CN111994897B - Simple preparation method of honeycomb porous carbon with high specific surface area - Google Patents
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Abstract
The invention relates to a simple preparation method of honeycomb porous carbon with high specific surface area. The method comprises the following steps: mixing zinc acetate and glycerin for reaction to obtain an organic complex containing glyceride acetate and zinc glycerin; and (3) removing the soft template glyceryl acetate after high-temperature calcination and cracking of the organic complex precipitate containing the glyceryl acetate and the zinc glycerate, and then cleaning with dilute acid to remove zinc oxide, and collecting to obtain the honeycomb porous carbon. The method has novel thought and simple and convenient operation, realizes the preparation of the honeycomb porous carbon with high specific surface area by the in-situ dual-template strategy and has the advantages of high specific surface area and uniform pore structure.
Description
Technical Field
The invention belongs to the technical field of nano porous carbon materials, and particularly relates to a preparation method of porous carbon.
Background
The cellular porous carbon has large specific surface area, excellent conductivity and stability, and can be widely applied to various fields such as energy storage and conversion, catalysis, adsorption, environment detection and the like. Therefore, research and development on porous carbon with high specific surface area has attracted a great deal of attention from researchers at home and abroad. The current preparation methods of porous carbon mainly comprise a template method and an activation method, wherein the template method is divided into a hard template and a soft template. The activation method mainly uses various activating agents to etch the carbon material at high temperature to different degrees to obtain porous carbon, and the activating agent with better effect is KOH. However, this method requires high-temperature secondary carbonization, is liable to generate a large amount of impurities, is associated with dangers, has high requirements on equipment and process technology, and is not suitable for mass production applications in laboratories and industries.
The template method is to mix a carbon precursor and a template agent by a physical or chemical method before carbonization, and remove the template agent by high-temperature calcination to obtain the porous carbon. However, the template agent needs to be prepared or purchased in advance, the preparation process is complicated, most of the soft templates are surfactants, and the cost is high. In addition, the uniformity of the carbon precursor and the template agent cannot be ensured by mixing the two, and the order of the pore structure is difficult to controlThe uniformity and homogeneity are difficult to ensure, especially in large-scale production preparations. Some hard templates need to be removed by acid or alkali with stronger corrosiveness, so that higher requirements are put on equipment, and the safety and environmental protection problems are not guaranteed. In order to increase the specific surface area, researchers have tried to prepare porous carbon by using a dual-template method, by selecting two different hard templates to be mixed or reacted with a carbon precursor (for example, chitosan is used as the carbon precursor, and silicon spheres and ZnO are used as the hard templates [ 1)]The method comprises the steps of carrying out a first treatment on the surface of the Gelatin is used as a carbon source, and magnesium nitrate and zinc nitrate are simultaneously used as a hard template [2 ]]) The hard template is removed after carbonization, and in the method, the particle size and the distribution of the hard template have randomness, so that porous carbon with uniform pore distribution is difficult to obtain. Because the hard template has larger size, the pore size distribution of the finally obtained porous carbon is mainly concentrated in mesopores and macropores, the specific surface area is low, and the application is limited. Another dual template strategy is to introduce hard and soft template pore-forming by specific reactions (e.g., phenolic resin as carbon source, ti 3 C 2 T X And F127 micelles as hard and soft templates [3 ] respectively]The method comprises the steps of carrying out a first treatment on the surface of the Polyaniline is used as a carbon source, siO 2 And polymethyl methacrylate as hard template and soft template [4 ] respectively]) The method can obtain the porous carbon with high specific surface area and micropores, mesopores and macropores, so that the application range of the porous carbon is widened, however, the method needs to consider the mixing mode and the mixing uniformity of the hard template, the soft template and the carbon precursor, and has higher requirements on experimental technology, and meanwhile, additional experimental steps are required to be added or other modifiers are introduced, so that the whole preparation process is more complicated and the difficulty is increased. With the extensive research and application of porous carbon in various fields, there is an urgent need to find a more inexpensive and simple preparation technique to obtain porous carbon with high specific surface area uniformity pore structure.
