CN104388077B - Silicon dioxide filled nanocluster composite material and preparation method and application thereof - Google Patents
Silicon dioxide filled nanocluster composite material and preparation method and application thereof Download PDFInfo
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- VYPSYNLAJGMNEJ-UHFFFAOYSA-N Silicium dioxide Chemical compound O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 title claims abstract description 129
- 239000002131 composite material Substances 0.000 title claims abstract description 85
- 239000000377 silicon dioxide Substances 0.000 title claims abstract description 46
- 235000012239 silicon dioxide Nutrition 0.000 title claims abstract description 13
- 238000002360 preparation method Methods 0.000 title claims description 10
- 239000002159 nanocrystal Substances 0.000 claims abstract description 49
- 230000000694 effects Effects 0.000 claims abstract description 16
- 239000002245 particle Substances 0.000 claims abstract description 6
- UHYPYGJEEGLRJD-UHFFFAOYSA-N cadmium(2+);selenium(2-) Chemical group [Se-2].[Cd+2] UHYPYGJEEGLRJD-UHFFFAOYSA-N 0.000 claims description 68
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N titanium dioxide Inorganic materials O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 27
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical group CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 18
- 239000006185 dispersion Substances 0.000 claims description 15
- 230000005540 biological transmission Effects 0.000 claims description 13
- 239000004530 micro-emulsion Substances 0.000 claims description 11
- 239000002904 solvent Substances 0.000 claims description 10
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 claims description 10
- YXFVVABEGXRONW-UHFFFAOYSA-N Toluene Chemical compound CC1=CC=CC=C1 YXFVVABEGXRONW-UHFFFAOYSA-N 0.000 claims description 9
- 238000002835 absorbance Methods 0.000 claims description 9
- 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 9
- 239000003921 oil Substances 0.000 claims description 9
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 claims description 8
- XUIMIQQOPSSXEZ-UHFFFAOYSA-N Silicon Chemical compound [Si] XUIMIQQOPSSXEZ-UHFFFAOYSA-N 0.000 claims description 7
- 239000007788 liquid Substances 0.000 claims description 7
- 229910052710 silicon Inorganic materials 0.000 claims description 7
- 239000010703 silicon Substances 0.000 claims description 7
- 239000001257 hydrogen Substances 0.000 claims description 6
- 229910052739 hydrogen Inorganic materials 0.000 claims description 6
- 239000004094 surface-active agent Substances 0.000 claims description 6
- 230000002195 synergetic effect Effects 0.000 claims description 6
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 claims description 5
- 238000010438 heat treatment Methods 0.000 claims description 5
- JEIPFZHSYJVQDO-UHFFFAOYSA-N iron(III) oxide Inorganic materials O=[Fe]O[Fe]=O JEIPFZHSYJVQDO-UHFFFAOYSA-N 0.000 claims description 5
- RTZKZFJDLAIYFH-UHFFFAOYSA-N Diethyl ether Chemical compound CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 claims description 4
- BERDEBHAJNAUOM-UHFFFAOYSA-N copper(I) oxide Inorganic materials [Cu]O[Cu] BERDEBHAJNAUOM-UHFFFAOYSA-N 0.000 claims description 4
- KRFJLUBVMFXRPN-UHFFFAOYSA-N cuprous oxide Chemical compound [O-2].[Cu+].[Cu+] KRFJLUBVMFXRPN-UHFFFAOYSA-N 0.000 claims description 4
- 238000000354 decomposition reaction Methods 0.000 claims description 4
- 239000000463 material Substances 0.000 claims description 4
- 230000001699 photocatalysis Effects 0.000 claims description 4
- 239000003054 catalyst Substances 0.000 claims description 3
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 3
- 238000007146 photocatalysis Methods 0.000 claims description 3
- 238000003756 stirring Methods 0.000 claims description 3
- 239000000126 substance Substances 0.000 claims description 3
- IMNFDUFMRHMDMM-UHFFFAOYSA-N N-Heptane Chemical compound CCCCCCC IMNFDUFMRHMDMM-UHFFFAOYSA-N 0.000 claims description 2
- WYURNTSHIVDZCO-UHFFFAOYSA-N Tetrahydrofuran Chemical compound C1CCOC1 WYURNTSHIVDZCO-UHFFFAOYSA-N 0.000 claims description 2
- 230000015572 biosynthetic process Effects 0.000 claims description 2
- 229910052802 copper Inorganic materials 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims description 2
