CN108097271A - A kind of preparation method of antimony trisulfide-molybdenum disulfide composite photo-catalyst - Google Patents
A kind of preparation method of antimony trisulfide-molybdenum disulfide composite photo-catalyst Download PDFInfo
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- CN108097271A CN108097271A CN201711266646.4A CN201711266646A CN108097271A CN 108097271 A CN108097271 A CN 108097271A CN 201711266646 A CN201711266646 A CN 201711266646A CN 108097271 A CN108097271 A CN 108097271A
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- molybdenum disulfide
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- gel
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 73
- 239000002131 composite material Substances 0.000 title claims abstract description 32
- 239000011941 photocatalyst Substances 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 24
- 229910052787 antimony Inorganic materials 0.000 title claims description 20
- WATWJIUSRGPENY-UHFFFAOYSA-N antimony atom Chemical compound [Sb] WATWJIUSRGPENY-UHFFFAOYSA-N 0.000 title claims description 20
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims abstract description 45
- 229940007424 antimony trisulfide Drugs 0.000 claims abstract description 30
- NVWBARWTDVQPJD-UHFFFAOYSA-N antimony(3+);trisulfide Chemical compound [S-2].[S-2].[S-2].[Sb+3].[Sb+3] NVWBARWTDVQPJD-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002904 solvent Substances 0.000 claims abstract description 17
- 238000002425 crystallisation Methods 0.000 claims abstract description 16
- 230000008025 crystallization Effects 0.000 claims abstract description 15
- 239000007863 gel particle Substances 0.000 claims abstract description 11
- 238000001035 drying Methods 0.000 claims abstract description 5
- 239000000084 colloidal system Substances 0.000 claims abstract description 4
- YPMOSINXXHVZIL-UHFFFAOYSA-N sulfanylideneantimony Chemical compound [Sb]=S YPMOSINXXHVZIL-UHFFFAOYSA-N 0.000 claims abstract description 4
- 239000011259 mixed solution Substances 0.000 claims description 60
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 claims description 22
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 22
- RWSOTUBLDIXVET-UHFFFAOYSA-N Dihydrogen sulfide Chemical compound S RWSOTUBLDIXVET-UHFFFAOYSA-N 0.000 claims description 21
- 229910000037 hydrogen sulfide Inorganic materials 0.000 claims description 21
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 21
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 21
- 239000000243 solution Substances 0.000 claims description 21
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 20
- 238000010438 heat treatment Methods 0.000 claims description 18
- IIQJBVZYLIIMND-UHFFFAOYSA-J potassium;antimony(3+);2,3-dihydroxybutanedioate Chemical compound [K+].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O IIQJBVZYLIIMND-UHFFFAOYSA-J 0.000 claims description 17
- 235000015393 sodium molybdate Nutrition 0.000 claims description 15
- 239000011684 sodium molybdate Substances 0.000 claims description 15
- TVXXNOYZHKPKGW-UHFFFAOYSA-N sodium molybdate (anhydrous) Chemical group [Na+].[Na+].[O-][Mo]([O-])(=O)=O TVXXNOYZHKPKGW-UHFFFAOYSA-N 0.000 claims description 15
- 238000006243 chemical reaction Methods 0.000 claims description 13
- 238000001027 hydrothermal synthesis Methods 0.000 claims description 13
- LYCAIKOWRPUZTN-UHFFFAOYSA-N Ethylene glycol Chemical compound OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 claims description 12
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 12
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 claims description 12
- 239000001257 hydrogen Substances 0.000 claims description 12
- 229910052739 hydrogen Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical compound [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims description 11
- 239000005864 Sulphur Substances 0.000 claims description 11
- 239000012153 distilled water Substances 0.000 claims description 11
- 235000019441 ethanol Nutrition 0.000 claims description 11
- 239000007789 gas Substances 0.000 claims description 11
- 229910052757 nitrogen Inorganic materials 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 11
- 230000005070 ripening Effects 0.000 claims description 10
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims description 10
- WVDDGKGOMKODPV-UHFFFAOYSA-N Benzyl alcohol Chemical compound OCC1=CC=CC=C1 WVDDGKGOMKODPV-UHFFFAOYSA-N 0.000 claims description 9
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 9
- DNIAPMSPPWPWGF-UHFFFAOYSA-N Propylene glycol Chemical compound CC(O)CO DNIAPMSPPWPWGF-UHFFFAOYSA-N 0.000 claims description 9
- 238000002156 mixing Methods 0.000 claims description 9
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- 150000001298 alcohols Chemical class 0.000 claims description 5
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 claims description 4
- XUJNEKJLAYXESH-REOHCLBHSA-N L-Cysteine Chemical compound SC[C@H](N)C(O)=O XUJNEKJLAYXESH-REOHCLBHSA-N 0.000 claims description 4
