CN111760579A - Preparation method and application of tungsten-molybdenum bisulfide composite photocatalyst - Google Patents
Preparation method and application of tungsten-molybdenum bisulfide composite photocatalyst Download PDFInfo
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- CN111760579A CN111760579A CN202010665872.5A CN202010665872A CN111760579A CN 111760579 A CN111760579 A CN 111760579A CN 202010665872 A CN202010665872 A CN 202010665872A CN 111760579 A CN111760579 A CN 111760579A
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- 239000002131 composite material Substances 0.000 title claims abstract description 38
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 31
- 238000002360 preparation method Methods 0.000 title claims abstract description 21
- -1 tungsten-molybdenum bisulfide Chemical compound 0.000 title claims abstract description 14
- 230000029087 digestion Effects 0.000 claims abstract description 20
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- 239000011259 mixed solution Substances 0.000 claims abstract description 14
- 238000003756 stirring Methods 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- DOIKGWMZXKJLJV-UHFFFAOYSA-N [W].[Mo](=S)=S Chemical compound [W].[Mo](=S)=S DOIKGWMZXKJLJV-UHFFFAOYSA-N 0.000 claims abstract description 11
- 239000000243 solution Substances 0.000 claims abstract description 8
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 7
- 238000001816 cooling Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 7
- 239000002244 precipitate Substances 0.000 claims abstract description 7
- 238000005406 washing Methods 0.000 claims abstract description 7
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 5
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011593 sulfur Substances 0.000 claims abstract description 5
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 5
- 150000003657 tungsten Chemical class 0.000 claims abstract description 5
- 150000002500 ions Chemical class 0.000 claims description 23
- UGFAIRIUMAVXCW-UHFFFAOYSA-N Carbon monoxide Chemical compound [O+]#[C-] UGFAIRIUMAVXCW-UHFFFAOYSA-N 0.000 claims description 13
- 239000003546 flue gas Substances 0.000 claims description 13
- 229910001385 heavy metal Inorganic materials 0.000 claims description 11
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 8
- APUPEJJSWDHEBO-UHFFFAOYSA-P ammonium molybdate Chemical compound [NH4+].[NH4+].[O-][Mo]([O-])(=O)=O APUPEJJSWDHEBO-UHFFFAOYSA-P 0.000 claims description 5
- 235000018660 ammonium molybdate Nutrition 0.000 claims description 5
- 239000011609 ammonium molybdate Substances 0.000 claims description 5
- 229940010552 ammonium molybdate Drugs 0.000 claims description 5
- XSQUKJJJFZCRTK-UHFFFAOYSA-N Urea Natural products NC(N)=O XSQUKJJJFZCRTK-UHFFFAOYSA-N 0.000 claims description 4
- YOUIDGQAIILFBW-UHFFFAOYSA-J tetrachlorotungsten Chemical compound Cl[W](Cl)(Cl)Cl YOUIDGQAIILFBW-UHFFFAOYSA-J 0.000 claims description 4
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 3
- FQNHWXHRAUXLFU-UHFFFAOYSA-N carbon monoxide;tungsten Chemical group [W].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-].[O+]#[C-] FQNHWXHRAUXLFU-UHFFFAOYSA-N 0.000 claims description 3
- 230000002829 reductive effect Effects 0.000 claims description 3
- 235000015393 sodium molybdate Nutrition 0.000 claims description 3
- 239000011684 sodium molybdate Substances 0.000 claims description 3
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical compound [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 3
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 3
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims description 3
- XMVONEAAOPAGAO-UHFFFAOYSA-N sodium tungstate Chemical compound [Na+].[Na+].[O-][W]([O-])(=O)=O XMVONEAAOPAGAO-UHFFFAOYSA-N 0.000 claims description 3
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 3
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 3
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 0.000 claims description 2
- 239000000463 material Substances 0.000 description 21
- 230000001699 photocatalysis Effects 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 12
- 229910000070 arsenic hydride Inorganic materials 0.000 description 7
- 230000003197 catalytic effect Effects 0.000 description 7
- 238000000034 method Methods 0.000 description 7
- 238000000120 microwave digestion Methods 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 229910052961 molybdenite Inorganic materials 0.000 description 4
