CN110357068B - Synthetic method of hierarchical porous carbon nano material - Google Patents
Synthetic method of hierarchical porous carbon nano material Download PDFInfo
- Publication number
- CN110357068B CN110357068B CN201910755174.1A CN201910755174A CN110357068B CN 110357068 B CN110357068 B CN 110357068B CN 201910755174 A CN201910755174 A CN 201910755174A CN 110357068 B CN110357068 B CN 110357068B
- Authority
- CN
- China
- Prior art keywords
- acid
- porous carbon
- precursor
- zinc
- hierarchical porous
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y30/00—Nanotechnology for materials or surface science, e.g. nanocomposites
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B82—NANOTECHNOLOGY
- B82Y—SPECIFIC USES OR APPLICATIONS OF NANOSTRUCTURES; MEASUREMENT OR ANALYSIS OF NANOSTRUCTURES; MANUFACTURE OR TREATMENT OF NANOSTRUCTURES
- B82Y40/00—Manufacture or treatment of nanostructures
-
- C—CHEMISTRY; METALLURGY
- C01—INORGANIC CHEMISTRY
- C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
- C01B32/00—Carbon; Compounds thereof
- C01B32/05—Preparation or purification of carbon not covered by groups C01B32/15, C01B32/20, C01B32/25, C01B32/30
Abstract
The invention provides a method for synthesizing a hierarchical porous carbon nano material, which comprises the following steps: A) mixing organic micromolecules containing polychelating groups or ortho-hydroxyl groups and inorganic zinc salt in an alkaline aqueous solution for reaction to obtain a precursor precipitated in a precipitation form; B) and carrying out high-temperature pyrolysis on the precursor to obtain the hierarchical porous carbon nanomaterial. According to the invention, zinc, organic micromolecules containing multi-chelating groups or ortho-hydroxyl groups and zinc are stirred in alkaline aqueous solution at room temperature to form a coordination polymer or a coordination compound as a precursor, then the chelated zinc in the precursor is agglomerated and nano-scale dispersed zinc particles are formed in the high-temperature pyrolysis process to realize the pore-forming effect of the template, meanwhile, the zinc nanoparticles can be evaporated through further high-temperature treatment, and the hierarchical porous carbon nanomaterial can be obtained without subsequent etching. The synthesis method provided by the invention is simple, low in cost, strong in controllability, high in universality and mild in condition.
Description
Technical Field
The invention belongs to the technical field of nano materials, and particularly relates to a method for synthesizing a hierarchical porous carbon nano material.
Background
The traditional porous carbon material is obtained by taking biomass materials (such as asphalt, coconut shells, lignocellulose, corn stalks and the like) as precursors and combining physical or chemical activation means through high-temperature pyrolysis. Through the simple and low-cost synthesis method, a series of biomass-derived porous carbon materials have been developed industrially and widely applied to the fields of gas or liquid separation, water treatment, air purification and the like. However, the biomass material is affected by the production area, the growth environment and the characteristics thereof, the structure and the composition thereof are complex, and the content of impurities is high, so that the microstructure and the properties of the derived carbon material have poor controllability. In addition, the pore size obtained by physical or chemical activation is usually concentrated in the range of micropores. With the continuous and deep research on the application of porous carbon materials, the construction of a hierarchical pore structure in a carbon material is widely considered as one of important means for preparing high-performance carbon materials oriented to a plurality of new nanotechnology application fields such as energy storage and conversion, heterogeneous catalysis, gas adsorption and the like. Compared with the traditional carbon material with a single pore size, the hierarchical porous carbon material has higher material transmission efficiency, can provide larger contact area with object substances (molecules, atoms and ions), and can be further used for preparing high-performance lithium battery cathode materials, oxygen reduction catalysts, hydrogen adsorption materials and the like. Therefore, the construction of the carbon-rich material with a determined structure and composition as a precursor from a molecular level and the development of other nano pore-forming technologies are one of important means for realizing the controllable synthesis of the hierarchical porous carbon material and are the basis for further exploring the high-performance carbon-based material.
The controllable synthesis method of the hierarchical porous carbon material established at present can be divided into three categories.
The first type is to use chemically synthesized macromolecules as precursors to realize the preparation of hierarchical porous carbon by a template method or a template-activation combined method. The method can regulate and control the nanometer structure and the element composition of the carbon product by changing the structure and the dosage of the template agent and replacing the types of the macromolecules.
In the second method, ionic liquid is used as a precursor, and pore forming is carried out by adopting a template method or a molten salt method, so as to obtain the hierarchical porous carbon material.
The third concept of constructing the controllable synthesis of the hierarchical porous carbon material is to pyrolyze a metal organic framework Material (MOFs), metal nodes connected with ligand small molecules can generate a nano template in situ in the carbonization process, so that the pore-forming effect is realized, and meanwhile, the components of the MOFs derived carbon material can be simply realized by replacing metal ions or bridging ligands in the structure, so that different miscellaneous elements can be doped in the carbon framework and different types of metals can be loaded.
Although the established methods described above provide a variety of approaches to the controlled synthesis of hierarchical porous carbon materials, this field still faces two challenges. The first challenge is how to widely use low-cost small molecules to prepare the hierarchical porous carbon material, and further establish a relatively large material system to support the analysis of the nano structure and the composition and performance structure-activity relationship, and finally indicate the direction for designing the high-performance carbon-based material. The second challenge faced in the research field of controllable synthesis of the hierarchical porous carbon material is to develop a green sustainable synthesis technology and realize the macro and cheap preparation of the material system. The existing synthesis method of the graded porous carbon material usually needs a large amount of organic solvents, has low raw material cost and complex preparation process, and is not beneficial to the wide application and exploration of the graded porous carbon material.