- LRHPLDYGYMQRHN-UHFFFAOYSA-N N-Butanol Chemical compound CCCCO LRHPLDYGYMQRHN-UHFFFAOYSA-N 0.000 claims description 4
- AKHNMLFCWUSKQB-UHFFFAOYSA-L sodium thiosulfate Chemical compound [Na+].[Na+].[O-]S([O-])(=O)=S AKHNMLFCWUSKQB-UHFFFAOYSA-L 0.000 claims description 4
- 235000019345 sodium thiosulphate Nutrition 0.000 claims description 4
- YUKQRDCYNOVPGJ-UHFFFAOYSA-N thioacetamide Chemical compound CC(N)=S YUKQRDCYNOVPGJ-UHFFFAOYSA-N 0.000 claims description 4
- DLFVBJFMPXGRIB-UHFFFAOYSA-N thioacetamide Natural products CC(N)=O DLFVBJFMPXGRIB-UHFFFAOYSA-N 0.000 claims description 4
- 235000019445 benzyl alcohol Nutrition 0.000 claims description 3
- 235000011187 glycerol Nutrition 0.000 claims description 2
- 238000007873 sieving Methods 0.000 claims description 2
- 238000003980 solgel method Methods 0.000 claims description 2
- 235000013772 propylene glycol Nutrition 0.000 claims 1
- 230000001699 photocatalysis Effects 0.000 abstract description 10
- 239000002351 wastewater Substances 0.000 abstract description 5
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 238000000034 method Methods 0.000 abstract description 4
- 239000002245 particle Substances 0.000 abstract description 4
- 239000013078 crystal Substances 0.000 abstract description 3
- 238000009826 distribution Methods 0.000 abstract description 3
- 239000000975 dye Substances 0.000 abstract description 3
- 230000031700 light absorption Effects 0.000 abstract description 3
- 230000008569 process Effects 0.000 abstract description 3
- 238000011161 development Methods 0.000 abstract description 2
- 238000001179 sorption measurement Methods 0.000 abstract description 2
- 238000000926 separation method Methods 0.000 abstract 1
- 239000003054 catalyst Substances 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 6
- 230000008901 benefit Effects 0.000 description 5
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 4
- 239000003292 glue Substances 0.000 description 4
- 239000000463 material Substances 0.000 description 4
- 238000011160 research Methods 0.000 description 4
- 239000004065 semiconductor Substances 0.000 description 4
- ZOKXTWBITQBERF-UHFFFAOYSA-N Molybdenum Chemical compound [Mo] ZOKXTWBITQBERF-UHFFFAOYSA-N 0.000 description 3
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 3
- SZXAQBAUDGBVLT-UHFFFAOYSA-H antimony(3+);2,3-dihydroxybutanedioate Chemical compound [Sb+3].[Sb+3].[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O.[O-]C(=O)C(O)C(O)C([O-])=O SZXAQBAUDGBVLT-UHFFFAOYSA-H 0.000 description 3
- 230000008859 change Effects 0.000 description 3
- 239000003795 chemical substances by application Substances 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 229910052750 molybdenum Inorganic materials 0.000 description 3
- 239000011733 molybdenum Substances 0.000 description 3
- 229910052700 potassium Inorganic materials 0.000 description 3
- 239000011591 potassium Substances 0.000 description 3
- KAESVJOAVNADME-UHFFFAOYSA-N Pyrrole Chemical compound C=1C=CNC=1 KAESVJOAVNADME-UHFFFAOYSA-N 0.000 description 2
- AUJJPYKPIQVRDH-UHFFFAOYSA-N antimony potassium Chemical compound [K].[Sb] AUJJPYKPIQVRDH-UHFFFAOYSA-N 0.000 description 2
- 239000011651 chromium Substances 0.000 description 2
- JOPOVCBBYLSVDA-UHFFFAOYSA-N chromium(6+) Chemical compound [Cr+6] JOPOVCBBYLSVDA-UHFFFAOYSA-N 0.000 description 2
- 230000005611 electricity Effects 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000012046 mixed solvent Substances 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- WVDDGKGOMKODPV-ZQBYOMGUSA-N phenyl(114C)methanol Chemical compound O[14CH2]C1=CC=CC=C1 WVDDGKGOMKODPV-ZQBYOMGUSA-N 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 239000002994 raw material Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 239000004408 titanium dioxide Substances 0.000 description 2
- 235000017060 Arachis glabrata Nutrition 0.000 description 1
- 244000105624 Arachis hypogaea Species 0.000 description 1
- 235000010777 Arachis hypogaea Nutrition 0.000 description 1
- 235000018262 Arachis monticola Nutrition 0.000 description 1
- 244000060234 Gmelina philippensis Species 0.000 description 1
- UICKUOVXTQKMMX-UHFFFAOYSA-N [Mo]=S.[Sb]=S Chemical compound [Mo]=S.[Sb]=S UICKUOVXTQKMMX-UHFFFAOYSA-N 0.000 description 1
- 230000032683 aging Effects 0.000 description 1
- 230000005540 biological transmission Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 239000004020 conductor Substances 0.000 description 1
- 238000007796 conventional method Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 230000018109 developmental process Effects 0.000 description 1
- 230000005284 excitation Effects 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 238000005461 lubrication Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000008204 material by function Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000003002 pH adjusting agent Substances 0.000 description 1
