber catalyst and preparation method and application thereof - Google Patents
ZnWO (zinc-oxygen) device 4 /g-C 3 N 4 Heterostructure nanofiber catalyst and preparation method and application thereof Download PDFInfo
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- 239000003054 catalyst Substances 0.000 title claims abstract description 44
- 239000002121 nanofiber Substances 0.000 title claims abstract description 19
- 238000002360 preparation method Methods 0.000 title claims abstract description 14
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 title claims abstract description 8
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 23
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims abstract description 19
- 239000011941 photocatalyst Substances 0.000 claims abstract description 16
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 15
- 238000001354 calcination Methods 0.000 claims abstract description 14
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims abstract description 13
- 239000001257 hydrogen Substances 0.000 claims abstract description 13
- 229910052739 hydrogen Inorganic materials 0.000 claims abstract description 13
- 230000001699 photocatalysis Effects 0.000 claims abstract description 13
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910052757 nitrogen Inorganic materials 0.000 claims abstract description 10
- 239000002243 precursor Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 8
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 8
- 239000010937 tungsten Substances 0.000 claims abstract description 8
- 238000001035 drying Methods 0.000 claims abstract description 7
- 238000000227 grinding Methods 0.000 claims abstract description 7
- 238000002156 mixing Methods 0.000 claims abstract description 7
- FEWJPZIEWOKRBE-UHFFFAOYSA-N Tartaric acid Natural products [H+].[H+].[O-]C(=O)C(O)C(O)C([O-])=O FEWJPZIEWOKRBE-UHFFFAOYSA-N 0.000 claims abstract description 6
- 235000002906 tartaric acid Nutrition 0.000 claims abstract description 6
- 239000011975 tartaric acid Substances 0.000 claims abstract description 6
- ZOIORXHNWRGPMV-UHFFFAOYSA-N acetic acid;zinc Chemical compound [Zn].CC(O)=O.CC(O)=O ZOIORXHNWRGPMV-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000004246 zinc acetate Substances 0.000 claims abstract description 4
- 239000000956 alloy Substances 0.000 claims abstract description 3
- 229910045601 alloy Inorganic materials 0.000 claims abstract description 3
- 239000000243 solution Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 8
- 229910021641 deionized water Inorganic materials 0.000 claims description 8
- XKRFYHLGVUSROY-UHFFFAOYSA-N Argon Chemical compound [Ar] XKRFYHLGVUSROY-UHFFFAOYSA-N 0.000 claims description 6
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Chemical compound NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 5
- 229920000877 Melamine resin Polymers 0.000 claims description 4
- JDSHMPZPIAZGSV-UHFFFAOYSA-N melamine Chemical compound NC1=NC(N)=NC(N)=N1 JDSHMPZPIAZGSV-UHFFFAOYSA-N 0.000 claims description 4
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 4
- GSEJCLTVZPLZKY-UHFFFAOYSA-N Triethanolamine Chemical compound OCCN(CCO)CCO GSEJCLTVZPLZKY-UHFFFAOYSA-N 0.000 claims description 3
- 239000002253 acid Substances 0.000 claims description 3
- 229910052786 argon Inorganic materials 0.000 claims description 3
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical compound CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 claims description 2
- 239000004202 carbamide Substances 0.000 claims description 2
- QGBSISYHAICWAH-UHFFFAOYSA-N dicyandiamide Chemical compound NC(N)=NC#N QGBSISYHAICWAH-UHFFFAOYSA-N 0.000 claims description 2
- 229910052751 metal Inorganic materials 0.000 claims description 2
- 239000002184 metal Substances 0.000 claims description 2
- 229910052573 porcelain Inorganic materials 0.000 claims description 2
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 claims description 2
- XZMCDFZZKTWFGF-UHFFFAOYSA-N Cyanamide Chemical compound NC#N XZMCDFZZKTWFGF-UHFFFAOYSA-N 0.000 claims 1
- 230000009286 beneficial effect Effects 0.000 abstract description 3
- 238000006243 chemical reaction Methods 0.000 abstract description 2
- 239000007864 aqueous solution Substances 0.000 abstract 1
- 230000031700 light absorption Effects 0.000 abstract 1
- 230000009257 reactivity Effects 0.000 abstract 1
- 238000010438 heat treatment Methods 0.000 description 8