- 229910052982 molybdenum disulfide Inorganic materials 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 239000011148 porous material Substances 0.000 description 4
- 239000000779 smoke Substances 0.000 description 4
- 239000000126 substance Substances 0.000 description 4
- 150000004763 sulfides Chemical class 0.000 description 4
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229910052976 metal sulfide Inorganic materials 0.000 description 3
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 description 3
- 230000003647 oxidation Effects 0.000 description 3
- 238000007254 oxidation reaction Methods 0.000 description 3
- 238000007146 photocatalysis Methods 0.000 description 3
- 238000001878 scanning electron micrograph Methods 0.000 description 3
- 239000004065 semiconductor Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- 239000005997 Calcium carbide Substances 0.000 description 2
- 229910052785 arsenic Inorganic materials 0.000 description 2
- RQNWIZPPADIBDY-UHFFFAOYSA-N arsenic atom Chemical compound [As] RQNWIZPPADIBDY-UHFFFAOYSA-N 0.000 description 2
- 230000008901 benefit Effects 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000006243 chemical reaction Methods 0.000 description 2
- 239000013078 crystal Substances 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 230000036541 health Effects 0.000 description 2
- 238000001027 hydrothermal synthesis 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
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 230000009467 reduction Effects 0.000 description 2
- CLZWAWBPWVRRGI-UHFFFAOYSA-N tert-butyl 2-[2-[2-[2-[bis[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]amino]-5-bromophenoxy]ethoxy]-4-methyl-n-[2-[(2-methylpropan-2-yl)oxy]-2-oxoethyl]anilino]acetate Chemical compound CC1=CC=C(N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)C(OCCOC=2C(=CC=C(Br)C=2)N(CC(=O)OC(C)(C)C)CC(=O)OC(C)(C)C)=C1 CLZWAWBPWVRRGI-UHFFFAOYSA-N 0.000 description 2
- 229910052723 transition metal Inorganic materials 0.000 description 2
- 229910052721 tungsten Inorganic materials 0.000 description 2
- 229910000640 Fe alloy Inorganic materials 0.000 description 1
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000000571 coke Substances 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 239000000356 contaminant Substances 0.000 description 1
- 230000008878 coupling Effects 0.000 description 1
- 230000001808 coupling effect Effects 0.000 description 1
- 238000010168 coupling process Methods 0.000 description 1
- 238000005859 coupling reaction Methods 0.000 description 1
- 238000003795 desorption Methods 0.000 description 1
- 230000002708 enhancing effect Effects 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 231100000086 high toxicity Toxicity 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 239000011733 molybdenum Substances 0.000 description 1
- 239000002135 nanosheet Substances 0.000 description 1
- 230000001590 oxidative effect Effects 0.000 description 1
- 239000002367 phosphate rock Substances 0.000 description 1
- OJMIONKXNSYLSR-UHFFFAOYSA-N phosphorous acid Chemical compound OP(O)O OJMIONKXNSYLSR-UHFFFAOYSA-N 0.000 description 1
- 238000013032 photocatalytic reaction Methods 0.000 description 1
- 238000000746 purification Methods 0.000 description 1
- 230000008707 rearrangement Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 238000000926 separation method Methods 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 239000004094 surface-active agent Substances 0.000 description 1
- 230000002195 synergetic effect Effects 0.000 description 1
- 238000003786 synthesis reaction Methods 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
- KPGXUAIFQMJJFB-UHFFFAOYSA-H tungsten hexachloride Chemical compound Cl[W](Cl)(Cl)(Cl)(Cl)Cl KPGXUAIFQMJJFB-UHFFFAOYSA-H 0.000 description 1
- 239000011701 zinc Substances 0.000 description 1
- 229910052725 zinc Inorganic materials 0.000 description 1
Images
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
- B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
- B01J27/04—Sulfides
- B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
- B01J27/051—Molybdenum
-
- 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
- B01D53/8665—Removing heavy metals or compounds thereof, e.g. mercury
-
- B01J35/39—
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/08—Heat treatment
- B01J37/10—Heat treatment in the presence of water, e.g. steam
