CN107055587A - A kind of preparation method of the nano composite sulfide of core shell structure - Google Patents
A kind of preparation method of the nano composite sulfide of core shell structure Download PDFInfo
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- CN107055587A CN107055587A CN201710406918.XA CN201710406918A CN107055587A CN 107055587 A CN107055587 A CN 107055587A CN 201710406918 A CN201710406918 A CN 201710406918A CN 107055587 A CN107055587 A CN 107055587A
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- sulfide
- nano composite
- shell structure
- core shell
- metal
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- 239000002114 nanocomposite Substances 0.000 title claims abstract description 61
- 239000011258 core-shell material Substances 0.000 title claims abstract description 54
- UCKMPCXJQFINFW-UHFFFAOYSA-N Sulphide Chemical compound [S-2] UCKMPCXJQFINFW-UHFFFAOYSA-N 0.000 title claims abstract description 51
- 238000002360 preparation method Methods 0.000 title claims abstract description 35
- 229910052976 metal sulfide Inorganic materials 0.000 claims abstract description 30
- NINIDFKCEFEMDL-UHFFFAOYSA-N Sulfur Chemical group [S] NINIDFKCEFEMDL-UHFFFAOYSA-N 0.000 claims abstract description 20
- 229910021645 metal ion Inorganic materials 0.000 claims abstract description 15
- 150000004696 coordination complex Chemical class 0.000 claims abstract description 14
- 229910000897 Babbitt (metal) Inorganic materials 0.000 claims abstract description 12
- 239000011593 sulfur Substances 0.000 claims abstract description 12
- 229910052717 sulfur Inorganic materials 0.000 claims abstract description 12
- 150000001875 compounds Chemical class 0.000 claims abstract description 5
- 239000007791 liquid phase Substances 0.000 claims abstract description 5
- 239000000463 material Substances 0.000 claims description 33
- 239000000126 substance Substances 0.000 claims description 33
- 239000000243 solution Substances 0.000 claims description 29
- 239000000047 product Substances 0.000 claims description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 24
- WRIDQFICGBMAFQ-UHFFFAOYSA-N (E)-8-Octadecenoic acid Natural products CCCCCCCCCC=CCCCCCCC(O)=O WRIDQFICGBMAFQ-UHFFFAOYSA-N 0.000 claims description 20
- LQJBNNIYVWPHFW-UHFFFAOYSA-N 20:1omega9c fatty acid Natural products CCCCCCCCCCC=CCCCCCCCC(O)=O LQJBNNIYVWPHFW-UHFFFAOYSA-N 0.000 claims description 20
- QSBYPNXLFMSGKH-UHFFFAOYSA-N 9-Heptadecensaeure Natural products CCCCCCCC=CCCCCCCCC(O)=O QSBYPNXLFMSGKH-UHFFFAOYSA-N 0.000 claims description 20
- 239000005642 Oleic acid Substances 0.000 claims description 20
- ZQPPMHVWECSIRJ-UHFFFAOYSA-N Oleic acid Natural products CCCCCCCCC=CCCCCCCCC(O)=O ZQPPMHVWECSIRJ-UHFFFAOYSA-N 0.000 claims description 20
- QXJSBBXBKPUZAA-UHFFFAOYSA-N isooleic acid Natural products CCCCCCCC=CCCCCCCCCC(O)=O QXJSBBXBKPUZAA-UHFFFAOYSA-N 0.000 claims description 20
- ZQPPMHVWECSIRJ-KTKRTIGZSA-N oleic acid Chemical compound CCCCCCCC\C=C/CCCCCCCC(O)=O ZQPPMHVWECSIRJ-KTKRTIGZSA-N 0.000 claims description 20
- 238000003756 stirring Methods 0.000 claims description 20
- 239000007864 aqueous solution Substances 0.000 claims description 19
- 238000010438 heat treatment Methods 0.000 claims description 19
- PXHVJJICTQNCMI-UHFFFAOYSA-N Nickel Chemical compound [Ni] PXHVJJICTQNCMI-UHFFFAOYSA-N 0.000 claims description 18
- 238000006243 chemical reaction Methods 0.000 claims description 15
- HCHKCACWOHOZIP-UHFFFAOYSA-N Zinc Chemical compound [Zn] HCHKCACWOHOZIP-UHFFFAOYSA-N 0.000 claims description 14
- 239000007787 solid Substances 0.000 claims description 14
- 229910052725 zinc Inorganic materials 0.000 claims description 14
- 239000011701 zinc Substances 0.000 claims description 14
- 229910052793 cadmium Inorganic materials 0.000 claims description 13
- BDOSMKKIYDKNTQ-UHFFFAOYSA-N cadmium atom Chemical compound [Cd] BDOSMKKIYDKNTQ-UHFFFAOYSA-N 0.000 claims description 13
- 239000012265 solid product Substances 0.000 claims description 13
- DNJIEGIFACGWOD-UHFFFAOYSA-N ethanethiol Chemical compound CCS DNJIEGIFACGWOD-UHFFFAOYSA-N 0.000 claims description 12
- 239000007788 liquid Substances 0.000 claims description 12
- 239000008367 deionised water Substances 0.000 claims description 11
- 229910021641 deionized water Inorganic materials 0.000 claims description 11
- 239000002184 metal Substances 0.000 claims description 11
- 229910052751 metal Inorganic materials 0.000 claims description 11
- 238000001816 cooling Methods 0.000 claims description 10
- 238000009938 salting Methods 0.000 claims description 10
- 238000000354 decomposition reaction Methods 0.000 claims description 9
- 229910052759 nickel Inorganic materials 0.000 claims description 9
- 239000005864 Sulphur Substances 0.000 claims description 8
- 229940093495 ethanethiol Drugs 0.000 claims description 8
- 238000001291 vacuum drying Methods 0.000 claims description 7
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims description 6
- 238000001035 drying Methods 0.000 claims description 4
- 125000004836 hexamethylene group Chemical group [H]C([H])([*:2])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[*:1] 0.000 claims description 4
- 238000005406 washing Methods 0.000 claims description 4
