CN110560045A - Bi2WO6intercalation MgAl-LDH material and preparation method and application thereof - Google Patents
Bi2WO6intercalation MgAl-LDH material and preparation method and application thereof Download PDFInfo
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- CN110560045A CN110560045A CN201910898548.5A CN201910898548A CN110560045A CN 110560045 A CN110560045 A CN 110560045A CN 201910898548 A CN201910898548 A CN 201910898548A CN 110560045 A CN110560045 A CN 110560045A
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- 239000000463 material Substances 0.000 title claims abstract description 45
- 238000002360 preparation method Methods 0.000 title claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 62
- 239000000843 powder Substances 0.000 claims abstract description 38
- 239000011777 magnesium Substances 0.000 claims abstract description 36
- 239000000725 suspension Substances 0.000 claims abstract description 35
- 238000009830 intercalation Methods 0.000 claims abstract description 30
- 239000007788 liquid Substances 0.000 claims abstract description 30
- 238000000926 separation method Methods 0.000 claims abstract description 30
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 26
- 229910052782 aluminium Inorganic materials 0.000 claims abstract description 21
- 229910052749 magnesium Inorganic materials 0.000 claims abstract description 20
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 claims abstract description 17
- 229910052797 bismuth Inorganic materials 0.000 claims abstract description 15
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 claims abstract description 15
- XAGFODPZIPBFFR-UHFFFAOYSA-N aluminium Chemical compound [Al] XAGFODPZIPBFFR-UHFFFAOYSA-N 0.000 claims abstract description 13
- FYYHWMGAXLPEAU-UHFFFAOYSA-N Magnesium Chemical compound [Mg] FYYHWMGAXLPEAU-UHFFFAOYSA-N 0.000 claims abstract description 12
- 239000002105 nanoparticle Substances 0.000 claims abstract description 12
- 229910052721 tungsten Inorganic materials 0.000 claims abstract description 12
- 239000010937 tungsten Substances 0.000 claims abstract description 12
- 239000003513 alkali Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims description 105
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 claims description 24
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 claims description 12
- 238000003756 stirring Methods 0.000 claims description 12
- 238000004108 freeze drying Methods 0.000 claims description 10
- 238000000034 method Methods 0.000 claims description 10
- 238000005119 centrifugation Methods 0.000 claims description 9
- JHXKRIRFYBPWGE-UHFFFAOYSA-K bismuth chloride Chemical compound Cl[Bi](Cl)Cl JHXKRIRFYBPWGE-UHFFFAOYSA-K 0.000 claims description 7
- RXPAJWPEYBDXOG-UHFFFAOYSA-N hydron;methyl 4-methoxypyridine-2-carboxylate;chloride Chemical group Cl.COC(=O)C1=CC(OC)=CC=N1 RXPAJWPEYBDXOG-UHFFFAOYSA-N 0.000 claims description 7
- 239000002351 wastewater Substances 0.000 claims description 7
- TWRXJAOTZQYOKJ-UHFFFAOYSA-L Magnesium chloride Chemical compound [Mg+2].[Cl-].[Cl-] TWRXJAOTZQYOKJ-UHFFFAOYSA-L 0.000 claims description 6
- CSNNHWWHGAXBCP-UHFFFAOYSA-L Magnesium sulfate Chemical compound [Mg+2].[O-][S+2]([O-])([O-])[O-] CSNNHWWHGAXBCP-UHFFFAOYSA-L 0.000 claims description 6
- YIXJRHPUWRPCBB-UHFFFAOYSA-N magnesium nitrate Chemical group [Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O YIXJRHPUWRPCBB-UHFFFAOYSA-N 0.000 claims description 6
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical group [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 5
- 239000011259 mixed solution Substances 0.000 claims description 4
- 239000012265 solid product Substances 0.000 claims description 4
- BNGXYYYYKUGPPF-UHFFFAOYSA-M (3-methylphenyl)methyl-triphenylphosphanium;chloride Chemical group [Cl-].CC1=CC=CC(C[P+](C=2C=CC=CC=2)(C=2C=CC=CC=2)C=2C=CC=CC=2)=C1 BNGXYYYYKUGPPF-UHFFFAOYSA-M 0.000 claims description 3
- DIZPMCHEQGEION-UHFFFAOYSA-H aluminium sulfate (anhydrous) Chemical compound [Al+3].[Al+3].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O DIZPMCHEQGEION-UHFFFAOYSA-H 0.000 claims description 3
- 229910001629 magnesium chloride Inorganic materials 0.000 claims description 3
- 229910052943 magnesium sulfate Inorganic materials 0.000 claims description 3
- 235000019341 magnesium sulphate Nutrition 0.000 claims description 3
- 238000004519 manufacturing process Methods 0.000 claims 2
- 230000001699 photocatalysis Effects 0.000 abstract description 9
- 238000006243 chemical reaction Methods 0.000 description 33
- 239000008367 deionised water Substances 0.000 description 32
- 229910021641 deionized water Inorganic materials 0.000 description 32
- 239000000047 product Substances 0.000 description 14
- 238000005406 washing Methods 0.000 description 11
- 239000000975 dye Substances 0.000 description 10
- -1 metal complex compounds Chemical class 0.000 description 10
- 238000001816 cooling Methods 0.000 description 9
- 238000001035 drying Methods 0.000 description 9
- 229940091250 magnesium supplement Drugs 0.000 description 9
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 9
- 239000004810 polytetrafluoroethylene Substances 0.000 description 9
- 239000002244 precipitate Substances 0.000 description 9
- 238000005303 weighing Methods 0.000 description 9
- MFUVDXOKPBAHMC-UHFFFAOYSA-N magnesium;dinitrate;hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O MFUVDXOKPBAHMC-UHFFFAOYSA-N 0.000 description 8
- 238000007789 sealing Methods 0.000 description 8
- STZCRXQWRGQSJD-GEEYTBSJSA-M methyl orange Chemical compound [Na+].C1=CC(N(C)C)=CC=C1\N=N\C1=CC=C(S([O-])(=O)=O)C=C1 STZCRXQWRGQSJD-GEEYTBSJSA-M 0.000 description 6
- 229940012189 methyl orange Drugs 0.000 description 6
- 230000006798 recombination Effects 0.000 description 6
