CN103803664B - A kind of preparation method of tricobalt tetroxide band core nano-hollow ball - Google Patents
A kind of preparation method of tricobalt tetroxide band core nano-hollow ball Download PDFInfo
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- CN103803664B CN103803664B CN201210456025.3A CN201210456025A CN103803664B CN 103803664 B CN103803664 B CN 103803664B CN 201210456025 A CN201210456025 A CN 201210456025A CN 103803664 B CN103803664 B CN 103803664B
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Abstract
The present invention relates to a kind of preparation method of tricobalt tetroxide band core nano-hollow ball, it is characterized in that, comprise the steps: that (1) prepares burden: dissolve in deionized water by glucose with containing the inorganic salt of cobalt, dripping ammoniacal liquor regulates pH to be 7 ~ 10, again solution is moved into in the hydrothermal reaction kettle of tetrafluoroethylene, tighten sealing; (2) isothermal reaction: reactor is put into constant temperature oven standing and reacting; (3) wash; (4) dry; (5) calcine.Raw material of the present invention is cheaply easy to get, and template synchronously generates in building-up process, and eliminate the operation of synthesis template separately, technique is simple, and the morphology control of synthetic materials is stablized.Products therefrom can be applicable to the fields such as lithium ion battery material, catalyzer, gas sensor, targeted drug.
Description
Technical field
The invention belongs to material chemistry technical field, relate to a kind of chemical preparation process of Co 3 O band core nano-hollow ball.
Background technology
Along with the development of micro Nano material technology, some inorganic micro nano structures with special appearance cause the extensive concern of people.Tiny balloon with removable kernel effectively can be optimized the performance of material in catalysis, stored energy, sensing etc. or realize more complicated multifunctionality.Compared with traditional core shell structure, band core its shell of tiny balloon and kernel can be same material.Report TiO at present
2, SiO
2, ZnS, Co
3o
4the synthesis of nucleocapsid homogeneity tiny balloon.
Co
3o
4be a kind of important spinel strucutre oxides, be widely used in the field such as storage and conversion, commercial catalysts, gas sensor of energy.Existing synthesis Co
3o
4the technology of nucleocapsid homogeneity tiny balloon is mainly divided into two kinds: one is the synthetic method based on " Ostwald slaking " mechanism, and the people such as B. Liu utilize this principle in ethanolic soln 100
oc reacts and within 24 hours, obtains kernel and be incomplete spherical crown and Co together with shell growth
3o
4microballoon, is actually a kind of semi-hollow structure (B. Liu, H. C. Zeng, Small 2005,1,566).Another kind method adopts Template synthesis, and the people such as X. Wang adopt PVP to be template high-temperature solvent thermal synthesis Co in ethylene glycol solution
3o
4, obtain Co through calcining
3o
4polytrope shell structure (X. Wang, X. Wu, Y. Guo, Y. Zhong, X. Cao, Y. Ma and J. Yao, Adv. Funct. Mater., 2010,20,1680.).
Summary of the invention
In order to overcome the deficiencies in the prior art, the invention provides chemical process synthesis pure phase Co cheap fast
3o
4band core nano-hollow ball.
A preparation method for tricobalt tetroxide band core nano-hollow ball, is characterized in that, comprise the steps:
(1) prepare burden: dissolve in deionized water by glucose with containing the inorganic salt of cobalt, drip ammoniacal liquor and regulate pH to be 7 ~ 10, then solution is moved into in the hydrothermal reaction kettle of tetrafluoroethylene, tighten sealing;
(2) isothermal reaction: reactor is put into constant temperature oven standing and reacting;
(3) wash;
(4) dry;
(5) calcine.
The concentration of described glucose in the end in mixing solutions is 0.02 ~ 0.1 g/mL.
The inorganic salt of described cobalt are one in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride, cobaltous acetate or its combination, and in the end in mixing solutions, the concentration of cobalt ion is 0.1 ~ 0.5 mol/L.
Described isothermal reaction temperature is 120 ~ 180 DEG C; The time of described isothermal reaction is 5 ~ 12 hours; Described heat-preserving equipment is the baking oven of energy temperature control.
