CN109879269B - Method for synthesizing mesoporous carbon material by using bamboo powder as carbon source - Google Patents
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Abstract
A method for synthesizing mesoporous carbon material by using bamboo powder as a carbon source comprises the following steps: (1) pre-treating; (2) degradation treatment; (3) oxidation treatment; (4) hydrothermal synthesis; (5) and (4) heating and carbonizing. The method takes bamboo powder as a biological carbon source, and utilizes a soft template method to hydrothermally synthesize the ordered mesoporous carbon material with high specific surface area, wherein the aperture is 4.2-5.0 nm, and the pore volume is 0.2-0.4 cm 3 Per gram, specific surface area of 372.6m 2 (iv) g. The raw materials used in the invention have wide sources and low price, so the production cost is low, and the materials in the whole synthesis process belong to green, environment-friendly and renewable materials, thereby conforming to the green chemical synthesis concept.
Description
Technical Field
The invention relates to a method for synthesizing a mesoporous carbon material, in particular to a method for synthesizing a mesoporous carbon material by taking bamboo powder as a carbon source.
Background
The mesoporous carbon material has the characteristics of large specific surface area, uniform and adjustable mesoporous aperture, good stability and conductivity and the like, and has wide application prospects in various fields such as adsorption and separation, catalysis, gas storage, electrochemical energy storage and conversion, and even biomedicine.
The synthesis of ordered mesoporous carbon mainly comprises a hard template method and a soft template method. Although the hard template method requires additional steps to prepare the mesoporous silica template, mesoscopic channels of the prepared ordered mesoporous carbon are generated by stacking pores among carbon rods, the pore size distribution is wide, a silicon-based mesoporous material serving as the hard template cannot be recycled, the cost is expensive, the process is complex and the time is consuming. Therefore, this preparation method cannot be used for mass production and industrial application. The soft template method is also called an organic-organic template method or a supramolecular template method, and is different from a hard template material for maintaining a structure through a covalent bond, and the material used as the soft template is a soft substance with a specific structure and forms and maintains a mesoporous structure through intermolecular or intramolecular non-covalent bond acting force (short-range repulsion and long-range attraction). According to the difference of Synthesis process, the soft template method has three main Synthesis routes, namely hydrothermal Synthesis (hydro Synthesis), solvent volatilization induced self-assembly (EISA) and low-temperature aqueous phase Synthesis (aqueous route).
The prior art for preparing mesoporous carbon materials still has some defects to be overcome, for example, H is mostly needed to be used 3 PO 3 、ZnCl 2 And the alkali is used as an active agent to change the property of the carbon material, a large amount of organic solvent is consumed, environmental pollution is caused, the preparation cost of the carbon source is too high, and the industrial production is not facilitated.
CN 106542515A discloses a method for synthesizing a mesoporous carbon material; dissolving a carbon precursor and a template agent in water to form a uniform solution, wherein the mass of the carbon precursor is 0.5-10%, the mass of the template agent is 0.2-2%, and the balance is water solvent; the obtained solution is spin-coated or directly poured on the surface of a container to form a coating film; placing the coated container in a closed device, and vacuumizing at room temperature to 70 ℃ to completely volatilize the solvent water; placing the obtained sample at 80-150 ℃ for further thermal polymerization and curing for 10-60 h; and roasting the cured sample at 600-1000 ℃ under the protection of nitrogen to obtain the ordered mesoporous carbon material. The carbon precursor used in the method has higher cost and high requirements on instruments and equipment, and is not suitable for large-scale production.
Disclosure of Invention
The invention aims to solve the technical problems of overcoming the defects in the prior art and providing the method for synthesizing the mesoporous carbon material by taking the bamboo powder as the carbon source, which has the advantages of easily available raw materials, low instrument requirement, low production cost and environmental friendliness.