- 238000005215 recombination Methods 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000013078 crystal Substances 0.000 description 5
- 238000006731 degradation reaction Methods 0.000 description 5
- XNDZQQSKSQTQQD-UHFFFAOYSA-N 3-methylcyclohex-2-en-1-ol Chemical compound CC1=CC(O)CCC1 XNDZQQSKSQTQQD-UHFFFAOYSA-N 0.000 description 4
- VSCWAEJMTAWNJL-UHFFFAOYSA-K aluminium trichloride Chemical compound Cl[Al](Cl)Cl VSCWAEJMTAWNJL-UHFFFAOYSA-K 0.000 description 4
- JGDITNMASUZKPW-UHFFFAOYSA-K aluminium trichloride hexahydrate Chemical compound O.O.O.O.O.O.Cl[Al](Cl)Cl JGDITNMASUZKPW-UHFFFAOYSA-K 0.000 description 4
- 229940009861 aluminum chloride hexahydrate Drugs 0.000 description 4
- 230000015556 catabolic process Effects 0.000 description 4
- 229940050906 magnesium chloride hexahydrate Drugs 0.000 description 4
- DHRRIBDTHFBPNG-UHFFFAOYSA-L magnesium dichloride hexahydrate Chemical compound O.O.O.O.O.O.[Mg+2].[Cl-].[Cl-] DHRRIBDTHFBPNG-UHFFFAOYSA-L 0.000 description 4
- 239000002245 particle Substances 0.000 description 4
- 230000003197 catalytic effect Effects 0.000 description 3
- 239000007795 chemical reaction product Substances 0.000 description 3
- 230000000052 comparative effect Effects 0.000 description 3
- 230000002687 intercalation Effects 0.000 description 3
- 238000002156 mixing Methods 0.000 description 3
- 241001465754 Metazoa Species 0.000 description 2
- 238000009825 accumulation Methods 0.000 description 2
- 229940063656 aluminum chloride Drugs 0.000 description 2
- 230000003321 amplification Effects 0.000 description 2
- 238000012512 characterization method Methods 0.000 description 2
- 238000005034 decoration Methods 0.000 description 2
- 238000004090 dissolution Methods 0.000 description 2
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 2
- 229960002337 magnesium chloride Drugs 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000003199 nucleic acid amplification method Methods 0.000 description 2
- 239000013618 particulate matter Substances 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 241000894007 species Species 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 238000004627 transmission electron microscopy Methods 0.000 description 2
- 208000019838 Blood disease Diseases 0.000 description 1
- 229910020350 Na2WO4 Inorganic materials 0.000 description 1
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 description 1
- PYKYMHQGRFAEBM-UHFFFAOYSA-N anthraquinone Natural products CCC(=O)c1c(O)c2C(=O)C3C(C=CC=C3O)C(=O)c2cc1CC(=O)OC PYKYMHQGRFAEBM-UHFFFAOYSA-N 0.000 description 1
- 150000004056 anthraquinones Chemical class 0.000 description 1
- 125000000751 azo group Chemical group [*]N=N[*] 0.000 description 1
- 239000002585 base Substances 0.000 description 1
- 210000003169 central nervous system Anatomy 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- RKTYLMNFRDHKIL-UHFFFAOYSA-N copper;5,10,15,20-tetraphenylporphyrin-22,24-diide Chemical compound [Cu+2].C1=CC(C(=C2C=CC([N-]2)=C(C=2C=CC=CC=2)C=2C=CC(N=2)=C(C=2C=CC=CC=2)C2=CC=C3[N-]2)C=2C=CC=CC=2)=NC1=C3C1=CC=CC=C1 RKTYLMNFRDHKIL-UHFFFAOYSA-N 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 238000011049 filling Methods 0.000 description 1
- 208000014951 hematologic disease Diseases 0.000 description 1
- 208000018706 hematopoietic system disease Diseases 0.000 description 1
- 238000000024 high-resolution transmission electron micrograph Methods 0.000 description 1
- 150000004677 hydrates Chemical class 0.000 description 1
- 210000003734 kidney Anatomy 0.000 description 1
- 210000004185 liver Anatomy 0.000 description 1
- 238000003760 magnetic stirring Methods 0.000 description 1
- 238000005297 material degradation process Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 229910017604 nitric acid Inorganic materials 0.000 description 1
- 230000002085 persistent effect Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 239000011941 photocatalyst Substances 0.000 description 1
- 230000029553 photosynthesis Effects 0.000 description 1
- 238000010672 photosynthesis Methods 0.000 description 1
- 231100000572 poisoning Toxicity 0.000 description 1
- 230000000607 poisoning effect Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
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
- 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—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Landscapes
- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Materials Engineering (AREA)
- Hydrology & Water Resources (AREA)
- Water Supply & Treatment (AREA)
- Environmental & Geological Engineering (AREA)
- Health & Medical Sciences (AREA)
- Life Sciences & Earth Sciences (AREA)
- Toxicology (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Catalysts (AREA)
Abstract
The invention provides a Bi2WO6An intercalated MgAl-LDH material, a preparation method and application thereof, belonging to the technical field of photocatalytic materials. The preparation method provided by the invention comprises the following steps: dissolving a magnesium source and an aluminum source in water to obtain a solution A; dissolving alkali in water to obtain a solution B; dissolving a tungsten source in water to obtain a solution C; dropwise adding the solution A and the solution B into the solution C at the same time, performing a first hydrothermal reaction, and performing first solid-liquid separation to obtain WO4 2‑Intercalation MgAl-LDH powder; subjecting said WO to4 2‑Dispersing the intercalated MgAl-LDH powder and a bismuth source into water, carrying out a second hydrothermal reaction on the obtained suspension, and carrying out a second solid-liquid separation to obtain Bi2WO6Intercalation MgAl-LDH material. The invention is prepared byBi2WO6The nano particles are loaded between MgAl-LDH layers, so that Bi is greatly improved2WO6the photocatalytic performance of (a).