Reference is made to:
[1]Maria
Andrzej Olejniczak,Jerzy P./>
Hierarchical porous carbon templated with silica spheres of a diameter of 14nm from pure chitosan or a chitosan/ZnCl 2 solution.J.Porous Mat.,2018,25,1633-1648.
[2]Chen X.Y.,Chen C.,Zhang Z.J.,Xie D.H.,Gelatin-derived nitrogen-doped porous carbon via a dual-template carbonization method for high performance supercapacitors,J.Mater.Chem.A,2013,1,10903-10911.
[3]Wang J.,Tang J.,Ding B.,Malgras V.,Chang Z.,Hao X.,Wang Y.,Dou H.,Zhang X.,Yamauchi Y.,Hierarchical porous carbons with layer-by-layer motif architectures from confined soft-template self-assembly in layered materials.Nat.Commun.,2017,8,15717-15717.
[4]Wang Q.,Cao Q.,Wang X.,Jing B.,Kuang H.,Zhou L.,Dual template method to prepare hierarchical porous carbon nanofibers for high-power supercapacitors.J.Solid State Electr.,2013,17,2731-2739.
disclosure of Invention
The present invention addresses the above-described problems by providing a simple method for producing a honeycomb porous carbon having a high specific surface area. Solves the problems of high production cost, complex process, difficult pore forming, uneven holes and the like of the existing porous carbon material.
The invention is realized by the following technical scheme:
provided is a simple preparation method of honeycomb porous carbon with high specific surface area, comprising the following steps:
(1) Mixing zinc acetate and glycerin for reaction to obtain an organic complex precipitate containing glyceride acetate and zinc glycerin;
(2) And (3) removing the soft template glyceryl acetate after high-temperature calcination and cracking of the organic complex precipitate containing the glyceryl acetate and the zinc glycerate, and then cleaning with dilute acid to remove the hard template zinc oxide, and collecting to obtain the honeycomb porous carbon.
According to the scheme, the dosage ratio of zinc acetate to glycerin is preferably 2.5-9.2 g zinc acetate based on anhydrous zinc acetate: 100mL of glycerol.
According to the scheme, the zinc acetate is zinc acetate dihydrate or anhydrous zinc acetate.
According to the scheme, in the step (1), after the reaction is finished, the precipitate is collected, washed by ethanol and dried in vacuum to obtain the organic complex precipitate containing the glycerol acetate and the zinc glycerolate for later use.
According to the scheme, the reaction temperature is 120-180 ℃ and the reaction time is 30-300 min. The reaction can be carried out by adopting any heating mode and device, condensed water is needed to be led when the reaction is carried out in the round-bottomed flask, and proper reaction conditions are selected according to the actual reactant consumption.
According to the above scheme, the high temperature calcination of the present invention is required to be carried out under vacuum or inert atmosphere. High purity nitrogen or argon is commonly used as inert shielding gas.
According to the scheme, the dilute acid is dilute hydrochloric acid or dilute sulfuric acid. According to the scheme, the high-temperature calcination temperature ranges from 600 ℃ to 1000 ℃ and the calcination time ranges from 60 min to 180min. The product of the esterification reaction, glycerin acetate, is decomposed out as an in-situ soft template agent in the high-temperature calcination process, and rich uniformity holes are left. Placing the sample in a corundum crucible or a porcelain boat with good texture and high temperature resistance for calcination, and covering; the heating device is a tube furnace or a muffle furnace.
