CN110479316A - A kind of α-molybdenum trioxide@molybdenum disulfide material, preparation method and applications - Google Patents
A kind of α-molybdenum trioxide@molybdenum disulfide material, preparation method and applications Download PDFInfo
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- CN110479316A CN110479316A CN201910864684.2A CN201910864684A CN110479316A CN 110479316 A CN110479316 A CN 110479316A CN 201910864684 A CN201910864684 A CN 201910864684A CN 110479316 A CN110479316 A CN 110479316A
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- moo
- molybdenum
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- molybdenum trioxide
- molybdenum disulfide
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- 229910052982 molybdenum disulfide Inorganic materials 0.000 title claims abstract description 73
- 239000000463 material Substances 0.000 title claims abstract description 63
- JKQOBWVOAYFWKG-UHFFFAOYSA-N molybdenum trioxide Inorganic materials O=[Mo](=O)=O JKQOBWVOAYFWKG-UHFFFAOYSA-N 0.000 title claims abstract description 46
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 229910052961 molybdenite Inorganic materials 0.000 claims abstract description 43
- 229910003149 α-MoO3 Inorganic materials 0.000 claims abstract description 42
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 24
- NASFKTWZWDYFER-UHFFFAOYSA-N sodium;hydrate Chemical compound O.[Na] NASFKTWZWDYFER-UHFFFAOYSA-N 0.000 claims abstract description 20
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 20
- GRYLNZFGIOXLOG-UHFFFAOYSA-N Nitric acid Chemical compound O[N+]([O-])=O GRYLNZFGIOXLOG-UHFFFAOYSA-N 0.000 claims abstract description 18
- 229910017604 nitric acid Inorganic materials 0.000 claims abstract description 18
- VLAPMBHFAWRUQP-UHFFFAOYSA-L molybdic acid Chemical compound O[Mo](O)(=O)=O VLAPMBHFAWRUQP-UHFFFAOYSA-L 0.000 claims abstract description 17
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 12
- 239000000203 mixture Substances 0.000 claims abstract description 10
- 239000004094 surface-active agent Substances 0.000 claims abstract description 9
- 239000002002 slurry Substances 0.000 claims abstract description 8
- 238000006555 catalytic reaction Methods 0.000 claims abstract description 5
- 239000011258 core-shell material Substances 0.000 claims abstract description 5
- 238000004090 dissolution Methods 0.000 claims abstract description 5
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 18
- 238000001816 cooling Methods 0.000 claims description 10
- 235000019441 ethanol Nutrition 0.000 claims description 10
- 239000006228 supernatant Substances 0.000 claims description 10
- MEFBJEMVZONFCJ-UHFFFAOYSA-N molybdate Chemical compound [O-][Mo]([O-])(=O)=O MEFBJEMVZONFCJ-UHFFFAOYSA-N 0.000 claims description 8
- -1 that is Inorganic materials 0.000 claims description 8
- 238000005406 washing Methods 0.000 claims description 7
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 claims description 6
- CWQXQMHSOZUFJS-UHFFFAOYSA-N molybdenum disulfide Chemical compound S=[Mo]=S CWQXQMHSOZUFJS-UHFFFAOYSA-N 0.000 claims description 6
- 238000003756 stirring Methods 0.000 claims description 5
- 239000002351 wastewater Substances 0.000 claims description 5
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 2
- KCXVZYZYPLLWCC-UHFFFAOYSA-N EDTA Chemical compound OC(=O)CN(CC(O)=O)CCN(CC(O)=O)CC(O)=O KCXVZYZYPLLWCC-UHFFFAOYSA-N 0.000 claims description 2
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 2
- 239000004698 Polyethylene Substances 0.000 claims description 2
- 229920002538 Polyethylene Glycol 20000 Polymers 0.000 claims description 2
- 239000002202 Polyethylene glycol Substances 0.000 claims description 2
- 239000004743 Polypropylene Substances 0.000 claims description 2
- 229960001484 edetic acid Drugs 0.000 claims description 2
- 239000007788 liquid Substances 0.000 claims description 2
- 229920000573 polyethylene Polymers 0.000 claims description 2
- 229920001223 polyethylene glycol Polymers 0.000 claims description 2
- 229920001155 polypropylene Polymers 0.000 claims description 2
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 2
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 claims 1
- 229920000428 triblock copolymer Polymers 0.000 claims 1
- BKEOXUSOEGMVTL-UHFFFAOYSA-N trimethyl-$l^{3}-bromane Chemical compound CBr(C)C BKEOXUSOEGMVTL-UHFFFAOYSA-N 0.000 claims 1
- 238000000034 method Methods 0.000 description 14
- 239000011651 chromium Substances 0.000 description 11
- 239000000243 solution Substances 0.000 description 11
- 230000001699 photocatalysis Effects 0.000 description 10
- 238000004458 analytical method Methods 0.000 description 8
