CN112028109B - Composite nano material and preparation method and application thereof - Google Patents
Composite nano material and preparation method and application thereof Download PDFInfo
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- CN112028109B CN112028109B CN202010856009.8A CN202010856009A CN112028109B CN 112028109 B CN112028109 B CN 112028109B CN 202010856009 A CN202010856009 A CN 202010856009A CN 112028109 B CN112028109 B CN 112028109B
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- 239000002086 nanomaterial Substances 0.000 title claims abstract description 72
- 239000002131 composite material Substances 0.000 title claims abstract description 61
- 238000002360 preparation method Methods 0.000 title claims abstract description 37
- 239000000243 solution Substances 0.000 claims abstract description 71
- OMZSGWSJDCOLKM-UHFFFAOYSA-N copper(II) sulfide Chemical compound [S-2].[Cu+2] OMZSGWSJDCOLKM-UHFFFAOYSA-N 0.000 claims abstract description 56
- 229910000510 noble metal Inorganic materials 0.000 claims abstract description 34
- 238000006243 chemical reaction Methods 0.000 claims abstract description 22
- 239000010949 copper Substances 0.000 claims abstract description 20
- 239000003638 chemical reducing agent Substances 0.000 claims abstract description 19
- 238000010438 heat treatment Methods 0.000 claims abstract description 18
- 239000001267 polyvinylpyrrolidone Substances 0.000 claims abstract description 15
- 235000013855 polyvinylpyrrolidone Nutrition 0.000 claims abstract description 15
- 229920000036 polyvinylpyrrolidone Polymers 0.000 claims abstract description 15
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims abstract description 12
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims abstract description 12
- 229940112669 cuprous oxide Drugs 0.000 claims abstract description 12
- 239000010865 sewage Substances 0.000 claims abstract description 10
- 150000004763 sulfides Chemical class 0.000 claims abstract description 9
- 239000003513 alkali Substances 0.000 claims abstract description 8
- 238000002156 mixing Methods 0.000 claims abstract description 8
- 239000012266 salt solution Substances 0.000 claims abstract description 6
- 239000002057 nanoflower Substances 0.000 claims description 28
- CIWBSHSKHKDKBQ-JLAZNSOCSA-N Ascorbic acid Chemical compound OC[C@H](O)[C@H]1OC(=O)C(O)=C1O CIWBSHSKHKDKBQ-JLAZNSOCSA-N 0.000 claims description 24
- 229910052737 gold Inorganic materials 0.000 claims description 15
- 239000010931 gold Substances 0.000 claims description 15
- 238000000034 method Methods 0.000 claims description 15
- 229910000033 sodium borohydride Inorganic materials 0.000 claims description 13
- 239000012279 sodium borohydride Substances 0.000 claims description 13
- 229960005070 ascorbic acid Drugs 0.000 claims description 12
- 235000010323 ascorbic acid Nutrition 0.000 claims description 11
- 239000011668 ascorbic acid Substances 0.000 claims description 11
- 239000002253 acid Substances 0.000 claims description 8
- PCHJSUWPFVWCPO-UHFFFAOYSA-N gold Chemical compound [Au] PCHJSUWPFVWCPO-UHFFFAOYSA-N 0.000 claims description 7
- 229910052979 sodium sulfide Inorganic materials 0.000 claims description 6
- KDLHZDBZIXYQEI-UHFFFAOYSA-N Palladium Chemical compound [Pd] KDLHZDBZIXYQEI-UHFFFAOYSA-N 0.000 claims description 4
- BASFCYQUMIYNBI-UHFFFAOYSA-N platinum Chemical compound [Pt] BASFCYQUMIYNBI-UHFFFAOYSA-N 0.000 claims description 4
- SQGYOTSLMSWVJD-UHFFFAOYSA-N silver(1+) nitrate Chemical compound [Ag+].[O-]N(=O)=O SQGYOTSLMSWVJD-UHFFFAOYSA-N 0.000 claims description 4
- 229910052783 alkali metal Inorganic materials 0.000 claims description 3
- -1 alkali metal bicarbonate Chemical class 0.000 claims description 3
- WQZGKKKJIJFFOK-GASJEMHNSA-N Glucose Natural products OC[C@H]1OC(O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-GASJEMHNSA-N 0.000 claims description 2
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 claims description 2
- 229910000288 alkali metal carbonate Inorganic materials 0.000 claims description 2
- 150000008041 alkali metal carbonates Chemical class 0.000 claims description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 claims description 2
- UYJXRRSPUVSSMN-UHFFFAOYSA-P ammonium sulfide Chemical compound [NH4+].[NH4+].[S-2] UYJXRRSPUVSSMN-UHFFFAOYSA-P 0.000 claims description 2
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 claims description 2
- WQZGKKKJIJFFOK-VFUOTHLCSA-N beta-D-glucose Chemical compound OC[C@H]1O[C@@H](O)[C@H](O)[C@@H](O)[C@@H]1O WQZGKKKJIJFFOK-VFUOTHLCSA-N 0.000 claims description 2
- 239000008103 glucose Substances 0.000 claims description 2
- 238000004519 manufacturing process Methods 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- YJVFFLUZDVXJQI-UHFFFAOYSA-L palladium(ii) acetate Chemical compound [Pd+2].CC([O-])=O.CC([O-])=O YJVFFLUZDVXJQI-UHFFFAOYSA-L 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- DPLVEEXVKBWGHE-UHFFFAOYSA-N potassium sulfide Chemical compound [S-2].[K+].[K+] DPLVEEXVKBWGHE-UHFFFAOYSA-N 0.000 claims description 2
- 229910001961 silver nitrate Inorganic materials 0.000 claims description 2
- YWYZEGXAUVWDED-UHFFFAOYSA-N triammonium citrate Chemical compound [NH4+].[NH4+].[NH4+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O YWYZEGXAUVWDED-UHFFFAOYSA-N 0.000 claims description 2
