CN106829918A - A kind of preparation method of the controllable micropore carbon nano rod of size - Google Patents
A kind of preparation method of the controllable micropore carbon nano rod of size Download PDFInfo
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- CN106829918A CN106829918A CN201510882516.8A CN201510882516A CN106829918A CN 106829918 A CN106829918 A CN 106829918A CN 201510882516 A CN201510882516 A CN 201510882516A CN 106829918 A CN106829918 A CN 106829918A
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Abstract
The present invention relates to a kind of preparation method of the controllable micropore carbon nano rod of size, using low concentration ultrasonic method, by adjusting reaction system reclaimed water volume content (12.5% 50%) various sizes of bar-shaped metal-organic framework materials of Fast back-projection algorithm；So that metal-organic framework materials are as template and double as carbon source, high temperature cabonization obtains metal oxide/carbon composite；The micropore carbon nano rod with high specific surface area and developed pore structure is obtained using acid solution dissolving removal metal oxide.Water content is lower in reaction system, and the size of micropore carbon nano rod is smaller and Size Distribution is narrower.Microporous carbon nanometer rods pattern of the present invention is homogeneous, and size adjustable, preparation process is simple, yield is high and with low cost, is adapted to batch production.
Description
Technical field
The invention belongs to inorganic nonmetallic nanometer material preparation method technical field, specifically a kind of size is controllable
Micropore carbon nano rod preparation method.
Background technology
Micro-pore carbon material is because with mechanical stability and heat endurance higher, good electric conductivity, higher
The features such as specific surface area, separated in energy storage, fuel cell, ultracapacitor, catalysis and gas, doctor
The fields such as medicine show the application value of brilliance, the focus as Recent study.
Metal organic framework (MOF) material is organic with binary, ternary or quaternary by metallic ion coordination center
Self assembly is formed oxygen-containing Carboxylic acid ligand in a solvent, has been turned into preparing micro-pore carbon material for template using MOF
The focus of recent research.Using MOF as template, by introducing carbon source, such as furfuryl alcohol (Journal of the
American Chemical Society, 2008,130,5390-5391), phenolic resin (Carbon, 2010,
48,3599-3606) and glycerine (Journal of Applied Electrochemistry, 2011,
41,71-75) etc. micro-pore carbon material is can obtain after high temperature cabonization.Additionally, using direct high temperature cabonization MOF templates
Material can also prepare high-specific surface area micro-pore carbon material (Chemical Communications, 2012,
48,7259-7261；Chemical Communications,2013,49,2192-2194；Chemistry
of Materials,2012,24,464-470).Up to the present, carbon is prepared using MOF mould materials
Though the research work comparing of material is more, also have the following disadvantages：First, use solvent heat MOF mould materials more
Method takes (Nanoscale, 2014,6,4387-4394) more long with synthetic method, synthesis is directly heated；2nd,
MOF mould material sizes are larger and pattern it is uneven (Bulletin of the Korean Chemical Society,
2009,30,2921-2926)；3rd, the size of micro-pore carbon material cannot be carried out effectively in range of small
Regulation and control.
Present invention aim at providing, a kind of synthesis step is simple and quick, and the MOF templates of size adjustable prepare chi
The method of very little controllable micropore carbon nano rod.The invention using low concentration ultrasonic method by adjusting reaction system in
Water volume content Fast back-projection algorithm various sizes of bar-shaped MOF, high temperature cabonization MOF and acid solution dissolving removal metal oxygen
The method of compound, realizes the quick controlledly synthesis of small size micropore carbon nano rod.
The content of the invention
It is an object of the invention to provide a kind of preparation method of the controllable micropore carbon nano rod of size, using low
Concentration ultrasonic method by adjusting the reaction system various sizes of bar-shaped MOF of reclaimed water volume content Fast back-projection algorithm, without
Additionally introduce carbon source and can be prepared by the controllable micropore carbon nano rod of the size with high specific surface area, be micropore
The quick controlledly synthesis of carbon material provides new method.
The technical scheme is that：
(1) preparation of metal-organic framework materials:By slaine and organic carboxyl acid part be dissolved in respectively water and
Wiring solution-forming in organic solvent, organic carboxyl acid ligand solution is mixed with metal salt solution, ultrasonic reaction, from
The heart, washing, are dried to obtain metal-organic framework materials；
(2) preparation of micropore carbon nano rod：By above-mentioned steps gained metal-organic framework materials high temperature cabonization,
Metal oxide/carbon composite is obtained；Metal oxide in acid solution dissolving removal composite obtains micropore
Carbon nano rod.
