Phenolic resin and pitch-based mesoporous carbon and preparation method thereof

Abstract

The invention discloses phenolic resin and pitch-based mesoporous carbon and a preparation method thereof, and belongs to the technical field of nano materials. The method comprises the following steps: (1) mixing phenol, formaldehyde and a basic catalyst, and reacting to obtain a phenolic resin prepolymer; (2) mixing the phenolic resin prepolymer, asphalt with the softening temperature of 45-280 DEG C and a surfactant, carrying out acid catalytic reaction, and carrying out curing treatment after solvent evaporation induced self-assembly; and (3) calcining the cured product in an inert atmosphere at 600-1400 DEG C for 1-10 hours to obtain the mesoporous carbon. According to the invention, the structural stability of the hard carbon precursor and the conductivity advantage of the soft carbon precursor are cooperated, so that the performance defect of mesoporous carbon of a single precursor is overcome; the preparation process is simple, the cost is low, a template removal step is not needed, and the catalyst is suitable for the fields of energy storage devices, fuel cells, catalyst carriers, environmental restoration and the like.

Description

Technical Field

[0001] The invention belongs to the technical field of nanomaterials, and particularly relates to a phenolic resin and asphalt-based mesoporous carbon and a preparation method thereof. Background Art

[0002] Mesoporous carbon consists of a carbon skeleton and uniform mesopores, has a large specific surface area and pore volume, and has interconnected mesopores. It has a wide range of applications in catalysis, adsorption, energy conversion and storage, biomedicine, and environmental remediation. At present, various mesoporous carbons synthesized from hard carbon precursors have been synthesized, such as phenolic resin-based mesoporous carbon. Although it has a rigid skeleton and is not easy to collapse, its electrical conductivity is poor. Mesoporous carbon prepared from soft carbon precursors (pitch) has good electrical conductivity, but its structure is prone to collapse during long-term service. Therefore, its application in related fields is limited.

[0003] Based on this, there is an urgent need to develop a new mesoporous carbon preparation technology that can coordinate the structural stability of hard carbon and the high conductivity of soft carbon through composite carbon source design, and simplify the synthesis process to reduce costs, thereby expanding its high-end applications in multiple fields. Summary of the Invention

[0004] Based on the above technical problems, the object of the present invention is to provide a phenolic resin and asphalt-based mesoporous carbon and a preparation method thereof.

[0005] The present invention provides a method for preparing phenolic resin and pitch-based mesoporous carbon, comprising the following steps:

[0006] (1) mixing phenol, formaldehyde and an alkaline catalyst to react to obtain a phenolic resin prepolymer;

[0007] (2) mixing the phenolic resin prepolymer, asphalt with a softening temperature of 45 to 280° C., and a surfactant, performing an acid-catalyzed reaction, inducing self-assembly through solvent volatilization, and then performing a curing treatment;

[0008] (3) calcining the solidified product at 600-1400° C. for 1-10 hours under an inert atmosphere to obtain the mesoporous carbon.

[0009] Furthermore, the alkaline catalyst is selected from sodium hydroxide and potassium hydroxide.

[0010] Furthermore, the mass ratio of the phenolic resin prepolymer, asphalt and surfactant is 0.1-5:0.1-0.5:0.5-1.

[0011] Furthermore, the surfactant is selected from F127, P123, F108, PS-b-PEO, and PCS-b-PMMA.

[0012] Furthermore, the acid in step (2) is selected from nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, formic acid and oxalic acid.

[0013] Furthermore, the amount of the acid catalyst added is 0.5% to 10% of the total mass of the phenolic resin prepolymer, asphalt and surfactant.

[0014] Furthermore, the curing treatment conditions are: drying at room temperature for 1 to 4 hours, and then drying at 50 to 100° C. for 12 to 24 hours.

[0015] The present invention provides a phenolic resin and asphalt-based mesoporous carbon prepared by the above method, wherein the mesoporous carbon includes an ordered mesoporous structure and a disordered mesoporous structure.

