CN110357068A - A kind of synthetic method of classifying porous carbon nanomaterial - Google Patents
A kind of synthetic method of classifying porous carbon nanomaterial Download PDFInfo
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Abstract
The present invention provides a kind of synthetic methods of classifying porous carbon nanomaterial, the following steps are included: A) small organic molecule containing more chelation groups or adjacent hydroxyl group and inorganic zinc salt are mixed in alkaline aqueous solution and reacted, obtain the presoma being precipitated with precipitation form；B the presoma) is subjected to high temperature pyrolysis, obtains classifying porous carbon nanomaterial.Small organic molecule and zinc of the present invention by zinc and containing more chelation groups or adjacent hydroxyl group are stirred at room temperature in alkaline aqueous solution and to form coordination polymer or complex as presoma, the zinc particle that nano-dispersion occurs to reunite and formed for the zinc being then chelated in presoma during high temperature pyrolysis realizes template pore-creating effect, zinc nanoparticles can be realized by further high-temperature process and be evaporated simultaneously, and then need not carry out subsequent etching and classifying porous carbon nanomaterial can be obtained.Synthetic method provided by the invention is simple, low cost, controllability is strong, universality is high and mild condition.
Description
Technical field
The invention belongs to technical field of nano material, and in particular to a kind of synthetic method of classifying porous carbon nanomaterial.
Background technique
Conventional porous carbon material is that biological material (such as pitch, coconut husk, lignocellulosic, cornstalk) is presoma,
In conjunction with physics or chemical activation means, obtained through high temperature pyrolysis.Simple by this, low cost synthetic method, industrially
A series of biomass derived porous carbon materials are developed, and are widely used in separation, water process, the air cleaning of gas or liquid
Equal fields.But biological material is by the place of production, growing environment and self-characteristic influence, structure and complicated composition and impurity content
It is higher, thus it is caused to derive the microstructure of carbon material and property with poor controllability.In addition, physically or chemically being lived
Change the pore size obtained to be generally focused in range of micropores.And with deepening continuously to porous carbon materials application study, in carbon
Grade cellular structure is constructed in material is widely regarded as preparation towards energy storage and conversion, heterogeneous catalysis, gas absorption etc.
One of the important means of multiple emerging nanotechnology application field high performance carbon materials.Compared to the carbon that tradition has single pore size
For material, the mass transfer of classifying porous carbon material is more efficient, and can provide and guest species (molecule, atom, ion)
Bigger contact area, and then can be used for preparing high performance lithium cell cathode material, oxygen reduction catalyst, hydrogen adsorption materials
Deng.Therefore, have the carbon-rich material for determining structure and composition as presoma from molecular level building, and develop other and receive
Rice boring technique is to realize one of the important means of classifying porous carbon material controlledly synthesis, and further explore high performance carbon
The basis of sill.
The classifying porous carbon material controllable synthesis method established at present can be divided into three classes.
The first kind is the side that is combined by template or template-activation using chemically synthesized macromolecule as presoma
Method realizes the preparation of graded porous carbon.This method can pass through the structure and dosage and replacement macromolecule kind of change template
Class come to carbon product nanostructure and element composition regulate and control.
Second class method is to use ionic liquid as presoma, carries out pore-creating using template or molten-salt growth method, and then obtain
Classifying porous carbon material.
It is pyrogenic metal organic framework materials (MOFs) that third class, which constructs the thinking that classifying porous carbon material is controllably combined to,
The metal node meeting in-situ preparation nano-form of linking ligand small molecule in carbonisation, and then realize pore-creating effect, simultaneously
The component of the derivative carbon material of MOFs can simply by replacing structure metal ion or bridged ligands realize, and then realize and exist
Different miscellaneous element and load different type metal are adulterated in carbon frame.