The technical scheme adopted by the invention for solving the technical problems is as follows: a method for synthesizing mesoporous carbon material by using bamboo powder as a carbon source comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with acid solution to remove impurities, and drying to obtain impurity-removed bamboo powder;
(2) degradation treatment: removing impurities from bamboo powder and FeCl 3 Mixing the acidic solutions uniformly, performing degradation reaction, cooling, collecting degradation reaction products, washing with boiling water, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding hydrogen peroxide solution into black solid bamboo powder in a reaction bottle, heating, stirring until the black solid bamboo powder is completely dissolved, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: taking brown-yellow solid bamboo powder as a carbon source, a nonionic surfactant as a template agent and a polyol substance as a cross-linking agent, and carrying out hydrothermal synthesis to obtain a black-brown solid, namely a carbonized substrate;
(5) heating and carbonizing: and (3) heating the carbonized substrate by a stepped program under the rare gas atmosphere, and heating and carbonizing to obtain the mesoporous carbon material.
Further, in the step (4), the carbon source, the template agent and the cross-linking agent are as follows: the mass ratio of the water is 0.5-5: 0.5-6: 1-5: 10-60, preferably 1-3: 20-50, and more preferably 1.5-2: 1.6-2.8: 40.
Further, the template agent in the step (4) is a nonionic surfactant template agent P123; the cross-linking agent is glycerol.
Further, the stepwise temperature programming in the step (5) is to perform stepwise heating carbonization at a temperature rise rate of 1 ℃/min, and comprises two carbonization stages; the heat preservation temperature of the first carbonization stage is 300-500 ℃, and the retention time is 0.5-1.5 h; the heat preservation temperature of the second carbonization stage is 700-900 ℃, and the retention time is 2-4 h.
Further, the FeCl in the step (2) 3 The adding amount of the acid solution is 1-3 times of the mass of the pretreated bamboo powder.
Further, the degradation reaction in the step (2) is hydrothermal for 8-10 h (preferably 9 h) at the temperature of 150-180 ℃.
Further, in the step (3), the hydrogen peroxide solution is added in an amount of 25 to 40% by mass (preferably 30%) based on the mass of the black solid bamboo powder by 2 to 5 times (preferably 3 times).
Further, the heating temperature in the step (3) is 90-100 ℃.
The invention has the beneficial effects that: bamboo powder is used as a biological carbon source, raw materials are easy to obtain, the requirements on instruments are low, the production cost is low, the soft template method is utilized to hydrothermally synthesize the ordered mesoporous carbon material with high specific surface area, the aperture is 4.2-5.0 nm, and the pore volume is 0.2-0.4 cm 3 Per gram, the specific surface area is 372.6m 2 (ii)/g; the materials used in the whole synthesis process are green renewable materials, and accord with the synthesis concept of green chemistry.
Drawings
FIG. 1 is an IR spectrum of a carbon source used in example 1 of the present invention (carbon 1 is a carbon source which has not been subjected to hydrogen peroxide treatment, and carbon 2 is a carbon source which has been subjected to hydrogen peroxide treatment);
FIG. 2 is a UV spectrum of a raw carbon source used in example 1 of the present invention;
FIG. 3 is a mass spectrum 1 of a raw carbon source used in example 1 of the present invention;
FIG. 4 is a mass spectrum 2 of a raw carbon source used in example 1 of the present invention;
FIG. 5 is a diagram illustrating the distribution of the pore size of mesoporous carbon prepared in example 1 of the present invention;
FIG. 6 is a characteristic nitrogen adsorption-desorption isotherm plot of the mesoporous carbon prepared in example 1 of the present invention;
FIG. 7 is a transmission electron micrograph of mesoporous carbon prepared in example 2 of the present invention.
Detailed Description
The invention is further illustrated by the following examples and figures.
The chemical reagents used in the examples of the present invention, unless otherwise specified, are commercially available in a conventional manner.
