CN112044431A - Method for loading metal nanocrystalline on amorphous nano material by one-step method - Google Patents
Method for loading metal nanocrystalline on amorphous nano material by one-step method Download PDFInfo
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- CN112044431A CN112044431A CN202010922189.5A CN202010922189A CN112044431A CN 112044431 A CN112044431 A CN 112044431A CN 202010922189 A CN202010922189 A CN 202010922189A CN 112044431 A CN112044431 A CN 112044431A
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- 238000011068 loading method Methods 0.000 title claims abstract description 46
- 239000002086 nanomaterial Substances 0.000 title claims abstract description 42
- 238000000034 method Methods 0.000 title claims abstract description 41
- 229910052751 metal Inorganic materials 0.000 title claims abstract description 32
- 239000002184 metal Substances 0.000 title claims abstract description 32
- 239000000463 material Substances 0.000 claims abstract description 20
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 17
- 239000002114 nanocomposite Substances 0.000 claims abstract description 16
- 239000003607 modifier Substances 0.000 claims abstract description 14
- 238000007146 photocatalysis Methods 0.000 claims abstract description 6
- 230000001699 photocatalysis Effects 0.000 claims abstract description 6
- 239000002159 nanocrystal Substances 0.000 claims description 83
- VYPSYNLAJGMNEJ-UHFFFAOYSA-N silicon dioxide Inorganic materials O=[Si]=O VYPSYNLAJGMNEJ-UHFFFAOYSA-N 0.000 claims description 37
- 239000002077 nanosphere Substances 0.000 claims description 33
- 229910052681 coesite Inorganic materials 0.000 claims description 32
- 229910052906 cristobalite Inorganic materials 0.000 claims description 32
- 239000000377 silicon dioxide Substances 0.000 claims description 32
- 229910052682 stishovite Inorganic materials 0.000 claims description 32
- 229910052905 tridymite Inorganic materials 0.000 claims description 32
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims description 27
- 239000006185 dispersion Substances 0.000 claims description 18
- 229910001868 water Inorganic materials 0.000 claims description 18
- 239000002245 particle Substances 0.000 claims description 16
- 238000002360 preparation method Methods 0.000 claims description 16
- 229910021486 amorphous silicon dioxide Inorganic materials 0.000 claims description 12
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 11
- 238000006243 chemical reaction Methods 0.000 claims description 11
- 239000007788 liquid Substances 0.000 claims description 11
- 238000003756 stirring Methods 0.000 claims description 10
- 238000005406 washing Methods 0.000 claims description 10
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 6
- 238000006555 catalytic reaction Methods 0.000 claims description 6
- 230000009467 reduction Effects 0.000 claims description 6
- 229910052709 silver Inorganic materials 0.000 claims description 6
- 239000002243 precursor Substances 0.000 claims description 5
- 239000004793 Polystyrene Substances 0.000 claims description 4
- GWEVSGVZZGPLCZ-UHFFFAOYSA-N Titan oxide Chemical compound O=[Ti]=O GWEVSGVZZGPLCZ-UHFFFAOYSA-N 0.000 claims description 4
- 239000008367 deionised water Substances 0.000 claims description 4
- 229910021641 deionized water Inorganic materials 0.000 claims description 4
- 239000004005 microsphere Substances 0.000 claims description 4
- 229910021392 nanocarbon Inorganic materials 0.000 claims description 4
- 229920002223 polystyrene Polymers 0.000 claims description 4
- 230000008569 process Effects 0.000 claims description 4
- 239000013049 sediment Substances 0.000 claims description 4
- OGIDPMRJRNCKJF-UHFFFAOYSA-N titanium oxide Inorganic materials [Ti]=O OGIDPMRJRNCKJF-UHFFFAOYSA-N 0.000 claims description 4
- 150000001875 compounds Chemical class 0.000 claims description 3
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 3
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 3
- 238000002156 mixing Methods 0.000 claims description 3
- 229910021577 Iron(II) chloride Inorganic materials 0.000 claims description 2
- QAOWNCQODCNURD-UHFFFAOYSA-N Sulfuric acid Chemical compound OS(O)(=O)=O QAOWNCQODCNURD-UHFFFAOYSA-N 0.000 claims description 2
- 239000008139 complexing agent Substances 0.000 claims description 2
- 239000012153 distilled water Substances 0.000 claims description 2
- 239000004222 ferrous gluconate Substances 0.000 claims description 2
- 235000013924 ferrous gluconate Nutrition 0.000 claims description 2
- 229960001645 ferrous gluconate Drugs 0.000 claims description 2
- 125000000350 glycoloyl group Chemical group O=C([*])C([H])([H])O[H] 0.000 claims description 2
