CN115646378A - A kind of biological colloidal gel and its preparation method and application - Google Patents

Abstract

The invention discloses a biomass colloidal gel and its preparation method and application. The method comprises: dispersing anthraquinone small molecules and porous graphene in a sodium bicarbonate solution or a phosphate buffer solution to obtain a mixture; The mass ratio of anthraquinone small molecules to porous graphene is 1:0.14-7; the pH value of the mixture is 8-10; the mixture is ultrasonically cooled at 30-70°C to obtain a biomass colloid gel. Using small anthraquinone molecules and lignin-based porous graphene as the main raw materials, biomass colloidal gels were prepared by self-assembly through intermolecular non-covalent interactions in a weakly alkaline system. The biomass gel is a colloidal gel at room temperature, which has good temperature responsiveness. Tests show that the biomass colloidal gel has excellent specific capacity, significant shear thinning characteristics, large shear strain, Self-healing properties, frequency independence and time stability.

Description

A kind of biological colloidal gel and its preparation method and application

technical field

The invention relates to the technical field of gel preparation, in particular to a biomass colloid gel and its preparation method and application.

Background technique

Biomass materials are the most potential renewable materials, and promoting the resource utilization of abundant and green biomass materials is an effective technical way to realize "double carbon".

In recent years, biomass materials have become a hot energy storage electrode material. However, at present, in the process of preparation and application of biomass materials, there are disadvantages such as difficult to control the physical and chemical structure, low specific capacity, poor activity, low cycle stability, simple button-type assembly, no flexibility, and inability to finely prepare large-scale designs. .

Therefore, prior art still needs further improvement and promotion.

Contents of the invention

In view of the above deficiencies in the prior art, the object of the present invention is to provide a biomass colloidal gel and its preparation method and application, aiming to solve the problem of low specific capacity of the existing biomass colloidal gel.

A preparation method of biological colloidal gel, wherein, comprises the steps:

Anthraquinone small molecules and porous graphene are dispersed in sodium bicarbonate solution or phosphate buffer solution to obtain a mixture; the mass ratio of the anthraquinone small molecules to porous graphene is 1:0.14-7; the mixture The pH value is 8-10;

The mixture is ultrasonically cooled under the condition of 30-70° C. to obtain a biomass colloidal gel.

Optionally, the preparation method of the described biological colloidal gel, wherein, the anthraquinone small molecules are selected from: A sort of.

Optionally, the preparation method of the biomass colloidal gel, wherein the porous graphene is lignin-based porous graphene.

Optionally, the preparation method of the biomass colloidal gel, wherein the total mass fraction of the small anthraquinone molecules and the porous graphene in the mixture is 1.8-2.3%.

Optionally, the preparation method of the biological colloidal gel, wherein, the molar concentration of the sodium bicarbonate solution is 0.16-0.22mol/L; the molar concentration of the phosphate buffer solution is 0.1-0.15mol /L.

Optionally, the preparation method of the biomass colloidal gel, wherein, the mass ratio of the anthraquinone small molecules to the porous graphene is 2:1-1:3.

Optionally, the preparation method of the biomass colloidal gel, wherein, in the step, the mixture is ultrasonically cooled at 30-70° C. to obtain the biomass colloidal gel, which specifically includes: The mixture is sonicated at a temperature of 40-60° C. and then naturally cooled to 25° C. to obtain a biomass colloidal gel.

Optionally, the preparation method of the biological colloidal gel, wherein the ultrasonic time is 0.5-4.5 hours.

A biological colloidal gel, wherein the biological colloidal gel is prepared by the above-mentioned preparation method.

A kind of above-mentioned biomass colloidal gel, as the application of printing ink formulation material.

Beneficial effects: Compared with the prior art, the preparation method of the biomass colloidal gel provided by the present invention is easy to operate, does not require any solvent, and the instruments and reaction conditions used are also easy to implement, the synthesis steps are simple, and the prepared biological Colloidal gel is in a gel state at room temperature, has good temperature response, high specific capacity and excellent rheological properties. Compared with solid powder or granular biomass materials, it has better electrode properties. or device design.