Although above-mentioned established method provides the approach of multiplicity for the controlledly synthesis of classifying porous carbon material, this
It is challenged of both still suffering from one field.First item challenge is that cheap small molecule how is widely used to go to prepare
Classifying porous carbon material, and then more huge material system is established to support nanostructure and composition and performance structure-activity relationship
Parsing, and finally point the direction for design high performance carbon sill.This research field of the controlledly synthesis of classifying porous carbon material
The Section 2 challenge faced is the sustainable synthetic technology of development green, the magnanimity for realizing the material system, inexpensively preparation.Divide at present
The synthetic method of grade porous carbon materials usually requires complicated using a large amount of organic solvents, cost of material, preparation process, is unfavorable for point
The extensive use and exploration of grade porous carbon materials.
Summary of the invention
In view of this, the technical problem to be solved in the present invention is that providing a kind of synthesis side of classifying porous carbon nanomaterial
Method, synthetic method provided by the invention is simple, low cost, controllability is strong, universality is high and mild condition.
The present invention provides a kind of synthetic methods of classifying porous carbon nanomaterial, comprising the following steps:
A) small organic molecule containing more chelation groups or adjacent hydroxyl group and inorganic zinc salt are mixed in alkaline aqueous solution
Conjunction is reacted, and the presoma being precipitated with precipitation form is obtained；
B the presoma) is subjected to high temperature pyrolysis, obtains classifying porous carbon nanomaterial.
Preferably, step A) in, mixed raw material further includes the aliphatic chain molecule of chelation group-containing in alkaline aqueous solution.
Preferably, the aliphatic chain molecule of the chelation group-containing is selected from succinic acid, adipic acid, suberic acid, decanedioic acid or complete
Fluorine decanedioic acid, additive amount be the small organic molecule mole of more chelation groups or adjacent hydroxyl group a quarter to two/
One.
Preferably, the alkaline aqueous solution is prepared to obtain by triethylamine, ammonium hydroxide, potassium hydroxide or sodium hydroxide.
Preferably, the pH value of the alkaline aqueous solution is 7~14.
Preferably, the small organic molecule containing more chelation groups is selected from imidazoles -2- formic acid, 1H- benzimidazole -5- carboxylic
Acid, 5- carboxyl benzotriazole, 4,4 '-(the fluoro- 1- trifluoromethyl of 2,2,2- tri-) ethylenebis (1,2- phthalic acid), terephthaldehyde
Acid, 4,4- biphenyl dicarboxylic acid, D-His, 1,5- naphthalenedisulfonic acid, 4,4 '-biphenyl disulfonic acid, 8-hydroxyquinoline-5-sulfonic acid hydration
Object, 2,2 '-bipyridyls -4,4 '-dicarboxylic acids, 4- Carboxybenzeneboronic acid, tea polyphenols, caffeic acid, tetrahydroxy quinone, 5,5', 6,6'- tetra-
Hydroxyl -3,3,3', 3'- tetramethyl -1,1'- spiral biindolyl, benzimidazole, benzotriazole, 2-Phenylbenzimidazole -5- sulphur
Acid, two hydrate of 5-sulphosalicylic acid；
Preferably, the molecule containing adjacent hydroxyl group is selected from catechol, 3,4- dihydroxytoluene, Dopamine hydrochloride, 2,3-
Dihydroxy naphthlene, pyrogallol, cachou extract, baicalein, propylgallate, diosmetin, 3,4- dihydroxy cyanophenyl, 2,3- dihydroxy
One of yl pyridines.
Preferably, the inorganic zinc salt is selected from two water zinc acetates, zinc nitrate hexahydrate, anhydrous zinc chloride or basic carbonate
Zinc.
Preferably, the small organic molecule containing more chelation groups or adjacent hydroxyl group and the molar ratio of inorganic zinc salt are
2:1~1:6；
Alkaline matter in the small organic molecule and alkaline aqueous solution containing more chelation groups or adjacent hydroxyl group
Molar ratio is 2:1~1:8.
Preferably, the high temperature pyrolysis are as follows: under the protective atmosphere of nitrogen or argon hydrogen, by the Means of Pyrolyzed Precursor with 2~
10 DEG C/min rises to 800~1000 DEG C, keeps 2~5h；400~600 DEG C are down to 2~10 DEG C/min again, natural cooling obtains
Classifying porous carbon nanomaterial.
