CN111804295A - Method for preparing oxygen vacancy-containing bismuth tungstate ultrathin slice, oxygen vacancy-containing bismuth tungstate ultrathin slice and application thereof - Google Patents
Method for preparing oxygen vacancy-containing bismuth tungstate ultrathin slice, oxygen vacancy-containing bismuth tungstate ultrathin slice and application thereof Download PDFInfo
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- CN111804295A CN111804295A CN201910292517.5A CN201910292517A CN111804295A CN 111804295 A CN111804295 A CN 111804295A CN 201910292517 A CN201910292517 A CN 201910292517A CN 111804295 A CN111804295 A CN 111804295A
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- 229910052760 oxygen Inorganic materials 0.000 title claims abstract description 47
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 title claims abstract description 47
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 title claims abstract description 44
- 239000001301 oxygen Substances 0.000 title claims abstract description 44
- 229910052797 bismuth Inorganic materials 0.000 title claims abstract description 40
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 title claims abstract description 40
- 238000000034 method Methods 0.000 title claims abstract description 33
- WSFSSNUMVMOOMR-UHFFFAOYSA-N Formaldehyde Chemical compound O=C WSFSSNUMVMOOMR-UHFFFAOYSA-N 0.000 claims abstract description 111
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 claims abstract description 10
- 230000002194 synthesizing effect Effects 0.000 claims abstract description 6
- 239000001569 carbon dioxide Substances 0.000 claims abstract description 5
- 229910002092 carbon dioxide Inorganic materials 0.000 claims abstract description 5
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 3
- 238000006243 chemical reaction Methods 0.000 claims description 23
- 239000003054 catalyst Substances 0.000 claims description 10
- IOLCXVTUBQKXJR-UHFFFAOYSA-M potassium bromide Chemical compound [K+].[Br-] IOLCXVTUBQKXJR-UHFFFAOYSA-M 0.000 claims description 10
- 238000001035 drying Methods 0.000 claims description 9
- 230000001699 photocatalysis Effects 0.000 claims description 7
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims description 6
- 230000000593 degrading effect Effects 0.000 claims description 6
- 238000010438 heat treatment Methods 0.000 claims description 6
- 229910017604 nitric acid Inorganic materials 0.000 claims description 6
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims description 5
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical compound Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 5
- 239000007787 solid Substances 0.000 claims description 5
- 230000008569 process Effects 0.000 claims description 4
- 239000011541 reaction mixture Substances 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- 238000001816 cooling Methods 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 230000035484 reaction time Effects 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 abstract description 2
- 230000015556 catabolic process Effects 0.000 description 14
- 238000006731 degradation reaction Methods 0.000 description 14
- 239000000047 product Substances 0.000 description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 14
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 12
- 230000000052 comparative effect Effects 0.000 description 12
- 239000000463 material Substances 0.000 description 12
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 12
- 239000003153 chemical reaction reagent Substances 0.000 description 10
- 230000005540 biological transmission Effects 0.000 description 9
- 239000003814 drug Substances 0.000 description 8
- 229940079593 drug Drugs 0.000 description 8
- 238000012360 testing method Methods 0.000 description 8
- 230000007547 defect Effects 0.000 description 7
- 239000008367 deionised water Substances 0.000 description 7
- 229910021641 deionized water Inorganic materials 0.000 description 7
- 239000007789 gas Substances 0.000 description 7
- 238000001069 Raman spectroscopy Methods 0.000 description 6
- 230000003197 catalytic effect Effects 0.000 description 6
- 230000003647 oxidation Effects 0.000 description 6
- 238000007254 oxidation reaction Methods 0.000 description 6
- 239000011259 mixed solution Substances 0.000 description 5
- 238000001228 spectrum Methods 0.000 description 5
- 238000004435 EPR spectroscopy Methods 0.000 description 4
- 238000001237 Raman spectrum Methods 0.000 description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 4
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 4
- 239000000243 solution Substances 0.000 description 4
- QWMFKVNJIYNWII-UHFFFAOYSA-N 5-bromo-2-(2,5-dimethylpyrrol-1-yl)pyridine Chemical group CC1=CC=C(C)N1C1=CC=C(Br)C=N1 QWMFKVNJIYNWII-UHFFFAOYSA-N 0.000 description 3
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical group O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 description 3
- 239000006185 dispersion Substances 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 230000007613 environmental effect Effects 0.000 description 3
- 238000001914 filtration Methods 0.000 description 3
- 239000010931 gold Substances 0.000 description 3
- 229910000510 noble metal Inorganic materials 0.000 description 3
