CN104860357A - Monodispersed nano-sheet and/or nano-ring as well as preparation and application thereof - Google Patents
Monodispersed nano-sheet and/or nano-ring as well as preparation and application thereof Download PDFInfo
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- 239000002063 nanoring Substances 0.000 title claims abstract description 43
- 238000002360 preparation method Methods 0.000 title claims abstract description 17
- 239000002135 nanosheet Substances 0.000 title claims abstract description 15
- 238000000034 method Methods 0.000 claims abstract description 28
- 150000001868 cobalt Chemical class 0.000 claims abstract description 24
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Chemical compound O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 22
- 239000012153 distilled water Substances 0.000 claims abstract description 19
- 239000003513 alkali Substances 0.000 claims abstract description 18
- 238000003756 stirring Methods 0.000 claims abstract description 14
- 239000007791 liquid phase Substances 0.000 claims abstract description 13
- 239000003960 organic solvent Substances 0.000 claims abstract description 13
- 239000012046 mixed solvent Substances 0.000 claims abstract description 8
- 238000001556 precipitation Methods 0.000 claims abstract description 7
- 238000001035 drying Methods 0.000 claims abstract description 6
- 238000001914 filtration Methods 0.000 claims abstract description 4
- 238000005406 washing Methods 0.000 claims abstract description 4
- 238000001816 cooling Methods 0.000 claims abstract description 3
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 28
- 239000000126 substance Substances 0.000 claims description 15
- 239000013078 crystal Substances 0.000 claims description 9
- 238000006555 catalytic reaction Methods 0.000 claims description 8
- 229960004756 ethanol Drugs 0.000 claims description 8
- 238000001514 detection method Methods 0.000 claims description 7
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 6
- 239000007772 electrode material Substances 0.000 claims description 6
- BDERNNFJNOPAEC-UHFFFAOYSA-N propan-1-ol Chemical compound CCCO BDERNNFJNOPAEC-UHFFFAOYSA-N 0.000 claims description 6
- ZMXDDKWLCZADIW-UHFFFAOYSA-N N,N-Dimethylformamide Chemical compound CN(C)C=O ZMXDDKWLCZADIW-UHFFFAOYSA-N 0.000 claims description 5
- 230000032683 aging Effects 0.000 claims description 4
- 229960000935 dehydrated alcohol Drugs 0.000 claims description 4
- 230000035484 reaction time Effects 0.000 claims description 4
- 238000010992 reflux Methods 0.000 claims description 4
- 239000002904 solvent Substances 0.000 claims description 4
- UFMZWBIQTDUYBN-UHFFFAOYSA-N cobalt dinitrate Chemical compound [Co+2].[O-][N+]([O-])=O.[O-][N+]([O-])=O UFMZWBIQTDUYBN-UHFFFAOYSA-N 0.000 claims description 3
- 229910001981 cobalt nitrate Inorganic materials 0.000 claims description 3
- QAHREYKOYSIQPH-UHFFFAOYSA-L cobalt(II) acetate Chemical compound [Co+2].CC([O-])=O.CC([O-])=O QAHREYKOYSIQPH-UHFFFAOYSA-L 0.000 claims description 3
- 230000001276 controlling effect Effects 0.000 claims description 3
- 230000001105 regulatory effect Effects 0.000 claims description 3
- GVPFVAHMJGGAJG-UHFFFAOYSA-L cobalt dichloride Chemical compound [Cl-].[Cl-].[Co+2] GVPFVAHMJGGAJG-UHFFFAOYSA-L 0.000 claims description 2
- 238000002425 crystallisation Methods 0.000 claims description 2
- 230000008025 crystallization Effects 0.000 claims description 2
- 229910021503 Cobalt(II) hydroxide Inorganic materials 0.000 abstract description 13
- 238000006243 chemical reaction Methods 0.000 abstract description 8
- 206010067171 Regurgitation Diseases 0.000 abstract 1
- 238000002156 mixing Methods 0.000 abstract 1
- ASKVAEGIVYSGNY-UHFFFAOYSA-L cobalt(ii) hydroxide Chemical compound [OH-].[OH-].[Co+2] ASKVAEGIVYSGNY-UHFFFAOYSA-L 0.000 description 11
- 239000000463 material Substances 0.000 description 7
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 6
- 230000015572 biosynthetic process Effects 0.000 description 6
- 238000003786 synthesis reaction Methods 0.000 description 5
- -1 nanometer rod Substances 0.000 description 4
- 239000012071 phase Substances 0.000 description 4
- 238000004098 selected area electron diffraction Methods 0.000 description 4
- 230000005540 biological transmission Effects 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 3
- 239000003963 antioxidant agent Substances 0.000 description 2
