CN117599777A - Tungsten bismuth molybdate solid solution photocatalyst and preparation method thereof - Google Patents
Tungsten bismuth molybdate solid solution photocatalyst and preparation method thereof Download PDFInfo
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- 239000011941 photocatalyst Substances 0.000 title claims abstract description 63
- 239000006104 solid solution Substances 0.000 title claims abstract description 59
- WUTHJWCAESRVMV-UHFFFAOYSA-N [W].[Bi] Chemical compound [W].[Bi] WUTHJWCAESRVMV-UHFFFAOYSA-N 0.000 title claims abstract description 55
- 238000002360 preparation method Methods 0.000 title claims abstract description 29
- 239000000243 solution Substances 0.000 claims abstract description 119
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims abstract description 78
- 238000003756 stirring Methods 0.000 claims abstract description 34
- 230000015556 catabolic process Effects 0.000 claims abstract description 24
- 238000006731 degradation reaction Methods 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 20
- 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 abstract description 18
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 18
- 238000001816 cooling Methods 0.000 claims abstract description 16
- FBXVOTBTGXARNA-UHFFFAOYSA-N bismuth;trinitrate;pentahydrate Chemical compound O.O.O.O.O.[Bi+3].[O-][N+]([O-])=O.[O-][N+]([O-])=O.[O-][N+]([O-])=O FBXVOTBTGXARNA-UHFFFAOYSA-N 0.000 claims abstract description 15
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 12
- 238000005406 washing Methods 0.000 claims abstract description 12
- 235000015393 sodium molybdate Nutrition 0.000 claims abstract description 11
- 239000011684 sodium molybdate Substances 0.000 claims abstract description 11
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 9
- 239000008367 deionised water Substances 0.000 claims description 15
- 229910021641 deionized water Inorganic materials 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 14
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 9
- 239000002245 particle Substances 0.000 claims description 9
- 238000006243 chemical reaction Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 3
- 238000003760 magnetic stirring Methods 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 14
- 239000000463 material Substances 0.000 abstract description 13
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 abstract description 9
- 229910052760 oxygen Inorganic materials 0.000 abstract description 9
- 239000001301 oxygen Substances 0.000 abstract description 9
- 230000003197 catalytic effect Effects 0.000 abstract description 2
- 239000012855 volatile organic compound Substances 0.000 description 14
- 230000000052 comparative effect Effects 0.000 description 13
- 230000000593 degrading effect Effects 0.000 description 10
- 230000000694 effects Effects 0.000 description 10
- 229910052797 bismuth Inorganic materials 0.000 description 8
- JCXGWMGPZLAOME-UHFFFAOYSA-N bismuth atom Chemical compound [Bi] JCXGWMGPZLAOME-UHFFFAOYSA-N 0.000 description 8
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 8
- RWVGQQGBQSJDQV-UHFFFAOYSA-M sodium;3-[[4-[(e)-[4-(4-ethoxyanilino)phenyl]-[4-[ethyl-[(3-sulfonatophenyl)methyl]azaniumylidene]-2-methylcyclohexa-2,5-dien-1-ylidene]methyl]-n-ethyl-3-methylanilino]methyl]benzenesulfonate Chemical compound [Na+].C1=CC(OCC)=CC=C1NC1=CC=C(C(=C2C(=CC(C=C2)=[N+](CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=2C(=CC(=CC=2)N(CC)CC=2C=C(C=CC=2)S([O-])(=O)=O)C)C=C1 RWVGQQGBQSJDQV-UHFFFAOYSA-M 0.000 description 7
- 239000003054 catalyst Substances 0.000 description 6
- DKUYEPUUXLQPPX-UHFFFAOYSA-N dibismuth;molybdenum;oxygen(2-) Chemical compound [O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[O-2].[Mo].[Mo].[Bi+3].[Bi+3] DKUYEPUUXLQPPX-UHFFFAOYSA-N 0.000 description 6
- 238000012360 testing method Methods 0.000 description 6
- PBYZMCDFOULPGH-UHFFFAOYSA-N tungstate Chemical compound [O-][W]([O-])(=O)=O PBYZMCDFOULPGH-UHFFFAOYSA-N 0.000 description 6
- 238000002441 X-ray diffraction Methods 0.000 description 5
- 239000000969 carrier Substances 0.000 description 5
- 238000005265 energy consumption Methods 0.000 description 5
- 239000004005 microsphere Substances 0.000 description 5
- 230000005012 migration Effects 0.000 description 5
- 238000013508 migration Methods 0.000 description 5
- 239000002135 nanosheet Substances 0.000 description 5
- 238000007146 photocatalysis Methods 0.000 description 4
- 239000002994 raw material Substances 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- 238000000926 separation method Methods 0.000 description 4
- 238000009827 uniform distribution Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- 239000013078 crystal Substances 0.000 description 3
- 238000004090 dissolution Methods 0.000 description 3
- 239000007789 gas Substances 0.000 description 3
- 150000002500 ions Chemical class 0.000 description 3
- 238000001782 photodegradation Methods 0.000 description 3
- 230000008569 process Effects 0.000 description 3
- 238000005215 recombination Methods 0.000 description 3
- 230000006798 recombination Effects 0.000 description 3
- CURLTUGMZLYLDI-UHFFFAOYSA-N Carbon dioxide Chemical compound O=C=O CURLTUGMZLYLDI-UHFFFAOYSA-N 0.000 description 2
- 238000010521 absorption reaction Methods 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 238000002474 experimental method Methods 0.000 description 2