- XLYOFNOQVPJJNP-ZSJDYOACSA-N heavy water Substances [2H]O[2H] XLYOFNOQVPJJNP-ZSJDYOACSA-N 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- VRIVJOXICYMTAG-IYEMJOQQSA-L iron(ii) gluconate Chemical compound [Fe+2].OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O.OC[C@@H](O)[C@@H](O)[C@H](O)[C@@H](O)C([O-])=O VRIVJOXICYMTAG-IYEMJOQQSA-L 0.000 claims description 2
- 229910052603 melanterite Inorganic materials 0.000 claims description 2
- 229910021642 ultra pure water Inorganic materials 0.000 claims description 2
- 239000012498 ultrapure water Substances 0.000 claims description 2
- 229910052737 gold Inorganic materials 0.000 claims 1
- 229910052742 iron Inorganic materials 0.000 claims 1
- 229910052763 palladium Inorganic materials 0.000 claims 1
- 229910052697 platinum Inorganic materials 0.000 claims 1
- 229910052703 rhodium Inorganic materials 0.000 claims 1
- 229910052707 ruthenium Inorganic materials 0.000 claims 1
- 238000001132 ultrasonic dispersion Methods 0.000 claims 1
- 230000015572 biosynthetic process Effects 0.000 abstract description 4
- 238000003786 synthesis reaction Methods 0.000 abstract description 4
- 230000002708 enhancing effect Effects 0.000 abstract 1
- 239000013078 crystal Substances 0.000 description 19
- 239000011162 core material Substances 0.000 description 17
- 230000007774 longterm Effects 0.000 description 12
- 238000004626 scanning electron microscopy Methods 0.000 description 8
- 238000010521 absorption reaction Methods 0.000 description 7
- 230000000694 effects Effects 0.000 description 7
- 239000003795 chemical substances by application Substances 0.000 description 6
- 230000003287 optical effect Effects 0.000 description 6
- 238000000862 absorption spectrum Methods 0.000 description 5
- 239000002131 composite material Substances 0.000 description 5
- 239000000126 substance Substances 0.000 description 5
- 238000004627 transmission electron microscopy Methods 0.000 description 5
- 235000011114 ammonium hydroxide Nutrition 0.000 description 4
- 230000008859 change Effects 0.000 description 4
- 239000007822 coupling agent Substances 0.000 description 4
- 238000002173 high-resolution transmission electron microscopy Methods 0.000 description 4
- 238000001878 scanning electron micrograph Methods 0.000 description 4
- 238000002198 surface plasmon resonance spectroscopy Methods 0.000 description 4
- NLXLAEXVIDQMFP-UHFFFAOYSA-N Ammonium chloride Substances [NH4+].[Cl-] NLXLAEXVIDQMFP-UHFFFAOYSA-N 0.000 description 3
- BQCADISMDOOEFD-UHFFFAOYSA-N Silver Chemical compound [Ag] BQCADISMDOOEFD-UHFFFAOYSA-N 0.000 description 3
- PLKATZNSTYDYJW-UHFFFAOYSA-N azane silver Chemical compound N.[Ag] PLKATZNSTYDYJW-UHFFFAOYSA-N 0.000 description 3
- 239000011258 core-shell material Substances 0.000 description 3
- 229910000069 nitrogen hydride Inorganic materials 0.000 description 3
- 238000005381 potential energy Methods 0.000 description 3
- 238000010942 self-nucleation Methods 0.000 description 3
- 239000004332 silver Substances 0.000 description 3
- 230000009471 action Effects 0.000 description 2
- 230000009286 beneficial effect Effects 0.000 description 2
- 230000005540 biological transmission Effects 0.000 description 2
- 238000003384 imaging method Methods 0.000 description 2
- 239000011159 matrix material Substances 0.000 description 2
- XZWYZXLIPXDOLR-UHFFFAOYSA-N metformin Chemical compound CN(C)C(=N)NC(N)=N XZWYZXLIPXDOLR-UHFFFAOYSA-N 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
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- 239000007787 solid Substances 0.000 description 2
- 238000013169 thromboelastometry Methods 0.000 description 2
- 238000001392 ultraviolet--visible--near infrared spectroscopy Methods 0.000 description 2
- KEQXNNJHMWSZHK-UHFFFAOYSA-L 1,3,2,4$l^{2}-dioxathiaplumbetane 2,2-dioxide Chemical compound [Pb+2].[O-]S([O-])(=O)=O KEQXNNJHMWSZHK-UHFFFAOYSA-L 0.000 description 1
- BNZCDZDLTIHJAC-UHFFFAOYSA-N 2-azaniumylethylazanium;sulfate Chemical compound NCC[NH3+].OS([O-])(=O)=O BNZCDZDLTIHJAC-UHFFFAOYSA-N 0.000 description 1
- QTBSBXVTEAMEQO-UHFFFAOYSA-M Acetate Chemical compound CC([O-])=O QTBSBXVTEAMEQO-UHFFFAOYSA-M 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 238000002441 X-ray diffraction Methods 0.000 description 1
- 238000002835 absorbance Methods 0.000 description 1
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 description 1
- 238000000779 annular dark-field scanning transmission electron microscopy Methods 0.000 description 1
- 230000003197 catalytic effect Effects 0.000 description 1
- 230000001276 controlling effect Effects 0.000 description 1
- 238000010586 diagram Methods 0.000 description 1
- IMBKASBLAKCLEM-UHFFFAOYSA-L ferrous ammonium sulfate (anhydrous) Chemical compound [NH4+].[NH4+].[Fe+2].[O-]S([O-])(=O)=O.[O-]S([O-])(=O)=O IMBKASBLAKCLEM-UHFFFAOYSA-L 0.000 description 1
- 229940062993 ferrous oxalate Drugs 0.000 description 1
- 235000003891 ferrous sulphate Nutrition 0.000 description 1