Disclosure of Invention
In view of this, the technical problem to be solved by the present invention is to provide a method for synthesizing a hierarchical porous carbon nanomaterial, which is simple, low in cost, strong in controllability, high in universality and mild in conditions.
The invention provides a method for synthesizing a hierarchical porous carbon nano material, which comprises the following steps:
A) mixing organic micromolecules containing polychelating groups or ortho-hydroxyl groups and inorganic zinc salt in an alkaline aqueous solution for reaction to obtain a precursor precipitated in a precipitation form;
B) and carrying out high-temperature pyrolysis on the precursor to obtain the hierarchical porous carbon nanomaterial.
Preferably, in step a), the mixed raw materials in the alkaline aqueous solution further include a chelating group-containing aliphatic chain molecule.
Preferably, the chelating group-containing aliphatic chain molecule is selected from succinic acid, adipic acid, suberic acid, sebacic acid or perfluorinated sebacic acid, and the addition amount is one fourth to one half of the molar weight of the organic micromolecule of the polychelating group or the ortho-hydroxyl group.
Preferably, the alkaline aqueous solution is prepared from triethylamine, ammonia water, potassium hydroxide or sodium hydroxide.
Preferably, the pH value of the alkaline aqueous solution is 7-14.
Preferably, the organic small molecule containing multi-chelating groups is selected from imidazole-2-carboxylic acid, 1H-benzimidazole-5-carboxylic acid, 5-carboxybenzotriazole, 4 '- (2,2, 2-trifluoro-1-trifluoromethyl) ethylene bis (1, 2-phthalic acid), terephthalic acid, 4-biphenyldicarboxylic acid, D-histidine, 1, 5-naphthalenedisulfonic acid, 4' -biphenyldisulfonic acid, 8-hydroxyquinoline-5-sulfonic acid hydrate, 2,2 '-bipyridine-4, 4' -dicarboxylic acid, 4-carboxyphenylboronic acid, tea polyphenol, caffeic acid, tetrahydroxybenzoquinone, 5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spirobiindole, benzimidazole, benzotriazole, 2-phenylbenzimidazole-5-sulfonic acid, 5-sulfosalicylic acid dihydrate;
preferably, the molecule containing an ortho-hydroxyl group is selected from one of catechol, 3, 4-dihydroxytoluene, dopamine hydrochloride, 2, 3-dihydroxynaphthalene, pyrogallol, catechin, baicalein, propyl gallate, diosmetin, 3, 4-dihydroxybenzonitrile, and 2, 3-dihydroxypyridine.
Preferably, the inorganic zinc salt is selected from zinc acetate dihydrate, zinc nitrate hexahydrate, anhydrous zinc chloride or basic zinc carbonate.
Preferably, the molar ratio of the organic micromolecules containing poly-chelating groups or ortho-hydroxyl groups to the inorganic zinc salt is 2: 1-1: 6;
the molar ratio of the organic micromolecules containing multiple chelating groups or ortho-hydroxyl groups to the alkaline substances in the alkaline aqueous solution is 2: 1-1: 8.
Preferably, the high-temperature pyrolysis is: under the protective atmosphere of nitrogen or argon-hydrogen, raising the temperature of the pyrolysis precursor to 800-1000 ℃ at the speed of 2-10 ℃/min, and keeping for 2-5 h; and reducing the temperature to 400-600 ℃ at the speed of 2-10 ℃/min, and naturally cooling to obtain the hierarchical porous carbon nano material.
Compared with the prior art, the invention provides a method for synthesizing a hierarchical porous carbon nano material, which comprises the following steps: A) mixing organic micromolecules containing polychelating groups or ortho-hydroxyl groups and inorganic zinc salt in an alkaline aqueous solution for reaction to obtain a precursor precipitated in a precipitation form; B) and carrying out high-temperature pyrolysis on the precursor to obtain the hierarchical porous carbon nanomaterial. According to the invention, zinc, organic micromolecules containing multi-chelating groups or ortho-hydroxyl groups and zinc are stirred in alkaline aqueous solution at room temperature to form a coordination polymer or a coordination compound as a precursor, then the chelated zinc in the precursor is agglomerated and nano-scale dispersed zinc particles are formed in the high-temperature pyrolysis process to realize the pore-forming effect of the template, meanwhile, the zinc nanoparticles can be evaporated through further high-temperature treatment, and the hierarchical porous carbon nanomaterial can be obtained without subsequent etching. The synthesis method provided by the invention is simple, low in cost, strong in controllability, high in universality and mild in condition.