- 239000004533 oil dispersion Substances 0.000 claims description 2
- 229910052763 palladium Inorganic materials 0.000 claims description 2
- 229910052697 platinum Inorganic materials 0.000 claims description 2
- 229910052709 silver Inorganic materials 0.000 claims description 2
- LFQCEHFDDXELDD-UHFFFAOYSA-N tetramethyl orthosilicate Chemical compound CO[Si](OC)(OC)OC LFQCEHFDDXELDD-UHFFFAOYSA-N 0.000 claims description 2
- 239000002023 wood Substances 0.000 claims 1
- 238000000034 method Methods 0.000 abstract description 5
- 239000000203 mixture Substances 0.000 abstract description 5
- 238000010521 absorption reaction Methods 0.000 abstract 1
- 229910052681 coesite Inorganic materials 0.000 description 45
- 229910052906 cristobalite Inorganic materials 0.000 description 45
- 229910052682 stishovite Inorganic materials 0.000 description 45
- 229910052905 tridymite Inorganic materials 0.000 description 45
- 239000002086 nanomaterial Substances 0.000 description 13
- 238000007792 addition Methods 0.000 description 12
- 239000002105 nanoparticle Substances 0.000 description 6
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 description 6
- DBMJMQXJHONAFJ-UHFFFAOYSA-M Sodium laurylsulphate Chemical compound [Na+].CCCCCCCCCCCCOS([O-])(=O)=O DBMJMQXJHONAFJ-UHFFFAOYSA-M 0.000 description 5
- 239000004141 Sodium laurylsulphate Substances 0.000 description 5
- 235000019333 sodium laurylsulphate Nutrition 0.000 description 5
- 239000000243 solution Substances 0.000 description 3
- IJGRMHOSHXDMSA-UHFFFAOYSA-N Atomic nitrogen Chemical compound N#N IJGRMHOSHXDMSA-UHFFFAOYSA-N 0.000 description 2
- CTQNGGLPUBDAKN-UHFFFAOYSA-N O-Xylene Chemical compound CC1=CC=CC=C1C CTQNGGLPUBDAKN-UHFFFAOYSA-N 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 150000001875 compounds Chemical class 0.000 description 2
- 238000005516 engineering process Methods 0.000 description 2
- 230000003993 interaction Effects 0.000 description 2
- 238000002156 mixing Methods 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 239000002096 quantum dot Substances 0.000 description 2
- 239000010453 quartz Substances 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- 239000002253 acid Substances 0.000 description 1
- 238000013019 agitation Methods 0.000 description 1
- 239000003708 ampul Substances 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
- 230000003197 catalytic effect Effects 0.000 description 1
- 238000006555 catalytic reaction Methods 0.000 description 1
- 238000006243 chemical reaction Methods 0.000 description 1
- 238000005253 cladding Methods 0.000 description 1
- 239000011248 coating agent Substances 0.000 description 1
- 238000000576 coating method Methods 0.000 description 1
- 238000010276 construction Methods 0.000 description 1
- 230000007797 corrosion Effects 0.000 description 1
- 238000005260 corrosion Methods 0.000 description 1
- 230000007547 defect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- VDQVEACBQKUUSU-UHFFFAOYSA-M disodium;sulfanide Chemical compound [Na+].[Na+].[SH-] VDQVEACBQKUUSU-UHFFFAOYSA-M 0.000 description 1
- 239000003814 drug Substances 0.000 description 1
- 238000007306 functionalization reaction Methods 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 150000002431 hydrogen Chemical class 0.000 description 1
- 238000005286 illumination Methods 0.000 description 1
- 238000003384 imaging method Methods 0.000 description 1
- 238000004519 manufacturing process Methods 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910044991 metal oxide Inorganic materials 0.000 description 1
- 150000004706 metal oxides Chemical class 0.000 description 1
- 239000000693 micelle Substances 0.000 description 1
- 238000012544 monitoring process Methods 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 229910052757 nitrogen Inorganic materials 0.000 description 1
- 231100000252 nontoxic Toxicity 0.000 description 1
- 230000003000 nontoxic effect Effects 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 239000001301 oxygen Substances 0.000 description 1
- 229910052760 oxygen Inorganic materials 0.000 description 1
- 238000012552 review Methods 0.000 description 1
- 238000007789 sealing Methods 0.000 description 1
- 239000011734 sodium Substances 0.000 description 1
- 229910052979 sodium sulfide Inorganic materials 0.000 description 1
- 238000001228 spectrum Methods 0.000 description 1
