CN112299405B - Preparation method of low-temperature easily-graphitized three-dimensional biomass porous carbon with high specific surface area - Google Patents
Preparation method of low-temperature easily-graphitized three-dimensional biomass porous carbon with high specific surface area Download PDFInfo
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- CN112299405B CN112299405B CN202011301688.9A CN202011301688A CN112299405B CN 112299405 B CN112299405 B CN 112299405B CN 202011301688 A CN202011301688 A CN 202011301688A CN 112299405 B CN112299405 B CN 112299405B
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Abstract
The invention discloses a preparation method of a low-temperature easily-graphitized three-dimensional biomass porous carbon with a high specific surface area. The method has the advantages of simple and convenient process, low requirement on equipment, easy implementation and low preparation cost; the high-specific-surface three-dimensional porous carbon prepared by the method has a high specific surface area and abundant three-dimensional structures; can be used as a good adsorbing material. The specific surface area is obviously higher than that of the same material.
Description
Technical Field
The invention belongs to the technical field of adsorption, and relates to a preparation method of three-dimensional high-specific-surface biomass porous carbon, in particular to preparation of three-dimensional biomass porous carbon generated by carbonizing a precursor compound generated by decomposing biomass garlic and cane sugar.
Background
The porous carbon material is a porous material prepared by carbonizing, activating or other methods with a plant source carbon element-containing material or a compound containing carbon elements. The porous carbon material has high specific surface area, developed pore structure, excellent heat resistance, corrosion resistance and other performances, and has good application prospects in the fields of adsorption, catalysis, energy storage and the like.
Dyes are widely used in various industries such as textile, paint, tanning, plastics, rubber, pharmacy, electroplating and food processing, and printing and dyeing wastewater discharged without proper treatment will cause serious damage to aquatic plants and animals. Most synthetic dyes are harmful, thermostable, light-fast, and difficult to biodegrade due to their complex chemical structure. This has led to an increasing demand for effective removal of these dyes from wastewater in the last few decades. Malachite Green (MG) is a basic and cationic triphenylmethane dye that has been widely used in the dyeing of silk, cotton, wool, plastics and paper, and in the fish industry as a germicide and medical disinfectant to control fungal and protozoal infections. However, MG has been reported to produce a number of toxicological symptoms, including carcinogenicity, teratogenicity, mutagenicity and pleural infection. Therefore, in the last few years, much attention has been paid to how to effectively remove toxic and harmful MG from wastewater.
Disclosure of Invention
The invention aims to provide a simple, convenient and environment-friendly preparation method of low-temperature easily-graphitized three-dimensional biomass porous carbon with a high specific surface area, aiming at the defects of the prior art.
In order to achieve the purpose, the invention adopts the following technical scheme:
a preparation method of low-temperature easily-graphitized three-dimensional biomass porous carbon with high specific surface area is characterized by comprising the following steps: adopting cane sugar and zinc nitrate as raw materials, and placing the raw materials in a constant-temperature drying oven at 170 ℃ to dehydrate and decompose the zinc nitrate so as to obtain an initial pore structure; and then adding the biomass garlic slurry, drying, and then putting into a tubular furnace for carbonization under the protection of nitrogen to obtain the three-dimensional biomass porous carbon.
The method specifically comprises the following steps:
(1) treatment of biomass garlic
Cleaning biomass garlic, airing, cutting into small pieces, putting the small pieces into a grinder, adding deionized water, grinding into slurry, and cooling for later use;
(2) treatment of sucrose and zinc nitrate
Weighing sucrose and zinc nitrate, placing the sucrose and the zinc nitrate into a beaker, melting the sucrose and the zinc nitrate in a water bath at 80 ℃, continuously stirring the mixture to be uniformly mixed, immediately transferring the mixture into a constant-temperature drying box at 170 ℃ to react for 1 hour after the mixture is completely melted and uniformly mixed, taking out the mixture after the reaction is completely finished, cooling the mixture, and grinding the mixture into powder to obtain a precursor of the three-dimensional high specific surface porous carbon;
(3) preparation of three-dimensional high-specific-surface easily-graphitized biomass porous carbon
Putting the powdery carbon precursor prepared in the step (2) and the biomass garlic slurry treated in the step (1) into a mortar for grinding to enable the powdery carbon precursor and the biomass garlic slurry to be uniformly mixed, drying, putting the mixture into a corundum ark, carrying out high-temperature annealing treatment in a nitrogen atmosphere tube furnace, and further carrying out graphitization treatment after the annealing treatment;
(4) after graphitization treatment, placing a sample in a beaker, adding 1M dilute hydrochloric acid for acid washing for three times, and washing with deionized water after acid washing until the pH value is not changed; and drying at constant temperature to obtain the porous carbon.