Drawings
FIG. 1 is a scanning electron micrograph of a hierarchical porous carbon nanomaterial prepared in example 1 of the present invention;
FIG. 2 is data of pore size distribution of the hierarchical porous carbon nanomaterial prepared in example 1 of the present invention;
FIG. 3 is a scanning electron micrograph of the hierarchical porous carbon nanomaterial prepared in example 2 of the present invention;
FIG. 4 is data of pore size distribution of the hierarchical porous carbon nanomaterial prepared in example 2 of the present invention;
FIG. 5 is a scanning electron micrograph of the hierarchical porous carbon nanomaterial prepared in example 3 of the present invention;
FIG. 6 is pore size distribution data of the hierarchical porous carbon nanomaterial prepared in example 3 of the present invention;
FIG. 7 is a scanning electron micrograph of the hierarchical porous carbon nanomaterial prepared in example 4 of the present invention;
FIG. 8 is data of pore size distribution of the hierarchical porous carbon nanomaterial prepared in example 4 of the present invention;
FIG. 9 is a SEM photograph of the hierarchical porous carbon nanomaterial prepared in example 5 of the present invention;
FIG. 10 is pore size distribution data of the hierarchical porous carbon nanomaterial prepared in example 5 of the present invention;
FIG. 11 is a SEM photograph of the hierarchical porous carbon nanomaterial prepared in example 6 of the present invention;
fig. 12 is data of pore size distribution of the hierarchical porous carbon nanomaterial prepared in example 6 of the present invention.
Detailed Description
The invention provides a method for synthesizing a hierarchical porous carbon nano material, which comprises the following steps:
A) mixing organic micromolecules containing polychelating groups or ortho-hydroxyl groups and inorganic zinc salt in an alkaline aqueous solution for reaction to obtain a precursor precipitated in a precipitation form;
B) and carrying out high-temperature pyrolysis on the precursor to obtain the hierarchical porous carbon nanomaterial.
The invention firstly mixes organic micromolecules containing multiple chelating groups or ortho-hydroxyl groups and inorganic zinc salt in an alkaline aqueous solution for reaction to obtain a precursor precipitated in a precipitation form.
Specifically, organic micromolecules containing polychelating groups or ortho-diphenols are dissolved in alkaline aqueous solution to obtain mixed solution;
the organic micromolecule containing polychelating groups is selected from imidazole-2-formic acid, 1H-benzimidazole-5-carboxylic acid, 5-carboxyl benzotriazole, 4 '- (2,2, 2-trifluoro-1-trifluoromethyl) ethylidene bis (1, 2-phthalic acid), terephthalic acid, 4-biphenyldicarboxylic acid, D-histidine, 1, 5-naphthalenedisulfonic acid, 4' -biphenyldisulfonic acid, 8-hydroxyquinoline-5-sulfonic acid hydrate, 2,2 '-bipyridyl-4, 4' -dicarboxylic acid, 4-carboxyl phenylboronic acid, tea polyphenol, caffeic acid, tetrahydroxybenzoquinone, 5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spirobiindole, benzimidazole, benzotriazole, 2-phenylbenzimidazole-5-sulfonic acid, 5-sulfosalicylic acid dihydrate; preferred are terephthalic acid and 5,5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spirobiindole.
The molecule containing the ortho-hydroxyl group is selected from one of catechol, 3, 4-dihydroxytoluene, dopamine hydrochloride, 2, 3-dihydroxynaphthalene, pyrogallol, catechin, baicalein, propyl gallate, diosmetin, 3, 4-dihydroxybenzonitrile and 2, 3-dihydroxypyridine, and preferably catechol or 3, 4-dihydroxybenzonitrile.
The alkaline aqueous solution is prepared from triethylamine, ammonia water, potassium hydroxide or sodium hydroxide. The pH value of the alkaline aqueous solution is 7-14.
According to different organic micromolecules, a series of hierarchical porous carbon nano materials with different pore size distribution, element doping and morphology can be obtained.
The organic small molecules generally do not have good water solubility, and the solubility of the organic small molecules in an aqueous solution can be effectively improved by using an alkaline aqueous solution as a solvent through a salt forming effect, so that the use of an organic solvent is avoided; in addition, the use of the alkaline aqueous solution also contributes to deprotonation of functional groups such as carboxyl, hydroxyl, sulfonic acid, imino, boronic acid and the like in the organic micromolecules, and further realizes coordination between molecules and zinc.
Then, adding inorganic zinc salt into the mixed solution, mixing, and reacting to obtain a precursor precipitated in a precipitation form;
wherein the inorganic zinc salt is selected from zinc acetate dihydrate, zinc nitrate hexahydrate, anhydrous zinc chloride or basic zinc carbonate. Adding inorganic zinc salt into the mixed solution, and precipitating a large amount of precipitate in the reaction process of mixing and stirring. The reaction temperature is room temperature, and the reaction time is 1-24 hours. In the present invention, the room temperature is defined as 25. + -. 5 ℃.
The inorganic zinc salt and the organic micromolecules can form coordination polymers or coordination compounds with low vapor pressure through coordination, so that the volatility of the organic micromolecules is improved, and the preparation of the hierarchical porous carbon nanometer material from the organic micromolecules is realized.
Then, the precipitated precipitate was centrifuged and dried to obtain a precursor. And (3) removing moisture from the precipitate through high-speed centrifugation, and then putting the precipitate into a heating oven to remove residual moisture to obtain a pyrolysis precursor.
The molar ratio of the organic micromolecules containing poly-chelating groups or o-hydroxyl groups to the inorganic zinc salt is 2: 1-1: 6, preferably 1: 1-1: 4;
the molar ratio of the organic micromolecules containing poly-chelating groups or ortho-hydroxyl groups to the alkaline substances in the alkaline aqueous solution is 2: 1-1: 8, and preferably 1: 1-1: 6.
And finally, carrying out high-temperature pyrolysis on the precursor to obtain the hierarchical porous carbon nanomaterial.