- KDLHZDBZIXYQEI-UHFFFAOYSA-N palladium Substances [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 description 3
- 239000010453 quartz Substances 0.000 description 3
- 229910052724 xenon Inorganic materials 0.000 description 3
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 3
- 238000003917 TEM image Methods 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 238000000862 absorption spectrum Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000011161 development Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000011941 photocatalyst Substances 0.000 description 2
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 238000001878 scanning electron micrograph Methods 0.000 description 2
- 238000000926 separation method Methods 0.000 description 2
- 239000012265 solid product Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 2
- ZNOKGRXACCSDPY-UHFFFAOYSA-N tungsten trioxide Chemical compound O=[W](=O)=O ZNOKGRXACCSDPY-UHFFFAOYSA-N 0.000 description 2
- 239000012855 volatile organic compound Substances 0.000 description 2
- 239000000853 adhesive Substances 0.000 description 1
- 230000001070 adhesive effect Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 229910000416 bismuth oxide Inorganic materials 0.000 description 1
- 230000000903 blocking effect Effects 0.000 description 1
- 239000013590 bulk material Substances 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 231100000315 carcinogenic Toxicity 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- CETPSERCERDGAM-UHFFFAOYSA-N ceric oxide Chemical compound O=[Ce]=O CETPSERCERDGAM-UHFFFAOYSA-N 0.000 description 1
- 229910000422 cerium(IV) oxide Inorganic materials 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 230000001351 cycling effect Effects 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 230000002950 deficient Effects 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- TYIXMATWDRGMPF-UHFFFAOYSA-N dibismuth;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[Bi+3].[Bi+3] TYIXMATWDRGMPF-UHFFFAOYSA-N 0.000 description 1
- 238000001362 electron spin resonance spectrum Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 238000003912 environmental pollution Methods 0.000 description 1
- 239000004744 fabric Substances 0.000 description 1
- 239000011094 fiberboard Substances 0.000 description 1
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 230000002779 inactivation Effects 0.000 description 1
- 239000012774 insulation material Substances 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 230000007774 longterm Effects 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000010525 oxidative degradation reaction Methods 0.000 description 1
- 229910052763 palladium Inorganic materials 0.000 description 1
- 238000001782 photodegradation Methods 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 239000011120 plywood Substances 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000002243 precursor Substances 0.000 description 1
- 238000002360 preparation method Methods 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000006479 redox reaction Methods 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 238000006722 reduction reaction Methods 0.000 description 1
- 229910052703 rhodium Inorganic materials 0.000 description 1
- 239000010948 rhodium Substances 0.000 description 1
- MHOVAHRLVXNVSD-UHFFFAOYSA-N rhodium atom Chemical compound [Rh] MHOVAHRLVXNVSD-UHFFFAOYSA-N 0.000 description 1
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 description 1
- 238000003756 stirring Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
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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
- 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
- B01J23/31—Chromium, molybdenum or tungsten combined with bismuth
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D53/00—Separation of gases or vapours; Recovering vapours of volatile solvents from gases; Chemical or biological purification of waste gases, e.g. engine exhaust gases, smoke, fumes, flue gases, aerosols
- B01D53/34—Chemical or biological purification of waste gases
- B01D53/74—General processes for purification of waste gases; Apparatus or devices specially adapted therefor
- B01D53/86—Catalytic processes
- B01D53/8668—Removing organic compounds not provided for in B01D53/8603 - B01D53/8665
-
- 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
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
-
- B01J35/30—
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2255/00—Catalysts
- B01D2255/80—Type of catalytic reaction
- B01D2255/802—Photocatalytic
Abstract
The invention provides a method for preparing an oxygen vacancy-containing bismuth tungstate ultrathin sheet. The method comprises the following steps: step 1) synthesizing oxygen-free vacancy bismuth tungstate (Bi) by hydrothermal method2WO6) And 2) synthesizing the oxygen vacancy-containing bismuth tungstate ultrathin sheet from the oxygen vacancy-free bismuth tungstate ultrathin sheet obtained in the step 1) by a vacuum aluminothermic method. The invention also provides the oxygen vacancy-containing bismuth tungstate ultrathin sheet prepared by the method, and a method for photocatalytic degradation of formaldehyde into carbon dioxide by using the oxygen vacancy-containing bismuth tungstate ultrathin sheet.