- 239000011790 ferrous sulphate Substances 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- OWZIYWAUNZMLRT-UHFFFAOYSA-L iron(2+);oxalate Chemical compound [Fe+2].[O-]C(=O)C([O-])=O OWZIYWAUNZMLRT-UHFFFAOYSA-L 0.000 description 1
- 238000000707 layer-by-layer assembly Methods 0.000 description 1
- 230000031700 light absorption Effects 0.000 description 1
- 239000002082 metal nanoparticle Substances 0.000 description 1
- 239000002105 nanoparticle Substances 0.000 description 1
- 229910000510 noble metal Inorganic materials 0.000 description 1
- 238000000643 oven drying Methods 0.000 description 1
- 239000000276 potassium ferrocyanide Substances 0.000 description 1
- 239000000376 reactant Substances 0.000 description 1
- 230000035484 reaction time Effects 0.000 description 1
- 150000003839 salts Chemical class 0.000 description 1
- -1 spheres Substances 0.000 description 1
- XOGGUFAVLNCTRS-UHFFFAOYSA-N tetrapotassium;iron(2+);hexacyanide Chemical compound [K+].[K+].[K+].[K+].[Fe+2].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-].N#[C-] XOGGUFAVLNCTRS-UHFFFAOYSA-N 0.000 description 1
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- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/48—Silver or gold
- B01J23/50—Silver
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Abstract
The invention discloses a method for loading metal nanocrystalline on amorphous nano material by one-step method, which uses ferrous-based modifier, utilizes the nanocrystalline attached on amorphous nano core as a growth base point, epitaxially grows and coats a shell layer, directly loads the metal nanocrystalline on the surface of the amorphous nano core by one-step method with high efficiency, and directly loads the ultra-small-size nanocrystalline on the surface of the amorphous nano core for the first time, thereby providing an effective feasible method for further synthesis and application of the nano composite material The method has wide application in the aspects of enhancing photocatalysis, preparing biomedical materials, protecting ultraviolet and blue light and the like.
Description
The technical field is as follows:
the invention relates to the technical field of nano composite structure materials, in particular to a method for loading metal nanocrystals on an amorphous nano material by a one-step method.
Background art:
the nano core-shell structure is a composite mode of the nano composite material, and the composite material prepared by the core-shell structure can compound the characteristics of two or more materials, so that a rich composite mode is provided for the structure and characteristic design and application of the nano material. The load of the metal crystal nanocrystals on the amorphous nano-core material is always a research hotspot of the nano-composite structure material, and is different from the preparation of the nano-core-shell structure (metal nanoparticles are used as cores and amorphous materials are used as shell layers) in which the amorphous material is coated on the metal core, the load of the metal nano-crystal nano-composite material is difficult because the amorphous nano-particles are used as cores, and the problems that the direct load cannot be realized, the nanocrystal self-nucleation is realized, the load rate is low, the nanocrystal size is difficult to control, and the product concentration is low are faced. How to efficiently load nanocrystalline on amorphous crystals or crystals with different crystal forms to prepare a nanocomposite structure material with high load rate is always a research hotspot and difficulty in the field of nanocomposite material synthesis and preparation.
In the traditional 'layer-by-layer assembly method', connecting agents such as coupling agents, surface modifiers and the like are needed to respectively carry out surface modification on amorphous nano cores and nano crystals, and then the nano crystals are loaded on the surfaces of the cores through the successive action of the coupling agents and the surface modification. The mode of indirectly attaching or loading the nanocrystals by utilizing the interaction of the linking agent is difficult to load the nanocrystals with ultra-small sizes, has complex preparation process, multiple product influencing factors, low loading rate, long time consumption, low product concentration and difficult enlargement or large-scale preparation. The coupling agent, the surface modifier and other connecting agents are used for loading the nanocrystalline, so that a steric hindrance effect is easily formed, and meanwhile, the coupling agent and the surface modifier can also influence the surface characteristics of the nanocrystalline, such as catalysis, conductivity and the like, and are not beneficial to the application of products.