Compared with prior art, the present invention provides a kind of synthetic method of classifying porous carbon nanomaterial, including it is following
Step: A) small organic molecule containing more chelation groups or adjacent hydroxyl group and inorganic zinc salt are mixed into alkaline aqueous solution
Row reaction, obtains the presoma being precipitated with precipitation form；B the presoma) is subjected to high temperature pyrolysis, graded porous carbon is obtained and receives
Rice material.The present invention passes through zinc and small organic molecule and the zinc room in alkaline aqueous solution containing more chelation groups or adjacent hydroxyl group
Temperature stirring forms coordination polymer or complex as presoma, the zinc being then chelated in presoma during high temperature pyrolysis
The zinc particle for occurring to reunite and formed nano-dispersion realizes template pore-creating effect, while zinc nanoparticles can be by further
High-temperature process realizes evaporation, and then need not carry out subsequent etching and classifying porous carbon nanomaterial can be obtained.It is provided by the invention
Synthetic method is simple, low cost, controllability is strong, universality is high and mild condition.
Detailed description of the invention
Fig. 1 is the stereoscan photograph of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 1；
Fig. 2 is the pore size distribution data of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 1；
Fig. 3 is the stereoscan photograph of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 2；
Fig. 4 is the pore size distribution data of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 2；
Fig. 5 is the stereoscan photograph of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 3；
Fig. 6 is the pore size distribution data of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 3；
Fig. 7 is the stereoscan photograph of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 4；
Fig. 8 is the pore size distribution data of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 4；
Fig. 9 is the stereoscan photograph of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 5；
Figure 10 is the pore size distribution data of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 5；
Figure 11 is the stereoscan photograph of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 6；
Figure 12 is the pore size distribution data of classifying porous carbon nanomaterial prepared by the embodiment of the present invention 6.
Specific embodiment
The present invention provides a kind of synthetic methods of classifying porous carbon nanomaterial, comprising the following steps:
A) small organic molecule containing more chelation groups or adjacent hydroxyl group and inorganic zinc salt are mixed in alkaline aqueous solution
Conjunction is reacted, and the presoma being precipitated with precipitation form is obtained；
B the presoma) is subjected to high temperature pyrolysis, obtains classifying porous carbon nanomaterial.
The present invention is first by the small organic molecule containing more chelation groups or adjacent hydroxyl group and inorganic zinc salt in alkaline water
Mixing is reacted in solution, obtains the presoma being precipitated with precipitation form.
Specifically, the small organic molecule containing more chelation groups or ortho position diphenol is dissolved in alkaline aqueous solution, mixed
Solution；
The small organic molecule containing more chelation groups is selected from imidazoles -2- formic acid, 1H- benzimidazole-5-carboxylic acid, 5- carboxyl
Benzotriazole, 4,4 '-(the fluoro- 1- trifluoromethyl of 2,2,2- tri-) ethylenebis (1,2- phthalic acid), terephthalic acid (TPA), 4,4- connection
Phthalic acid, D-His, 1,5- naphthalenedisulfonic acid, 4,4 '-biphenyl disulfonic acid, 8-hydroxyquinoline-5-sulfonic acid hydrate, 2,2 '-
Bipyridyl -4,4 '-dicarboxylic acids, 4- Carboxybenzeneboronic acid, tea polyphenols, caffeic acid, tetrahydroxy quinone, 5,5', tetrahydroxy -3 6,6'-,
3,3', 3'- tetramethyl -1,1'- spiral biindolyl, benzimidazole, benzotriazole, 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID, 5- sulfo group
Two hydrate of salicylic acid；Preferably terephthalic acid (TPA), 5,5', 6,6'- tetrahydroxy -3,3,3', 3'- tetramethyl -1,1'- spiral
Biindolyl.
The molecule containing adjacent hydroxyl group is selected from catechol, 3,4- dihydroxytoluene, Dopamine hydrochloride, 2,3- dihydroxy
Base naphthalene, pyrogallol, cachou extract, baicalein, propylgallate, diosmetin, 3,4- dihydroxy cyanophenyl, 2,3- dihydroxy pyrrole
One of pyridine, preferably catechol or 3,4- dihydroxy cyanophenyl.