Description
Technical Field
The invention relates to the field of catalysts, in particular to a method for preparing an oxygen vacancy-containing bismuth tungstate ultrathin sheet, an oxygen vacancy-containing bismuth tungstate ultrathin sheet prepared by the method, and a method for photocatalytic degradation of formaldehyde into carbon dioxide by using the oxygen vacancy-containing bismuth tungstate ultrathin sheet.
Background
Formaldehyde is an important precursor for the synthesis of many compounds and other materials, and millions of tons of formaldehyde are used annually in the fields of building and interior decoration materials, such as plywood, adhesives, fiber boards, permanent press fabrics, thermal insulation materials and some decorative coatings. Formaldehyde, one of the most common harmful indoor air pollutants among Volatile Organic Compounds (VOCs), has carcinogenic toxicity and volatility, and the main sources are interior decorative materials and a large number of household products. Therefore, the method can effectively eliminate the formaldehyde under the environmental conditions of normal pressure, normal temperature and certain humidity, and becomes a popular research field of environmental pollution treatment.
In recent years, one of the main research centers of researchers has been the thermal oxidative degradation of formaldehyde, a common material such as palladium-supported titanium dioxide (Pd/TiO)2) Gold-supported titanium dioxide (Au/TiO)2) And gold-supported ceria (Au/CeO)2) And the like. However, most of them are noble metal-based catalysts, i.e., supported platinum, gold, palladium and rhodium catalysts. The high price and poor poisoning resistance have both hindered the practical use of noble metal-based catalysts. Moreover, many studies have been conducted to apply the catalyst to a high concentration of formaldehyde gas in a mobile phase to test the catalytic degradation performance, which is contrary to the practical application environment. In general, the formaldehyde concentration in the still air in the house reaches the level of tens of ppm, which is not suitable for human residence.
Therefore, there is a need to develop a non-noble metal catalyst which has the ability of degrading low-concentration formaldehyde, and is low in cost and stable in activity. The photocatalysis is a promising technology in the field of environmental application undoubtedly by virtue of the advantages of no need of an external heating source, cleanness, environmental protection and the like. Under the mild environment of normal temperature and normal pressure, the photocatalyst absorbs photon energy from sunlight to generate photo-generated electrons and holes, and further oxidation-reduction reaction can be driven. However, due to the wide band gap of these photocatalysts, most of them can only absorb and utilize ultraviolet light which is only about 5% of solar energy. This results in a large portion of the light in the solar energy being wasted, for example, less than half of the visible light. In addition, the rapid recombination of the photo-excited electron-hole pairs also greatly inhibits the conversion efficiency of the photocatalytic oxidation of formaldehyde. Therefore, it is very necessary to design a formaldehyde degradation catalyst with a new structure to fully solve the above-mentioned challenges.
In view of this, development of a method for preparing defective bismuth tungstate (Bi)2WO6) The ultrathin sheet method is imperative to be applied to optimizing visible light catalytic degradation of formaldehyde.
Disclosure of Invention
One object of the present invention is: a new method for preparing oxygen vacancy-containing bismuth tungstate ultrathin slices is developed.
The above object of the present invention is achieved by the following means.
The invention provides a method for preparing oxygen vacancy-containing bismuth tungstate ultrathin slices, which comprises the following steps: step 1) synthesizing an oxygen vacancy-free bismuth tungstate ultrathin sheet by a hydrothermal method, and step 2) synthesizing an oxygen vacancy-containing bismuth tungstate ultrathin sheet from the oxygen vacancy-free bismuth tungstate ultrathin sheet obtained in the step 1) by a vacuum aluminothermic method.
In some embodiments, the step 1) comprises:
dissolving tungstate, bismuth nitrate and potassium bromide in a nitric acid solution; heating the obtained solution in a sealed reactor for reaction; after the reaction was complete, the reaction mixture was cooled and the solid was isolated; and washing and drying to obtain the powdery bismuth tungstate ultrathin slice without oxygen vacancies.