Description of drawings

Fig. 1 is the schematic flow chart of the preparation method of biomass colloidal gel provided by the embodiment of the present invention;

Fig. 2 is the structural model of the biomass colloidal gel of the embodiment of the present invention;

Fig. 3 is the non-covalent interaction configuration between rhein and lignin-based porous graphene provided by the embodiment of the present invention;

Fig. 4 is the non-covalent interaction configuration between alizarin red and lignin-based porous graphene provided by the embodiment of the present invention;

Fig. 5 is the microscopic morphology of the rhein/lignin-based porous graphene (R/P) colloidal gel of different mass ratios that the embodiment of the present invention provides;

Fig. 6 is the microscopic appearance of the alizarin red/lignin-based porous graphene (A/P) colloidal gel of different mass ratios that the embodiment of the present invention provides;

Fig. 7 is the phase state picture of the rhein/lignin-based porous graphene (R/P) hybrid system of different mass ratios provided by the embodiment of the present invention;

Fig. 8 is the phase state picture of the alizarin red/lignin-based porous graphene (A/P) mixed system of different mass ratios provided by the embodiment of the present invention;

Fig. 9 is the specific capacity of different mass ratios of rhein/lignin-based porous graphene (R/P) colloidal gel provided by the embodiments of the present invention under different current densities;

Fig. 10 is the specific capacity of the alizarin red/lignin-based porous graphene (A/P) colloidal gel of different mass ratios provided by the embodiments of the present invention under different current densities;

Fig. 11 is the specific capacity at different current densities of the supercapacitor prepared by screen printing with the biomass gel ink provided by the embodiment of the present invention.

Detailed ways

The present invention provides a biomass colloidal gel and its preparation method and application. In order to make the purpose, technical solution and effect of the present invention more clear and definite, the present invention will be further described in detail below. It should be understood that the specific embodiments described here are only used to explain the present invention, not to limit the present invention.

In order to solve the problems that the physical and chemical structure of the existing biomass colloidal gel is difficult to control and the specific capacity is low in the preparation process. The present embodiment provides a kind of preparation method of biomass colloidal gel, comprises the following steps:

S10, dispersing anthraquinone small molecules and porous graphene in sodium bicarbonate solution or phosphate buffer solution to obtain a mixture; the mass ratio of the anthraquinone small molecules to porous graphene is 1:0.14-7; The pH of the mixture is 8-10.

Step S20 is included after the step S10, cooling the mixture after ultrasonication at 30-70° C. to obtain a biomass colloidal gel.

As shown in Figure 1, under the air atmosphere, the anthraquinone small molecule and the lignin-based porous graphene are added to a _0.2M NaHCO solution (pH = 8.3) or in a reaction vessel of 0.1M PBS (pH=8.0-9.4), and ensure that the total mass fraction of the small anthraquinone molecules and the lignin-based porous graphene in the mixed system is 1.92%. Stir to make it evenly mixed to obtain a mixture, heat the mixture, make the temperature of the mixture under the condition of 30-70° C. for ultrasonic treatment, and then naturally cool to room temperature (25° C.) to obtain a biomass colloidal gel. Wherein, the structural model of the biomass colloidal gel is shown in FIG. 2 .

The small anthraquinone molecules include, but are not limited to, rhein, emodin, chrysophanol, rubidin, hydroxylizarin, and alizarin red.

In this example, through the non-covalent interaction force between small anthraquinone molecules and lignin-based porous graphene, the biomass colloidal gel was self-assembled. After the reaction, there was no need for purification, and the biomass colloidal gel was directly obtained. quality gel.

In this example, the biomass colloidal gel is in a gel state at room temperature, because the non-covalent interaction force between small anthraquinone molecules and lignin-based porous graphene is a relatively weak intermolecular The force, coupled with the material properties of graphene and small anthraquinone molecules, has a certain responsiveness to changes in the external environment, and small anthraquinone molecules and lignin-based porous graphene have a synergistic effect in improving the specific capacity. Therefore, the prepared biomass colloidal gel has better temperature response, excellent rheological properties and higher specific capacity, and has better electrode or The design of the device, the test shows that the biomass colloidal gel ink has good printability, the printed energy storage device has excellent electrochemical performance, and the integration of the printed device can be realized. In addition, the anthraquinone small molecule and the lignin-based porous graphene of the present invention have a synergistic enhancement effect on energy storage. In addition, compared with other gels, the preparation method of biomass colloidal gel provided in this example is simple and easy to understand, easy to operate, does not require any solvent, and the instruments and reaction conditions used are also easy to implement, and the synthesis steps are simple. . Compared with manganese-based inks, precious metal inks, conductive polymer inks, graphene inks, carbon nanotube inks, and MXene inks, the biomass colloidal gel inks prepared in this example have excellent gel elasticity and time stability. At the same time, it has high specific capacity, energy density and excellent cycle stability, which can meet the general research requirements.