[0016] Furthermore, the mesoporous carbon is an ordered mesoporous structure with a specific surface area of 300 to 550 m 2 / g, and the pore size distribution is 1 to 40 nm.

[0017] The present invention also provides the use of the above-mentioned mesoporous carbon in energy storage devices, fuel cell catalyst carriers, sewage treatment agents or electromagnetic shielding materials.

[0018] Beneficial effects of the present invention: The present invention overcomes the performance defects of a single precursor mesoporous carbon by synergizing the structural stability of the hard carbon precursor and the electrical conductivity advantages of the soft carbon precursor; and the preparation process is simple, low-cost, and does not require a template removal step, and is suitable for energy storage devices, fuel cells, catalyst carriers, and environmental remediation. BRIEF DESCRIPTION OF THE DRAWINGS

[0019] Figure 1 This is a transmission electron micrograph of the phenolic resin and asphalt-based disordered mesoporous carbon obtained in Example 1 of the present invention;

[0020] Figure 2 This is a transmission electron micrograph of the phenolic resin and asphalt-based ordered mesoporous carbon obtained in Example 2 of the present invention;

[0021] Figure 3 This is a transmission electron micrograph of the phenolic resin and asphalt-based ordered mesoporous carbon obtained in Example 3 of the present invention;

[0022] Figure 4 Nitrogen adsorption and desorption isotherms of phenolic resin and asphalt-based ordered mesoporous carbon obtained in Example 3 of the present invention;

[0023] Figure 5 This is a pore size distribution diagram of the phenolic resin and asphalt-based ordered mesoporous carbon obtained in Example 3 of the present invention;

[0024] Figure 6 This is a transmission electron micrograph of the phenolic resin and asphalt-based ordered mesoporous carbon obtained in Example 4 of the present invention;

[0025] Figure 7 This is a transmission electron micrograph of the phenolic resin and asphalt-based ordered mesoporous carbon obtained in Example 5 of the present invention;

[0026] Figure 8 This is a transmission electron micrograph of the phenolic resin and asphalt-based ordered mesoporous carbon obtained in Example 6 of the present invention;

[0027] Figure 9 This is a transmission electron micrograph of the phenolic resin and asphalt-based ordered mesoporous carbon obtained in Example 7 of the present invention;

[0028] Figure 10 This is a transmission electron micrograph of the phenolic resin and asphalt-based ordered mesoporous carbon obtained in Example 8 of the present invention. DETAILED DESCRIPTION

[0029] The technical solutions of the present invention are described clearly and completely below with reference to the embodiments. It is obvious that the embodiments described are only a portion of the embodiments of the present invention, not all of them. All other embodiments derived by persons of ordinary skill in the art based on the embodiments of the present invention without creative effort are also within the scope of protection of the present invention.

[0030] Example 1

[0031] Phenol, formaldehyde solution and sodium hydroxide solution were mixed and heated to obtain phenolic resin prepolymer, 0.5 g of which was dissolved in tetrahydrofuran; 0.1 g of asphalt with a softening temperature of 150 degrees was dissolved in tetrahydrofuran; 0.5 g of surfactant: F127 was dissolved in tetrahydrofuran; the above three solutions were mixed, 0.1 g of concentrated nitric acid (~67%) was added, and the mixture was dried at room temperature for 1 to 4 hours by the self-assembly method induced by solvent evaporation, placed in a 50°C oven for 24 hours, and then in a 100°C oven for 24 hours, and then the material was calcined at a high temperature of 650°C in an inert atmosphere for 3 hours to obtain a disordered mesoporous material (such as Figure 1 ).