In some embodiments, the tungstate salt comprises an alkali tungstate salt, such as sodium tungstate.
In some embodiments, the tungstate salt: the bismuth nitrate: the molar ratio of the potassium bromide is (6-12): (17-28): (1-2).
In some embodiments, the tungstate salt is sodium tungstate dihydrate, and the bismuth nitrate is bismuth nitrate pentahydrate.
In some embodiments, the concentration of the nitric acid solution is 1.0 to 1.2 mass%.
In some embodiments, the reaction is at a reaction temperature of 120 to 130 ℃ and a reaction time of 20 to 26 hours.
In some embodiments, the isolated solid is washed several times with water and ethanol.
In some embodiments, the step 2) comprises:
respectively placing the bismuth tungstate ultrathin sheets without oxygen vacancies obtained in the step 1) and aluminum powder into two chambers of a double-chamber tubular furnace, raising the temperature of the chamber containing the bismuth tungstate ultrathin sheets to 280-320 ℃, raising the temperature of the chamber containing the aluminum powder to 700-750 ℃, and keeping for 2-3 h; and then naturally cooling the obtained product, and washing and drying to obtain the oxygen vacancy-containing bismuth tungstate ultrathin slice.
In some embodiments, the resulting product is washed several times with water and ethanol.
In some embodiments, the oxygen-vacancy containing bismuth tungstate ultrathin flakes are ultrathin flakes having a cell layer thickness of 0.5 to 3, preferably 0.5 to 1.
The invention also provides the oxygen vacancy-containing bismuth tungstate ultrathin slice prepared by the method.
The invention also provides a method for degrading formaldehyde into carbon dioxide by photocatalysis, wherein the oxygen vacancy-containing bismuth tungstate ultrathin slice is used as a catalyst.
In some embodiments, the method of photocatalytically degrading formaldehyde to carbon dioxide comprises degrading 10ppm to 500ppm formaldehyde under visible light conditions.
According to the invention, the prepared material realizes efficient visible light-driven low-concentration formaldehyde degradation performance at normal temperature and normal pressure.
The technical scheme of the invention at least has the following beneficial technical effects:
the preparation method of the invention has simple operation, and can prepare Bi containing a large amount of stable oxygen vacancies without high-strength reduction environment2WO6An ultrathin sheet; the established practical method for the photocatalytic oxidation of formaldehyde has high efficiency and high stability, can realize short-time high-efficiency formaldehyde photodegradation under low concentration, is closer to the practical application condition, and accords with the sustainable development concept.
Without being bound by any theory, it is believed that the two-dimensional material of atomic scale thickness has improved electronic, optical, mechanical properties relative to the corresponding bulk material, and also has some new properties, such as huge surface area and mostly uncoordinated dangling bonds. These characteristics can achieve the effects of enhancing the absorption utilization of light and improving the separation efficiency of carriers. In the present invention, orthorhombic bismuth tungstate will produce many uncoordinated surface atoms when the material is reduced to atomic thickness, which means that more reactants adsorb active sites, which is beneficial to the photocatalytic oxidation of formaldehyde. In addition, the catalyst defects can expand the light absorption of the material, introduce new defect energy levels in the band gap of the material and adjust the electron energy band structure, and even capture photo-generated electrons to improve the separation efficiency of photo-generated electrons and holes.
Drawings
FIG. 1 shows vacancy-free Bi prepared in example 12WO6Ultrathin flakes (a) and vacancy-containing Bi prepared in example 22WO6XRD diffraction pattern of ultrathin sheet (b).
FIG. 2 shows vacancy-free Bi prepared in example 12WO6Ultrathin flakes (a, c) and vacancy-containing Bi prepared in example 22WO6Transmission Electron Micrographs (TEM) and High Resolution Transmission Electron Micrographs (HRTEM) of the ultrathin flakes (b, d), scale 2 nm.
FIG. 3 shows vacancy-free Bi prepared in example 12WO6Ultrathin flakes (a) and vacancy-containing Bi prepared in example 22WO6Electron paramagnetic resonance spectrum of the ultrathin sheet (b).
FIG. 4 shows Bi prepared in comparative example 12WO6XRD diffraction pattern (a) and scanning electron micrograph (b) of the block.