- 230000003078 antioxidant effect Effects 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 238000000835 electrochemical detection Methods 0.000 description 2
- 238000005530 etching Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 239000000203 mixture Substances 0.000 description 2
- 239000002057 nanoflower Substances 0.000 description 2
- 230000001681 protective effect Effects 0.000 description 2
- 230000005070 ripening Effects 0.000 description 2
- 229910000980 Aluminium gallium arsenide Inorganic materials 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
- 241000675108 Citrus tangerina Species 0.000 description 1
- MYMOFIZGZYHOMD-UHFFFAOYSA-N Dioxygen Chemical compound O=O MYMOFIZGZYHOMD-UHFFFAOYSA-N 0.000 description 1
- 241000628997 Flos Species 0.000 description 1
- 229910001218 Gallium arsenide Inorganic materials 0.000 description 1
- HBBGRARXTFLTSG-UHFFFAOYSA-N Lithium ion Chemical compound [Li+] HBBGRARXTFLTSG-UHFFFAOYSA-N 0.000 description 1
- 239000004793 Polystyrene Substances 0.000 description 1
- 235000006040 Prunus persica var persica Nutrition 0.000 description 1
- 240000006413 Prunus persica var. persica Species 0.000 description 1
- 229910010413 TiO 2 Inorganic materials 0.000 description 1
- 238000010521 absorption reaction Methods 0.000 description 1
- 150000001450 anions Chemical class 0.000 description 1
- 238000003486 chemical etching Methods 0.000 description 1
- 239000003795 chemical substances by application Substances 0.000 description 1
- 229910017052 cobalt Inorganic materials 0.000 description 1
- 239000010941 cobalt Substances 0.000 description 1
- GUTLYIVDDKVIGB-UHFFFAOYSA-N cobalt atom Chemical compound [Co] GUTLYIVDDKVIGB-UHFFFAOYSA-N 0.000 description 1
- GFHNAMRJFCEERV-UHFFFAOYSA-L cobalt chloride hexahydrate Chemical compound O.O.O.O.O.O.[Cl-].[Cl-].[Co+2] GFHNAMRJFCEERV-UHFFFAOYSA-L 0.000 description 1
- 239000000084 colloidal system Substances 0.000 description 1
- 229910052802 copper Inorganic materials 0.000 description 1
- GDVKFRBCXAPAQJ-UHFFFAOYSA-A dialuminum;hexamagnesium;carbonate;hexadecahydroxide Chemical compound [OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[OH-].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Mg+2].[Al+3].[Al+3].[O-]C([O-])=O GDVKFRBCXAPAQJ-UHFFFAOYSA-A 0.000 description 1
- 230000029087 digestion Effects 0.000 description 1
- 229910001882 dioxygen Inorganic materials 0.000 description 1
- 238000004134 energy conservation Methods 0.000 description 1
- 230000007613 environmental effect Effects 0.000 description 1
- 229910052737 gold Inorganic materials 0.000 description 1
- 229910021389 graphene Inorganic materials 0.000 description 1
- 229960001545 hydrotalcite Drugs 0.000 description 1
- 229910001701 hydrotalcite Inorganic materials 0.000 description 1
- 238000007689 inspection Methods 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 239000010410 layer Substances 0.000 description 1
- 229910052745 lead Inorganic materials 0.000 description 1
- 229910001416 lithium ion Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 238000001451 molecular beam epitaxy Methods 0.000 description 1
- 239000002086 nanomaterial Substances 0.000 description 1
- 239000002071 nanotube Substances 0.000 description 1
- 239000002070 nanowire Substances 0.000 description 1
- 229910052759 nickel Inorganic materials 0.000 description 1
- 230000003287 optical effect Effects 0.000 description 1
- 230000003647 oxidation Effects 0.000 description 1
- 238000007254 oxidation reaction Methods 0.000 description 1
- 239000002245 particle Substances 0.000 description 1
- 229910052697 platinum Inorganic materials 0.000 description 1
- 229920002223 polystyrene Polymers 0.000 description 1
- 239000011148 porous material Substances 0.000 description 1
- 239000012716 precipitator Substances 0.000 description 1
- 239000002994 raw material Substances 0.000 description 1
- 229910052710 silicon Inorganic materials 0.000 description 1
- 229910052709 silver Inorganic materials 0.000 description 1
- XLOMVQKBTHCTTD-UHFFFAOYSA-N zinc oxide Inorganic materials [Zn]=O XLOMVQKBTHCTTD-UHFFFAOYSA-N 0.000 description 1
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- Inorganic Compounds Of Heavy Metals (AREA)
- Manufacture Of Metal Powder And Suspensions Thereof (AREA)
Abstract
