CN109824093A - A kind of Co being layered porous hollow core-shell structure3O4High-efficiency synthesis method - Google Patents
A kind of Co being layered porous hollow core-shell structure3O4High-efficiency synthesis method Download PDFInfo
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Abstract
The present invention provides a kind of Co for being layered porous hollow core-shell structure3O4High-efficiency synthesis method.This method using CTAB as stabilizer, water is solvent, Co (NO3)2·6H2O is raw material, 2-methylimidazole is organic ligand, under mild conditions using Syntheses in water method, has synthesized the ZIF-67 predecessor of cube；The Co for the hollow core-shell structure that obtained ZIF-67 predecessor is layered after 450 DEG C of calcining 2h, cooled to room temperature in air3O4.Not only high-efficient using self-template methods, process is simple, stable structure, can also be achieved the accurate control of the pattern to target product, geometrical homogenization etc., has many advantages, such as that synthesis path is simple, yield is high, morphology controllable and reproducible.The Co of multilayered structure is obtained prepared by this method3O4Size be about 500nm, specific surface area is about 130m2g‑1, had potential application in fields such as supercapacitor, heterogeneous catalysis and lithium ion batteries.
Description
Technical field
The present invention relates to inorganic nanometer functional field of material preparation, and in particular to a kind of hollow core-shell structure for preparing layering
Co3O4Method.
Background technique
With society be constantly progressive, the mankind sharply increase energy demand, Recent study person to low cost, efficiently
Rate, environmental-friendly energy conversion and the research for storage material are extremely paid close attention to.Cobaltosic oxide (Co3O4) it is a kind of important p-type
Semiconductor has the advantages that abundant raw material, to prepare simple, at low cost, environmental-friendly and specific capacitance higher, in scientific circles and industry
Boundary has received widespread attention.The characteristic that the cobaltosic oxide of Nano grade has storage capability big, cheap and high specific capacitance
Deng being widely used in electrode material, lithium ion battery, photochemical catalyst, fuel cell, the gas sensing of supercapacitor
Device etc..However, Co3O4Nano-electrode material usually easily occurs during lithiumation/de- lithium circulation circulating battery significant
Volume expansion, leads to the dusting of electrode material and the sharp-decay of chemical property, seriously limits its commercial applications.It is right
Co3O4Electrode material carries out the microstructure design of nanoscale, such as: hollow core-shell structure can effectively buffer volumes
Deformation discharges mechanical stress suffered in removal lithium embedded process.Layering porous structure can make nano-electrode material and electrolyte
Contact is more abundant, causes lithium ion that can enter electrode material internal transmission faster.Therefore, rationally designing has pattern can
Control, Co of uniform size and multi-level hollow core-shell structure3O4Nano material is extremely important.
Co3O4Preparation method mainly have hydrothermal synthesis method, electrochemical deposition method, high temperature thermal decomposition method, sluggish precipitation,
Sol-gel method etc..Nanoscale Co is prepared at present3O4It is primarily present bad dispersibility, morphology controllable is poor, and process flow is long, cost
The problem of being also easy to produce in high and generating process containing waste water such as cobalt ions, sulfate radical, ammonia nitrogens.Document [ACS Applied
Material Interfaces, 2014,6:7117-7125] Co of specific surface area very little is prepared for using high temperature hydro-thermal method3O4It receives
Rice grain, serious agglomeration occurs during removal lithium embedded causes capacity sharply to decline.Document [ACS Nano, 2015,9:
1775-1781] use high temperature thermal decomposition method to obtain the Co of hollow structure3O4Nano particle utilizes hollow structure in the circulating cycle
Peculiar advantage alleviates the too fast problem of capacity attenuation well.The Co of above method preparation3O4Although nano material is to a certain degree
On solve the problems, such as electrode material volume expansion during removal lithium embedded.But all there are complex steps in the above method, synthesis
The features such as low efficiency, morphology controllable is poor.Doing template using metal-organic framework in recent years is a kind of prepare with specific
The important channel of the nano material of pattern passes through the metal organic framework (MOF) of inorganic salts and organic ligand being self-assembly of
With various structures and form, such as octahedra, spherical and dodecahedron particle etc..But synthesis has by this method
The Co of layered hollow core-shell structure3O4But it is rarely reported.