According to the invention, glycerol and zinc acetate are used as raw materials, glycerol is used as a solvent and a reactant at the same time, and the high specific surface area honeycomb porous carbon can be controlled by utilizing an in-situ double-template strategy through simple compounding and esterification reaction (zinc acetate is hydrolyzed at a preset temperature to generate zinc hydroxide, zinc hydroxide is compounded with glycerol to generate zinc glycerate and acetic acid, and residual alcohol hydroxyl in the structure is subjected to esterification reaction with acetic acid to generate glycerol zinc glycerate, so that the organic complex precipitate of glycerol acetate and zinc glycerate with a crosslinked structure is finally generated). Specifically, glycerol is used as a precursor, zinc acetate raw materials are matched, a hydrolysis product zinc hydroxide of zinc acetate in the reaction process is used as a precipitator, reactants participate in the generation of zinc glycerate, and a product zinc oxide obtained after high-temperature calcination is used as an in-situ hard template agent to enrich the pore structure and regulate the morphology of a solid product. The esterified product glycerol acetate of the residual alcoholic hydroxyl and acetic acid in the glycerol zinc structure is a nonionic surfactant, has regular chemical structure characteristics, can be used as a soft template to be present in a final product structure, leaves a large number of uniform holes after high-temperature treatment, and is calcined at a high temperature to obtain a porous carbon and zinc oxide compound. The method for preparing the porous carbon with high specific surface area by the in-situ dual-template is low in cost, simple and feasible, and can realize large-scale production and application. The porous carbon has wide application prospect in the fields of electrocatalysis, adsorption, gas storage, electrochemical energy storage and the like.
According to the invention, the compound reaction and the esterification reaction can be simultaneously regulated and controlled by regulating and controlling the dosage and the reaction condition of the glycerol and the zinc acetate, and the porous carbon structure and the specific surface area are effectively regulated and controlled, so that the adjustability of the porous carbon pore structure and the specific surface area is realized.
The invention has the beneficial effects that:
1. the invention selects the cheap raw materials as the precursor, obtains the organic complex through one-step reaction, generates the soft template and the hard template simultaneously in situ, and then obtains the honeycomb porous carbon with high specific surface area through high-temperature calcination. The preparation of the honeycomb porous carbon with high specific surface area can be controlled by an in-situ dual-template strategy through a simple one-step method, and the method has universality.
2. The raw materials used in the invention are easy to obtain, the price is low, the operation process is safe and simple, and the preparation in large batch can be realized.
3. The porous carbon obtained by the method has high specific surface area and uniform pore structure, and the controllability of the porous structure can be realized by changing reaction conditions, so that the material can be widely applied to various fields.
Drawings
Figure 1 is an XRD pattern of the sample after calcination of example 1.
Fig. 2 is an XRD pattern and a scanning electron microscope pattern of the porous carbon of example 1, wherein: a is XRD pattern, B is scanning electron microscope pattern
FIG. 3 is a graph showing the adsorption-desorption curve and pore size distribution of porous carbon of example 1, wherein: graph A shows the adsorption-desorption curve of nitrogen, and graph B shows the pore size distribution map.
FIG. 4 is a scanning electron microscope image of porous carbon of example 2, wherein: the image A is a low power scanning electron microscope image, and the image B is a high power scanning electron microscope image.
Fig. 5 is a graph showing the nitrogen adsorption-desorption curve and pore size distribution of the porous carbon of example 2, wherein: graph A shows the nitrogen adsorption-desorption curve, and graph B shows the pore size distribution.
FIG. 6 is a transmission electron microscopy image of porous carbon of example 3, wherein: the image A is a low power transmission electron microscope image, and the image B is a high power transmission electron microscope image.
Fig. 7 is a nitrogen adsorption-desorption curve and pore size distribution diagram of the porous carbon of example 3, wherein: graph A shows the adsorption-desorption curve of nitrogen, and graph B shows the pore size distribution map.
FIG. 8 is a transmission electron microscopy image of porous carbon of example 4, wherein: the image A is a low power transmission electron microscope image, and the image B is a high power transmission electron microscope image.
FIG. 9 is a transmission electron microscopy image of porous carbon of example 5, wherein: the image A is a low power transmission electron microscope image, and the image B is a high power transmission electron microscope image.
Detailed Description
Example 1
100mL of glycerin, 2.5g of zinc acetate and heating reflux reaction at 150 ℃ for 2 hours are added into a 250mL round bottom flask, white solid precipitate is collected, washed three times with ethanol and dried in vacuum to obtain organic complex powder.