- WNAHIZMDSQCWRP-UHFFFAOYSA-N dodecane-1-thiol Chemical compound CCCCCCCCCCCCS WNAHIZMDSQCWRP-UHFFFAOYSA-N 0.000 claims description 3
- 238000009835 boiling Methods 0.000 claims description 2
- 239000002105 nanoparticle Substances 0.000 abstract description 8
- 239000002245 particle Substances 0.000 abstract description 7
- 238000005979 thermal decomposition reaction Methods 0.000 abstract description 6
- 239000000203 mixture Substances 0.000 abstract description 4
- 238000005342 ion exchange Methods 0.000 abstract description 3
- 230000015556 catabolic process Effects 0.000 abstract description 2
- 238000006731 degradation reaction Methods 0.000 abstract description 2
- 229960000907 methylthioninium chloride Drugs 0.000 abstract description 2
- 238000007146 photocatalysis Methods 0.000 abstract description 2
- 230000001699 photocatalysis Effects 0.000 abstract description 2
- 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 abstract description 2
- 229940043267 rhodamine b Drugs 0.000 abstract description 2
- RBTBFTRPCNLSDE-UHFFFAOYSA-N 3,7-bis(dimethylamino)phenothiazin-5-ium Chemical compound C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 RBTBFTRPCNLSDE-UHFFFAOYSA-N 0.000 abstract 1
- 229910052980 cadmium sulfide Inorganic materials 0.000 description 33
- JPVYNHNXODAKFH-UHFFFAOYSA-N Cu2+ Chemical compound [Cu+2] JPVYNHNXODAKFH-UHFFFAOYSA-N 0.000 description 22
- 229910001431 copper ion Inorganic materials 0.000 description 22
- WUPHOULIZUERAE-UHFFFAOYSA-N 3-(oxolan-2-yl)propanoic acid Chemical compound OC(=O)CCC1CCCO1 WUPHOULIZUERAE-UHFFFAOYSA-N 0.000 description 15
- 239000011257 shell material Substances 0.000 description 15
- WWNBZGLDODTKEM-UHFFFAOYSA-N sulfanylidenenickel Chemical compound [Ni]=S WWNBZGLDODTKEM-UHFFFAOYSA-N 0.000 description 12
- 238000000034 method Methods 0.000 description 11
- MBMLMWLHJBBADN-UHFFFAOYSA-N Ferrous sulfide Chemical compound [Fe]=S MBMLMWLHJBBADN-UHFFFAOYSA-N 0.000 description 10
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 9
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 description 9
- 208000011580 syndromic disease Diseases 0.000 description 9
- 239000005083 Zinc sulfide Substances 0.000 description 8
- 239000012535 impurity Substances 0.000 description 8
- 239000011941 photocatalyst Substances 0.000 description 8
- DRDVZXDWVBGGMH-UHFFFAOYSA-N zinc;sulfide Chemical compound [S-2].[Zn+2] DRDVZXDWVBGGMH-UHFFFAOYSA-N 0.000 description 8
- 239000008236 heating water Substances 0.000 description 7
- WLZRMCYVCSSEQC-UHFFFAOYSA-N cadmium(2+) Chemical compound [Cd+2] WLZRMCYVCSSEQC-UHFFFAOYSA-N 0.000 description 6
- 208000014903 transposition of the great arteries Diseases 0.000 description 6
- -1 ethane thiols Chemical class 0.000 description 4
- KFGJUQRJVQDJHL-UHFFFAOYSA-N ethanethiol Chemical compound CCS.CCS KFGJUQRJVQDJHL-UHFFFAOYSA-N 0.000 description 4
- 238000011049 filling Methods 0.000 description 4
- UHOVQNZJYSORNB-UHFFFAOYSA-N Benzene Chemical compound C1=CC=CC=C1 UHOVQNZJYSORNB-UHFFFAOYSA-N 0.000 description 3
- MPTQRFCYZCXJFQ-UHFFFAOYSA-L copper(II) chloride dihydrate Chemical class O.O.[Cl-].[Cl-].[Cu+2] MPTQRFCYZCXJFQ-UHFFFAOYSA-L 0.000 description 3
- 230000005291 magnetic effect Effects 0.000 description 3
- 239000011824 nuclear material Substances 0.000 description 3
- 238000002411 thermogravimetry Methods 0.000 description 3
- 238000012032 thrombin generation assay Methods 0.000 description 3
- 230000008901 benefit Effects 0.000 description 2
- 238000006555 catalytic reaction Methods 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002086 nanomaterial Substances 0.000 description 2
- 230000008569 process Effects 0.000 description 2
- 238000003980 solgel method Methods 0.000 description 2
- 238000004073 vulcanization Methods 0.000 description 2
- 102000004190 Enzymes Human genes 0.000 description 1
- 108090000790 Enzymes Proteins 0.000 description 1
- FZWLAAWBMGSTSO-UHFFFAOYSA-N Thiazole Chemical compound C1=CSC=N1 FZWLAAWBMGSTSO-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 239000002253 acid Substances 0.000 description 1
- 238000013459 approach Methods 0.000 description 1
- LHQLJMJLROMYRN-UHFFFAOYSA-L cadmium acetate Chemical class [Cd+2].CC([O-])=O.CC([O-])=O LHQLJMJLROMYRN-UHFFFAOYSA-L 0.000 description 1
- XIEPJMXMMWZAAV-UHFFFAOYSA-N cadmium nitrate Chemical class [Cd+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XIEPJMXMMWZAAV-UHFFFAOYSA-N 0.000 description 1
- 239000003054 catalyst Substances 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 239000002131 composite material Substances 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000009792 diffusion process Methods 0.000 description 1
- 238000012377 drug delivery Methods 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 238000005189 flocculation Methods 0.000 description 1
- 230000016615 flocculation Effects 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- 238000001027 hydrothermal synthesis Methods 0.000 description 1
- 239000011159 matrix material Substances 0.000 description 1
- 239000002905 metal composite material Substances 0.000 description 1
- CXKWCBBOMKCUKX-UHFFFAOYSA-M methylene blue Chemical compound [Cl-].C1=CC(N(C)C)=CC2=[S+]C3=CC(N(C)C)=CC=C3N=C21 CXKWCBBOMKCUKX-UHFFFAOYSA-M 0.000 description 1
