CN107469834A - A kind of ZnS/CuS nanometer sheets composite photo-catalyst preparation method - Google Patents
A kind of ZnS/CuS nanometer sheets composite photo-catalyst preparation method Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 35
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 239000011941 photocatalyst Substances 0.000 title abstract description 6
- WEVYAHXRMPXWCK-UHFFFAOYSA-N Acetonitrile Chemical compound CC#N WEVYAHXRMPXWCK-UHFFFAOYSA-N 0.000 claims abstract description 30
- 239000002135 nanosheet Substances 0.000 claims abstract description 23
- 239000000243 solution Substances 0.000 claims abstract description 17
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 15
- UMGDCJDMYOKAJW-UHFFFAOYSA-N thiourea Chemical compound NC(N)=S UMGDCJDMYOKAJW-UHFFFAOYSA-N 0.000 claims abstract description 14
- 239000010949 copper Substances 0.000 claims abstract description 11
- 239000011259 mixed solution Substances 0.000 claims abstract description 11
- 238000003756 stirring Methods 0.000 claims abstract description 11
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims abstract description 8
- 238000001816 cooling Methods 0.000 claims abstract description 7
- TVZPLCNGKSPOJA-UHFFFAOYSA-N copper zinc Chemical compound [Cu].[Zn] TVZPLCNGKSPOJA-UHFFFAOYSA-N 0.000 claims abstract description 7
- 239000008367 deionised water Substances 0.000 claims abstract description 7
- 229910021641 deionized water Inorganic materials 0.000 claims abstract description 7
- 238000001027 hydrothermal synthesis Methods 0.000 claims abstract description 7
- 239000002055 nanoplate Substances 0.000 claims abstract description 7
- 239000000047 product Substances 0.000 claims abstract description 7
- 239000006228 supernatant Substances 0.000 claims abstract description 7
- XIOUDVJTOYVRTB-UHFFFAOYSA-N 1-(1-adamantyl)-3-aminothiourea Chemical compound C1C(C2)CC3CC2CC1(NC(=S)NN)C3 XIOUDVJTOYVRTB-UHFFFAOYSA-N 0.000 claims abstract description 5
- 239000011701 zinc Substances 0.000 claims abstract description 5
- 238000006243 chemical reaction Methods 0.000 claims abstract description 4
- 239000004094 surface-active agent Substances 0.000 claims abstract description 4
- SXTLQDJHRPXDSB-UHFFFAOYSA-N copper;dinitrate;trihydrate Chemical compound O.O.O.[Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O SXTLQDJHRPXDSB-UHFFFAOYSA-N 0.000 claims abstract description 3
- 239000002994 raw material Substances 0.000 claims abstract description 3
- 238000002604 ultrasonography Methods 0.000 claims abstract description 3
- 229910052802 copper Inorganic materials 0.000 claims description 8
- OSFGNZOUZOPXBL-UHFFFAOYSA-N nitric acid;trihydrate Chemical compound O.O.O.O[N+]([O-])=O OSFGNZOUZOPXBL-UHFFFAOYSA-N 0.000 claims description 6
- 229920001223 polyethylene glycol Polymers 0.000 claims description 4
- LZZYPRNAOMGNLH-UHFFFAOYSA-M Cetrimonium bromide Chemical compound [Br-].CCCCCCCCCCCCCCCC[N+](C)(C)C LZZYPRNAOMGNLH-UHFFFAOYSA-M 0.000 claims description 3
- 239000002202 Polyethylene glycol Substances 0.000 claims description 3
- 239000003795 chemical substances by application Substances 0.000 claims description 3
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims description 3
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims description 3
- RCEAADKTGXTDOA-UHFFFAOYSA-N OS(O)(=O)=O.CCCCCCCCCCCC[Na] Chemical group OS(O)(=O)=O.CCCCCCCCCCCC[Na] RCEAADKTGXTDOA-UHFFFAOYSA-N 0.000 claims description 2
- 239000000203 mixture Substances 0.000 claims description 2
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims description 2
- DGAQECJNVWCQMB-PUAWFVPOSA-M Ilexoside XXIX Chemical compound C[C@@H]1CC[C@@]2(CC[C@@]3(C(=CC[C@H]4[C@]3(CC[C@@H]5[C@@]4(CC[C@@H](C5(C)C)OS(=O)(=O)[O-])C)C)[C@@H]2[C@]1(C)O)C)C(=O)O[C@H]6[C@@H]([C@H]([C@@H]([C@H](O6)CO)O)O)O.[Na+] DGAQECJNVWCQMB-PUAWFVPOSA-M 0.000 claims 1
- 230000003213 activating effect Effects 0.000 claims 1
- 238000002156 mixing Methods 0.000 claims 1