- GRVFOGOEDUUMBP-UHFFFAOYSA-N sodium sulfide (anhydrous) Chemical compound [Na+].[Na+].[S-2] GRVFOGOEDUUMBP-UHFFFAOYSA-N 0.000 claims 1
- 239000002245 particle Substances 0.000 abstract description 3
- 240000007594 Oryza sativa Species 0.000 abstract description 2
- 235000007164 Oryza sativa Nutrition 0.000 abstract description 2
- 235000009566 rice Nutrition 0.000 abstract description 2
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 18
- 230000003197 catalytic effect Effects 0.000 description 14
- BTJIUGUIPKRLHP-UHFFFAOYSA-N 4-nitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1 BTJIUGUIPKRLHP-UHFFFAOYSA-N 0.000 description 13
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 12
- 239000000463 material Substances 0.000 description 11
- 150000003839 salts Chemical class 0.000 description 11
- 239000008367 deionised water Substances 0.000 description 9
- 229910021641 deionized water Inorganic materials 0.000 description 9
- 238000002835 absorbance Methods 0.000 description 7
- 230000015556 catabolic process Effects 0.000 description 7
- 239000013078 crystal Substances 0.000 description 7
- 238000006731 degradation reaction Methods 0.000 description 7
- BWFPGXWASODCHM-UHFFFAOYSA-N copper monosulfide Chemical compound [Cu]=S BWFPGXWASODCHM-UHFFFAOYSA-N 0.000 description 6
- 238000003756 stirring Methods 0.000 description 6
- OPQARKPSCNTWTJ-UHFFFAOYSA-L copper(ii) acetate Chemical compound [Cu+2].CC([O-])=O.CC([O-])=O OPQARKPSCNTWTJ-UHFFFAOYSA-L 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- 229940079101 sodium sulfide Drugs 0.000 description 5
- ZGHLCBJZQLNUAZ-UHFFFAOYSA-N sodium sulfide nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[Na+].[S-2] ZGHLCBJZQLNUAZ-UHFFFAOYSA-N 0.000 description 5
- 238000012360 testing method Methods 0.000 description 5
- 239000003814 drug Substances 0.000 description 4
- 239000002114 nanocomposite Substances 0.000 description 4
- 238000000527 sonication Methods 0.000 description 4
- 239000003381 stabilizer Substances 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 229940079593 drug Drugs 0.000 description 3
- 230000000694 effects Effects 0.000 description 3
- 239000012467 final product Substances 0.000 description 3
- 239000002159 nanocrystal Substances 0.000 description 3
- 239000010970 precious metal Substances 0.000 description 3
- 238000007789 sealing Methods 0.000 description 3
- 239000002585 base Substances 0.000 description 2
- 239000012876 carrier material Substances 0.000 description 2
- 238000005119 centrifugation Methods 0.000 description 2
- 239000003795 chemical substances by application Substances 0.000 description 2
- 238000001816 cooling Methods 0.000 description 2
- 230000007423 decrease Effects 0.000 description 2
- 238000010586 diagram Methods 0.000 description 2
- 238000002354 inductively-coupled plasma atomic emission spectroscopy Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002105 nanoparticle Substances 0.000 description 2
- 238000010899 nucleation Methods 0.000 description 2
- 230000006911 nucleation Effects 0.000 description 2
- 229910052760 oxygen Inorganic materials 0.000 description 2
- 239000012071 phase Substances 0.000 description 2
- 239000000843 powder Substances 0.000 description 2
- 238000004626 scanning electron microscopy Methods 0.000 description 2
- 238000010942 self-nucleation Methods 0.000 description 2
- 230000005476 size effect Effects 0.000 description 2
- 238000001228 spectrum Methods 0.000 description 2
- 239000000126 substance Substances 0.000 description 2
- UFBJCMHMOXMLKC-UHFFFAOYSA-N 2,4-dinitrophenol Chemical compound OC1=CC=C([N+]([O-])=O)C=C1[N+]([O-])=O UFBJCMHMOXMLKC-UHFFFAOYSA-N 0.000 description 1
- BXRFQSNOROATLV-UHFFFAOYSA-N 4-nitrobenzaldehyde Chemical compound [O-][N+](=O)C1=CC=C(C=O)C=C1 BXRFQSNOROATLV-UHFFFAOYSA-N 0.000 description 1
- RYGMFSIKBFXOCR-UHFFFAOYSA-N Copper Chemical compound [Cu] RYGMFSIKBFXOCR-UHFFFAOYSA-N 0.000 description 1
- 239000002211 L-ascorbic acid Substances 0.000 description 1
- 235000000069 L-ascorbic acid Nutrition 0.000 description 1
- ZLMJMSJWJFRBEC-UHFFFAOYSA-N Potassium Chemical compound [K] ZLMJMSJWJFRBEC-UHFFFAOYSA-N 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 229910000102 alkali metal hydride Inorganic materials 0.000 description 1
- 150000008046 alkali metal hydrides Chemical class 0.000 description 1
- 150000001340 alkali metals Chemical class 0.000 description 1
- 239000012670 alkaline solution Substances 0.000 description 1
- 230000000259 anti-tumor effect Effects 0.000 description 1
- QVGXLLKOCUKJST-UHFFFAOYSA-N atomic oxygen Chemical compound [O] QVGXLLKOCUKJST-UHFFFAOYSA-N 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 238000012984 biological imaging Methods 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000006227 byproduct Substances 0.000 description 1
- 235000013339 cereals Nutrition 0.000 description 1
- 239000003153 chemical reaction reagent Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- 229910000365 copper sulfate Inorganic materials 0.000 description 1
- ORTQZVOHEJQUHG-UHFFFAOYSA-L copper(II) chloride Chemical compound Cl[Cu]Cl ORTQZVOHEJQUHG-UHFFFAOYSA-L 0.000 description 1
- XTVVROIMIGLXTD-UHFFFAOYSA-N copper(II) nitrate Chemical compound [Cu+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O XTVVROIMIGLXTD-UHFFFAOYSA-N 0.000 description 1