Summary of the invention
The purpose of the present invention is to provide a kind of Co of the hollow core-shell structure of layering3O4Preparation method.
A kind of Co of the hollow core-shell structure of layering provided by the invention3O4Preparation method, comprising the following steps:
(1) by CTAB and Co (NO3)2·6H2O is dissolved in water, and acquired solution is added rapidly to 2-methylimidazole solution
In, 20~60min is reacted at 30~50 DEG C；
(2) after reaction to step (1), solid matter is isolated, 1~3h is calcined at 350~500 DEG C, is obtained
The Co of the hollow core-shell structure of layering3O4。
Further, in step (1), Co (NO3)2·6H2The molar ratio of O and 2-methylimidazole is 1:20~1:35.
Further, in step (1), 2-methylimidazole solution is the aqueous solution of 2-methylimidazole.
Further, in step (2), by being centrifugated out solid matter.
Further, in step (2), calcining carries out in air atmosphere tube-type atmosphere furnace.
Above-mentioned preparation method does not need to add any template, is solvent using CTAB as stabilizer, water, Co (NO3)2·
6H2O is raw material, 2-methylimidazole is organic ligand, under mild reaction conditions, is synthesized first of uniform size and not easy to reunite
Cube structure ZIF-67 presoma, then the hollow core-shell structure with layering is prepared by simple one-step calcination
Co3O4.Not only method and step is simple for this method, and reaction condition is mild, environment-friendly high-efficiency, and can pattern to target product, size,
The accurate control of geometrical homogenization etc..The Co for the porous hollow core-shell structure of layering that this method obtains3O4Average grain diameter 500nm,
Specific surface area is about 130m2g-1, purity is high, good dispersion and even size distribution.
Cobaltosic oxide is a kind of typical transition metal oxide, and theoretical capacity is much better than graphite, in supercapacitor
With good application prospect with lithium ion battery etc..The porous hollow core-shell structure of the layering that above-mentioned preparation method obtains
Co3O4Have many advantages, such as that specific surface area is high, therefore also have more excellent Potential performance, heterogeneous catalysis, energy storage,
The fields such as gas sensor, supercapacitor and lithium ion battery have great potential using value.
Detailed description of the invention
Fig. 1 is the Co of the hollow core-shell structure of layering3O4XRD diagram.
Fig. 2 is the Co of the hollow core-shell structure of layering3O4SEM and TEM figure.
Specific embodiment
The present invention will be further described in the following with reference to the drawings and specific embodiments.
The Co of the hollow core-shell structure of layering is prepared according to the following steps3O4:
(1) by 20mg CTAB and 2mmol Co (NO3)2·6H2O is dissolved in 20mL deionized water, stir at room temperature to
It is completely dissolved, acquired solution is added rapidly to 140mL dissolved in the aqueous solution of 4.5g 2-methylimidazole, is reacted at 40 DEG C
30min；
(2) to after reaction, using precipitating is centrifugally separating to obtain, be washed 3 times with dehydrated alcohol, be dried in vacuo at 80 DEG C
Dry 12h, has obtained the presoma ZIF-67 of cube in case；Finally product is placed in the tube-type atmosphere furnace of air atmosphere, 450
DEG C calcining 2h, the Co for the hollow core-shell structure being layered3O4。
Wherein, cobalt nitrate hexahydrate (Co (NO3)2·6H2O is analyzed pure), 2-methylimidazole (C4H6N2> 98%), used
Solvent is deionized water.
Product is analyzed, XRD diffraction pattern with D/Max 2500V/PC X-ray diffractometer measure (CuK α radiate, λ=40kV,200mA)；Transmission electron microscope picture is obtained on Technai-S-twin transmission electron microscope
, acceleration voltage 200kV.
Fig. 1 is the Co of the hollow core-shell structure of layering3O4XRD diagram, it can be seen that peak and Co that sample is all3O4's
Standard card (JCPDS NO.42-1467) fits like a glove, and is fully converted to Co after illustrating presoma ZIF67 calcining3O4, determine most
Final product is the Co of high-purity3O4, other miscellaneous phases are not present.