In the high-temperature pyrolysis process, zinc in the precursor structure can form nano-scale dispersed zinc particles in situ through agglomeration, and then the nano-scale dispersed zinc particles are used as a template agent to play a pore-forming role; along with the continuous proceeding of the pyrolysis process and after reaching a certain temperature, the zinc nanoparticles with low boiling point escape from the interior and the surface of the carbon material due to the evaporation effect, and then the hierarchical porous carbon nanomaterial can be obtained without subsequent etching treatment.
In order to ensure that the zinc nanoparticles can be sufficiently separated from the carbon material in the pyrolysis treatment, the pyrolysis step of the hierarchical porous carbon nanomaterial comprises the following steps: under the protective atmosphere of nitrogen or argon-hydrogen, raising the temperature of the mixture to 800-1000 ℃ at the speed of 2-10 ℃/min, and keeping the temperature for 2-5 h; and reducing the temperature to 400-600 ℃ at the speed of 2-10 ℃/min, and naturally cooling to obtain the hierarchical porous carbon nano material.
The natural cooling is cooling at room temperature.
In the present invention, the room temperature is defined as 25. + -. 5 ℃.
In some embodiments of the present invention, in step a), the raw material mixed in the alkaline aqueous solution further comprises a chelating group-containing aliphatic chain molecule selected from succinic acid, adipic acid, suberic acid, sebacic acid or perfluorosebacic acid, and the amount of the chelating group-containing aliphatic chain molecule added is one fourth to one half, preferably one third to one half, of the molar weight of the organic small molecule having multiple chelating groups or ortho-hydroxyl groups
The additional addition of fatty chain molecules containing chelating groups can participate in the formation of precursor materials; due to the poor thermal stability of the molecular chain segment of the aliphatic chain, the molecular chain segment can be cracked, decomposed and released with gas in the pyrolysis process, thereby providing another pore-forming mode.
In some embodiments of the invention, aqueous solutions of different basicities are used as solvents during precursor synthesis. The coordination structure of the organic micromolecules and zinc and the zinc content in the precursor structure can be changed by using water solutions with different alkalinity as solvents, so that the size and the loading capacity of zinc nanoparticles generated in situ in the high-temperature pyrolysis process are changed, and finally the aperture regulation and control effect is realized; specifically, the alkaline aqueous solution is prepared from triethylamine, ammonia water, potassium hydroxide or sodium hydroxide, the alkalinity of the aqueous solution is regulated and controlled by changing the molar ratio of the alkaline chemical to the organic micromolecules, the concentrations of deprotonated organic micromolecules and hydroxyl ions in the solution are regulated and controlled, the alkalinity is increased, the concentrations of the deprotonated organic micromolecules and the hydroxyl ions are increased, the ratio of ligands taking zinc ions as central ions is changed, namely more hydroxyl ion ligands participate in coordination, the zinc content in the precursor structure is further influenced, and finally the specific surface area is increased along with the increase of the alkali dosage.
According to the invention, zinc, organic micromolecules containing multi-chelating groups or ortho-hydroxyl groups and zinc are stirred in alkaline aqueous solution at room temperature to form a coordination polymer or a coordination compound as a precursor, then the chelated zinc in the precursor is agglomerated and nano-scale dispersed zinc particles are formed in the high-temperature pyrolysis process to realize the pore-forming effect of the template, meanwhile, the zinc nanoparticles can be evaporated through further high-temperature treatment, and the hierarchical porous carbon nanomaterial can be obtained without subsequent etching. The synthesis method provided by the invention is simple, low in cost, strong in controllability, high in universality and mild in condition.
For further understanding of the present invention, the synthesis method of the hierarchical porous carbon nanomaterial provided by the present invention is described below with reference to the following examples, and the scope of the present invention is not limited by the following examples.
Example 1
a. Dispersing 0.8g of terephthalic acid into 80ml of water, adding 2.67ml of triethylamine, stirring for half an hour, adding 5.73g of zinc nitrate hexahydrate, and continuously stirring for 24 hours to obtain a precursor precipitated in a precipitate form;
b. removing water from the aqueous solution containing the precursor through centrifugation, adding clear water, repeatedly washing for three times through centrifugation, and finally putting the aqueous solution into an oven for drying;
c. transferring the completely dried precursor into a quartz crucible, putting the quartz crucible into a tube furnace, introducing nitrogen as protective gas, heating the tube furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; cooling to 500 deg.C at a rate of 5 deg.C/min, and naturally cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining a hierarchical porous carbon nano material;
FIG. 1 is a scanning electron micrograph of a hierarchical porous carbon nanomaterial obtained by pyrolysis of a chelate precursor of terephthalic acid and zinc nitrate hexahydrate in example 1 of the present invention;
FIG. 2 is data of pore size distribution of hierarchical porous carbon nanomaterial obtained by pyrolysis of a chelate precursor of terephthalic acid and zinc nitrate hexahydrate in example 1 of the present invention;
as can be seen from fig. 1 and 2, the carbon nanomaterial prepared in this example is composed of micron-or nano-sized bulk particles, and has a hierarchical porous structure.
