CN109879269B - Method for synthesizing mesoporous carbon material by using bamboo powder as carbon source - Google Patents

Abstract

A method for synthesizing mesoporous carbon materials using bamboo powder as a carbon source, comprising the following steps: (1) pretreatment; (2) degradation treatment; (3) oxidation treatment; (4) hydrothermal synthesis; (5) heating carbonization . ^The invention uses bamboo powder as a biological carbon source, and utilizes a soft template method to hydrothermally synthesize ordered mesoporous carbon materials with high specific surface area. at 372.6 m ² /g. The raw materials used in the invention have wide sources and low prices, so the production cost is low, and the materials in the whole synthesis process belong to the green, environment-friendly and renewable materials, which conform to the concept of green chemical synthesis.

Description

A method for synthesizing mesoporous carbon materials using bamboo powder as carbon source

technical field

The invention relates to a method for synthesizing mesoporous carbon materials, in particular to a method for synthesizing mesoporous carbon materials using bamboo powder as a carbon source.

Background technique

Mesoporous carbon materials have the characteristics of huge specific surface area, uniform and adjustable mesopore pore size, good stability and electrical conductivity, etc. fields have broad application prospects.

There are two main methods for the synthesis of ordered mesoporous carbons: hard template method and soft template method. The technology of synthesizing ordered mesoporous carbon materials by hard template method is quite mature, and each step in the synthesis process has a variety of options. However, since the hard template method requires additional steps to prepare mesoporous silica templates, The mesoscopic pores of the obtained ordered mesoporous carbon are generated by the accumulation of pores between carbon rods, and the pore size distribution will be relatively wide. The silicon-based mesoporous material used as a hard template cannot be recycled, and the cost is relatively expensive, complicated and time-consuming. . Therefore, this preparation method cannot be used for large-scale production and industrial application. The soft template method is also called organic-organic template method or supramolecular template method. Different from the hard template material that maintains the structure through covalent bonds, the material used as a soft template is a soft substance with a specific structure. Non-covalent bonding forces (short-range repulsion and long-range attraction) form and maintain the mesoporous structure. According to the different synthesis process, the soft template method has three main synthetic routes, namely hydrothermal synthesis (hydrothermal synthesis), solvent volatilization-induced self-organization (EISA) and low temperature aqueous synthesis (aqueous route).

The existing preparation technology of mesoporous carbon materials still has some defects that need to be overcome. For example, most of them need to use H ₃ PO ₃ , ZnCl ₂ and alkali as active agents to change the properties of carbon materials, consume a lot of organic solvents and cause environmental pollution. The cost is too high, which is not conducive to industrial production.

CN 106542515A discloses a method for synthesizing mesoporous carbon materials; a carbon precursor and a templating agent are dissolved in water to form a homogeneous solution, wherein the mass of the carbon precursor is 0.5% to 10%, and the mass of the templating agent is 0.2% to 2% %, the rest are water solvents; the obtained solution is spin-coated or directly poured on the surface of the container to form a coating film; the container after the coating film is placed in a closed device, and vacuumed at room temperature to 70 ° C to make the solvent water volatilize complete; the obtained sample was further thermopolymerized and cured at 80-150 °C for 10-60 h; the cured sample was calcined at 600-1000 °C under nitrogen protection to obtain an ordered mesoporous carbon material. The carbon precursor used in this method has high cost and high equipment requirements, so it is not suitable for large-scale production.

SUMMARY OF THE INVENTION

The technical problem to be solved by the present invention is to overcome the above-mentioned defects in the prior art, and to provide a method for synthesizing mesoporous carbon materials with bamboo powder as a carbon source, which is easy to obtain raw materials, low in instrument requirements, low in production cost, and environmentally friendly. .