The preparation method of the micropore carbon nano rod that the present invention is provided, the slaine described in step (1) is
In zinc acetate, cobalt acetate, chromic acetate, acetic acid zirconium, nickel acetate, ferric acetate, aluminum acetate, manganese acetate one
Plant or or more than two kinds.
The preparation method of the micropore carbon nano rod that the present invention is provided, the organic carboxyl acid described in step (1)
Part is terephthalic acid (TPA), phthalic acid, M-phthalic acid, 2- amino terephthalic acid (TPA), 2- hydroxyls pair
One kind in phthalic acid, trimesic acid, trimellitic acid, benzene-1, PMA or two kinds
More than.
The preparation method of the micropore carbon nano rod that the present invention is provided, the volume of the water described in step (1)
Content is 12.5%-50%；Organic solvent is methyl alcohol, ethanol, propyl alcohol, N, N'- dimethylformamides, N, N'-
One or two or more kinds in DEF or N, N'- dimethylacetylamide.
The preparation method of the micropore carbon nano rod that the present invention is provided, slaine described in step (1) with
The mol ratio of Carboxylic acid ligand is 1-2：1；Slaine molar concentration is 0.00625-0.0125mol/L.
The preparation method of the micropore carbon nano rod that the present invention is provided, the ultrasonic reaction described in step (1)
Temperature is 20-35 DEG C；Reaction time is 5-90min；Supersonic frequency is 53KHz, and power is 500W.
The preparation method of the micropore carbon nano rod that the present invention is provided, the carbonization described in step (2) is guarantor
High-temperature calcination under shield atmosphere, wherein protective atmosphere are in nitrogen, helium, neon, argon gas, Krypton or xenon
One or two or more kinds；Calcining heat is 600-1200 DEG C；Calcination time is 3-12h.
The preparation method of the micropore carbon nano rod that the present invention is provided, the acid solution described in step (2) is salt
One or two or more kinds in acid, nitric acid, sulfuric acid or hydrofluoric acid.
The preparation method of the micropore carbon nano rod that the present invention is provided, the acid solution dissolving described in step (1)
Metal oxide required time is 6-24h in removal carbonized product.
The present invention has following excellent beneficial effect compared with prior art：
(1) micropore carbon nano rod mould material MOF synthesis steps are simple and quick, and size is small and adjustable；
(2) micropore carbon nano rod has pattern homogeneous, size adjustable, high-specific surface area, the characteristic of pore volume high；
(3) micropore carbon nano rod preparation process is simple, yield is high, with low cost, is adapted to batch production.
Brief description of the drawings
Fig. 1 is the transmission electron microscope picture of MOF templates in embodiment 1, its diameter about 30nm, length about 500nm.
Fig. 2 is the transmission electron microscope picture of MOF templates in embodiment 2, its diameter about 75nm, about 2 μm of length；Can be with
Find out the volume content of regulation reaction system reclaimed water, various sizes of MOF templates can be obtained, and then obtain
Various sizes of carbon nano rod.Compared with the MOF templates reported, the present invention is due to the feed concentrations for using
The regulation of relatively low and reaction system reclaimed water volume content is appropriate, results in the small size MOF of different size, enters
And carbonization forms the controllable micropore carbon nano rod of size uniform.Reaction system reclaimed water volume content in comparative example 1
Regulation is improper to be led to not to form micropore carbon nano rod.
Fig. 3 is the transmission electron microscope picture of micropore carbon nano rod in embodiment 3, it can be seen that gained carbon nano rod can
With the appearance and size of well maintained MOF templates, and form the pore structure of prosperity.
Fig. 4 is the X-ray diffractogram of micropore carbon nano rod in embodiment 3, it can be seen that gained carbon nano rod
There is obvious characteristic diffraction peak at 25 ° and 44 °.
Specific embodiment
The present invention is used as template and carbon source, high temperature cabonization and acid solution dissolving by using metal-organic framework materials
Micro-pore carbon material is obtained after removal metal oxide.The following examples will give further the present invention
It is bright but not thereby limiting the invention.
Embodiment 1
The ethanol solution of trimesic acid is mixed with the aqueous solution of Zinc diacetate dihydrate, supersonic frequency 53KHz,
Under conditions of power 500W, 25 DEG C of ultrasonic reaction 30min.Wherein the molar concentration of trimesic acid is 0.0125
Mol/L, trimesic acid is 1 with the molar ratio of Zinc diacetate dihydrate：1, the volume content of water is 12.5%.
Centrifugation, washing, dry prepared zinc metal-organic framework materials；The lower 800 DEG C of calcining 5h of blanket of nitrogen are simultaneously used
10% hydrofluoric acid dips 12h removes metal oxide, obtains micropore carbon nano rod.