Example 2
a. Dispersing 0.8g of terephthalic acid and 0.209mg of suberic acid into 80ml of water, adding 3.34ml of triethylamine, stirring for half an hour, adding 7.16g of zinc nitrate hexahydrate, and continuously stirring for 24 hours to obtain a precursor precipitated in a precipitate form;
b. removing water from the aqueous solution containing the precursor through centrifugation, adding clear water, repeatedly washing for three times through centrifugation, and finally putting the aqueous solution into an oven for drying;
c. transferring the completely dried precursor into a quartz crucible, putting the quartz crucible into a tube furnace, introducing nitrogen as protective gas, heating the tube furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; cooling to 500 deg.C at a rate of 5 deg.C/min, and naturally cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining a hierarchical porous carbon nano material;
FIG. 3 is a scanning electron micrograph of a hierarchical porous carbon nanomaterial obtained by pyrolysis of a chelate precursor of terephthalic acid, suberic acid and zinc nitrate hexahydrate in example 2 of the present invention;
FIG. 4 is data of pore size distribution of hierarchical porous carbon nanomaterial obtained from pyrolysis of terephthalic acid, suberic acid and chelate precursor of zinc nitrate hexahydrate in example 2 of the present invention;
as can be seen from the comparison of fig. 1 and 2 and fig. 3 and 4, the carbon nanomaterial of the present embodiment has a morphology and a pore size distribution that are significantly different from those of the carbon nanomaterial of the embodiment 1. The additional addition of aliphatic chain molecules causes the carbon nanomaterial synthesized in example 2 to have a looser carbon nanoparticle structure, and the pore size distribution also changes toward the increase in size.
Example 3
a. Dispersing 0.8g of 5,5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spiro-indole in 50ml of water, adding 751.8mg of potassium hydroxide, stirring for half an hour, adding 2.79g of zinc nitrate hexahydrate, and continuously stirring for 24 hours to obtain a precursor precipitated in a precipitate form;
b. removing water from the aqueous solution containing the precursor through centrifugation, adding clear water, repeatedly washing for three times through centrifugation, and finally putting the aqueous solution into an oven for drying;
c. transferring the completely dried precursor into a quartz crucible, putting the quartz crucible into a tube furnace, introducing nitrogen as protective gas, heating the tube furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; cooling to 500 deg.C at a rate of 5 deg.C/min, and naturally cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining a hierarchical porous carbon nano material;
FIG. 5 is a scanning electron microscope photograph of a hierarchical porous carbon nanomaterial obtained by pyrolysis of a chelate precursor of 5,5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spirobiindole and zinc nitrate hexahydrate in example 3 of the present invention;
FIG. 6 is pore size distribution data obtained from pyrolysis of a chelated precursor of 5,5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, 1' -spirobiindole with zinc nitrate hexahydrate of example 3 of the present invention;
as can be seen from the comparison of fig. 1 and 2 and fig. 5 and 6, the carbon nanomaterial of the present embodiment has a morphology and a pore size distribution that are significantly different from those of the carbon nanomaterial of the embodiment 1. The change of the organic small molecular structure causes the carbon nano-material synthesized in the example 3 to present disordered micro-or nano-scale dispersed carbon particles, the pore size distribution of which is also greatly different, and the characteristic of graded porous distribution is still maintained.
Example 4
a. Dispersing 0.5g of catechol into 50ml of water, adding 3.63ml of NaOH solution with the concentration of 0.2g/ml, stirring for half an hour, adding 5.40g of zinc acetate dihydrate, and continuously stirring for 6 hours to obtain a precursor precipitated in a precipitate form;
b. removing water from the aqueous solution containing the precursor through centrifugation, adding clear water, repeatedly washing for three times through centrifugation, and finally putting the aqueous solution into an oven for drying;
c. transferring the completely dried precursor into a quartz crucible, putting the quartz crucible into a tube furnace, introducing nitrogen as protective gas, heating the tube furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; cooling to 500 deg.C at a rate of 5 deg.C/min, and naturally cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining a hierarchical porous carbon nano material;
FIG. 7 is a scanning electron microscope photograph of a hierarchical porous carbon nanomaterial obtained by pyrolyzing a chelate precursor of catechol and zinc acetate dihydrate in a NaOH alkaline solution in an amount 4 times the molar weight of catechol in example 4 of the present invention;
FIG. 8 is the pore size distribution data of the hierarchical porous carbon nanomaterial obtained by pyrolyzing the chelate precursors of catechol and zinc acetate dihydrate in NaOH alkaline solution in an amount 4 times the molar weight of catechol in example 4 of the present invention;
it can be seen from fig. 7 and 8 that the carbon nanomaterial prepared in this example has a hierarchical porous structure. Calculating the specific surface area of 2043m according to a nitrogen adsorption and desorption isotherm2G, pore volume 1.81cm3/g。
Example 5
a. Dispersing 0.5g of catechol into 50ml of water, adding 5.45ml of NaOH solution with the concentration of 0.2g/ml, stirring for half an hour, adding 5.40g of zinc acetate dihydrate, and continuously stirring for 6 hours to obtain a precursor precipitated in a precipitate form;
b. removing water from the aqueous solution containing the precursor through centrifugation, adding clear water, repeatedly washing for three times through centrifugation, and finally putting the aqueous solution into an oven for drying;