- 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 description 2
- 230000004298 light response Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 229910052750 molybdenum Inorganic materials 0.000 description 2
- 230000003647 oxidation Effects 0.000 description 2
- 238000007254 oxidation reaction Methods 0.000 description 2
- 230000001590 oxidative effect Effects 0.000 description 2
- 238000013032 photocatalytic reaction Methods 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000001737 promoting effect Effects 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 241001198704 Aurivillius Species 0.000 description 1
- 206010007269 Carcinogenicity Diseases 0.000 description 1
- 241000282414 Homo sapiens Species 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- IKHGUXGNUITLKF-XPULMUKRSA-N acetaldehyde Chemical compound [14CH]([14CH3])=O IKHGUXGNUITLKF-XPULMUKRSA-N 0.000 description 1
- 238000005054 agglomeration Methods 0.000 description 1
- 230000002776 aggregation Effects 0.000 description 1
- 239000000809 air pollutant Substances 0.000 description 1
- 231100001243 air pollutant Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000001569 carbon dioxide Substances 0.000 description 1
- 229910002092 carbon dioxide Inorganic materials 0.000 description 1
- 230000007670 carcinogenicity Effects 0.000 description 1
- 231100000260 carcinogenicity Toxicity 0.000 description 1
- 238000007084 catalytic combustion reaction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 239000006184 cosolvent Substances 0.000 description 1
- 125000004122 cyclic group Chemical group 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000005034 decoration Methods 0.000 description 1
- 238000009826 distribution Methods 0.000 description 1
- 238000005516 engineering process Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 238000009776 industrial production Methods 0.000 description 1
- 238000005342 ion exchange Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000012423 maintenance Methods 0.000 description 1
- 230000014759 maintenance of location Effects 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- WSFSSNUMVMOOMR-NJFSPNSNSA-N methanone Chemical compound O=[14CH2] WSFSSNUMVMOOMR-NJFSPNSNSA-N 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 description 1
- 239000011943 nanocatalyst Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 238000006053 organic reaction Methods 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 239000002957 persistent organic pollutant Substances 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 239000000376 reactant Substances 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
- 238000001878 scanning electron micrograph Methods 0.000 description 1
- 238000001338 self-assembly Methods 0.000 description 1
- 238000005245 sintering Methods 0.000 description 1
- 239000007790 solid phase Substances 0.000 description 1
- 238000001179 sorption measurement Methods 0.000 description 1
- 238000002336 sorption--desorption measurement Methods 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- WFKWXMTUELFFGS-UHFFFAOYSA-N tungsten Chemical compound [W] WFKWXMTUELFFGS-UHFFFAOYSA-N 0.000 description 1
- 239000010937 tungsten Substances 0.000 description 1
Classifications
-
- 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
- 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
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G41/00—Compounds of tungsten
- C01G41/006—Compounds containing, besides tungsten, two or more other elements, with the exception of oxygen or hydrogen
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/64—Nanometer sized, i.e. from 1-100 nanometer
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2006/00—Physical properties of inorganic compounds
- C01P2006/12—Surface area
Abstract
The invention relates to the technical field of catalytic materials, in particular to a tungsten bismuth molybdate solid solution photocatalyst and a preparation method thereof. The preparation method comprises the following steps: bismuth nitrate pentahydrate is dissolved in dilute nitric acid solution and stirred uniformly to obtain solution A; dissolving sodium tungstate dihydrate and sodium molybdate with different molar ratios in water, and uniformly stirring to obtain a solution B; adding the solution B into the solution A, and uniformly stirring to obtain a solution C; adding HTAB into the solution C, and uniformly stirring to obtain a solution D; and (3) carrying out hydrothermal reaction on the solution D, cooling to room temperature, taking out the product, centrifugally washing and drying to obtain the tungsten-bismuth molybdate solid solution photocatalyst. The preparation method of the tungsten bismuth molybdate solid solution photocatalyst is simple, low in cost and controllable in conditions, and the obtained product has stable structure, small size, rich specific surface area and surface oxygen vacancies, and shows excellent photocatalytic performance and excellent cycle performance stability for degradation of gaseous toluene.
Description
Technical Field
The invention relates to the technical field of catalytic materials, in particular to a tungsten bismuth molybdate solid solution photocatalyst and a preparation method thereof.