- 238000005728 strengthening Methods 0.000 description 1
- 238000002604 ultrasonography Methods 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 1
- 229910052724 xenon Inorganic materials 0.000 description 1
- FHNFHKCVQCLJFQ-UHFFFAOYSA-N xenon atom Chemical compound [Xe] FHNFHKCVQCLJFQ-UHFFFAOYSA-N 0.000 description 1
Classifications
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- Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
- Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
- Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
- Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
- Y02E60/30—Hydrogen technology
- Y02E60/36—Hydrogen production from non-carbon containing sources, e.g. by water electrolysis
Landscapes
- Silicon Compounds (AREA)
- Catalysts (AREA)
Abstract
The invention discloses a silicon dioxide filled nanocluster composite material, which comprises silicon dioxide and at least two inorganic nanocrystals, wherein one is an inorganic nanocrystal with a surface plasma resonance effect, and the other is an inorganic nanocrystal with overlapped absorption; assembling the at least two inorganic nanocrystals to obtain nanoclusters; the silicon dioxide is distributed in the whole nanocluster to form a nanocluster composite material; the particle size of the inorganic nanocrystalline is 1-100 nm; the diameter of the nanocluster composite material is 50-1000 nm. The nanocluster composite material has the characteristics of simplicity, convenience, easiness in obtaining and adjustable size and composition, and has important significance in practical application. The invention also discloses a method for preparing the silicon dioxide filled nanocluster composite material and application thereof.
Description
Technical field
The present invention relates to nano material and preparation field thereof.More particularly, to a kind of silica-filled type nanocluster composite and its preparation method and application.
Background technology
Fast-developing nanometer science and technology is prepared for diversified novel nano material.These nano materials overcome some defects of block materials, and show some new physics and chemical property, all show huge application prospect in a lot of fields.But, single nano material also shows some shortcomings, such as major part nano material simultaneously and includes that the nano materials such as metal nano material, magnetic Nano material and quantum dot are difficult to Direct Uniform and disperse in aqueous, and makes it apply and be very limited.Additionally, a lot of quantum dots and metal oxide nano-material are susceptible to corrosion reaction in acid condition, and loss of stability.Thus, it usually needs at a kind of material more stablized and can regulate and control further of these nano-material surfaces cladding.Thus these nano materials are carried out certain modification or functionalization and forms compound system.Silicon dioxide is owing to it is nontoxic, transparent, hydrophilic and is prone to unique character such as modification so that the nano material of coated with silica has important application prospect (list of references Y.Jin, A.Li at bio-imaging, biological monitoring, medicine transmission, oncotherapy, the energy and catalytic field, S.G.Hazelton, S.Liang, C.L.John, P.D.Selid, D.T.Pierce, J.X.Zhao, Coordination Chemistry Reviews, 2009,253,2,998 3014；S.Liu,M.-Y.Han,Chem.Asian J.2010,5,36–45；).At present, have been developed in the method for coating of multiple silicon dioxide, such as St ber method and reverse micelle method etc., and can be by changing different parameters to regulate and control (the list of references A.Guerrero-Mart í nez such as the thickness of coated with silica, J.P é rez-Juste, L.M.Liz-Marz á n, Adv.Mater.2010,22,1,182 1195；J.Wang,Z.H.Shah,S.Zhang,R.Lu,Nanoscale,2014,6,4418–4437).But current method focuses mostly in the thickness changing outer layer coated with silica layer, and to the nano-particle being coated with between, especially closely also rarely have report such as the regulation and control of (0-5 nanometer etc.) between nano-particle.And regulation and control in-plant to nano-particle have material impact in terms of the character of nano material and application such as fluorescence, electronics and energy transmission etc..