c. transferring the completely dried precursor into a quartz crucible, putting the quartz crucible into a tube furnace, introducing nitrogen as protective gas, heating the tube furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; cooling to 500 deg.C at a rate of 5 deg.C/min, and naturally cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining a hierarchical porous carbon nano material;
FIG. 9 is a scanning electron microscope photograph of a hierarchical porous carbon nanomaterial obtained by pyrolyzing a chelate precursor of catechol and zinc acetate dihydrate in 6 times molar amount of NaOH alkaline solution in accordance with example 4 of the present invention;
FIG. 10 is the pore size distribution data of the hierarchical porous carbon nanomaterial obtained by pyrolyzing the chelate precursors of catechol and zinc acetate dihydrate in 6 times molar weight of catechol NaOH alkaline solution in example 4 of the present invention;
from FIGS. 9 and 10, it can be seen that the structure and the pore size distribution are basically unchanged after the alkalinity is enhanced, and the material still has a hierarchical porous structure, but the specific surface area and the pore volume of the material are improved, and the specific surface area and the pore volume are 2448m respectively2/g，2.15cm3/g。
Example 6
a. Dispersing 0.5g of 3, 4-dihydroxy benzonitrile into 50ml of water, adding 2.96ml of NaOH solution with the concentration of 0.2g/ml, stirring for half an hour, adding 3.25g of zinc acetate dihydrate, and continuously stirring for 6 hours to obtain a precursor precipitated in a precipitate form;
b. removing water from the aqueous solution containing the precursor through centrifugation, adding clear water, repeatedly washing for three times through centrifugation, and finally putting the aqueous solution into an oven for drying;
c. transferring the completely dried precursor into a quartz crucible, putting the quartz crucible into a tube furnace, introducing nitrogen as protective gas, heating the tube furnace to 1000 ℃ at the speed of 5 ℃/min, and keeping the temperature for 2 hours; cooling to 500 deg.C at a rate of 5 deg.C/min, and naturally cooling to room temperature; the pressure in the tube furnace is kept constant. Obtaining a hierarchical porous carbon nano material;
FIG. 11 is a scanning electron microscope photograph of the hierarchical porous carbon nanomaterial obtained by pyrolyzing a chelated precursor of 3, 4-dihydroxybenzonitrile and zinc acetate dihydrate in 4 times the molar amount of 3, 4-dihydroxybenzonitrile in NaOH alkaline solution in example 4 in accordance with the present invention;
FIG. 12 is the pore size distribution data of the hierarchical porous carbon nanomaterial obtained by pyrolyzing the chelate precursor of 3, 4-dihydroxybenzonitrile and zinc acetate dihydrate in 4 times the molar amount of 3, 4-dihydroxybenzonitrile in NaOH alkaline solution in example 4 in accordance with the present invention;
as can be seen from comparison of fig. 11 and 12 and fig. 6 and 7, the carbon nanomaterial of the present embodiment has a morphology and a pore size distribution that are significantly different from those of the carbon nanomaterial of the embodiment 4. The change of the organic small molecular structure prompts the carbon material of different morphologies synthesized by the embodiment 6, the pore size distribution of the carbon material is also greatly different, but the characteristic of hierarchical porous distribution is still maintained, and the specific surface area and the pore volume of the carbon material are respectively 1202m2/g，1.00cm3/g。
The foregoing is only a preferred embodiment of the present invention, and it should be noted that, for those skilled in the art, various modifications and decorations can be made without departing from the principle of the present invention, and these modifications and decorations should also be regarded as the protection scope of the present invention.
Claims (7)
1. A method for synthesizing a hierarchical porous carbon nanomaterial is characterized by comprising the following steps:
A) mixing organic micromolecules containing polychelating groups or ortho-hydroxyl groups and inorganic zinc salt in an alkaline aqueous solution for reaction to obtain a precursor precipitated in a precipitation form,
the organic micromolecules containing the ortho-hydroxyl groups are selected from one of catechol, 3, 4-dihydroxytoluene, dopamine hydrochloride, 2, 3-dihydroxynaphthalene, pyrogallol, catechin, baicalein, propyl gallate, diosmetin, 3, 4-dihydroxybenzonitrile and 2, 3-dihydroxypyridine;
the organic micromolecule containing polychelating groups is selected from imidazole-2-formic acid, 1H-benzimidazole-5-carboxylic acid, 5-carboxyl benzotriazole, 4 '- (2,2, 2-trifluoro-1-trifluoromethyl) ethylidene bis (1, 2-phthalic acid), terephthalic acid, 4-biphenyldicarboxylic acid, D-histidine, 1, 5-naphthalenedisulfonic acid, 4' -biphenyldisulfonic acid, 8-hydroxyquinoline-5-sulfonic acid hydrate, 2,2 '-bipyridyl-4, 4' -dicarboxylic acid, 4-carboxyl phenylboronic acid, tea polyphenol, caffeic acid, tetrahydroxybenzoquinone, 5',6,6' -tetrahydroxy-3, 3,3',3' -tetramethyl-1, one of 1' -spirobiindole, benzimidazole, benzotriazole, 2-phenylbenzimidazole-5-sulfonic acid, and 5-sulfosalicylic acid dihydrate;
the molar ratio of the organic micromolecules containing multiple chelating groups or ortho-hydroxyl groups to the inorganic zinc salt is 2: 1-1: 6;
the molar ratio of the organic micromolecules containing multiple chelating groups or ortho-hydroxyl groups to alkaline substances in an alkaline aqueous solution is 2: 1-1: 8;
B) and carrying out high-temperature pyrolysis on the precursor to obtain the hierarchical porous carbon nanomaterial.
2. The method of claim 1, wherein in step a), the raw materials mixed in the alkaline aqueous solution further comprise fatty chain molecules containing chelating groups.
3. The synthesis method according to claim 2, wherein the chelating group-containing aliphatic chain molecule is selected from succinic acid, adipic acid, suberic acid, sebacic acid or perfluorosebacic acid, and the amount of the chelating group-containing aliphatic chain molecule is one fourth to one half of the molar weight of the organic small molecule of the polychelating group or the ortho-hydroxyl group.
4. The synthesis method according to claim 1, wherein the basic aqueous solution is prepared from triethylamine, ammonia water, potassium hydroxide or sodium hydroxide.