- 238000000593 microemulsion method Methods 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 238000004549 pulsed laser deposition Methods 0.000 description 1
- 230000005855 radiation Effects 0.000 description 1
- 230000004044 response Effects 0.000 description 1
- 239000012266 salt solution Substances 0.000 description 1
- 239000013077 target material Substances 0.000 description 1
- 125000000101 thioether group Chemical group 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G3/00—Compounds of copper
- C01G3/12—Sulfides
-
- 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
-
- 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
- B01J27/043—Sulfides with iron group metals or platinum group metals
-
- 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
-
- 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
- B01J35/396—Distribution of the active metal ingredient
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G11/00—Compounds of cadmium
- C01G11/02—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G53/00—Compounds of nickel
- C01G53/11—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
- C01G9/00—Compounds of zinc
- C01G9/08—Sulfides
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2002/00—Crystal-structural characteristics
- C01P2002/70—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data
- C01P2002/72—Crystal-structural characteristics defined by measured X-ray, neutron or electron diffraction data by d-values or two theta-values, e.g. as X-ray diagram
-
- 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
- C01P2004/82—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases
- C01P2004/84—Particles consisting of a mixture of two or more inorganic phases two phases having the same anion, e.g. both oxidic phases one phase coated with the other
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- Chemical & Material Sciences (AREA)
- Organic Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Materials Engineering (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Inorganic Chemistry (AREA)
- Inorganic Compounds Of Heavy Metals (AREA)
- Luminescent Compositions (AREA)
Abstract
The invention discloses a kind of preparation method of the nano composite sulfide of core shell structure, a kind of preparation method of the nano composite sulfide of core shell structure, presoma is done with a kind of sulfur-bearing metal complex, metal sulfide A is made through liquid phase thermal decomposition, using A as core, by ion exchange, another metal ion species B is attached to A surfaces, obtain the nano composite sulfide A B of core shell structure；The present invention is simple to operate, environment-friendly, obtains the controllable nucleocapsid composition metal sulfide of homogeneous nano particle, size, pattern, atomic ratio, particle is between 10 20 nm；Ultraviolet light and visible ray can be effectively absorbed, to organic pollution thing rhodamine B, methylene blue has significant degradation；It is effective to prevent the compound of light induced electron and hole, improve its photocatalysis efficiency.
Description
Technical field
The invention belongs to technical field of nano material, the nano composite sulfide of more particularly to a kind of core shell structure
Preparation method.
Background technology
As one kind of nano composite material, nuclear-shell structured nano-composite material be by certain active force by it is different into
Divide, the sheathing material of structure and size is coated on the composite formed on nano level inner nuclear material surface.Core-shell type nano
Particulate is changed by Active sites by appropriate coating, usually shows to be different from template core or the property better than template core
Can, such as different surface chemistry composition, the increase of stability, higher specific surface area, different magnetic and optical property.Make
For shell material, core surface electric charge, functional group and response characteristic are changed, the stability and dispersiveness of kernel is improved, increases simultaneously
Plus the characteristic such as optics, magnetics and the catalysis of inner nuclear material；Equally, inner nuclear material also provides support for surface coated outer shell,
So nucleome and case material can be selected and combined by the wish of people, core-shell material is constructed, compound particle is had not
The property of stratum nucleare and shell one-component is same as, to meet specific requirement.Compared with single component, nanometer nuclear shell nano-structure material
The physics of material is greatly improved with chemical property, and this is to widening material in fields such as electronics, magnetic, optics and catalysis
Using being very important.Core shell structure particle provides new approaches for design new type functional nano composite material, by material
Scholar and the highest attention of chemist.The material such as bimetallic sulfide core shell structure and multi-layer core-shell structure is in solar-electricity
There is very tempting application prospect in terms of pond, catalyst, drug delivery and the environmentally sensitive material of protection such as biology enzyme.