The invention content is as follows:
the invention aims to provide a method for loading metal nanocrystals on an amorphous nano material by a one-step method, which uses a ferrous-based modifier without using a connecting agent, utilizes the nanocrystals attached to an amorphous nano core as a growth base point, epitaxially grows and coats a shell layer, directly and efficiently loads the metal nanocrystals on the surface of the amorphous nano core by the one-step method, and directly and efficiently loads ultra-small-size nanocrystals on the surface of the amorphous nano core for the first time, thereby providing an effective and feasible method for further synthesis and application of a nano composite material, and the method has the advantages of simple process, short period, low cost, high product concentration, high nanocrystal loading rate, stable product appearance and chemical characteristics, excellent optical characteristics and strong size effect of the nanocrystals, and the prepared nano composite material has the advantages of high nanocrystal loading rate, uniform size, strong stability and strong local surface plasmon resonance effect, the absorption spectrum has a strong absorption peak, compared with a dispersion liquid without loaded nano-crystal, the dispersion liquid of the loaded product shows obvious color change, has wide application in the aspects of catalysis, enhanced photocatalysis, biological medical treatment, ultraviolet and blue light protection and the like, can also be used as a matrix or an intermediate for further preparing a nano composite material, and the high-efficiency loaded ultra-small nano-crystal also provides conditions for researching the chemical and physical properties of the ultra-small nano material, thereby solving the problems that the metal nano material cannot be directly loaded on the surface of an amorphous nano core, the loading rate is low, the crystal self-nucleation is realized, and the size of the nano crystal is difficult to control.
The invention is realized by the following technical scheme:
a method for loading metal nanocrystals on an amorphous nanomaterial core in a one-step process, the method comprising the steps of:
dispersing amorphous nano materials in deionized water (DIwater) or distilled water or ultrapure water to prepare dispersion liquid with the concentration of 0.01-0.03mol/L, adding a ferrous (Fe (II)) based modifier with the concentration of 0.1-0.3mol/L, stirring for 0.5-2.5h, wherein the molar ratio of the amorphous nano materials to the ferrous (Fe (II)) based modifier in a reaction system is (2-5):1, 3000 and 8000rpm, centrifugally washing, dispersing sediments in water after washing, ultrasonically dispersing and uniformly stirring, adding a metal nano crystal precursor solution with the concentration of 0.05-0.3mol/L, violently stirring for 5-10min, reacting for 1-2h under the ultrasonic condition, centrifugally washing for three times by using water, dispersing in water to prepare product dispersion liquid, and storing in a room.
The amorphous nanomaterial is selected from SiO2Nano meterAny one of amorphous nano materials such as spheres, polystyrene microspheres, nano titanium oxide and nano carbon particles.
The modifying agent containing Fe (II)) group is Fe2+The compound of (1), comprising: FeSO4·7H2O (ferrous sulfate), (NH)3)2·Fe(SO4)2·6H2O (ferrous ammonium sulfate), Fe (NO)3)2·6H2O、2(C2H3O2) Fe (ferrous acetate or acetate), Fe (C)2O4)·2H2O (ferrous oxalate), ferrous gluconate, C2H8N2·H2SO4·FeSO4·4H2O (ferrous ethylenediamine sulfate), FeCl2·4H2O、K4[Fe(CN)6]·3H2O (potassium ferrocyanide) and Na4Fe(CN)6、Na4Fe(CN)6·10H2Ferrous salts such as O and the like and ferrous complexing agents.
The reduction potential of the metal nanocrystalline precursor is larger than Fe3+/Fe2+(fe (ii)) reduction potential (0.358-0.771V) the metal nanocrystals comprise: ag. The reduction potential of the precursor of the nanocrystalline is higher than 0.358-0.771V.
The metal nanocrystals efficiently loaded on the amorphous nanomaterial core typically have a particle size of less than 25nm, and even ultra-small metal nanocrystals having a particle size of less than 10nm can be efficiently loaded.
When the amorphous nano material is SiO2When the nanosphere is used, the preparation method comprises the following steps: preparing a solution A and a solution B, wherein the solution A is formed by mixing Tetraethoxysilane (TEOS) and water; solution B from NH3·H2O, water and absolute ethyl alcohol; the solution A, B is mixed and stirred vigorously for 30min to obtain TEOS: NH3·H2O:H2The molar concentration ratio of O to EtOH is 1 (0.8-1.5) to (0.4-0.8) to (6-8), the reaction is carried out for 3h at the temperature of 20-70 ℃, centrifugal absolute ethyl alcohol at 3000-8000rpm is used for washing for 2-3 times, and the centrifugal sediment is dried at the temperature of 105 ℃ to prepare amorphous SiO2Nanospheres. SiO can be regulated and controlled by regulating and controlling the proportion of reactants, the using amount of ammonia water and the reaction temperature2Particle size of nanospheres, SiO2The particle size of the nanospheres is as follows: 30-500 nm. SiO 22The reaction can be expanded by 5-10 times during the preparation of the nanospheres.
Other amorphous nano-material polystyrene microspheres, nano titanium oxide, nano carbon particles and the like can be directly purchased into commercial products.
The invention also protects the application of the prepared nano composite material nano crystal in the aspects of catalysis, enhanced photocatalysis, biological medical treatment, ultraviolet and blue light protection.