Embodiment 2
The ethanol solution of trimesic acid is mixed with the aqueous solution of Zinc diacetate dihydrate, supersonic frequency 53KHz,
Under conditions of power 500W, 25 DEG C of ultrasonic reaction 30min.Wherein the molar concentration of trimesic acid is 0.0125
Mol/L, trimesic acid is 1 with the molar ratio of Zinc diacetate dihydrate：1, the volume content of water is 25%.
Centrifugation, washing, dry prepared zinc metal-organic framework materials；The lower 800 DEG C of calcining 5h of blanket of nitrogen are simultaneously used
10% hydrofluoric acid dips 12h removes metal oxide, obtains micropore carbon nano rod.
Embodiment 3
The ethanol solution of trimesic acid is mixed with the aqueous solution of Zinc diacetate dihydrate, supersonic frequency 53KHz,
Under conditions of power 500W, 25 DEG C of ultrasonic reaction 30min.Wherein the molar concentration of trimesic acid is 0.0125
Mol/L, trimesic acid is 1 with the molar ratio of Zinc diacetate dihydrate：1, the volume content of water is 50%.
Centrifugation, washing, dry prepared zinc metal-organic framework materials；The lower 800 DEG C of calcining 5h of blanket of nitrogen are simultaneously used
10% hydrofluoric acid dips 12h removes metal oxide, obtains micropore carbon nano rod.
Embodiment 4-8 difference from Example 1 see the table below：
Comparative example 1
The ethanol solution of trimesic acid is mixed with the aqueous solution of Zinc diacetate dihydrate, supersonic frequency 53KHz, work(
Under conditions of rate 500W, 25 DEG C of ultrasonic reaction 30min.Wherein the molar concentration of trimesic acid is 0.0125
Mol/L, trimesic acid is 1 with the molar ratio of Zinc diacetate dihydrate：1, the volume content of water is 6.25%.
Centrifugation, washing, dry prepared zinc metal-organic framework materials；The lower 800 DEG C of calcining 5h of blanket of nitrogen are simultaneously used
10% hydrofluoric acid dips 12h removes metal oxide, obtains micropore carbon nanomaterial.Result shows this
Uniform rod-like nano material cannot be obtained under part.
Claims (10)
1. the preparation method of the controllable micropore carbon nano rod of a kind of size, it is characterised in that：Using ultrasonic method
Synthesize bar-shaped metal-organic framework materials by adjusting reaction system reclaimed water volume content (12.5%-50%),
So that metal-organic framework materials are as template and double as carbon source, microporous carbon is obtained after high temperature cabonization and acid soak
Nanometer rods；A diameter of 10nm-200nm of porous carbon nano rod, length is 300nm -10 μm,
Aperture is 0.1-2nm.
2. according to the preparation method of micropore carbon nano rod described in claim 1, it is characterised in that：The method
Comprise the following steps that：
(1) preparation of metal-organic framework materials:Slaine and organic carboxyl acid part are dissolved in water respectively
With wiring solution-forming in organic solvent, organic carboxyl acid ligand solution is mixed with metal salt solution, ultrasonic reaction,
Centrifugation, washing, are dried to obtain metal-organic framework materials；
(2) preparation of micropore carbon nano rod：By above-mentioned steps gained metal-organic framework materials high temperature cabonization,
Metal oxide/carbon composite is obtained；Metal oxide in acid solution dissolving removal composite obtains micropore
Carbon nano rod.
3. according to the preparation method of micropore carbon nano rod described in claim 2, it is characterised in that：Step (1)
Described in slaine be zinc acetate, chromic acetate, acetic acid zirconium, nickel acetate, cobalt acetate, ferric acetate, acetic acid
One kind in aluminium, manganese acetate or or more than two kinds.
4. according to the preparation method of micropore carbon nano rod described in claim 2, it is characterised in that：Step (1)
Described in organic carboxyl acid part for terephthalic acid (TPA), phthalic acid, M-phthalic acid, 2- amino to benzene
Dioctyl phthalate, 2- hydroxyterephthalic acids, trimesic acid, trimellitic acid, benzene-1, equal benzene four
One or two or more kinds in acid.
5. according to the preparation method of micropore carbon nano rod described in claim 2, it is characterised in that：Step (1)
The volume content of water described in solution is 12.5%-50%；Organic solvent is methyl alcohol, ethanol, propyl alcohol, N, N'-
One kind in dimethylformamide, N, N'- DEFs or N, N'- dimethylacetylamide or two kinds
More than.
6., according to the preparation method of micropore carbon nano rod described in claim 2,3,4 or 5, its feature exists
In：Slaine and the mol ratio of Carboxylic acid ligand described in step (1) are 1-2：1；Slaine molar concentration
It is 0.00625-0.0125mol/L.