5. The synthesis method according to claim 1, wherein the pH value of the alkaline aqueous solution is 7-14.
6. The method of synthesis according to claim 1, wherein the inorganic zinc salt is selected from zinc acetate dihydrate, zinc nitrate hexahydrate, anhydrous zinc chloride or basic zinc carbonate.
7. The synthesis method according to claim 1, characterized in that the pyrolysis is:
under the protective atmosphere of nitrogen or argon-hydrogen, raising the temperature of the pyrolysis precursor to 800-1000 ℃ at the speed of 2-10 ℃/min, and keeping for 2-5 h; and reducing the temperature to 400-600 ℃ at the speed of 2-10 ℃/min, and naturally cooling to obtain the hierarchical porous carbon nano material.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910755174.1A CN110357068B (en) | 2019-08-15 | 2019-08-15 | Synthetic method of hierarchical porous carbon nano material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201910755174.1A CN110357068B (en) | 2019-08-15 | 2019-08-15 | Synthetic method of hierarchical porous carbon nano material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN110357068A CN110357068A (en) | 2019-10-22 |
| CN110357068B true CN110357068B (en) | 2021-08-13 |
Family
ID=68224618
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201910755174.1A Active CN110357068B (en) | 2019-08-15 | 2019-08-15 | Synthetic method of hierarchical porous carbon nano material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN110357068B (en) |
Families Citing this family (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN111346635B (en) * | 2020-03-04 | 2021-12-14 | 中国科学技术大学 | Intermetallic compound nano catalyst, preparation method and application thereof |
| CN111994897B (en) * | 2020-09-08 | 2023-05-02 | 许昌学院 | Simple preparation method of honeycomb porous carbon with high specific surface area |
| CN113659137A (en) * | 2021-08-17 | 2021-11-16 | 广东工业大学 | Nitrogen-doped three-dimensional nano-network structure carbon material and preparation method and application thereof |
| CN113683074B (en) * | 2021-09-13 | 2023-01-24 | 河北省科学院能源研究所 | Heteroatom-doped porous carbon material and preparation method and application thereof |
| CN115010946B (en) * | 2022-06-23 | 2024-03-15 | 华南理工大学 | Metal-organic coordination polymer M 2 CA X Preparation method and application thereof |
| CN115196617B (en) * | 2022-08-04 | 2023-12-19 | 亳州市亚珠新材料有限公司 | Preparation method of boron doped porous carbon rod-shaped material |
| CN117525426A (en) * | 2023-12-29 | 2024-02-06 | 贝特瑞新材料集团股份有限公司 | Carbon material and preparation method thereof, negative electrode material and preparation method thereof, and lithium ion battery |
Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104843665A (en) * | 2015-03-26 | 2015-08-19 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere and preparation method and application thereof |
| CN105384161A (en) * | 2015-11-23 | 2016-03-09 | 南京航空航天大学 | Preparation method and application of graded porous carbon material |
| KR101714574B1 (en) * | 2015-10-14 | 2017-03-09 | 국방과학연구소 | Metal-organic carbon composites and preparation method thereof |
| CN106865527A (en) * | 2017-04-14 | 2017-06-20 | 中国科学技术大学 | A kind of synthetic method of carbon nanomaterial and application |
| CN106876730A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | The porous carbon-supported base metal elctro-catalyst of N doping is prepared and electro-catalysis application |
| CN107500262A (en) * | 2017-07-19 | 2017-12-22 | 中国建筑材料科学研究总院 | Porous carbon materials and its preparation method and application |
| CN108147390A (en) * | 2017-12-07 | 2018-06-12 | 西安交通大学 | A kind of metal-natural polyphenol complex nanosphere and its nano porous metal/C-base composte material and preparation method |
| CN110813241A (en) * | 2019-12-17 | 2020-02-21 | 国网山东综合能源服务有限公司 | Nitrogen-oxygen co-doped porous carbon material and preparation method and application thereof |
Family Cites Families (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| JP3750024B2 (en) * | 2002-09-30 | 2006-03-01 | 松下電器産業株式会社 | Method for producing porous body |
| US8657923B2 (en) * | 2008-02-26 | 2014-02-25 | Nissan Motor Co., Ltd. | Microporous carbon material, manufacturing method thereof, and hydrogen storage method using microporous carbon material |
| 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 |
| 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 |
-
2019
- 2019-08-15 CN CN201910755174.1A patent/CN110357068B/en active Active
Patent Citations (9)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
| CN104843665A (en) * | 2015-03-26 | 2015-08-19 | 中国科学院化学研究所 | Single-layer and multi-layer hollow carbon nanosphere and preparation method and application thereof |
| KR101714574B1 (en) * | 2015-10-14 | 2017-03-09 | 국방과학연구소 | Metal-organic carbon composites and preparation method thereof |
| CN105384161A (en) * | 2015-11-23 | 2016-03-09 | 南京航空航天大学 | Preparation method and application of graded porous carbon material |
| CN106876730A (en) * | 2015-12-13 | 2017-06-20 | 中国科学院大连化学物理研究所 | The porous carbon-supported base metal elctro-catalyst of N doping is prepared and electro-catalysis application |
| CN106865527A (en) * | 2017-04-14 | 2017-06-20 | 中国科学技术大学 | A kind of synthetic method of carbon nanomaterial and application |