The preparation method of current nucleocapsid metal composite sulfide mainly have hydro-thermal method and solvent-thermal method, microemulsion method, colloidal sol-
Gel method, template, solid-bed break-up method, liquid phase thermal decomposition method, electrochemical processes and electrochemical deposition method, microwave radiation technology are polynary
Alcohol reducing process, Laser induced diffusion, epitaxial growth method, pulsed laser deposition etc..These methods are all corresponding
Aspect has the advantage of itself, but there is also certain defect simultaneously.Product grain such as solid-bed break-up method is easily reunited；
Heterogeneous flocculation can cause the Quality Down of clad in sol-gel process；Then there are some limits because of matrix material in template etc.
System.Therefore, a kind of preparation side of the nano composite sulfide of new, easy, more perfect core shell structure is sought
Method is very necessary.
The content of the invention
In order to solve the above problems, the invention provides a kind of preparation side of the nano composite sulfide of core shell structure
Method, compared with homogenous material, prepared target material effectively prevents the compound of light induced electron and hole, expands to too
The absorption region of sunlight, improves its photocatalysis efficiency.
To achieve the above object, the technical solution adopted by the present invention is：
A kind of preparation method of the nano composite sulfide of core shell structure, comprises the following steps：
Step（1）, 0.1-2g sulfur-bearing metal complexs are put into 20-200mL oleic acid, agitating and heating obtains uniform solution, after
It is continuous to be heated to complex decomposition, metal sulfide is obtained, continues isothermal reaction 5-30 min；
Step（2）, by step（1）After obtained metal sulfide cooling, it is centrifuged, the washing of gained solid product is taken simultaneously
Accessory substance is centrifuged off, solid metal sulphide A is obtained；
Step（3）, then by step（2）Obtained metal sulfide A is scattered in deionized water, and the lower water bath with thermostatic control of stirring adds
Heat, and another metal ion species B aqueous solution is added dropwise, treats completion of dropwise addition, continues heated at constant temperature 5-10 min, by resulting solution from
The heart, washing, drying, obtained target product are the nano composite sulfide A@B of core shell structure.
Further, the step（1）In, sulfur-bearing metal complex is the metal complex containing sulfydryl；Contain sulfydryl
Metal complex be following complex in any one, mercaptobenzothiazoler close cadmium, ethane thiol close cadmium, TGA close
Cadmium, lauryl mercaptan close the sulphur cluster complex of cadmium；Mercaptobenzothiazoler closes zinc, ethane thiol and closes the sulphur cluster that zinc, TGA close zinc
Complex；Mercaptobenzothiazoler closes nickel, ethane thiol and closes the sulphur cluster complex that nickel, TGA close nickel；Mercaptobenzothiazoler is closed
Ferrous, ethane thiol closes ferrous sulphur cluster complex.
Further, the step（1）In, sulfur-bearing metal complex is solvable in oleic acid, and sulfur-bearing metal complex is in oil
Solution temperature in acid is 180-240 DEG C, and decomposition temperature is less than the boiling point of oleic acid.
Further, the step（2）In, by step（1）Obtained metal sulfide is cooled to 30-40 DEG C.
Further, the step（2）In, gained solid product is washed using hexamethylene and is centrifuged off accessory substance.
Further, the step（3）In, the temperature of water bath with thermostatic control and heated at constant temperature is 60-70 DEG C.
Further, the step（3）In, another metal ion species B of the dropwise addition aqueous solution, metal ion B water
Solution is the aqueous solution of soluble-salt, and concentration sets as needed.
Further, the step（3）In, constant with the amount of metal sulfide A materials, another metal ion species B's adds
Enter the 5-40% for the amount that amount is metal sulfide A materials；The amount concentration of its metal ion B substance is 0.03-0.06 mol/L, can
The concentration of molten metal salt solution determines shell thickness.The solubility product constants of metal sulfide A in aqueous are more than metal ion B
Solubility product constant in aqueous.
Further, the step（3）In, dried using vacuum drying chamber.
A kind of preparation method of the nano composite sulfide of core shell structure, forerunner is with a kind of sulfur-bearing metal complex
Body, thermally decomposes through liquid phase and metal sulfide A is made, using A as core, by ion exchange, another metal ion species B is attached to A
Surface, obtains the nano composite sulfide A@B of core shell structure.
Compared with prior art, the invention has the advantages that：
The preparation method of the nano composite sulfide of core shell structure of the present invention, it is simple to operate, it is environment-friendly, obtain
To nano particle is homogeneous, the nano composite sulfide that size, pattern, atomic ratio are controllable, particle is between 10-20 nm；
Ultraviolet light and visible ray can be effectively absorbed, to organic pollution thing rhodamine B, methylene blue has significant degradation；
It is effective to prevent the compound of light induced electron and hole, improve the efficiency of its photochemical catalyzing.