7. according to the preparation method of micropore carbon nano rod described in claim 1 or 2, it is characterised in that：It is super
Phonoresponse temperature is 20-35 DEG C；Reaction time is 5-90min；Supersonic frequency is 53KHz, and power is
500W。
8. according to the preparation method of micropore carbon nano rod described in claim 1 or 2, it is characterised in that：Institute
The carbonization stated be protective atmosphere under high-temperature calcination, wherein protective atmosphere be nitrogen, helium, neon, argon gas,
One or two or more kinds in Krypton or xenon；Calcining heat is 600-1200 DEG C；Calcination time is 3-12h.
9. according to the preparation method of micropore carbon nano rod described in claim 1 or 2, it is characterised in that：Institute
The acid solution stated is one or two or more kinds in hydrochloric acid, nitric acid, sulfuric acid or hydrofluoric acid.
10. according to the preparation method of micropore carbon nano rod described in claim 1 or 2, it is characterised in that：
Metal oxide required time is 6-24h in acid solution dissolving removal carbonized product.
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Cited By (7)
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| CN108154984A (en) * | 2017-12-26 | 2018-06-12 | 山东大学 | A kind of porous ferroferric oxide/carbon nano rod shape electromagnetic wave absorbent material and preparation method and application |
| CN108461306A (en) * | 2018-03-28 | 2018-08-28 | 浙江大学 | A kind of multi-layer N doped carbon nanometer rod composite materials and preparation method thereof |
| CN109485102A (en) * | 2018-12-19 | 2019-03-19 | 大连理工大学 | A kind of preparation method of special construction metallic compound/carbon composite |
| CN109637833A (en) * | 2018-10-31 | 2019-04-16 | 中山大学 | A kind of poly-metal deoxide/graphitic carbon nano stick array and its preparation method and application |
| CN110787790A (en) * | 2019-11-13 | 2020-02-14 | 武汉纺织大学 | Sea urchin-shaped metal oxide porous photocatalytic material and preparation method and application thereof |
| CN110801837A (en) * | 2019-11-13 | 2020-02-18 | 武汉纺织大学 | Silver/zinc oxide/carbon hollow composite photocatalyst and preparation method and application thereof |
| CN111498830A (en) * | 2020-03-30 | 2020-08-07 | 南京航空航天大学 | Undoped one-dimensional porous carbon material and preparation method thereof |
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| CN104211040A (en) * | 2013-11-14 | 2014-12-17 | 中国石油大学(北京) | Preparation method of porous carbon nano rod with high specific area |
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Cited By (11)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN108154984A (en) * | 2017-12-26 | 2018-06-12 | 山东大学 | A kind of porous ferroferric oxide/carbon nano rod shape electromagnetic wave absorbent material and preparation method and application |
| CN108461306A (en) * | 2018-03-28 | 2018-08-28 | 浙江大学 | A kind of multi-layer N doped carbon nanometer rod composite materials and preparation method thereof |
| CN108461306B (en) * | 2018-03-28 | 2019-07-12 | 浙江大学 | A kind of multi-layer N doped carbon nanometer rod composite material and preparation method thereof |
| CN109637833A (en) * | 2018-10-31 | 2019-04-16 | 中山大学 | A kind of poly-metal deoxide/graphitic carbon nano stick array and its preparation method and application |
| CN109485102A (en) * | 2018-12-19 | 2019-03-19 | 大连理工大学 | A kind of preparation method of special construction metallic compound/carbon composite |
| CN110787790A (en) * | 2019-11-13 | 2020-02-14 | 武汉纺织大学 | Sea urchin-shaped metal oxide porous photocatalytic material and preparation method and application thereof |
| CN110801837A (en) * | 2019-11-13 | 2020-02-18 | 武汉纺织大学 | Silver/zinc oxide/carbon hollow composite photocatalyst and preparation method and application thereof |
| CN110787790B (en) * | 2019-11-13 | 2022-04-29 | 武汉纺织大学 | Sea urchin-shaped metal oxide porous photocatalytic material and preparation method and application thereof |
| CN110801837B (en) * | 2019-11-13 | 2022-07-05 | 武汉纺织大学 | Silver/zinc oxide/carbon hollow composite photocatalyst and preparation method and application thereof |
| CN111498830A (en) * | 2020-03-30 | 2020-08-07 | 南京航空航天大学 | Undoped one-dimensional porous carbon material and preparation method thereof |
| CN111498830B (en) * | 2020-03-30 | 2023-09-15 | 南京航空航天大学 | Undoped one-dimensional porous carbon material and preparation method thereof |
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Application publication date: 20170613 |