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/34—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation
- B01J37/341—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation
- B01J37/344—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy
- B01J37/346—Irradiation by, or application of, electric, magnetic or wave energy, e.g. ultrasonic waves ; Ionic sputtering; Flame or plasma spraying; Particle radiation making use of electric or magnetic fields, wave energy or particle radiation of electromagnetic wave energy of microwave energy
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2257/00—Components to be removed
- B01D2257/60—Heavy metals or heavy metal compounds
- B01D2257/602—Mercury or mercury compounds
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01D—SEPARATION
- B01D2258/00—Sources of waste gases
- B01D2258/02—Other waste gases
- B01D2258/0283—Flue gases
Abstract
The invention discloses a preparation method of a tungsten-molybdenum bisulfide composite photocatalyst, belonging to the technical field of photocatalysts; under the condition of stirring, respectively adding tungsten salt, molybdate and a sulfur source into deionized water for dissolving, and stirring until the color of the solution is not deepened any more to obtain a mixed solution; placing the mixed solution into a digestion tank, digesting for 20-60 min under the microwave condition at the temperature of 150-200 ℃, cooling, taking out a precipitate, sequentially washing with deionized water and absolute ethyl alcohol, and drying to obtain the tungsten-molybdenum disulfide composite photocatalyst.
Description
Technical Field
The invention relates to a preparation method of a double-sulfide efficient adsorption synergistic photocatalytic material for removing gaseous heavy metals in reductive flue gas, belonging to the technical field of photocatalysis.
Background
Heavy metal pollution seriously affects human health and environmental safety, and atmospheric heavy metal pollution is an important form of heavy metal pollution. Heavy metal pollution in the atmosphere has the characteristics of strong mobility, wide coverage and the like, causes direct harm to human health, and has the characteristics of nondegradable property, biotoxicity, bioaccumulation and the like. Heavy metal pollution in reducing flue gas is serious, taking yellow phosphorus tail gas as an example, about 2500-3000 mg/m is generated every 1t of yellow phosphorus is produced3The tail gas of (2), wherein the mercury is 40-400 mu g/m380-180 mg/m of arsenic3. The mercury and arsenic in the yellow phosphorus tail gas are mainly from phosphorite and coke in the raw materials, and the mercury is mainly gaseous elemental mercury (Hg) in the reducing atmosphere of the yellow phosphorus tail gas0) Is mainly in the form of arsenic hydride (AsH)3) Exist in the form of (1).
At present, the Hg in the reducing atmosphere is aimed at0And AsH3The purification technology mainly focuses on catalytic oxidation and adsorption. In recent years, the photocatalytic technology has attracted attention as a new technology due to its advantages of mild reaction conditions, deep oxidation capability at room temperature, no secondary pollution, direct utilization of solar energy, simple equipment, and the like. The metal sulfide is considered to be an excellent photocatalyst, and the metal sulfide has a wide application prospect in the fields of photocatalytic oxidation and the like due to the proper valence band conduction band position of the metal sulfide. The sulfide has a narrower band gap and a relatively more negative valence band position compared with a traditional oxide semiconductor, and can be used as an excellent candidate material for visible light catalysis. Common MoS2、WS2Because of its excellent optical and catalytic properties, it belongs to semiconductor transition metal sulfide. When they are of bulk structure, their energy bands belong to the indirect band gap, respectively 1.2eV (MoS)2) And 1.4eV (WS)2) When they are exfoliated into nanosheets, the band gap is indirectThe band gaps become direct band gaps, respectively 1.8eV (MoS)2) And 1.9eV (WS)2) Has new optical and catalytic properties; and the application of the catalyst in the photocatalytic removal of gaseous pollutants is relatively rarely reported, and particularly the catalyst can be used for simultaneously catalytically oxidizing gaseous elemental mercury (Hg)0) And AsH3The photocatalyst of (2) has not been reported.