Description
Technical Field
The invention relates to the technical field of photocatalytic materials, in particular to Bi2WO6An intercalated MgAl-LDH material, a preparation method and application thereof.
Background
with the wide application of dyes in daily life, the pollution of underground water caused by the dyes is more and more serious. Dyes readily absorb and reflect sunlight, thereby being able to block photosynthesis by aquatic plants and interfere with the growth of aquatic species in the natural environment. More seriously, the low biodegradability of the dye leads to its constant accumulation, causing persistent pollution. Dyes can be classified into a plurality of structural species, for example, azo, anthraquinone, or metal complex compounds, depending on their structure. These organic pollutants may irritate the skin of humans and animals and cause blood disorders, liver and kidney damage, and poisoning of the central nervous system in humans and animals. Therefore, there is considerable research interest in finding solutions that easily treat these contaminants and prevent their accumulation.
The semiconductor photocatalysis technology is adopted, and infinite solar energy is utilized to degrade organic pollutants in wastewater, which is the solution with the most application prospect. Nano-sized Bi2WO6Has narrow band gap (2.5eV), and is an effective photocatalyst for dye degradation under visible light. However, Bi due to its rapid recombination of electron-hole pairs2WO6The photocatalytic efficiency of (a) is still low.
disclosure of Invention
the object of the present invention is to provide a Bi2WO6An intercalated MgAl-LDH material is prepared through mixing Bi2WO6The nano particles are loaded between MgAl-LDH layers, and Bi is improved2WO6the photocatalytic performance of (a).
In order to achieve the above object, the present invention provides the following technical solutions:
The invention provides a Bi2WO6The preparation method of the intercalated MgAl-LDH material comprises the following steps:
dissolving a magnesium source and an aluminum source in water to obtain a solution A; dissolving alkali in water to obtain a solution B; dissolving a tungsten source in water to obtain a solution C;
Dropwise adding the solution A and the solution B into the solution C at the same time, performing a first hydrothermal reaction, and performing first solid-liquid separation to obtain WO4 2-Intercalation MgAl-LDH powder;
Subjecting said WO to4 2-Dispersing the intercalated MgAl-LDH powder and a bismuth source into water, carrying out a second hydrothermal reaction on the obtained suspension, and carrying out a second solid-liquid separation to obtain Bi2WO6Intercalation MgAl-LDH material.
Preferably, the magnesium source is magnesium nitrate, magnesium sulfate or magnesium chloride; the aluminum source is aluminum nitrate, aluminum sulfate or aluminum chloride; the alkali is sodium hydroxide or potassium hydroxide; the tungsten source is sodium tungstate or ammonium tungstate; the bismuth source is bismuth nitrate or bismuth trichloride.
Preferably, the molar ratio of Mg to Al in the solution A is (2-2.2): 1; the total amount of Mg and Al in the solution A and OH in the solution B-The molar ratio of (1) to (2.3-2.4); the molar ratio of the total amount of Mg and Al in the solution A to W in the solution C is 1: (1.1-1.2); the molar ratio of Bi in the bismuth source to W in the solution C is (1-3): 1.
Preferably, the specific operation of simultaneously dripping the solution A and the solution B into the solution C is as follows: and dropwise adding the solution A into the solution C under the conditions of constant temperature of 50-70 ℃ and stirring speed of 150-500 r/min, and simultaneously dropwise adding the solution B to control the pH value of the mixed solution to be 8-11.
Preferably, the temperature of the first hydrothermal reaction is 130-160 ℃, and the time is 9-12 h.
Preferably, the temperature of the second hydrothermal reaction is 200-210 ℃ and the time is 15-24 h.
Preferably, the first solid-liquid separation and the second solid-liquid separation adopt a centrifugal mode, and the rotating speed of the centrifugal mode is 4000-10000 r/min independently; the centrifugation time is independently 5-10 min.
preferably, after the first solid-liquid separation and the second solid-liquid separation, the method further comprises freeze-drying the obtained solid product.
The invention provides Bi prepared by the preparation method in the scheme2WO6An intercalated MgAl-LDH material comprising MgAl-LDH and Bi between the MgAl-LDH layers2WO6And (3) nanoparticles.