Fig. 2 is the Co of multi-layer hollow core-shell structure3O4SEM and TEM figure.As can be seen that Co from Fig. 2 a3O4It is uniform
Cube, size is about 500nm.Fig. 2 b-2d is Co3O4Transmission electron microscope picture, can be observed from Fig. 2 b the compound be point
The porous hollow core-shell structure of layer.Fig. 2 c shows that the interplanar distance of 0.24nm is high-visible, with cubic spinel type Co3O4's
(311) crystal face is corresponding.The product known to electronic diffraction ring in Fig. 2 d is polycrystalline.
Claims (8)
1. a kind of Co of the hollow core-shell structure of layering3O4Preparation method, comprising the following steps:
(1) by CTAB and Co (NO3)2·6H2O is dissolved in water, and acquired solution is added rapidly in 2-methylimidazole solution,
20~60min is reacted at 30~50 DEG C；
(2) after reaction to step (1), solid matter is isolated, 1~3h is calcined at 350~500 DEG C, is layered
Hollow core-shell structure Co3O4。
2. according to the method described in claim 1, it is characterized by: in step (1), Co (NO3)2·6H2O and 2- methyl miaow
The molar ratio of azoles is 1:20~1:35.
3. according to the method described in claim 1, it is characterized by: 2-methylimidazole solution is 2- methyl miaow in step (1)
The aqueous solution of azoles.
4. according to the method described in claim 1, it is characterized by: in step (2), by being centrifugated out solid matter.
5. according to the method described in claim 1, it is characterized by: being calcined in air atmosphere tube-type atmosphere furnace in step (2)
It carries out.
6. the Co of the hollow core-shell structure for the layering that method described in any claim obtains according to claim 1~53O4。
7. the Co of the hollow core-shell structure of layering according to claim 63O4Application.
8. application according to claim 7, it is characterised in that: the Co of the hollow core-shell structure of the layering3O4For more
Mutually catalysis, energy storage, gas sensor, supercapacitor or field of lithium ion battery.
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Cited By (4)
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| CN110813202A (en) * | 2019-11-26 | 2020-02-21 | 东莞理工学院 | Co3O4Preparation method and application of @ ZIF-67 core-shell structure material |
| CN111162264A (en) * | 2020-01-17 | 2020-05-15 | 上海应用技术大学 | Graphene-based carbon-coated ZIF-67-derived cobalt oxide composite material and preparation method and application thereof |
| CN112635755A (en) * | 2020-12-22 | 2021-04-09 | 江西理工大学 | In-situ growth surface coordination polymerization reaction for preparing hollow Co3O4Method of nanosphere |
| CN114146710A (en) * | 2021-12-02 | 2022-03-08 | 中国科学院上海高等研究院 | Reverse water gas reaction catalyst and preparation method and application thereof |
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|---|---|---|---|---|
| CN110813202A (en) * | 2019-11-26 | 2020-02-21 | 东莞理工学院 | Co3O4Preparation method and application of @ ZIF-67 core-shell structure material |
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| CN111162264A (en) * | 2020-01-17 | 2020-05-15 | 上海应用技术大学 | Graphene-based carbon-coated ZIF-67-derived cobalt oxide composite material and preparation method and application thereof |
| CN112635755A (en) * | 2020-12-22 | 2021-04-09 | 江西理工大学 | In-situ growth surface coordination polymerization reaction for preparing hollow Co3O4Method of nanosphere |
| CN112635755B (en) * | 2020-12-22 | 2021-12-07 | 江西理工大学 | In-situ growth surface coordination polymerization reaction for preparing hollow Co3O4Method of nanosphere |
| CN114146710A (en) * | 2021-12-02 | 2022-03-08 | 中国科学院上海高等研究院 | Reverse water gas reaction catalyst and preparation method and application thereof |
| CN114146710B (en) * | 2021-12-02 | 2023-10-27 | 中国科学院上海高等研究院 | Reverse water gas reaction catalyst and preparation method and application thereof |
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