The alkaline aqueous solution is prepared to obtain by triethylamine, ammonium hydroxide, potassium hydroxide or sodium hydroxide.The alkaline aqueous solution
PH value be 7~14.
It is different according to the small organic molecule of use, it is available a series of with different pore size distribution, element doping and shape
The classifying porous carbon nanomaterial of looks.
The small organic molecule does not have good water solubility usually, uses alkaline aqueous solution that can effectively pass through as solvent
At the dissolubility of small organic molecule described in salt effect significant increase in aqueous solution, and then avoid the use of organic solvent；In addition,
The use of alkaline aqueous solution also contributes to the functional groups such as carboxyl, hydroxyl, sulfonic group, imino group, boronate in organic boy
Deprotonation, and then realize molecule and zinc coordination.
Then, inorganic zinc salt mixing is added in Xiang Suoshu mixed solution, is reacted, obtains before being precipitated with precipitation form
Drive body；
Wherein, the inorganic zinc salt is selected from two water zinc acetates, zinc nitrate hexahydrate, anhydrous zinc chloride or basic zinc carbonate.
Inorganic zinc salt is added into mixed solution, being mixed carries out that a large amount of precipitatings are precipitated in reaction process.The temperature of the reaction
For room temperature condition, the time of the reaction is 1~24 hour.In the present invention, the room temperature is defined as 25 ± 5 DEG C.
Inorganic zinc salt can be formed by coordination and the small organic molecule coordination polymer with low-steam pressure or
Complex, and then improve the volatility of small organic molecule, it realizes from small organic molecule and prepares classifying porous carbon nanomaterial.
Then, by the precipitating centrifugation and drying of precipitation, presoma is obtained.Above-mentioned deposit is gone to remove water through high speed centrifugation
Point, after be put into heated oven removal residual moisture, obtain Means of Pyrolyzed Precursor.
The small organic molecule containing more chelation groups or adjacent hydroxyl group and the molar ratio of inorganic zinc salt are 2:1~1:
6, preferably 1:1~1:4；
Alkaline matter in the small organic molecule and alkaline aqueous solution containing more chelation groups or adjacent hydroxyl group
Molar ratio is 2:1~1:8, preferably 1:1~1:6.
Finally, the presoma is carried out high temperature pyrolysis, classifying porous carbon nanomaterial is obtained.
During high temperature pyrolysis, the zinc of nano-dispersion can be formed in situ in the zinc in precursor construction by agglomeration
Particle, and then play the role of pore-creating as template；With the lasting progress of pyrolytic process and after reaching certain temperature, have
Low-boiling zinc nanoparticles are handled since evaporation is from carbon material inside and surface evolution without subsequent etching
Obtain classifying porous carbon nanomaterial.
In order to enable zinc nanoparticles to be sufficiently disengaged from carbon material, the graded porous carbon nanometer material in pyrolysis processing
The pyrolysis step of material are as follows: under the protective atmosphere of nitrogen or argon hydrogen, the mixture is risen to 800 with 2~10 DEG C/min~
1000 DEG C, keep 2~5h；400~600 DEG C are down to 2~10 DEG C/min again, natural cooling obtains graded porous carbon nanometer material
Material.
The natural cooling is to be cooled down at room temperature.
In the present invention, the room temperature is defined as 25 ± 5 DEG C.
In certain specific embodiments of the invention, step A) in, mixed raw material further includes containing in alkaline aqueous solution
The aliphatic chain molecule of the aliphatic chain molecule of chelation group, the chelation group-containing is selected from succinic acid, adipic acid, suberic acid, the last of the ten Heavenly stems two
Acid or perfluor decanedioic acid, additive amount are a quarter of the small organic molecule mole of more chelation groups or adjacent hydroxyl group to two
/ mono-, preferably one third to half.
The additional addition of the aliphatic chain molecule of chelation group-containing may participate in form persursor material；Due to aliphatic chain molecule chain
The thermal stability of section is poor, thus gas can be broken, decompose and discharged in pyrolytic process, and then provides another pore-creating side
Formula.