The technical scheme adopted by the present invention to solve the technical problem is as follows: A method for synthesizing mesoporous carbon material with bamboo powder as carbon source, comprising the following steps:

(1) Remove impurities from bamboo powder: wash the bamboo powder with an acidic solution to remove impurities, and dry to obtain bamboo powder for removal of impurities;

(2) Degradation treatment: mix the impurity-removing bamboo powder and FeCl ₃ acid solution evenly, carry out the degradation reaction, cool, collect the degradation reaction product, wash with boiling water, and dry to obtain black solid bamboo powder;

(3) Oxidation treatment: add hydrogen peroxide solution to the black solid bamboo powder in the reaction flask, heat and stir until the black solid bamboo powder is completely dissolved, then add MnO ₂ to remove the unreacted hydrogen peroxide , filtered, and spin-dried to obtain brownish-yellow solid bamboo powder;

(4) Hydrothermal synthesis: take the brown-yellow solid bamboo powder as the carbon source, the nonionic surfactant as the template agent, and the polyols as the cross-linking agent, perform hydrothermal synthesis to obtain a black-brown solid, which is carbonization substrate;

(5) Heating carbonization: In a rare gas atmosphere, the carbonized substrate is heated and carbonized through a step-like temperature program to obtain a mesoporous carbon material.

Further, in step (4), the mass ratio of carbon source: template agent: cross-linking agent: water is 0.5-5: 0.5-6: 1-5: 10-60, preferably 1-3: 1-3: 1-3 : 20 to 50, more preferably 1.5 to 2: 2: 1.6 to 2.8: 40.

Further, the templating agent in step (4) is a nonionic surfactant templating agent P123; the cross-linking agent is glycerol.

Further, in step (5), the step-by-step temperature program is to perform step-by-step heating and carbonization at a heating rate of 1°C/min, including two carbonization stages; The time is 0.5-1.5h; the holding temperature in the second carbonization stage is 700-900°C, and the retention time is 2-4h.

Further, the amount of FeCl ₃ acidic solution added in step (2) is equivalent to 1-3 times the mass of the pretreated bamboo powder.

Further, the degradation reaction in step (2) is hydrothermal at 150-180° C. for 8-10 hours (preferably 9 hours).

Further, the mass fraction of the hydrogen peroxide solution described in the step (3) is 25-40% (preferably 30%), and the addition amount is equivalent to 2-5 times (preferably 3 times) the mass of the black solid bamboo powder.

Further, the heating temperature in step (3) is 90-100°C.

The beneficial effects of the invention are as follows: the bamboo powder is used as the biological carbon source, the raw materials are readily available, the equipment requirements are low, and the production cost is low, and the ordered mesoporous carbon material with high specific surface area is hydrothermally synthesized by the soft template method, and its pore diameter is 4.2-5.0 nm, the pore volume is 0.2～0.4cm ³ /g, and the specific surface area is 372.6m ² /g; the materials used in the whole synthesis process are green and renewable materials, which conform to the synthesis concept of green chemistry.

Description of drawings

Fig. 1 is the infrared spectrogram of the carbon source used in Example 1 of the present invention (carbon 1 is the carbon source that has not been treated with hydrogen oxide, and carbon 2 is the carbon source that has been treated with hydrogen oxide);

Fig. 2 is the ultraviolet spectrogram of the raw material carbon source used in the embodiment of the present invention 1;

Fig. 3 is the mass spectrum 1 of the raw material carbon source used in Example 1 of the present invention;

Fig. 4 is the mass spectrum 2 of the raw material carbon source used in Example 1 of the present invention;

Fig. 5 is the pore size distribution diagram of the mesoporous carbon prepared in Example 1 of the present invention;

6 is a characteristic nitrogen adsorption-desorption isotherm diagram of the mesoporous carbon prepared in Example 1 of the present invention;

7 is a transmission electron microscope image of the mesoporous carbon prepared in Example 2 of the present invention.

Detailed ways

The present invention will be further described below with reference to the embodiments and accompanying drawings.

The chemical reagents used in the examples of the present invention are obtained through conventional commercial channels unless otherwise specified.