- 230000000052 comparative effect Effects 0.000 description 8
- 238000007146 photocatalysis Methods 0.000 description 8
- 230000000694 effects Effects 0.000 description 7
- NBIIXXVUZAFLBC-UHFFFAOYSA-N Phosphoric acid Chemical compound OP(O)(O)=O NBIIXXVUZAFLBC-UHFFFAOYSA-N 0.000 description 4
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 description 3
- 238000006243 chemical reaction Methods 0.000 description 3
- 239000008367 deionised water Substances 0.000 description 3
- 229910021641 deionized water Inorganic materials 0.000 description 3
- 238000001514 detection method Methods 0.000 description 3
- 230000031700 light absorption Effects 0.000 description 3
- 239000002244 precipitate Substances 0.000 description 3
- 238000001179 sorption measurement Methods 0.000 description 3
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 description 2
- 238000002441 X-ray diffraction Methods 0.000 description 2
- 229910000147 aluminium phosphate Inorganic materials 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 239000003054 catalyst Substances 0.000 description 2
- 230000003197 catalytic effect Effects 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000010835 comparative analysis Methods 0.000 description 2
- 235000013399 edible fruits Nutrition 0.000 description 2
- 229910001385 heavy metal Inorganic materials 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 239000002904 solvent Substances 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- 241000894006 Bacteria Species 0.000 description 1
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 241001529739 Prunella <angiosperm> Species 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000009395 breeding Methods 0.000 description 1
- 230000001488 breeding effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- ZCDOYSPFYFSLEW-UHFFFAOYSA-N chromate(2-) Chemical compound [O-][Cr]([O-])(=O)=O ZCDOYSPFYFSLEW-UHFFFAOYSA-N 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 229910001430 chromium ion Inorganic materials 0.000 description 1
- 239000003426 co-catalyst Substances 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 239000010949 copper Substances 0.000 description 1
- XJWSAJYUBXQQDR-UHFFFAOYSA-M dodecyltrimethylammonium bromide Chemical compound [Br-].CCCCCCCCCCCC[N+](C)(C)C XJWSAJYUBXQQDR-UHFFFAOYSA-M 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 239000000706 filtrate Substances 0.000 description 1
- 238000001914 filtration Methods 0.000 description 1
- 235000013373 food additive Nutrition 0.000 description 1
- 239000002778 food additive Substances 0.000 description 1
- 239000010842 industrial wastewater Substances 0.000 description 1
- 150000002500 ions Chemical class 0.000 description 1
- 230000001665 lethal effect Effects 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 239000012528 membrane Substances 0.000 description 1
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 1
- 229910052753 mercury Inorganic materials 0.000 description 1
- 244000005700 microbiome Species 0.000 description 1
- 239000011259 mixed solution Substances 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 150000002989 phenols Chemical class 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 229920000642 polymer Polymers 0.000 description 1
- 230000001376 precipitating effect Effects 0.000 description 1
- 238000001556 precipitation Methods 0.000 description 1
- 238000003672 processing method Methods 0.000 description 1
- 230000001681 protective effect Effects 0.000 description 1
- 102000004169 proteins and genes Human genes 0.000 description 1
- 108090000623 proteins and genes Proteins 0.000 description 1
- 230000006798 recombination Effects 0.000 description 1
- 238000005215 recombination Methods 0.000 description 1
- 238000000985 reflectance spectrum Methods 0.000 description 1
- 238000005070 sampling Methods 0.000 description 1
- 231100000331 toxic Toxicity 0.000 description 1
- 230000002588 toxic effect Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 230000009466 transformation Effects 0.000 description 1
- 239000003403 water pollutant Substances 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 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—
-
- B01J35/39—
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/02—Oxides; Hydroxides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G39/00—Compounds of molybdenum
- C01G39/06—Sulfides
-
- 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
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/10—Particle morphology extending in one dimension, e.g. needle-like
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/80—Particles consisting of a mixture of two or more inorganic phases