Disclosure of Invention
Aiming at the problems in the prior art, the invention provides a preparation method of a tungsten-molybdenum disulfide composite photocatalyst and MoS2/WS2The double-sulfide composite photocatalyst is used for removing heavy metals in reducing flue gas; the double sulfides have similar crystal structures and symmetry, and unique electronic properties of the double sulfides in the aspects of band gaps, light absorption, spin-orbit coupling strength and the like are utilized, so that extremely powerful conditions are provided for the construction of heterojunctions and the design of high-freedom heterojunctions; thereby obviously enhancing the photocatalytic activity of the catalyst and being used for removing Hg in reducing flue gas by photocatalysis0And AsH3。
MoS of the invention2/WS2The preparation method of the bisulphide composite photocatalyst comprises the following specific steps:
(1) under the condition of stirring, respectively adding tungsten salt, molybdate and a sulfur source into deionized water for dissolving, and stirring until the color of the solution is not deepened any more to obtain a mixed solution;
the tungsten salt is one of tungsten chloride, tungsten hexacarbonyl, sodium tungstate and the like;
the molybdate is one of ammonium molybdate and sodium molybdate;
the sulfur source is one of thiourea, sodium sulfide and thioacetamide;
the molar ratio of the Mo ions to the W ions to the S ions is 1-12: 0.81-7.5: 17-25;
(2) and (2) placing the mixed solution obtained in the step (1) into a digestion tank, digesting for 20-60 min under the microwave condition at the temperature of 150-200 ℃, cooling, taking out the precipitate, sequentially washing with deionized water and absolute ethyl alcohol, and drying to obtain the tungsten-molybdenum disulfide composite photocatalyst.
Heating to 150-200 ℃ at a heating rate of 8-10 ℃/min.
The invention also aims to apply the tungsten-molybdenum disulfide composite photocatalyst prepared by the method to removal of gaseous heavy metals in reducing flue gas.
The carbothermic reduction method is widely applied to chemical and metallurgical industries, and is mainly used for producing important raw materials in the metallurgical and chemical industries, such as yellow phosphorus, calcium carbide, iron alloy, zinc and the like, and reducing tail gas, such as yellow phosphorus tail gas, closed calcium carbide furnace tail gas, blast furnace gas and the like, is produced in the carbothermic reduction processing process.
The invention adopts a microwave hydrothermal method to prepare the bisulphide composite catalyst, has a layered structure and can exert higher photocatalytic property. The valence band and the conduction band of the heterojunction constructed by double sulfides are independent, and the mutual influence between adjacent crystals can cause the rearrangement of charges, the reconstruction of energy bands and the change of structures, so that a new functional channel can be opened, and more novel optical phenomena and related properties can be caused. The composite has the advantages of short synthesis time, large specific surface area, wide corresponding light absorption wavelength range, abundant edge structures, capability of providing a large number of active sites for photocatalytic reaction, and good photocatalytic response.
The material of the double sulfide has higher photocatalytic activity and MoS2And WS2The layered stacking can form a heterostructure with a valence band and a conduction band respectively in different single layers, and strong coupling effect can be generated between layers, so that the material has more novel optical property, the load factor of a photon-generated carrier is more effectively reduced, the effective separation of photon-generated electrons and holes is realized, and the efficient photocatalysis effect is realized. The method for preparing MoS by microwave-hydrothermal integrated reaction2/WS2The catalyst realizes the preparation regulation and control of the bisulphide catalyst by adjusting the proportion of Mo and W, and the microwave hydrothermal temperature and time.