Example 1
The embodiment comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with 5 wt% hydrochloric acid solution at 100 deg.C for 4 hr, removing metal impurities from bamboo powder, and oven drying in 105 deg.C oven to obtain impurity-removed bamboo powder;
(2) degradation treatment: removing impurities from 6g of bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acid solution mix well (6 g FeCl) 3 6H 2 Adding O into bamboo powder, adding 4 drops of 37% hydrochloric acid solution, performing degradation treatment (9 h in a 180 ℃ oven), cooling, collecting reaction product, washing with 100 ℃ water for 0.5h, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding 3g of the black solid bamboo powder obtained in the step (2) into a reaction bottle, adding 30mL of hydrogen peroxide solution (mass fraction of 30%), heating to 100 ℃ under stirring, continuously stirring for 3h to completely dissolve the black solid bamboo powder, adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water to serve as a template agent, adding 2.8mL of glycerol to serve as a cross-linking agent, and continuously stirring; taking 3g of the brown yellow solid bamboo powder obtained in the step (3) as a carbon source, dissolving the carbon source in 30mL of deionized water, adding the deionized water into the template agent, stirring for 2h at 40 ℃, putting the obtained mixed solution into a hydrothermal reaction kettle, and performing hydrothermal reaction for three days at 130 ℃; filtering, drying and collecting black brown solid which is the carbonized substrate;
(5) heating and carbonizing: heating and carbonizing a carbonized substrate by a stepped temperature program (1 ℃/min) under the nitrogen atmosphere, carbonizing at 300 ℃ for 1.5h, and then carbonizing at 700 ℃ for 2h to obtain a black solid, namely the mesoporous carbon material.
An infrared spectrum and an ultraviolet spectrum of the carbon source used in this example; the mass spectrum 1 and the mass spectrum 2 are respectively shown in the figure 1, the figure 2, the figure 3 and the figure 4; the distribution diagram of the pore diameter and the characteristic nitrogen adsorption-desorption isotherm diagram of the mesoporous carbon are shown in FIG. 5 and FIG. 6, respectively.
The mesoporous carbon material prepared by the embodiment has the aperture of 4.6nm and the specific surface area of 368.5 m 2 G, pore volume 0.27 cm 3 /g。
Example 2
The embodiment comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with 5% hydrochloric acid solution at 100 deg.C for 4 hr, removing metal impurities in bamboo powder, and oven drying in 105 deg.C oven to obtain bamboo powder with impurities removed;
(2) degradation treatment: removing impurities from 6g of bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acidic solution (6 g FeCl) 3 6H 2 Adding O into bamboo powder, adding 4 drops of 37% hydrochloric acid, performing degradation treatment (heating in oven at 180 deg.C for 9 hr), cooling, collecting reaction product, washing at 100 deg.C for 0.5 hr, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding 30mL of hydrogen peroxide solution (mass fraction of 30%) into 3g of the black solid bamboo powder obtained in the step (2) in a reaction bottle, heating to 100 ℃ under stirring, continuously stirring for 3h to completely dissolve the black solid bamboo powder, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water to serve as a template agent, adding 1.6mL of glycerol to serve as a cross-linking agent, and continuously stirring; and (3) taking 3g of brown solid bamboo powder obtained in the step (3) as a carbon source, dissolving in 30mL of deionized water, adding into the template agent, stirring for 2h at 40 ℃, putting the obtained mixed solution into a hydrothermal reaction kettle, and carrying out hydrothermal treatment at 130 ℃ for three days. Filtering, drying and collecting a black brown solid which is a carbonized substrate;
(5) heating and carbonizing: heating and carbonizing the carbonized substrate by a stepped temperature program (1 ℃/min) under the nitrogen atmosphere, carbonizing at 300 ℃ for 1.5h, and then carbonizing at 700 ℃ for 2h to obtain the collected black solid, namely the mesoporous carbon material.
FIG. 7 is a transmission electron micrograph of mesoporous carbon prepared in example 2 of the present invention.