The invention provides the Bi of the scheme2WO6the intercalated MgAl-LDH material is applied to the treatment of dye wastewater.
The invention provides a Bi2WO6The preparation method of the intercalated MgAl-LDH material comprises the following steps: dissolving a magnesium source and an aluminum source in water to obtain a solution A; dissolving alkali in water to obtain a solution B; dissolving a tungsten source in water to obtain a solution C; dropwise adding the solution A and the solution B into the solution C at the same time, performing a first hydrothermal reaction, and performing first solid-liquid separation to obtain WO4 2-Intercalation MgAl-LDH powder; subjecting said WO to4 2-Dispersing the intercalated MgAl-LDH powder and a bismuth source into water, carrying out a second hydrothermal reaction on the obtained suspension, and carrying out a second solid-liquid separation to obtain Bi2WO6Intercalation MgAl-LDH material. The invention is prepared by mixing Bi2WO6The nano particles are loaded between the layers of MgAl-LDH, on one hand, Bi is reduced2WO6particle size of (B) increased Bi2WO6The catalytic ability of (a); on the other hand, Bi2WO6Through the recombination with MgAl-LDH, the recombination rate of electron-hole pairs is reduced, thereby increasing Bi2WO6The photocatalytic performance of (a).
drawings
FIG. 1 shows the preparation of Bi according to example 12WO6The X-ray diffraction patterns of the intercalated MgAl-LDH material and the pure MgAl-LDH powder;
FIG. 2 shows Bi obtained in example 12WO6The X-ray diffraction small-angle amplification map of the intercalated MgAl-LDH material and the pure MgAl-LDH powder;
FIG. 3 shows Bi obtained in example 1 of the present invention2WO6a field emission scanning electron microscope picture of the intercalation MgAl-LDH material;
FIG. 4 shows Bi obtained in example 1 of the present invention2WO6Transmission electron microscopy of intercalated MgAl-LDH material;
FIG. 5 shows Bi obtained in example 1 of the present invention2WO6A high resolution transmission electron microscopy image of particulate matter in the intercalated MgAl-LDH material;
FIG. 6 shows Bi obtained in example 1 of the present invention2WO6Intercalation MgAl-LDH material and pure Bi2WO6A fluorescence spectrogram of the pure MgAl-LDH powder;
FIG. 7 shows Bi obtained in example 1 of the present invention2WO6And (3) an intercalation MgAl-LDH material degradation efficiency graph for methyl orange.
Detailed Description
The invention provides a Bi2WO6The preparation method of the intercalated MgAl-LDH material comprises the following steps:
Dissolving a magnesium source and an aluminum source in water to obtain a solution A; dissolving alkali in water to obtain a solution B; dissolving a tungsten source in water to obtain a solution C;
Dropwise adding the solution A and the solution B into the solution C at the same time, performing a first hydrothermal reaction, and performing first solid-liquid separation to obtain WO4 2-Intercalation MgAl-LDH powder;
Subjecting said WO to4 2-Dispersing the intercalated MgAl-LDH powder and a bismuth source into water, carrying out a second hydrothermal reaction on the obtained suspension, and carrying out a second solid-liquid separation to obtain Bi2WO6Intercalation MgAl-LDH material.
In the present invention, the starting materials used are all commercially available products well known in the art, unless otherwise specified.
In the invention, a magnesium source and an aluminum source are dissolved in water to obtain a solution A. In the present invention, the magnesium source is preferably magnesium nitrate, magnesium sulfate or magnesium chloride; the aluminum source is preferably aluminum nitrate, aluminum sulfate or aluminum chloride; the water is preferably deionized water. Since the magnesium source and the aluminum source used in the present invention mostly contain crystal water, the magnesium source and the aluminum source of the present invention include the above-listed compounds and hydrates thereof. The present invention does not require any particular manipulation of the dissolution, and the dissolution may be performed in any manner known in the art. In the invention, the molar ratio of Mg to Al in the solution A is preferably (2-2.2): 1; the concentration of Mg in the solution A is preferably 0.05-2 mol/L.
The invention dissolves alkali in water to obtain solution B. In the present invention, the base is preferably sodium hydroxide or potassium hydroxide; the water is preferably deionized water. In the present invention, the amount of the alkali is preferably determined depending on the contents of Mg and Al in the solution a; the total amount of Mg and Al in the solution A and OH in the solution B-The molar ratio of (A) to (B) is preferably 1 (2.3 to 2.4). In the present invention, OH in the solution B-The concentration of (b) is preferably 0.05 to 2 mol/L.
The invention dissolves tungsten source in water to obtain solution C. In the present invention, the tungsten source is preferably sodium tungstate or ammonium tungstate; the water is preferably deionized water. In the present invention, the amount of the tungsten source is preferably determined according to the contents of Mg and Al in the solution a; the molar ratio of the total amount of Mg and Al in the solution A to W in the solution C is preferably 1: (1.1-1.2).
After obtaining the solution A, the solution B and the solution C, the solution A and the solution B are simultaneously dripped into the solution C, then a first hydrothermal reaction is carried out, and WO is obtained after first solid-liquid separation4 2-Intercalation MgAl-LDH powder.