- 239000007789 gas Substances 0.000 description 7
- 239000000843 powder Substances 0.000 description 7
- 229910052782 aluminium Inorganic materials 0.000 description 5
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 description 5
- 239000011888 foil Substances 0.000 description 5
- 238000001816 cooling Methods 0.000 description 4
- 238000005516 engineering process Methods 0.000 description 4
- 238000004519 manufacturing process Methods 0.000 description 4
- 238000007789 sealing Methods 0.000 description 4
- MKYBYDHXWVHEJW-UHFFFAOYSA-N N-[1-oxo-1-(2,4,6,7-tetrahydrotriazolo[4,5-c]pyridin-5-yl)propan-2-yl]-2-[[3-(trifluoromethoxy)phenyl]methylamino]pyrimidine-5-carboxamide Chemical compound O=C(C(C)NC(=O)C=1C=NC(=NC=1)NCC1=CC(=CC=C1)OC(F)(F)F)N1CC2=C(CC1)NN=N2 MKYBYDHXWVHEJW-UHFFFAOYSA-N 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000000047 product Substances 0.000 description 3
- 230000001007 puffing effect Effects 0.000 description 3
- QGZKDVFQNNGYKY-UHFFFAOYSA-N Ammonia Chemical compound N QGZKDVFQNNGYKY-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 2
- 239000000969 carrier Substances 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002485 combustion reaction Methods 0.000 description 2
- 239000002131 composite material Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 238000005286 illumination Methods 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 238000007146 photocatalysis Methods 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 230000007480 spreading Effects 0.000 description 2
- 238000003892 spreading Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- 239000011701 zinc Substances 0.000 description 2
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- FEWJPZIEWOKRBE-JCYAYHJZSA-N Dextrotartaric acid Chemical compound OC(=O)[C@H](O)[C@@H](O)C(O)=O FEWJPZIEWOKRBE-JCYAYHJZSA-N 0.000 description 1
- 229910021529 ammonia Inorganic materials 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 238000004364 calculation method Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- ZIPLUEXSCPLCEI-UHFFFAOYSA-N cyanamide group Chemical group C(#N)[NH-] ZIPLUEXSCPLCEI-UHFFFAOYSA-N 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 239000007857 degradation product Substances 0.000 description 1
- 238000010494 dissociation reaction Methods 0.000 description 1
- 230000005593 dissociations Effects 0.000 description 1
- 239000003792 electrolyte Substances 0.000 description 1
- 238000005265 energy consumption Methods 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000002803 fossil fuel Substances 0.000 description 1
- 229910002804 graphite Inorganic materials 0.000 description 1
- 239000010439 graphite Substances 0.000 description 1
- 239000005431 greenhouse gas Substances 0.000 description 1
- 238000011031 large-scale manufacturing process Methods 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 239000000463 material Substances 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- QJGQUHMNIGDVPM-UHFFFAOYSA-N nitrogen group Chemical group [N] QJGQUHMNIGDVPM-UHFFFAOYSA-N 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000033116 oxidation-reduction process Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- -1 peroxy ions Chemical class 0.000 description 1
- 238000004451 qualitative analysis Methods 0.000 description 1
- 238000004445 quantitative analysis Methods 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 150000003657 tungsten Chemical class 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 150000003751 zinc Chemical class 0.000 description 1
- DJWUNCQRNNEAKC-UHFFFAOYSA-L zinc acetate Chemical compound [Zn+2].CC([O-])=O.CC([O-])=O DJWUNCQRNNEAKC-UHFFFAOYSA-L 0.000 description 1
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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
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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
- B01J23/002—Mixed oxides other than spinels, e.g. perovskite
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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
- B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
- B01J23/24—Chromium, molybdenum or tungsten
- B01J23/30—Tungsten
-
- 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
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/082—Decomposition and pyrolysis
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- 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