The invention has the following beneficial effects: the method for efficiently loading the metal nanocrystals on the surface of the amorphous nano-core by one step and directly loading the ultra-small-size nanocrystals on the surface of the amorphous nano-core for the first time by using the ferrous-based modifier as a growth base point without using a connecting agent and using the nanocrystals attached to the amorphous nano-core as a growth base point provides an effective feasible method for further synthesis and application of the nanocomposite, has the advantages of simple process, short period, low cost, high product concentration, high nanocrystal loading rate, stable product morphology and chemical characteristics and excellent optical characteristics, the nanocrystals have very strong size effect, the prepared nanocomposite has high nanocrystal loading rate, uniform size and strong stability, has very strong local surface plasmon resonance effect, and the absorption spectrum has very strong absorption peak compared with the dispersion liquid without loading nanocrystals, the dispersion liquid of the loaded product shows obvious color change, has wide application in the aspects of catalysis, enhanced photocatalysis, preparation of biomedical materials, ultraviolet and blue light protection and the like, can also be used as a matrix or an intermediate for further preparing the nano composite material, and the high-efficiency loaded ultra-small-size nano crystal also provides conditions for researching the chemical and physical properties of the ultra-small nano material, thereby solving the problems that the metal nano material cannot be directly loaded on the surface of an amorphous nano core, the loading rate is low, the crystal self-nucleation is realized, and the size of the nano crystal is difficult to control.
Description of the drawings:
FIG. 1 is an amorphous SiO solid prepared in accordance with example 1 of the present invention2Nanospheres and high loading SiO prepared in example 32-Scanning Electron Microscopy (SEM) contrast images of AgNCs;
wherein a and b are amorphous nano material SiO prepared in example 12SEM image of nanosphere (I-1 #); c, d are SiO as prepared in example 32SEM picture of AgNCs (II-1 #).
FIG. 2 is an amorphous SiO solid prepared in example 2 of the invention2Nanospheres and high loading SiO prepared in example 42SEM comparison of AgNCs;
wherein a and b are amorphous nano material SiO prepared in example 22SEM image of nanosphere (I-2 #); c, d are SiO as prepared in example 42SEM picture of AgNCs (II-2 #).
FIG. 3 shows the amorphous SiO nanomaterials of examples 3-4 of the present invention2X-ray diffraction (XRD) contrast before and after nanosphere loading;
wherein a is the amorphous SiO of example 32XRD contrast diagram before and after loading of nanosphere (I-1 #); b is amorphous SiO as in example 42(I-2#) XRD contrast before and after loading.
FIG. 4 is SiO for the product of example 32SEM comparison of the long-term stability of AgNCs (II-1 #);
wherein a-c is initial SiO2-low to high power SEM of AgNCs (II-1 #); d-f is SiO after long-term storage2-low to high power SEM for AgNCs (II-1 #).
FIG. 5 is SiO, a product of example 32SEM-EDS after long-term storage for more than 33 months for AgNCs (II-1 #).
FIG. 6 is SiO, a product of example 32-TEMs with high loading rate and long-term stability of AgNCs (II-1 #);
wherein a-c is SiO with the storage period of more than 33 months2-low to high TEM of AgNCs (II-1 #); d is SiO2High Resolution TEM (HRTEM) of Ag nanocrystals loaded on AgNCs, partially embedded in amorphous SiO2The spacing between crystal planes of the crystal lattice stripes is 0.24nm and corresponds to a (111) crystal plane of Ag; e-g is SiO2-AgNCs (II-1#) high angle annular dark field-scanning transmission electron microscope (HAADF-STEM) pictures from low to high magnification, amorphous SiO2The particle diameters of the nano-sphere and the Ag nano-crystal are 190-210nm and 3-25nm respectively(ii) a h-k is SiO2-DEX imaging of AgNCs; l is a cross section of the distribution of the content of the line scanning element corresponding to h; m is single SiO2AgNCs corresponds to h single SiO2EDS by AgNCs, inset by element content; n is the line scan element content curve corresponding to l, which is O, Si and Ag in sequence.
FIG. 7 is SiO for the product of example 42SEM comparison of the long-term stability of AgNCs (II-2 #);
wherein a-c is initial SiO2-low to high power SEM of AgNCs (II-2 #); d-f is SiO after long-term storage2-low to high power SEM for AgNCs (II-2 #). SiO of high-load Ag nano crystal2AgNCs (II-2#) has long-term stability, amorphous SiO2Ag nano crystal loaded on the nanosphere is partially embedded in SiO2In the nano-sphere, partial crystals of the Ag nano-crystals are embedded in SiO2The nano-spheres are not easy to fall off, and partial crystals of the Ag nano-crystals are inlaid or adsorbed on SiO2On the nanospheres, the surface potential of the portion of the crystal that interacts with the nanospheres is reduced and the total surface area of the exposed Ag nanospheres is reduced, resulting in a reduction in SiO2The total potential energy of Ag nanocrystals loaded on the AgNCs is reduced, the stability is enhanced, and a firm and stable amorphous-crystalline composite structure is formed. SiO 22The stable storage period of AgNCs (II-2#) is more than 33 months.
FIG. 8 is SiO, a product of example 42SEM-EDS after long-term storage for more than 33 months for AgNCs (II-2 #).