Background
Volatile organic compounds (volatile organic compounds, VOCs), such as benzene, toluene, formaldehyde, and acetaldehyde, are common air pollutants, which are mainly derived from industrial production and architectural decoration materials. VOCs have strong toxicity and carcinogenicity, and cause serious harm to life and living environment of human beings. In recent decades, there has been a great deal of attention on how to eliminate VOCs, and related personnel use various techniques such as physical adsorption, chemical absorption, and catalytic combustion to eliminate VOCs. However, the conventional technique has low efficiency in removing VOCs. Thus, there is an urgent need to develop more efficient, cost effective and environmentally friendly VOCs abatement techniques.
Photocatalysis is a green and low-energy-consumption process, has wide application prospect, and can realize various organic reactions through photocatalysis technology under the conditions of low temperature, low pressure and air, and finally convert pollutants into water and carbon dioxide. The principle of photocatalytic oxidation is to excite a semiconductor with light, and electrons and holes generated by the semiconductor and other active oxygen can participate in oxidation-reduction reactions.
In recent years, flower-like microsphere semiconductor materials formed by self-assembly of two-dimensional (2D) nanosheets are widely applied to the field of photocatalysis, such as photocatalysis for fixing N 2 Organic synthesis, decomposition of water and reduction of CO 2 And degrading contaminants, etc. Compared with the two-dimensional nano-sheet, the three-dimensional flower-shaped microsphere material has larger specific surface area and can provide more active sites for catalytic reaction. In the publicAmong the metal oxide semiconductor materials responsive to a plurality of visible light, bismuth molybdate (Bi 2 MoO 6 ) And bismuth tungstate (Bi) 2 WO 6 ) Belonging to Aurivillius family of layered perovskite, having the general formula Bi 2 A n-1 B n O 3n+3 Has excellent photocatalytic degradation performance. Bi (Bi) 2 WO 6 As a visible light photocatalyst, it can be used for pollutant degradation, however, due to its high photo-generated carrier recombination rate, a wide band gap and a absorbing edge of only 460nm, the visible light utilization efficiency is greatly limited. Bi in the related art 2 MoO 6 Is used as a visible light photocatalyst, the absorption edge of which can be extended to 520nm, and Bi 2 MoO 6 Has a specific Bi ratio of 2 WO 6 The much smaller band gap is a more ideal photocatalyst from the viewpoint of utilizing visible light, but its photocatalytic activity is much lower than Bi 2 WO 6 . Because the radii of W and Mo ions are very close, a flower-shaped microsphere solid solution structure with larger specific surface area can be formed by replacing part of Mo ions with W ions, the advantages of two single materials can be simultaneously maintained, and Bi is improved 2 MoO 6 While improving the oxidizing property of Bi 2 WO 6 The visible light utilization rate of the material can be better improved.
Common preparation of Bi 2 W x Mo 1-x O 6 The solid solution photocatalyst has the advantages of complex preparation process flow, high cost of required raw materials, high consumption of a large amount of energy, centimeter-level grain size of the obtained material, large grain size and low photocatalytic activity, and the solid solution photocatalyst has the advantages of hydrothermal method, solid phase sintering method, room temperature precipitation method, ion exchange method, microwave hydrothermal method and the like.
Disclosure of Invention
The invention provides a tungsten bismuth molybdate solid solution photocatalyst and a preparation method thereof, which are used for solving the problems of large energy consumption, long time consumption, complex preparation steps, large size of the obtained material, poor photocatalytic activity and the like in the existing preparation method of the tungsten bismuth molybdate solid solution photocatalyst.
According to a first aspect of the present invention, the present invention provides a method for preparing a bismuth tungsten molybdate solid solution photocatalyst, comprising the steps of:
bismuth nitrate pentahydrate is dissolved in dilute nitric acid solution and stirred uniformly to obtain solution A;
dissolving sodium tungstate dihydrate and sodium molybdate with different molar ratios in water, and uniformly stirring to obtain a solution B;
adding the obtained solution B into the solution A, and uniformly stirring to obtain a solution C;
adding HTAB into the obtained solution C, and uniformly stirring to obtain solution D;
and carrying out hydrothermal reaction on the obtained solution D, cooling to room temperature, taking out the product, centrifugally washing, and drying to obtain the tungsten-bismuth molybdate solid solution photocatalyst.
In the scheme, the preparation method of the tungsten-bismuth molybdate solid solution photocatalyst comprises the steps of preparing the bismuth-containing solution A, preparing the tungsten-molybdenum-containing solution B, mixing the solution A and the solution B to obtain the solution C, adding the solution C into the HTAB to modify to obtain the solution D, introducing surface oxygen vacancies into the material by the addition of the HTAB, better promoting the separation and migration of photo-generated carriers by the existence of the oxygen vacancies, improving the activity of photocatalytic degradation of gaseous toluene, and carrying out one-step hydrothermal reaction on the solution D to enable the 2D nanosheet raw material to be self-assembled into the 3D flower-shaped microsphere tungsten-bismuth molybdate solid solution photocatalyst. Compared with the existing preparation method, the preparation method is simple, does not need multiple steps to be sequentially carried out, does not need the synergistic effect of high temperature and cosolvent, reduces the complexity of the steps to a great extent, and reduces the energy consumption and the raw material cost. The tungsten bismuth molybdate solid solution photocatalyst prepared by the preparation method has rich surface oxygen vacancies, can regulate the energy band structure, improve the light absorption performance and increase the active site, and is beneficial to promoting the separation of photo-generated carriers, thereby improving the activity of photocatalytic degradation of organic pollutants and improving the degradation speed and degradation rate of the p-gaseous toluene.