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- 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
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- General Health & Medical Sciences (AREA)
- Combustion & Propulsion (AREA)
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Abstract
The invention belongs to the technical field of photocatalytic water splitting, and in particular relates to a ZnWO 4 /g‑C 3 N 4 Heterostructure nanofiber catalyst and preparation method and application thereof. The preparation method comprises the following steps: dissolving a tungsten source in a hydrogen peroxide solution; preparing zinc acetate aqueous solution, adding tartaric acid, stirring, and then dripping into hydrogen peroxide solution of tungsten source; drying and calcining to obtain ZnWO 4 A photocatalyst; znWO (zinc-oxygen) alloy 4 Mixing and grinding the photocatalyst and the nitrogen-rich precursor, and calcining to obtain ZnWO 4 /g‑C 3 N 4 Heterostructure photocatalysts. The invention adopts ZnWO 4 /g‑C 3 N 4 Heterogeneous materialThe structure is used as a hydrogen evolution photocatalyst to construct a Z-type photocatalytic water splitting reaction system. ZnWO in the invention 4 With g-C 3 N 4 The proportion is adjustable, which is beneficial to the regulation of the reactivity; znWO (zinc-oxygen) preparation method 4 /g‑C 3 N 4 The heterostructure nanofiber catalyst has good light absorption characteristics, and the utilization rate of sunlight is greatly improved.
Description
Technical Field
The invention belongs to the technical field of photocatalytic water splitting, and in particular relates to a ZnWO 4 /g-C 3 N 4 Heterostructure nanofiber catalyst and preparation method and application thereof.
Background
Climate change is one of the most urgent worldwide problems, with fossil fuel combustion being the main source of emissions, accounting for 80% of 2018 global greenhouse gas emissions. Some solar hydrogen production processes, such as photoelectrochemical water splitting, often require corrosive electrolytes, limiting their performance stability and environmental sustainability. Clean energy hydrogen can also be converted directly from solar and chemical energy by photocatalytic water splitting. H 2 Has the characteristics of clean combustion, high energy density and the like, plays a key role in achieving the global climate change mitigation goal. The photocatalysis technology utilizes the light energy in the nature to directly generate hydrogen and oxygen by water molecules. The photocatalysis technology is considered to be the novel technology with the development prospect most because of the characteristics of environmental protection, low energy consumption, no secondary pollution of degradation products and the like, and the solar energy has the advantages of zero cost, richness and inexhaustible, thus being an energy source capable of meeting the long-term demands of people. The photocatalytic water splitting hydrogen production technology provides a very promising method for solving the problems of energy shortage and environmental pollution.
Zinc tungstate (ZnWO) 4 ) Because of its high carrier density, it is a promising material for optical applications. When zinc tungstate powder is prepared, ammonium tungstate is dissolved in hydrogen peroxide solution to provide peroxy ions, and exciton dissociation is induced to generate holes due to the existence of peroxy ionsThe generation of photo-generated carriers is promoted, and the recombination of hole electrons is suppressed, so that the photocatalytic performance and the solar energy utilization efficiency can be improved.
Disclosure of Invention
The purpose of the invention is that: the Z-type photocatalytic water splitting reaction system is developed, and the aim of preparing hydrogen by splitting water under illumination can be fulfilled.
In order to achieve the above object, the present invention provides a ZnWO 4 /g-C 3 N 4 The preparation method of the heterostructure nanofiber catalyst comprises the following steps:
step 1): dissolving a tungsten source in a hydrogen peroxide solution to obtain a uniform and transparent solution;
step 2): zinc acetate is dissolved in deionized water, tartaric acid is added, and the solution is added into the mixed solution in the step 1 after stirring until the solution is dissolved.