The invention discloses a monodispersed nano-sheet and/or a nano-ring as well as preparation and application thereof. The monodispersed nano-sheet and/or the nano-ring comprise(s) the component of beta-Co(OH)2. The preparation method of the nano-sheet adopts a mixed solvent liquid phase precipitation method, namely: firstly, adding cobalt salt, distilled water, an organic solvent and alkali to a beaker in a stoichiometry ratio, wherein the volume ratio of the distilled water to the organic solvent is (3-9):1, the concentration of the cobalt salt is 2.5-10mM, and the weight ratio of the alkali to the cobalt salt is (6-24):1; then, mixing the cobalt salt, the distilled water, the organic solvent and the alkali for 10-20 min, and then performing a stirring and regurgitation reaction at the temperature of 70-100 DEG C for 0.5-2h; after cooling, performing washing, filtration and drying so as to obtain the monodispersed beta-Co(OH)2 nano-sheet. The monodispersed nano-sheet and/or the nano-ring, as well as the preparation and the application thereof, disclosed by the invention, are simple to operate and low in temperature, have low requirements for equipment, and are low in cost, high in efficiency, and easy to industrially apply and generalize.
Description
Technical field
The present invention relates to technical field of nano material, be specifically related to one and prepare monodispersed β-Co (OH)
2the simple and easy method of nanometer sheet and nano-rings.
Background technology
Stratiform cobaltous hydroxide is a kind of hydrotalcite-like materials of single metal, and the same with the hydrotalcite material of routine have the adjustable sex change of structure and the performance such as interlayer anion is commutative.The performance of stratiform cobaltous hydroxide uniqueness, makes it will have broad application prospects in lithium ion battery, catalysis, detection, absorption, magnetic etc.There are two difficult problems producing in cobaltous hydroxide process: easily form colloid or floss during (1) cobaltous hydroxide precipitation and be difficult to filter; (2) cobaltous hydroxide reacts not exclusively under low alkalinity condition, and foreign matter content is high, is easily become the Co (OH) of brownish black by the dioxygen oxidation in air
3.Patent [CN101696039B] discloses under the protection of antioxidant, is that spherical cobalt hydroxide prepared by precipitation agent with NaOH; Patent [CN200810120911.2] discloses under the protection of antioxidant, NaOH solution and protective material solution is injected continuously in turbid solution, displaces the negatively charged ion in cobalt subsalt, and by adjust ph, makes α-Co (OH)
2change into peach β-Co (OH)
2, the cobaltous hydroxide of gained is fine and close crystal particle.
On the other hand, ring texture has broad application prospects in fields such as optical, electrical, magnetic, catalysis, storage and microwave absorbing because of its special configuration and unique physical and chemical performance.The performance of nano-rings mainly relies on its pattern, size and composition.For this reason, different preparation method'ss (e.g., liquid phase chemical etching method, physical etchings technology, molten-salt growth method, template and molecular beam epitaxy etc.) is used to synthesis of nano ring and (comprises, TiO
2, ZnO, Graphene, GaAs/AlGaAs, Co/CoO, Fe
3o
4/ polystyrene, K
2ti
6o
13, Ag, Co, Au, Ni, Si, Pt, Cu, Pb etc.).The pattern of cobaltous hydroxide has important impact to its performance and application.Current people have successfully synthesized cobaltous hydroxide nanometer sheet, nano flower, nano wire, nanometer rod, nanotube, and about the still rarely seen report of preparation of cobaltous hydroxide nano-rings.Physical etchings technology needs special template and large-scale equipment, and because of complex process, cost is higher and be restricted.Chemical synthesis has low cost, the advantage that simple to operate, output is high, but is generally only applicable to the synthesis of exotic materials and specific nanometer ring texture.
In the present invention, we adopt mixed solvent-precipitation-ageing process, by the size changing the volume ratio of mixed solvent, digestion time regulates and controls nano-rings.Nanometer sheet of the present invention and nano-rings have monodispersity, the characteristics such as size adjustable, and these materials have broad application prospects in fields such as catalysis, electrode materials, biosensor, detections.