- ARUVKPQLZAKDPS-UHFFFAOYSA-L copper(II) sulfate Chemical compound [Cu+2].[O-][S+2]([O-])([O-])[O-] ARUVKPQLZAKDPS-UHFFFAOYSA-L 0.000 description 1
- NWFNSTOSIVLCJA-UHFFFAOYSA-L copper;diacetate;hydrate Chemical compound O.[Cu+2].CC([O-])=O.CC([O-])=O NWFNSTOSIVLCJA-UHFFFAOYSA-L 0.000 description 1
- 230000003247 decreasing effect Effects 0.000 description 1
- 239000003937 drug carrier Substances 0.000 description 1
- 238000001035 drying Methods 0.000 description 1
- 238000004146 energy storage Methods 0.000 description 1
- 230000002349 favourable effect Effects 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000013067 intermediate product Substances 0.000 description 1
- 238000002844 melting Methods 0.000 description 1
- 230000008018 melting Effects 0.000 description 1
- 239000002923 metal particle Substances 0.000 description 1
- 238000001000 micrograph Methods 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 239000012074 organic phase Substances 0.000 description 1
- 239000003960 organic solvent Substances 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 230000001699 photocatalysis Effects 0.000 description 1
- 238000007146 photocatalysis Methods 0.000 description 1
- 229920003023 plastic Polymers 0.000 description 1
- 229910052700 potassium Inorganic materials 0.000 description 1
- 239000011591 potassium Substances 0.000 description 1
- 239000010453 quartz Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 239000004065 semiconductor Substances 0.000 description 1
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 239000001509 sodium citrate Substances 0.000 description 1
- NLJMYIDDQXHKNR-UHFFFAOYSA-K sodium citrate Chemical compound O.O.[Na+].[Na+].[Na+].[O-]C(=O)CC(O)(CC([O-])=O)C([O-])=O NLJMYIDDQXHKNR-UHFFFAOYSA-K 0.000 description 1
- 229940048181 sodium sulfide nonahydrate Drugs 0.000 description 1
- WMDLZMCDBSJMTM-UHFFFAOYSA-M sodium;sulfanide;nonahydrate Chemical compound O.O.O.O.O.O.O.O.O.[Na+].[SH-] WMDLZMCDBSJMTM-UHFFFAOYSA-M 0.000 description 1
- 239000002904 solvent Substances 0.000 description 1
- 238000004729 solvothermal method Methods 0.000 description 1
- 239000007858 starting material Substances 0.000 description 1
- 238000006467 substitution reaction Methods 0.000 description 1
- 230000009044 synergistic interaction Effects 0.000 description 1
- 238000001308 synthesis method Methods 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- 230000002194 synthesizing effect Effects 0.000 description 1
- 238000010998 test method Methods 0.000 description 1
- 238000002560 therapeutic procedure Methods 0.000 description 1
- 230000001988 toxicity Effects 0.000 description 1
- 231100000419 toxicity Toxicity 0.000 description 1
- XYYVDQWGDNRQDA-UHFFFAOYSA-K trichlorogold;trihydrate;hydrochloride Chemical compound O.O.O.Cl.Cl[Au](Cl)Cl XYYVDQWGDNRQDA-UHFFFAOYSA-K 0.000 description 1
- 230000005641 tunneling Effects 0.000 description 1
- 238000005303 weighing Methods 0.000 description 1
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- 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
-
- A—HUMAN NECESSITIES
- A61—MEDICAL OR VETERINARY SCIENCE; HYGIENE
- A61K—PREPARATIONS FOR MEDICAL, DENTAL OR TOILETRY PURPOSES
- A61K47/00—Medicinal preparations characterised by the non-active ingredients used, e.g. carriers or inert additives; Targeting or modifying agents chemically bound to the active ingredient
- A61K47/02—Inorganic compounds
-
- 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
- C02F1/70—Treatment of water, waste water, or sewage by reduction
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/01—Particle morphology depicted by an image
- C01P2004/03—Particle morphology depicted by an image obtained by SEM
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/30—Particle morphology extending in three dimensions
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- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
- C01P2004/00—Particle morphology
- C01P2004/60—Particles characterised by their size
- C01P2004/62—Submicrometer sized, i.e. from 0.1-1 micrometer
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- 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
-
- C—CHEMISTRY; METALLURGY
- C02—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F—TREATMENT OF WATER, WASTE WATER, SEWAGE, OR SLUDGE
- C02F2101/00—Nature of the contaminant
- C02F2101/30—Organic compounds
- C02F2101/308—Dyes; Colorants; Fluorescent agents
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- Chemical & Material Sciences (AREA)
- Health & Medical Sciences (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- Life Sciences & Earth Sciences (AREA)
- Hydrology & Water Resources (AREA)
- Environmental & Geological Engineering (AREA)
- Water Supply & Treatment (AREA)
- Engineering & Computer Science (AREA)
- Medicinal Chemistry (AREA)
- Pharmacology & Pharmacy (AREA)
- Epidemiology (AREA)
- Animal Behavior & Ethology (AREA)
- General Health & Medical Sciences (AREA)
- Public Health (AREA)
- Veterinary Medicine (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
- Pharmaceuticals Containing Other Organic And Inorganic Compounds (AREA)
Abstract