-
- 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
- C02F2305/00—Use of specific compounds during water treatment
- C02F2305/10—Photocatalysts
Abstract
The invention discloses a kind of α-molybdenum trioxide@molybdenum disulfide materials, preparation method and applications, belong to catalysis material technical field.Wherein, α-molybdenum trioxide@molybdenum disulfide material be in rodlike core-shell structure, core by club shaped structure α-MoO3Composition, shell are by MoS2The film of composition.The preparation method comprises the following steps: two molybdic acid hydrate sodium are added to the water, ultrasonic dissolution adds concentrated nitric acid, is stirred to react, and then carries out hydro-thermal reaction, obtains α-MoO3Presoma；By α-MoO3Presoma, surfactant, two molybdic acid hydrate sodium and thiocarbamide are added in acetonitrile, are stirred to react, are obtained α-MoO3Slurry；By α-MoO3Slurry carries out hydro-thermal reaction to get α-MoO3@MoS2Material.α-MoO of the invention3@MoS2Material feedstock is easy to get, is at low cost, preparation process is simple, has great application value in fields such as catalysis materials.
Description
Technical field
The invention belongs to catalysis material technical fields, and in particular to a kind of α-molybdenum trioxide@molybdenum disulfide material, preparation
Method and its application.
Background technique
Water pollutant includes organic pollutant and inorganic pollution.Organic pollutant mainly includes oxygen consumption non-toxic organic object
(such as protein, fat and carbohydrate) and toxic organic compound (such as phenolic compound, organic agricultural chemicals and polycyclic aromatic hydrocarbon, dye
Material and food additives etc.).Inorganic pollution mainly includes lead, chromium, every the heavy metal ion such as, mercury and copper.Wherein chromium ion is
Cr (VI) is more easily absorbed by the body, and accumulates in human body, and toxicity is stronger, even has lethal effect to aquatile, and not
It can be decomposed by the microorganisms, be listed in one of maximum concentration element of harm to the human body, be internationally recognized three kinds of carcinogenic substance heavy metals
One of.
Currently, the processing method of chromate waste water mainly has materialization treatment process, method of chemical treatment and biological treatment.Wherein,
Materialization treatment process there are one-time investments big, complex process, takes up a large area and operating cost is higher, operational administrative level requirement
The problems such as stringent, therefore the industrial wastewater very big for water, the method are economically not suitable for.There are technique streams for method of chemical treatment
Journey is long, and the device is complicated and to cause secondary pollution problems.Biological treatment is the growth and breeding by bacterium, by restoring,
The problems such as absorption absorbs and the effects of ultraproduct is tired, removes the process of Cr (VI) in waste water, long there is also process flow.
Photocatalytic method is restored under conditions of light to the Cr (VI) in water using photochemical catalyst, and Cr is restored
(III), Cr (OH) then is generated with OH- again3Precipitation form is got rid of, and the method is environmentally protective in terms of handling waste water, processing
Simple process.Although spending not small in the preparation production of photochemical catalyst, sunlight is inexhaustible, inexhaustible, is not required to cost, such as
Fruit can obtain effective and reasonable using in the industry will greatly push social industrial expansion, therefore photocatalysis is still
The hot spot to make internal disorder or usurp grinds with great concentration in many team.
MoO3Based on its unique layer structure, electronic structure, stability and photocatalytic activity, it is widely used as light and urges
Agent.However, MoO3Band gap magnitude (2.8e V~3.2e V) is larger, can only respond ultraviolet light and small part visible light, limit
Its potentiality in photocatalysis field application.In addition, MoO3Photo-generated carrier recombination rate it is higher.Therefore, it widens visible light-responded
Range and raising photo-generated carrier component efficiency are to raising MoO3Photocatalytic activity it is most important.MoS2As a kind of co-catalyst
There is good catalytic activity, however, MoS2Tend to that multilayer stacking states are presented, active site is predominantly located at edge
It is restricted its efficiency.