Step 3): drying the obtained solution in a baking oven, and calcining to obtain ZnWO 4 A photocatalyst;
step 4): znWO (zinc-oxygen) alloy 4 Mixing the photocatalyst and the nitrogen-rich precursor, fully grinding, and placing into a closed porcelain boat for calcining to obtain a target product ZnWO 4 /g-C 3 N 4 Heterostructure photocatalysts.
A ZnWO as described above 4 /g-C 3 N 4 The mass concentration of hydrogen peroxide in the heterostructure nanofiber catalyst in step 1) is 30%.
A ZnWO as described above 4 /g-C 3 N 4 In the step 1), the tungsten source is one of tungsten hexachloride, ammonium tungstate hydrate, sodium tungstate dihydrate or tungsten metal.
A ZnWO as described above 4 /g-C 3 N 4 In the step 3), the calcination is carried out by heating to 400 ℃ at 2 ℃/min, heating to 600 ℃ at 1 ℃/min, and maintaining at 600 ℃ for 4 hours.
A ZnWO as described above 4 /g-C 3 N 4 Heterostructure nanofiber catalyst, in step 4), the nitrogen-rich precursor is cyanamide, dicyandiamide, melamine,Urea, thiourea, and the like.
A ZnWO as described above 4 /g-C 3 N 4 Heterostructure nanofiber catalyst, step 4), the calcination is performed by heating to 550 ℃ at a rate of 5 ℃/min, and maintaining at 550 ℃ for 2 hours,
a ZnWO as described above 4 /g-C 3 N 4 Application of heterostructure nanofiber catalyst in photocatalytic water splitting.
Under the conditions of normal temperature and normal pressure, the application of the method comprises the steps of ZnWO 4 /g-C 3 N 4 The heterostructure nanofiber catalyst is placed into a mixed solution of deionized water, triethanolamine and chloroplatinic acid, argon is introduced, and water is decomposed to generate hydrogen under irradiation of visible light.
Compared with the prior art, the invention has the following beneficial technical effects:
(1) The invention relates to a ZnWO 4 /g-C 3 N 4 The preparation method of the heterostructure photocatalyst comprises the steps of dissolving zinc salt in deionized water, adding tartaric acid, and stirring for 30 min; dissolving tungsten salt in hydrogen peroxide solution, stirring for 30min, mixing the obtained two solutions, stirring uniformly, placing in a baking oven, drying and puffing the sample, grinding, placing in a muffle furnace for calcination, washing, and drying to obtain ZnWO 4 And (3) powder. Then the obtained ZnWO 4 After the powder and the nitrogen-rich precursor are fully ground, the powder and the nitrogen-rich precursor are uniformly distributed at the bottom of the square boat, the square boat is sealed by two layers of aluminum foil paper, the powder and the nitrogen-rich precursor are transferred to a muffle furnace for calcination, the temperature is firstly increased to 400 ℃ at 2 ℃/min, then is increased to 600 ℃ at 1 ℃/min, and the temperature is kept at 600 ℃ for 2 hours, wherein the atmosphere in the sealed square boat is reducing gases such as nitrogen, ammonia and the like generated by the heated decomposition of the nitrogen-rich precursor. The whole preparation process of the invention has simple operation, strong controllability and good repeatability, and is suitable for large-scale production.
(2) ZnWO obtained according to the above-described process 4 /g-C 3 N 4 The heterostructure can absorb ultraviolet light-visible light, and is beneficial to improving the utilization rate of solar energy.
(3) ZnWO obtained according to the above-described process 4 /g-C 3 N 4 Heterostructure photogeneration carrierThe photon is Z-type transfer mechanism, realizing the high-efficiency separation of photon-generated carriers, and compared with the traditional II-type heterostructure, the photon-generated electron has stronger photocatalytic reduction capability, and the hydrogen production efficiency of the water can reach 460.11 mu mol/h.
Drawings
FIG. 1 shows ZnWO prepared in example 1 4 Catalyst, g-C prepared in example 2 3 N 4 Catalyst and ZnWO prepared in example 3 4 /g-C 3 N 4 XRD pattern of heterostructure photocatalyst.