- 229910052708 sodium Inorganic materials 0.000 claims 1
- 239000011734 sodium Substances 0.000 claims 1
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 abstract description 42
- 239000005083 Zinc sulfide Substances 0.000 abstract description 41
- 238000000034 method Methods 0.000 abstract description 18
- 239000000463 material Substances 0.000 abstract description 7
- 230000001699 photocatalysis Effects 0.000 abstract description 5
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 abstract description 4
- 230000015556 catabolic process Effects 0.000 description 9
- 238000006731 degradation reaction Methods 0.000 description 9
- 229910001385 heavy metal Inorganic materials 0.000 description 7
- 150000002500 ions Chemical class 0.000 description 6
- 229920001343 polytetrafluoroethylene Polymers 0.000 description 6
- 239000004810 polytetrafluoroethylene Substances 0.000 description 6
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 5
- -1 copper Chemical class 0.000 description 5
- 238000005516 engineering process Methods 0.000 description 5
- 238000007254 oxidation reaction Methods 0.000 description 5
- PYWVYCXTNDRMGF-UHFFFAOYSA-N rhodamine B Chemical compound [Cl-].C=12C=CC(=[N+](CC)CC)C=C2OC2=CC(N(CC)CC)=CC=C2C=1C1=CC=CC=C1C(O)=O PYWVYCXTNDRMGF-UHFFFAOYSA-N 0.000 description 5
- 229940043267 rhodamine b Drugs 0.000 description 5
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 4
- 238000010521 absorption reaction Methods 0.000 description 4
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 4
- 239000003054 catalyst Substances 0.000 description 4
- 244000005700 microbiome Species 0.000 description 4
- 230000003647 oxidation Effects 0.000 description 4
- JGPSMWXKRPZZRG-UHFFFAOYSA-N zinc;dinitrate;hexahydrate Chemical class O.O.O.O.O.O.[Zn+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O JGPSMWXKRPZZRG-UHFFFAOYSA-N 0.000 description 4
- XLOMVQKBTHCTTD-UHFFFAOYSA-N Zinc monoxide Chemical compound [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000007788 liquid Substances 0.000 description 3
- 239000012528 membrane Substances 0.000 description 3
- 238000001556 precipitation Methods 0.000 description 3
- 239000013049 sediment Substances 0.000 description 3
- 238000000926 separation method Methods 0.000 description 3
- 239000000126 substance Substances 0.000 description 3
- XOLBLPGZBRYERU-UHFFFAOYSA-N tin dioxide Chemical compound O=[Sn]=O XOLBLPGZBRYERU-UHFFFAOYSA-N 0.000 description 3
- 239000002351 wastewater Substances 0.000 description 3
- 206010013786 Dry skin Diseases 0.000 description 2
- MHAJPDPJQMAIIY-UHFFFAOYSA-N Hydrogen peroxide Chemical compound OO MHAJPDPJQMAIIY-UHFFFAOYSA-N 0.000 description 2
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 description 2
- MCMNRKCIXSYSNV-UHFFFAOYSA-N ZrO2 Inorganic materials O=[Zr]=O MCMNRKCIXSYSNV-UHFFFAOYSA-N 0.000 description 2
- 230000008859 change Effects 0.000 description 2
- 238000002144 chemical decomposition reaction Methods 0.000 description 2
- 238000001311 chemical methods and process Methods 0.000 description 2
- 230000000593 degrading effect Effects 0.000 description 2
- 239000003651 drinking water Substances 0.000 description 2
- 235000020188 drinking water Nutrition 0.000 description 2
- 238000001035 drying Methods 0.000 description 2
- 239000000975 dye Substances 0.000 description 2
- 230000007613 environmental effect Effects 0.000 description 2
- 239000003344 environmental pollutant Substances 0.000 description 2
- 235000019441 ethanol Nutrition 0.000 description 2
- 239000003673 groundwater Substances 0.000 description 2
- JEGUKCSWCFPDGT-UHFFFAOYSA-N h2o hydrate Chemical compound O.O JEGUKCSWCFPDGT-UHFFFAOYSA-N 0.000 description 2
- 238000005342 ion exchange Methods 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 231100000252 nontoxic Toxicity 0.000 description 2
- 230000003000 nontoxic effect Effects 0.000 description 2
- RVTZCBVAJQQJTK-UHFFFAOYSA-N oxygen(2-);zirconium(4+) Chemical compound [O-2].[O-2].[Zr+4] RVTZCBVAJQQJTK-UHFFFAOYSA-N 0.000 description 2