The mesoporous carbon material prepared in the embodiment has the pore diameter of 4.8nm and the specific surface area of 370.6 m 2 G, pore volume 0.40 cm 3 /g。
Example 3
The embodiment comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with 5% hydrochloric acid solution at 100 deg.C for 4 hr, removing metal impurities in bamboo powder, and oven drying in 105 deg.C oven to obtain bamboo powder with impurities removed;
(2) degradation treatment: removing impurities from 6g of bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acidic solution (6 g FeCl) 3 6H 2 Adding O into bamboo powder, adding 4 drops of 37% hydrochloric acid, performing degradation treatment (heating in oven at 180 deg.C for 9 hr), cooling, collecting reaction product, washing at 100 deg.C for 0.5 hr, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding 30mL of hydrogen peroxide solution (30 wt%) into 3g of the black solid bamboo powder obtained in step (2) in a reaction bottle, heating to 100 deg.C under stirring, stirring for 3 hr to completely dissolve the black solid bamboo powder, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water to serve as a template agent, adding 1.6mL of glycerol to serve as a cross-linking agent, continuously stirring, taking 1.5g of brown yellow solid obtained in the step (3) as a carbon source, dissolving in 30mL of deionized water, adding into the template agent, and stirring for 2 hours at 40 ℃; putting the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal treatment at 130 ℃ for three days, filtering, drying, and collecting black brown solid, namely the carbonized substrate;
(5) heating and carbonizing: heating and carbonizing the carbonized substrate by a stepwise temperature program (1 ℃/min) under the nitrogen atmosphere, carbonizing at 300 ℃ for 1.5h, then carbonizing at 700 ℃ for 2h, and collecting black solids to obtain the mesoporous carbon material.
The mesoporous carbon material prepared by the embodiment has the aperture of 4.7nm and the specific surface area of 359.8m 2 G, pore volume 0.29cm 3 /g。
Example 4
The method comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with 5% hydrochloric acid solution at 100 deg.C for 4 hr, removing metal impurities in bamboo powder, and oven drying in 105 deg.C oven to obtain bamboo powder with impurities removed;
(2) degradation treatment: 6g of impurity-removed bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acidic solution (6 g FeCl) 3 6H 2 Adding O into bamboo powder, adding 4 drops of 37% hydrochloric acid, performing degradation treatment (heating in oven at 180 deg.C for 9 hr), cooling, collecting reaction product, washing at 100 deg.C for 0.5 hr, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding 30mL of hydrogen peroxide solution (30 wt%) into 3g of the black solid bamboo powder obtained in step (2) in a reaction bottle, heating to 100 deg.C under stirring, stirring for 3 hr to completely dissolve the black solid bamboo powder, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water, adding 1.6mL of glycerol, stirring, dissolving 3g of the brown yellow solid (carbon source) in 30mL of deionized water, adding the mixture into a surfactant solution, stirring for 2h at 40 ℃, putting the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 130 ℃ for three days, filtering, drying, and collecting a black brown solid, namely a carbonized substrate;
(5) heating and carbonizing: heating and carbonizing the carbonized substrate by a stepwise temperature program (1 ℃/min) under the nitrogen atmosphere, carbonizing at 400 ℃ for 1.5h, then carbonizing at 700 ℃ for 2h, and collecting black solids to obtain the mesoporous carbon material.