The invention discloses a composite nano material and a preparation method and application thereof. The composite nano material is hollow cubic copper sulfide nano rice coated with nano noble metal. The preparation method of the composite nano material comprises the following steps: 1) Mixing a polyvinylpyrrolidone solution and a Cu (II) salt solution, adding alkali, adding a reducing agent, and mixing for reaction to obtain a cuprous oxide solution; 2) Heating the cuprous oxide solution, and adding sulfide salt to react to obtain a hollow cubic copper sulfide solution; 3) And (3) centrifuging the hollow cubic copper sulfide solution, heating, and adding a noble metal source solution for reaction. The composite nano material prepared by the invention has controllable appearance, uniform particle size and high biological safety, and can be applied to the field of biomedicine or organic dye sewage treatment.
Description
Technical Field
The invention relates to the technical field of nano materials, in particular to a composite nano material and a preparation method and application thereof.
Background
The nano material is composed of nano particles with the nano magnitude (1-100 nm), and has the small size effect, the surface and interface effect, the quantum size effect and the macroscopic quantum tunneling effect. Thus, nanomaterials exhibit some special properties such as high specific heat capacity, low melting point, magnetic properties, elastic modulus, etc. However, a single-component nanomaterial may not meet the actual requirements, and thus, when two or more materials are compounded, the properties are greatly improved by the synergistic interaction between the materials, and new properties are imparted.
The copper sulfide semiconductor nano material has outstanding performance and has wide application in a plurality of fields, such as: photocatalysis, anti-tumor therapy, biological imaging, drug release, biochemical sensing, energy storage and the like. In particular, nanocomposites of copper sulfide and noble metals have attracted considerable attention in recent years from researchers because both of these components have tunable localized surface plasmon effects. However, there is a large problem of lattice mismatch between these two components, and thus this type of nanocomposite has certain difficulties in synthesis.
At present, the method for synthesizing the copper sulfide and precious metal nano composite material is mainly a high-temperature solvent thermal synthesis method. Materials of this type prepared by the high temperature solvothermal synthesis method tend to have relatively high crystalline crystallinity but require harsh reaction conditions such as: high temperature, high pressure, no oxygen, equal organic phase, low product purity, uncontrollable appearance, high biological toxicity and the like, and is not suitable for large-scale preparation. Therefore, how to improve the preparation method of the copper sulfide and precious metal nanocomposite so that the reaction conditions are milder and the biological safety is better becomes a technical problem which needs to be solved urgently by researchers.
Disclosure of Invention
In order to overcome the problems of the prior art, one object of the present invention is to provide a composite nanomaterial, another object of the present invention is to provide a preparation method of the composite nanomaterial, and another object of the present invention is to provide an application of the composite nanomaterial.
The present invention is made based on the following recognition and findings of the inventors:
the traditional template growth method is used for preparing the noble metal coated copper sulfide nano material, and after the inner core copper sulfide is generated, a large amount of ascorbic acid is still required to be introduced as a reducing agent to realize the growth of nano noble metal crystals; however, the existence of a large amount of ascorbic acid in the reaction system causes the self-nucleation of nano noble metal crystals, forms a plurality of independent nano noble metal particles (byproducts), affects the yield of the final product (nano noble metal-coated hollow cubic copper sulfide), causes impure surface of the product, adheres a large amount of ascorbic acid, and prevents the effective use of the components and exposed crystal faces of the material, thereby affecting the subsequent application; in addition, the ascorbic acid attached to the surface of the material tends to cause instability of physical and chemical properties of the material, and the material is easy to adhere to the wall during centrifugation, so that other stabilizers (such as sodium citrate) are required to protect the stability of the material. The inventor finds that the reducibility of polyvinylpyrrolidone (PVP) on the surface of the core copper sulfide is activated by properly increasing the temperature of a reaction system, growth sites and nucleation growth are provided for nano noble metal crystals, ascorbic acid is not required to be introduced in the growth process of noble metals, the self-nucleation of the nano noble metal crystals is avoided, the obtained final product has high purity, the polyvinylpyrrolidone can directly stabilize the whole reaction system, and the obtained product has good physical and chemical stability.