Example 1

This embodiment includes the following steps:

(1) Bamboo powder removal: Wash the bamboo powder with a hydrochloric acid solution with a mass fraction of 5% at 100 °C for 4 hours to remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the bamboo powder for removal of impurities;

(2) Degradation treatment: Mix 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution in the hydrothermal reactor evenly (6g FeCl ₃ 6H ₂ O is configured as a solution and added to the bamboo powder, and 4 drops are added in the process, the mass concentration is 37%. The hydrochloric acid solution) was degraded (hydrothermal in an oven at 180 °C for 9 h), cooled, the reaction product was collected, washed with water at 100 °C for 0.5 h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In the reaction flask, take 3g of the black solid bamboo powder obtained in step (2), add 30mL of hydrogen peroxide solution (mass fraction 30%), heat to 100°C under stirring, and continue stirring for 3h. The solid bamboo powder is all dissolved, and _MnO is added to remove unreacted hydrogen peroxide, filter, spin dry to obtain the brownish-yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2 g of nonionic surfactant P123 in 40 mL of deionized water as a template agent, then add 2.8 mL of glycerol as a cross-linking agent, and continue to stir; take 3 g of the brownish-yellow solid obtained in step (3) The bamboo powder was dissolved in 30 mL of deionized water as a carbon source, added to the above-mentioned template agent, stirred at 40 °C for 2 h, the resulting mixed solution was placed in a hydrothermal reaction kettle, and hydrothermally heated at 130 °C for three days; The brown solid is the carbonized substrate;

(5) Heating carbonization: Under nitrogen atmosphere, the carbonized substrate is heated and carbonized by a step-by-step temperature program (1 °C/min), carbonized at 300 °C for 1.5 hours, and then carbonized at 700 °C for 2 hours to obtain a black solid. It is a mesoporous carbon material.

The infrared spectrum and ultraviolet spectrum of the carbon source used in this example; mass spectrometry 1 and mass spectrometry 2 are shown in Figure 1, Figure 2, Figure 3 and Figure 4, respectively; the pore size distribution of the prepared mesoporous carbon, the characteristic nitrogen adsorption- The desorption isotherms are shown in Figure 5 and Figure 6, respectively.

The pore size of the mesoporous carbon material prepared in this example is 4.6 nm, the specific surface area is 368.5 m ² /g, and the pore volume is 0.27 cm ³ /g.

Example 2

This embodiment includes the following steps:

(1) Bamboo powder removal: Wash the bamboo powder with a mass fraction of 5% hydrochloric acid solution at 100 °C for 4 hours, remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the impurity-removing bamboo powder;

(2) Degradation treatment: in the hydrothermal reaction kettle, 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution (6g FeCl ₃ 6H ₂ O are configured into a solution and added to the bamboo powder, and 4 drops of hydrochloric acid with a mass concentration of 37% are added in the process. ) mixed evenly, degraded (water-heated in an oven at 180°C for 9h), cooled, collected the reaction product, washed with water at 100°C for 0.5h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In a reaction flask, add 30 mL of hydrogen peroxide solution (30% by mass) to 3 g of the black solid bamboo powder obtained in step (2), heat to 100° C. under stirring, and continue stirring for 3 hours. The black solid bamboo powder all dissolves, then adds MnO ₂ removes the unreacted hydrogen peroxide, filters, spins dry, obtains the brownish yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2 g of nonionic surfactant P123 in 40 mL of deionized water as a template agent, then add 1.6 mL of glycerol as a cross-linking agent, and continue stirring; take 3 g of the brown solid obtained in step (3) The bamboo powder in the form of carbon was dissolved in 30 mL of deionized water as a carbon source, added to the above-mentioned template agent, stirred at 40 °C for 2 h, and the resulting mixed solution was placed in a hydrothermal reaction kettle, and hydrothermally heated at 130 °C for three days. The black-brown solid collected by filtration and drying is the carbonized substrate;

(5) Heating carbonization: under nitrogen atmosphere, the carbonized substrate is heated and carbonized through a step-like temperature program (1 °C/min), carbonized at 300 °C for 1.5 hours, and then carbonized at 700 °C for 2 hours to obtain the collected black The solid is the mesoporous carbon material.

7 is a transmission electron microscope image of the mesoporous carbon prepared in Example 2 of the present invention.

The pore size of the mesoporous carbon material prepared in this example is 4.8 nm, the specific surface area is 370.6 m ² /g, and the pore volume is 0.40 cm ³ /g.