| CN107500262A (en) * | 2017-07-19 | 2017-12-22 | 中国建筑材料科学研究总院 | Porous carbon materials and its preparation method and application |
| CN108147390A (en) * | 2017-12-07 | 2018-06-12 | 西安交通大学 | A kind of metal-natural polyphenol complex nanosphere and its nano porous metal/C-base composte material and preparation method |
| CN110813241A (en) * | 2019-12-17 | 2020-02-21 | 国网山东综合能源服务有限公司 | Nitrogen-oxygen co-doped porous carbon material and preparation method and application thereof |
Non-Patent Citations (3)
| Title |
|---|
| CO2 sorption behavior of imidazole, benzimidazole and benzoic acid based coordination polymers;Rashmi A.Agarwal et al.;《Coordination Chemistry Reviews》;20161105;第332卷;全文 * |
| 配合物为前驱体的多孔金属氧化物制备和表征;陈睿;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20150515(第5期);78-79页 * |
| 金属有机骨架及其衍生结构的构筑与功能特性;李锐;《中国博士学位论文全文数据库 工程科技Ⅰ辑》;20150415(第4期);全文 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN110357068A (en) | 2019-10-22 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN110357068B (en) | Synthetic method of hierarchical porous carbon nano material | |
| Zeng et al. | Core–shell CdS@ ZIF-8 structures for improved selectivity in photocatalytic H 2 generation from formic acid | |
| Ren et al. | Recent progress on MOF‐derived heteroatom‐doped carbon‐based electrocatalysts for oxygen reduction reaction | |
| Yu et al. | Point‐defect engineering: leveraging imperfections in graphitic carbon nitride (g‐C3N4) photocatalysts toward artificial photosynthesis | |
| Sun et al. | N self-doped ZnO derived from microwave hydrothermal synthesized zeolitic imidazolate framework-8 toward enhanced photocatalytic degradation of methylene blue | |
| CN109956463B (en) | Carbon nano tube and preparation method thereof | |
| He et al. | Fast and scalable synthesis of uniform zirconium-, hafnium-based metal–organic framework nanocrystals | |
| Chaemchuen et al. | Robust and efficient catalyst derived from bimetallic Zn/Co zeolitic imidazolate frameworks for CO2 conversion | |
| Shi et al. | Effective exposure of nitrogen heteroatoms in 3D porous graphene framework for oxygen reduction reaction and lithium–sulfur batteries | |
| Xie et al. | Degradation of tetracycline hydrochloride through efficient peroxymonosulfate activation by B, N co-doped porous carbon materials derived from metal-organic frameworks: Nonradical pathway mechanism | |
| Song et al. | Metal/metal oxide nanostructures derived from metal–organic frameworks | |
| Chen et al. | Enhanced photocatalytic degradation of RhB by two-dimensional composite photocatalyst | |
| Feng et al. | Engineering functional mesoporous materials from plant polyphenol based coordination polymers | |
| Zhong et al. | Controllable transformation from 1D Co-MOF-74 to 3D CoCO 3 and Co 3 O 4 with ligand recovery and tunable morphologies: the assembly process and boosting VOC degradation | |
| Zhang et al. | Hollow BCN microrods with hierarchical multichannel structure as a multifunctional material: Synergistic effects of structural topology and composition | |
| CN111056545A (en) | Preparation method of MOFs-derived hollow porous carbon microspheres | |
| CN109950563B (en) | Non-noble metal oxygen reduction reaction catalyst with high-dispersion metal active sites and preparation method thereof | |
| CN103553023A (en) | Preparation method of nitrogen hybridized spherical mesoporous carbon | |
| Zhao et al. | MnOx@ N-doped carbon nanosheets derived from Mn-MOFs and g-C3N4 for peroxymonosulfate activation: Electron-rich Mn center induced by N doping | |
| He et al. | Polymer-coating-induced synthesis of FeNx enriched carbon nanotubes as cathode that exceeds 1.0 W cm− 2 peak power in both proton and anion exchange membrane fuel cells | |
| CN105693506A (en) | Synthesis method of porous titanium crystal metal organic framework material | |
| Ye et al. | Controllable dimensions and regular geometric architectures from self-assembly of lithium-containing polyhedral oligomeric silsesquioxane: Build for enhancing the fire safety of epoxy resin | |
| mei Qi et al. | Design of UiO-66@ BiOIO3 heterostructural composites with remarkable boosted photocatalytic activities in removing diverse industrial pollutants | |
| Huang et al. | Organic frameworks induce synthesis and growth mechanism of well-ordered dumbbell-shaped ZnO particles | |
| Jing et al. | Cyano‐Rich g‐C3N4 in Photochemistry: Design, Applications, and Prospects |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant | ||
| TR01 | Transfer of patent right |
Effective date of registration: 20221026 Address after: 230000 China (Anhui) Pilot Free Trade Zone, Hefei, Anhui Province 2899 Kongquetai Road, High tech Zone, Hefei, Liandong U Valley, Building 4, Hefei Hi tech International Enterprise Port Patentee after: Anhui Weishui New Energy Technology Co.,Ltd. Address before: 230000 96 Jinzhai Road, Hefei City, Anhui Province Patentee before: Liang Haiwei Patentee before: Tong Lei Effective date of registration: 20221026 Address after: 230000 96 Jinzhai Road, Hefei City, Anhui Province Patentee after: Liang Haiwei Patentee after: Tong Lei Address before: 230026 Jinzhai Road, Baohe District, Hefei, Anhui Province, No. 96 Patentee before: University of Science and Technology of China |
|
| TR01 | Transfer of patent right |