Therefore, develop a kind of simplicity, pervasive, can the compound system of coated with silica of spacing of nano-particle of Effective Regulation significant.
Summary of the invention
It is an object of the present invention to provide a kind of silica-filled type nanocluster composite, this nanocluster composite has simplicity and is easy to get, size and the adjustable characteristic of composition, the most significant.
Further object is that the preparation method that a kind of silica-filled type nanocluster composite is provided.
Third object of the present invention is to provide the application of a kind of silica-filled type nanocluster composite.
For reaching above-mentioned purpose, the present invention uses following technical proposals:
A kind of silica-filled type nanocluster composite, including silicon dioxide and at least two inorganic nano-crystal, one of which is to have the inorganic nano-crystal of surface plasmon resonance effect, the another kind of inorganic nano-crystal for having overlapping absorbance therewith；Described at least two inorganic nano-crystal assembles and obtains nanocluster；Described silicon dioxide is distributed in whole nanocluster formation nanocluster composite；The particle diameter of described inorganic nano-crystal is 1-100nm；A diameter of 50-1000nm of described nanocluster composite.
Preferably, the particle diameter of described inorganic nano-crystal is 3-20nm.
Preferably, the inorganic nano-crystal described in surface plasmon resonance effect is one or more in Au, Ag and Cu；The inorganic nano-crystal described in it is highly preferred that with surface plasmon resonance effect is Au.
Preferably, the inorganic nano-crystal described in overlapping absorbance is CdSe, CdS, CuSe, CuInS, Cu2O and Fe2O3In one or more；The inorganic nano-crystal described in it is highly preferred that with overlapping absorbance is CdSe.
Preferably, described few two kinds of inorganic nano-crystals also include having the synergistic inorganic nano-crystal of electric transmission；Preferably, the inorganic nano-crystal described in electric transmission effect is Pt, Pd, ZnO and TiO2In one or more；The inorganic nano-crystal described in it is highly preferred that with electric transmission effect is TiO2。
Preferably, one or more during the pattern of described inorganic nano-crystal is spherical, nanotube, nanometer rods, nanometer sheet, cube and octahedron；It is highly preferred that the pattern of described inorganic nano-crystal is spherical.
For reaching above-mentioned second purpose, the preparation method of a kind of silica-filled type nanocluster composite of the present invention, comprise the steps:
Silicon source and at least two inorganic nano-crystal are dispersed in oil-based solvent, one of which inorganic nano-crystal is the inorganic nano-crystal with surface plasmon resonance effect, another kind of inorganic nano-crystal is the inorganic nano-crystal therewith with overlapping absorbance, forms oily dispersion；
This oily dispersion is formed microemulsion with aqueous surfactant solution；
Heating this microemulsion makes oil-based solvent evaporate completely, obtains aqueous liquid dispersion, more separated, be dried to obtain nanocluster composite.
Preferably, described at least two inorganic nano-crystal also includes having the synergistic inorganic nano-crystal of electric transmission.
Preferably, the described inorganic nano-crystal with surface plasmon resonance effect concentration in oily dispersion is 0.1-10mg/mL, the described inorganic nano-crystal with overlapping absorbance concentration in oily dispersion is 1-50mg/mL, described to have electric transmission synergistic inorganic nano-crystal concentration in oily dispersion be 1-50mg/mL, and the addition in described silicon source and the volume ratio of oil-based solvent are 1:1000-1:10；The concentration of described aqueous surfactant solution is 0.1-20mg/mL.
Preferably, described silicon source is tetraethyl orthosilicate and/or methyl silicate；It is highly preferred that described silicon source is tetraethyl orthosilicate.