- 235000020232 peanut Nutrition 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- 230000009257 reactivity Effects 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 239000011593 sulfur Substances 0.000 description 1
- 230000007704 transition Effects 0.000 description 1
- 229910052723 transition metal Inorganic materials 0.000 description 1
- 150000003624 transition metals Chemical class 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- 229920002554 vinyl polymer Polymers 0.000 description 1
- 238000004073 vulcanization Methods 0.000 description 1
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- 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
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J35/00—Catalysts, in general, characterised by their form or physical properties
- B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
- B01J35/39—Photocatalytic properties
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/30—Treatment of water, waste water, or sewage by irradiation
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/10—Inorganic compounds
- C02F2101/20—Heavy metals or heavy metal compounds
- C02F2101/22—Chromium or chromium compounds, e.g. chromates
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
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- Chemical & Material Sciences (AREA)
- Engineering & Computer Science (AREA)
- Organic Chemistry (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Health & Medical Sciences (AREA)
- Toxicology (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Catalysts (AREA)
Abstract
The present invention discloses a kind of preparation method of antimony trisulfide molybdenum disulfide composite photo-catalyst, molybdenum disulfide colloidal solution is uniformly mixed with antimony sulphide colloid solution, then it is 4.8 10.2 to adjust pH value, translucent colloidal sol is obtained, translucent colloidal sol is aged separation solvent and gel, then by gel drying, it is ground up, sieved, grain size is selected in 0.5 10 μm of dry gel particle as presoma, maintained at 200 350 DEG C 0.5 5 hours to presoma crystallization to get；Antimony trisulfide molybdenum disulfide composite photo-catalyst even particle distribution that the preparation method of the present invention obtains, crystal form are relatively unified, and purity is high, and stability is strong, it is fast to transmit electron velocity, light absorption is strong, is not easy to reunite, adsorption area is big, possesses higher photocatalytic activity, light removal waste water from dyestuff field is can be widely used for, and preparation method simple process and low cost is honest and clean, product excellent catalytic effect has good development prospect.
Description
Technical field
The present invention relates to chemical fields, more particularly relate to a kind of preparation of antimony trisulfide-molybdenum disulfide composite photo-catalyst
Method.
Background technology
Photocatalysis technology is with its is easy to operate, pollution-free, can directly utilize the advantages that sunlight and becomes current Solar use
One of research hotspot.Traditional photochemical catalyst titanium dioxide with its it is nontoxic, stable, inexpensive, catalytic activity is good the advantages that, obtain wide
General concern.It could show that photocatalysis is lived since the energy gap of titanium dioxide is wider, under the excitation of the ultraviolet light less than 400nm
Property, 4% or so of solar energy is only accounted for using solar energy.And visible ray (400-750nm) occupies sunlight total energy
Efficient visible-light photocatalysis material is developed and developed to the 43% of amount, expands the wave-length coverage of sun light absorption, becomes current light
The research hotspot in catalyticing research field.
Antimony trisulfide is the semi-conducting material of V-VI races direct band gap, and band gap is about 1.5~2.2eV, has stratiform
Structure and high anisotropy easily form one-dimensional nano structure and the nano-superstructure constructed by monodimension nanometer material, nowadays
It has been successfully prepared the nanostructureds such as the flower-shaped, hedgehog being made of nanometer rods and peanut shape.The nano-sulfur of these different-shapes
Changing antimony has novel and excellent performance, is mainly manifested in the aspect of performance such as light, electricity, mechanics.Therefore, Many researchers are directed to
Research to appearance of nano material controllable preparation.Antimony trisulfide is in biology, chemical industry, military affairs, catalyst, sensor, photoelectronics etc.
The application that there are many fields, in addition, still one of numerous semiconductor functional materials with application prospect, in some Disciplinary Frontiers
Embody its application value such as：Photoconductive detector, fast ion conducting material, solar energy transition material etc..