Example 3

This embodiment includes the following steps:

(1) Bamboo powder removal: Wash the bamboo powder with a mass fraction of 5% hydrochloric acid solution at 100 °C for 4 hours, remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the impurity-removing bamboo powder;

(2) Degradation treatment: in the hydrothermal reaction kettle, 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution (6g FeCl ₃ 6H ₂ O are configured into a solution and added to the bamboo powder, and 4 drops of hydrochloric acid with a mass concentration of 37% are added in the process. ) mixed evenly, degraded (water-heated in an oven at 180°C for 9h), cooled, collected the reaction product, washed with water at 100°C for 0.5h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In a reaction flask, add 30 mL of hydrogen peroxide solution (30% by mass) to 3 g of the black solid bamboo powder obtained in step (2), heat to 100° C. under stirring, and continue stirring for 3 hours. The black solid bamboo powder all dissolves, then adds MnO ₂ removes the unreacted hydrogen peroxide, filters, spins dry, obtains the brownish yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2 g of nonionic surfactant P123 in 40 mL of deionized water as a template agent, then add 1.6 mL of glycerol as a cross-linking agent, continue stirring, and take 1.5 g of the brownish yellow obtained in step (3) The solid was dissolved in 30 mL of deionized water as a carbon source, added to the above template agent, and stirred at 40 °C for 2 h; the mixed solution was placed in a hydrothermal reactor, heated at 130 °C for three days, filtered, dried, and the black-brown solid was collected. is a carbonized substrate;

(5) Heating carbonization: under nitrogen atmosphere, the carbonized substrate was heated and carbonized through a step-like temperature program (1 °C/min), carbonized at 300 °C for 1.5 h, and then carbonized at 700 °C for 2 h to collect black solids to obtain a medium. Porous carbon material.

The pore size of the mesoporous carbon material prepared in this example is 4.7 nm, the specific surface area is 359.8 m ² /g, and the pore volume is 0.29 cm ³ /g.

Example 4

Include the following steps:

(1) Bamboo powder removal: Wash the bamboo powder with a mass fraction of 5% hydrochloric acid solution at 100 °C for 4 hours, remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the impurity-removing bamboo powder;

(2) Degradation treatment: in the hydrothermal reaction kettle, 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution (6g FeCl ₃ 6H ₂ O are configured into a solution and added to the bamboo powder, and 4 drops of hydrochloric acid with a mass concentration of 37% are added in the process. ) mixed evenly, degraded (water-heated in an oven at 180°C for 9h), cooled, collected the reaction product, washed with water at 100°C for 0.5h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In a reaction flask, add 30 mL of hydrogen peroxide solution (30% by mass) to 3 g of the black solid bamboo powder obtained in step (2), heat to 100° C. under stirring, and continue stirring for 3 hours. The black solid bamboo powder all dissolves, then adds MnO ₂ removes the unreacted hydrogen peroxide, filters, spins dry, obtains the brownish yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2g of nonionic surfactant P123 in 40mL of deionized water, then add 1.6mL of glycerol, stir, take 3g of the above brown-yellow solid (carbon source) and dissolve it in 30mL of deionized water, add into the surfactant solution, stirred at 40°C for 2h, put the mixed solution into a hydrothermal reactor, hydrothermally heated at 130°C for three days, filtered, dried, and collected the black-brown solid as the carbonized substrate;

(5) Heating carbonization: under nitrogen atmosphere, the carbonized substrate was heated and carbonized by a step-like temperature program (1 °C/min), carbonized at 400 °C for 1.5 h, and then carbonized at 700 °C for 2 h, and the black solid was collected to obtain Mesoporous carbon materials.

The pore size of the mesoporous carbon material prepared in this example is 4.3 nm, the specific surface area is 355.6 m ² /g, and the pore volume is 0.30 cm ³ /g.