Preferably, described oil-based solvent is scattered for inorganic nano-crystal solvent to be included but not limited to one or more in toluene, dimethylbenzene, hexamethylene, normal hexane, normal heptane, ether and oxolane；It is highly preferred that described oil-based solvent is hexamethylene.
Preferably, the medium oil dispersion liquid of described microemulsion is 1:100-1:8 with the volume ratio of aqueous surfactant solution.
Preferably, the condition forming microemulsion is ultrasonic or stirring；It is highly preferred that the condition forming microemulsion is ultrasonic.
Preferably, the temperature of heating is 323-363K, it is highly preferred that the temperature of heating is 343K.
Present invention also offers the application of a kind of nanocluster efficiently utilizing surface plasmon resonance effect, including the application as photocatalysis Decomposition Aquatic product hydrogen catalyst or as the application strengthening fluorescence.
Beneficial effects of the present invention is as follows:
(1) the silica-filled type nanocluster composite that the present invention provides, simple and easy to get, the size of nanocluster, form controlled；
(2) the silica-filled type nanocluster composite prepared by the present invention has more preferable photochemical catalyzing H2-producing capacity, has more preferable reinforced effects in fluorescence intensity is tested；
(3) preparation method of the silica-filled type nanocluster composite that the present invention provides, need not synthesize and there is the nanocrystalline of special construction, preparation method mild condition, generally it is suitable for, be conducive to its actual popularization and application, in fields such as catalysis, sensing, biomedicines, there is great application prospect.
Accompanying drawing explanation
Below in conjunction with the accompanying drawings the detailed description of the invention of the present invention is described in further detail.
Fig. 1 is the silica-filled type Au/CdSe@SiO that embodiment 1 obtains2The transmission electron microscope photo of nanocluster composite；
Fig. 2 is silica-filled type Au/CdSe/TiO that embodiment 2 obtains2@SiO2The transmission electron microscope photo of nanocluster composite；
Fig. 3 is the silica-filled type Au/CdSe@SiO obtained by the different TEOS content of interpolation that embodiment 4-8 obtains2The fluorescence intensity contrast collection of illustrative plates of nanocluster composite；
Fig. 4 is the silica-filled type Au/CdSe@SiO obtained by the different TEOS content of interpolation that embodiment 3-8 obtains2The photocatalytic hydrogen production by water decomposition activity comparison diagram of nanocluster composite.
Detailed description of the invention
In order to be illustrated more clearly that the present invention, below in conjunction with preferred embodiments and drawings, the present invention is described further.Parts similar in accompanying drawing are indicated with identical reference.It will be appreciated by those skilled in the art that following specifically described content is illustrative and be not restrictive, should not limit the scope of the invention with this.
Embodiment 1
The preparation method of a kind of silica-filled type nanocluster composite, comprises the following steps:
Under room temperature, 1ml is dispersed with tetraethyl orthosilicate (TEOS), Au is nanocrystalline and CdSe is nanocrystalline hexamethylene forms microemulsion with 10ml sodium lauryl sulphate (SDS) aqueous solution under ultrasound condition, and ultrasonic power is 20%, ultrasonic 5min.Wherein, particle diameter nanocrystalline for Au is 9nm, the concentration in hexamethylene dispersion liquid be the nanocrystalline particle diameter of 1mg/ml, CdSe be 3nm, the concentration in hexamethylene dispersion liquid be 5mg/ml, TEOS addition be 100ul, the concentration of sodium lauryl sulphate is 3mg/ml.
Microemulsion is heated under 343K 4h, is centrifuged, is dried to obtain silica-filled type Au/CdSe@SiO2Nanocluster composite.
Fig. 1 is the silica-filled type Au/CdSe@SiO obtained2The electromicroscopic photograph of nanocluster composite, it can be seen that Au/CdSe@SiO2Nanocluster composite is by SiO2, Au is nanocrystalline and the nanocrystalline composition of CdSe, SiO2It is filled in whole Au/CdSe cluster, and Au/CdSe cluster is coated with completely.Au/CdSe@SiO2The size of nanocluster composite is about 100nm.