The energy gap of different energy gaps, wherein multilayer molybdenum disulfide is presented in molybdenum disulfide due to the crystal number of plies is different
For 1.2rV, the energy gap of individual layer molybdenum disulfide is 1.8eV.Molybdenum disulfide is a kind of semi-conducting material of function admirable, simultaneously
As a kind of transition metal stratiform sulfide, because the performances such as its good optics, electricity, lubrication and catalyst cause people
Extensive concern.The molybdenum disulfide marginal texture of Nano grade is complicated, has very high unsaturation, reactivity is high, in light
Catalyst field causes the extensive concern of people.
Individually using antimony trisulfide as during photochemical catalyst, caused due to its relatively narrow band-gap energy and relatively low quantum efficiency
Its photocatalytic activity is not high, therefore, by becoming very necessary with the compound photocatalysis performance for going to improve antimony trisulfide of other materials.
The content of the invention
It is an object of the invention to overcome defect existing in the prior art, a kind of antimony trisulfide-molybdenum disulfide complex light is provided
The preparation method of catalyst, the antimony trisulfide which obtains-molybdenum disulfide composite photo-catalyst are had excellent performance, and stability is strong, operation
Property it is high, the hexavalent chromium in industrial wastewater can be effectively removed.
To achieve these goals, the technical solution adopted by the present invention is as follows：
The preparation method of antimony trisulfide-molybdenum disulfide composite photo-catalyst of the present invention, it is molten to be dissolved in alcohols by molybdenum disulfide
In agent, gel is prepared using sol-gel method with antimony sulphide colloid solution, is obtained after dry and crystallization.
Preferably, the preparation method of the antimony trisulfide-molybdenum disulfide composite photo-catalyst comprises the following steps：
(1) it is sodium molybdate and sulphur source is soluble in water, hydrothermal synthesis reaction is carried out, obtains molybdenum disulfide；
(2) molybdenum disulfide is added in alcohols solvent, ultrasonic disperse 10-25min obtains mixed solution A；
(3) polyvinylpyrrolidone and potassium antimony tartrate are instilled while stirring in the distilled water containing hydrogen sulfide gas,
It is not open close enter hydrogen sulfide into solution be free of Sb3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, is mixed
Solution B；
(4) mixed solution A is uniformly mixed with mixed solution B, it is 4.8-10.2 then to add in pH adjusting agent and adjust pH value,
Obtain translucent colloidal sol；
(5) gel will be obtained after translucent colloidal sol ripening, then separates solvent and gel；
(6) gel drying is taken, is ground up, sieved, obtains presoma；
(7) presoma of step (6) is maintained at 200-350 DEG C 0.5-5 hours to presoma crystallization to get.
Preferably, when step (1) sodium molybdate and sulphur source carry out hydrothermal synthesis reaction, it is 170- to control heating temperature
225 DEG C, heating time 15-23h.
Preferably, the sulphur source of the step (1) is one in l-cysteine, thioacetamide, sodium thiosulfate, thiocarbamide
Kind.
Preferably, the molar ratio of the sodium molybdate of the step (1) and sulphur source is 1：3-7.
Preferably, the alcohols solvent of the step (2) be methanol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol, propylene glycol, the third three
Mixing more than one or both of alcohol, benzyl alcohol.
Preferably, the polyvinylpyrrolidone and the molar ratio of potassium antimony tartrate that the step (3) adds in are 2.5-5：1.
Preferably, in the step (4), the molar ratio of molybdenum disulfide and antimony trisulfide in mixed solution B is in mixed solution A
0.5-3：6-10.
Preferably, the drying temperature of gel is 45-180 DEG C in the step (6).
Preferably, in the step (6), when sieving, selects grain size in 0.5-10 μm of dry gel particle as forerunner
Body.
The present invention also provides the application processes of the antimony trisulfide-molybdenum disulfide photochemical catalyst：The composite photo-catalyst is added
Be added in the waste water containing hexavalent chromium, light-catalyzed reaction carried out under visible ray or near infrared light, complete to Cr VI from
The reduction of son contains the antimony trisulfide described in 0.5-1.5g-molybdenum disulfide composite photo-catalyst in the waste water of per unit litre.
The present invention is by adopting the above-described technical solution, have the advantages that：
1st, the present invention uses molybdenum disulfide colloidal solution and antimony sulphide colloid solution as raw material, using sol-gel-crystallization
Preparation method, antimony trisulfide-molybdenum disulfide composite photo-catalyst even particle distribution of acquisition, crystal form is made after high temperature crystallization relatively to unite
One, purity is high, and stability is strong, solves using impurity content of beary metal height, distribution of particles in product made from conventional method not
Uniformly, the problems such as photocatalysis performance is poor；The antimony trisulfide that preparation method provided by the invention obtains-molybdenum disulfide composite photo-catalyst
In antimony trisulfide have transmission electron velocity it is fast, light absorption is strong, is not easy to reunite, and adsorption area is big, and molybdenum disulfide has smaller band
Gap width, and photoresponse scope is wide, and the photocatalytic activity of semi-conducting material can be improved as effective co-catalyst, the two is mutually auxiliary
It coordinates, the composite photo-catalyst is made to possess higher photocatalytic activity, photocatalysis efficiency and access times can be improved, reduce light and urge
The use cost of agent.