Summary of the invention
Therefore, the present invention provides a kind of α-molybdenum trioxide@molybdenum disulfide materials, preparation method and applications.
In order to achieve the above objectives, inventor is studied for a long period of time and is largely practiced, and is able to propose technical solution of the present invention,
Specific implementation process is as follows:
1. a kind of α-molybdenum trioxide@molybdenum disulfide material, the α-molybdenum trioxide@molybdenum disulfide material, that is, α-MoO3@MoS2
Material is in rodlike core-shell structure；The core by club shaped structure molybdenum trioxide, that is, α-MoO3Composition；The shell is for molybdenum disulfide
MoS2The film of composition.
2. a kind of α-molybdenum trioxide@molybdenum disulfide material preparation method, comprising the following steps:
S1, two molybdic acid hydrate sodium are added to the water, ultrasonic dissolution adds concentrated nitric acid, under the conditions of 20~40 DEG C, stirs
0.5~2h of reaction is mixed to get molybdate nitric acid solution；
S2, under the conditions of 160~200 DEG C, molybdate nitric acid solution is subjected to 8~16h of hydro-thermal reaction, after it is cooling,
Supernatant is removed, is precipitated, is washed, it is dry, obtain α-MoO3Presoma；
S3, by α-MoO3Presoma, surfactant, two molybdic acid hydrate sodium and thiocarbamide are added in acetonitrile, 20~50
1~3h is stirred under the conditions of DEG C, obtains α-MoO3Slurry；
S4, under the conditions of 170~190 DEG C, by α-MoO3Slurry carries out 9~10h of hydro-thermal reaction, after cooling, removal
Supernatant is precipitated, washing, dry to get α-MoO3@MoS2Material；
In the S1, two molybdic acid hydrate sodium, water and concentrated nitric acid are calculated as 1~2:100~200:5~15 by g:mL:mL；
In the S3, α-MoO3Presoma, surfactant, two molybdic acid hydrate sodium, thiocarbamide and acetonitrile press g:g:g:g:mL
It is calculated as 0.8~2:1~20:0.1~0.3:0.05~10:300~2000.
Wherein, purpose ultrasonic in S1 is to keep two molybdic acid hydrate sodium evenly dispersed in water；Gained molybdic acid sal prunella in S1
Acid solution is clear mixed solution；After removing supernatant in S1, what is obtained is precipitated as white precipitate；Supernatant is removed in S4
Afterwards, what is obtained is precipitated as black precipitate.
Preferably, in the S1, the mode that concentrated nitric acid is added is to be added dropwise.
Preferably, in the S2 and S4, the type of cooling is natural cooling under room temperature.
Preferably, in the S2 and S4, drying mode is to dry 12h under the conditions of 60 DEG C.
Preferably, water described in above-mentioned steps is deionized water.
Preferably, in the S3, surfactant is total for polyethylene oxide-polypropylene oxide-polyethylene oxide three block
Polymers, that is, P123, cetyl trimethylammonium bromide, PEG 20000, ethylenediamine tetra-acetic acid, polyvinylpyrrolidone
58000, one of dodecyl trimethyl ammonium bromide and polyethylene glycol 10000 or a variety of.
Preferably, in the S2 and S4, washing is first washed with water 2 times, then is washed 2 times with alcohol.
Preferably, the alcohol is methanol or ethyl alcohol.
Preferably, in the S1, molybdate, water and concentrated nitric acid are calculated as 1.7:140:10 by g:mL:mL.
Preferably, in the S3, α-MoO3Presoma, surfactant, two molybdic acid hydrate sodium, thiocarbamide and acetonitrile press g:g:
G:g:mL is calculated as 1:5:0.2:0.1:340.
Preferably, in the S4, the temperature of hydro-thermal reaction is 180 DEG C, time 10h.
3. the application that α-molybdenum trioxide@molybdenum disulfide material is used as catalysis material in the treatment of waste water.