Described washing is the nano-powder for obtaining after isothermal reaction, with deionized water and ethanol alternately washing, whizzer precipitation or pumping and filtering device is adopted to filter after each washing, filtration product is disperseed again in deionized water or ethanol, repeatedly filter until filtrate pH value is 7, last washing with alcohol is with convenient and dry.
Described drying be for washing after nano-powder, be placed in the baking oven of 50 ~ 70 DEG C and dry.
Described calcining be for dry after nano-powder, be placed in the retort furnace of 450 ~ 700 DEG C calcine 3 ~ 8 hours.
The present invention is with the cobalt salt of cheapness and glucose for raw material, and template synchronously generates in building-up process, and eliminate the operation of synthesis template separately, technique is simple, and the morphology control of synthetic materials is stablized.Products therefrom can be applicable to the fields such as lithium ion battery material, catalyzer, gas sensor, targeted drug.
Accompanying drawing explanation
Fig. 1 is for adopting the present invention's (embodiment 1) synthesis Co
3o
4with the XRD spectra of core nano-hollow ball.
Fig. 2 is for adopting the present invention's (embodiment 1) synthesis Co
3o
4with the stereoscan photograph of core nano-hollow ball.
Embodiment
Embodiment 1:
4g glucose and 20 mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs are dissolved in 80mL deionized water, drip ammoniacal liquor regulate pH be 9, then capacity that solution is moved into be 100 mL with in the hydrothermal reaction kettle of tetrafluoroethylene, tighten sealing.Reactor is put into 180 DEG C of constant temperature oven standing and reacting 8 hours; Generation product deionized water and dehydrated alcohol replace repeatedly washing to neutral, put into 60 DEG C of baking ovens and are incubated drying in 8 hours, obtain Co
3o
4-C mixture powder; By Co
3o
4-C mixture powder is put into 600 DEG C of retort furnace calcinings and is obtained Co in 6 hours
3o
4band core nano-hollow ball powder, productive rate is 93.9%.
The XRD figure of product is composed as shown in Figure 1, with Co
3o
4standard diagram (JCPDS Card 42-1467) is well corresponding, shows that product is pure Co
3o
4.Product transmission electron microscope photo as shown in Figure 2, hollow ball mean sizes about 1.2 dimension rice, wall thickness about 40 nanometer, size of cores about 600 nanometer, all have an appointment the granulometric composition of 30 nanometers by core and shell.
Embodiment 2:
2g glucose and 10 mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs are dissolved in 80mL deionized water, drip ammoniacal liquor regulate pH be 9, then capacity that solution is moved into be 100 mL with in the hydrothermal reaction kettle of tetrafluoroethylene, tighten sealing.Reactor is put into 150 DEG C of constant temperature oven standing and reacting 8 hours; Generation product deionized water and dehydrated alcohol replace repeatedly washing to neutral, put into 60 DEG C of baking ovens and are incubated drying in 8 hours, obtain Co
3o
4-C mixture powder; By Co
3o
4-C mixture powder is put into 500 DEG C of retort furnace calcinings and is obtained Co in 8 hours
3o
4band core nano-hollow ball powder, productive rate is 71.8%.
Embodiment 3:
8g glucose and 50 mmol Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKESs are dissolved in 80mL deionized water, drip ammoniacal liquor regulate pH be 9, then capacity that solution is moved into be 100 mL with in the hydrothermal reaction kettle of tetrafluoroethylene, tighten sealing.Reactor is put into 180 DEG C of constant temperature oven standing and reacting 8 hours; Generation product deionized water and dehydrated alcohol replace repeatedly washing to neutral, put into 60 DEG C of baking ovens and are incubated drying in 8 hours, obtain Co
3o
4-C mixture powder; By Co
3o
4-C mixture powder is put into 700 DEG C of retort furnace calcinings and is obtained Co in 6 hours
3o
4band core nano-hollow ball powder, productive rate is 89.5 %.
Embodiment 4,5;
Repeat embodiment 1, but replace Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES with cobalt chloride and cobaltous acetate respectively, obtain Co
3o
4band core nano-hollow ball powder.Productive rate is respectively 91.1% and 80.8%.
Above-mentioned is can understand and apply the invention for ease of those skilled in the art to the description of embodiment.Person skilled in the art obviously easily can make various amendment to these embodiments, and General Principle described herein is applied in other embodiment and need not through performing creative labour.Therefore, the invention is not restricted to embodiment here, those skilled in the art are according to announcement of the present invention, and the improvement made for the present invention and amendment all should within protection scope of the present invention.