Example 5

This embodiment includes the following steps:

(1) Bamboo powder removal: Wash the bamboo powder with a mass fraction of 5% hydrochloric acid solution at 100 °C for 4 hours, remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the impurity-removing bamboo powder;

(2) Degradation treatment: in the hydrothermal reaction kettle, 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution (6g FeCl ₃ 6H ₂ O are configured into a solution and added to the bamboo powder, and 4 drops of hydrochloric acid with a mass concentration of 37% are added in the process. ) mixed evenly, degraded (water-heated in an oven at 180°C for 9h), cooled, collected the reaction product, washed with water at 100°C for 0.5h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In a reaction flask, add 30 mL of hydrogen peroxide solution (30% by mass) to 3 g of the black solid bamboo powder obtained in step (2), heat to 100° C. under stirring, and continue stirring for 3 hours. The black solid bamboo powder all dissolves, then adds MnO ₂ removes the unreacted hydrogen peroxide, filters, spins dry, obtains the brownish yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2g of nonionic surfactant P123 in 40mL of deionized water as a template agent, then add 1.6mL of glycerol as a cross-linking agent, continue stirring, and take 3g of the brown solid obtained in step (3) The bamboo powder was dissolved in 30 mL of deionized water as a carbon source, added to the above template agent, stirred at 40 °C for 2 h, put the mixed solution into a hydrothermal reactor, hydrothermally heated at 130 °C for three days, filtered, dried, and collected the black The brown solid is the carbonized substrate;

(5) Heating carbonization: under nitrogen atmosphere, the carbonized substrate is heated and carbonized through a step-by-step temperature program (1 °C/min), carbonized at 500 °C for 1.5 hours, and then carbonized at 700 °C for 2 hours, and the black solid obtained is collected. , to obtain mesoporous carbon materials.

The pore size of the mesoporous carbon material prepared in this example is 4.3 nm, the specific surface area is 360.8 m ² /g, and the pore volume is 0.32 cm ³ /g.

Example 6

This embodiment includes the following steps:

(1) Bamboo powder removal: Wash the bamboo powder with a mass fraction of 5% hydrochloric acid solution at 100 °C for 4 hours, remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the impurity-removing bamboo powder;

(2) Degradation treatment: in the hydrothermal reaction kettle, 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution (6g FeCl ₃ 6H ₂ O are configured into a solution and added to the bamboo powder, and 4 drops of hydrochloric acid with a mass concentration of 37% are added in the process. ) mixed evenly, degraded (water-heated in an oven at 180°C for 9h), cooled, collected the reaction product, washed with water at 100°C for 0.5h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In a reaction flask, add 30 mL of hydrogen peroxide solution (30% by mass) to 3 g of the black solid bamboo powder obtained in step (2), heat to 100° C. under stirring, and continue stirring for 3 hours. The black solid bamboo powder all dissolves, then adds MnO ₂ removes the unreacted hydrogen peroxide, filters, spins dry, obtains the brownish yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2g of nonionic surfactant P123 in 40mL of deionized water as a template agent, then add 1.6mL of glycerol as a cross-linking agent, continue stirring, and take 3g of the brown solid obtained in step (3) The bamboo powder was dissolved in 30 mL of deionized water as a carbon source, added to the above-mentioned template agent, stirred at 40 °C for 2 h, put the mixed solution into a hydrothermal reaction kettle, hydrothermally heated at 130 °C for three days, filtered, dried, and collected black. The brown solid is the carbonized substrate;

(5) Heating and carbonization: The carbonized substrate was heated and carbonized by a step temperature program (1°C/min) under nitrogen atmosphere, carbonized at 300°C for 1.5 hours, and then carbonized at 600°C for 2 hours. The black solid obtained was collected. A mesoporous carbon material is obtained.

The pore size of the mesoporous carbon material prepared in this example is 4.9 nm, the specific surface area is 310.5 m ² /g, and the pore volume is 0.22 cm ³ /g.

Example 7

This embodiment includes the following steps:

(1) Bamboo powder removal: wash the bamboo powder with a mass fraction of 5% hydrochloric acid solution at 100 °C for 4 hours, remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the impurity-removing bamboo powder;