In the present invention, the specific operation of simultaneously adding the solution a and the solution B dropwise to the solution C is preferably: and dropwise adding the solution A into the solution C under the conditions of constant temperature of 50-70 ℃ and stirring speed of 150-500 r/min, and simultaneously dropwise adding the solution B to control the pH value of the mixed solution to be 8-11. The dropping speed of the solution A and the solution B is not specially limited, and the pH value of the mixed solution can be ensured to be 8-11 in the dropping process.
In the invention, the temperature of the first hydrothermal reaction is preferably 130-160 ℃, and the time is preferably 9-12 h. In the first hydrothermal reaction process, a magnesium source and an aluminum source react to generate MgAl-LDH, and meanwhile, MgAl-LDH is generatedinserting a tungsten source between the layers of MgAl-LDH to obtain WO4 2-And (3) suspension of intercalated MgAl-LDH powder.
After the first hydrothermal reaction is finished, the invention carries out the first hydrothermal reaction to obtain a product system (WO)4 2-Suspension of intercalated MgAl-LDH powder) is subjected to first solid-liquid separation to obtain WO4 2-Intercalation MgAl-LDH powder. Before the first solid-liquid separation, the method preferably further comprises washing the first hydrothermal reaction product system with deionized water for 5-6 times. In the invention, the first solid-liquid separation mode is preferably centrifugation, and the rotation speed of the centrifugation is preferably 4000-10000 r/min; the time for centrifugation is preferably 5-10 min. After the first solid-liquid separation, the invention preferably further comprises freeze-drying the solid product obtained after the first solid-liquid separation to obtain WO4 2-Intercalation MgAl-LDH powder. In the invention, the freeze drying is preferably carried out in a freeze dryer, the temperature of the freeze drying is preferably-10 to-50 ℃, and the time of the freeze drying is preferably 15 to 22 hours.
To obtain WO4 2-After the MgAl-LDH powder is intercalated, the WO is added into the powder4 2-Dispersing the intercalated MgAl-LDH powder and a bismuth source into water, carrying out a second hydrothermal reaction on the obtained suspension, and carrying out a second solid-liquid separation to obtain Bi2WO6Intercalation MgAl-LDH material. In the present invention, the bismuth source is preferably bismuth nitrate or bismuth trichloride; the bismuth source is preferably used in an amount according to preparation WO4 2-the using amount of a tungsten source is determined when the MgAl-LDH powder is intercalated, and the molar ratio of Bi in the bismuth source to W in the solution C is preferably (1-3): 1. The invention has no special requirement on the dosage of the water, and can lead WO to be used4 2-The intercalated MgAl-LDH powder and the bismuth source are uniformly dispersed.
In the invention, the temperature of the second hydrothermal reaction is preferably 200-210 ℃, and the time is preferably 15-24 h. In the second hydrothermal reaction process, the bismuth source reacts with tungstate radical to generate Bi2WO6And inserted between the layers of MgAl-LDH.
after the second hydrothermal reaction is finished, the invention is implementedThe second hydrothermal reaction product system is subjected to second solid-liquid separation to obtain Bi2WO6Intercalation MgAl-LDH material. Before the second solid-liquid separation, the method preferably further comprises washing the second hydrothermal reaction product system with deionized water for 5-6 times. In the invention, the second solid-liquid separation mode is preferably centrifugation, and the rotation speed of the centrifugation is preferably 4000-10000 r/min; the time for centrifugation is preferably 5-10 min. After the second solid-liquid separation, the present invention preferably further comprises freeze-drying the solid product obtained after the second solid-liquid separation to obtain Bi2WO6Intercalation MgAl-LDH material. In the invention, the freeze drying is preferably carried out in a freeze dryer, the temperature of the freeze drying is preferably-10 to-50 ℃, and the time of the freeze drying is preferably 15 to 22 hours.
The invention provides Bi prepared by the preparation method in the scheme2WO6An intercalated MgAl-LDH material comprising MgAl-LDH and Bi between the MgAl-LDH layers2WO6And (3) nanoparticles. The invention is prepared by mixing Bi2WO6The nano particles are loaded between the layers of MgAl-LDH, on one hand, Bi is reduced2WO6Particle size of (B) increased Bi2WO6the catalytic ability of (a); on the other hand, Bi2WO6Through the recombination with MgAl-LDH, the recombination rate of electron-hole pairs is reduced, thereby increasing Bi2WO6The photocatalytic performance of (a).
The invention provides the Bi of the scheme2WO6The intercalated MgAl-LDH material is applied to the treatment of dye wastewater. The invention is not particularly limited to the specific embodiments of the applications described, and may be applied in any manner known in the art. The invention has no special requirements on the specific source and the composition of the dye wastewater, and the dye wastewater well known in the field can be used.
The following examples are given to illustrate Bi according to the present invention2WO6The intercalated MgAl-LDH material and the preparation method and use thereof are explained in detail but they are not to be construed as limiting the scope of the invention.