[0032] Example 2

[0033] Phenol, formaldehyde solution and sodium hydroxide solution were mixed and heated to obtain phenolic resin prepolymer, 0.1 g of which was dissolved in tetrahydrofuran; 0.5 g of asphalt with a softening temperature of 150 degrees was dissolved in tetrahydrofuran; 0.5 g of surfactant: F127 was dissolved in tetrahydrofuran; the above three solutions were mixed, 0.5 g of concentrated nitric acid (~67%) was added, and the mixture was dried at room temperature for 1 to 4 hours by a self-assembly method induced by solvent evaporation, placed in a 50°C oven for 24 hours, and then in a 100°C oven for 24 hours, and then the material was calcined at 650°C in an inert atmosphere for 3 hours to obtain a disordered mesoporous material (such as Figure 2 ).

[0034] Example 3

[0035] Phenol, formaldehyde solution and sodium hydroxide solution were mixed and heated to obtain phenolic resin prepolymer, 0.45 g of which was dissolved in tetrahydrofuran; 0.15 g of asphalt with a softening temperature of 150 degrees was dissolved in tetrahydrofuran; 0.5 g of surfactant: F127 was dissolved in tetrahydrofuran; the above three solutions were mixed, 0.15 g of concentrated nitric acid (~67%) was added, and the mixture was dried at room temperature for 1 to 4 hours by the self-assembly method induced by solvent evaporation, placed in a 50°C oven for 24 hours, and then in a 100°C oven for 24 hours, and then the material was calcined at 650°C in an inert atmosphere for 3 hours to obtain an ordered mesoporous material (such as Figure 3 ), BET specific surface area reaches 509m 2 / g, pore size 3.7nm (such as Figure 4 , 5).

[0036] Example 4

[0037] Phenol, formaldehyde solution and sodium hydroxide solution were mixed and heated to obtain phenolic resin prepolymer, 0.5 g of which was dissolved in tetrahydrofuran; 0.5 g of asphalt with a softening temperature of 150 degrees was dissolved in tetrahydrofuran; 1.0 g of surfactant F127 was dissolved in tetrahydrofuran; the above three solutions were mixed, 0.5 g of concentrated nitric acid (~67%) was added, and the mixture was dried at room temperature for 1 to 4 hours by the self-assembly method induced by solvent evaporation, placed in a 50°C oven for 24 hours, and then in a 100°C oven for 24 hours, and then the material was calcined at 650°C in an inert atmosphere for 3 hours to obtain a disordered mesoporous material (such as Figure 6 ).

[0038] Example 5

[0039] Phenol, formaldehyde solution and sodium hydroxide solution were mixed and heated to obtain a phenolic resin prepolymer, 0.45 g of which was dissolved in tetrahydrofuran; 0.15 g of asphalt with a softening temperature of 150 degrees was dissolved in tetrahydrofuran; 0.5 g of surfactant: PS-b-PEO was dissolved in tetrahydrofuran; the above three solutions were mixed, 0.15 g of concentrated nitric acid (~67%) was added, and the mixture was dried at room temperature for 1 to 4 hours by a self-assembly method induced by solvent evaporation, placed in a 50°C oven for 24 hours, and then in a 100°C oven for 24 hours, and then the material was calcined at 650°C in an inert atmosphere for 3 hours to obtain a disordered mesoporous material (such as Figure 7 ).

[0040] Example 6

[0041] Phenol, formaldehyde solution and sodium hydroxide solution were mixed and heated to obtain phenolic resin prepolymer, 0.45 g of which was dissolved in tetrahydrofuran; 0.15 g of asphalt with a softening temperature of 45 degrees was dissolved in tetrahydrofuran; 0.5 g of surfactant: F127 was dissolved in tetrahydrofuran; the above three solutions were mixed, 0.15 g of concentrated nitric acid (~67%) was added, and the mixture was dried at room temperature for 1 to 4 hours by the self-assembly method induced by solvent evaporation, placed in a 50°C oven for 24 hours, and then in a 100°C oven for 24 hours, and then the material was calcined at 650°C in an inert atmosphere for 3 hours to obtain an ordered mesoporous material (such as Figure 8 ).