Brief description of the drawings
Fig. 1 is the XRD picture of CdS@CuS nano composite photo-catalysts；
Fig. 2 is the XRD picture of ZnS@CuS nano composite photo-catalysts；
Fig. 3 is the XRD picture of ZnS@CdS nano composite photo-catalysts；
Fig. 4 is the XRD picture of NiS@CdS nano composite photo-catalysts.
Embodiment
The present invention is further described with reference to embodiment.
Embodiment 1
A kind of nano composite sulfide CdS@CuS of core shell structure preparation method, 0.44 g mercaptobenzothiazolers are closed
Cadmium is added in the three-necked flask for the 250mL for filling 45mL oleic acid, and being heated to 220 DEG C under the stirring for continuing magneton makes solid molten
Xie Hou, continuing to be heated to 300 DEG C of isothermal reaction 5min makes complex thermal decomposition complete, stops heating；Product is carried out after cooling
Centrifugal treating, and gained solid is taken, with ethanol washed product and accessory substance and impurity are centrifuged off, then gained solid is dissolved in
Ionized water, when magneton is stirred, then heating water bath to 65 DEG C starts that the aqueous solution containing 0.056g Copper dichloride dihydrates is added dropwise,
Continue heated at constant temperature 5min after completion of dropwise addition, resulting solution is centrifuged and removing accessory substance and impurity is washed with deionized, is obtained
It is the XRD picture of CdS@CuS nano composite photo-catalysts in the present embodiment to composition metal sulfide CdS@CuS, Fig. 1.
The preparation method of the nano composite sulfide of a kind of core shell structure, with a kind of sulfur-bearing metal complex sulfydryl benzene
And thiazole closes cadmium and does presoma, is thermally decomposed through liquid phase and metal sulfide A is made, using A as core, by ion exchange, made another
Copper ion in Copper dichloride dihydrate is attached to A surfaces, obtains the nano composite sulfide CdS@CuS of core shell structure.
Embodiment 2
A kind of nano composite sulfide ZnS@CuS of core shell structure preparation method, 0.26 g mercaptobenzothiazolers are closed
Zinc is added in the three-necked flask for the 250mL for filling 30mL oleic acid, and being heated to 180 DEG C under the stirring for continuing magneton makes solid molten
Xie Hou, continuing to be heated to 280 DEG C of isothermal reaction 10min makes complex thermal decomposition complete, stops heating；Product is carried out after cooling
Centrifugal treating, and gained solid is taken, with ethanol washed product and accessory substance and impurity are centrifuged off, then gained solid is dissolved in
Ionized water, when magneton is stirred, then heating water bath to 65 DEG C starts that the aqueous solution containing 0.056g Copper dichloride dihydrates is added dropwise,
Continue heated at constant temperature 5min after completion of dropwise addition, resulting solution is centrifuged and removing accessory substance and impurity is washed with deionized, is obtained
It is the XRD picture of ZnS@CuS nano composite photo-catalysts in the present embodiment to composition metal sulfide ZnS@CuS, Fig. 2.
Embodiment 3
A kind of nano composite sulfide ZnS@CdS of core shell structure preparation method, 0.26 g mercaptobenzothiazolers are closed
Zinc is added in the three-necked flask for the 250mL for filling 30mL oleic acid, and being heated to 240 DEG C under the stirring for continuing magneton makes solid molten
Xie Hou, continuing to be heated to 290 DEG C of isothermal reaction 5min makes complex thermal decomposition complete, stops heating；Product is carried out after cooling
Centrifugal treating, and gained solid is taken, with ethanol washed product and accessory substance and impurity are centrifuged off, then gained solid is dissolved in
Ionized water, when magneton is stirred, then heating water bath starts that the aqueous solution containing 0.087g cadmium acetates is added dropwise, knot is added dropwise to 65 DEG C
Continue heated at constant temperature 5min after beam, resulting solution is centrifuged and removing accessory substance and impurity is washed with deionized, is combined
Metal sulfide ZnS@CdS, Fig. 3 are the XRD picture of ZnS@CdS nano composite photo-catalysts in the present embodiment.
Embodiment 4
A kind of nano composite sulfide NiS@CdS of core shell structure preparation method, 0.23 g mercaptobenzothiazolers are closed
Nickel is added in the three-necked flask for the 250mL for filling 45mL oleic acid, and being heated to 240 DEG C under the stirring for continuing magneton makes solid molten
Xie Hou, continuing to be heated to 290 DEG C of isothermal reaction 10min makes complex thermal decomposition complete, stops heating；Product is carried out after cooling
Centrifugal treating, and gained solid is taken, with ethanol washed product and accessory substance and impurity are centrifuged off, then gained solid is dissolved in
Ionized water, when magneton is stirred, then heating water bath starts that the aqueous solution containing 0.077g cadmium nitrates is added dropwise, knot is added dropwise to 65 DEG C
Continue heated at constant temperature 5min after beam, resulting solution is centrifuged and removing accessory substance and impurity is washed with deionized, is combined
Metal sulfide NiS@CdS, Fig. 4 are the XRD picture of NiS@CdS nano composite photo-catalysts in the present invention.