- 239000002957 persistent organic pollutant Substances 0.000 description 2
- 231100000719 pollutant Toxicity 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003672 processing method Methods 0.000 description 2
- 238000005067 remediation Methods 0.000 description 2
- 239000002352 surface water Substances 0.000 description 2
- 239000002699 waste material Substances 0.000 description 2
- 239000003403 water pollutant Substances 0.000 description 2
- 229910052725 zinc Inorganic materials 0.000 description 2
- VYZAMTAEIAYCRO-UHFFFAOYSA-N Chromium Chemical compound [Cr] VYZAMTAEIAYCRO-UHFFFAOYSA-N 0.000 description 1
- 208000031320 Teratogenesis Diseases 0.000 description 1
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 description 1
- 230000035508 accumulation Effects 0.000 description 1
- 238000009825 accumulation Methods 0.000 description 1
- PBCJIPOGFJYBJE-UHFFFAOYSA-N acetonitrile;hydrate Chemical compound O.CC#N PBCJIPOGFJYBJE-UHFFFAOYSA-N 0.000 description 1
- 230000001154 acute effect Effects 0.000 description 1
- 231100000570 acute poisoning Toxicity 0.000 description 1
- 239000003463 adsorbent Substances 0.000 description 1
- 239000003905 agrochemical Substances 0.000 description 1
- 150000001336 alkenes Chemical class 0.000 description 1
- 231100000693 bioaccumulation Toxicity 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 159000000007 calcium salts Chemical class 0.000 description 1
- 230000000711 cancerogenic effect Effects 0.000 description 1
- 150000001720 carbohydrates Chemical class 0.000 description 1
- 231100000357 carcinogen Toxicity 0.000 description 1
- 239000003183 carcinogenic agent Substances 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000009388 chemical precipitation Methods 0.000 description 1
- 229910052804 chromium Inorganic materials 0.000 description 1
- 239000011651 chromium Substances 0.000 description 1
- 231100000739 chronic poisoning Toxicity 0.000 description 1
- 238000000975 co-precipitation Methods 0.000 description 1
- 150000001875 compounds Chemical class 0.000 description 1
- 238000009833 condensation Methods 0.000 description 1
- 230000005494 condensation Effects 0.000 description 1
- 238000011109 contamination Methods 0.000 description 1
- 238000000354 decomposition reaction Methods 0.000 description 1
- 238000000502 dialysis Methods 0.000 description 1
- 238000004090 dissolution Methods 0.000 description 1
- 230000035622 drinking Effects 0.000 description 1
- 238000003894 drinking water pollution Methods 0.000 description 1
- 230000005611 electricity Effects 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
- 238000010353 genetic engineering Methods 0.000 description 1
- 230000002427 irreversible effect Effects 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 238000004519 manufacturing process Methods 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
- 230000004060 metabolic process Effects 0.000 description 1
- 229910021645 metal ion Inorganic materials 0.000 description 1
- 238000002703 mutagenesis Methods 0.000 description 1
- 231100000350 mutagenesis Toxicity 0.000 description 1
- 150000002894 organic compounds Chemical class 0.000 description 1
- GSWAOPJLTADLTN-UHFFFAOYSA-N oxidanimine Chemical compound [O-][NH3+] GSWAOPJLTADLTN-UHFFFAOYSA-N 0.000 description 1
- 230000036284 oxygen consumption Effects 0.000 description 1
- 238000006385 ozonation reaction Methods 0.000 description 1
- 230000002688 persistence Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 238000013033 photocatalytic degradation reaction Methods 0.000 description 1
- 239000000419 plant extract Substances 0.000 description 1
- 231100000614 poison Toxicity 0.000 description 1
- 230000007096 poisonous effect Effects 0.000 description 1
- 125000005575 polycyclic aromatic hydrocarbon group Chemical group 0.000 description 1
- 230000008092 positive 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