Summary of the invention
The present invention aims to provide one and has monodispersity and homogeneity is good, the nanometer sheet of the characteristics such as size adjustable and nano-rings; Also provide that technique is simple, mild condition, environmental protection, the energy-conservation chemical liquid phase reaction preparing dispersed nano ring; The dispersed nano sheet provided and nano-rings have broad application prospects.
The present invention solves its technical problem and adopts following technical scheme:
Mono-dispersed nano sheet provided by the invention and/or nano-rings, its component is β-Co (OH)
2.
Described dispersed nano sheet and/or nano-rings, it is single crystal structure, and profile is hexagon, and the length of side is 0.2 ~ 4.62 μm, and thickness is 120 ~ 260nm, and the internal diameter of ring is 0.12 ~ 1.47 μm.
The preparation method of mono-dispersed nano sheet provided by the invention, specifically: adopt mixed solvent liquid-phase precipitation method, namely first stoichiometrically cobalt salt, distilled water, organic solvent and alkali are added in beaker, wherein, the volume ratio of distilled water and organic solvent is 3:1 ~ 9:1, the concentration of cobalt salt is 2.5mM ~ 10mM, alkali is 6:1 ~ 24:1 with the ratio of cobalt salt amount of substance, stir 10 ~ 20min again, then 0.5 ~ 2h is reacted at 70 ~ 100 DEG C through stirring and refluxing, washing after cooling, filtration, obtain single dispersing β-Co (OH) finally by drying
2nanometer sheet.
In aforesaid method, described organic solvent is the one in ethanol, propyl alcohol, acetone, DMF.
The preparation method of mono-dispersed nano ring provided by the invention, be adopt mixed solvent liquid-phase precipitation-aging method, the method step is:
A) cobalt salt, distilled water, dehydrated alcohol and alkali are stoichiometrically added in beaker, stir 10 ~ 20min; React 0.5 ~ 2h at 70 ~ 100 DEG C through stirring and refluxing subsequently, obtain solution A; The volume ratio of water and ethanol is 3:1 ~ 9:1, and the concentration of cobalt salt is 2.5 ~ 10mM, and alkali is 6:1 ~ 24:1 with the ratio of cobalt salt amount of substance;
B) at room temperature in solution A, drip a certain amount of distilled water, continue ageing 24 ~ 48h; Finally wash, filter, obtain described single dispersing β-Co (OH) after drying
2nano-rings; After regulating, the volume ratio of distilled water and dehydrated alcohol is 3:1 ~ 39:1; Ageing process adopts continuously or batch type.
Described employing mixed solvent liquid-phase precipitation-aging method, that is: to the nanometer sheet that liquid-phase precipitation is formed, utilize Oswald slaking principle and β-Co (OH)
2different solubility in different solvents, regulates β-Co (OH) by ratio, the reaction times controlling solvent
2the dissolving of nanometer sheet and crystallization behavior, thus prepare single dispersing β-Co (OH)
2nano-rings.
In aforesaid method, described cobalt salt adopts cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, the one in Cobaltous diacetate.
In aforesaid method, described alkali is vulkacit H.
Single dispersing β-Co (OH) prepared by aforesaid method provided by the invention
2nanometer sheet and/or nano-rings, its application in catalysis, electrode materials, biosensor, detection.
The present invention, owing to have employed above-mentioned technical scheme, makes it compared with prior art, has following advantage and positively effect:
(1) nano-rings provided and nanometer sheet have monodispersity and homogeneity is good, the characteristics such as size adjustable.
(2) nano-rings prepared of present method and nanometer sheet, without the need to protective material, particularly nano-rings formation mechenism is novel, is easy to industrial application and promotes.
(3) size of the nano-rings prepared of present method and nanometer sheet is controlled, size range wider (length of side is 0.2 ~ 4.62 μm, and thickness is 120 ~ 260nm, and the internal diameter of ring is 0.12 ~ 1.47 μm).
(4) present method is raw materials used cheap and easy to get, and temperature of reaction is low, and preparation cost is low, and efficiency is high.
(5) present method preparation process is simple, reproducible.
(6) application is wide: the cobaltous hydroxide nano-rings provided and nanometer sheet have broad application prospects in fields such as catalysis, electrode materials, biosensor, detections.
In a word.Formation mechenism of the present invention is unique, simple to operate, temperature is low, less demanding to equipment, and cost is low, and efficiency is high, is easy to industrial application and promotes.It is high that nanometer sheet of the present invention and nano-rings have purity, and foreign matter content is few, monodispersity and homogeneity good, the characteristics such as size adjustable.These materials have broad application prospects in fields such as catalysis, electrode materials, biosensor, detections.