In order to achieve the purpose, the technical scheme adopted by the invention is as follows:
embodiments of the first aspect of the invention provide a composite nanomaterial, which is nano precious metal coated hollow cubic copper sulphide nanoflowers.
Preferably, in the composite nano material, the molar ratio of the nano noble metal to the hollow cubic copper sulfide nano rice is (1-5): 10; further preferably, the molar ratio of the nano noble metal to the hollow cubic copper sulfide nanoflower is (2-4): 10.
preferably, in the composite nano material, the nano noble metal is selected from at least one of nano gold, nano silver, nano palladium and nano platinum. In some embodiments of the present invention, the nano noble metal is nano gold.
In a second aspect, embodiments of the present invention provide a method for preparing a composite nanomaterial according to the first aspect of the present invention, comprising the steps of:
1) Mixing a polyvinylpyrrolidone solution and a Cu (II) salt solution, adding alkali, adding a reducing agent, and mixing for reaction to obtain a cuprous oxide solution;
2) Heating the cuprous oxide solution, and adding sulfide salt to react to obtain a hollow cubic copper sulfide solution;
3) And (3) centrifuging the hollow cubic copper sulfide solution, heating, and adding a noble metal source solution for reaction to obtain the composite nano material.
Preferably, in the step 1) of the preparation method of the composite nano material, the concentration of the polyvinylpyrrolidone solution is 5 g/L-20 g/L; more preferably, the concentration of the polyvinylpyrrolidone solution is 8g/L to 15g/L.
Preferably, in the step 1) of the preparation method of the composite nano material, the concentration of the Cu (II) salt solution is 0.05 mol/L-0.2 mol/L; more preferably, the concentration of the Cu (II) salt solution is 0.08mol/L to 0.15mol/L.
Preferably, in the step 1) of the preparation method of the composite nano material, the mass ratio of the polyvinylpyrrolidone to the Cu (II) salt is (30-100): 1; more preferably, the mass ratio of polyvinylpyrrolidone to Cu (ii) salt is (40 to 60): 1.
preferably, in step 1) of the preparation method of the composite nano material, the Cu (II) salt is selected from at least one of copper nitrate, copper acetate, copper chloride and copper sulfate. In some embodiments of the invention, the Cu (II) salt is copper acetate.
Preferably, in step 1) of the preparation method of the composite nano material, the molar ratio of the Cu (II) salt to the alkali is 1: (10-30); further preferably, the molar ratio of Cu (ii) salt to base is 1: (15 to 20).
Preferably, in step 1) of the preparation method of the composite nanomaterial, the base is at least one selected from alkali metal hydroxide, alkali metal carbonate and alkali metal bicarbonate; further preferably, the alkali is selected from one or a combination of sodium hydroxide and potassium hydroxide. In practical application, the preparation can be carried out in the form of an alkaline solution. By adding alkali, the pH value of the solution can be adjusted to be alkaline, and the coordination of Cu (II) salt to form Cu (OH) is further accelerated 4 2- The intermediate is favorable for the generation of cuprous oxide.
Preferably, in step 1) of the preparation method of the composite nano material, the molar ratio of the Cu (II) salt to the reducing agent is 1: (1-5); further preferably, the molar ratio of Cu (ii) salt to reducing agent is 1: (2-4).
Preferably, in step 1) of the preparation method of the composite nano material, the reducing agent is selected from at least one of sodium borohydride, ascorbic acid, glucose and ammonium citrate. In some embodiments of the invention, ascorbic acid is selected as the reducing agent.
Preferably, in the step 2) of the preparation method of the composite nano material, the heating temperature is 80-95 ℃; further preferably, the heating temperature is 85 to 90 ℃.
Preferably, in step 2) of the preparation method of the composite nano material, the molar ratio of the sulfide salt to the Cu (II) salt in step 1) is (2-8): 1; more preferably, the molar ratio of the sulfide salt to the Cu (II) salt is (3-5): 1.
preferably, in step 2) of the preparation method of the composite nanomaterial, the sulfide salt is selected from at least one of sodium sulfide, potassium sulfide and ammonium sulfide. In some embodiments of the invention, the salt sulfide is sodium sulfide.
In the step 2) of the preparation method of the composite nano material, after the sulfide salt is added for reaction, the solution is gradually changed into dark green from light yellow, and then the reaction is continued for 1 to 3 hours.
Preferably, in step 3) of the preparation method of the composite nano material, the rotation speed of centrifugal treatment is 7000 r/min to 9000 r/min; further preferably, the rotation speed of the centrifugal treatment is 7500 rpm to 8500 rpm.
Preferably, in step 3), the time of centrifugal treatment is 10-30 minutes; more preferably, the time for the centrifugation treatment is 15 minutes to 25 minutes.
Preferably, in the step 3) of the preparation method of the composite nano material, the heating temperature is 50-70 ℃; more preferably, the heating temperature is 55 to 65 ℃. In some embodiments of the invention, the heating temperature of step 3) is 60 ℃.