2nd, antimony trisulfide-molybdenum disulfide composite photo-catalyst that preparation method provided by the invention obtains is in visible ray or near red
Under outer light there is good catalytic performance, can be widely used for light removal waste water from dyestuff field, especially contain Cr VI in light removal
The waste water from dyestuff of ion has excellent performance, there is significant social benefit.
3rd, for the present invention after antimony trisulfide-molybdenum disulfide gel is obtained, the organic solvent among filtrate may be recovered processing,
Secondary use, saving about and raw material can reduce production cost；The preparation method of the present invention is simple for process, simple operation, reacts item
Part is easy to control, of low cost, product excellent catalytic effect, has good development prospect.
Specific embodiment
To make the objectives, technical solutions, and advantages of the present invention more comprehensible, preferred embodiment is enumerated below, to this hair
Bright further description.However, it is necessary to illustrate, many details listed in specification are used for the purpose of making reader to this
The one or more aspects of invention can also realize the present invention's there are one thorough explanation even without these specific details
These aspects.
Embodiment 1
By sodium molybdate and l-cysteine according to 1：3 molar ratio is soluble in water, carries out hydrothermal synthesis reaction, control heating temperature
It spends for 170 DEG C, heating time 15h obtains molybdenum disulfide；Molybdenum disulfide is dissolved in methanol, ultrasonic disperse 10min is obtained
Mixed solution A, it is spare；Instill polyvinylpyrrolidone and antimony tartrate while stirring in the distilled water containing hydrogen sulfide gas
Potassium, the polyvinylpyrrolidone of instillation and the molar ratio of potassium antimony tartrate are 2.5：1, it is not open close enter hydrogen sulfide into solution not
Containing Sb3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, obtains mixed solution B；Mixed solution A is molten with mixing
Liquid B is uniformly mixed, and it is 4.8 then to adjust pH value, obtains translucent colloidal sol；Gel will be obtained after translucent colloidal sol ripening,
Then solvent and gel are separated, is ground up, sieved after taking gel dry at 45 DEG C, grain size is taken to make in 0.5 μm of dry gel particle
For presoma, presoma is maintained at 350 DEG C 0.5 hour to presoma crystallization to get antimony trisulfide-curing of the present invention
Molybdenum composite photo-catalyst；The molar ratio of molybdenum disulfide and antimony trisulfide in mixed solution B is 0.5 in the mixed solution A：6.
Embodiment 2
By sodium molybdate and thioacetamide according to 1：3.8 molar ratio is soluble in water, carries out hydrothermal synthesis reaction, and control adds
Hot temperature is 177 DEG C, and heating time 16h obtains molybdenum disulfide；Molybdenum disulfide is dissolved in ethyl alcohol, ultrasonic disperse 12min,
Mixed solution A is obtained, it is spare；Instill polyvinylpyrrolidone and winestone while stirring in the distilled water containing hydrogen sulfide gas
Sour antimony potassium, the polyvinylpyrrolidone of instillation and the molar ratio of potassium antimony tartrate are 3：1, it is not open close enter hydrogen sulfide into solution
Without Sb3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, obtains mixed solution B；By mixed solution A with mixing
Solution B is uniformly mixed, and it is 5.2 then to adjust pH value, obtains translucent colloidal sol；It will be coagulated after translucent colloidal sol ripening
Then glue separates solvent and gel, be ground up, sieved after taking gel dry at 68 DEG C, take dry gel particle of the grain size at 1.5 μm
As presoma, presoma is maintained at 320 DEG C 1.5 hours to presoma crystallization to get-two sulphur of antimony trisulfide of the present invention
Change molybdenum composite photo-catalyst；The molar ratio of molybdenum disulfide and antimony trisulfide in mixed solution B is 1.2 in the mixed solution A：6.8.