[0042] Example 7

[0043] Phenol, formaldehyde solution and sodium hydroxide solution were mixed and heated to obtain phenolic resin prepolymer, 0.45 g of which was dissolved in tetrahydrofuran; 0.15 g of asphalt with a softening temperature of 200 degrees was dissolved in tetrahydrofuran; 0.5 g of surfactant: F127 was dissolved in tetrahydrofuran; the above three solutions were mixed, 0.15 g of concentrated nitric acid (~67%) was added, and the mixture was dried at room temperature for 1 to 4 hours by the self-assembly method induced by solvent evaporation, placed in a 50°C oven for 24 hours, and then in a 100°C oven for 24 hours, and then the material was calcined at 650°C in an inert atmosphere for 3 hours to obtain an ordered mesoporous material (such as Figure 9 ).

[0044] Example 8

[0045] Phenol, formaldehyde solution and sodium hydroxide solution were mixed and heated to obtain phenolic resin prepolymer, 0.45 g of which was dissolved in tetrahydrofuran; 0.15 g of asphalt with a softening temperature of 280 degrees was dissolved in tetrahydrofuran; 0.5 g of surfactant: F127 was dissolved in tetrahydrofuran; the above three solutions were mixed, 0.15 g of concentrated nitric acid (~67%) was added, and the mixture was dried at room temperature for 1 to 4 hours by the self-assembly method induced by solvent evaporation, placed in a 50°C oven for 24 hours, and then in a 100°C oven for 24 hours, and then the material was calcined at 650°C in an inert atmosphere for 3 hours to obtain an ordered mesoporous material (such as Figure 10 ).

[0046] While embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions, and variations may be made to these embodiments without departing from the principles and spirit of the invention, and that the scope of the invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing phenolic resin and pitch-based mesoporous carbon, characterized in that: The following steps are involved: (1) mixing phenol, formaldehyde and an alkaline catalyst to react to obtain a phenolic resin prepolymer; (2) mixing the phenolic resin prepolymer, asphalt with a softening temperature of 45 to 280° C., and a surfactant, performing an acid-catalyzed reaction, inducing self-assembly through solvent volatilization, and then performing a curing treatment; (3) calcining the solidified product at 600-1400° C. for 1-10 hours under an inert atmosphere to obtain the mesoporous carbon.

2. The preparation method according to claim 1, characterized in that The alkaline catalyst is selected from sodium hydroxide and potassium hydroxide.

3. The preparation method according to claim 1, characterized in that The mass ratio of the phenolic resin prepolymer, asphalt and surfactant is 0.1-5:0.1-0.5:0.5-1.

4. The preparation method according to claim 1, characterized in that The surfactant is selected from F127, P123, F108, PS-b-PEO, and PCS-b-PMMA.

5. The preparation method according to claim 1, characterized in that The acid in step (2) is selected from nitric acid, sulfuric acid, hydrochloric acid, perchloric acid, formic acid and oxalic acid.

6. The preparation method according to claim 1, characterized in that The amount of the acid catalyst added is 0.5% to 10% of the total mass of the phenolic resin prepolymer, asphalt and surfactant.

7. The preparation method according to claim 1, characterized in that The curing treatment conditions are: drying at room temperature for 1 to 4 hours, and then drying at 50 to 100° C. for 12 to 24 hours.

8. A phenolic resin and pitch-based mesoporous carbon prepared by the method of any one of claims 1 to 7, characterized in that: The mesoporous carbon includes an ordered mesoporous structure and a disordered mesoporous structure.

9. The mesoporous carbon according to claim 8, characterized in that The mesoporous carbon has an ordered mesoporous structure and a specific surface area of 300 to 550 m 2 / g, and the pore size distribution is 1 to 40 nm.

10. Use of the mesoporous carbon according to claim 8 or 9 in energy storage devices, fuel cell catalyst supports, sewage treatment agents or electromagnetic shielding materials.

Images