Preferably, in the step 3) of the preparation method of the composite nano material, the mass concentration of the noble metal source solution is 0.5-2%; more preferably, the noble metal source solution has a mass concentration of 0.8% to 1.2%.
Preferably, in step 3) of the preparation method of the composite nano material, the noble metal source is selected from at least one of chloroauric acid, silver nitrate, silver ammonia, palladium acetate and chloroplatinic acid. In some embodiments of the invention, the noble metal source is chloroauric acid.
In the step 3) of the preparation method of the composite nano material, after the noble metal source solution is added for reaction, the solution gradually changes from dark green to dark blue, and then the reaction is continued for 10 to 30 minutes.
The embodiment of the third aspect of the invention provides an application of the composite nano material in the biomedical field or organic dye sewage treatment, wherein the composite nano material is the composite nano material in the embodiment of the first aspect of the invention or the composite nano material prepared by the preparation method in the embodiment of the second aspect of the invention.
Preferably, the composite nano material is used as a drug carrier material when applied to the field of biomedicine.
Preferably, when the composite nano material is applied to organic dye sewage treatment, the composite nano material, an organic dye reducing agent and the organic dye sewage are mixed for treatment.
Preferably, when the composite nano material is applied to organic dye sewage treatment, the molar ratio of the composite nano material to the organic dye is (3-5): 1; more preferably, the molar ratio of the composite nanomaterial to the organic dye is (3.5-4.5): 1.
preferably, when the composite nano material is applied to organic dye sewage treatment, the molar ratio of the organic dye reducing agent to the organic dye is (2000-3000): 1; more preferably, the molar ratio of the organic dye reducing agent to the organic dye is (2400 to 2600): 1.
preferably, when the composite nano material is applied to organic dye sewage treatment, the organic dye reducing agent is selected from at least one of alkali metal hydride and alkali metal borohydride; further preferably, the organic dye reducing agent is at least one selected from sodium borohydride and potassium borohydride.
Preferably, when the composite nano material is applied to the sewage treatment of the organic dye, the organic dye comprises at least one of 4-nitrophenol, 2, 4-dinitrophenol and 4-nitrobenzaldehyde.
The invention has the beneficial effects that:
the invention provides a template growth method, does not need harsh reaction conditions such as high temperature, high pressure, organic solvent and the like, and obtains a green environment-friendly nano noble metal-coated hollow cubic copper sulfide nano material (hollow cubic copper sulfide @ noble metal nanoflower) with controllable appearance, uniform particle size and high biological safety by introducing amphiphilic molecule polyvinylpyrrolidone as a crystal face sealing agent, a stabilizing agent and a reducing agent, and the green environment-friendly nano noble metal-coated hollow cubic copper sulfide nano material can be applied to the field of biomedicine or organic dye sewage treatment.
Specifically, compared with the prior art, the invention has the following advantages:
1) According to the preparation method, no additional reducing agent is required to be added in the growth process of the noble metal, and the polyvinylpyrrolidone on the surface of the copper sulfide core can be used as the reducing agent and the stabilizing agent, so that the growth sites and the nucleation growth are provided for the noble metal nanocrystals.
2) The preparation method can effectively control the shape and size of the core-copper sulfide and shell-noble metal nanocrystals, and the obtained final product is in a nanometer level (100-200 nm), and has more outstanding advantages compared with a micrometer level material.
3) The composite nano material prepared by the invention has high noble metal yield which can reach 95 percent or above.
4) The composite nano material prepared by the invention is in a uniform phase with water, and is suitable for application in the field of biomedicine.
5) The core copper sulfide of the composite nano material prepared by the invention is a hollow structure and can be used for carrying and releasing medicaments.
6) The composite nano material prepared by the invention has good catalytic degradation efficiency on organic dye 4-nitrophenol in water.
Drawings
FIG. 1 is a scanning electron microscope image of a hollow cubic copper sulfide nanomaterial;
FIG. 2 is a scanning electron microscope photograph of nanogold coated hollow cubic copper sulfide nanoflowers;
FIG. 3 is a graph showing the absorbance of nanogold-coated hollow cubic copper sulfide nanoflower and sodium borohydride in the catalytic degradation of a 4-nitrophenol solution;
FIG. 4 is a graph showing the absorbance of sodium borohydride in the catalytic degradation of a 4-nitrophenol solution;
FIG. 5 is a graph of the catalytic kinetics of 4-nitrophenol; curve a represents the catalytic kinetics curve for sodium borohydride to 4-nitrophenol solution, and curve B represents the catalytic kinetics curve for nanogold coated hollow cubic copper sulfide nanoflower and sodium borohydride to 4-nitrophenol solution.
Detailed Description
The present invention will be described in further detail with reference to specific examples. The starting materials, reagents or equipment used in the examples are, unless otherwise specified, either conventionally commercially available or may be obtained by methods known in the art. Unless otherwise indicated, the testing or testing methods are conventional in the art.
Examples of production of composite nanomaterial
1. Preparation of the solution
Preparing a copper acetate solution: 0.40g of copper acetate monohydrate (Cu (CH) 3 COO)·H 2 O, 99%) was added to 20mL of triple deionized water and dissolved by sonication to give a 0.1mol/L copper acetate solution.
Preparing a sodium hydroxide solution: 0.40g of sodium hydroxide (NaOH, 99%) particles were weighed into 10mL of triple deionized water and dissolved by sonication to give a 1mol/L sodium hydroxide solution.