FIG. 2 shows ZnWO prepared in example 1 4 Catalyst, g-C prepared in example 2 3 N 4 Catalyst and ZnWO prepared in example 3 4 /g-C 3 N 4 Comparison of photocatalytic hydrogen evolution activity of heterostructure catalysts.
Detailed Description
Example 1
ZnWO 4 The preparation method of the catalyst comprises the following steps: 2.55g of ammonium tungstate hydrate is dissolved in 20mL of 30% hydrogen peroxide solution, stirred until the ammonium tungstate hydrate is completely dissolved, 2.1g of zinc acetate salt is dissolved in 10mL of deionized water, 4.5g of tartaric acid is added, and the mixture is stirred for 30 min. Mixing the obtained two solutions, stirring uniformly, placing in an oven at 80 ℃, drying and puffing the sample, grinding, uniformly spreading on the bottom of a square boat, sealing the square boat with two layers of aluminum foil paper, transferring into a muffle furnace for calcination, heating to 400 ℃ at 2 ℃/min, heating to 600 ℃ at 1 ℃/min, maintaining at 600 ℃ for 4 hours, and naturally cooling to obtain ZnWO 4 A powder catalyst.
Example 2
g-C 3 N 4 The preparation method of the catalyst comprises the following steps: uniformly distributing 2.0g melamine at the bottom of a square boat, sealing the square boat with aluminum foil for two layers, transferring into a muffle furnace, heating to 550 ℃ at a speed of 5 ℃/min, maintaining at 550 ℃ for 2h, and naturally cooling to obtain g-C 3 N 4 A powder catalyst.
Example 3
ZnWO 4 /g-C 3 N 4 The preparation method of the heterostructure catalyst comprises the following steps:
firstly, 2.55g of ammonium tungstate hydrate is dissolved in 20mL of 30% hydrogen peroxide solution, stirred until the ammonium tungstate hydrate is completely dissolved, 2.1g of zinc acetate is dissolved in 10mL of deionized water, 4.5g of tartaric acid is added, and the solution is stirred for 30 min. Mixing the obtained two solutions, stirring uniformly, placing in an oven at 80 ℃, drying and puffing the sample, grinding, uniformly spreading on the bottom of a square boat, sealing the square boat with two layers of aluminum foil paper, transferring into a muffle furnace for calcination, heating to 400 ℃ at 2 ℃/min, heating to 600 ℃ at 1 ℃/min, maintaining at 600 ℃ for 4 hours, and naturally cooling to obtain the product ZnWO 4 A photocatalyst. The ZnWO to be obtained thereafter 4 Mixing photocatalyst and 2.0g melamine, grinding and uniformly distributing at the bottom of a square boat, sealing the square boat with aluminum foil to form two layers, transferring into a muffle furnace, calcining at a speed of 5 ℃/min, maintaining at 550 ℃ for 2h, and naturally cooling to obtain ZnWO 4 /g-C 3 N 4 Heterostructure catalysts.
FIG. 1 shows ZnWO prepared in example 1 4 Catalyst, g-C prepared in example 2 3 N 4 Catalyst and ZnWO prepared in example 3 4 /g-C 3 N 4 XRD pattern of heterostructure catalyst. As can be seen from FIG. 1, g-C 3 N 4 With two characteristic peaks at 13.2℃and 27.4℃respectively, corresponding to the graphite phase g-C 3 N 4 (XRD Standard card JCPDS No. 85-1726). ZnWO (zinc-oxygen) preparation method 4 The characteristic peak appearing on the single inclined phase ZnWO 4 (XRD Standard card JCPDS 73-0554). Composite sample ZnWO 4 /g-C 3 N 4 ZnWO can be observed in heterostructured catalysts 4 And g-C 3 N 4 Characteristic peaks of (2) indicating ZnWO 4 /g-C 3 N 4 Heterostructure catalysts were successfully prepared.