In one embodiment of this example, the anthraquinone small molecule is a natural product in herbal plants, a commonly used Chinese herbal medicine, and has been considered safe; in addition, the rhein in the anthraquinone small molecule has Higher content of electrochemically active substances and lower biological toxicity, less negative impact on the environment. Therefore, biomass colloidal gel is a renewable green energy storage material.

In an implementation manner of this embodiment, the mass ratio of the anthraquinone small molecule to the lignin-based porous graphene can be 7:1, 5:1, 3:1, 2:1, 1:1 , 1:2, 1:3, 1:5, 1:7, the total mass fraction of the anthraquinone small molecule and the lignin-based porous graphene in the mixed system is 1.92%. Lignin-based porous graphene exhibits similar noncovalent interactions with different anthraquinone molecules. As shown in Figure 3 and Table 1:

Table 1

E _tot : total energy of each model E _ads : adsorption energy of each model

There are three non-covalent interaction configurations between rhein and lignin-based porous graphene. After the non-covalent interaction of rhein, all the doped oxygen atoms originally located in the plane of lignin-based porous graphene are repelled out of the plane, indicating that there is a strong interaction between rhein and lignin-based porous graphene. non-covalent interactions. The energy parameters of its non-covalent interaction model also show that the adsorption energy of configuration c is much lower than that of configurations a and b, indicating that the optimal configuration for the interaction between rhein and lignin-based porous graphene is that the molecular planes of rhein are parallel on lignin-based porous graphene. Similarly, as shown in Figure 4 and Table 2:

Table 2

E _tot : total energy of each model E _ads : adsorption energy of each model

There are four non-covalent interaction configurations between alizarin red and lignin-based porous graphene. After the non-covalent interaction of alizarin red, all the doped oxygen atoms originally located in the plane of lignin-based porous graphene are repelled out of the plane, indicating that there is an existence between alizarin red and lignin-based porous graphene Strong non-covalent interactions. The energy parameters of its non-covalent interaction model also show that the adsorption energy of configuration d is much lower than that of configurations a, b and c, indicating that the optimal configuration for the interaction between alizarin red and lignin-based porous graphene is alizarin red The molecular plane is parallel to the lignin-based porous graphene. The above optimized model confirmed that π-π stacking is involved in the non-covalent self-assembly process between small anthraquinone molecules and lignin-based porous graphene.

Biomass colloidal gels obtained with different mass ratios exhibited different intermolecular non-covalent interactions. The main non-covalent interactions between small anthraquinone molecules and lignin-based porous graphene are the hydrogen bonding between the hydroxyl groups of small anthraquinone molecules and the doped oxygen atoms of lignin-based porous graphene and the intermolecular π- π stacking effect. In the biomass colloidal gel with a mass ratio of 2:1-1:3, there is a strong non-covalent interaction between small anthraquinone molecules and lignin-based porous graphene; when the mass ratio is 2: When 1-7:1 or 1:3-1:7, small anthraquinone molecules or lignin-based porous graphene are excessive, resulting in weakened non-covalent interactions between molecules. Scanning electron microscopy experiments show that the mass ratio of different ratios is different in microscopic morphology (as shown in Fig. 5 to Fig. 6). Different component ratios are important for the gelation of mixed systems because the phase state of each mixed system may behave differently due to the existence of different microscopic interactions. The degree of non-covalent interaction of each of the different mass ratios will also affect their rheological properties.

In one implementation of this example, the temperature of the ultrasound can be 30°C to 35°C, 35°C to 40°C, 40°C to 45°C, 45°C to 50°C, 50°C to 55°C, 55°C To 60 ℃, 60 ℃ to 70 ℃, natural cooling to room temperature (25 ℃) after ultrasonic at the above temperature, has a faster gelation rate.