Embodiment 2
Repeating embodiment 1, it differs only in TiO2Nanocrystalline join in hexamethylene, TiO2Nanocrystalline particle diameter is 10nm, and the concentration in hexamethylene dispersion liquid is 1mg/ml, available silica-filled type Au/CdSe/TiO2@SiO2Nanocluster composite.
By prepared silica-filled type Au/CdSe/TiO2@SiO2Nanocluster composite transmission electron microscope characterizes, and Fig. 2 is silica-filled type Au/CdSe/TiO obtained2@SiO2The electromicroscopic photograph of nanocluster composite, it can be seen that Au/CdSe/TiO2@SiO2Nanocluster composite is by SiO2, Au is nanocrystalline, CdSe is nanocrystalline and TiO2Nanocrystalline composition, SiO2It is filled in whole Au/CdSe/TiO2Cluster, and by Au/CdSe/TiO2Cluster is coated with completely.Au/CdSe/TiO2@SiO2The size of nanocluster composite is about 100nm.
Embodiment 3
Repeating embodiment 1, its addition differing only in TEOS is 50ul, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 4
Repeating embodiment 1, its addition differing only in TEOS is 20ul, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 5
Repeating embodiment 1, its addition differing only in TEOS is 10ul, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 6
Repeating embodiment 1, its addition differing only in TEOS is 5ul, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 7
Repeating embodiment 1, its addition differing only in TEOS is 1ul, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 8
Repeating embodiment 1, its addition differing only in TEOS is 0ul, available Au/CdSe nanocluster composite.
By the Au/CdSe@SiO of the different TEOS additions that embodiment 4-8 prepares2The fluorescence intensity spectrum of nanocluster composite contrasts, and comparing result is as shown in Figure 3.Compared with Au/CdSe nanocluster composite, Au/CdSe@SiO2The fluorescence intensity of nanocluster composite significantly improves, and can by change TEOS addition regulate and control Au and CdSe nanocrystalline between SiO2Thickness, thus regulate and control Au and CdSe nanocrystalline between interaction and make its fluorescence intensity change.
By the Au/CdSe@SiO of the different TEOS additions that embodiment 3-8 prepares2Nanocluster composite is applied in the test of photocatalysis Decomposition Aquatic product hydrogen, in the quartz ampoule of 60mL, adds containing 10mg catalyst and 0.15M Na2S·9H2O and 0.25M Na2SO320ml aqueous solution.In quartz test tube, logical nitrogen 30min gets rid of the sealing of oxygen blend rubber plug, under agitation illumination 1h, and light source is 300W xenon lamp, filters the wavelength ultraviolet light less than 400nm with optical filter.With Shimadzu GC-2014 gas chromatograph for determination hydrogen generating quantity, produce hydrogen activity comparing result as shown in Figure 4.
Result shows, compared with Au/CdSe nanocluster composite, and Au/CdSe@SiO2Nanocluster composite has a more preferable photochemical catalyzing H2-producing capacity, and can by change the addition of TEOS regulate and control Au and CdSe nanocrystalline between SiO2Thickness, thus by regulation and control Au and CdSe nanocrystalline between interaction regulate and control Au/CdSe@SiO2The H2-producing capacity of nanocluster composite.
Embodiment 9
Repeating embodiment 1, it differs only in and changes size nanocrystalline for CdSe into 2.8nm, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 10
Repeating embodiment 1, it differs only in and changes size nanocrystalline for CdSe into 5nm, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 11
Repeating embodiment 1, it differs only in and changes concentration nanocrystalline for CdSe into 10mg/ml, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 12
Repeating embodiment 1, it differs only in and changes concentration nanocrystalline for CdSe into 20mg/ml, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 13
Repeating embodiment 1, it differs only in and changes hexamethylene into normal hexane, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 14
Repeating embodiment 1, it differs only in and changes ultrasonic power into 10%, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 15
Repeating embodiment 1, it differs only in and changes ultrasonic power into 30%, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 16
Repeating embodiment 1, it differs only in and changes ultrasonic time into 2min, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 17
Repeating embodiment 1, it differs only in and changes ultrasonic time into 10min, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 18
Repeating embodiment 1, it differs only in and changes stirring into by ultrasonic, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 19
Repeating embodiment 1, it differs only in and changes mixing time into 10min, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 20
Repeating embodiment 1, it differs only in and changes mixing time into 30min, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 21
Repeating embodiment 1, it differs only in and changes sodium lauryl sulphate concentration into 0.3mg/ml, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 22
Repeating embodiment 1, it differs only in and changes sodium lauryl sulphate concentration into 5mg/ml, still can get Au/CdSe@SiO2Nanocluster composite.
