CN111760579B - Preparation method and application of tungsten-molybdenum disulfide composite photocatalyst - Google Patents
Preparation method and application of tungsten-molybdenum disulfide composite photocatalyst Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 33
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 26
- 238000002360 preparation method Methods 0.000 title claims abstract description 16
- DOIKGWMZXKJLJV-UHFFFAOYSA-N [W].[Mo](=S)=S Chemical compound [W].[Mo](=S)=S DOIKGWMZXKJLJV-UHFFFAOYSA-N 0.000 title claims abstract description 9
- 230000029087 digestion Effects 0.000 claims abstract description 20
- 239000011259 mixed solution Substances 0.000 claims abstract description 15
- 239000008367 deionised water Substances 0.000 claims abstract description 14
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 14
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 14
- -1 tungsten-molybdenum bisulfide Chemical compound 0.000 claims abstract description 10
- 239000002244 precipitate Substances 0.000 claims abstract description 9
- 239000000243 solution Substances 0.000 claims abstract description 9
- 238000003756 stirring Methods 0.000 claims abstract description 9
- 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
- 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
- 230000002829 reductive effect Effects 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
- MGRWKWACZDFZJT-UHFFFAOYSA-N molybdenum tungsten Chemical compound [Mo].[W] MGRWKWACZDFZJT-UHFFFAOYSA-N 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
- 239000000463 material Substances 0.000 description 20
- 230000001699 photocatalysis Effects 0.000 description 17
- 239000003054 catalyst Substances 0.000 description 16
- 239000007789 gas Substances 0.000 description 13
- RBFQJDQYXXHULB-UHFFFAOYSA-N arsane Chemical compound [AsH3] RBFQJDQYXXHULB-UHFFFAOYSA-N 0.000 description 10
- 229910000070 arsenic hydride Inorganic materials 0.000 description 10
- 230000003197 catalytic effect Effects 0.000 description 8
- OBSZRRSYVTXPNB-UHFFFAOYSA-N tetraphosphorus Chemical compound P12P3P1P32 OBSZRRSYVTXPNB-UHFFFAOYSA-N 0.000 description 7
- 238000010438 heat treatment Methods 0.000 description 6
- 238000000120 microwave digestion Methods 0.000 description 6
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 5
- 238000000034 method Methods 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 4
- 238000003760 magnetic stirring Methods 0.000 description 4
- 230000003287 optical effect Effects 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- 238000007254 oxidation reaction Methods 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
- 230000008859 change Effects 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
- 230000004048 modification Effects 0.000 description 3
- 238000012986 modification 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
- 150000004763 sulfides Chemical class 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
- 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
- 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
- 238000001179 sorption measurement Methods 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
- BWGNESOTFCXPMA-UHFFFAOYSA-N Dihydrogen disulfide Chemical compound SS BWGNESOTFCXPMA-UHFFFAOYSA-N 0.000 description 1
- 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
- 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
- 238000004519 manufacturing process Methods 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
- 238000002336 sorption--desorption measurement Methods 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
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- 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
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- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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; and (2) placing the mixed solution into a digestion tank, digesting for 20-60min 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.
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, and taking yellow phosphorus tail gas as an example, the yellow phosphorus is generated by 2500 to 3000mg/m every 1t of yellow phosphorus production 3 The tail gas of (1), wherein the mercury is contained in the tail gas of (40) - (400) mu g/m 3 80 to 180mg/m of arsenic 3 . 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 gas 0 ) 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 at 0 And AsH 3 The 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, and simple equipment. 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 MoS 2 、WS 2 Because 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 gaps, 1.2eV (MoS) respectively 2 ) And 1.4eV (WS) 2 ) When they are exfoliated into nanosheets, the bandgaps change from indirect to direct, 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 catalyzing and oxidizing gaseous elemental mercury (Hg) 0 ) And AsH 3 Photocatalyst ofNo report is found.