FIG. 9 is SiO, a product of example 42-TEMs with high loading rate and long-term stability of AgNCs (II-2 #);
wherein a-c is SiO with the storage period of more than 33 months2-low to high TEM of AgNCs (II-2 #); d is SiO2High Resolution TEM (HRTEM) of Ag nanocrystals loaded on AgNCs, partially embedded in amorphous SiO2The spacing between crystal planes of the crystal lattice stripes is 0.24nm and corresponds to a (111) crystal plane of Ag; e-g is SiO2-AgNCs (II-2#) high angle annular dark field-scanning transmission electron microscope (HAADF-STEM) picture from low to high magnification, the grain size of the nano-core and Ag nano-crystal is 210-230nm and 5-25nm respectively; h-k is SiO2-DEX imaging of AgNCs;l is a cross section of the distribution of the content of the line scanning element corresponding to h; m is single SiO2AgNCs corresponds to h single SiO2EDS by AgNCs, inset by element content; n is the line scan element content curve corresponding to l, which is O, Si and Ag in sequence.
FIG. 10 shows the high-loading ultra-small-sized nanocrystalline SiO prepared in example 5 of the present invention2-AgNCs(SiO2: 500nm, AgNCs: 5-10 nm).
FIG. 11 is a graph of the UV-Vis-NIR absorbance spectra of the products of example 1 and example 3;
wherein a is example 1 (SiO)2(I-1#)) and example 3 (SiO)2-AgNCs # (II-1#)) dispersions, milky white and reddish brown respectively; b is the UV-Vis-NIR absorbance spectra of the products of example 1 and example 3. Amorphous SiO2The nanosphere has no absorption peak at 200-1200nm, has a strong absorption peak at 200-1200nm after loading silver nanocrystal, has a peak position of 448nm and high absorbance at 340-560nm, strongly absorbs ultraviolet rays, has an ultraviolet and blue light protection function, and enhances photocatalysis.
The specific implementation mode is as follows:
the following is a further description of the invention and is not intended to be limiting.
Example 1: preparation of amorphous SiO2Nanosphere (particle size: 200 + -10nm)
Amorphous SiO2Preparing nanospheres by preparing solution A and solution B, wherein solution A is prepared from 3.17ml TEOS and 25ml H2O is mixed; solution B from 2.52ml (25 wt%) NH3·H2O and 1.8ml H2O and 25ml EtOH; mixing solution A and B, stirring vigorously for 30min, reacting at 50 deg.C for 3h, centrifuging at 5000rpm for 2-3 times, washing with anhydrous ethanol, and oven drying at 105 deg.C to obtain amorphous SiO2Nanospheres (marked as I-1#, particle size: 200 + -10 nm). SiO 22Scanning Electron Microscopy (SEM) images of nanospheres see a, b, SiO in FIG. 12The reaction can be expanded by 5-10 times during the preparation of the nanospheres.
Example 2: preparation of amorphous SiO2Nanosphere (particle size: 220 + -10nm)
Reference example 1, differentIs characterized in that SiO2Nanosphere (I-2#, particle size: 220. + -.10 nm) 3.78ml (25 wt%) NH was used3·H2O is reacted for 3h at room temperature, and the Scanning Electron Microscope (SEM) images of the reaction solution are shown as a, b and SiO in FIG. 22The reaction can be expanded by 5-10 times during the preparation of the nanospheres.
Example 3: preparation of highly loaded SiO2-AgNCs(II-1#)
0.72g of SiO prepared in example 12The nanospheres were dispersed in 30ml deionized water, 30ml 0.15M K4[Fe(CN)6]·3H2Stirring for 1h by O, centrifugally washing for 3 times at 5000rpm, redispersing the washed sediment in 30ml of DI water, ultrasonically dispersing and uniformly stirring, adding 15ml of 0.175mol/L silver ammonia solution, violently stirring for 5-10min, reacting for 1h under the ultrasonic condition, centrifugally washing for three times by DI water, and redispersing in 30ml of DI water to obtain SiO2-AgNCs (II-1#) dispersion, SiO of load nanocrystal2The dispersion liquid presents milk white and efficiently loads nanocrystalline SiO2The AgNCs dispersion appeared reddish brown due to localized surface plasmon resonance effects of the silver nanocrystals. High-load SiO2Scanning Electron Microscopy (SEM) images of AgNCs see FIGS. 1(c, d) and 5, SiO2The reaction can be expanded by 3-5 times when the AgNCs is prepared.
Example 4: preparation of highly loaded SiO2-AgNCs(II-2#)
Reference example 3 with the exception that the SiO prepared in example 2 was used2Nanospheres, SiO prepared by adding silver ammonia solution and reacting for 2h2The AgNCs (II-2#) dispersion is stored indoors for later use. High-load SiO2Scanning Electron Microscopy (SEM) of AgNCs see C, d and FIG. 8 in FIG. 2, SiO2The reaction can be expanded by 3-5 times when the AgNCs is prepared.