The beneficial effects of the present invention are:
α of the invention-molybdenum trioxide@molybdenum disulfide material is in rodlike core-shell structure, and core is the molybdenum trioxide of club shaped structure
That is α-MoO3Composition, shell are molybdenum disulfide, that is, MoS2The film of composition, because of its area load MoS2Film reduces band gap magnitude, opens up
The wide response range of visible light and photo-generated carrier component efficiency is improved, meanwhile, MoS2It forms film and is covered on club shaped structure
α-MoO3Surface, solve MoS2The case where in multilayer stacking states, make MoS2More edge active sites are exposed, from
And improve MoS2Photocatalytic activity, therefore, α-MoO3@MoS2Material is relative to independent α-MoO3And MoS2For, shell
MoS2More edge active sites are exposed, have given full play to catalytic activity, and then have stronger photocatalysis to imitate Cr (VI)
Fruit.
Detailed description of the invention
Fig. 1 is α of the invention-molybdenum trioxide@molybdenum disulfide material scanning electron microscope (SEM) figure；
Fig. 2 is α of the invention-molybdenum trioxide@molybdenum disulfide material X-ray diffraction (XRD) figure；
Fig. 3 is α of the invention-molybdenum trioxide@molybdenum disulfide material transmission electron microscope figure；
Fig. 4 is α of the invention-molybdenum trioxide@molybdenum disulfide material and α-molybdenum trioxide density of photocurrent figure；
Fig. 5 is α of the invention-molybdenum trioxide@molybdenum disulfide material and α-molybdenum trioxide ultraviolet-visible diffuse reflectance spectrum
Figure；
Fig. 6 is α of the invention-molybdenum trioxide@molybdenum disulfide material photocatalysis effect figure.
Specific embodiment
Below by specific embodiment, the invention will be further described, so that those skilled in the art can be better
Understand the present invention and can be practiced, but illustrated embodiment is not as a limitation of the invention.
Embodiment 1
A kind of preparation method of α-molybdenum trioxide@molybdenum disulfide material, comprising the following steps:
S1, bis- molybdic acid hydrate sodium of 1.7g is added in 140mL water, ultrasonic dissolution adds 10mL concentrated nitric acid, at 30 DEG C
Under the conditions of, 1h is stirred to react to get molybdate nitric acid solution；
S2, molybdate nitric acid solution is subjected to hydro-thermal reaction, after it is cooling, remove supernatant, precipitated, first use water
Washing 2 times, then with ethanol washing 2 times, it is dry, obtain α-MoO3Presoma；
S3, the α-MoO by 1g3Presoma, the two molybdic acid hydrate sodium of P123,0.2g of 5g and the thiocarbamide of 0.1g are added to
In 340mL acetonitrile, it is stirred to react 2h under the conditions of 30 DEG C, obtains α-MoO3Slurry；
S4, under the conditions of 180 DEG C, by α-MoO3Slurry carries out solvent thermal reaction 10h, after it is cooling, remove supernatant,
It is precipitated, is first washed with water 2 times, then with ethanol washing 2 times to get α-MoO3@MoS2Material.
By α-MoO obtained by the present embodiment3@MoS2Material does scanning electron microscope detection, parameter setting are as follows: SEM HV:
30.0KV, SEM MAG:6.33KX, WD:16.11mm, View field:32.8 μm, as a result as shown in Figure 1.
The observation analysis from Fig. 1 is it is found that α-MoO3@MoS2Material is in size, is evenly distributed, and length is 5 μm, and diameter is
The club shaped structure of 300nm.It is learnt through comprehensive analysis, the present embodiment is most preferred embodiment.
By α-MoO obtained by the present embodiment3@MoS2Material does XRD detection and analysis, as a result as shown in Figure 2.
Analysis is it is found that α-MoO from Fig. 23@MoS2The characteristic diffraction peak of material includes MoO3(110), (040), (211)
And MoS2(002), the characteristic diffraction peak of (100), sufficiently demonstrating obtained material is α-MoO3@MoS2Material.
By α-MoO obtained by the present embodiment3@MoS2Material does transmission electron microscope figure, as a result as shown in Figure 3.
The observation analysis from Fig. 3 is it is found that α-MoO obtained by the present embodiment3@MoS2Material is in apparent core-shell structure, and
Outer membrane is MoS2, kernel is α-MoO3。
By α-MoO obtained by the present embodiment3@MoS2Material and α-MoO3Density of photocurrent analysis is done, as a result such as Fig. 4 institute
Show.
The comparative analysis from Fig. 4 is it is found that α-MoO of the invention3@MoS2Material due to light induced electron and hole it is compound
Rate reduces, so its density of photocurrent increases.