Embodiment 3
By sodium molybdate and sodium thiosulfate according to 1：4.3 molar ratio is soluble in water, carries out hydrothermal synthesis reaction, and control adds
Hot temperature is 186 DEG C, and heating time 17h obtains molybdenum disulfide；Molybdenum disulfide is dissolved in ethyl alcohol, ultrasonic disperse 15min,
Mixed solution A is obtained, it is spare；Instill polyvinylpyrrolidone and winestone while stirring in the distilled water containing hydrogen sulfide gas
Sour antimony potassium, the polyvinylpyrrolidone of instillation and the molar ratio of potassium antimony tartrate are 3.4：1, it is not open close enter hydrogen sulfide to solution
In be free of Sb3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, obtains mixed solution B；By mixed solution A with mixing
It closes solution B to be uniformly mixed, it is 5.6 then to adjust pH value, obtains translucent colloidal sol；It will be coagulated after translucent colloidal sol ripening
Then glue separates solvent and gel, be ground up, sieved after taking gel dry at 90 DEG C, take dry gel particle of the grain size at 3.2 μm
As presoma, presoma is maintained at 300 DEG C 2.6 hours to presoma crystallization to get-two sulphur of antimony trisulfide of the present invention
Change molybdenum composite photo-catalyst；The molar ratio of molybdenum disulfide and antimony trisulfide in mixed solution B is 3 in the mixed solution A：8.8.
Embodiment 4
By sodium molybdate and thiocarbamide according to 1：4.7 molar ratio is soluble in water, carries out hydrothermal synthesis reaction, controls heating temperature
For 190 DEG C, heating time 18h obtains molybdenum disulfide；Molybdenum disulfide is dissolved in the in the mixed solvent of ethyl alcohol and propyl alcohol, ultrasound
Scattered 17min, obtains mixed solution A, spare；Instill polyvinyl pyrrole while stirring in the distilled water containing hydrogen sulfide gas
Alkanone and potassium antimony tartrate, the polyvinylpyrrolidone of instillation and the molar ratio of potassium antimony tartrate are 3.8：1, it is not open close enter sulphur
Change hydrogen and Sb is free of into solution3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, obtains mixed solution B；It will mixing
Solution A is uniformly mixed with mixed solution B, and it is 6.2 then to adjust pH value, obtains translucent colloidal sol；At translucent colloidal sol ageing
Gel is obtained after reason, then separates solvent and gel, is ground up, sieved after taking gel dry at 116 DEG C, takes grain size at 4.5 μm
Dry gel particle as presoma, presoma is maintained at 280 DEG C 3.2 hours to presoma crystallization to get institute of the present invention
State antimony trisulfide-molybdenum disulfide composite photo-catalyst；Molybdenum disulfide rubs with antimony trisulfide in mixed solution B in the mixed solution A
You are than being 2.7：10.
Embodiment 5
By sodium molybdate and l-cysteine according to 1：5.3 molar ratio is soluble in water, carries out hydrothermal synthesis reaction, control heating
Temperature is 195 DEG C, and heating time 19h obtains molybdenum disulfide；Molybdenum disulfide is dissolved in the mixed solvent of ethylene glycol and glycerine
In, ultrasonic disperse 20min obtains mixed solution A, spare；It is instilled while stirring in the distilled water containing hydrogen sulfide gas poly-
Vinylpyrrolidone and potassium antimony tartrate, the polyvinylpyrrolidone of instillation and the molar ratio of potassium antimony tartrate are 4.2：1, not
It is open close enter hydrogen sulfide into solution be free of Sb3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, obtains mixed solution
B；Mixed solution A is uniformly mixed with mixed solution B, it is 6.8 then to adjust pH value, obtains translucent colloidal sol；It will be translucent molten
Gel is obtained after glue ripening, then separates solvent and gel, is ground up, sieved after taking gel dry at 132 DEG C, takes grain size
In 5.9 μm of dry gel particles as presoma, presoma is maintained at 263 DEG C 3.6 hours to presoma crystallization to get this
Invent the antimony trisulfide-molybdenum disulfide composite photo-catalyst；Molybdenum disulfide in mixed solution B with vulcanizing in the mixed solution A
The molar ratio of antimony is 1.9：8.
Embodiment 6
By sodium molybdate and sodium thiosulfate according to 1：5.7 molar ratio is soluble in water, carries out hydrothermal synthesis reaction, and control adds
Hot temperature is 206 DEG C, and heating time 20h obtains molybdenum disulfide；The mixing that molybdenum disulfide is dissolved in benzyl alcohol and propylene glycol is molten
In agent, ultrasonic disperse 22min obtains mixed solution A, spare；It is instilled while stirring in the distilled water containing hydrogen sulfide gas
Polyvinylpyrrolidone and potassium antimony tartrate, the polyvinylpyrrolidone of instillation and the molar ratio of potassium antimony tartrate are 4.5：1, and
It is constantly passed through hydrogen sulfide and Sb is free of into solution3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, obtains mixing molten
Liquid B；Mixed solution A is uniformly mixed with mixed solution B, it is 7.5 then to adjust pH value, obtains translucent colloidal sol；It will be translucent
Gel is obtained after colloidal sol ripening, then separates solvent and gel, is ground up, sieved after taking gel dry at 146 DEG C, takes grain
Footpath in 6.9 μm of dry gel particle as presoma, presoma is maintained at 245 DEG C 4 hours to presoma crystallization to get this
Invent the antimony trisulfide-molybdenum disulfide composite photo-catalyst；Molybdenum disulfide in mixed solution B with vulcanizing in the mixed solution A
The molar ratio of antimony is 2.5：7.