Accompanying drawing explanation
The selected area electron diffraction collection of illustrative plates that Fig. 1 ~ Fig. 3 is respectively the XRD phase structure collection of illustrative plates of products therefrom in embodiment 1, the shape appearance figure observed under scanning electron microscope and observes under transmission electron microscope.
Fig. 4 ~ Figure 16 is respectively the pattern observed under scanning electron microscope of embodiment 2 ~ embodiment 14 products therefrom.
Figure 17 ~ Figure 20 is respectively the XRD phase structure collection of illustrative plates of products therefrom in embodiment 15, the shape appearance figure observed under scanning electron microscope and transmission electron microscope and selected area electron diffraction collection of illustrative plates.
Figure 21 ~ Figure 22 is respectively shape appearance figure that in embodiment 16, products therefrom observes under scanning electron microscope and to different concns NO
2 -the Electrochemical Detection figure of ion.
Figure 23 ~ Figure 27 is respectively the shape appearance figure observed under scanning electron microscope of embodiment 17 ~ embodiment 21 products therefrom.
Embodiment
The present invention is a kind of mono-dispersed nano sheet and/or nano-rings and Synthesis and applications thereof.Described nanometer sheet and nano-rings are the β-Co (OH) of single crystal structure
2, its profile is hexagon, and the length of side is 0.2 ~ 4.62 μm, and thickness is 120 ~ 260nm, and the internal diameter of ring is 0.12 ~ 1.47 μm.Adopting mixed solvent-low temperature liquid phase precipitator method, regulating and controlling β-Co (OH) by changing temperature of reaction (70 ~ 100 DEG C), time (0.5 ~ 2h), concentration, the volume ratio of water and organic solvent and alkali ratio
2the size of nanometer sheet.By β-Co (OH)
2nanometer sheet at room temperature further ripening 24 ~ 48h can obtain β-Co (OH)
2nano-rings.β-Co (OH)
2nano-rings adopts mixed solvent-precipitation-ageing process preparation, that is: by obtained β-Co (OH)
2nanometer sheet can obtain β-Co (OH) at the further ripening 24 ~ 48h of room temperature liquid phase
2nano-rings.
In order to understand the present invention better, illustrate content of the present invention further below in conjunction with embodiment, but content of the present invention is not only confined to the following examples.
Embodiment 1
First by 0.237g cobalt chloride hexahydrate, (amount of substance is 0.001mol, concentration is 5mM), 180mL distilled water, 20mL ethanol and 1.68g vulkacit H (amount of substance is 0.012mol) [ratio of alkali and cobalt salt amount of substance (be called for short alkali than) is 12:1] join in the beaker of 400mL, stir 10min, again beaker is put into oil bath pan, at 90 DEG C of reaction 1h, at room temperature cool subsequently, obtain described single dispersing β-Co (OH) finally by washing, filtration, drying
2nanometer sheet.Products therefrom is pink, and its thing phase and the pattern observed under scanning electron microscope, structure and selected area electron diffraction collection of illustrative plates are respectively as Figure 1-3.Visible, product is monodispersed regular hexagonal β-Co (OH)
2nanometer sheet.This nanometer sheet is single crystal structure, and size is even, and corner angle are clearly clear, the length of side 1.51 ~ 3.27 μm.
Embodiment 2:
Identical with embodiment 1 step, but temperature of reaction is 70 DEG C.Products therefrom is pink, and the pattern observed under scanning electron microscope is as shown in Figure 4, visible, and product is monodispersed regular hexagonal β-Co (OH)
2nanometer sheet, size is even, and corner is comparatively mellow and full, the length of side 0.72 ~ 1.99 μm, thickness 0.12 ~ 0.26 μm.
Embodiment 3:
Identical with embodiment 1 step, but temperature of reaction is 100 DEG C.Products therefrom is pink, and the pattern observed under scanning electron microscope is as shown in Figure 5, visible, and product majority is monodispersed regular hexagonal β-Co (OH)
2nanometer sheet, sharpness of border, corner angle are clearly demarcated, the length of side 1.0 ~ 1.92 μm.