In certain specific embodiments of the invention, precursor synthesis process use the aqueous solution of different basicity as
Solvent.Use the aqueous solution of different basicity that the coordination structure and presoma of the small organic molecule and zinc can be changed as solvent
Zn content in structure, and then change generated in-situ zinc nanoparticles size and carrying capacity during high temperature pyrolysis, it is final to realize
Aperture control effect；Specifically, the alkaline aqueous solution is prepared to obtain by triethylamine, ammonium hydroxide, potassium hydroxide or sodium hydroxide, lead to
The basicity regulation for changing the molar ratio realization aqueous solution of the alkaline chemical and small organic molecule is crossed, regulates and controls in solution and goes matter
The concentration of small organic molecule and hydroxide ion after sonization, basicity increase, the small organic molecule of deprotonation and hydroxyl from
The concentration of son increases, and participation changes by the ratio of the ligand of center ion of zinc ion, i.e., more hydroxide ions
Ligand participate in coordination, and then influence precursor construction in Zn content, finally make specific surface area with the increase of base amount and
Increase.
Small organic molecule and zinc of the present invention by zinc and containing more chelation groups or adjacent hydroxyl group are in alkaline aqueous solution
It is stirred at room temperature to form coordination polymer or complex as presoma, then be chelated in presoma during high temperature pyrolysis
The zinc particle that nano-dispersion occurs to reunite and formed for zinc realizes template pore-creating effect, while zinc nanoparticles can be by further
High-temperature process realize evaporation, and then subsequent etching need not be carried out, classifying porous carbon nanomaterial can be obtained.The present invention provides
Synthetic method it is simple, low cost, controllability is strong, universality is high and mild condition.
For a further understanding of the present invention, below with reference to embodiment to classifying porous carbon nanomaterial provided by the invention
Synthetic method is illustrated, and protection scope of the present invention is not limited by the following examples.
Embodiment 1
A. 0.8g terephthalic acid (TPA) is distributed in 80ml water, rear addition 2.67ml triethylamine, after agitated half an hour, then
5.73g zinc nitrate hexahydrate is added, continues stirring 24 hours, obtains the presoma being precipitated with precipitation form；
B. the above-mentioned aqueous solution containing presoma is removed into moisture removal by centrifugation, add clear water and repeats to wash by being centrifuged
It washs three times, is finally putting into baking oven and is dried；
C. complete presoma will have been dried to be transferred in silica crucible, be put into tube furnace, then pass to nitrogen conduct
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；500 are cooled to again with the rate of 5 DEG C/min
DEG C, finally it is down to room temperature naturally again；Normal pressure is kept in tube furnace.Obtain classifying porous carbon nanomaterial；
Fig. 1 is point that the embodiment of the present invention 1 is obtained by the chelating presoma of pyrolysis terephthalic acid (TPA) and zinc nitrate hexahydrate
The stereoscan photograph of the porous carbon nanomaterial of grade；
Fig. 2 is point that the embodiment of the present invention 1 is obtained by the chelating presoma of pyrolysis terephthalic acid (TPA) and zinc nitrate hexahydrate
The pore size distribution data of the porous carbon nanomaterial of grade；
Carbon nanomaterial manufactured in the present embodiment is blocky by micron or nano-scale it can be seen from Fig. 1 and Fig. 2
Grain composition, and there is graded porous structure.
