Biomass colloid gel and preparation method and application thereof

Abstract

The application discloses a biomass gelatinous gel and a preparation method and application thereof, and the method comprises the following steps: 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 the anthraquinone small molecules to the porous graphene is 1:0.14-7; the pH value of the mixture is 8-10; and the mixture is cooled after being ultrasonically treated at 30-70 DEG C to obtain the biomass gelatinous gel. The biomass gelatinous gel is prepared by self-assembly of anthraquinone small molecules and lignin-based porous graphene as main raw materials in a weak alkaline system through non-covalent interaction between molecules. The biomass gel is a room-temperature gelatinous gel, has good temperature responsiveness, and has excellent specific capacity, remarkable shear thinning characteristics, large shear strain, self-healing characteristics, non-frequency dependence and time stability through tests.

Description

Technical Field

[0001] This invention relates to the field of gel preparation technology, and in particular to a biomass gel, its preparation method, and its application. Background Technology

[0002] As the most promising renewable material, biomass materials are an effective technological way to achieve "dual carbon" reduction by promoting the resource utilization of abundant and environmentally friendly biomass materials.

[0003] In recent years, biomass materials have become a hot topic in energy storage electrode materials. However, current biomass materials have drawbacks in preparation and application, such as difficulty in controlling physicochemical structure, low specific capacity, poor activity, low cycle stability, simple coin-type assembly, lack of flexibility, and inability to be fabricated in a large-area, designable, and refined manner.

[0004] Therefore, the existing technology still needs further improvement and enhancement. Summary of the Invention

[0005] In view of the shortcomings of the prior art, the purpose of this invention is to provide a biomass gel, its preparation method and application, in order to solve the problem of low specific capacity of existing biomass gels.

[0006] A method for preparing a biomass gel, comprising the following steps:

[0007] 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 the porous graphene is 1:0.14-7; the pH value of the mixture is 8-10;

[0008] The mixture was sonicated at 30-70°C and then cooled to obtain a biomass gel.

[0009] Optionally, in the method for preparing the biomass gel, the anthraquinone small molecule is selected from one of the following: rhein, emodin, chrysophanol, alizarin, hydroxyalizarin, and alizarin red.

[0010] Optionally, in the method for preparing the biomass gel, the porous graphene is lignin-based porous graphene.

[0011] Optionally, in the method for preparing the biomass gel, the total mass fraction of the anthraquinone small molecules and porous graphene in the mixture is 1.8-2.3%.

[0012] Optionally, in the method for preparing the biomass gel, the molar concentration of the sodium bicarbonate solution is 0.16-0.22 mol / L; and the molar concentration of the phosphate buffer solution is 0.1-0.15 mol / L.

[0013] Optionally, in the method for preparing the biomass gel, the mass ratio of the anthraquinone small molecules to the porous graphene is 2:1 to 1:3.

[0014] Optionally, the method for preparing the biomass gel, wherein the step of sonicating the mixture at 30-70°C and then cooling it to obtain the biomass gel specifically includes: sonicating the mixture at 40-60°C and then naturally cooling it to 25°C to obtain the biomass gel.

[0015] Optionally, in the method for preparing the biomass gel, the ultrasonic time is 0.5-4.5 hours.

[0016] A biomass gel, wherein the biomass gel is prepared using the preparation method described above.

[0017] The above-mentioned biomass gel is used as a material in printing ink formulation.

[0018] Beneficial effects: Compared with the prior art, the preparation method of biomass gel provided by the present invention is easy to operate, requires no solvent, and the instruments and reaction conditions are easy to achieve. The synthesis steps are simple, and the prepared biomass gel is in a gel state at room temperature. It has good temperature response, high specific capacity and excellent rheological properties. Compared with solid powder or granular biomass materials, it has better designability for electrodes or devices. Attached Figure Description

[0019] Figure 1 This is a schematic diagram of the process for preparing biomass gels according to an embodiment of the present invention;

[0020] Figure 2 This is a structural model of biomass gel-gel in an embodiment of the present invention;

[0021] Figure 3 The non-covalent interaction configuration between rhein and lignin-based porous graphene provided in the embodiments of the present invention;

[0022] Figure 4 The non-covalent interaction configuration between alizarin red and lignin-based porous graphene provided in the embodiments of the present invention;

[0023] Figure 5Microstructure of rhein / lignin-based porous graphene (R / P) gels with different mass ratios provided in embodiments of the present invention;

[0024] Figure 6 Microstructure of alizarin red / lignin-based porous graphene (A / P) gels with different mass ratios provided in embodiments of the present invention;