Embodiment 4:
Identical with embodiment 1 step, but cobalt salt concentration is 2.5mM.Products therefrom is pink, and the pattern observed under scanning electron microscope is as shown in Figure 6, visible, and product is monodispersed hexagon β-Co (OH)
2nanometer sheet, size is even, and corner angle are clearly demarcated, long 0.20 ~ 0.51 μm of minor face, the long length of side 0.45 ~ 0.91 μm.
Embodiment 5:
Identical with embodiment 1 step, but the reaction times be 0.5h.Products therefrom is pink, and the pattern observed under scanning electron microscope as shown in Figure 7.Visible product is monodispersed regular hexagonal β-Co (OH)
2nanometer sheet, corner is mellow and full, and the size of sheet is even, the length of side 0.89 ~ 1.89 μm.
Embodiment 6:
Identical with embodiment 1 step, but the reaction times be 2h.Products therefrom is pink, and the pattern observed under scanning electron microscope as shown in Figure 8.Product is monodispersed regular hexagonal β-Co (OH)
2nanometer sheet, corner angle are clearly demarcated, the length of side 1.06 ~ 1.85 μm.
Embodiment 7:
Identical with embodiment 1 step, but H
2o/EtOH volume ratio is 3:1.Products therefrom is pink, and the pattern observed under scanning electron microscope as shown in Figure 9.Visible product is monodispersed regular hexagonal β-Co (OH) of uniform size
2nanometer sheet, size is comparatively large, and corner angle are clearly clear, the length of side 1.88 ~ 4.62 μm.
Embodiment 8:
Identical with embodiment 1 step, but alkali (amount of substance is 0.012mol) is 6:1 with the ratio of cobalt salt (amount of substance is 0.002mol, and concentration is 10mM) amount of substance.Products therefrom is pink, and the pattern observed under scanning electron microscope as shown in Figure 10.Visible, product is monodispersed regular hexagonal β-Co (OH)
2nanometer sheet, corner angle are clearly demarcated, the length of side 1.03 ~ 3.57 μm, thickness 0.18 ~ 0.23 μm.
Embodiment 9:
Identical with embodiment 1 step, but alkali (amount of substance is 0.024mol) is 24:1 with the ratio of cobalt salt (amount of substance is 0.001mol, and concentration is 5mM) amount of substance.Products therefrom is pink, and the pattern observed under scanning electron microscope as shown in figure 11.Visible, product is monodispersed regular hexagonal β-Co (OH)
2nanometer sheet.Corner angle are clearly clear, and size is relatively more even, the length of side 1.33 ~ 2.30 μm.
Embodiment 10:
Identical with embodiment 1 step, but cobalt salt is Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES (quality 0.2910g, 0.001mol, concentration is 5mM).Products therefrom is pink, and the pattern observed under scanning electron microscope as shown in figure 12.Visible, product is monodispersed regular hexagonal β-Co (OH)
2nanometer sheet, corner angle are clearly demarcated, and size is even, the length of side 0.50 ~ 1.87 μm.
Embodiment 11:
Identical with embodiment 1 step, but cobalt salt is Cobaltous diacetate (quality 0.2491g, 0.001mol, concentration is 5mM).Products therefrom is tangerine pink colour, and the pattern observed under scanning electron microscope as shown in figure 13.Visible, product is by the multi-disc layer β-Co (OH) be staggeredly stacked from the hexagon spiral at same center
2nano flower, flower is in monodisperse status and size is comparatively even, the diameter 1.50 ~ 3.0 μm of flower.
Embodiment 12:
Identical with embodiment 10 step, but organic solvent is propyl alcohol.Products therefrom is pink, and the pattern observed under scanning electron microscope is as shown in figure 14, visible, and product is monodispersed regular hexagonal β-Co (OH)
2nanometer sheet, corner angle are clearly demarcated, the length of side 0.89 ~ 2.90 μm.
Embodiment 13:
Identical with embodiment 10 step, but organic solvent is acetone, and products therefrom is pink, and as shown in figure 15, product is monodispersed comparatively regular hexagonal β-Co (OH) to the pattern observed under scanning electron microscope
2nanometer sheet, corner angle are clearly clear, the length of side 0.64 ~ 2.24 μm.
Embodiment 14:
Identical with embodiment 10 step, but organic solvent is DMF.Products therefrom is taupe, and as shown in figure 16, product is monodispersed regular hexagonal β-Co (OH) to the pattern observed under scanning electron microscope
2nanometer sheet, corner angle are mellow and full, and size is even, the length of side 1.47 ~ 2.15 μm.