Embodiment 2
A. 0.8g terephthalic acid (TPA) and 0.209mg suberic acid are distributed in 80ml water, rear addition 3.34ml triethylamine,
After agitated half an hour, 7.16g zinc nitrate hexahydrate is added, continues stirring 24 hours, is obtained before being precipitated with precipitation form
Drive body；
B. the above-mentioned aqueous solution containing presoma is removed into moisture removal by centrifugation, add clear water and repeats to wash by being centrifuged
It washs three times, is finally putting into baking oven and is dried；
C. complete presoma will have been dried to be transferred in silica crucible, be put into tube furnace, then pass to nitrogen conduct
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；500 are cooled to again with the rate of 5 DEG C/min
DEG C, finally it is down to room temperature naturally again；Normal pressure is kept in tube furnace.Obtain classifying porous carbon nanomaterial；
Fig. 3 is that the embodiment of the present invention 2 is obtained by the chelating presoma of pyrolysis terephthalic acid (TPA), suberic acid and zinc nitrate hexahydrate
The stereoscan photograph of the classifying porous carbon nanomaterial arrived；
Fig. 4 is that the embodiment of the present invention 2 is obtained by the chelating presoma of pyrolysis terephthalic acid (TPA), suberic acid and zinc nitrate hexahydrate
The pore size distribution data of the classifying porous carbon nanomaterial arrived；
By Fig. 1,2 and Fig. 3,4 comparison, which can be seen that the present embodiment and have, differs markedly from 1 carbon nanomaterial of embodiment
Pattern and pore-size distribution.The carbon nanomaterial that the aliphatic chain molecule being additionally added promotes embodiment 2 to synthesize presents more loose
Carbon nano-particle structure, pore-size distribution also towards size increase direction change.
Embodiment 3
A. by 0.8g 5,5', 6,6'- tetrahydroxy -3,3,3', 3'- tetramethyl -1,1'- spiral biindolyl is distributed to 50ml
In water, 751.8mg potassium hydroxide is added afterwards, after agitated half an hour, adds 2.79g zinc nitrate hexahydrate, continues stirring 24
Hour, obtain the presoma being precipitated with precipitation form；
B. the above-mentioned aqueous solution containing presoma is removed into moisture removal by centrifugation, add clear water and repeats to wash by being centrifuged
It washs three times, is finally putting into baking oven and is dried；
C. complete presoma will have been dried to be transferred in silica crucible, be put into tube furnace, then pass to nitrogen conduct
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；500 are cooled to again with the rate of 5 DEG C/min
DEG C, finally it is down to room temperature naturally again；Normal pressure is kept in tube furnace.Obtain classifying porous carbon nanomaterial；
Fig. 5 is the embodiment of the present invention 3 by being pyrolyzed 5,5', 6,6'- tetrahydroxy -3,3,3', 3'- tetramethyl -1,1'- spiral connection
The stereoscan photograph for the classifying porous carbon nanomaterial that the chelating presoma of indoles and zinc nitrate hexahydrate obtains；
Fig. 6 is the embodiment of the present invention 3 by being pyrolyzed 5,5', 6,6'- tetrahydroxy -3,3,3', 3'- tetramethyl -1,1'- spiral connection
The pore size distribution data that the chelating presoma of indoles and zinc nitrate hexahydrate obtains；
By Fig. 1,2 and Fig. 5,6 comparison, which can be seen that the present embodiment and have, differs markedly from 1 carbon nanomaterial of embodiment
Pattern and pore-size distribution.The carbon nanomaterial that the change of small organic molecule structure promotes embodiment 3 to synthesize presents more unordered
Micron or nanoscale dispersion carbon particle, larger difference also occurs for pore-size distribution, but still maintains classifying porous point
The characteristics of cloth.