Example 1
(1) Weighing 4.615g of magnesium nitrate hexahydrate and 3.376g of aluminum nitrate nonahydrate according to the molar ratio of Mg to Al of 2:1, and dissolving the magnesium nitrate hexahydrate and the aluminum nitrate nonahydrate in 50mL of deionized water to prepare a solution A; by OH-Weighing 2.516g of NaOH and dissolving the NaOH in 25mL of deionized water according to the molar ratio of (Mg + Al) of 2.33:1 to prepare a solution B; 7.578g of sodium tungstate is weighed according to the molar ratio of W (Mg + Al) elements of 1.16:1 and dissolved in 25mL of deionized water to prepare solution C;
(2) under the conditions that the pH value is constant at 10, the constant temperature is 60 ℃ and the stirring is violent (the rotating speed is 500r/min), the solution A and the solution B prepared in the step (1) are simultaneously dripped into the solution C to form suspension;
(3) Pouring the suspension prepared in the step (2) into a 80mL polytetrafluoroethylene high-pressure reaction kettle for sealing, transferring the reaction kettle into an oven, setting the temperature at 140 ℃ for reaction for 10 hours, and cooling to room temperature after the reaction is finished to obtain the suspension;
(4) centrifuging and washing the suspension prepared in the step (3) for 6 times by using deionized water, wherein the rotating speed of a centrifuge is 10000r/min, the centrifuging time is 5min, and drying the obtained centrifugal product in a freeze dryer for 22h to prepare WO4 2-Intercalation MgAl-LDH powder;
(5) Weighing 0.5g of the powder prepared in the step (4) and 0.38g of bismuth nitrate according to the molar ratio of the Bi to the W element of 2:1, adding the powder and the bismuth nitrate into 60mL of deionized water, and uniformly stirring to form a suspension;
(6) pouring the suspension prepared in the step (5) into a 80mL polytetrafluoroethylene high-pressure reaction kettle for sealing, transferring the reaction kettle into an oven, setting the temperature at 204 ℃ for reaction for 24 hours, and cooling to room temperature after the reaction is finished to obtain a precipitate;
(7) Centrifuging and washing the precipitate prepared in the step (6) for 6 times by using deionized water, wherein the rotating speed of the centrifuge is 10000r/min, the centrifuging time is 5min, and drying the obtained centrifugal product in a freeze dryer for 22h to obtain Bi2WO6Intercalation MgAl-LDH material.
Example 2
(1) 4.846g of magnesium nitrate hexahydrate and 3.376g of aluminum nitrate nonahydrate are weighed according to the molar ratio of Mg to Al of 2.1:1, and the magnesium nitrate hexahydrate and the aluminum nitrate nonahydrate are dissolved in 60mL of deionized water to prepare a solution A; by OH-the molar ratio of (Mg + Al) is 2.2.623g of NaOH is weighed at 35:1 and dissolved in 30mL of deionized water to prepare solution B; 5.418g of ammonium tungstate is weighed according to the molar ratio of W (Mg + Al) elements of 1.1:1 and dissolved in 30mL of deionized water to prepare a solution C;
(2) Under the conditions that the pH is constant at 8, the constant temperature is 50 ℃, and the stirring is violent (the rotating speed is 450r/min), simultaneously dripping the solution A and the solution B prepared in the step (1) into the solution C to form suspension;
(3) Pouring the suspension prepared in the step (2) into a 80mL polytetrafluoroethylene high-pressure reaction kettle for sealing, transferring the reaction kettle into an oven, setting the temperature at 130 ℃ for reaction for 12 hours, and cooling to room temperature after the reaction is finished to obtain the suspension;
(4) Centrifuging and washing the suspension prepared in the step (3) for 5 times by using deionized water, wherein the rotating speed of a centrifuge is 4000r/min, the centrifuging time is 10min, and drying the obtained centrifugal product in a freeze dryer for 15h to prepare WO4 2-Intercalation MgAl-LDH powder;
(5) weighing 0.5g of the powder prepared in the step (4) and 0.76g of bismuth nitrate according to the molar ratio of Bi to W elements of 1.5:1, adding the powder and the bismuth nitrate into 50mL of deionized water, and uniformly stirring to form a suspension;
(6) Pouring the suspension prepared in the step (5) into a 80mL polytetrafluoroethylene high-pressure reaction kettle for sealing, transferring the reaction kettle into an oven, setting the temperature at 200 ℃ for reaction for 24 hours, and cooling to room temperature after the reaction is finished to obtain a precipitate;
(7) Centrifuging and washing the precipitate prepared in the step (6) for 5 times by using deionized water, wherein the rotating speed of a centrifuge is 4000r/min, the centrifuging time is 10min, and drying the obtained centrifugal product in a freeze dryer for 15h to obtain Bi2WO6intercalation MgAl-LDH material.
Example 3
(1) Weighing 4.025g of magnesium chloride hexahydrate and 2.173g of aluminum chloride hexahydrate according to the molar ratio of Mg to Al of 2.2:1, and dissolving the magnesium chloride hexahydrate and the aluminum chloride hexahydrate in 60mL of deionized water to prepare a solution A; by OH-3.878g of KOH is weighed and dissolved in 40mL of deionized water to prepare solution B, wherein the molar ratio of (Mg + Al) is 2.4: 1; 5.874g of sodium tungstate is weighed according to the molar ratio of W (Mg + Al) elements of 1.2:1 and dissolved in 30mL of deionized water to prepare solution C;
(2) Under the conditions that the pH is constant at 11, the constant temperature is 65 ℃ and the stirring is violent (the rotating speed is 500r/min), the solution A and the solution B prepared in the step (1) are simultaneously dripped into the solution C to form suspension;
(3) Pouring the suspension prepared in the step (2) into a 80mL polytetrafluoroethylene high-pressure reaction kettle for sealing, transferring the reaction kettle into an oven, setting the temperature at 160 ℃ for reaction for 11 hours, and cooling to room temperature after the reaction is finished to obtain the suspension;
(4) Centrifuging and washing the suspension prepared in the step (3) for 6 times by using deionized water, wherein the rotating speed of a centrifuge is 10000r/min, the centrifuging time is 5min, and drying the obtained centrifugal product in a freeze dryer for 20h to prepare WO4 2-Intercalation MgAl-LDH powder;
(5) Weighing 0.5g of the powder prepared in the step (4) and 1.127g of bismuth trichloride according to the molar ratio of the Bi to the W element of 2:1, adding the powder and the bismuth trichloride into 50mL of deionized water, and uniformly stirring to form a suspension;
(6) pouring the suspension prepared in the step (5) into a 80mL polytetrafluoroethylene high-pressure reaction kettle for sealing, transferring the reaction kettle into an oven, setting the temperature to 207 ℃ for reaction for 20 hours, and cooling to room temperature after the reaction is finished to obtain a precipitate;
(7) Centrifuging and washing the precipitate prepared in the step (6) for 6 times by using deionized water, wherein the rotating speed of the centrifuge is 10000r/min, the centrifuging time is 5min, and drying the obtained centrifugal product in a freeze dryer for 20h to obtain Bi2WO6Intercalation MgAl-LDH material.