Preparing an ascorbic acid solution: 176mg of ascorbic acid (C) was weighed 6 H 8 O 6 97%) was added to 10mL of triple deionized water and dissolved by sonication to give a 0.1mol/L ascorbic acid solution.
Preparing a sodium sulfide solution: 0.48g of sodium sulfide nonahydrate (Na) was weighed out 2 S·9H 2 O, 99%) was added to 20mL of triple deionized water and dissolved by sonication to give a 0.1mol/L sodium sulfide solution.
Preparing a chloroauric acid solution: 1g of chloroauric acid trihydrate (HAuCl) 4 ·3H 2 O, au 23.5-23.8%) is added to 80mL of triple deionized water and dissolved by ultrasonic to obtain a 1wt% chloroauric acid solution.
2. Preparation of hollow cubic copper sulfide
(1) Preparation of cuprous oxide: adding 500 mu L of copper acetate (0.1 mol/L) solution into 50mL of deionized water containing 0.5g of polyvinylpyrrolidone, magnetically stirring for 10min, dropwise adding 900 mu L of sodium hydroxide (1 mol/L), continuously stirring for 2min, dropwise adding 1.5mL of ascorbic acid (0.1 mol/L) solution, continuously stirring, stopping stirring when the solution gradually turns to light yellow from light blue, and standing for 20min to obtain the cuprous oxide solution.
(2) Preparation of copper sulfide: and (2) stirring and heating the prepared cuprous oxide solution, injecting 2mL of sodium sulfide (0.1 mol/L) solution at one time when the temperature is heated to 90 ℃, gradually changing the solution from light yellow to dark green, continuously reacting for 2h, cooling to room temperature, sealing for later use, obtaining a hollow cubic copper sulfide solution, and storing for several months at room temperature.
SEM analysis is carried out on the hollow cubic copper sulfide of the intermediate product, and figure 1 is a scanning electron microscope picture of the hollow cubic copper sulfide nano material. Based on the contrast of the individual hollow cubic copper sulfide edges and the middle portion in fig. 1, the copper sulfide edges were found to be lighter in color and the middle portion was found to be darker in color, indicating that the copper sulfide nanomaterial was a hollow cubic structure.
3. Preparation of hollow cubic copper sulfide nanoflower coated with nanogold
10mL of the prepared hollow cubic copper sulfide solution was placed in a plastic centrifuge tube, centrifuged at 8000 rpm for 20min, washed with deionized water twice, finally resuspended in 10mL of deionized water, dried and weighed to 10.96mg. Then placing 10mL of centrifuged 1mmol/L hollow cubic copper sulfide solution into a 20mL glass reaction bottle, starting stirring and heating, dropwise adding 100 mu L of 1wt% (about 30 mmol/L) chloroauric acid solution when the temperature rises to 60 ℃, gradually changing the solution from dark green to dark blue, continuing to react for 20min, taking out the reaction bottle, standing and cooling to room temperature to obtain the nano-gold-coated hollow cubic copper sulfide nanoflower, drying and weighing 11.52mg, wherein the yield of the nano-gold on the hollow cubic copper sulfide nanoflower can be calculated to reach 95%. The nano-gold coated hollow cubic copper sulfide nanoflower is tested by inductively coupled plasma atomic emission spectrometry (ICP-AES), and the results show that the mass concentrations of gold and copper are 59mg/L and 63.5mg/L respectively, so that the molar ratio of the nano-gold to the hollow cubic copper sulfide nanoflower is calculated to be 3.
SEM analysis is carried out on the prepared product of the hollow cubic copper sulphide nanoflower coated with the nano-gold, and figure 2 is a scanning electron microscope picture of the hollow cubic copper sulphide nanoflower coated with the nano-gold. Comparison of the product morphology of fig. 1 reveals that the flower-like grown gold nanoparticles in fig. 2 have completely covered the copper sulfide core, indicating successful preparation of the nanogold-coated hollow cubic copper sulfide nanoflowers.
Tests show that amphiphilic molecule polyvinylpyrrolidone is introduced into a water phase solution by using a template growth method to serve as a crystal face sealing agent, a reducing agent and a stabilizing agent, so that the appearance and the grain size of the inner core copper sulfide and the uniform growth of the outer shell gold nanocrystal are accurately controlled, and the preparation of nano-grade gold-coated hollow copper sulfide nanoflowers with good biological safety is realized.
Application example
The hollow cubic copper sulfide nanoflower coated with nanogold is applied to catalytic degradation of organic dye 4-nitrophenol, and the specific experimental conditions and the test method are as follows:
preparing 0.5mol/L sodium borohydride (NaBH) 4 ) Solution: 0.19g of NaBH is weighed out 4 The powder is put into 10mL of deionized water for three times to obtain 0.5mol/L NaBH 4 And (3) solution.
Preparing 10 mmol/L4-nitrophenol (C) 6 H 5 NO 3 4-NTP) solution: 0.012g of 4-NTP powder is weighed into 10mL of absolute ethanol, and 10mmol/L of 4-NTP solution is obtained.