FIG. 5 shows Bi prepared in comparative example 12WO6Bulk (a), vacancy-free Bi prepared in example 12WO6Ultrathin flakes (b) and vacancy-containing Bi prepared in example 22WO6Raman spectrum of the ultrathin sheet (c).
FIG. 6 shows vacancy free Bi prepared in example 12WO6Ultrathin sheets (a) and prepared in example 2Bi containing oxygen vacancies2WO6UV-VIS absorption spectrum of the ultrathin sheet (b).
FIG. 7 shows Bi prepared in comparative example 22WO6The thick plate had (a) XRD diffraction pattern and (b) scanning electron micrograph.
FIG. 8 shows that the materials prepared in examples 1 and 2 and comparative examples 1 and 2 catalyze the degradation of formaldehyde to CO under different test conditions2Rate (formaldehyde concentration 500 ppm).
Fig. 9 shows the catalytic degradation rate of the materials prepared in examples 1 and 2 and comparative example 1 in a low concentration (10ppm) formaldehyde environment.
FIG. 10 shows oxygen vacancy-containing Bi prepared in example 22WO6Test pattern of catalytic cycling stability of ultra-thin sheets in a high concentration (500ppm) formaldehyde environment.
Detailed Description
Example 1
0.165g of sodium tungstate dihydrate (national drug group chemical reagent limited, purity of 99% or more), 0.485g of bismuth nitrate pentahydrate (national drug group chemical reagent limited, purity of 99% or more) and 10mg of potassium bromide (national drug group chemical reagent limited, purity of 99% or more) were dissolved in a mixed solution of 40mL of deionized water and 500 μ L of concentrated nitric acid (national drug group chemical reagent limited, concentration of 67 mass%) in sequence, and after stirring for 30 minutes at 200r/min in an electric jacket stirrer (08-2T, manufactured by Shanghai Meipu instruments and meters), the obtained mixed solution was transferred to a 50mL high-pressure reaction vessel, sealed, and put into an oven (XMTD-8222, manufactured by Shanghai Jing Macro Experimental facilities limited) to react for 24 hours at 120 ℃. After the reaction, the reaction mixture was naturally cooled to room temperature, and then centrifuged in a high-speed centrifuge (HC-3518, a scientific instrument Co., Ltd., Zhongjia, Anhui) at 10000rpm to obtain a solid product, which was washed with deionized water and ethanol several times. Finally, the sheet product was dried in a vacuum oven (60 ℃ C.) to obtain a sheet product, which was stored in a desiccator for later use.
The flake products were measured with XRD instrument (Philips X' Pert Pro Super differential), transmission electron microscope (JEOL JEM-ARM200F), high-resolution transmission electron microscope (JEOL JEM-ARM200F), and electron paramagnetic resonance spectrometer (XRD-XRD)JES-FA200), a Raman spectrometer (RenishawRM3000Micro-Raman system) and an ultraviolet-visible near-infrared spectrophotometer (Shimadzu SOLID3700), and the obtained XRD spectrum, Transmission Electron Microscope (TEM), high-resolution transmission electron microscope (HRTEM) photograph, Electron Paramagnetic Resonance (EPR) spectrum, Raman spectrum and ultraviolet-visible absorption spectrum are respectively shown in FIG. 1(a), FIG. 2(a, c), FIG. 3(a), FIG. 5(b) and FIG. 6(a), thereby confirming that the Bi is Bi containing no oxygen vacancy2WO6Ultra-thin flakes (atomic scale flakes), wherein said Bi free of oxygen vacancies2WO6The thickness of the ultrathin sheet is 0.5 to 1 unit cell layer thickness.
Example 2
200mg of synthesized Bi free of oxygen vacancy2WO6The ultrathin pieces are uniformly paved at the bottom of a quartz boat, the ultrathin pieces are placed at the downstream end (left part) of the air flow of a double-cavity tube furnace (Kejing OTF-1200X-II), another quartz boat is placed at the upstream position (right part) which is about 10 cm away from the downstream end, and 15-20 g of aluminum powder (national drug group chemical reagent limited, the purity is more than or equal to 99%) is contained in the quartz boat. The temperature rise program is set, so that the left part of the double-cavity tube furnace is kept at 300 ℃, the right part of the double-cavity tube furnace is kept at 700 ℃ and kept for 2 hours. A simulated vacuum environment is created by continuous work of connecting a vacuum pump, and a temperature rise program of the tube furnace is started at the same time. After natural cooling, the sample is washed with water and ethanol for several times and dried in vacuum for later use.