Embodiment 4
A. 0.5g catechol is distributed in 50ml water, the rear 3.63ml concentration that is added is the NaOH solution of 0.2g/ml, warp
After stirring half an hour, bis- water zinc acetate of 5.40g is added, continues stirring 6 hours, obtains the presoma being precipitated with precipitation form；
B. the above-mentioned aqueous solution containing presoma is removed into moisture removal by centrifugation, add clear water and repeats to wash by being centrifuged
It washs three times, is finally putting into baking oven and is dried；
C. complete presoma will have been dried to be transferred in silica crucible, be put into tube furnace, then pass to nitrogen conduct
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；500 are cooled to again with the rate of 5 DEG C/min
DEG C, finally it is down to room temperature naturally again；Normal pressure is kept in tube furnace.Obtain classifying porous carbon nanomaterial；
Fig. 7 is the embodiment of the present invention 4 by being pyrolyzed catechol and two water in the NaOH lye of 4 times of catechol moles
The stereoscan photograph for the classifying porous carbon nanomaterial that the chelating presoma of zinc acetate obtains；
Fig. 8 is the embodiment of the present invention 4 by being pyrolyzed catechol and two water in the NaOH lye of 4 times of catechol moles
The pore size distribution data for the classifying porous carbon nanomaterial that the chelating presoma of zinc acetate obtains；
It can be seen that carbon nanomaterial manufactured in the present embodiment is with graded porous structure by Fig. 7 and Fig. 8.According to nitrogen
Adsorption and desorption isotherms calculate to obtain specific surface area 2043m2/ g, pore volume 1.81cm3/g。
Embodiment 5
A. 0.5g catechol is distributed in 50ml water, the rear 5.45ml concentration that is added is the NaOH solution of 0.2g/ml, warp
After stirring half an hour, bis- water zinc acetate of 5.40g is added, continues stirring 6 hours, obtains the presoma being precipitated with precipitation form；
B. the above-mentioned aqueous solution containing presoma is removed into moisture removal by centrifugation, add clear water and repeats to wash by being centrifuged
It washs three times, is finally putting into baking oven and is dried；
C. complete presoma will have been dried to be transferred in silica crucible, be put into tube furnace, then pass to nitrogen conduct
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；500 are cooled to again with the rate of 5 DEG C/min
DEG C, finally it is down to room temperature naturally again；Normal pressure is kept in tube furnace.Obtain classifying porous carbon nanomaterial；
Fig. 9 is the embodiment of the present invention 4 by being pyrolyzed catechol and two water in the NaOH lye of 6 times of catechol moles
The stereoscan photograph for the classifying porous carbon nanomaterial that the chelating presoma of zinc acetate obtains；
Figure 10 is the embodiment of the present invention 4 by being pyrolyzed the catechol and two in the NaOH lye of 6 times of catechol moles
The pore size distribution data for the classifying porous carbon nanomaterial that the chelating presoma of water zinc acetate obtains；
It can be seen that structure and pore-size distribution are basically unchanged after enhancing alkalinity, still have classification more by Fig. 9 and Figure 10
Pore structure, but the specific surface area of material increases with pore volume, and specific surface area and pore volume are respectively 2448m2/ g,
2.15cm3/g。
Embodiment 6
A. 0.5g 3,4- dihydroxy cyanophenyl is distributed in 50ml water, the rear 2.96ml concentration that is added is the NaOH of 0.2g/ml
Solution after agitated half an hour, adds bis- water zinc acetate of 3.25g, continues stirring 6 hours, what acquisition was precipitated with precipitation form
Presoma；
B. the above-mentioned aqueous solution containing presoma is removed into moisture removal by centrifugation, add clear water and repeats to wash by being centrifuged
It washs three times, is finally putting into baking oven and is dried；
C. complete presoma will have been dried to be transferred in silica crucible, be put into tube furnace, then pass to nitrogen conduct
Gas is protected, tube furnace is warming up to 1000 DEG C with the rate of 5 DEG C/min, keeps 2h；500 are cooled to again with the rate of 5 DEG C/min
DEG C, finally it is down to room temperature naturally again；Normal pressure is kept in tube furnace.Obtain classifying porous carbon nanomaterial；
Figure 11 is the embodiment of the present invention 4 by being pyrolyzed the 3,4- bis- in the NaOH lye of 4 times of 3,4- dihydroxy cyanophenyl moles
The stereoscan photograph for the classifying porous carbon nanomaterial that the chelating presoma of 4-hydroxy-benzonitrile and two water zinc acetates obtains；
Figure 12 is the embodiment of the present invention 4 by being pyrolyzed the 3,4- bis- in the NaOH lye of 4 times of 3,4- dihydroxy cyanophenyl moles
The pore size distribution data for the classifying porous carbon nanomaterial that the chelating presoma of 4-hydroxy-benzonitrile and two water zinc acetates obtains；
By Figure 11,12 and Fig. 6,7 comparison, which can be seen that the present embodiment and have, differs markedly from 4 carbon nanometer material of embodiment
The pattern and pore-size distribution of material.The change of small organic molecule structure promotes the carbon material of the synthesis different-shape of embodiment 6, aperture
The characteristics of being distributed and larger difference also occurs, but still maintaining classifying porous distribution, specific surface area and pore volume are respectively
1202m2/ g, 1.00cm3/g。
The above is only a preferred embodiment of the present invention, it is noted that for the ordinary skill people of the art
For member, various improvements and modifications may be made without departing from the principle of the present invention, these improvements and modifications are also answered
It is considered as protection scope of the present invention.