And (3) placing the obtained product in a tubular furnace, treating at 800 ℃ for 1h under the protection of nitrogen, naturally cooling and lightly grinding to obtain black porous carbon and ZnO mixture powder, and obtaining obvious ZnO characteristic peaks which are consistent with characteristic peaks of standard cards (# 99-0111) of the ZnO mixture powder according to XRD test results (figure 1).
Adding the powder into a dilute hydrochloric acid solution, stirring to remove a hard template, washing with water to be neutral, and drying to obtain the honeycomb porous carbon.
Characterization of the material using an X-ray diffractometer and scanning electron microscope revealed that the resulting porous carbon was free of impurities, with abundant macropores and mesopores of uniform pore size (fig. 2).
FIG. 3 is a graph showing the adsorption-desorption curve and pore size distribution of nitrogen in the porous carbon obtained in the present example, and the test result shows that the porous carbon has a honeycomb structure with a BET specific surface area of 2212m 2 g -1 The micropore diameter distribution is concentrated at 1.09nm, the mesopore diameter distribution is concentrated at 13.21nm, and the total pore volume reaches 5.16cm 3 g -1 。
Example 2
4.2g of zinc acetate is weighed into a high-pressure reaction kettle, 100mL of glycerol is added, after stirring and dissolution, the solvent thermal reaction is kept at 150 ℃ for 1h, and white precipitate is obtained by centrifugal alcohol washing.
Under the protection of nitrogen, the obtained product is treated for 2 hours at 600 ℃ and is ground to obtain the mixture of porous carbon and zinc oxide.
Adding the mixture into a dilute hydrochloric acid solution, performing ultrasonic dispersion, stirring overnight, washing with water to neutrality, and drying to obtain the honeycomb porous carbon with high specific surface area.
As shown in FIG. 4, the obtained porous carbon has a rich pore structure, and the pores are uniformly distributed in the whole carbon body structure and are in a honeycomb shape as seen from an enlarged scanning electron microscope.
FIG. 5 is a graph showing the adsorption-desorption curve and pore size distribution of porous carbon in this example, showing that the material has a high adsorption capacity of nitrogen and a BET specific surface area of up to 2089m 2 g -1 From the pore size distribution map of the material, it was found that the mesoporous pore size distribution thereof was concentrated at 13.54nm, and the average microporous pore size was 1.10nm.
Example 3
5.9g of zinc acetate was weighed and placed in a round bottom flask, 100mL of glycerol was added and stirred for reaction, and the reaction was kept at 120℃for 5 hours under reflux. And collecting the precipitate after the reaction, and obtaining the organic complex after centrifugal alcohol washing and drying.
And (3) placing the solid in a tube furnace for vacuum calcination, preserving the temperature for 3 hours at 900 ℃ to obtain black solid, grinding the product which is zinc oxide and porous carbon, adding dilute hydrochloric acid to remove a hard template, washing with water to be neutral, and vacuum drying the final black solid to obtain honeycomb porous carbon.
The porous carbon in this example is seen from the transmission electron microscope image of FIG. 6The pores are very abundant, a large number of pores of about 10-20nm are uniformly distributed in the whole carbon body structure, and the pore walls are thinner. FIG. 7 shows that the mesoporous pore size distribution of the porous carbon obtained in this example is mainly concentrated at 12.96nm, and the nitrogen adsorption amount is as high as 6852cm 3 g -1 The total pore volume is 7.80cm 3 g -1 Its specific surface area is up to 3526m 2 g -1 。
Example 4
9g of zinc acetate dihydrate is weighed and mixed with 100mL of glycerin, the mixture is subjected to reflux reaction for 30min through a round bottom flask at the temperature of 180 ℃, the precipitate is collected after centrifugation, and the precipitate is obtained after centrifugal washing with ethanol for three times and drying.
And (3) calcining the obtained solid in a tube furnace, introducing nitrogen for protection, and preserving heat for 2 hours at 700 ℃ to obtain black solid. The solid is a mixture of zinc oxide and porous carbon, the zinc oxide is etched by dilute hydrochloric acid, the zinc oxide is washed until the zinc oxide is neutral, the final black solid is collected, and the honeycomb porous carbon is obtained by drying in a vacuum drying oven.