The thin sheet product was characterized by using XRD (Philips X' Pert Pro Super differential spectrometer), transmission electron microscope (JEOL JEM-ARM200F), high-resolution transmission electron microscope (JEOL JEM-ARM200F), electron paramagnetic resonance spectrometer (JES-FA200), Raman spectrometer (RenishawRM3000Micro-Raman system), ultraviolet-visible near infrared spectrophotometer (Shimadzu SOLID3700), and the obtained XRD spectrum, Transmission Electron Microscope (TEM), high-resolution transmission electron microscope (HRTEM) photograph, Electron Paramagnetic Resonance (EPR) spectrum, Raman spectrum and ultraviolet-visible absorption spectrum were shown in FIG. 1(b), FIG. 2(b, d), FIG. 3(b), FIG. 5(c), and FIG. 6(b), respectively, whereby it was confirmed that it was a Bi containing oxygen vacancies2WO6Ultra-thin flakes (atomic scale flakes), wherein said Bi containing oxygen vacancies2WO6The thickness of the ultrathin sheet is 0.5 to 1 unit cell layer thickness. And compareIn Bi containing no oxygen vacancy2WO6The absorption of the ultra-thin sheet in the visible light region is significantly enhanced.
Comparative example 1
Uniformly mixing a certain amount of bismuth oxide (the purity is more than or equal to 99 percent by the national pharmaceutical group chemical reagent company limited) and tungsten trioxide (the purity is more than or equal to 99 percent by the national pharmaceutical group chemical reagent company limited) in an ethanol solution according to the molar ratio of 1:1, and then placing the mixture in an oven at 60 ℃ for drying. The solid powder obtained by drying is calcined in a tube furnace (Coco OTF-1200X-S) at 900 ℃ for 12h, and the obtained solid powder is ground for standby.
The product was characterized by XRD (Philips X' Pert Pro Super differential), scanning electron microscope (Zeiss Supra 40) and Raman spectrometer (RenisshawRM 3000Micro-Raman system) to obtain XRD spectrum, Scanning Electron Microscope (SEM) and Raman spectrum. Shown in FIGS. 4(a, b) and 5(a), respectively, and thus confirmed to be Bi having a size in the micrometer range2WO6And (5) blocking.
Comparative example 2
0.165g of sodium tungstate dihydrate (national drug group chemical reagent limited, purity of 99% or more) and 0.485g of bismuth nitrate pentahydrate (national drug group chemical reagent limited, purity of 67% or more) were dissolved in a mixed solution of 40mL of deionized water and 500. mu.L of concentrated nitric acid (national drug group chemical reagent limited, concentration of 67% by mass) in sequence, and the mixed solution was stirred for 30 minutes at 200r/min in an electric jacket stirrer (08-2T, manufactured by Shanghai Meipu instruments), and then the obtained mixed solution was transferred to a 50mL high-pressure reaction vessel, sealed, and placed in an oven (XMTD-8222, Shanghai Jing Macro Experimental facilities, Ltd.) to react at 120 ℃ for 24 hours. After the reaction, the reaction mixture was naturally cooled to room temperature, and then centrifuged in a high-speed centrifuge (HC-3518, a scientific instrument Co., Ltd., Zhongjia, Anhui) at 10000rpm to obtain a solid product, which was washed with deionized water and ethanol several times. Finally, the product was dried in a vacuum oven (60 ℃ C.) to obtain a sheet-like product, which was stored in a desiccator for further use.
Respectively using an XRD instrument (Philips X' Pert Pro Super differential) and a transmission electron microscope (JEOL JEM-ARM200F) to characterize the flaky product, and obtaining an XRD spectrumFIG. 7(a, b), a Transmission Electron Micrograph (TEM) showing the above-mentioned two elements, respectively, and it was confirmed that they are not Bi2WO6Ultra-thin flakes of Bi2WO6And (5) thick slices.