Further, in the solution B, the molar ratio of the sodium tungstate dihydrate to the sodium molybdate is (1-7): (1-7), preferably 1: (1-7), more preferably 1:3.
In the scheme, the molar ratio of the sodium tungstate dihydrate to the sodium molybdate in the solution B is limited within a reasonable range, so that the proportion of tungsten to molybdenum in the tungsten-bismuth molybdate solid solution photocatalyst can be controlled within the reasonable range, and the tungsten-bismuth molybdate solid solution photocatalyst with smaller particle size, uniform distribution, excellent performance and low cost can be obtained. When the molar ratio of sodium tungstate dihydrate to sodium molybdate in the solution B is too low, the prepared sample easily forms stacked nano-sheets with larger particle size, thicker layer thickness and smaller specific surface area; when the molar ratio of sodium tungstate dihydrate to sodium molybdate in the solution B is too high, the prepared sample is uneven in distribution and poor in crystallinity, and the nanoparticles generate obvious agglomeration phenomenon.
Further, in the solution C, the molar ratio of bismuth nitrate pentahydrate, sodium tungstate dihydrate, sodium molybdate and HTAB is 40: (2.5-20): (2.5-20): (0.2-20), preferably 40 (2.5-10): (10-17.5): (2-10), more preferably 40:5:15:2.74.
in the scheme, the molar ratio of bismuth nitrate pentahydrate, sodium tungstate dihydrate, sodium molybdate and HTAB in the solution C is controlled within a reasonable range value, so that the tungsten-bismuth molybdate solid solution photocatalyst with smaller particle size, uniform distribution, excellent performance and low cost is more favorable to be obtained.
Further, the temperature of the hydrothermal reaction is 150-190 ℃ and the time is 10-15h; preferably, the temperature of the hydrothermal reaction is 170 ℃ and the time is 12 hours.
In the scheme, the temperature and time of the hydrothermal reaction are controlled within reasonable range values, so that the improvement of the hydrothermal reaction efficiency is facilitated, and the tungsten-bismuth molybdate solid solution photocatalyst with smaller particle size, uniform distribution and excellent performance is more facilitated to be obtained.
Further, the molar concentration of the dilute nitric acid solution is 0.05-0.06mol/L, preferably 0.057mol/L.
In the scheme, the molar concentration of the dilute nitric acid solution is controlled within a reasonable range value, so that the bismuth nitrate is dissolved.
Further, the molar concentration of bismuth nitrate pentahydrate in the solution A is 0.1-0.15mol/L, preferably 0.1143mol/L.
In the scheme, the molar concentration of bismuth nitrate pentahydrate in the solution A is limited within a reasonable range, so that the dissolution of bismuth nitrate is facilitated, and the subsequent mixing and reaction are facilitated.
Further, stirring conditions for obtaining the solution a, the solution B, the solution C, and the solution D each independently satisfy at least one of the following features (1) to (3):
(1) The stirring time is 0.5-1.5h, preferably 1h;
(2) Stirring at room temperature;
(3) The stirring adopts magnetic stirring.
In the scheme, the time, the temperature and the mode in the stirring condition are limited within reasonable range values, so that the dissolution of reactants is facilitated, and a mild and efficient dissolution process is facilitated.
Further, natural cooling is adopted for cooling after the reaction of the solution D;
and/or the solvent used for centrifugal washing of the product is deionized water and/or absolute ethyl alcohol.
In the scheme, natural cooling is adopted by limiting cooling after the solution D is reacted, so that the maintenance of the morphology of the tungsten bismuth molybdate solid solution photocatalyst in the cooling process is facilitated. The solvent adopted by the centrifugal washing of the limited product is deionized water and/or absolute ethyl alcohol, so that the introduction of impurities into the tungsten bismuth molybdate solid solution photocatalyst can be avoided, and the performance of the tungsten bismuth molybdate solid solution photocatalyst is further influenced.
According to a second aspect of the invention, the invention also provides a tungsten bismuth molybdate solid solution photocatalyst prepared by the preparation method.
Further, the particle diameter of the tungsten bismuth molybdate solid solution photocatalyst is 50-80nm, specific surface area of 30-40m 2 /g; the degradation rate of the tungsten bismuth molybdate solid solution photocatalyst to gaseous toluene is more than 95% within 3 hours.