The mesoporous carbon material prepared in the example has the pore diameter of 4.3nm and the specific surface area of 355.6 m 2 G, pore volume 0.30 cm 3 /g。
Example 5
The embodiment comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with 5% hydrochloric acid solution at 100 deg.C for 4 hr, removing metal impurities from bamboo powder, and oven drying in 105 deg.C oven to obtain impurity-removed bamboo powder;
(2) degradation treatment: in that6g of impurity-removed bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acidic solution (6 g FeCl) 3 6H 2 Adding O into bamboo powder, adding 4 drops of 37% hydrochloric acid, performing degradation treatment (heating in oven at 180 deg.C for 9 hr), cooling, collecting reaction product, washing at 100 deg.C for 0.5 hr, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding 30mL of hydrogen peroxide solution (30 wt%) into 3g of the black solid bamboo powder obtained in step (2) in a reaction bottle, heating to 100 deg.C under stirring, stirring for 3 hr to completely dissolve the black solid bamboo powder, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water to serve as a template, adding 1.6mL of glycerol to serve as a cross-linking agent, continuously stirring, taking 3g of brown-yellow solid bamboo powder obtained in the step (3) as a carbon source, dissolving in 30mL of deionized water, adding into the template, stirring for 2h at 40 ℃, putting the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 130 ℃ for three days, filtering, drying, and collecting black-brown solid to serve as a carbonized substrate;
(5) heating and carbonizing: heating and carbonizing the carbonized substrate by a stepwise temperature program (1 ℃/min) under the nitrogen atmosphere, carbonizing at 500 ℃ for 1.5h, then carbonizing at 700 ℃ for 2h, and collecting the obtained black solid to obtain the mesoporous carbon material.
The mesoporous carbon material prepared by the embodiment has the aperture of 4.3nm and the specific surface area of 360.8 m 2 G, pore volume 0.32 cm 3 /g。
Example 6
The embodiment comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with 5% hydrochloric acid solution at 100 deg.C for 4 hr, removing metal impurities in bamboo powder, and oven drying in 105 deg.C oven to obtain bamboo powder with impurities removed;
(2) degradation treatment: removing impurities from 6g of bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acidic solution (6 g FeCl) 3 6H 2 Adding O into bamboo powder, adding 4 drops of 37% hydrochloric acid, performing degradation treatment (heating in oven at 180 deg.C for 9 hr), cooling, collecting reaction product, washing at 100 deg.C for 0.5 hr, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding 30mL of hydrogen peroxide solution (mass fraction of 30%) into 3g of the black solid bamboo powder obtained in the step (2) in a reaction bottle, heating to 100 ℃ under stirring, continuously stirring for 3h to completely dissolve the black solid bamboo powder, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water to serve as a template, adding 1.6mL of glycerol to serve as a cross-linking agent, continuously stirring, taking 3g of brown-yellow solid bamboo powder obtained in the step (3) as a carbon source, dissolving in 30mL of deionized water, adding into the template, stirring for 2h at 40 ℃, putting the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 130 ℃ for three days, filtering, drying, and collecting black-brown solid to serve as a carbonized substrate;
(5) heating and carbonizing: heating and carbonizing the carbonized substrate by stepwise temperature programming (1 ℃/min) under the nitrogen atmosphere, carbonizing at 300 ℃ for 1.5h, then carbonizing at 600 ℃ for 2h, and collecting the obtained black solid to obtain the mesoporous carbon material.
The mesoporous carbon material prepared by the embodiment has the aperture of 4.9nm and the specific surface area of 310.5 m 2 G, pore volume 0.22 cm 3 /g。
Example 7
The embodiment comprises the following steps:
(1) removing impurities from the bamboo powder, namely washing the bamboo powder with a hydrochloric acid solution with the mass fraction of 5% at 100 ℃ for 4h, removing metal impurities in the bamboo powder, and drying in an oven at 105 ℃ to obtain the impurity-removed bamboo powder;
(2) degradation treatment: 6g of impurity-removed bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acidic solution (6 g FeCl) 3 6H 2 O is prepared into solution and added into the bamboo powder, 4 drops of hydrochloric acid with the mass concentration of 37 percent are added in the process) and are mixed evenlyPerforming degradation treatment (heating in an oven at 180 deg.C for 9 h), cooling, collecting reaction product, washing with water at 100 deg.C for 0.5h, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding 30mL of hydrogen peroxide solution (30 wt%) into 3g of the black solid bamboo powder obtained in step (2) in a reaction bottle, heating to 100 deg.C under stirring, stirring for 3 hr to completely dissolve the black solid bamboo powder, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water to serve as a template, adding 1.6mL of glycerol to serve as a cross-linking agent, continuously stirring, taking 3g of brown-yellow solid bamboo powder obtained in the step (3) as a carbon source, dissolving in 30mL of deionized water, adding into the template, stirring for 2h at 40 ℃, putting the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 130 ℃ for three days, filtering, drying, and collecting black-brown solid to serve as a carbonized substrate;
(5) heating and carbonizing: heating and carbonizing the carbonized substrate by stepwise temperature programming (1 ℃/min) under the nitrogen atmosphere, carbonizing at 300 ℃ for 1.5h, then carbonizing at 500 ℃ for 2h, and collecting the obtained black solid to obtain the mesoporous carbon material.