Example 4
(1) Weighing 4.025g of magnesium chloride hexahydrate and 2.173g of aluminum chloride hexahydrate according to the molar ratio of Mg to Al of 2.2:1, and dissolving the magnesium chloride hexahydrate and the aluminum chloride hexahydrate in 50mL of deionized water to prepare a solution A; by OH-2.765g of NaOH is weighed and dissolved in 30mL of deionized water to prepare solution B, wherein the molar ratio of (Mg + Al) is 2.4: 1; 6.774g of ammonium tungstate is weighed according to the molar ratio of W (Mg + Al) elements of 1.2:1 and dissolved in 30mL of deionized water to prepare solution C;
(2) Under the conditions that the pH is constant at 11, the constant temperature is 70 ℃, and the stirring is violent (the rotating speed is 500r/min), simultaneously dripping the solution A and the solution B prepared in the step (1) into the solution C to form suspension;
(3) Pouring the suspension prepared in the step (2) into a 80mL polytetrafluoroethylene high-pressure reaction kettle for sealing, transferring the reaction kettle into an oven, setting the temperature at 160 ℃ for reaction for 12 hours, and cooling to room temperature after the reaction is finished to obtain the suspension;
(4) Centrifuging and washing the suspension prepared in the step (3) for 6 times by using deionized water, wherein the rotating speed of a centrifuge is 10000r/min, the centrifuging time is 10min, and drying the obtained centrifugal product in a freeze dryer for 22h to prepare WO4 2-intercalation MgAl-LDH powder;
(5) Weighing 0.5g of the powder prepared in the step (4) and 1.14g of bismuth trichloride according to the molar ratio of Bi to W elements of 1.8:1, adding the powder and the bismuth trichloride into 60mL of deionized water, and uniformly stirring to form a suspension;
(6) Pouring the suspension prepared in the step (5) into a 80mL polytetrafluoroethylene high-pressure reaction kettle for sealing, transferring the reaction kettle into an oven, setting the temperature at 210 ℃ for reaction for 24 hours, and cooling to room temperature after the reaction is finished to obtain a precipitate;
(7) Centrifuging and washing the precipitate prepared in the step (6) for 6 times by using deionized water, wherein the rotating speed of the centrifuge is 10000r/min, the centrifuging time is 10min, and drying the obtained centrifugal product in a freeze dryer for 22h to obtain Bi2WO6Intercalation MgAl-LDH material.
Comparative example
Bi2WO6The preparation method comprises the following steps:
Weighing 2.5mmol Na at room temperature2WO4·2H2o dissolved in 20mL deionized water, 5mmol Bi (NO)3)3·5H2dissolving O in 20mL of dilute nitric acid (2mol/L) at 80 ℃, and completely dissolving Na2WO4Solution was added slowly dropwise to Bi (NO)3)3Adding the solution into a magnetic stirring machine, stirring for 1h to obtain a white suspension, dropwise adding NaOH into the white suspension to adjust the pH value to 4, then transferring the white suspension into a 100mL high-pressure reaction kettle with a polytetrafluoroethylene lining, adding deionized water to ensure that the filling amount reaches 60%, the hydrothermal temperature is 200 ℃, the hydrothermal time is 12h, then naturally cooling to room temperature, washing the obtained precipitate with the deionized water for several times, drying in a freeze dryer, and finally obtaining a light yellow sample, namely Bi2WO6。
structural and performance characterization
FIG. 1 shows the preparation of Bi according to example 12WO6The X-ray diffraction patterns of the intercalated MgAl-LDH material and the pure MgAl-LDH powder. As can be seen from FIG. 1, the diffraction peaks of the XRD pattern of the product were changed, and the diffraction peaks with 2. theta. at 28.29 °, 46.96 ° and 55.82 ° corresponded to Bi, respectively2WO6(PDF No.79-2381) diffraction peaks of (131), (260) and (133) crystal planes, and diffraction peaks of 2 theta at 9.91 degrees and 19.911 degrees correspond to diffraction peaks of (003) and (006) crystal planes of MgAl-LDH, and the synthetic product has Bi2WO6And a MgAl-LDH phase.
FIG. 2 shows Bi obtained in example 12WO6the X-ray diffraction small-angle amplification spectrum of the intercalation MgAl-LDH material and the pure MgAl-LDH powder. The comparison of the spectrogram shows that Bi2WO6The diffraction peaks belonging to MgAl-LDH (003) and (006) crystal planes in the/MgAl-LDH spectrum are shifted at low angles, and Bi is known2WO6The nanoparticles have been intercalated between the layers of MgAl-LDH.