The invention has the beneficial effects that:
(1) the catalyst has the characteristics of simple preparation method, low cost and the like, and the material prepared by adopting a microwave hydrothermal method has better photocatalytic performance;
(2) the heterostructure composite transition metal sulfide photocatalyst combines the characteristics of different semiconductors, the composite of sulfides enables the composite catalyst to have more proper energy band positions, meanwhile, unsaturated sulfur bonds and the like at the edge of the catalyst can provide a large number of active sites, and Hg in flue gas can be efficiently catalyzed and oxidized0And AsH3；
(3) The method adopts the regulation of digestion temperature and time, can increase the specific surface area and light absorption strength of the material, and shows high activity and stability in the process of removing gaseous heavy metals, which shows that the catalyst has high utilization value in the field of removing heavy metal pollutants in reducing flue gas;
(4) in the preparation process of the material, substances such as a surfactant with high toxicity and high hazard are not involved, and the preparation process is green and environment-friendly.
Drawings
FIG. 1 shows the material prepared in example 1 with different molar ratios of molybdenum to tungsten vs. Hg0A removal efficiency result graph of (1);
FIG. 2 shows the material pairs Hg prepared at different digestion temperatures0The removal efficiency results of (1);
FIG. 3 shows the material pairs Hg prepared at different digestion times0The removal efficiency results of (1);
FIG. 4 is a MoS prepared at 40min digestion time2/WS2SEM images of the material;
FIG. 5 MoS prepared at different digestion times2/WS2SEM images of the material;
FIG. 6 is a graph of catalyst pairs prepared at different digestion times versus gaseous AsH3The photocatalytic removal efficiency of (a);
fig. 7 is an X-ray diffraction (XRD) pattern corresponding to the composite catalyst.
Detailed Description
The invention will be described in more detail with reference to the following figures and examples, but the scope of the invention is not limited thereto.
Example 1: the preparation method of the tungsten-molybdenum bisulphide composite photocatalyst comprises the following steps:
(1) under the condition of magnetic stirring, respectively adding tungsten chloride (tungsten hexachloride), ammonium molybdate and thiourea into deionized water according to the molar ratio of Mo ions, W ions and S ions of 1:7.5:17, 6.5:4:21 and 11:0.8:25 for dissolving, and continuously stirring;
(2) stirring the solution in the step (1) until the color is not deepened any more to obtain a mixed solution;
(3) placing the mixed solution obtained in the step (2) into a 100mL digestion tank, carrying out microwave digestion for 40min at the temperature of 180 ℃ (the heating rate is 10 ℃/min), cooling, taking out precipitates, washing with deionized water and absolute ethyl alcohol in sequence to remove surface ions, and drying at 60 ℃ to obtain the tungsten-molybdenum disulfide composite photocatalyst;
and (3) detecting the catalytic performance: 0.1g of the bis-sulfide composite catalyst prepared in this example was weighed and used for photocatalytic removal of Hg from simulated flue gas under an ultraviolet lamp0The simulated smoke is as follows: 2% of O2、Hg0The inlet concentration was 1000. mu.g/m3The gas flow rate is 700mL/min, the wavelength of an ultraviolet lamp is 253.7nm, the power of the ultraviolet lamp is 9W, and the model is TUV PL-S, Philips and Netherlands; the results are shown in FIG. 1 for materials of different molybdenum-tungsten mass ratios to Hg0The removal efficiency of (2) can be seen, three materials with an ion ratio of 6.5:4:21 to Hg0The removal efficiency of (2) is highest.