The tungsten bismuth molybdate solid solution photocatalyst is a photocatalyst which has the advantages of wide visible light response range, small size, large specific surface area, low electron-hole recombination rate and high photogenerated carrier migration efficiency, has obvious effect on degrading volatile organic compounds, and can realize the degradation rate of p-gaseous toluene within 3 hours up to more than 95 percent.
The beneficial effects of the invention are as follows:
(1) The preparation method of the tungsten-bismuth molybdate solid solution photocatalyst is simple, the reaction condition is mild, the energy consumption is low, the morphology of the obtained tungsten-bismuth molybdate solid solution photocatalyst is controllable, the particle size is small, the specific surface area is large, the tungsten-bismuth molybdate solid solution photocatalyst shows excellent photocatalytic performance and excellent cycle performance retention under the simulated actual environment (temperature: room temperature; light source: visible light), after four cycle tests, the crystal structure is not obviously changed, the degradation rate can still be kept above 90 percent, and the tungsten-bismuth molybdate solid solution photocatalyst has wide practical application value.
(2) The tungsten bismuth molybdate solid solution photocatalyst disclosed by the invention is rich in oxygen vacancies, meanwhile, the strong oxidizing property of bismuth tungstate and the strong visible light activity of bismuth molybdate are maintained, the recombination of electrons and holes is inhibited, and the migration efficiency of photo-generated carriers is improved. At the same time, the catalyst generates a large amount of active free radicals such as 1 O 2 (OH) and h + The bismuth-based photocatalyst with excellent photocatalytic performance has good application prospect and economic value in photocatalytic degradation of VOCs.
(3) The invention widens the visible light response range of single bismuth tungstate and the oxidation performance of single bismuth molybdate, and the photocatalytic activity of the tungsten bismuth molybdate nano catalyst for degrading gaseous toluene is 10-12 times of that of pure bismuth tungstate and 13-15 times of that of pure bismuth molybdate.
Drawings
In order to more clearly illustrate the invention or the technical solutions of the prior art, the following description will briefly explain the drawings used in the embodiments or the description of the prior art, and it is obvious that the drawings in the following description are some embodiments of the invention, and other drawings can be obtained according to the drawings without inventive effort for a person skilled in the art.
FIG. 1 shows Bi prepared in examples 1 to 3, example 5, example 6 and comparative examples 1 to 2 of the present invention 2 W x Mo 1-x O 6 XRD pattern of (b);
FIG. 2 shows Bi prepared in example 1 of the present invention 2 W x Mo 1-x O 6 SEM pictures at different magnification;
FIG. 3 shows Bi prepared in example 1 and comparative example 3 of the present invention 2 W x Mo 1-x O 6 An EPR map of (c);
FIG. 4 shows Bi prepared in examples 1 to 3, example 5, example 6 and comparative examples 1 to 2 according to the present invention 2 W x Mo 1-x O 6 A degradation curve for degrading gaseous toluene under visible light;
FIG. 5 shows Bi prepared in examples 1, 4, 7 and comparative example 3 of the present invention 2 W x Mo 1-x O 6 A degradation curve for degrading gaseous toluene under visible light;
FIG. 6 shows Bi prepared in example 1 and examples 8 to 11 of the present invention 2 W x Mo 1-x O 6 A degradation curve for degrading gaseous toluene under visible light;
FIG. 7 is a graph of the photodegradation constants obtained from the degradation data of FIG. 4;
FIG. 8 shows Bi prepared in example 1 of the present invention 2 W x Mo 1-x O 6 Four cycle degradation curves for degrading gaseous toluene under visible light;
FIG. 9 shows Bi prepared in example 1 of the present invention 2 W x Mo 1-x O 6 XRD patterns before and after four cycles of degradation of gaseous toluene under visible light.
Detailed Description
For the purpose of making the objects, technical solutions and advantages of the present invention more apparent, the technical solutions of the present invention will be clearly and completely described below with reference to the accompanying drawings, and it is apparent that the described embodiments are some embodiments of the present invention, not all embodiments. All other embodiments, which can be made by those skilled in the art based on the embodiments of the invention without making any inventive effort, are intended to be within the scope of the invention.