Embodiment 7
By sodium molybdate and thioacetamide according to 1：6.2 molar ratio is soluble in water, carries out hydrothermal synthesis reaction, and control adds
Hot temperature is 210 DEG C, and heating time 21h obtains molybdenum disulfide；Molybdenum disulfide is dissolved in ethylene glycol, ultrasonic disperse
23min obtains mixed solution A, spare；Instill polyvinylpyrrolidone while stirring in the distilled water containing hydrogen sulfide gas
And potassium antimony tartrate, the polyvinylpyrrolidone of instillation and the molar ratio of potassium antimony tartrate are 4.7：1, it is not open close enter hydrogen sulfide
Sb is free of into solution3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, obtains mixed solution B；By mixed solution
A is uniformly mixed with mixed solution B, and it is 8.4 then to adjust pH value, obtains translucent colloidal sol；After translucent colloidal sol ripening
Gel is obtained, then separates solvent and gel, is ground up, sieved after taking gel dry at 160 DEG C, takes grain size solidifying in 8 μm do
Glue particle maintained as presoma, by presoma at 230 DEG C 4.3 hours to presoma crystallization to get vulcanization of the present invention
Antimony-molybdenum disulfide composite photo-catalyst；The molar ratio of molybdenum disulfide and antimony trisulfide in mixed solution B is in the mixed solution A
2.8：9.
Embodiment 8
By sodium molybdate and thiocarbamide according to 1：6.5 molar ratio is soluble in water, carries out hydrothermal synthesis reaction, controls heating temperature
For 218 DEG C, heating time 22h obtains molybdenum disulfide；Molybdenum disulfide is dissolved in benzyl alcohol, ultrasonic disperse 24min is obtained
Mixed solution A, it is spare；Instill polyvinylpyrrolidone and antimony tartrate while stirring in the distilled water containing hydrogen sulfide gas
Potassium, the polyvinylpyrrolidone of instillation and the molar ratio of potassium antimony tartrate are 4.8：1, it is not open close enter hydrogen sulfide into solution not
Containing Sb3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, obtains mixed solution B；Mixed solution A is molten with mixing
Liquid B is uniformly mixed, and it is 9.6 then to adjust pH value, obtains translucent colloidal sol；Gel will be obtained after translucent colloidal sol ripening,
Then solvent and gel are separated, is ground up, sieved after taking gel dry at 170 DEG C, takes dry gel particle conduct of the grain size at 9 μm
Presoma, presoma is maintained at 215 DEG C 4.6 hours to presoma crystallization to get antimony trisulfide-molybdenum disulfide of the present invention
Composite photo-catalyst；The molar ratio of molybdenum disulfide and antimony trisulfide in mixed solution B is 1.7 in the mixed solution A：6.2.
Embodiment 9
By sodium molybdate and thiocarbamide according to 1：7 molar ratio is soluble in water, carries out hydrothermal synthesis reaction, controls the heating temperature to be
225 DEG C, heating time 23h obtains molybdenum disulfide；Molybdenum disulfide is dissolved in benzyl alcohol, ultrasonic disperse 25min is mixed
Solution A is closed, it is spare；Instill polyvinylpyrrolidone and antimony tartrate while stirring in the distilled water containing hydrogen sulfide gas
Potassium, the polyvinylpyrrolidone of instillation and the molar ratio of potassium antimony tartrate are 5：1, it is not open close enter hydrogen sulfide be free of into solution
Sb3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, obtains mixed solution B；By mixed solution A and mixed solution B
It is uniformly mixed, it is 10.2 then to adjust pH value, obtains translucent colloidal sol；Gel will be obtained after translucent colloidal sol ripening, so
Solvent and gel are separated afterwards, are ground up, sieved after taking gel dry at 180 DEG C, are taken dry gel particle conduct of the grain size at 10 μm
Presoma, presoma is maintained at 200 DEG C 5 hours it is multiple to get antimony trisulfide-molybdenum disulfide of the present invention to presoma crystallization
Closing light catalyst；The molar ratio of molybdenum disulfide and antimony trisulfide in mixed solution B is 1.4 in the mixed solution A：7.3.