Example 2: the preparation method of the tungsten-molybdenum bisulphide composite photocatalyst comprises the following steps:
(1) under the condition of magnetic stirring, respectively adding tungsten chloride, ammonium molybdate and thiourea into deionized water according to the molar ratio of Mo ions, W ions and S ions of 6.5:4:21 for dissolving, and continuously stirring;
(2) stirring the solution in the step (1) until the color is not deepened any more to obtain a mixed solution;
(3) placing the mixed solution in the step (2) into a 100mL digestion tank, performing microwave digestion for 40min at the temperature of 150 ℃, 180 ℃ and 200 ℃ (the heating rate is 10 ℃/min), cooling, taking out precipitates, washing with deionized water and absolute ethyl alcohol in sequence to remove surface ions, and drying at 60 ℃ to obtain the tungsten-molybdenum disulfide composite photocatalyst;
and (3) detecting the catalytic performance: 0.1g of the bis-sulfide composite catalyst prepared in this example was weighed and used for photocatalytic removal of Hg from simulated flue gas under an ultraviolet lamp0The simulated smoke is as follows: 2% of O2、Hg0The inlet concentration was 1000. mu.g/m3The gas flow rate is 700mL/min, the wavelength of an ultraviolet lamp is 253.7nm, the power of the ultraviolet lamp is 9W, and the model is TUV PL-S, Philips and Netherlands; the results are shown in FIG. 2 for material pairs of Hg prepared at different digestion temperatures0The removal efficiency of (2) is shown in the figure, and the preparation condition is 180 ℃ for Hg0The removal efficiency of (2) is highest.
Example 3: the preparation method of the tungsten-molybdenum bisulphide composite photocatalyst comprises the following steps:
(1) under the condition of magnetic stirring, adding tungsten hexacarbonyl, sodium molybdate and sodium sulfide into deionized water respectively according to the molar ratio of Mo ions, W ions and S ions of 6.5:4:21 for dissolving, and continuously stirring;
(2) stirring the solution in the step (1) until the color is not deepened any more to obtain a mixed solution;
(3) placing the mixed solution obtained in the step (2) into a 100mL digestion tank, performing microwave digestion for 20min, 40min and 60min at the temperature of 180 ℃ (the heating rate is 10 ℃/min), cooling, taking out precipitates, washing with deionized water and absolute ethyl alcohol in sequence to remove surface ions, and drying at 60 ℃ to obtain the tungsten-molybdenum disulfide composite photocatalyst;
TABLE 1 MoS prepared at different digestion times2/WS2List of specific surface area, pore volume and average pore diameter
| Samples | BET surface area (m2/g) | Pore volume(cm3/g) | Average pore diameter(nm) |
| 40min | 95.031 | 0.186 | 2.103 |
| 60min | 42.449 | 0.133 | 2.105 |
| 20min | 29.387 | 0.047 | 2.375 |
And (3) detecting the catalytic performance: 0.1g of the bis-sulfide composite catalyst prepared in this example was weighed and used for photocatalytic removal of Hg from simulated flue gas under an ultraviolet lamp0The simulated smoke is as follows: 2% of O2，Hg0The inlet concentration was 1000. mu.g/m3The gas flow rate is 700ml/min, the wavelength of an ultraviolet lamp is 253.7nm, the power of the ultraviolet lamp is 9W, and the model is TUV PL-S, Philips and Netherlands; the results are shown in FIG. 3 for material pairs of Hg prepared at different digestion temperatures0The removal efficiency of (2) can be seen from the figure, and the Hg can be obtained when the microwave digestion is carried out for 40min0The highest removal efficiency. Meanwhile, according to the microwave digestion time and the BET result, correspondingly, the microwave digestion time is 40min, so that a larger specific surface area can be obtained, the number of active sites is increased, and the removal efficiency is improved.
FIG. 4 is a MoS prepared at 40min digestion time2/WS2SEM image of the material, it can be seen that the material is mainly of lamellar structure, so that more active sites can be provided,in order to obtain a greater contaminant removal capacity.
FIG. 5 shows MoS prepared at different digestion times2/WS2N of the material2According to the adsorption and desorption curve and the combination of the table 1, the maximum specific surface area can be obtained within 40min of digestion time, and the specific surface areas of the materials prepared within 20min and 60min are obviously smaller than the maximum specific surface area prepared within 40 min; the increase in specific surface area is therefore also a factor linked to the increase in removal efficiency.