Embodiment 15:
Identical with embodiment 10 step, but H
2o/EtOH volume ratio is 3:1, and at room temperature continuously stirring 24h.Products therefrom is pink, and its thing phase and the pattern observed under scanning electron microscope and transmission electron microscope, structure and selected area electron diffraction collection of illustrative plates are respectively as shown in figures 17 to 20.Visible, product is monodispersed regular hexagonal β-Co (OH)
2nano-rings, this nano-rings is single crystal structure, and edge is comparatively coarse, the length of side 1.02 ~ 2.63 μm, 0.31 ~ 1.28 μm, aperture.
Embodiment 16:
Identical with embodiment 15 step, but H
2o/EtOH volume ratio is 6:1.Products therefrom is pink, and the pattern observed under scanning electron microscope as shown in figure 21.Visible, product is monodispersed regular hexagonal β-Co (OH)
2nanometer loop, edge is comparatively coarse, the length of side 1.13 ~ 2.42 μm, 0.32 ~ 1.23 μm, aperture.This nano-rings to the Electrochemical Detection of nitrite anions as shown in figure 22.Visible, β-Co (OH)
2nanometer loop has obvious electrocatalytic effect to nitrite anions, and this characteristic can be used for the inspection of nitrite anions.
Embodiment 17:
Identical with embodiment 10 step, but extract reaction solution 50mL, dropwise add 50mL distilled water, the ratio making final distilled water and ethanol is 19:1, and intermittent stirring 24h under room temperature.Products therefrom is pink, and as shown in figure 23, product is monodispersed regular hexagonal β-Co (OH) to the pattern observed under scanning electron microscope
2the mixture of nanometer sheet and nano-rings, wherein nano-rings size is comparatively even, and corner angle are clear smooth, the length of side 1.12 ~ 2.40 μm, 0.12 ~ 0.49 μm, aperture.
Embodiment 18:
Identical with embodiment 17 step, but the distilled water added is 150mL, makes the ratio of final distilled water and ethanol be 39:1.Products therefrom is pink, and as shown in figure 24, product is monodispersed regular hexagonal β-Co (OH) to the pattern observed under scanning electron microscope
2nanometer loop, the size of sheet is even, and corner is smooth, the length of side 1.07 ~ 2.64 μm, and pore size is comparatively homogeneous, about 0.24 ~ 0.62 μm.
Embodiment 19:
Identical with embodiment 18 step, but at room temperature continuously stirring 24h.Products therefrom is pink, and as shown in figure 25, product is monodispersed regular hexagonal β-Co (OH) to the pattern observed under scanning electron microscope
2nanometer loop, corner angle are more coarse, the length of side 1.07 ~ 2.89 μm, 0.29 ~ 0.84 μm, aperture.
Embodiment 20:
Identical with embodiment 19 step, but H
2o/EtOH volume ratio is 6:1, makes the ratio of final distilled water and ethanol be 27:1.Products therefrom is pink, and as shown in figure 26, product is monodispersed regular hexagonal β-Co (OH) to the pattern observed under scanning electron microscope
2nanometer loop, corner is more coarse, the length of side 1.09 ~ 2.41 μm, 0.30 ~ 1.47 μm, aperture.
Embodiment 21:
Identical with embodiment 20 step, but at room temperature continuously stirring 48h.Products therefrom is pink, and as shown in figure 27, product is monodispersed hexagon β-Co (OH) to the pattern observed under scanning electron microscope
2nanometer loop, edge roughness, aperture is comparatively large, about 0.42 ~ 1.28 μm.
Single dispersing β-Co (OH) prepared by above-described embodiment
2nanometer sheet and/or nano-rings, its application in catalysis, electrode materials, biosensor, detection.
Claims (9)
1. mono-dispersed nano sheet and/or nano-rings, is characterized in that: its component is β-Co (OH)
2.
2. dispersed nano sheet as claimed in claim 1 and/or nano-rings, is characterized in that: it is single crystal structure, and profile is hexagon, and the length of side is 0.2 ~ 4.62 μm, and thickness is 120 ~ 260nm, and the internal diameter of ring is 0.12 ~ 1.47 μm.
3. the preparation method of mono-dispersed nano sheet, it is characterized in that adopting mixed solvent liquid-phase precipitation method, specifically: first stoichiometrically cobalt salt, distilled water, organic solvent and alkali are added in beaker, wherein, the volume ratio of distilled water and organic solvent is 3:1 ~ 9:1, the concentration of cobalt salt is 2.5mM ~ 10mM, alkali is 6:1 ~ 24:1 with the ratio of cobalt salt amount of substance, stir 10 ~ 20min again, then 0.5 ~ 2h is reacted at 70 ~ 100 DEG C through stirring and refluxing, washing after cooling, filtration, obtain single dispersing β-Co (OH) finally by drying
2nanometer sheet.