By α-MoO obtained by the present embodiment3@MoS2Material does UV-Vis DRS analysis, as a result as shown in Figure 5.
The comparative analysis from Fig. 5 is it is found that α-MoO3To light absorption boundary in 440nm, α-MoO3@MoS2Its light absorption of material
Boundary is relative to α-MoO3Red shift occurs, it was demonstrated that the two forms composite material.
Embodiment 2
In the present embodiment, except the α-MoO of 1g in S33Presoma replaces with 2g, P123 5g, and two molybdic acid hydrate sodium are 3g,
Thiocarbamide is 0.5g, and the temperature of acetonitrile 500mL, hydro-thermal reaction are other than 190 DEG C, remaining is same as Example 1.
Embodiment 3
In the present embodiment, except bis- molybdic acid hydrate sodium of 1.7g replaces with 1g, water 100mL in S1, in concentrated nitric acid 5mL, S3
The temperature of hydro-thermal reaction is 170 DEG C, and the time is other than 9h, remaining is same as Example 1.
Comparative examples 1
It by bis- molybdic acid hydrate sodium of 1.7g, is added in 140ml water, ultrasonic dissolution, then 10ml concentrated nitric acid is added dropwise.In 30 DEG C of conditions
It is lower, it stirs 1 hour, obtains molybdate nitric acid solution.Clear solution is subjected to hydro-thermal reaction again, after cooling, removes supernatant,
White precipitate is used into water respectively, ethyl alcohol respectively washs 2 times, then dries 12h under the conditions of 60 DEG C, obtain α-MoO3。
Comparative examples 2
Bis- molybdic acid hydrate sodium of 2g, 12gP123,9g thiocarbamide are added in 1500ml acetonitrile, stir 2h under the conditions of 30 DEG C, so
Solvent thermal reaction 10h is carried out under the conditions of 180 DEG C afterwards, it is cooling, supernatant is removed, precipitating is respectively washed two with water and ethyl alcohol respectively
It is secondary, 12h finally is dried under the conditions of 60 DEG C, obtains MoS2。
Examples 1 to 3 and the resulting material of comparative examples 1~2 are subjected to the detection of photocatalysis adsorption effect, concrete operations
Are as follows: take Cr (VI) solution that 100ml concentration is 100mg/L in beaker, respectively Example 1~3 and comparative examples 1~2
Resulting material 100mg first carries out being protected from light absorption 0.5h at room temperature, reaches absorption-parsing balance and then using xenon lamp
Source carries out photocatalysis treatment, and filter is obtained by filtration using filter respectively at 20min, 40min, 60min, 80min, 100min sampling
Liquid takes 100 μ L of filtrate, is added in 10mL colorimetric cylinder, and 0.5ml dilute sulfuric acid is added, and (1:1 is dilute by volume with deionized water for the concentrated sulfuric acid
Release) with after 0.5ml phosphoric acid,diluted (1:1 dilutes by volume for concentrated phosphoric acid and deionized water), it adds 2ml color developing agent and (takes 0.2g bis-
Phe Sc is dissolved in 50ml acetone, adds 100ml volumetric flask, adds water constant volume to graduation mark), after carrying out color development treatment, adopt
Cr (VI) concentration is tested with UV-4802 type ultra-violet and visible spectrophotometer, as a result as shown in Figure 6.
In Fig. 6, abscissa is adsorption time, and ordinate is the percentage composition of Cr (VI) in detected solution, α-MoO3It is corresponding
MoO made from comparative examples 13Material, MoS2MoS made from corresponding comparative examples 22Material, α-MoO3@MoS2- 1 is corresponding real
Apply α-MoO made from example 13@MoS2Material, α-MoO3@MoS2α-MoO made from -2 corresponding embodiments 23@MoS2Material, α-
MoO3@MoS2α-MoO made from -3 corresponding embodiments 33@MoS2Material, analysis is it is found that α-made from Examples 1 to 3 from figure
MoO3@MoS2The photocatalysis effect of material is than α-MoO made from comparative examples 13With MoS made from comparative examples 22More preferably,
Wherein, when adsorption time is more than 130min, the percentage composition of the Cr (VI) in solution is 0.2% hereinafter, illustrating to pass through reality
Apply α-MoO made from example 13@MoS2The photocatalysis effect of material is best.