Embodiment 23
Repeating embodiment 1, it differs only in nanocrystalline for CdSe, and to change CdS into nanocrystalline, available Au/CdS@SiO2Nanocluster composite.
Embodiment 24
Repeating embodiment 1, it differs only in and changes Cu into by nanocrystalline for CdSe2O is nanocrystalline, available Au/Cu2O@SiO2Nanocluster composite.
Embodiment 25
Repeating embodiment 1, it differs only in nanocrystalline for CdSe, and to change CuInS into nanocrystalline, available Au/CuInS@SiO2Nanocluster composite.
Embodiment 26
Repeating embodiment 1, it differs only in and changes Fe into by nanocrystalline for CdSe2O3Nanocrystalline, available Au/Fe2O3@SiO2Nanocluster composite.
Embodiment 27
Repeating embodiment 1, it differs only in and changes CuSe nanometer rods into by nanocrystalline for CdSe, available Au/CuSe@SiO2Nanocluster composite.
Embodiment 28
Repeating embodiment 2, it differs only in and changes nanocrystalline for Au size into 6nm, still can get Au/CdSe/TiO2@SiO2Nanocluster composite.
Embodiment 29
Repeating embodiment 2, it differs only in and changes nanocrystalline for Au size into 3nm, still can get Au/CdSe/TiO2@SiO2Nanocluster composite.
Embodiment 30
Repeating embodiment 2, it differs only in and changes Fe into by nanocrystalline for CdSe2O3Nanocrystalline, available Au/Fe2O3/TiO2@SiO2Nanocluster composite.
Embodiment 31
Repeating embodiment 2, it differs only in nanocrystalline for Au, and to change Cu into nanocrystalline, and to change CdS into nanocrystalline by nanocrystalline for CdSe, will still can get Cu/CdS/TiO2Nanocluster composite.
Embodiment 32
Repeating embodiment 2, it differs only in nanocrystalline for Au, and to change Ag into nanocrystalline, and to change CdS into nanocrystalline, by TiO by nanocrystalline for CdSe2The nanocrystalline ZnO nano that changes into is brilliant, will still can get Ag/CdS/ZnO nanocluster composite.
Embodiment 33
Repeating embodiment 2, it differs only in and changes Cu into by nanocrystalline for CdSe2O is nanocrystalline, will still can get Au/Cu2O/TiO2Nanocluster composite.
Embodiment 34
Repeating embodiment 2, it differs only in nanocrystalline for Au, and to change Ag into nanocrystalline, changes Fe into by nanocrystalline for CdSe2O3Nanocrystalline, by TiO2Nanocrystalline to change Pt into nanocrystalline, will still can get Ag/Fe2O3/ Pt nanocluster composite.
Embodiment 35
Repeating embodiment 2, it differs only in nanocrystalline for Au, and to change Ag into nanocrystalline, and to change CuInS into nanocrystalline, by TiO by nanocrystalline for CdSe2Nanocrystalline to change Pd into nanocrystalline, will still can get Ag/CuInS/Pd nanocluster composite.
Embodiment 36
Repeating embodiment 2, it differs only in nanocrystalline for nanocrystalline for the 9nm Au Au changing 50nm into, by nanocrystalline, by 10nm TiO for nanocrystalline for the 3nm CdSe CdSe changing 4nm into2The nanocrystalline TiO changing 100nm into2Nanocrystalline, still can get Au/CdSe/TiO2Nanocluster composite.