4. preparation method as claimed in claim 3, is characterized in that: described organic solvent is the one in ethanol, propyl alcohol, acetone, DMF.
5. the preparation method of mono-dispersed nano ring, is characterized in that adopting mixed solvent liquid-phase precipitation-aging method, the steps include:
A) cobalt salt, distilled water, dehydrated alcohol and alkali are stoichiometrically added in beaker, stir 10 ~ 20min; React 0.5 ~ 2h at 70 ~ 100 DEG C through stirring and refluxing subsequently, obtain solution A; The volume ratio of water and ethanol is 3:1 ~ 9:1, and the concentration of cobalt salt is 2.5 ~ 10mM, and alkali is 6:1 ~ 24:1 with the ratio of cobalt salt amount of substance;
B) at room temperature in solution A, drip a certain amount of distilled water, continue ageing 24 ~ 48h; Finally wash, filter, obtain described single dispersing β-Co (OH) after drying
2nano-rings; After regulating, the volume ratio of distilled water and dehydrated alcohol is 3:1 ~ 39:1; Ageing process adopts continuously or batch type.
6. preparation method as claimed in claim 5, is characterized in that adopting mixed solvent liquid-phase precipitation-aging method, that is: to the nanometer sheet that liquid-phase precipitation is formed, utilizes Oswald slaking principle and β-Co (OH)
2different solubility in different solvents, regulates β-Co (OH) by ratio, the reaction times controlling solvent
2the dissolving of nanometer sheet and crystallization behavior, thus prepare single dispersing β-Co (OH)
2nano-rings.
7. the preparation method as described in claim 3 or 5, is characterized in that: described cobalt salt adopts cobalt chloride, Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, the one in Cobaltous diacetate.
8. the preparation method as described in claim 3 or 5, is characterized in that: described alkali is vulkacit H.
9. the single dispersing β-Co (OH) that in claim 3 to 8 prepared by arbitrary described method
2nanometer sheet and/or nano-rings, its application in catalysis, electrode materials, biosensor, detection.
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| CN113134361A (en) * | 2021-03-30 | 2021-07-20 | 江苏大学 | Ag/alpha-Co (OH)2Preparation method of oxygen evolution catalyst |
| CN113798503A (en) * | 2021-09-18 | 2021-12-17 | 赣南医学院 | Method for preparing metal cobalt nanosheet |
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| CN105923659A (en) * | 2016-05-30 | 2016-09-07 | 衢州华友钴新材料有限公司 | Method for preparing battery-grade superfine flaky cobalt hydroxide |
| CN106920932A (en) * | 2017-03-10 | 2017-07-04 | 上海应用技术大学 | A kind of leaf of bamboo shape Co (OH)2/ graphene combination electrode material and preparation method thereof |
| CN106920932B (en) * | 2017-03-10 | 2019-12-03 | 上海应用技术大学 | A kind of leaf of bamboo shape Co (OH)2/ graphene combination electrode material and preparation method thereof |
| CN111908417A (en) * | 2019-05-10 | 2020-11-10 | 中国科学院化学研究所 | Perovskite single crystal nanoring and preparation method and application thereof |
| CN111908417B (en) * | 2019-05-10 | 2023-11-28 | 中国科学院化学研究所 | Perovskite single crystal nano ring and preparation method and application thereof |
| CN112403466A (en) * | 2020-11-06 | 2021-02-26 | 上海簇睿低碳能源技术有限公司 | Preparation method of core-shell catalyst for dry reforming of methane and carbon dioxide |
| CN112403466B (en) * | 2020-11-06 | 2023-01-03 | 上海簇睿低碳能源技术有限公司 | Preparation method of core-shell catalyst for dry reforming of methane and carbon dioxide |
| CN113134361A (en) * | 2021-03-30 | 2021-07-20 | 江苏大学 | Ag/alpha-Co (OH)2Preparation method of oxygen evolution catalyst |
| CN113134361B (en) * | 2021-03-30 | 2023-08-25 | 江苏大学 | Ag/alpha-Co (OH) 2 Preparation method of oxygen evolution catalyst |
| CN113798503A (en) * | 2021-09-18 | 2021-12-17 | 赣南医学院 | Method for preparing metal cobalt nanosheet |
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