In one implementation of this example, the ultrasonic time can be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, 4.5 hours, under the ultrasonic time, Can make the gelation complete.

The following specific examples will further explain the biological colloidal gel provided by the present invention, its preparation method and application.

Example 1

Under air atmosphere, 8.75g small anthraquinone molecules and 1.25g lignin-based porous graphene (A/P=7:1 and R/P=7:1) were added to a solution containing 0.5mL 0.2M NaHCO ₃ ( pH=8.3) in a reactor, then stirred to make it evenly mixed, heated to 30°C and accompanied by ultrasonic treatment for 0.5 hours;

After the sonication is completed, naturally cool to room temperature (25° C.) to obtain the biomass colloidal gel.

Example 2

Under air atmosphere, 8.35g small anthraquinone molecules and 1.67g lignin-based porous graphene (A/P=5:1 and R/P=5:1) were added to a solution containing 0.5mL 0.2M NaHCO ₃ ( pH=8.3) in a reactor, then stirred to make it evenly mixed, heated to 35°C and accompanied by ultrasonic treatment for 1.0 hour;

After the sonication is completed, naturally cool to room temperature (25° C.) to obtain the biomass colloidal gel.

Example 3

Under air atmosphere, 7.5g small anthraquinone molecules and 2.5g lignin-based porous graphene (A/P=3:1 and R/P=3:1) were added to a solution containing 0.5mL 0.2M NaHCO ₃ ( pH=8.3) in a reactor, then stirred to make it evenly mixed, heated to 40°C and accompanied by ultrasonic treatment for 1.5 hours;

After the sonication is completed, naturally cool to room temperature (25° C.) to obtain the biomass colloidal gel.

Example 4

Under air atmosphere, 6.6g small anthraquinone molecules and 3.3g lignin-based porous graphene (A/P=2:1 and R/P=2:1) were added to a solution containing 0.5mL 0.2M NaHCO ₃ ( pH=8.3) in a reactor, then stirred to make it evenly mixed, heated to 45°C and accompanied by ultrasonic treatment for 2.0 hours;

After the sonication is completed, naturally cool to room temperature (25° C.) to obtain the biomass colloidal gel.

Example 5

Under air atmosphere, 5g small anthraquinone molecules and 5g lignin-based porous graphene (A/P=1:1 and R/P=1:1) were added to 0.5mL 0.2M NaHCO ₃ solution (pH= 8.3) in the reactor, then stirred to make it evenly mixed, heated to 50°C and accompanied by ultrasonic treatment for 2.5 hours;

After the sonication is completed, naturally cool to room temperature (25° C.) to obtain the biomass colloidal gel.

Example 6

Under the air atmosphere, 3.3g small anthraquinone molecules and 6.6g lignin-based porous graphene (A/P=1:2 and R/P=1:2) were added to a solution containing 0.5mL 0.2M NaHCO ₃ ( pH = 8.3) in a reactor, then stirred to make it evenly mixed, heated to 55 ° C and accompanied by ultrasonic treatment for 3.0 hours;

After the sonication is completed, naturally cool to room temperature (25° C.) to obtain the biomass colloidal gel.

Example 7

Under air atmosphere, 2.5g small anthraquinone molecules and 7.5g lignin-based porous graphene (A/P=1:3 and R/P=1:3) were added to a solution containing 0.5mL 0.2M NaHCO ₃ ( pH=8.3) in a reactor, then stirred to make it evenly mixed, heated to 60°C and accompanied by ultrasonic treatment for 3.5 hours;

After the sonication is completed, naturally cool to room temperature (25° C.) to obtain the biomass colloidal gel.

Example 8

Under air atmosphere, 1.67g small anthraquinone molecules and 8.35g lignin-based porous graphene (A/P=1:5 and R/P=1:5) were added to a solution containing 0.5mL 0.2M NaHCO ₃ ( pH=8.3) in a reactor, then stirred to make it evenly mixed, heated to 65°C and accompanied by ultrasonic treatment for 4.0 hours;

After the sonication is completed, naturally cool to room temperature (25° C.) to obtain the biomass colloidal gel.