Embodiment 37
Repeat embodiment 32, it differs only in nanocrystalline for nanocrystalline for the 9nm Ag Ag changing 50nm into, by nanocrystalline for nanocrystalline for the 3nm CdS CdS changing 20nm into, the ZnO nano that 10nm ZnO nano crystalline substance changes into 100nm is brilliant, still can get Ag/CdS/ZnO nanocluster composite.
Obviously; the above embodiment of the present invention is only for clearly demonstrating example of the present invention; and it is not the restriction to embodiments of the present invention; for those of ordinary skill in the field; can also make other changes in different forms on the basis of the above description; here cannot all of embodiment be given exhaustive, every belong to obvious change that technical scheme extended out or the variation row still in protection scope of the present invention.
Claims (6)
1. a silica-filled type nanocluster composite, it is characterised in that: include silicon dioxide
With at least two inorganic nano-crystal, one of which is to have the inorganic nano of surface plasmon resonance effect
Crystalline substance, the another kind of inorganic nano-crystal for having overlapping absorbance therewith；Described at least two inorganic nano-crystal group
Dress obtains nanocluster；Described silicon dioxide is distributed in whole nanocluster formation nanocluster composite wood
Material；The particle diameter of described inorganic nano-crystal is 1-100nm；Described nanocluster composite a diameter of
50-1000nm；
The described inorganic nano-crystal with surface plasmon resonance effect is the one in Au, Ag and Cu
Or it is multiple；
The described inorganic nano-crystal with overlapping absorbance is CdSe, CdS, CuSe, CuInS, Cu2O and
Fe2O3In one or more；
Described at least two inorganic nano-crystal also includes having the synergistic inorganic nano-crystal of electric transmission；
It is described that to have the synergistic inorganic nano-crystal of electric transmission be Pt, Pd, ZnO and TiO2In one or
Multiple；
The preparation method of described nanocluster comprises the steps:
Silicon source and at least two inorganic nano-crystal are dispersed in oil-based solvent, one of which inorganic nano-crystal
For having the inorganic nano-crystal of surface plasmon resonance effect, another kind of inorganic nano-crystal is for have therewith
The inorganic nano-crystal of overlapping absorbance, forms oily dispersion；
This oily dispersion is formed microemulsion with aqueous surfactant solution；
Heating this microemulsion makes oil-based solvent evaporate completely, obtains aqueous liquid dispersion, more separated, dry
Dry obtain nanocluster composite.
One the most according to claim 1 silica-filled type nanocluster composite, it is special
Levy and be: the particle diameter of described inorganic nano-crystal is 3-20nm.
One the most according to claim 1 silica-filled type nanocluster composite, it is special
Levy and be: described in there is dense in oily dispersion of the inorganic nano-crystal of surface plasmon resonance effect
Degree for 0.1-10mg/mL, described in there is the inorganic nano-crystal of the overlapping absorbance concentration in oily dispersion
For 1-50mg/mL, described in there is the synergistic inorganic nano-crystal of electric transmission in oily dispersion
Concentration is 1-50mg/mL, and the addition in described silicon source and the volume ratio of oil-based solvent are 1:1000-1:10；
The concentration of described aqueous surfactant solution is 0.1-20mg/mL.
One the most according to claim 1 silica-filled type nanocluster composite, it is special
Levy and be: described silicon source is tetraethyl orthosilicate and/or methyl silicate；Described oil-based solvent be toluene, two
One or more in toluene, hexamethylene, normal hexane, normal heptane, ether and oxolane.
One the most according to claim 1 silica-filled type nanocluster composite, it is special
Levy and be: the medium oil dispersion liquid of described microemulsion is 1:100-1:8 with the volume ratio of aqueous surfactant solution；
The condition forming microemulsion is ultrasonic or stirring；The temperature of heating is 323-363K.
6. the nanocluster composite as described in any one of claim 1-5 is as photocatalysis Decomposition Aquatic product
The application of hydrogen catalyst.
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