Taking 900 mu L of nano-gold coated hollow cubic copper sulfide nanoflower solution with concentration of 0.8mmol/L and 900 mu L of NaBH 4 The solution (0.5 mol/L) is mixed evenly in a quartz cuvette, 18 mu L of 4-NTP ethanol solution (10 mmol/L) is added, and the mixture is immediately tested by using a UV2550 ultraviolet spectrophotometer (test conditions: the spectrum scanning range is 300-550 nm, the scanning speed is medium speed, and the spectrum bandwidth is 1 nm), and the data at this time is defined as the absorption of the system when the reaction time t = 0. The reaction was then spectrally collected every 2min and the absorbance at 405nm was recorded. By making one without addingComparative example of nanogold coated hollow cubic copper sulphide nanoflowers.
FIG. 3 is an absorbance diagram of nano-gold coated hollow cubic copper sulfide nanoflower and sodium borohydride on catalytic degradation of a 4-nitrophenol solution, and FIG. 4 is an absorbance diagram of sodium borohydride on catalytic degradation of the 4-nitrophenol solution. As can be seen from FIG. 3, when nanogold-coated hollow cubic copper sulfide nanoflowers were present in the test system, 4-NTP was rapidly catalytically degraded, the absorbance of 4-NTP at 405nm gradually decreased with time, and at 18min, about 75% of 4-NTP had been degraded. As can be seen from FIG. 4, when there is no nanogold-coated hollow cubic copper sulfide nanoflower, the absorbance of 4-NTP at 405nm is slightly reduced, namely after 18min, which indicates that the nanogold-coated hollow cubic copper sulfide nanoflower has good catalytic degradation efficiency for 4-NTP.
FIG. 5 is a graph showing the catalytic kinetics of 4-nitrophenol. In FIG. 5, curve A shows the catalytic kinetics of sodium borohydride to 4-nitrophenol solution, and curve B shows the catalytic kinetics of nanogold coated hollow cubic copper sulfide nanoflower and sodium borohydride to 4-nitrophenol solution. As can be seen from fig. 5, when only sodium borohydride is present in the reaction system, the trend of curve a decreases insignificantly, and once the hollow cubic copper sulfide nanoflower coated with nanogold exists, curve B rapidly decreases, only 18min, and about 75% of 4-NTP has been degraded, indicating that the hollow cubic copper sulfide nanoflower coated with nanogold has high catalytic activity for 4-NTP.
In addition, the nanogold-coated hollow cubic copper sulfide nanoflowers provided by the invention have good biological safety and are suitable for the biomedical field, such as carrier materials for preparing medicines, and the carrier materials are used for carrying and releasing the medicines.
The above embodiments are preferred embodiments of the present invention, but the present invention is not limited to the above embodiments, and any other changes, modifications, substitutions, combinations, and simplifications which do not depart from the spirit and principle of the present invention should be construed as equivalents thereof, and all such modifications are intended to be included in the scope of the present invention.
Claims (9)
1. A composite nanomaterial characterized by: the composite nano material is hollow cubic copper sulfide nanoflower coated with nano noble metal;
the preparation method of the composite nano material comprises the following steps:
1) Mixing a polyvinylpyrrolidone solution and a Cu (II) salt solution, adding alkali, adding a reducing agent, and mixing for reaction to obtain a cuprous oxide solution;
2) Heating the cuprous oxide solution, and adding sulfide salt to react to obtain a hollow cubic copper sulfide solution;
3) Centrifuging and heating the hollow cubic copper sulfide solution, and adding a noble metal source solution for reaction to obtain the composite nano material;
in the step 3), the heating temperature is 50-70 ℃.
2. The composite nanomaterial of claim 1, wherein: the molar ratio of the nano noble metal to the hollow cubic copper sulfide nanoflower is (1-5): 10.
3. a composite nanomaterial according to claim 2, wherein: the nano noble metal is at least one selected from nano gold, nano silver, nano palladium and nano platinum.
4. A method for preparing the composite nanomaterial of any one of claims 1 to 3, wherein: the method comprises the following steps:
1) Mixing a polyvinylpyrrolidone solution and a Cu (II) salt solution, adding alkali, adding a reducing agent, and mixing for reaction to obtain a cuprous oxide solution;
2) Heating the cuprous oxide solution, and adding sulfide salt to react to obtain a hollow cubic copper sulfide solution;
3) Centrifuging a hollow cubic copper sulfide solution, heating, and adding a noble metal source solution for reaction to obtain the composite nano material;
in the step 3), the heating temperature is 50-70 ℃.
5. The method of claim 4, wherein: in the step 1), the alkali is at least one selected from alkali metal hydroxide, alkali metal carbonate and alkali metal bicarbonate; the reducing agent is at least one selected from sodium borohydride, ascorbic acid, glucose and ammonium citrate.
6. The method of claim 4, wherein: in the step 2), the heating temperature is 80-95 ℃.
7. The method of claim 4, wherein: in the step 2), the sulfide salt is at least one selected from sodium sulfide, potassium sulfide and ammonium sulfide.
8. The method of claim 4, wherein: in the step 3), the noble metal source is at least one selected from chloroauric acid, silver nitrate, silver ammonia, palladium acetate and chloroplatinic acid.
9. The application of the composite nano material in the biomedical field or organic dye sewage treatment is characterized in that: the composite nanomaterial according to any one of claims 1 to 3, or a composite nanomaterial produced by the production method according to any one of claims 4 to 8.
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