(2) Degradation treatment: in the hydrothermal reaction kettle, 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution (6g FeCl ₃ 6H ₂ O are configured into a solution and added to the bamboo powder, and 4 drops of hydrochloric acid with a mass concentration of 37% are added in the process. ) mixed evenly, degraded (water-heated in an oven at 180°C for 9h), cooled, collected the reaction product, washed with water at 100°C for 0.5h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In a reaction flask, add 30 mL of hydrogen peroxide solution (30% by mass) to 3 g of the black solid bamboo powder obtained in step (2), heat to 100° C. under stirring, and continue stirring for 3 hours. The black solid bamboo powder all dissolves, then adds MnO ₂ removes the unreacted hydrogen peroxide, filters, spins dry, obtains the brownish yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2g of nonionic surfactant P123 in 40mL of deionized water as a template agent, then add 1.6mL of glycerol as a cross-linking agent, continue stirring, and take 3g of the brown solid obtained in step (3) The bamboo powder was dissolved in 30 mL of deionized water as a carbon source, added to the above-mentioned template agent, stirred at 40 °C for 2 h, put the mixed solution into a hydrothermal reaction kettle, hydrothermally heated at 130 °C for three days, filtered, dried, and collected black. The brown solid is the carbonized substrate;

(5) Heating and carbonization: The carbonized substrate was heated and carbonized by a step temperature program (1°C/min) under nitrogen atmosphere, carbonized at 300°C for 1.5h, and then carbonized at 500°C for 2h, and collected the black solid obtained. A mesoporous carbon material is obtained.

The pore size of the mesoporous carbon material prepared in this example is 5.0 nm, the specific surface area is 280.6 m ² /g, and the pore volume is 0.20 cm ³ /g.

Example 8

This embodiment includes the following steps:

(1) Bamboo powder removal: Wash the bamboo powder with a mass fraction of 5% hydrochloric acid solution at 100 °C for 4 hours, remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the impurity-removing bamboo powder;

(2) Degradation treatment: in the hydrothermal reaction kettle, 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution (6g FeCl ₃ 6H ₂ O are configured into a solution and added to the bamboo powder, and 4 drops of hydrochloric acid with a mass concentration of 37% are added in the process. ) mixed evenly, degraded (water-heated in an oven at 180°C for 9h), cooled, collected the reaction product, washed with water at 100°C for 0.5h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In a reaction flask, add 30 mL of hydrogen peroxide solution (30% by mass) to 3 g of the black solid bamboo powder obtained in step (2), heat to 100° C. under stirring, and continue stirring for 3 hours. The black solid bamboo powder all dissolves, then adds MnO ₂ removes the unreacted hydrogen peroxide, filters, spins dry, obtains the brownish yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2g of nonionic surfactant P123 in 40mL of deionized water as a template agent, then add 1.6mL of glycerol as a cross-linking agent, continue stirring, and take 3g of the brown solid obtained in step (3) The bamboo powder was dissolved in 30 mL of deionized water as a carbon source, added to the above-mentioned template agent, stirred at 40 °C for 2 h, put the mixed solution into a hydrothermal reaction kettle, hydrothermally heated at 130 °C for three days, filtered, dried, and collected black. The brown solid is the carbonized substrate;

(5) Heating carbonization: under nitrogen atmosphere, the carbonized substrate is heated and carbonized through a step-by-step temperature program (1 °C/min), carbonized at 300 °C for 0.5 h, and then carbonized at 700 °C for 2 h, and the black color obtained is collected. solid to obtain a mesoporous carbon material.

The pore size of the mesoporous carbon material prepared in this example is 4.6 nm, the specific surface area is 349.2 m ² /g, and the pore volume is 0.32 cm ³ /g.

Example 9

This embodiment includes the following steps:

(1) Bamboo powder removal: Wash the bamboo powder with a mass fraction of 5% hydrochloric acid solution at 100 °C for 4 hours, remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the impurity-removing bamboo powder;

(2) Degradation treatment: in the hydrothermal reaction kettle, 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution (6g FeCl ₃ 6H ₂ O are configured into a solution and added to the bamboo powder, and 4 drops of hydrochloric acid with a mass concentration of 37% are added in the process. ) mixed evenly, degraded (water-heated in an oven at 180°C for 9h), cooled, collected the reaction product, washed with water at 100°C for 0.5h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In a reaction flask, add 30 mL of hydrogen peroxide solution (30% by mass) to 3 g of the black solid bamboo powder obtained in step (2), heat to 100° C. under stirring, and continue stirring for 3 hours. The black solid bamboo powder all dissolves, then adds MnO ₂ removes the unreacted hydrogen peroxide, filters, spins dry, obtains the brownish yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2g of nonionic surfactant P123 in 40mL of deionized water as a template agent, then add 1.6mL of glycerol as a cross-linking agent, continue stirring, and take 3g of the brown solid obtained in step (3) The bamboo powder was dissolved in 30 mL of deionized water as a carbon source, added to the above-mentioned template agent, stirred at 40 °C for 2 h, put the mixed solution into a hydrothermal reaction kettle, hydrothermally heated at 130 °C for three days, filtered, dried, and collected black. The brown solid is the carbonized substrate;