- 239000008213 purified water Substances 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 238000011084 recovery Methods 0.000 description 1
- 238000009738 saturating Methods 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 229910052717 sulfur Inorganic materials 0.000 description 1
- 238000009284 supercritical water oxidation Methods 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 229910001887 tin oxide Inorganic materials 0.000 description 1
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 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
- 230000001960 triggered effect Effects 0.000 description 1
- 238000000108 ultra-filtration Methods 0.000 description 1
- 238000005406 washing Methods 0.000 description 1
- 238000009279 wet oxidation reaction Methods 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
- 239000011787 zinc oxide Substances 0.000 description 1
- 229910000859 α-Fe Inorganic materials 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
-
- B01J35/39—
-
- 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
- C02F1/00—Treatment of water, waste water, or sewage
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/722—Oxidation by peroxides
-
- 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
- C02F1/72—Treatment of water, waste water, or sewage by oxidation
- C02F1/725—Treatment of water, waste water, or sewage by oxidation by catalytic oxidation
-
- 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
-
- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02W—CLIMATE CHANGE MITIGATION TECHNOLOGIES RELATED TO WASTEWATER TREATMENT OR WASTE MANAGEMENT
- Y02W10/00—Technologies for wastewater treatment
- Y02W10/30—Wastewater or sewage treatment systems using renewable energies
- Y02W10/37—Wastewater or sewage treatment systems using renewable energies using solar energy
Abstract
The invention belongs to technical field of nanometer material preparation, specially a kind of preparation method of ZnS/CuS nanosheet composite materials.The method comprising the steps of：1）Raw material nitrate trihydrate copper, zinc nitrate hexahydrate, thiocarbamide and surfactant are weighed in proportion, is then put into acetonitrile solution and carries out ultrasound, constant temperature stirring are then carried out, to form uniform copper zinc mixed solution；2）Above-mentioned solution is fitted into hydrothermal reaction kettle, reacted under specified temperature and time；3）Reaction is completed, and after natural cooling, removes supernatant, is respectively washed three times with deionized water and absolute ethyl alcohol, in an oven 60 DEG C of dry 5h, products obtained therefrom is Cu:Zn=x:Y composite nano plate.Photo-generated carrier can be efficiently separated with during photocatalyst using copper sulfide (CuS)/zinc sulphide (ZnS) bimetallic sulfide in the application, effectively improve photocatalytic activity.
Description
Technical field
The invention belongs to technical field of nanometer material preparation, specially a kind of preparation of ZnS/CuS nanosheet composite materials
Method.
Background technology
Water pollutant includes inorganic pollution and organic pollution.Inorganic pollution mainly includes lead, chromium, every, mercury and
The heavy metal ion such as copper, these heavy metal elements have in the environment difficult degradation, easily accumulation, irreversible, toxicity is big, metabolism is slow and
The characteristics of being easily bioaccumulation.Acute and chronic poisoning can be triggered or cause body canceration by drinking contaminated by heavy metals water for a long time.Have
Organic pollutants mainly include oxygen consumption non-toxic organic thing (such as protein, fat and carbohydrate) and toxic organic compound (such as phenol
Class compound, organic agricultural chemicals and polycyclic aromatic hydrocarbon, dyestuff and food additives etc.), these organic pollutions be teratogenesis, mutagenesis and
Carcinogen.