The mesoporous carbon material prepared by the embodiment has the aperture of 5.0nm and the specific surface area of 280.6 m 2 G, pore volume 0.20 cm 3 /g。
Example 8
The embodiment comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with 5% hydrochloric acid solution at 100 deg.C for 4 hr, removing metal impurities in bamboo powder, and oven drying in 105 deg.C oven to obtain bamboo powder with impurities removed;
(2) degradation treatment: removing impurities from 6g of bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acidic solution (6 g FeCl) 3 6H 2 Adding O into bamboo powder, adding 4 drops of 37% hydrochloric acid, performing degradation treatment (water heating in oven at 180 deg.C for 9 hr), cooling, collecting reaction product, washing with 100 deg.C water for 0.5 hr,drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding 30mL of hydrogen peroxide solution (30 wt%) into 3g of the black solid bamboo powder obtained in step (2) in a reaction bottle, heating to 100 deg.C under stirring, stirring for 3 hr to completely dissolve the black solid bamboo powder, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water to serve as a template, adding 1.6mL of glycerol to serve as a cross-linking agent, continuously stirring, taking 3g of brown-yellow solid bamboo powder obtained in the step (3) as a carbon source, dissolving in 30mL of deionized water, adding into the template, stirring for 2h at 40 ℃, putting the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 130 ℃ for three days, filtering, drying, and collecting black-brown solid to serve as a carbonized substrate;
(5) heating and carbonizing: heating and carbonizing the carbonized substrate by a stepwise temperature program (1 ℃/min) under the nitrogen atmosphere, carbonizing at 300 ℃ for 0.5h, then carbonizing at 700 ℃ for 2h, and collecting the obtained black solid to obtain the mesoporous carbon material.
The mesoporous carbon material prepared by the embodiment has the aperture of 4.6nm and the specific surface area of 349.2 m 2 G, pore volume 0.32 cm 3 /g。
Example 9
The embodiment comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with 5% hydrochloric acid solution at 100 deg.C for 4 hr, removing metal impurities from bamboo powder, and oven drying in 105 deg.C oven to obtain impurity-removed bamboo powder;
(2) degradation treatment: removing impurities from 6g of bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acidic solution (6 g FeCl) 3 6H 2 Adding O into bamboo powder, adding 4 drops of 37% hydrochloric acid, performing degradation treatment (heating with water in oven at 180 deg.C for 9 hr), cooling, collecting reaction product, washing with water at 100 deg.C for 0.5 hr, and drying to obtain black solid bamboo powder;
(3) oxidation treatment:adding 30mL of hydrogen peroxide solution (mass fraction of 30%) into 3g of the black solid bamboo powder obtained in the step (2) in a reaction bottle, heating to 100 ℃ under stirring, continuously stirring for 3h to completely dissolve the black solid bamboo powder, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water to serve as a template, adding 1.6mL of glycerol to serve as a cross-linking agent, continuously stirring, taking 3g of brown-yellow solid bamboo powder obtained in the step (3) as a carbon source, dissolving in 30mL of deionized water, adding into the template, stirring for 2h at 40 ℃, putting the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 130 ℃ for three days, filtering, drying, and collecting black-brown solid to serve as a carbonized substrate;
(5) heating and carbonizing: heating and carbonizing the carbonized substrate by a stepped temperature program (1 ℃/min) under the nitrogen atmosphere, carbonizing at 300 ℃ for 1h, then carbonizing at 700 ℃ for 2h, and collecting the obtained black solid to obtain the mesoporous carbon material.