Example 4
ZnWO 4 /g-C 3 N 4 Application of heterostructure photocatalyst in decomposing water and separating hydrogen under irradiation of visible light
1) Under the condition of normal temperature and normal pressure, the 20mgZnWO is added with the mixture 4 /g-C 3 N 4 The catalyst was placed in a mixed solution of 18mL deionized water, 2mL triethanolamine and 20 μl chloroplatinic acid, and placed in a reactor;argon was introduced into the vessel at a rate of 50mL/min for 30min to remove air; under the irradiation of visible light, 1000 mu L of gas in the reactor is extracted every 30min, and the collected catalytic products are subjected to qualitative and quantitative analysis by a gas chromatograph.
2) According to step 1), except that ZnWO prepared in example 3 is used 4 /g-C 3 N 4 Heterostructure photocatalysts are replaced by ZnWO prepared in example 1 respectively 4 Catalyst and g-C prepared in example 2 3 N 4 The catalyst and other conditions are unchanged, and the hydrogen production efficiency is measured by taking the gas of the catalyst respectively.
FIG. 2 is a graph showing the relationship between the hydrogen content and the illumination time, wherein the peak area of the extracted gas was measured by a gas chromatograph, and then the gas was converted into the amount of the substance by calculation, as shown in FIG. 2, after 120min, znWO 4 H of the catalyst 2 Yield was 283.59. Mu. Mol/h, g-C 3 N 4 H of the catalyst 2 The yield is 215.09 mu mol/h, and the activity is low; composite sample ZnWO 4 /g-C 3 N 4 H of heterostructure catalyst 2 The yield is 460.11 mu mol/h, compared with ZnWO 4 Catalyst and g-C 3 The N catalyst is improved, which shows that the Z-type heterostructure has stronger oxidation-reduction capability.
Claims (8)
1. ZnWO (zinc-oxygen) device 4 /g-C 3 N 4 The preparation method of the heterostructure nanofiber catalyst is characterized by comprising the following steps of:
step 1): dissolving a tungsten source in a hydrogen peroxide solution to obtain a uniform and transparent solution;
step 2): dissolving zinc acetate in deionized water, adding tartaric acid, stirring until the solution is dissolved, and dripping the solution into the mixed solution in the step 1;
step 3): drying the obtained solution in a baking oven, and calcining to obtain ZnWO 4 A photocatalyst;
step 4): znWO (zinc-oxygen) alloy 4 Mixing the photocatalyst and the nitrogen-rich precursor, fully grinding, and placing into a closed porcelain boat for calcining to obtain a target product ZnWO 4 /g-C 3 N 4 Heterostructure photocatalyst。
2. A ZnWO according to claim 1 4 /g-C 3 N 4 The heterostructure nanofiber catalyst is characterized in that in the step 1), the mass concentration of hydrogen peroxide is 30%.
3. A ZnWO according to claim 1 4 /g-C 3 N 4 The heterostructure nanofiber catalyst is characterized in that in the step 1), the tungsten source is one of tungsten hexachloride, ammonium tungstate hydrate, sodium tungstate dihydrate or tungsten metal.
4. A ZnWO according to claim 1 4 /g-C 3 N 4 The heterostructure nanofiber catalyst is characterized in that in the step 3), the temperature is increased to 400 ℃ at 2 ℃/min, then the temperature is increased to 600 ℃ at 1 ℃/min, and the temperature is kept at 600 ℃ for 4 hours.
5. A ZnWO according to claim 1 4 /g-C 3 N 4 The heterostructure nanofiber catalyst is characterized in that in the step 4), the nitrogen-rich precursor is any one or more of cyanamide, dicyandiamide, melamine, urea, thiourea and the like.
6. A ZnWO according to claim 1 4 /g-C 3 N 4 Heterostructure nanofiber catalyst characterized in that in step 4) the calcination is carried out with a temperature rise to 550 ℃ at a rate of 5 ℃/min and a hold at 550 ℃ for 2h.
7. A ZnWO according to any one of claims 1-6 4 /g-C 3 N 4 Application of heterostructure nanofiber catalyst in photocatalytic water splitting.