Example 5: preparation of high-load ultra-small-size nanocrystalline SiO2-AgNCs(SiO2：～500nm,AgNCs：5-10nm)
Reference example 3, except that 30ml of 0.2mol/L Fe (II) -based modifier (FeCl) was added2·4H2O) was stirred for 2h, 15ml of a 0.3mol/L silver ammonia solution was added. High-load ultra-small-size nanocrystalline SiO2AgNCs, amorphous SiO2The particle diameter of the nanosphere is 500nm, and the loaded ultra-small silver nanoThe grain diameter of the rice-grain is 9.08 +/-1.91 nm, and SiO is highly loaded2A high angle annular dark field image (HAADF-STEM) of AgNCs is shown in FIG. 9. High load rate, uniform size, and ultra-small size of the nanocrystal.
Example 6:
reference example 4 was made except that SiO was replaced with any one of polystyrene microspheres, nano titanium oxide and nano carbon particles2Nanospheres.
Example 7: SiO 22High load factor, stability and optical Properties of AgNCs
The nano-crystal loaded on the amorphous nano-material by the method has high loading rate, strong stability and specific optical characteristics. The products of examples 3 and 4, having a pot life of more than 33 months, were characterized by Scanning Electron Microscopy (SEM), Transmission Electron Microscopy (TEM) and high angle annular dark field-scanning transmission electron microscopy (HAADF-STEM) and analyzed for element content by EDS. Optical properties of the amorphous nanomaterial before and after loading were measured using an ultraviolet-visible-near infrared spectrophotometer. As can be seen from FIG. 4, SiO highly loaded with Ag nanocrystals2AgNCs (II-1#) has long-term stability, SiO2The upper loaded Ag nano crystal is partially embedded in SiO2Inner, SiO2The stable storage period of AgNCs (II-1#) is more than 33 months. The method has high nanocrystalline loading rate on the amorphous nano material, and the nanocrystalline loading rate is more than 14% (see fig. 5 and fig. 8). As can be seen from FIG. 5, SiO2SiO with long-term stability and high Ag nanocrystalline loading for AgNCs (II-1#)2SEM-EDS for AgNCs (II-1 #). SiO 22DES after storage of AgNCs for more than 33 months, the elemental content of Ag being indicative of SiO2The Ag nanocrystals loaded by the AgNCs have high loading rate, and the nanocrystal loading rate is more than 14 percent. As can be seen from FIG. 8, SiO2SiO with long-term stability and high Ag nanocrystalline load by AgNCs (II-2#)2SEM-EDS for AgNCs (II-2 #). SiO 22-DES after AgNCs storage for more than 33 months, the elemental content of Ag indicates SiO2The Ag nanocrystals loaded by the AgNCs have high loading rate, and the nanocrystal loading rate is more than 14 percent. EDS of the single nanomaterial prepared in example 3 shows that the supported nanocrystal content is greater than 20 wt% (see h-n in FIG. 6 and h-n). Example 4 the reaction time for loading the nanocrystals was extended and the product loading nanocrystal content was further increased to 24.42 wt% (h-n in fig. 9).
It is noted that the nanocrystalline partial crystal loaded by the method of the invention is embedded on the surface of the amorphous body (see a-d in figure 6 and a-d in figure 9), is not easy to fall off, has strong structural stability and chemical stability, and can be stored for a long time (see figure). Figures 4-9 show that dispersions of the product can be stored stably for long periods of time in the room, with a shelf life of greater than 33 months. And partial crystals of the nanocrystals are inlaid or adsorbed on the amorphous nanomaterial, the surface potential energy of the partial crystals under the action of the nanocrystals is reduced, the total surface area exposed by the Ag nanospheres is reduced, the total potential energy of the loaded nanocrystals on the product is reduced, the activity of the nanocrystals is maintained, the stability is enhanced, and a firm and stable amorphous-crystal composite structure is formed.
After the amorphous nano material is loaded with the nano crystal efficiently, a strong surface plasma resonance effect is formed, and an absorption spectrum has a strong resonance absorption peak (see b in fig. 11). SiO 22The optical properties of AgNCs are mainly reflected in the supported nanocrystals, SiO2Due to the fact that a large number of Ag nanocrystals are loaded, compared amorphous nano materials have no absorption peak in an ultraviolet-visible-near infrared light region (250-2The absorption peak of AgNCs is generated by Ag nanocrystals loaded by the AgNCs. The light absorption range is 340-. Before and after loading the nanocrystalline on the amorphous body, due to the local surface plasmon resonance effect of the loaded noble metal nanocrystalline, the dispersion liquid of the loaded product shows obvious color change compared with the dispersion liquid without loading the nanocrystalline. Example 3 the amorphous dispersion without supported nanocrystals was milky white, with a significant color change after supported nanocrystals, and the dispersion appeared reddish brown (a in fig. 11). Meanwhile, the loaded nanocrystal has small size, large specific surface area and strong catalytic activity, is suitable for catalysis and is widely applied.