Embodiment 5
A kind of preparation method of the nano composite sulfide of core shell structure, comprises the following steps：
Step（1）, 2g ethane thiols closed into cadmium be put into 200mL oleic acid, be heated with stirring to 240 DEG C, obtain uniform solution, continue
Complex decomposition is heated to, metal sulfide is obtained, continues the min of isothermal reaction 30；
Step（2）, by step（1）Obtained cadmium sulfide is cooled to 40 DEG C, and it is centrifuged, and takes gained solid product to use ring
Hexane washs and is centrifuged off accessory substance, obtains the cadmium sulfide that particle is 20nm；
Step（3）, then by step（2）Obtained cadmium sulfide is scattered in deionized water, the lower 70 DEG C of heating water baths of constant temperature of stirring,
And the aqueous solution of copper ion is added dropwise, completion of dropwise addition is treated, continues 70 DEG C of 10 min of heating of constant temperature, resulting solution is centrifuged, wash, put
In being dried in vacuum drying chamber, obtained target product is the nano composite sulfide CdS@CuS of core shell structure.
The step（3）In, constant with the amount of cadmium sulfide material, the addition of copper ion is the amount of cadmium sulfide material
40%；Wherein copper ion substance withdrawl syndrome is 0.06 mol/L, and the concentration of soluble metal salting liquid determines shell thickness.
Embodiment 6
A kind of preparation method of the nano composite sulfide of core shell structure, comprises the following steps：
Step（1）, 0.15g TGAs closed into cadmium be put into 100mL oleic acid, be heated with stirring to 220 DEG C, obtain uniform solution,
Continue to be heated to complex decomposition, obtain metal sulfide, continue isothermal reaction 15min；
Step（2）, by step（1）Obtained cadmium sulfide is cooled to 35 DEG C, and it is centrifuged, and takes gained solid product to use ring
Hexane washs and is centrifuged off accessory substance, obtains the cadmium sulfide that particle is 15nm；
Step（3）, then by step（2）Obtained cadmium sulfide is scattered in deionized water, the lower 65 DEG C of heating water baths of constant temperature of stirring,
And the aqueous solution of copper ion is added dropwise, completion of dropwise addition is treated, continues 65 DEG C of 8 min of heating of constant temperature, resulting solution is centrifuged, wash, put
In being dried in vacuum drying chamber, obtained target product is the nano composite sulfide CdS@CuS of core shell structure.
The step（3）In, constant with the amount of cadmium sulfide material, the addition of copper ion is the amount of cadmium sulfide material
30%；Wherein copper ion substance withdrawl syndrome is 0.05mol/L, and the concentration of soluble metal salting liquid determines shell thickness.
Embodiment 7
A kind of preparation method of the nano composite sulfide of core shell structure, comprises the following steps：
Step（1）, 0.1g lauryl mercaptans closed into cadmium be put into 20mL oleic acid, be heated with stirring to 180 DEG C, obtain uniform solution, after
It is continuous to be heated to complex decomposition, metal sulfide is obtained, continues the min of isothermal reaction 5；
Step（2）, by step（1）Obtained cadmium sulfide is cooled to 30 DEG C, and it is centrifuged, and takes gained solid product to use ring
Hexane washs and is centrifuged off accessory substance, obtains the cadmium sulfide that particle is 10nm；
Step（3）, then by step（2）Obtained cadmium sulfide is scattered in deionized water, the lower 60 DEG C of heating water baths of constant temperature of stirring,
And the aqueous solution of copper ion is added dropwise, completion of dropwise addition is treated, continues 60 DEG C of 5 min of heating of constant temperature, resulting solution is centrifuged, wash, put
In being dried in vacuum drying chamber, obtained target product is the nano composite sulfide CdS@CuS of core shell structure.
The step（3）In, constant with the amount of cadmium sulfide material, the addition of copper ion is the amount of cadmium sulfide material
5%；Wherein copper ion substance withdrawl syndrome is 0.03 mol/L, and the concentration of soluble metal salting liquid determines shell thickness.
Embodiment 8
A kind of preparation method of the nano composite sulfide of core shell structure, comprises the following steps：
Step（1）, 0.15g ethane thiols closed into zinc be put into 100mL oleic acid, agitating and heating obtains uniform solution, continues to heat
Decomposed to complex, obtain zinc sulphide, continue the min of isothermal reaction 15；
Step（2）, by step（1）After obtained zinc sulphide cooling, it is centrifuged, takes gained solid product to wash and centrifuge
Accessory substance is removed, nano particle zinc sulphide is obtained；
Step（3）, then by step（2）Obtained zinc sulphide is scattered in deionized water, the lower water bath with thermostatic control heating of stirring, and is dripped
Plus the aqueous solution of copper ion, completion of dropwise addition is treated, continues heated at constant temperature 8min, resulting solution is centrifuged, wash, dried, is obtained
Target product is the nano composite sulfide ZnS@CuS of core shell structure.
The step（3）In, constant with the amount for vulcanizing zinc material, the addition of copper ion is the amount of vulcanization zinc material
30%；Wherein copper ion substance withdrawl syndrome is 0.04 mol/L, and the concentration of soluble metal salting liquid determines shell thickness.