Application example 1: bi obtained2WO6Application of nanosheet in visible light formaldehyde degradation
The photocatalytic formaldehyde oxidation test was performed in a sealed 500mL off-line reactor (perfect light Limited, Beijing) with circulating water at 20 ℃ on the outside. In the course of the test, a certain amount of Bi obtained in examples 1 and 2 and comparative examples 1 and 2 was first added2WO6Dispersed in water to obtain a dispersion having a concentration of about 1mg/mL, and then dropped uniformly on the quartz glass. After drying by heating at 65 ℃ for 0.5 hour, Bi prepared on quartz glass is obtained2WO6A film. A300W xenon lamp with an AM1.5 filter is used for simulating sunlight as a light source for reaction, and a 400nm cut-off filter (Beijing Zhongzhijin source science and technology limited) is used for filtering ultraviolet light below 400nm to realize continuous irradiation of visible light. It should be noted that to ensure a reaction temperature of 20 ℃, quartz glass was placed at the bottom of the reactor. The reaction vessel was then sealed and vacuum treated three times, and then charged with synthetic air (20% O) containing 500ppm of formaldehyde2+80％N2) To achieve one atmosphere. Finally, 1.0mL of deionized water was injected into the apparatus to provide a certain humidity. The gas products evolved were quantitatively determined by an Agilent GC-7890B gas chromatograph equipped with a TDX-01 column, a Thermal Conductivity Detector (TCD) and a Flame Ionization Detector (FID).
FIG. 8 shows Bi obtained by examples 1 and 2 of the present invention and comparative examples 1 and 22WO6Catalyzing formaldehyde degradation to generate CO under different test conditions2The rate of (c). As can be seen in fig. 8, several materials have no ability to catalyze formaldehyde degradation in the absence of light; whereas the oxygen vacancy-containing defect state Bi prepared by example 2 was under visible light2WO6The ultrathin sheets had the highest formaldehyde degradation rate, 2.7 and 40 times that of the oxygen vacancy free bismuth tungstate ultrathin sheets prepared in example 1 and the bulk prepared in comparative example 1.
Application example 2: bi obtained2WO6Ultrathin sheet applied to visible light low-concentration formaldehyde degradation
In the course of the test, a certain amount of Bi obtained in examples 1, 2 and comparative example 1 was first introduced2WO6Dispersed in water to obtain a dispersion having a concentration of about 1mg/mL, and then dropped uniformly on the quartz glass. After drying by heating at 65 ℃ for 0.5 hour, Bi prepared on quartz glass is obtained2WO6A film. A300W xenon lamp with an AM1.5 filter is used for simulating sunlight as a light source for reaction, and a 400nm cut-off filter (Beijing Zhongzhijin source science and technology limited) is used for filtering ultraviolet light below 400nm to realize continuous irradiation of visible light. It should be noted that to ensure a reaction temperature of 20 ℃, quartz glass was placed at the bottom of the reactor. The reaction vessel was then sealed and vacuum treated three times, and then charged with synthetic air (20% O) containing 10ppm of formaldehyde2+80％N2) To achieve one atmosphere. Finally, 1.0mL of deionized water was injected into the apparatus to provide a certain humidity. The gas products evolved were quantitatively determined by an Agilent GC-7890B gas chromatograph equipped with a TDX-01 column, a Thermal Conductivity Detector (TCD) and a Flame Ionization Detector (FID).