The mesoporous carbon material prepared by the embodiment has the aperture of 4.4nm and the specific surface area of 358.4 m 2 G, pore volume 0.34 cm 3 /g。
Example 10
The embodiment comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with 5% hydrochloric acid solution at 100 deg.C for 4 hr, removing metal impurities in bamboo powder, and oven drying in 105 deg.C oven to obtain bamboo powder with impurities removed;
(2) degradation treatment: 6g of impurity-removed bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acidic solution (6 g FeCl 3 6H 2 Adding O into bamboo powder, adding 4 drops of 37% hydrochloric acid, performing degradation treatment (heating in oven at 180 deg.C for 9 hr), cooling, collecting reaction product, washing at 100 deg.C for 0.5 hr, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding 30mL of hydrogen peroxide solution (mass) into 3g of the black solid bamboo powder obtained in the step (2) in a reaction bottle30 percent of the weight fraction), heating to 100 ℃ under the stirring state, continuously stirring for 3 hours, completely dissolving the black solid bamboo powder, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water to serve as a template, adding 1.6mL of glycerol to serve as a cross-linking agent, continuously stirring, taking 3g of brown-yellow solid bamboo powder obtained in the step (3) as a carbon source, dissolving in 30mL of deionized water, adding into the template, stirring for 2h at 40 ℃, putting the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 130 ℃ for three days, filtering, drying, and collecting black-brown solid to serve as a carbonized substrate;
(5) heating and carbonizing: heating and carbonizing the carbonized substrate by a stepwise program (1 ℃/min) under the nitrogen atmosphere condition, carbonizing for 1.5h at 300 ℃, carbonizing for 3h at 700 ℃, and collecting the obtained black solid to obtain the mesoporous carbon material.
The mesoporous carbon material prepared by the embodiment has the aperture of 4.5nm and the specific surface area of 361.4 m 2 G, pore volume 0.36 cm 3 /g。
Example 11
The embodiment comprises the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with 5% hydrochloric acid solution at 100 deg.C for 4 hr, removing metal impurities from bamboo powder, and oven drying in 105 deg.C oven to obtain impurity-removed bamboo powder;
(2) degradation treatment: 6g of impurity-removed bamboo powder and FeCl in a hydrothermal reaction kettle 3 Acidic solution (6 g FeCl) 3 6H 2 Adding O into bamboo powder, adding 4 drops of 37% hydrochloric acid, performing degradation treatment (heating in oven at 180 deg.C for 9 hr), cooling, collecting reaction product, washing at 100 deg.C for 0.5 hr, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding 30mL of hydrogen peroxide solution (mass fraction of 30%) into 3g of the black solid bamboo powder obtained in the step (2) in a reaction bottle, heating to 100 ℃ under stirring, and continuing stirring for 3h to completely dissolve the black solid bamboo powderAdding MnO again after dissolving 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: dissolving 2g of nonionic surfactant P123 in 40mL of deionized water to serve as a template, adding 1.6mL of glycerol to serve as a cross-linking agent, continuously stirring, taking 3g of brown-yellow solid bamboo powder obtained in the step (3) as a carbon source, dissolving in 30mL of deionized water, adding into the template, stirring for 2h at 40 ℃, putting the mixed solution into a hydrothermal reaction kettle, carrying out hydrothermal reaction at 130 ℃ for three days, filtering, drying, and collecting black-brown solid to serve as a carbonized substrate;
(5) heating and carbonizing: heating and carbonizing the carbonized substrate by a stepped temperature program (1 ℃/min) under the nitrogen atmosphere, carbonizing at 300 ℃ for 1.5h, then carbonizing at 700 ℃ for 4h, and collecting the obtained black solid to obtain the mesoporous carbon material.