FIG. 7 shows the material prepared at 40min digestion time, peaks and MoS appearing in the figure2And WS2Has better correspondence and no redundant miscellaneous peak, and proves that the prepared substance is relatively pure MoS2/WS2A composite material.
Example 4: the preparation method of the tungsten-molybdenum bisulphide composite photocatalyst comprises the following steps:
(1) under the condition of magnetic stirring, respectively adding sodium tungstate, ammonium molybdate and thioacetamide into deionized water to dissolve according to the molar ratio of Mo ions, W ions and S ions of 6.5:4:21, and continuously stirring;
(2) stirring the solution in the step (1) until the color is not deepened any more to obtain a mixed solution;
(3) placing the mixed solution obtained in the step (2) into a 100mL digestion tank, carrying out microwave digestion for 40min at the temperature of 180 ℃ (the heating rate is 10 ℃/min), cooling, taking out precipitates, washing with deionized water and absolute ethyl alcohol in sequence to remove surface ions, and drying at 60 ℃ to obtain the tungsten-molybdenum disulfide composite photocatalyst;
and (3) detecting the catalytic performance: 0.1g of the bisulphide composite catalyst prepared in the example was weighed and used for photocatalytic removal of AsH in simulated flue gas under an ultraviolet lamp3The simulated smoke is as follows: 1% of O2，AsH3The inlet concentration was 40. mu.g/m3The gas flow rate was 400ml/min, the UV lamp wavelength was 253.7nm, the UV lamp power was 9W, and the model was TUV PL-S, Philips, Netherlands. The bisulphide composite photocatalyst pair AsH prepared in the step3The removal efficiency of the method reaches 87 percent at most, and the removal efficiency is kept at 6 percent for 200min0% or more, as shown in FIG. 6.
While the invention has been described in detail with reference to specific embodiments thereof, it will be apparent to one skilled in the art that various changes in the form and details can be made therein without departing from the spirit and scope of the invention. However, the technology according to the present invention is intended to cover any simple modification, equivalent change and modification of the above embodiments without departing from the technical content of the present invention, and still fall within the protection scope of the technical solution of the present invention.
Claims (7)
1. A preparation method of a tungsten-molybdenum bisulphide composite photocatalyst is characterized by comprising the following steps:
(1) under the condition of stirring, respectively adding tungsten salt, molybdate and a sulfur source into deionized water for dissolving, and stirring until the color of the solution is not deepened any more to obtain a mixed solution;
(2) and (2) placing the mixed solution obtained in the step (1) into a digestion tank, digesting for 20-60 min under the microwave condition at the temperature of 150-200 ℃, cooling, taking out the precipitate, sequentially washing with deionized water and absolute ethyl alcohol, and drying to obtain the tungsten-molybdenum disulfide composite photocatalyst.
2. The preparation method of the tungsten-molybdenum bisulfide composite photocatalyst, as claimed in claim 1, is characterized in that: the tungsten salt is one of tungsten chloride, tungsten hexacarbonyl and sodium tungstate.
3. The preparation method of the tungsten-molybdenum bisulfide composite photocatalyst, as claimed in claim 1, is characterized in that: the molybdate is one of ammonium molybdate and sodium molybdate.
4. The preparation method of the tungsten-molybdenum bisulfide composite photocatalyst, as claimed in claim 1, is characterized in that: the sulfur source is one of thiourea, sodium sulfide and thioacetamide.
5. The preparation method of the tungsten-molybdenum bisulfide composite photocatalyst, as claimed in claim 1, is characterized in that: the molar ratio of Mo ions to W ions to S ions is 1-12: 0.81-7.5: 17-25.
6. The use of the tungsten-molybdenum disulfide composite photocatalyst prepared by the preparation method of the tungsten-molybdenum disulfide composite photocatalyst according to any one of claims 1 to 5 in the removal of gaseous heavy metals in reducing flue gas.
7. Use according to claim 6, characterized in that: and treating the reductive flue gas by using a tungsten-molybdenum double sulfide composite photocatalyst in the presence of ultraviolet light.
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