Claims (4)
1. a preparation method for tricobalt tetroxide band core nano-hollow ball, is characterized in that, comprise the steps:
(1) prepare burden: dissolve in deionized water by glucose with containing the inorganic salt of cobalt, drip ammoniacal liquor and regulate pH to be 7 ~ 10, then solution is moved into in the hydrothermal reaction kettle of tetrafluoroethylene, tighten sealing;
The concentration of described glucose in the end in mixing solutions is 0.02 ~ 0.1 g/mL;
The inorganic salt of described cobalt are one in Jing Ti/Bao Pian COBALT NITRATE CRYSTALS/FLAKES, cobalt chloride, cobaltous acetate or its combination, and in the end in mixing solutions, the concentration of cobalt ion is 0.1 ~ 0.5 mol/L;
(2) isothermal reaction: reactor is put into constant temperature oven standing and reacting; Described isothermal reaction temperature is 120 ~ 180 DEG C; The time of described isothermal reaction is 5 ~ 12 hours;
(3) wash;
(4) dry;
(5) calcine.
2. the preparation method of a kind of tricobalt tetroxide band core nano-hollow ball according to claim 1, it is characterized in that, described washing is the nano-powder for obtaining after isothermal reaction, with deionized water and ethanol alternately washing, whizzer precipitation or pumping and filtering device is adopted to filter after each washing, filtration product is disperseed again in deionized water or ethanol, and repeatedly filter until filtrate pH value is 7, last washing with alcohol is with convenient and dry.
3. the preparation method of a kind of tricobalt tetroxide band core nano-hollow ball according to claim 1, is characterized in that, described drying be for washing after nano-powder, be placed in the baking oven of 50 ~ 70 DEG C and dry.
4. the preparation method of a kind of tricobalt tetroxide band core nano-hollow ball according to claim 1, is characterized in that, described calcining is for the nano-powder after drying, and is placed in the retort furnace of 450 ~ 700 DEG C and calcines 3 ~ 8 hours.
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| CN106745252B (en) * | 2016-12-13 | 2019-02-05 | 中南大学 | One kind having multi-layer hollow structure vanadic anhydride nanosphere and its preparation and application |
| CN107128979B (en) * | 2017-05-12 | 2019-05-14 | 华南理工大学 | A kind of preparation method of carbon-based hollow cobaltosic oxide |
| CN107673412A (en) * | 2017-11-17 | 2018-02-09 | 东华大学 | A kind of porous Co3O4 nanometer material and its preparation method and application |
| CN111477890A (en) * | 2020-04-26 | 2020-07-31 | 陈怀付 | Carbon fiber coated nano Co3O4Oxygen reduction catalyst and process for producing the same |
| CN115192605B9 (en) * | 2022-09-15 | 2023-12-22 | 北京理工大学 | Application of dimercaptosuccinic acid modified cobaltosic oxide nano-particles |
| CN115465898B (en) * | 2022-09-19 | 2024-01-30 | 陕西红马科技有限公司 | Method for preparing hollow sphere cobaltosic oxide by using bionic method |
Citations (1)
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| CN101624285A (en) * | 2008-07-08 | 2010-01-13 | 比亚迪股份有限公司 | Composition for preparing zirconia ceramics and ceramics |
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|---|---|---|---|---|
| CN101624285A (en) * | 2008-07-08 | 2010-01-13 | 比亚迪股份有限公司 | Composition for preparing zirconia ceramics and ceramics |
Non-Patent Citations (3)
| Title |
|---|
| A Generalized Synthesis of Metal Oxide Hollow Spheres Using a Hydrothermal Approach;Maria-Magdalena Titirici et al.;《Chem. Mater.》;20061231;第3808页实验部分、第3811页图4、第3811页表1 * |
| General Synthesis and Gas-Sensing Properties of Multiple-Shell Metal Oxide Hollow Microspheres;Xiaoyong Lai et al.;《Communications》;20110222;第2738-2741页 * |
| Preparation and characterization of hollow Co3O4 spheres;Weiwei Zhao et al.;《Materials Letters》;20070628;第772-774页 * |
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