The zinc nitrate used in the step (2) is zinc nitrate hexahydrate.
In the step (2), the mass ratio of the sucrose to the zinc nitrate is 1: 1.
the mass of the garlic pulp in the step (3) is 20% of the total mass of the mixture in the mortar.
The temperature of the high-temperature annealing in the step (3) is 700 ℃, and the time is 3 hours.
In the step (3), the graphitization temperature is 1100 ℃ and the time is 3 hours.
The invention has the beneficial effects that:
(1) the method has the advantages of simple and convenient process, low requirement on equipment, easy implementation and low preparation cost;
(2) the invention has low preparation cost, obvious three-dimensional structure and specific surface area up to 2000cm2The graphite has higher graphitization degree. The higher specific surface area greatly improves the adsorption capacity of the graphite, and the higher graphitization degree increases the conductivity of the graphite. The common activated carbon has poor adsorption capacity due to insufficient specific surface area, and although the specific surface area of the common activated carbon can be increased after activation, the manufacturing cost of the porous carbon is increased and environmental pollution is caused by the activation process. If the common activated carbon is to be graphitized, high-temperature heat treatment above 2000 ℃ is required, which greatly increases the production cost.
Drawings
FIG. 1 is a transmission electron micrograph of a material prepared in example;
FIG. 2 is a high-resolution transmission electron micrograph of a material prepared in example;
FIG. 3 is a BET plot of the material prepared in the examples;
FIG. 4 is a graph showing the adsorption profile of the material prepared in the examples.
Detailed Description
The invention is further illustrated by the following examples, without restricting its scope to these.
Examples
The preparation method of the low-temperature graphitizable three-dimensional biomass porous carbon with the high specific surface area comprises the following steps:
cleaning garlic purchased in the market, putting the garlic into a grinder, adding a certain amount of deionized water, and grinding to obtain slurry for later use.
At room temperature, placing sucrose and zinc nitrate hexahydrate (mass ratio is 1: 1) in a beaker, heating in a water bath to 80 ℃ to completely melt the zinc nitrate hexahydrate, continuously stirring to uniformly mix the sucrose and the zinc nitrate hexahydrate, quickly transferring the mixture into a constant-temperature drying box at 170 ℃ for foaming treatment, taking out the mixture after foaming is completed and cooling, placing the mixture in an agate mortar, grinding the mixture into powder, adding 20 wt% (based on the total mass) of the mixture into the powder, continuously grinding the mixture into uniform mixture, placing the mixture in a corundum square boat, placing the corundum square boat into a tubular furnace, performing high-temperature annealing treatment at 700 ℃ for 2 hours in a nitrogen atmosphere, and then performing high-temperature graphitization at 1100 ℃ for 2 hours. And then placing the obtained sample in a beaker, adding a certain amount of 1M HCl for acid washing for three times, finally washing with deionized water until the pH value is not changed, and placing the sample in a constant-temperature drying oven at 70 ℃ for drying to obtain a sample ZS 2-7-11.
In the adsorption performance test, 66mg/L of malachite green solution is selected for testing, 1mg of ZS2-7-11 is weighed and added into 30ml of 66mg/L of malachite green solution for stirring, and samples are taken once every 5min for 5 times in total.
FIG. 1 is a transmission electron micrograph illustrating a three-dimensional structure according to an embodiment.
FIG. 2 is a high magnification transmission electron micrograph of the example illustrating its high degree of graphitization.
FIG. 3 is a graph of specific surface area of examples illustrating its higher specific surface area and the presence of stacking pores and micropores.