8. The method according to claim 7, wherein ZnWO is added under normal temperature and pressure conditions 4 /g-C 3 N 4 The heterostructure nanofiber catalyst is placed into a mixed solution of deionized water, triethanolamine and chloroplatinic acid, argon is introduced, and water is decomposed to generate hydrogen under irradiation of visible light.
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Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549406A (en) * | 2014-12-19 | 2015-04-29 | 华南理工大学 | Composite visible light catalyst of g-C3N4/bismuth-based oxide and preparation method and application of composite visible light catalyst |
| CN106492786A (en) * | 2016-09-19 | 2017-03-15 | 江苏大学 | One kind prepares MnWO4/g‑C3N4The method of heterojunction composite photocatalyst |
| CN111659441A (en) * | 2020-06-12 | 2020-09-15 | 绍兴市鸣威新材料科技有限公司 | g-C3N4-Bi2WO6 heterojunction photocatalytic hydrogen production material and preparation method thereof |
| CN113952976A (en) * | 2021-11-09 | 2022-01-21 | 卢俊彩 | Z-type photocatalyst g-C3N4/RGO/ZnWO4Preparation method and application thereof |
| CN115957744A (en) * | 2023-01-29 | 2023-04-14 | 辽宁大学 | ZnWO 4 Preparation method and application of photocatalyst |
| CN116020514A (en) * | 2023-01-04 | 2023-04-28 | 辽宁大学 | W (W) 18 O 49 /C/g-C 3 N 4 Heterojunction nanofiber photocatalyst and preparation method and application thereof |
-
2023
- 2023-06-27 CN CN202310771357.9A patent/CN116809107A/en active Pending
Patent Citations (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN104549406A (en) * | 2014-12-19 | 2015-04-29 | 华南理工大学 | Composite visible light catalyst of g-C3N4/bismuth-based oxide and preparation method and application of composite visible light catalyst |
| CN106492786A (en) * | 2016-09-19 | 2017-03-15 | 江苏大学 | One kind prepares MnWO4/g‑C3N4The method of heterojunction composite photocatalyst |
| CN111659441A (en) * | 2020-06-12 | 2020-09-15 | 绍兴市鸣威新材料科技有限公司 | g-C3N4-Bi2WO6 heterojunction photocatalytic hydrogen production material and preparation method thereof |
| CN113952976A (en) * | 2021-11-09 | 2022-01-21 | 卢俊彩 | Z-type photocatalyst g-C3N4/RGO/ZnWO4Preparation method and application thereof |
| CN116020514A (en) * | 2023-01-04 | 2023-04-28 | 辽宁大学 | W (W) 18 O 49 /C/g-C 3 N 4 Heterojunction nanofiber photocatalyst and preparation method and application thereof |
| CN115957744A (en) * | 2023-01-29 | 2023-04-14 | 辽宁大学 | ZnWO 4 Preparation method and application of photocatalyst |
Non-Patent Citations (3)
| Title |
|---|
| LI ZHEN ET AL.: ""g-C3N4/ZnWO4 nanocomposites as efficient and stable S-scheme photocatalysts for hydrogen evolution"", 《MATERIALS SCIENCE IN SEMICONDUCTOR PROCESSING》, vol. 160, 16 March 2023 (2023-03-16), pages 1 - 7 * |
| MENGRU XUE ET AL.: ""A novel pathway toward efficient and stable C3N4-based photocatalyst for light driven H2 evolution:The synergistic effect between Pt and CoWO4"", 《INTERNATIONAL JOURNAL OF HYDROGEN ENERGY》, vol. 44, 4 October 2019 (2019-10-04), pages 28114 * |
| YAJUN WANG ET AL.: ""Graphite-like C3N4 hybridized ZnWO4 nanorods: Synthesis and its enhanced photocatalysis in visible light"", 《CRYSTENGCOMM》, vol. 14, 8 May 2012 (2012-05-08), pages 5065 - 5070 * |
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