Example 9

Under air atmosphere, 1.25g small anthraquinone molecules and 8.75g lignin-based porous graphene (A/P=1:7 and R/P=1:7) were added to a solution containing 0.5mL 0.2M NaHCO ₃ ( pH=8.3) in a reactor, then stirred to make it evenly mixed, heated to 70°C and accompanied by ultrasonic treatment for 4.5 hours;

After the sonication is completed, naturally cool to room temperature (25° C.) to obtain the biomass colloidal gel.

As shown in FIG. 7 to FIG. 8 , the biomass colloidal gels prepared in the above-mentioned Examples 1 to 9 show different phase states. Wherein the biomass colloidal gel prepared by embodiment 4 to embodiment 7 presents a colloidal gel state, it is experimentally verified, and the experimental results are as follows:

As shown in Figures 9 to 10, the biomass colloidal gel prepared in Example 6 (R/P=1:2 and A/P=1:2) has a higher specific capacity. Based on the preparation of ink.

As shown in Figure 11, the specific capacity of the supercapacitor prepared by screen printing with a mass ratio of 1:2 biomass gel ink is about 5 times that of the supercapacitor prepared by lignin-based porous graphene ink, indicating that the prepared The small anthraquinone molecules in the biomass colloidal gel and the lignin-based porous graphene have a synergistic effect in increasing the specific capacitance, so that the biomass materials can be used in large areas and high precision in the field of printed electronics, and the biomass materials have been improved. added value.

To sum up, the present invention provides a biomass colloidal gel and its preparation method and application. Using small anthraquinone molecules and lignin-based porous graphene as the main raw materials, biomass colloidal gels were prepared by self-assembly through intermolecular non-covalent interactions in a weakly alkaline system. The biomass gel is a colloidal gel at room temperature, which has good temperature responsiveness. Tests show that the biomass colloidal gel has excellent specific capacity, significant shear thinning characteristics, large shear strain, Self-healing properties, frequency independence and time stability. Due to the excellent rheological properties of the prepared biomass gel, it can be used as an ink raw material in printing ink formulations, and further prepared high-performance patterned energy storage electrodes or integrated devices.

It should be understood that the application of the present invention is not limited to the above examples, and those skilled in the art can make improvements or transformations according to the above descriptions, and all these improvements and transformations should belong to the protection scope of the appended claims of the present invention.

Claims (10)

1. The preparation method of the biomass colloidal gel is characterized by comprising the following steps:

dispersing anthraquinone micromolecules and porous graphene in a sodium bicarbonate solution or a phosphate buffer solution to obtain a mixture; the mass ratio of the anthraquinone small molecules to the porous graphene is 1.14-7; the pH value of the mixture is 8-10;

and (3) carrying out ultrasonic treatment on the mixture at the temperature of 30-70 ℃, and then cooling to obtain the biomass colloidal gel.

2. The method of preparing the biomass colloidal gel of claim 1, wherein the anthraquinone-based small molecules are selected from the group consisting of: rhein, emodin, chrysophanol, alizarin, madder, and alizarin red.

3. The method of preparing a biomass gel according to claim 1, wherein the porous graphene is lignin-based porous graphene.

4. The method for preparing biomass colloidal gel according to claim 1, wherein the total mass fraction of the anthraquinone small molecules and the porous graphene in the mixture is 1.8-2.3%.

5. The method of preparing the biomass pectin gel according to claim 1, wherein the molar concentration of the sodium bicarbonate solution is 0.16-0.22mol/L; the molar concentration of the phosphate buffer solution is 0.1-0.15mol/L.

6. The preparation method of the biomass colloidal gel as claimed in claim 1, wherein the mass ratio of the anthraquinone small molecules to the porous graphene is 2.

7. The method for preparing the biomass colloidal gel according to claim 1, wherein the step of cooling the mixture after ultrasonic treatment at 30-70 ℃ to obtain the biomass colloidal gel comprises the following steps: and (3) carrying out ultrasonic treatment on the mixture at the temperature of 40-60 ℃, and then naturally cooling to 25 ℃ to obtain the biomass colloidal gel.

8. The method of claim 7, wherein the sonication time is between 0.5 and 4.5 hours.

9. A biomass gel, characterized in that it is prepared by the method of any one of claims 1 to 8.

10. Use of the biomass gel of claim 9 as a printing ink formulation material.

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