FIG. 9 shows Bi obtained by examples 1 and 2 of the present invention and comparative example 12WO6The degradation rate of catalyzing formaldehyde oxidation at low concentration. As can be seen in FIG. 9, the oxygen vacancy-containing defect state Bi prepared by example 22WO6The ultrathin slice has the fastest formaldehyde degradation rate, can reach nearly 100 percent of formaldehyde conversion rate in 75min, and is 2.3 times of the oxygen-free vacancy bismuth tungstate ultrathin slice prepared in the example 1. And the concentration of the degraded formaldehyde reaches the national indoor air quality standard (less than or equal to 0.1mg m)-3)。
Application example 3: defect state Bi containing oxygen vacancy is obtained2WO6Ultrathin sheet applied to long-term stable visible light high-concentration formaldehyde degradation
During the test, a certain amount of Bi obtained in example 2 was first introduced2WO6Ultra-thin flakes were dispersed in water to obtain a dispersion with a concentration of about 1mg/mL, which was thenUniformly dropped on the quartz glass. After drying by heating at 65 ℃ for 0.5 hour, Bi prepared on quartz glass is obtained2WO6A film. A300W xenon lamp with an AM1.5 filter is used for simulating sunlight as a light source for reaction, and a 400nm cut-off filter (Beijing Zhongzhijin source science and technology limited) is used for filtering ultraviolet light below 400nm to realize continuous irradiation of visible light. It should be noted that to ensure a reaction temperature of 20 ℃, quartz glass was placed at the bottom of the reactor. The reaction vessel was then sealed and vacuum treated three times, and then charged with synthetic air (20% O) containing 500ppm of formaldehyde2+80％N2) To achieve one atmosphere. Finally, 1.0mL of deionized water was injected into the apparatus to provide a certain humidity. The gas products evolved were quantitatively determined by an Agilent GC-7890B gas chromatograph equipped with a TDX-01 column, a Thermal Conductivity Detector (TCD) and a Flame Ionization Detector (FID).
FIG. 10 shows the defect state Bi containing oxygen vacancies obtained by example 2 of the present invention2WO6The cycle stability of the ultrathin sheet in the catalytic oxidation process of high-concentration formaldehyde. As can be seen in FIG. 10, the oxygen vacancy-containing defect state Bi prepared by example 22WO6The ultrathin sheet can still maintain the catalytic activity for 50 hours even in high-concentration formaldehyde, and has no obvious inactivation.
The above description of the embodiments is only intended to facilitate the understanding of the method of the invention and its core idea. It should be noted that, for those skilled in the art, it is possible to make various improvements and modifications to the present invention without departing from the principle of the present invention, and those improvements and modifications also fall within the scope of the claims of the present invention.
Claims (10)
1. A process for preparing oxygen-vacancy-containing bismuth tungstate ultrathin flakes, the process comprising: step 1) synthesizing an oxygen vacancy-free bismuth tungstate ultrathin sheet by a hydrothermal method, and step 2) synthesizing an oxygen vacancy-containing bismuth tungstate ultrathin sheet from the oxygen vacancy-free bismuth tungstate ultrathin sheet obtained in the step 1) by a vacuum aluminothermic method.
2. The method of claim 1, wherein the step 1) comprises:
dissolving tungstate, bismuth nitrate and potassium bromide in a nitric acid solution; heating the obtained solution in a sealed reactor for reaction; after the reaction was complete, the reaction mixture was cooled and the solid was isolated; and washing and drying to obtain the powdery bismuth tungstate ultrathin slice without oxygen vacancies.
3. The method of claim 2, wherein the tungstate: the bismuth nitrate: the molar ratio of the potassium bromide is (6-12): (17-28): (1-2).
4. The method according to claim 2, wherein the concentration of the nitric acid solution is 1.0 to 1.2 mass%.
5. The process according to claim 2, wherein the reaction is carried out at a reaction temperature of 120 to 130 ℃ and a reaction time of 20 to 26 hours.
6. The method of claim 1, wherein the step 2) comprises:
respectively placing the bismuth tungstate ultrathin sheets without oxygen vacancies obtained in the step 1) and aluminum powder into two chambers of a double-chamber tubular furnace, raising the temperature of the chamber containing the bismuth tungstate ultrathin sheets to 280-320 ℃, raising the temperature of the chamber containing the aluminum powder to 700-750 ℃, and keeping for 2-3 h; and then naturally cooling the obtained product, and washing and drying to obtain the oxygen vacancy-containing bismuth tungstate ultrathin slice.
7. The process of claim 1, wherein the oxygen-vacancy containing bismuth tungstate ultrathin flakes are ultrathin flakes having a cell layer thickness of 0.5 to 1.
8. An oxygen-vacancy-containing bismuth tungstate ultrathin sheet prepared by the method of any one of claims 1 to 7.
9. A method for degrading formaldehyde into carbon dioxide by photocatalysis, wherein the oxygen vacancy-containing bismuth tungstate ultrathin sheets as claimed in claim 8 is used as a catalyst.
10. The method of claim 9, comprising degrading 10ppm to 500ppm formaldehyde under visible light conditions.
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