Claims (10)
1. A method for loading metal nanocrystals on an amorphous nanomaterial core by a one-step process, the method comprising the steps of: dispersing an amorphous nano material in deionized water or distilled water or ultrapure water to prepare a dispersion liquid with the concentration of 0.01-0.03mol/L, adding a ferrous modifier with the concentration of 0.1-0.3mol/L, stirring for 0.5-2.5h, carrying out centrifugal washing at 8000rpm of 1.5: 1 in a molar ratio of the amorphous nano material to the ferrous modifier in a reaction system, dispersing the washed sediment in water, carrying out ultrasonic dispersion and stirring uniformly, adding a metal nanocrystalline precursor solution with the concentration of 0.05-0.3mol/L, stirring vigorously for 5-10min, reacting for 1-2h under an ultrasonic condition, carrying out centrifugal washing for three times by using water, dispersing in water to prepare a product dispersion liquid, and storing indoors; the metal nanocrystals efficiently loaded on the amorphous nanomaterial core have a particle size of less than 25 nm.
2. The method of claim 1, wherein the amorphous nanomaterial is selected from SiO2Any one of nanospheres, polystyrene microspheres, nano titanium oxide and nano carbon particles.
3. The one-step method for loading metal nanocrystals onto an amorphous nanomaterial core according to claim 1 or 2, wherein the ferrous modifier is Fe-containing2+The compound of (1).
4. The one-step method for loading metal nanocrystals onto an amorphous nanomaterial core according to claim 1 or 2, wherein the ferrous modifier is selected from ferrous salts or ferrous complexing agents.
5. The method for loading metal nanocrystals onto amorphous nanomaterial cores according to claim 1 or 2, characterized in that the ferrous-based modifier is selected from FeSO4·7H2O、(NH3)2·Fe(SO4)2·6H2O、Fe(NO3)2·6H2O、2(C2H3O2)·Fe、Fe(C2O4)·2H2O, ferrous gluconate, C2H8N2·H2SO4·FeSO4·4H2O、FeCl2·4H2O、K4[Fe(CN)6]·3H2O、Na4Fe(CN)6、Na4Fe(CN)6·10H2O。
6. The one-step method for loading metal nanocrystals onto amorphous nanomaterial cores according to claim 1 or 2, wherein the reduction potential of the metal nanocrystal precursor is greater than Fe3+/Fe2+Reduction potential.
7. The one-step method for supporting metal nanocrystals on an amorphous nanomaterial core according to claim 1 or 2, wherein the metal nanocrystals are selected from any one of Ag, Au, Pt, Pd, Ru, Rh nanocrystals.
8. The method of claim 1 or 2, wherein the size of the metal nanocrystals efficiently loaded on the amorphous nanomaterial core is less than 10 nm.
9. The method of claim 1 or 2, wherein the amorphous nanomaterial is SiO when the amorphous nanomaterial is loaded with metal nanocrystals by the one-step method2When the nanosphere is used, the preparation method comprises the following steps: preparing a solution A and a solution B, wherein the solution A is formed by mixing tetraethoxysilane and water; solution B from NH3·H2O, water and absolute ethyl alcohol; the solution A, B is mixed and stirred vigorously to obtain TEOS: NH3·H2O:H2The molar concentration ratio of O to EtOH is 1 (0.8-1.5) to (0.4-0.8) to (6-8), the reaction is carried out for 3h at the temperature of 20-70 ℃, the centrifugal absolute ethanol at 3000-8000rpm is used for washing for 2-3 times, and the centrifugal sedimentDrying at 105 ℃ to obtain amorphous SiO2Nanospheres of SiO2The particle size of the nanospheres is as follows: 30-500 nm.
10. The application of the nano composite material nanocrystal in catalysis, enhanced photocatalysis, preparation of biomedical materials and ultraviolet and blue light protection is characterized in that the nano composite material nanocrystal is prepared by the method of loading metal nanocrystals on an amorphous nanomaterial core by the one-step method in claim 1.
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Citations (3)
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| US20160215104A1 (en) * | 2015-01-23 | 2016-07-28 | Xerox Corporation | Core-shell metal nanoparticle composite |
| CN109663927A (en) * | 2018-11-29 | 2019-04-23 | 西安交通大学 | One kind being based on light hollow SiO2The preparation method of the SERS substrate of/Au core-shell structure |
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Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
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| US20160215104A1 (en) * | 2015-01-23 | 2016-07-28 | Xerox Corporation | Core-shell metal nanoparticle composite |
| CN109663927A (en) * | 2018-11-29 | 2019-04-23 | 西安交通大学 | One kind being based on light hollow SiO2The preparation method of the SERS substrate of/Au core-shell structure |
Non-Patent Citations (2)
| Title |
|---|
| PARUL KHURANA ET AL.: ""Development of promising surface enhanced Raman scattering substrate: Freckled SiO2@Au nanocomposites"", 《MICROCHEMICAL JOURNAL》 * |
| 中国冶金百科全书总编辑委员会《有色金属冶金》卷编辑委员会: "《中国冶金百科全书：有色金属冶金》", 31 January 1999 * |
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