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 MoS 2 /WS 2 The double-sulfide composite photocatalyst is used for removing heavy metals in reductive 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 photocatalysis 0 And AsH 3 。
Invention MoS 2 /WS 2 The preparation method of the disulfide 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 obtaining a mixed solution when the solution is stirred until the color of the solution is not deepened any more;
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 ion to the W ion to the S ion is 1-12: 0.81-7.5: 17-25;
(2) And (2) placing the mixed solution in the step (1) into a digestion tank, digesting for 20 to 60min under the microwave condition at the temperature of 150 to 200 ℃, cooling, taking out a precipitate, washing with deionized water and absolute ethyl alcohol in sequence, 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. Due to mutual independence of valence band and conduction band of the double-sulfide heterojunction, mutual influence between adjacent crystals causes charge rearrangement, energy band reconstruction and structural change, so that a new functional channel can be opened, and more novel optical phenomena and related properties are 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 MoS 2 And WS 2 The 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 invention uses microwave-based hydrothermal integrated reaction to prepare MoS 2 /WS 2 The 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 beneficial effects of the invention are:
(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 ensures that the composite catalyst has more proper energy band position, simultaneously, unsaturated sulfur bonds and the like at the edge of the catalyst can provide a large number of active sites and can be high in activityEffectively catalytic oxidation of Hg in flue gas 0 And AsH 3 ；
(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. Hg 0 A removal efficiency result graph of (1);
FIG. 2 shows the material pairs Hg prepared at different digestion temperatures 0 The removal efficiency results of (1);
FIG. 3 shows the material pairs Hg prepared at different digestion times 0 The removal efficiency results of (1);
FIG. 4 is a MoS prepared at 40min digestion time 2 /WS 2 SEM images of the material;
FIG. 5 MoS prepared at different digestion times 2 /WS 2 SEM images of the material;
FIG. 6 is a graph of catalyst pairs prepared at different digestion times versus gaseous AsH 3 The 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, adding tungsten chloride (tungsten hexachloride), ammonium molybdate and thiourea into deionized water according to the molar ratio of Mo ion, W ion and S ion of 1;
(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, digesting the mixed solution for 40min by microwave at 180 ℃ (the heating rate is 10 ℃/min), cooling, taking out the precipitate, washing the precipitate by deionized water and absolute ethyl alcohol in sequence to remove surface ions, and drying the precipitate at 60 ℃ to obtain the tungsten-molybdenum bisulphide 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 lamp 0 The simulated smoke is as follows: 2% of 2 、Hg 0 The inlet concentration was 1000. Mu.g/m 3 The gas flow rate is 700mL/min, the ultraviolet lamp wavelength is 253.7nm, the ultraviolet lamp power 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 Hg 0 Of the three ion ratios 6.5 0 The 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;
(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 lamp 0 The simulated smoke is as follows: 2% of 2 、Hg 0 The inlet concentration was 1000. Mu.g/m 3 The 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 temperatures 0 The removal efficiency of (2) is shown in the figure, and the preparation condition is 180 ℃ to Hg 0 The 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;
(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 times 2 /WS 2 List of specific surface area, pore volume and average pore diameter
| Samples | BET surface area (m 2 /g) | Pore volume(cm 3 /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 bisulphide composite catalyst prepared in this example was weighed out and used for photocatalytic removal of Hg from simulated flue gas under an ultraviolet lamp 0 The simulated smoke is as follows: 2% of 2 ，Hg 0 The inlet concentration was 1000. Mu.g/m 3 The 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 temperatures 0 The removal efficiency of (2) can be seen from the figure, and the Hg can be obtained when the microwave digestion is carried out for 40min 0 The 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 time 2 /WS 2 SEM images of the material, it can be seen that the material is dominated by a lamellar structure, which provides more active sites for greater contaminant removal capacity.
FIG. 5 shows MoS prepared at different digestion times 2 /WS 2 N of the material 2 As can be seen from the adsorption/desorption curves in Table 1, the maximum digestion time at 40min was obtainedThe specific surface area of the material prepared in 20min and 60min is obviously smaller than the maximum specific surface area prepared in 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 figure 2 And WS 2 Has better correspondence and no redundant miscellaneous peak, and proves that the prepared substance is relatively pure MoS 2 /WS 2 A 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 according to the molar ratio of Mo ions, W ions and S ions of 6.5;
(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 lamp 3 The simulated smoke is as follows: 1% of 2 ，AsH 3 The inlet concentration was 40. Mu.g/m 3 The 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 by the step 3 The removal efficiency of (2) is up to 87% at most, and the removal efficiency is maintained to be more than 60% for 200min, 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 and modifications 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 (6)
1. Tungsten-molybdenum double-sulfide composite photocatalyst for removing gaseous heavy metal Hg in reductive flue gas 0 And AsH 3 The use of (1);
the preparation method of the tungsten-molybdenum bisulfide composite photocatalyst comprises 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 in the step (1) into a digestion tank, digesting for 20 to 60min under the microwave condition at the temperature of 150 to 200 ℃, cooling, taking out a precipitate, washing with deionized water and absolute ethyl alcohol in sequence, and drying to obtain the tungsten-molybdenum disulfide composite photocatalyst.
2. Use according to claim 1, characterized in that: the tungsten salt is one of tungsten chloride, tungsten hexacarbonyl and sodium tungstate.
3. Use according to claim 1, characterized in that: the molybdate is one of ammonium molybdate and sodium molybdate.
4. Use according to claim 1, characterized in that: the sulfur source is one of thiourea, sodium sulfide and thioacetamide.
5. Use according to claim 1, characterized in that: the molar ratio of the Mo ion to the W ion to the S ion is 1 to 12: 0.81 to 7.5:17 to 25.
6. Use according to claim 1, 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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