Embodiment described above is only to absolutely prove preferred embodiment that is of the invention and being lifted, protection model of the invention
It encloses without being limited thereto.Those skilled in the art's made equivalent substitute or transformation on the basis of the present invention, in the present invention
Protection scope within.Protection scope of the present invention is subject to claims.
Claims (9)
1. a kind of α-molybdenum trioxide@molybdenum disulfide material, which is characterized in that the α-molybdenum trioxide@molybdenum disulfide material, that is, α-
MoO3@MoS2Material is in rodlike core-shell structure；The core by club shaped structure molybdenum trioxide, that is, α-MoO3Composition；The shell is two
Molybdenum sulfide, that is, MoS2The film of composition.
2. a kind of preparation method of α-molybdenum trioxide@molybdenum disulfide material as described in power 1, which comprises the following steps:
S1, two molybdic acid hydrate sodium are added to the water, ultrasonic dissolution adds concentrated nitric acid, and under the conditions of 20~40 DEG C, stirring is anti-
Answer 0.5~2h to get molybdate nitric acid solution；
S2, under the conditions of 160~200 DEG C, molybdate nitric acid solution is subjected to 8~16h of hydro-thermal reaction, after cooling, removal
Supernatant is precipitated, and is washed, dry, obtains α-MoO3Presoma；
S3, by α-MoO3Presoma, surfactant, two molybdic acid hydrate sodium and thiocarbamide are added in acetonitrile, in 20~50 DEG C of conditions
1~3h of lower stirring, obtains α-MoO3Slurry；
S4, under the conditions of 170~190 DEG C, by α-MoO3Slurry carries out 9~10h of hydro-thermal reaction, after it is cooling, remove supernatant
Liquid is precipitated, washing, dry to get α-MoO3@MoS2Material；
In the S1, two molybdic acid hydrate sodium, water and concentrated nitric acid are calculated as 1~2:100~200:5~15 by g:mL:mL；
In the S3, α-MoO3Presoma, surfactant, two molybdic acid hydrate sodium, thiocarbamide and acetonitrile are calculated as by g:g:g:g:mL
0.8~2:1~20:0.1~0.3:0.05~10:300~2000.
3. a kind of α-molybdenum trioxide@molybdenum disulfide material preparation method according to claim 2, which is characterized in that described
In S3, surfactant is polyethylene oxide-polypropylene oxide-polyethylene oxide triblock copolymer, that is, P123, cetyl
Trimethylammonium bromide, PEG 20000, ethylenediamine tetra-acetic acid, polyvinylpyrrolidone 58000, trimethyl bromine
Change one of ammonium and polyethylene glycol 10000 or a variety of.
4. a kind of α-molybdenum trioxide@molybdenum disulfide material preparation method according to claim 2, which is characterized in that described
In S2 and S4, washing is first to be washed with water 2 times, then washed 2 times with alcohol.
5. a kind of α-molybdenum trioxide@molybdenum disulfide material preparation method according to claim 4, which is characterized in that described
Alcohol is methanol or ethyl alcohol.
6. a kind of α-molybdenum trioxide@molybdenum disulfide material preparation method according to claim 2, which is characterized in that described
In S1, two molybdic acid hydrate sodium, water and concentrated nitric acid are calculated as 1.7:140:10 by g:mL:mL.
7. a kind of α-molybdenum trioxide@molybdenum disulfide material preparation method according to claim 2, which is characterized in that described
In S3, α-MoO3Presoma, surfactant, two molybdic acid hydrate sodium, thiocarbamide and acetonitrile are calculated as 1:5:0.2 by g:g:g:g:mL:
0.1:340。
8. a kind of α-molybdenum trioxide@molybdenum disulfide material preparation method according to claim 2, which is characterized in that described
In S4, the temperature of hydro-thermal reaction is 180 DEG C, time 10h.
9. the application that α as described in claim 1-molybdenum trioxide@molybdenum disulfide material is used as catalysis material in the treatment of waste water.
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| CN114975941A (en) * | 2022-06-06 | 2022-08-30 | 郑州轻工业大学 | Bamboo-shaped MoO with tortoise back x /MoS 2 Hybrid material/C, preparation method and application thereof |
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