《National drinking water source water quality plays greatly bottom within 2016》Report is shown, disclosed in 31 provincial environmental administrations in 2016
There are 24 provinces in the water quality condition of (surface water water head site 995, groundwater source field 338) drinking water source area at 1333
Overproof water quality at totally 98, the exceeded ratio of groundwater source is apparently higher than surface water water source, and the duration polluted is compared with the latter more
It is long.If preventing and treating and processing speed are unable to catch up with the speed of pollution, drinking water pollution is just difficult to be contained.
At present, the means such as generally use chemical method, physical-chemical process and biotechnology processing water pollutant.
The removal of heavy metal ion is mainly chemical precipitation method, and principle is to make to be in ion like in waste water by chemical reaction
The heavy metal of state is converted into sediment not soluble in water, is then separated from waste liquid sediment by filtering, including ammonia
Oxide precipitation method, sulphide precipitation, calcium salt precipitation method and ferrite coprecipitation etc..The shortcomings that this method is after handling
Waste liquid does not often reach discharge standard, and if caused sediment deal with improperly, easily cause secondary pollution.To organic dirt
The removal for contaminating thing is typically chemical degradation method, mainly utilizes photocatalytic oxidation, wet oxidation process, supercritical water oxidation method electricity
Chemical oxidization method, Ozonation harmony chemical degradation etc., make organic pollution oxidation Decomposition and be converted into avirulent give birth to
Change degradation material, this method is to administer the effective ways of persistence organic pollutant.
Physical-chemical process mainly includes absorption method, ion-exchange and membrane separation process.Absorption is existing for solid-liquid interface
A kind of universal phenomenon, utilize the heavy metal ion in the loose porous and big adsorbent absorption effluent of specific surface area and organic contamination
Thing, to reach the purpose of purified water.Ion-exchange is to be carried out by means of the cation exchange groups in exchanger with the ion in waste water
Exchange, so as to remove the harmful ion in waste water.Membrane separation process be certain motive force effect under, it is saturating using the selection of pellicle
The property crossed is separated and concentrated, and common membrane separation process includes electroosmose process, diffusive dialysis method, hyperfiltration and ultrafiltration etc..
It is higher to manufacturing requirements because its program is complicated, it is restricted in popularization and application.
Biotechnology includes phytoremediation technology and microorganism remediation technology.Phytoremediation technology, grown using nature
Or the plant cultivated of genetic engineering and its microorganism system coexists, excessive accumulaiton certain or some pollutants, remove in environment
Pollutant.The mode of phytoremediation includes plant extract, plant degradation, plant stability and phytovolatilization etc..Microorganism remediation skill
Art, it is using the naturally occurring or functional microorganism group that manually cultivates, is absorbed under the conditions of control environment or poisonous dirt of degrading
Contaminate thing.The technology shows its high efficiency, low cost and non-secondary pollution in terms of heavy metal pollution and organic pollution is administered
Etc. advantage, turn into one of focus studied in environmental organism recovery technique field.
In above processing method, photocatalytic oxidation is because its treatment effect is high, the reaction time is short, easy to operate and be not easy
The advantages that causing secondary pollution, particularly contaminative is strong, low concentration, other processing methods be difficult to effectively to handle it is heavy metal-polluted
Dye and organic polluting water field have special application value.Conventional photochemical catalyst includes titanium dioxide (TiO2), oxidation
Zinc (ZnO), tin oxide (SnO2), zirconium dioxide (ZrO2), many oxide sulfide semiconductor such as cadmium sulfide (CdS), wherein two
Titanium oxide because its oxidability is strong, stablize nontoxic, turns into nano photocatalyst catalytic material most hot in the world by chemical property, but due to
Its band-gap energy is higher, it is relatively low to solar energy utilization ratio the shortcomings of, therefore be difficult to realize photocatalytic degradation under visible light conditions.In morning
It is phase, also once more to use cadmium sulfide (CdS) and zinc oxide (ZnO) to be used as photocatalyst material, but due to the chemistry of both
Property is unstable, can be light-catalysed while light dissolving occurs, and the harmful metal ion of dissolution has certain bio-toxicity, sent out
Seldom used them as at present as civilian catalysis material up to national, so cheap, the efficient nano-photocatalyst of exploitation
It is an importance of current absorption research.