FIG. 3 shows Bi obtained in example 1 of the present invention2WO6and (3) a field emission scanning electron microscope picture of the intercalated MgAl-LDH material. From the figure, it can be seen that the product has a regular square sheet structure and good dispersibility.
FIG. 4 shows Bi obtained in example 1 of the present invention2WO6Transmission electron microscopy of intercalated MgAl-LDH material. It is apparent from fig. 4 that the sample has a tetragonal plate-like structure with small particles sandwiched between the plate-like structures. The particles were analyzed by high resolution transmission electron microscopy to obtain FIG. 5. The interplanar spacing in the HRTEM image of the crystal is 0.315nm corresponding to Bi2WO6the (113) plane of (B) indicates that the particulate matter is Bi2WO6description of Bi2WO6The nanoparticles have been intercalated between the layers of MgAl-LDH.
FIG. 6 shows Bi obtained in example 1 of the present invention2WO6Intercalation MgAl-LDH material and pure Bi prepared by comparative example2WO6A fluorescence spectrogram of the pure MgAl-LDH powder; as can be seen from FIG. 6, Bi2WO6the/MgAl-LDH has the lowest fluorescence intensity, so the recombination efficiency of the electron-hole pair is the lowest.
FIG. 7 is a drawing showingBi obtained in inventive example 12WO6Degradation efficiency graph of intercalated MgAl-LDH material on methyl orange (in degradation test, the concentration of the methyl orange is 50mg/L, Bi is2WO6The dosage of the intercalated MgAl-LDH material is as follows: 1g/L), as can be seen from FIG. 7, use of Bi2WO6When the/MgAl-LDH material is used for treating the methyl orange wastewater, the degradation rate of the methyl orange in 2 hours almost reaches 100 percent, and Bi is used2WO6(prepared by a comparative example) the degradation rate of methyl orange in 2h is only about 30 percent, which shows that Bi is added to the solution2WO6The nano particles are loaded between MgAl-LDH layers, so that Bi is greatly improved2WO6the photocatalytic performance of (a).
Bi obtained in examples 2 to 42WO6The intercalated MgAl-LDH material is subjected to structure and performance characterization, the result is similar to that of example 1, and the products prepared in examples 2-4 are Bi2WO6Intercalation of nanoparticles into MgAl-LDH structure, and relative to pure Bi2WO6In other words, the catalytic performance is greatly improved.
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (10)
1. bi2WO6The preparation method of the intercalated MgAl-LDH material is characterized by comprising the following steps:
Dissolving a magnesium source and an aluminum source in water to obtain a solution A; dissolving alkali in water to obtain a solution B; dissolving a tungsten source in water to obtain a solution C;
Dropwise adding the solution A and the solution B into the solution C at the same time, performing a first hydrothermal reaction, and performing first solid-liquid separation to obtain WO4 2-Intercalation MgAl-LDH powder;
Subjecting said WO to4 2-dispersing the intercalated MgAl-LDH powder and a bismuth source into water, carrying out a second hydrothermal reaction on the obtained suspension, and carrying out a second solid-liquid separation to obtain Bi2WO6Intercalation MgAl-LDH material.
2. The production method according to claim 1, wherein the magnesium source is magnesium nitrate, magnesium sulfate, or magnesium chloride; the aluminum source is aluminum nitrate, aluminum sulfate or aluminum polychloride; the alkali is sodium hydroxide or potassium hydroxide; the tungsten source is sodium tungstate or ammonium tungstate; the bismuth source is bismuth nitrate or bismuth trichloride.
3. The method according to claim 1 or 2, wherein the molar ratio of Mg to Al in the solution A is (2-2.2): 1; the total amount of Mg and Al in the solution A and OH in the solution B-The molar ratio of (1) to (2.3-2.4); the molar ratio of the total amount of Mg and Al in the solution A to W in the solution C is 1: (1.1-1.2); the molar ratio of Bi in the bismuth source to W in the solution C is (1-3): 1.
4. The method according to claim 1, wherein the specific operation of simultaneously adding dropwise the solution A and the solution B to the solution C is: and dropwise adding the solution A into the solution C under the conditions of constant temperature of 50-70 ℃ and stirring speed of 150-500 r/min, and simultaneously dropwise adding the solution B to control the pH value of the mixed solution to be 8-11.
5. The preparation method according to claim 1, wherein the temperature of the first hydrothermal reaction is 130-160 ℃ and the time is 9-12 h.
6. The preparation method according to claim 1, wherein the temperature of the second hydrothermal reaction is 200 to 210 ℃ and the time is 15 to 24 hours.
7. The preparation method according to claim 1, wherein the first solid-liquid separation and the second solid-liquid separation are performed by centrifugation at 4000 to 10000r/min independently; the centrifugation time is independently 5-10 min.
8. The method according to claim 1 or 7, wherein after the first solid-liquid separation and the second solid-liquid separation, the method further comprises freeze-drying the obtained solid product.
9. Bi produced by the production method according to any one of claims 1 to 82WO6An intercalated MgAl-LDH material, comprising MgAl-LDH and Bi between the MgAl-LDH layers2WO6And (3) nanoparticles.
10. the Bi of claim 92WO6The intercalated MgAl-LDH material is applied to the treatment of dye wastewater.
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