FIG. 4 is a graph showing the adsorption of malachite green, which is a good result.
The above description is only a preferred embodiment of the present invention, and all equivalent changes and modifications made in accordance with the claims of the present invention should be covered by the present invention.
Claims (7)
1. A preparation method of low-temperature easily-graphitized three-dimensional biomass porous carbon with high specific surface area is characterized by comprising the following steps: adopting cane sugar and zinc nitrate as raw materials, and placing the raw materials in a constant-temperature drying oven at 170 ℃ to dehydrate and decompose the zinc nitrate so as to obtain an initial pore structure; and then adding the biomass garlic slurry, drying, and then putting into a tubular furnace for carbonization under the protection of nitrogen to obtain the three-dimensional biomass porous carbon.
2. The method of claim 1, wherein: the method specifically comprises the following steps:
(1) treatment of biomass garlic
Cleaning biomass garlic, airing, cutting into small pieces, putting the small pieces into a grinder, adding deionized water, grinding into slurry, and cooling for later use;
(2) treatment of sucrose and zinc nitrate
Weighing sucrose and zinc nitrate, placing the sucrose and the zinc nitrate into a beaker, melting the sucrose and the zinc nitrate in a water bath at 80 ℃, continuously stirring the mixture to be uniformly mixed, immediately transferring the mixture into a constant-temperature drying box at 170 ℃ to react for 1 hour after the mixture is completely melted and uniformly mixed, taking out the mixture after the reaction is completely finished, cooling the mixture, and grinding the mixture into powder to obtain a precursor of the three-dimensional high specific surface porous carbon;
(3) preparation of three-dimensional high-specific-surface easily-graphitized biomass porous carbon
Putting the powdery precursor prepared in the step (2) and the biomass garlic slurry treated in the step (1) into a mortar for grinding to enable the powdery precursor and the biomass garlic slurry to be uniformly mixed, drying, putting the mixture into a corundum ark, carrying out high-temperature annealing treatment in a nitrogen atmosphere tube furnace, and further carrying out graphitization treatment after the annealing treatment;
(4) after graphitization treatment, placing a sample in a beaker, adding 1M dilute hydrochloric acid for acid washing for three times, and washing with deionized water after acid washing until the pH value is not changed; and drying at constant temperature to obtain the porous carbon.
3. The method of claim 2, wherein: the zinc nitrate used in the step (2) is zinc nitrate hexahydrate.
4. The method of claim 2, wherein: in the step (2), the mass ratio of the sucrose to the zinc nitrate is 1: 1.
5. the method of claim 2, wherein: the mass of the garlic pulp in the step (3) is 20% of the total mass of the mixture in the mortar.
6. The method of claim 2, wherein: the temperature of the high-temperature annealing in the step (3) is 700 ℃, and the time is 3 hours.
7. The method of claim 2, wherein: in the step (3), the graphitization temperature is 1100 ℃ and the time is 3 hours.
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| CN101125190A (en) * | 2007-07-26 | 2008-02-20 | 关艳龙 | Powdered medicine active carbon mixture and preparation method thereof |
| GB2451509B (en) * | 2007-08-02 | 2012-03-14 | Forestry Commission | Charcoals |
| CN101767956B (en) * | 2010-02-04 | 2012-02-01 | 浙江建中竹业科技有限公司 | Bamboo carbon powder molding composition and molding method thereof |
| CN103183341B (en) * | 2013-04-02 | 2015-04-29 | 中国矿业大学 | Controllable synthesis method of N-doped graphitized carbon ball with hollow structures |
| CN105417533A (en) * | 2015-12-22 | 2016-03-23 | 北京理工大学 | Preparation method for graphene with high specific surface area |
| CN105845937B (en) * | 2016-05-12 | 2018-12-11 | 陕西科技大学 | A kind of method that three-dimensional porous carbon skeleton/graphene composite structure is constructed in original position |
| CN106938840A (en) * | 2017-03-20 | 2017-07-11 | 中国科学院宁波材料技术与工程研究所 | The preparation method and its product of a kind of carbon quantum dot for TEMP |
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