The mesoporous carbon material prepared by the embodiment has the aperture of 4.7nm and the specific surface area of 372.0 m 2 G, pore volume 0.37 cm 3 /g。
Claims (7)
1. A method for synthesizing a mesoporous carbon material by taking bamboo powder as a carbon source is characterized by comprising the following steps:
(1) removing impurities from bamboo powder: washing bamboo powder with acid solution to remove impurities, and drying to obtain impurity-removed bamboo powder;
(2) degradation treatment: removing impurities from bamboo powder and FeCl 3 Mixing the acidic solutions uniformly, performing degradation reaction, cooling, collecting degradation reaction products, washing with boiling water, and drying to obtain black solid bamboo powder;
(3) oxidation treatment: adding hydrogen peroxide solution into black solid bamboo powder in a reaction bottle, heating, stirring until the black solid bamboo powder is completely dissolved, and adding MnO 2 Removing unreacted hydrogen peroxide, filtering, and spin-drying to obtain brown-yellow solid bamboo powder;
(4) hydrothermal synthesis: taking brown-yellow solid bamboo powder as a carbon source, a nonionic surfactant as a template agent and a polyol substance as a cross-linking agent, and carrying out hydrothermal synthesis to obtain a black-brown solid, namely a carbonized substrate; the carbon source, the template agent and the crosslinking agent are as follows: the mass ratio of the water is 0.5-5: 0.5-6: 1-5: 10-60; the nonionic surfactant is P123; the polyalcohol substance is glycerol;
(5) heating and carbonizing: heating and carbonizing a carbonized substrate by a stepped program under the atmosphere of rare gas to obtain a mesoporous carbon material; the step-shaped temperature programming is to carry out step-shaped heating carbonization at the temperature rise rate of 1 ℃/min, and comprises two carbonization stages; the heat preservation temperature of the first carbonization stage is 300-500 ℃, and the retention time is 0.5-1.5 h; the heat preservation temperature of the second carbonization stage is 700-900 ℃, and the retention time is 2-4 h.
2. The method for synthesizing the mesoporous carbon material by using bamboo powder as the carbon source as claimed in claim 1, wherein in the step (4), the carbon source, the template agent and the crosslinking agent: the mass ratio of the water is 1-3: 20-50.
3. The method for synthesizing the mesoporous carbon material by using bamboo powder as the carbon source as claimed in claim 2, wherein in the step (4), the carbon source, the template agent, the cross-linking agent: the mass ratio of the water is 1.5-2: 1.6-2.8: 40.
4. The method for synthesizing mesoporous carbon material using bamboo powder as carbon source as claimed in any one of claims 1 to 3, wherein in the step (2), the FeCl is 3 The adding amount of the acid solution is 1-3 times of the mass of the pretreated bamboo powder.
5. The method for synthesizing the mesoporous carbon material with bamboo powder as the carbon source according to any one of claims 1 to 3, wherein in the step (2), the degradation reaction is hydrothermal at 150 to 180 ℃ for 8 to 10 hours.
6. The method for synthesizing the mesoporous carbon material with bamboo powder as the carbon source according to any one of claims 1 to 3, wherein in the step (3), the hydrogen peroxide solution is added in an amount of 25 to 40% by mass, which is 2 to 5 times the mass of the black solid bamboo powder.
7. The method for synthesizing the mesoporous carbon material using bamboo powder as the carbon source as claimed in any one of claims 1 to 3, wherein the heating temperature in the step (3) is 90 to 100 ℃.
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