Example 1
The embodiment provides a preparation method of a tungsten bismuth molybdate solid solution photocatalyst, which comprises the following steps:
(1) 4mmol of bismuth nitrate pentahydrate is dissolved in 35mL of dilute nitric acid solution with the concentration of 0.057mol/L and stirred for 1h to obtain solution A;
(2) Dissolving 0.5mmol of sodium tungstate dihydrate and 1.5mmol of sodium molybdate dihydrate in 35mL of deionized water, and stirring for 1h to obtain solution B;
(3) Dropping the solution B into the solution A, and stirring for 1h to obtain a solution C;
(4) Adding 0.1g of HTAB into the solution C, and stirring for 1 hour to obtain a solution D;
(5) Transferring the solution D into a polytetrafluoroethylene-lined hydrothermal reaction kettle, reacting at 170 ℃ for 12 hours, cooling to room temperature, taking out the product, centrifugally washing the product with deionized water and absolute ethyl alcohol for 3 times, and drying to obtain a sample, wherein the particle diameter of the sample is 50-80nm, and the specific surface area is 36.74m 2 /g。
Example 2
The embodiment provides a preparation method of a tungsten bismuth molybdate solid solution photocatalyst, which comprises the following steps:
(1) 4mmol of bismuth nitrate pentahydrate is dissolved in 35mL of dilute nitric acid solution with the concentration of 0.057mol/L and stirred for 1h to obtain solution A;
(2) Dissolving 0.25mmol of sodium tungstate dihydrate and 1.75mmol of sodium molybdate dihydrate in 35mL of deionized water, and stirring for 1h to obtain solution B;
(3) Dropping the solution B into the solution A, and stirring for 1h to obtain a solution C;
(4) Adding 0.1g of HTAB into the solution C, and stirring for 1h to obtain a solution D;
(5) Transferring the solution D into a polytetrafluoroethylene-lined hydrothermal reaction kettle, reacting for 12 hours at 170 ℃, cooling to room temperature, taking out the product, centrifugally washing the product with deionized water and absolute ethyl alcohol for 3 times, and drying to obtain a sample.
Example 3
The embodiment provides a preparation method of a tungsten bismuth molybdate solid solution photocatalyst, which comprises the following steps:
(1) 4mmol of bismuth nitrate pentahydrate is dissolved in 35mL of dilute nitric acid solution with the concentration of 0.057mol/L and stirred for 1h to obtain solution A;
(2) 1mmol of sodium tungstate dihydrate and 1mmol of sodium molybdate dihydrate are dissolved in 35mL of deionized water and stirred for 1h to obtain a solution B;
(3) Dropping the solution B into the solution A, and stirring for 1h to obtain a solution C;
(4) Adding 0.1g of HTAB into the solution C, and stirring for 1h to obtain a solution D;
(5) Transferring the solution D into a polytetrafluoroethylene-lined hydrothermal reaction kettle, reacting for 12 hours at 170 ℃, cooling to room temperature, taking out the product, centrifugally washing the product with deionized water and absolute ethyl alcohol for 3 times, and drying to obtain a sample.
Example 4
The embodiment provides a preparation method of a tungsten bismuth molybdate solid solution photocatalyst, which comprises the following steps:
(1) 4mmol of bismuth nitrate pentahydrate is dissolved in 35mL of dilute nitric acid solution with the concentration of 0.057mol/L and stirred for 1h to obtain solution A;
(2) Dissolving 0.5mmol of sodium tungstate dihydrate and 1.5mmol of sodium molybdate dihydrate in 35mL of deionized water, and stirring for 1h to obtain solution B;
(3) Dropping the solution B into the solution A, and stirring for 1h to obtain a solution C;
(4) Adding 0.5g of HTAB into the solution C, and stirring for 1h to obtain a solution D;
(4) Transferring the solution D into a polytetrafluoroethylene-lined hydrothermal reaction kettle, reacting for 12 hours at 170 ℃, cooling to room temperature, taking out the product, centrifugally washing the product with deionized water and absolute ethyl alcohol for 3 times, and drying to obtain a sample.
Example 5
The molar ratio of sodium tungstate dihydrate to sodium molybdate dihydrate in step (2) of example 1 was adjusted to 3:1, the remainder being the same as in example 1.
Example 6
The molar ratio of sodium tungstate dihydrate to sodium molybdate dihydrate in step (2) of example 1 was adjusted to 7:1, the remainder being the same as in example 1.
Example 7
The amount of HTAB added in step (3) of example 1 was adjusted to 0.02g, and the remainder was the same as in example 1.
Example 8
The temperature in step (5) in example 3 was adjusted to 150℃and the rest was the same as in example 3.
Example 9
The temperature in step (5) in example 3 was adjusted to 160℃and the rest was the same as in example 3.
Example 10
The temperature in step (5) in example 3 was adjusted to 180℃and the rest was the same as in example 3.
Example 11
The temperature in step (5) in example 3 was adjusted to 190℃and the rest was the same as in example 3.
Comparative example 1
The preparation method of the bismuth tungstate solid solution photocatalyst comprises the following steps:
(1) 4mmol of bismuth nitrate pentahydrate is dissolved in 35mL of dilute nitric acid solution with the concentration of 0.057mol/L and stirred for 1h to obtain solution A;
(2) 2mmol of sodium tungstate dihydrate is dissolved in 35mL of deionized water and stirred for 1h to obtain solution B;
(3) Dropping the solution B into the solution A, and stirring for 1h to obtain a solution C;
(4) Adding 0.1g of HTAB into the solution C, and stirring for 1h to obtain a solution D;
(4) Transferring the solution D into a polytetrafluoroethylene-lined hydrothermal reaction kettle, reacting for 12 hours at 170 ℃, cooling to room temperature, taking out the product, centrifugally washing the product with deionized water and absolute ethyl alcohol for 3 times, and drying to obtain a sample.