(5) Heating carbonization: under nitrogen atmosphere, the carbonized substrate is heated and carbonized through a step-by-step temperature program (1 °C/min), carbonized at 300 °C for 1 hour, and then carbonized at 700 °C for 2 hours, and the obtained black solid is collected. A mesoporous carbon material is obtained.

The pore size of the mesoporous carbon material prepared in this example is 4.4 nm, the specific surface area is 358.4 m ² /g, and the pore volume is 0.34 cm ³ /g.

Example 10

This embodiment includes the following steps:

(1) Bamboo powder removal: Wash the bamboo powder with a mass fraction of 5% hydrochloric acid solution at 100 °C for 4 hours, remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the impurity-removing bamboo powder;

(2) Degradation treatment: in the hydrothermal reaction kettle, 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution (6g FeCl ₃ 6H ₂ O are configured into a solution and added to the bamboo powder, and 4 drops of hydrochloric acid with a mass concentration of 37% are added in the process. ) mixed evenly, degraded (water-heated in an oven at 180°C for 9h), cooled, collected the reaction product, washed with water at 100°C for 0.5h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In a reaction flask, add 30 mL of hydrogen peroxide solution (30% by mass) to 3 g of the black solid bamboo powder obtained in step (2), heat to 100° C. under stirring, and continue stirring for 3 hours. The black solid bamboo powder all dissolves, then adds MnO ₂ removes the unreacted hydrogen peroxide, filters, spins dry, obtains the brownish yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2g of nonionic surfactant P123 in 40mL of deionized water as a template agent, then add 1.6mL of glycerol as a cross-linking agent, continue stirring, and take 3g of the brown solid obtained in step (3) The bamboo powder was dissolved in 30 mL of deionized water as a carbon source, added to the above-mentioned template agent, stirred at 40 °C for 2 h, put the mixed solution into a hydrothermal reaction kettle, hydrothermally heated at 130 °C for three days, filtered, dried, and collected black. The brown solid is the carbonized substrate;

(5) Heating carbonization: under nitrogen atmosphere, the carbonized substrate is heated and carbonized by a step-by-step temperature program (1 °C/min), carbonized at 300 °C for 1.5 hours, and then carbonized at 700 °C for 3 hours, and the black solid obtained is collected. , to obtain mesoporous carbon materials.

The pore size of the mesoporous carbon material prepared in this example is 4.5 nm, the specific surface area is 361.4 m ² /g, and the pore volume is 0.36 cm ³ /g.

Example 11

This embodiment includes the following steps:

(1) Bamboo powder removal: Wash the bamboo powder with a mass fraction of 5% hydrochloric acid solution at 100 °C for 4 hours, remove the metal impurities in the bamboo powder, and dry it in an oven at 105 °C to obtain the impurity-removing bamboo powder;

(2) Degradation treatment: in the hydrothermal reaction kettle, 6g of impurity-removing bamboo powder and FeCl ₃ acidic solution (6g FeCl ₃ 6H ₂ O are configured into a solution and added to the bamboo powder, and 4 drops of hydrochloric acid with a mass concentration of 37% are added in the process. ) mixed evenly, degraded (water-heated in an oven at 180°C for 9h), cooled, collected the reaction product, washed with water at 100°C for 0.5h, and dried to obtain black solid bamboo powder;

(3) Oxidation treatment: In a reaction flask, add 30 mL of hydrogen peroxide solution (30% by mass) to 3 g of the black solid bamboo powder obtained in step (2), heat to 100° C. under stirring, and continue stirring for 3 hours. The black solid bamboo powder all dissolves, then adds MnO ₂ removes the unreacted hydrogen peroxide, filters, spins dry, obtains the brownish yellow solid bamboo powder;