Claims (10)
1. a kind of synthetic method of classifying porous carbon nanomaterial, which comprises the following steps:
A) small organic molecule containing more chelation groups or adjacent hydroxyl group and inorganic zinc salt are mixed into alkaline aqueous solution
Row reaction, obtains the presoma being precipitated with precipitation form；
B the presoma) is subjected to high temperature pyrolysis, obtains classifying porous carbon nanomaterial.
2. synthetic method according to claim 1, which is characterized in that step A) in, the mixed raw material in alkaline aqueous solution
It further include the aliphatic chain molecule of chelation group-containing.
3. synthetic method according to claim 2, which is characterized in that the aliphatic chain molecule of the chelation group-containing is selected from fourth
Diacid, adipic acid, suberic acid, decanedioic acid or perfluor decanedioic acid, additive amount are the organic small of more chelation groups or adjacent hydroxyl group
The a quarter of molecule mole is to half.
4. synthetic method according to claim 1, which is characterized in that the alkaline aqueous solution is by triethylamine, ammonium hydroxide, hydrogen-oxygen
Change potassium or sodium hydroxide is prepared to obtain.
5. synthetic method according to claim 1, which is characterized in that the pH value of the alkaline aqueous solution is 7~14.
6. synthetic method according to claim 1, which is characterized in that the small organic molecule containing more chelation groups is selected from
Imidazoles -2- formic acid, 1H- benzimidazole-5-carboxylic acid, 5- carboxyl benzotriazole, 4,4 '-(the fluoro- 1- trifluoromethyls of 2,2,2- tri-) are sub-
Ethyl bis- (1,2- phthalic acids), terephthalic acid (TPA), 4,4- biphenyl dicarboxylic acid, D-His, 1,5- naphthalenedisulfonic acid, 4,4 '-connection
Benzenedisulfonic acid, 8-hydroxyquinoline-5-sulfonic acid hydrate, 2,2 '-bipyridyls -4,4 '-dicarboxylic acids, 4- Carboxybenzeneboronic acid, tea polyphenols,
Caffeic acid, tetrahydroxy quinone, 5,5', 6,6'- tetrahydroxy -3,3,3', 3'- tetramethyl -1,1'- spiral biindolyl, benzimidazole,
Benzotriazole, 2-PHENYLBENZIMIDAZOLE-5-SULFONIC ACID, two hydrate of 5-sulphosalicylic acid.
7. synthetic method according to claim 1, which is characterized in that the molecule containing adjacent hydroxyl group be selected from catechol,
3,4- dihydroxytoluene, Dopamine hydrochloride, 2,3- dihydroxy naphthlene, pyrogallol, cachou extract, baicalein, propylgallate, perfume (or spice)
One of leaf lignin, 3,4- dihydroxy cyanophenyl, 2,3- dihydroxy-pyridine.
8. synthetic method according to claim 1, which is characterized in that the inorganic zinc salt is selected from two water zinc acetates, six water
Close zinc nitrate, anhydrous zinc chloride or basic zinc carbonate.
9. synthetic method according to claim 1, which is characterized in that described containing more chelation groups or adjacent hydroxyl group
Small organic molecule and the molar ratio of inorganic zinc salt are 2:1~1:6；
Mole of alkaline matter in the small organic molecule and alkaline aqueous solution containing more chelation groups or adjacent hydroxyl group
Than for 2:1~1:8.
10. synthetic method according to claim 1, which is characterized in that the high temperature pyrolysis are as follows:
Under the protective atmosphere of nitrogen or argon hydrogen, the Means of Pyrolyzed Precursor is risen to 800~1000 DEG C with 2~10 DEG C/min, is protected
Hold 2~5h；400~600 DEG C are down to 2~10 DEG C/min again, natural cooling obtains classifying porous carbon nanomaterial.
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