Comparative example 2
The preparation method of the bismuth molybdate solid solution photocatalyst comprises the following steps:
(1) 4mmol of bismuth nitrate pentahydrate is dissolved in 35mL of dilute nitric acid solution with the concentration of 0.057mol/L and stirred for 1h to obtain solution A;
(2) 2mmol of sodium molybdate dihydrate is dissolved in 35mL of deionized water and stirred for 1h to obtain solution B;
(3) Dropping the solution B into the solution A, and stirring for 1h to obtain a solution C;
(4) Adding 0.1g of HTAB into the solution C, and stirring for 1h to obtain a solution D;
(4) Transferring the solution D into a polytetrafluoroethylene-lined hydrothermal reaction kettle, reacting for 12 hours at 170 ℃, cooling to room temperature, taking out the product, centrifugally washing the product with deionized water and absolute ethyl alcohol for 3 times, and drying to obtain a sample.
Comparative example 3
The amount of HTAB added in step (3) of example 1 was adjusted to 0g, and the remainder was the same as in example 1.
The catalyst samples prepared in examples 1 to 11 and comparative examples 1 to 3 were subjected to a gas-phase toluene degradation test (volatile organic compound degradation performance test in a closed test environment and under a visible light source condition, and photocatalytic performance of the samples was evaluated in detail) as follows:
(1) Uniformly distributing 0.2g of photocatalyst on a sample table, putting the sample table into a closed test cabin, introducing toluene gas with the concentration of 30ppm, and controlling the gas atmosphere and the humidity (0-50%) of the closed test cabin;
(2) After the reactor is placed for 1h in a dark place, the VOC gas reaches adsorption-desorption balance on the surface of the photocatalyst, then a light source (420 nm-780 nm) with visible light wavelength is applied to irradiate a catalyst sample, and the concentration of the VOC in a sealed environment is monitored every 30min, so that the photocatalytic degradation performance of the catalyst on the VOC is evaluated. The test results are shown in Table 1 and FIGS. 4 to 6.
Table 1 comparison of sample purification effects of examples 1 to 11 and comparative examples 1 to 3
As can be seen from the experimental results in Table 1, the tungsten bismuth molybdate solid solution photocatalyst of example 1 has the highest activity of degrading gaseous toluene under irradiation of visible light, and can achieve a degradation rate of up to 96.80% within 180min for 30ppm of gaseous toluene.
FIG. 1 is XRD patterns of examples 1-6 and comparative examples 1-2 using different ratios of raw materials. The successful preparation of bismuth tungstate, bismuth molybdate, and solid solution materials of bismuth tungsten molybdate in various proportions can be seen in fig. 1.
Fig. 2 is an SEM image of the bismuth tungsten molybdate solid solution photocatalyst prepared in example 1. As can be seen from fig. 2, the tungsten-bismuth molybdate solid solution photocatalyst has smaller particle size and uniform distribution, and is self-assembled into a 3D flower-shaped microsphere structure by a plurality of 2D nano sheets, and the structure has larger specific surface area, and can provide more active sites for catalytic reaction, thereby improving the activity of photocatalytic degradation of gaseous toluene.
FIG. 3 is an EPR graph of the bismuth tungsten molybdate solid solution photocatalyst prepared in example 1 and comparative example 3. (S1 is example 1 and S2 is comparative example 3) as can be seen from FIG. 3, the tungsten bismuth molybdate solid solution photocatalyst of the invention introduces surface oxygen vacancies into the material through HTAB modification, and the existence of the oxygen vacancies can better promote the separation and migration of photogenerated carriers, thereby improving the activity of photocatalytic degradation of gaseous toluene.
FIGS. 4 to 6 are degradation graphs of the solid solution photocatalyst of bismuth tungsten molybdate prepared in examples 1 to 11 and comparative examples 1 to 3 for degrading gaseous toluene under irradiation of visible light. By comparison, when the preparation temperature is 170 ℃, the W/Mo molar ratio is 1/3, and the HTAB addition amount is 0.1g, namely in the example 1, the prepared tungsten-bismuth molybdate solid solution photocatalyst has the highest activity of degrading gaseous toluene under the irradiation of visible light, and for 30ppm of gaseous toluene, the degradation rate can reach as high as 96.80 percent in 180 minutes.
FIG. 7 is a graph of the photo-degradation constants based on the degradation data of FIG. 4, as established and calculated for a quasi-first order kinetic model. In fig. 7, it can be seen that the photodegradation constant of the catalyst is significantly improved after the formation of the bismuth tungsten molybdate solid solution. Bi (Bi) 2 W 0.25 Mo 0.75 O 6 K value 0.0161min -1 Respectively pure Bi 2 WO 6 (0.00156min -1 ) 10.32 times of pure Bi 2 MoO 6 (0.00117min -1 ) 13.7 times of (1) indicating that sample Bi 2 W 0.25 Mo 0.75 O 6 Has excellent photocatalytic activity.