(4) Hydrothermal synthesis: Dissolve 2g of nonionic surfactant P123 in 40mL of deionized water as a template agent, then add 1.6mL of glycerol as a cross-linking agent, continue stirring, and take 3g of the brown solid obtained in step (3) The bamboo powder was dissolved in 30 mL of deionized water as a carbon source, added to the above-mentioned template agent, stirred at 40 °C for 2 h, put the mixed solution into a hydrothermal reaction kettle, hydrothermally heated at 130 °C for three days, filtered, dried, and collected black. The brown solid is the carbonized substrate;

(5) Heating carbonization: under nitrogen atmosphere, the carbonized substrate is heated and carbonized by a step-by-step temperature program (1 °C/min), carbonized at 300 °C for 1.5 hours, and then carbonized at 700 °C for 4 hours, and the black solid obtained is collected. , to obtain mesoporous carbon materials.

The pore size of the mesoporous carbon material prepared in this example is 4.7 nm, the specific surface area is 372.0 m ² /g, and the pore volume is 0.37 cm ³ /g.

Claims (7)

1. a method for synthesizing mesoporous carbon material with bamboo powder as carbon source, is characterized in that, comprises the following steps: (1) Remove impurities from bamboo powder: wash the bamboo powder with an acidic solution to remove impurities, and dry to obtain bamboo powder for removal of impurities; (2) Degradation treatment: mix the impurity-removing bamboo powder and FeCl ₃ acid solution evenly, carry out the degradation reaction, cool, collect the degradation reaction product, wash with boiling water, and dry to obtain black solid bamboo powder; (3) Oxidation treatment: add hydrogen peroxide solution to the black solid bamboo powder in the reaction flask, heat and stir until the black solid bamboo powder is completely dissolved, then add MnO ₂ to remove the unreacted hydrogen peroxide , filtered, and spin-dried to obtain brownish-yellow solid bamboo powder; (4) Hydrothermal synthesis: take the brown-yellow solid bamboo powder as the carbon source, the nonionic surfactant as the template agent, and the polyols as the cross-linking agent, perform hydrothermal synthesis to obtain a black-brown solid, which is carbonization substrate; the mass ratio of the carbon source: template agent: cross-linking agent: water is 0.5-5: 0.5-6: 1-5: 10-60; the nonionic surfactant is P123; the polyol Substances are glycerol; (5) Heating carbonization: in a rare gas atmosphere, the carbonized substrate is heated and carbonized through a step-like temperature program to obtain a mesoporous carbon material; the step-like temperature program is a heating rate of 1 °C/min. The step-type heating carbonization is carried out, including two carbonization stages; the holding temperature of the first carbonization stage is 300-500 °C, and the retention time is 0.5-1.5 h; the holding temperature of the second carbonization stage is 700-900 °C, and the retention time is 2 to 4 hours. 2. The method for synthesizing mesoporous carbon materials with bamboo powder as carbon source according to claim 1, wherein in step (4), the carbon source: template agent: cross-linking agent: the mass ratio of water is 1 ~3:1~3:1~3:20~50. 3. The method for synthesizing mesoporous carbon materials using bamboo powder as carbon source according to claim 2, wherein in step (4), the mass ratio of the carbon source: template agent: crosslinking agent: water is 1.5 ~2:2:1.6~2.8:40. 4. The method for synthesizing mesoporous carbon materials using bamboo powder as carbon source according to one of claims 1 to 3, wherein in step (2), the addition amount of the FeCl _acid solution is pretreated The quality of bamboo powder is 1 to 3 times. 5 . The method for synthesizing mesoporous carbon materials using bamboo powder as a carbon source according to one of claims 1 to 3, wherein in step (2), the degradation reaction is hydrothermal at 150 to 180°C for 8 to 10 hours . 6 . The method for synthesizing mesoporous carbon materials using bamboo powder as a carbon source according to one of claims 1 to 3, wherein in step (3), the mass fraction of the hydrogen peroxide solution is 25 to 40% , the addition amount is 2 to 5 times the quality of the black solid bamboo powder. 7 . The method for synthesizing mesoporous carbon materials using bamboo powder as a carbon source according to claim 1 , wherein in step (3), the heating temperature is 90-100° C. 8 .

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