The content of the invention
The goal of the invention of the present invention is to overcome problem above, there is provided a kind of preparation of ZnS/CuS nanosheet composite materials
Method.This method with nano combined of CuS nanoparticles/ZnS for photochemical catalyst, using the rhodamine B of difficult degradation and low cost to handle
Agent, improve application of the inorganic composite nano material in light degradation field.
In order to realize above goal of the invention, concrete technical scheme of the invention is as follows：
A kind of preparation method of the compound composite of ZnS/CuS nanometer sheets, it comprises the following steps：
1）Raw material nitrate trihydrate copper, zinc nitrate hexahydrate, thiocarbamide and surfactant are weighed in proportion, are then put into acetonitrile water
It is ultrasonically treated in solution, and constant temperature stirs, to form uniform copper zinc mixed solution；Nitrate trihydrate copper, zinc nitrate hexahydrate
Mass ratio with thiocarbamide is 0.1 ~ 3g：0.1~4g：0.2~5g.The quality of thiocarbamide and the volume ratio of acetonitrile solution are 0.2 ~ 5g：50-
200mL；The concentration of acetonitrile solution is 50wt%.
2）Above-mentioned solution is fitted into hydrothermal reaction kettle, reacted under specified temperature and time；
3）Reaction is completed, and after natural cooling, removes supernatant, is respectively washed three times, in baking oven with deionized water and absolute ethyl alcohol
In 60 DEG C of dry 5h, products obtained therefrom is Cu:Zn=x:Y composite nano plate.
Described surfactant is lauryl sodium sulfate, the polyethylene glycol of Mw=10000, the poly- second two of Mw=20000
Alcohol, neopelex, Mw=58000 polyvinylpyrrolidone and cetyl trimethylammonium bromide in it is any one
Kind or several mixtures.
The step 1）The condition of middle constant temperature stirring is：25 ~ 35 DEG C, 100 ~ 400r/min of stirring intensity of temperature, during stirring
Between 30 ~ 150min.
The condition of ultrasound：50 ~ 99Hz of intensity, 20 DEG C ~ 50 DEG C of temperature, 5 ~ 20min of time；
Step 2）Described in hydrothermal reaction condition be：150 ~ 250 DEG C of temperature, 4 ~ 10h of time.
The positive effect of the present invention is embodied in：
（One）Copper sulfide (CuS)/zinc sulphide (ZnS) bimetallic sulfide can efficiently separate photo-generated carrier, as light
Catalyst, it can improve efficiency of light absorption and photocatalytic activity.
（Two）The application with nano combined of CuS nanoparticles/ZnS for photochemical catalyst, with difficult degradation and the rhodamine B of low cost
For inorganic agent, application of the inorganic composite nano material in light degradation field is improved.
Brief description of the drawings
Fig. 1 is that CuS/ZnS mol ratios are 1:CuS and ZnS are detected in 1 CuS/ZnS nanosheet composite material XRD spectrums
The characteristic diffraction peak of phase.
Fig. 2 is CuS/ZnS nanosheet composite materials（CuS/ZnS mol ratios 1:2）EDX collection of illustrative plates
The elements such as Cu, Zn and S are detected in collection of illustrative plates, this shows that the nanosheet composite material of synthesis is made up of these three elements, water
Thermal synthesis method can synthesize CuS/ZnS composites.
Fig. 3 a are CuS/ZnS nanosheet composite materials（CuS/ZnS mol ratios 1:2）SEM figure, its medium scale be 1 μm.