Fig. 8 is a transmission electron microscope image of the porous carbon obtained in this example, and it is obvious that the abundant pores are uniformly distributed in the carbon body structure, and the carbon wall is thinner. The porous carbon in this example has a specific surface area of 2241m 2 g -1 The average mesoporous diameter is 13.83nm, the average microporous diameter is 1.06nm, and the total pore volume is 5.91cm 3 g -1 。
Example 5
9.2g of zinc acetate was added to a round bottom flask containing 100mL of glycerol, and the mixture was refluxed at 160℃for 2.5 hours, and a white precipitate was collected, washed with alcohol and dried to obtain a precipitate.
The solid was placed in a 1000 ℃ tube furnace and calcined with nitrogen for 1.5 hours to obtain a solid comprising zinc oxide and porous carbon. The solid was washed with dilute hydrochloric acid, dried, ground to a powder and collected to give a black cellular porous carbon.
Fig. 9 is a transmission electron microscope of the porous carbon in this example, and it is obvious that a large number of holes with uniform distribution exist in the powder structure. The porous carbon in this example had a specific surface area of 2278m 2 g -1 The total pore volume is 5.08cm 3 g -1 Average microThe pore diameter was 1.08nm and the average mesoporous diameter was 12.95nm.
In summary, the preparation method of the porous carbon is simple to operate, mild in technological conditions, and mainly utilizes the combination and esterification reaction of glycerol and different amounts of zinc acetate under different conditions to prepare an organic complex, an inorganic hard template and an organic soft template are generated at the same time in situ in one step, and pyrolysis and etching pore forming are combined, so that the honeycomb porous carbon material with a uniform pore structure and a high specific surface area is obtained. The adjustability of the porous carbon pore structure can be realized by controlling experimental conditions, so that the method is suitable for mass preparation of high-quality porous carbon materials. In addition, the invention effectively overcomes various problems and a plurality of defects existing in the prior art, and has important industrial production and utilization values.
The above 5 embodiments are only for illustrating the invention, and are not intended to limit the invention, and any experimental principles, techniques, methods similar to the invention are still covered by the claims of the present invention.
Claims (5)
1. A simple preparation method of honeycomb porous carbon with high specific surface area is characterized by comprising the following steps: mixing zinc acetate and glycerin for reaction to obtain an organic complex containing glyceride acetate and zinc glycerin, wherein: the dosage ratio of zinc acetate to glycerin is 2.5-9.2 g zinc acetate based on anhydrous zinc acetate: 100 Glycerin mL;
and (3) removing the soft template glyceryl acetate after high-temperature calcination and cracking of the organic complex precipitate containing the glyceryl acetate and the zinc glycerate, wherein the high-temperature calcination temperature is 600-1000 ℃ and the calcination time is 60-180 min, removing zinc oxide by washing with dilute acid, and collecting the honeycomb porous carbon.
2. The simple preparation method as claimed in claim 1, wherein: the zinc acetate is zinc acetate dihydrate or anhydrous zinc acetate.
3. The simple preparation method as claimed in claim 1, wherein: the reaction temperature is 120-180 ℃ and the reaction time is 30-300 min.
4. The simple preparation method as claimed in claim 1, wherein: the high temperature calcination is performed under vacuum or an inert atmosphere.
5. The simple preparation method as claimed in claim 1, wherein: the dilute acid is dilute hydrochloric acid or dilute sulfuric acid.
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| CN104282913A (en) * | 2014-10-23 | 2015-01-14 | 安徽师范大学 | Sheet-shaped porous carbon cladded ZnO nano composite material as well as preparation method and application thereof |
| RU2681005C1 (en) * | 2017-12-04 | 2019-03-01 | Федеральное государственное бюджетное учреждение науки Институт химии твердого тела Уральского отделения Российской академии наук | Method of obtaining mesoporous carbon |
| CN109761216A (en) * | 2019-03-22 | 2019-05-17 | 大连理工大学 | A kind of general, method that porous carbon materials are prepared based on organic zinc salt |
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