Fig. 8 to 9 are XRD patterns before and after 4 times of cyclic degradation curves of gaseous toluene under irradiation of visible light of the bismuth tungsten molybdate solid solution photocatalyst of example 1. As can be seen from FIG. 8, the tungsten bismuth molybdate solid solution photocatalyst of the invention has excellent cycle stability, can still maintain the degradation performance of more than 90% of the p-gaseous toluene after four total 12h cycle photocatalytic reactions, and has wide practical application prospect. As can be seen from fig. 9, the XRD spectra of the tungsten bismuth molybdate solid solution photocatalyst of the invention before and after four cycle experiments have no obvious difference, which shows that the tungsten bismuth molybdate solid solution photocatalyst has a stable crystal structure and excellent cycle stability.
In conclusion, the preparation method is simple, a large amount of energy consumption is not needed, the prepared tungsten bismuth molybdate solid solution photocatalyst is synthesized through hydrothermal one-step under the condition of physical stirring at room temperature, the prepared tungsten bismuth molybdate solid solution photocatalyst has a controllable crystal structure, a large specific surface area and rich surface oxygen vacancies, the active site of photocatalytic reaction is increased, and the separation and migration of photogenerated carriers are facilitated, so that the activity of photocatalytic degradation of gaseous toluene is improved, the degradation rate of 30ppm of gaseous toluene can be realized within 180min up to more than 95%, meanwhile, the catalyst also has excellent cycle stability, and the high degradation rate of more than 90% can be maintained after four times of cycle experiments.
Finally, it should be noted that: the above embodiments are only for illustrating the technical solution of the present invention, and are not limiting; although the invention has been described in detail with reference to the foregoing embodiments, it will be understood by those of ordinary skill in the art that: the technical scheme described in the foregoing embodiments can be modified or some technical features thereof can be replaced by equivalents; such modifications and substitutions do not depart from the spirit and scope of the technical solutions of the embodiments of the present invention.
Claims (10)
1. The preparation method of the tungsten bismuth molybdate solid solution photocatalyst is characterized by comprising the following steps of:
bismuth nitrate pentahydrate is dissolved in dilute nitric acid solution and stirred uniformly to obtain solution A;
dissolving sodium tungstate dihydrate and sodium molybdate with different molar ratios in water, and uniformly stirring to obtain a solution B;
adding the obtained solution B into the solution A, and uniformly stirring to obtain a solution C;
adding HTAB into the obtained solution C, and uniformly stirring to obtain solution D;
and carrying out hydrothermal reaction on the obtained solution D, cooling to room temperature, taking out the product, centrifugally washing, and drying to obtain the tungsten-bismuth molybdate solid solution photocatalyst.
2. The method according to claim 1, wherein the molar ratio of the sodium tungstate dihydrate to the sodium molybdate in the solution B is (1-7): (1-7), preferably 1: (1-7), more preferably 1:3.
3. The method according to claim 1, wherein the molar ratio of bismuth nitrate pentahydrate, sodium tungstate dihydrate, sodium molybdate and HTAB in solution C is 40: (2.5-20): (2.5-20): (0.2-20), preferably 40 (2.5-10): (10-17.5): (2-10), more preferably 40:5:15:2.74.
4. the preparation method according to claim 1, wherein the hydrothermal reaction is carried out at a temperature of 150-190 ℃ for 10-15 hours; preferably, the temperature of the hydrothermal reaction is 170 ℃ and the time is 12 hours.
5. The method according to claim 1, wherein the diluted nitric acid solution has a molar concentration of 0.05-0.06mol/L, preferably 0.057mol/L.
6. The preparation method according to claim 1, characterized in that the molar concentration of bismuth nitrate pentahydrate in the solution a is 0.1-0.15mol/L, preferably 0.1143mol/L.
7. The production method according to claim 1, wherein stirring conditions to obtain the solution a, the solution B, the solution C, and the solution D each independently satisfy at least one of the following features (1) to (3):
(1) The stirring time is 0.5-1.5h, preferably 1h;
(2) Stirring at room temperature;
(3) The stirring adopts magnetic stirring.
8. The method according to claim 1, wherein the cooling after the reaction of the solution D is natural cooling;
and/or the solvent used for centrifugal washing of the product is deionized water and/or absolute ethyl alcohol.
9. A bismuth tungsten molybdate solid solution photocatalyst prepared by the method of any one of claims 1-8.
10. The bismuth tungsten molybdate solid solution photocatalyst according to claim 9, wherein the particle diameter of the bismuth tungsten molybdate solid solution photocatalyst is 50 to 80nm and the specific surface area is 30 to 40m 2 /g; the degradation rate of the tungsten bismuth molybdate solid solution photocatalyst to gaseous toluene is more than 95% within 3 hours.
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