Embodiment 9
A kind of preparation method of the nano composite sulfide of core shell structure, comprises the following steps：
Step（1）, 0.15g TGAs closed into zinc be put into 150mL oleic acid, agitating and heating obtains uniform solution, continues to heat
Decomposed to complex, obtain zinc sulphide, continue the min of isothermal reaction 25；
Step（2）, by step（1）After obtained zinc sulphide cooling, it is centrifuged, takes gained solid product to wash and centrifuge
Accessory substance is removed, nano particle zinc sulphide is obtained；
Step（3）, then by step（2）Obtained zinc sulphide is scattered in deionized water, the lower water bath with thermostatic control heating of stirring, and is dripped
Plus the aqueous solution of copper ion, completion of dropwise addition is treated, continues heated at constant temperature 8min, resulting solution is centrifuged, wash, dried, is obtained
Target product is the nano composite sulfide ZnS@CuS of core shell structure.
The step（3）In, constant with the amount for vulcanizing zinc material, the addition of copper ion is the amount of vulcanization zinc material
30%；Wherein copper ion substance withdrawl syndrome is 0.05 mol/L, and the concentration of soluble metal salting liquid determines shell thickness.
Embodiment 10
A kind of preparation method of the nano composite sulfide of core shell structure, comprises the following steps：
Step（1）, 0.1g ethane thiols closed into nickel be put into 80mL oleic acid, agitating and heating obtains uniform solution, continues to be heated to
Complex is decomposed, and obtains nickel sulfide, continues isothermal reaction 15min；
Step（2）, by step（1）After obtained nickel sulfide cooling, it is centrifuged, takes gained solid product to wash and centrifuge
Accessory substance is removed, nano particle nickel sulfide is obtained；
Step（3）, then by step（2）Obtained nickel sulfide is scattered in deionized water, the lower water bath with thermostatic control heating of stirring, and is dripped
Plus the aqueous solution of cadmium ion, completion of dropwise addition is treated, continues the min of heated at constant temperature 5, resulting solution is centrifuged, wash, dried, is obtained
Target product is the nano composite sulfide NiS@CdS of core shell structure.
The step（3）In, constant with the amount of nickel sulfide material, the addition of cadmium ion is the amount of nickel sulfide material
40%；Wherein cadmium ion substance withdrawl syndrome is 0.03mol/L, and the concentration of soluble metal salting liquid determines shell thickness.
Embodiment 11
A kind of preparation method of the nano composite sulfide of core shell structure, comprises the following steps：
Step（1）, 0.18g TGAs closed into nickel be put into 150mL oleic acid, agitating and heating obtains uniform solution, continues to heat
Decomposed to complex, obtain nickel sulfide, continue the min of isothermal reaction 25；
Step（2）, by step（1）After obtained nickel sulfide cooling, it is centrifuged, takes gained solid product to wash and centrifuge
Accessory substance is removed, nano particle nickel sulfide is obtained；
Step（3）, then by step（2）Obtained nickel sulfide is scattered in deionized water, the lower water bath with thermostatic control heating of stirring, and is dripped
Plus the aqueous solution of cadmium ion, completion of dropwise addition is treated, continues heated at constant temperature 8min, resulting solution is centrifuged, wash, dried, is obtained
Target product is the nano composite sulfide NiS@CdS of core shell structure.
The step（3）In, constant with the amount of nickel sulfide material, the addition of cadmium ion is the amount of nickel sulfide material
20%；Wherein cadmium ion substance withdrawl syndrome is 0.05 mol/L, and the concentration of soluble metal salting liquid determines shell thickness.
Embodiment 12
A kind of preparation method of the nano composite sulfide of core shell structure, comprises the following steps：
Step（1）, 2g mercaptobenzothiazolers closed into ferrous iron be put into 20mL oleic acid, be heated with stirring to 180 DEG C, obtain homogeneous molten
Liquid, continues to be heated to complex decomposition, obtains metal sulfide, continue the min of isothermal reaction 30；
Step（2）, by step（1）Obtained ferrous sulfide is cooled to 30 DEG C, and it is centrifuged, and takes gained solid product to use
Hexamethylene washs and is centrifuged off accessory substance, obtains nano particle ferrous sulfide；
Step（3）, then by step（2）Obtained ferrous sulfide is scattered in deionized water, and the lower 70 DEG C of water-baths of constant temperature of stirring add
Heat, and the aqueous solution of copper ion is added dropwise, completion of dropwise addition is treated, continues 70 DEG C of 5 min of heating of constant temperature, resulting solution is centrifuged, washed,
Drying in vacuum drying chamber is placed in, obtained target product is the nano composite sulfide FeS@CuS of core shell structure.
The step（3）In, constant with the amount of ferrous sulfide material, the addition of copper ion is the amount of ferrous sulfide material
5%；Wherein copper ion substance withdrawl syndrome is 0.06 mol/L, and the concentration of soluble metal salting liquid determines shell thickness.