Claims (10)
1. a kind of preparation method of antimony trisulfide-molybdenum disulfide composite photo-catalyst, it is characterised in that：Molybdenum disulfide is dissolved in alcohol
In class solvent, gel is prepared using sol-gel method with antimony sulphide colloid solution, is obtained after dry and crystallization.
2. the preparation method of antimony trisulfide according to claim 1-molybdenum disulfide composite photo-catalyst, which is characterized in that bag
Include following steps：
(1) it is sodium molybdate and sulphur source is soluble in water, hydrothermal synthesis reaction is carried out, obtains molybdenum disulfide；
(2) molybdenum disulfide is added in alcohols solvent, ultrasonic disperse 10-25min obtains mixed solution A；
(3) polyvinylpyrrolidone and potassium antimony tartrate are instilled while stirring in the distilled water containing hydrogen sulfide gas, not
It is open close enter hydrogen sulfide into solution be free of Sb3+, nitrogen not sulfide hydrogen into the mixed system is then passed to, obtains mixed solution
B；
(4) mixed solution A is uniformly mixed with mixed solution B, it is 4.8-10.2 then to adjust pH value, obtains translucent colloidal sol；
(5) gel will be obtained after translucent colloidal sol ripening, then separates solvent and gel；
(6) gel drying is taken, is ground up, sieved, obtains presoma；
(7) presoma of step (6) is maintained at 200-350 DEG C 0.5-5 hours to presoma crystallization to get.
3. the preparation method of antimony trisulfide according to claim 2-molybdenum disulfide composite photo-catalyst, it is characterised in that：Institute
When stating step (1) sodium molybdate and sulphur source progress hydrothermal synthesis reaction, it is 170-225 DEG C to control heating temperature, heating time 15-
23h。
4. the preparation method of antimony trisulfide according to claim 2-molybdenum disulfide composite photo-catalyst, it is characterised in that：Institute
The sulphur source of step (1) is stated as one kind in l-cysteine, thioacetamide, sodium thiosulfate, thiocarbamide.
5. the preparation method of antimony trisulfide according to claim 2-molybdenum disulfide composite photo-catalyst, it is characterised in that：Institute
It is 1 to state the sodium molybdate of step (1) and the molar ratio of sulphur source：3-7.
6. the preparation method of antimony trisulfide according to claim 2-molybdenum disulfide composite photo-catalyst, it is characterised in that：Institute
The alcohols solvent of step (2) is stated as one kind in methanol, ethyl alcohol, propyl alcohol, butanol, ethylene glycol, propylene glycol, glycerine, benzyl alcohol
Or two or more mixing.
7. the preparation method of antimony trisulfide according to claim 2-molybdenum disulfide composite photo-catalyst, it is characterised in that：Institute
The molar ratio of the polyvinylpyrrolidone and potassium antimony tartrate of stating step (3) addition is 2.5-5：1.
8. the preparation method of antimony trisulfide according to claim 2-molybdenum disulfide composite photo-catalyst, it is characterised in that：Institute
It states in step (4), the molar ratio of molybdenum disulfide and antimony trisulfide in mixed solution B is 0.5-3 in mixed solution A：6-10.
9. the preparation method of antimony trisulfide according to claim 2-molybdenum disulfide composite photo-catalyst, it is characterised in that：Institute
The drying temperature for stating gel in step (6) is 45-180 DEG C.
10. the preparation method of antimony trisulfide as claimed in claim 2-molybdenum disulfide composite photo-catalyst, it is characterised in that：It is described
The step of (6) in, when sieving, selects grain size in 0.5-10 μm of dry gel particle as presoma.
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| CN110681400A (en) * | 2019-09-30 | 2020-01-14 | 内江师范学院 | H-molybdenum trioxide/bimetallic sulfide composite material, preparation method and application |
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536819A (en) * | 2015-12-01 | 2016-05-04 | 湘潭大学 | Graphene/antimony sulfide composite photocatalyst preparation method |
| CN106925302A (en) * | 2017-03-22 | 2017-07-07 | 湖南大学 | Molybdenum bisuphide antimony trisulfide composite and its preparation method and application |
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2017
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN105536819A (en) * | 2015-12-01 | 2016-05-04 | 湘潭大学 | Graphene/antimony sulfide composite photocatalyst preparation method |
| CN106925302A (en) * | 2017-03-22 | 2017-07-07 | 湖南大学 | Molybdenum bisuphide antimony trisulfide composite and its preparation method and application |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN110681400A (en) * | 2019-09-30 | 2020-01-14 | 内江师范学院 | H-molybdenum trioxide/bimetallic sulfide composite material, preparation method and application |
| CN110681400B (en) * | 2019-09-30 | 2022-06-07 | 内江师范学院 | H-molybdenum trioxide/bimetal sulfide composite material, preparation method and application |
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