Fig. 3 b are CuS/ZnS nanosheet composite materials（CuS/ZnS mol ratios 1:2）SEM figures, its medium scale is
200nm。
Fig. 4 a are CuS/ZnS nanosheet composite materials（CuS/ZnS mol ratios 1:4）SEM figure, its medium scale be 1 μm；
Fig. 4 b are CuS/ZnS nanosheet composite materials（CuS/ZnS mol ratios 1:4）SEM figure, its medium scale is 200nm；
Fig. 5 a are CuS/ZnS（CuS/ZnS mol ratios 3:1）The SEM figures of nanosheet composite material, its medium scale are 1 μm；
Fig. 5 b are CuS/ZnS（CuS/ZnS mol ratios 3:1）The SEM figures of nanosheet composite material, its medium scale is 200nm；
Fig. 6 a are CuS/ZnS（CuS/ZnS mol ratios 4:1）The SEM figures of nanosheet composite material, its medium scale are 1 μm；
Fig. 6 b are CuS/ZnS（CuS/ZnS mol ratios 4:1）The SEM figures of nanosheet composite material, its medium scale is 200nm.
Embodiment：
In order to make the purpose , technical scheme and advantage of the present invention be clearer, with reference to embodiment to this hair
It is bright to be described in further detail, but the scope that this should not be interpreted as to the above-mentioned theme of the present invention is only limitted to following embodiments.
Embodiment 1：
Weigh 0.322g nitrate trihydrates copper, 0.7934g zinc nitrate hexahydrates, 0.6976g thiocarbamides, 0.1g polyvinylpyrrolidones（Mw=
58000）Add in volume 160mL, mass fraction 50wt% acetonitrile mixed solution, ultrasonic 5min, and low whipping speed is
60min is stirred under 500r/min normal temperature and forms copper zinc mixed solution, above-mentioned solution is fitted into polytetrafluoroethylene (PTFE) pyroreaction kettle,
In 200 DEG C of hydro-thermal reaction 6h, after natural cooling, remove supernatant, respectively washed three times with deionized water and absolute ethyl alcohol, and
60 DEG C of dry 5h in an oven, products obtained therefrom are that CuS/ZnS mol ratios are 1:2 composite nano plate.
Embodiment 2：
0.1932g nitrate trihydrates copper, 0.9520g zinc nitrate hexahydrates, 0.6976g thiocarbamides, 0.1g PEG 20000s is weighed to add to
Volume 140mL, mass fraction 50wt% acetonitrile mixed solution in, ultrasonic 5min, and low whipping speed be 500r/min normal temperature under
Stir 60min and form copper zinc mixed solution, above-mentioned solution is fitted into polytetrafluoroethylene (PTFE) pyroreaction kettle, it is anti-in 200 DEG C of hydro-thermals
5h is answered, after natural cooling, removes supernatant, is respectively washed three times with deionized water and absolute ethyl alcohol, 60 DEG C of dryings in an oven
5h, products obtained therefrom are that CuS/ZnS mol ratios are 1:4 composite nano plate.
Embodiment 3：
Weigh 0.7248g nitrate trihydrates copper, 0.2974g zinc nitrate hexahydrates, 0.6976g thiocarbamides, 0.1g neopelexes
Add in 150mL, mass fraction 60wt% acetonitrile mixed solution, ultrasonic 5min, and low whipping speed is under 500r/min normal temperature
Stir 60min and form copper zinc mixed solution, above-mentioned solution is fitted into polytetrafluoroethylene (PTFE) pyroreaction kettle, it is anti-in 190 DEG C of hydro-thermals
8h is answered, after natural cooling, removes supernatant, is respectively washed three times with deionized water and absolute ethyl alcohol, 60 DEG C of dryings in an oven
5h, products obtained therefrom are that CuS/ZnS mol ratios are 3:1 composite nano plate.