Embodiment 13
A kind of preparation method of the nano composite sulfide of core shell structure, comprises the following steps：
Step（1）, 0.1g ethane thiols closed into ferrous iron be put into 200mL oleic acid, be heated with stirring to 240 DEG C, obtain uniform solution,
Continue to be heated to complex decomposition, obtain metal sulfide, continue the min of isothermal reaction 5；
Step（2）, by step（1）Obtained ferrous sulfide is cooled to 40 DEG C, and it is centrifuged, and takes gained solid product to use
Hexamethylene washs and is centrifuged off accessory substance, obtains nano particle ferrous sulfide；
Step（3）, then by step（2）Obtained ferrous sulfide is scattered in deionized water, and the lower 60 DEG C of water-baths of constant temperature of stirring add
Heat, and the aqueous solution of copper ion is added dropwise, completion of dropwise addition is treated, continues 60 DEG C of 10 min of heating of constant temperature, resulting solution is centrifuged, washed
Wash, be placed in drying in vacuum drying chamber, obtained target product is the nano composite sulfide FeS@CuS of core shell structure.
The step（3）In, constant with the amount of ferrous sulfide material, the addition of copper ion is the amount of ferrous sulfide material
5%；Wherein copper ion substance withdrawl syndrome is 0.06 mol/L, and the concentration of soluble metal salting liquid determines shell thickness.
Described above is only the preferred embodiment of the present invention, it should be pointed out that：For the ordinary skill people of the art
For member, under the premise without departing from the principles of the invention, some improvements and modifications can also be made, these improvements and modifications also should
It is considered as protection scope of the present invention.
Claims (10)
1. the preparation method of the nano composite sulfide of a kind of core shell structure, it is characterised in that comprise the following steps：
Step（1）, 0.1-2g sulfur-bearing metal complexs are put into 20-200mL oleic acid, agitating and heating obtains uniform solution, after
It is continuous to be heated to complex decomposition, metal sulfide is obtained, continues isothermal reaction 5-30 min；
Step（2）, by step（1）After obtained metal sulfide cooling, it is centrifuged, the washing of gained solid product is taken simultaneously
Accessory substance is centrifuged off, solid metal sulphide A is obtained；
Step（3）, then by step（2）Obtained metal sulfide A is scattered in deionized water, and the lower water bath with thermostatic control of stirring adds
Heat, and another metal ion species B aqueous solution is added dropwise, treats completion of dropwise addition, continues heated at constant temperature 5-10 min, by resulting solution from
The heart, washing, drying, obtained target product are the nano composite sulfide A@B of core shell structure.
2. the preparation method of the nano composite sulfide of core shell structure according to claim 1, it is characterised in that：Institute
State step（1）In, sulfur-bearing metal complex is the metal complex containing sulfydryl；Metal complex containing sulfydryl is to match somebody with somebody below
Any one in compound, mercaptobenzothiazoler, which closes cadmium, ethane thiol and closes cadmium, TGA, closes the sulphur that cadmium, lauryl mercaptan close cadmium
Cluster complex；Mercaptobenzothiazoler closes zinc, ethane thiol and closes the sulphur cluster complex that zinc, TGA close zinc；Mercaptobenzothiazoler
Close nickel, ethane thiol and close the sulphur cluster complex that nickel, TGA close nickel；Mercaptobenzothiazoler closes ferrous, ethane thiol and closes ferrous
Sulphur cluster complex.
3. the preparation method of the nano composite sulfide of core shell structure according to claim 1, it is characterised in that：Institute
State step（1）In, sulfur-bearing metal complex is solvable in oleic acid, and solution temperature of the sulfur-bearing metal complex in oleic acid is 180-
240 DEG C, and decomposition temperature is less than the boiling point of oleic acid.
4. the preparation method of the nano composite sulfide of core shell structure according to claim 1, it is characterised in that：Institute
State step（2）In, by step（1）Obtained metal sulfide is cooled to 30-40 DEG C.
5. the preparation method of the nano composite sulfide of core shell structure according to claim 1, it is characterised in that：Institute
State step（2）In, gained solid product is washed using hexamethylene and is centrifuged off accessory substance.
6. the preparation method of the nano composite sulfide of core shell structure according to claim 1, it is characterised in that：Institute
State step（3）In, the temperature of water bath with thermostatic control and heated at constant temperature is 60-70 DEG C.
7. the preparation method of the nano composite sulfide of core shell structure according to claim 1, it is characterised in that：Institute
State step（3）In, another metal ion species B of the dropwise addition aqueous solution, the metal ion B aqueous solution is the water-soluble of soluble-salt
Liquid, and concentration sets as needed.
8. the preparation method of the nano composite sulfide of core shell structure according to claim 1, it is characterised in that：Institute
State step（3）In, constant with the amount of metal sulfide A materials, another metal ion species B addition is metal sulfide A things
The 5-40% of the amount of matter；The amount concentration of its metal ion B substance is 0.03-0.06 mol/L, and the concentration of soluble metal salting liquid is determined
Determine shell thickness；It is normal that the solubility product constants of metal sulfide A in aqueous are more than the solubility products of metal ion B in aqueous
Number.
9. the preparation method of the nano composite sulfide of core shell structure according to claim 1, it is characterised in that：Institute
State step（3）In, dried using vacuum drying chamber.
10. according to the preparation method of the nano composite sulfide of any described core shell structures of claim 1-9, its feature
It is：Do presoma with a kind of sulfur-bearing metal complex, thermally decomposed through liquid phase and metal sulfide A is made, using A as core, by from
Son is exchanged, and another metal ion species B is attached to A surfaces, is obtained the nano composite sulfide A B of core shell structure.
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