Embodiment 4：
Weigh 0.9664g nitrate trihydrates copper, 0.2974g zinc nitrate hexahydrates, 0.6976g thiocarbamides, 0.1g neopelexes
Added to 0.05g cetyl trimethylammonium bromides in 160mL, mass fraction 45wt% acetonitrile mixed solution, ultrasonic 5min,
And low whipping speed is to stir 60min under 500r/min normal temperature to form copper zinc mixed solution, and above-mentioned solution is loaded into polytetrafluoroethyl-ne
In alkene pyroreaction kettle, in 190 DEG C of hydro-thermal reaction 8h, after natural cooling, remove supernatant, with deionized water and anhydrous second
Respectively three times, 60 DEG C of dry 5h, products obtained therefrom are that CuS/ZnS mol ratios are 4 to alcohol in an oven for washing:1 composite nano plate.
It is 1 to weigh the CuS/ZnS mol ratios being prepared in 0.15g above-described embodiments respectively:2、1:4、3:1 and 4:1
Nanosheet composite material is used as visible region（400W xenon lamps）Volume of degrading 100mL, concentration 20mg/L rhodamine B solution,
Under the radiation that 20 μ L hydrogen peroxide participate in after 2h, CuS/ZnS mol ratios are measured as 1:2、1:4、3:1 and 4:1 nanometer sheet is answered
Condensation material is respectively to the degradation rate of rhodamine B solution：97.2%th, 78.3%, 80.0% and 86.5%.ZnS under the same terms and
CuS is respectively 70.1% and 73.4% to the degradation rate of rhodamine B solution.This shows that the light of CuS/ZnS nanosheet composite materials is urged
Change photocatalysis performance when activity is higher than ZnS and CuS independent roles.
Claims (7)
1. a kind of preparation method of ZnS/CuS nanosheet composite materials, it is characterised in that comprise the following steps：
1）Raw material nitrate trihydrate copper, zinc nitrate hexahydrate, thiocarbamide and surfactant are weighed in proportion, are put into acetonitrile solution
It is middle to carry out ultrasound, constant temperature stirring is then carried out, to form uniform copper zinc mixed solution；
2）Above-mentioned solution is fitted into hydrothermal reaction kettle, reacted under specified temperature and time；
3）Reaction is completed, and after natural cooling, removes supernatant, is respectively washed three times, in baking oven with deionized water and absolute ethyl alcohol
In 60 DEG C of dry 5h, products obtained therefrom is Cu:Zn=x:Y composite nano plate.
2. the preparation method of ZnS/CuS nanosheet composite materials according to claim 1, it is characterised in that：Nitrate trihydrate copper,
The mass ratio of zinc nitrate hexahydrate and thiocarbamide is 0.1 ~ 3g：0.1~4g：0.2~5g.
3. the preparation method of ZnS/CuS nanosheet composite materials according to claim 1, it is characterised in that：The quality of thiocarbamide
Volume ratio with acetonitrile solution is 0.2 ~ 5g：50-200mL；The concentration of acetonitrile solution is 50wt%.
4. the preparation method of ZnS/CuS nanosheet composite materials according to claim 1, it is characterised in that：Described surface
Activating agent is lauryl sodium sulfate, the polyethylene glycol of Mw=10000, the polyethylene glycol of Mw=20000, DBSA
Sodium, Mw=58000 polyvinylpyrrolidone and cetyl trimethylammonium bromide in any one or a few mixture.
5. the preparation method of ZnS/CuS nanosheet composite materials according to claim 1, it is characterised in that the step 1）In
Constant temperature stirring condition be：25 ~ 35 DEG C, 100 ~ 400r/min of stirring intensity, 30 ~ 150min of mixing time of temperature.
6. the preparation method of ZnS/CuS nanosheet composite materials according to claim 1, it is characterised in that：It is described ultrasonic
Condition is：50 ~ 99Hz of intensity, 20 DEG C ~ 50 DEG C of temperature, 5 ~ 20min of time.
7. the preparation method of ZnS/CuS nanosheet composite materials according to claim 1, it is characterised in that step 2）Described in
Hydrothermal reaction condition be：150 ~ 250 DEG C of temperature, 4 ~ 10h of time.
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