[0025] Figure 7 Phase images of rhein / lignin-based porous graphene (R / P) mixed systems with different mass ratios provided in embodiments of the present invention;

[0026] Figure 8 Phase images of alizarin red / lignin-based porous graphene (A / P) mixed systems with different mass ratios provided in embodiments of the present invention;

[0027] Figure 9 The specific capacity of rhein / lignin-based porous graphene (R / P) gels with different mass ratios provided in the embodiments of the present invention at different current densities;

[0028] Figure 10 The specific capacity of alizarin red / lignin-based porous graphene (A / P) gels with different mass ratios at different current densities provided in the embodiments of the present invention;

[0029] Figure 11 The specific capacitance of a supercapacitor prepared by screen printing using biomass gel ink provided in this embodiment of the invention is shown at different current densities. Detailed Implementation

[0030] This invention provides a biomass gel, its preparation method, and its applications. To make the objectives, technical solutions, and effects of this invention clearer and more explicit, the invention is further described in detail below. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0031] To address the challenges of controlling the physicochemical structure and low specific capacity in the preparation of existing biomass gels, this embodiment provides a method for preparing biomass gels, comprising the following steps:

[0032] S10. Disperse 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 the porous graphene is 1:0.14-7; the pH value of the mixture is 8-10.

[0033] Following step S10 is step S20, in which the mixture is sonicated at 30-70°C and then cooled to obtain a biomass gel.

[0034] like Figure 1 As shown, under an air atmosphere, the anthraquinone small molecules and the lignin-based porous graphene were added to a reaction vessel containing 0.2M NaHCO3 solution (pH=8.3) or 0.1M PBS (pH=8.0-9.4) at a molar ratio of 1:0.14-7, ensuring that the total mass fraction of the anthraquinone small molecules and the lignin-based porous graphene in the mixture was 1.92%. The mixture was stirred until homogeneous, and then subjected to ultrasonic treatment at a temperature of 30-70℃. After natural cooling to room temperature (25℃), a biomass gel was obtained. The structural model of the biomass gel is shown below. Figure 2 As shown.

[0035] The anthraquinone small molecules include, but are not limited to, rhein, emodin, chrysophanol, alizarin, hydroxyalizarin, and alizarin red.

[0036] In this embodiment, biomass gel is prepared by self-assembly through the non-covalent interaction between anthraquinone small molecules and lignin-based porous graphene. After the reaction, no purification is required, and the biomass gel is obtained directly.

[0037] In this embodiment, the biomass gel is in a gel state at room temperature. Because the non-covalent interaction between anthraquinone small molecules and lignin-based porous graphene is a relatively weak intermolecular force, coupled with the material properties of graphene and anthraquinone small molecules, it exhibits a certain degree of responsiveness to changes in the external environment. Furthermore, the anthraquinone small molecules and lignin-based porous graphene have a synergistic effect in improving specific capacity. Therefore, the prepared biomass gel has good temperature responsiveness, excellent rheological properties, and high specific capacity. Compared to solid powder or granular biomass materials, it offers better design flexibility for electrodes or devices. Tests show that the biomass gel ink has good printability, and the printed energy storage device exhibits excellent electrochemical performance and can be integrated into the printed device. In addition, the anthraquinone small molecules and lignin-based porous graphene of this invention have a synergistic enhancing effect on energy storage. Moreover, compared to other gels, the biomass gel preparation method provided in this embodiment is simple, easy to understand, easy to operate, requires no solvent, and the instruments and reaction conditions used are easily achievable, with a concise synthesis procedure. Compared with manganese-based inks, precious metal inks, conductive polymer inks, graphene inks, carbon nanotube inks, and MXene inks, the biomass gel ink prepared in this embodiment has excellent gel elasticity and time stability, as well as high specific capacity, energy density, and excellent cycling stability, which can meet general research requirements.

[0038] In one embodiment of this invention, the anthraquinone small molecules are natural products from herbal plants, a commonly used traditional Chinese medicine, and are considered safe. Furthermore, the rhein in the anthraquinone small molecules has a high content of electrochemically active substances and low biotoxicity, resulting in minimal negative environmental impact. Therefore, biomass gel is a renewable green energy storage material.

[0039] In one embodiment of this study, the mass ratio of the anthraquinone small molecules to the lignin-based porous graphene can be 7:1, 5:1, 3:1, 2:1, 1:1, 1:2, 1:3, 1:5, or 1:7, and the total mass fraction of the anthraquinone small molecules and the lignin-based porous graphene in the mixed system is 1.92%. The lignin-based porous graphene exhibits similar non-covalent interactions with different anthraquinone molecules. For example... Figure 3 As shown in Table 1:

[0040] Table 1

[0041]

[0042] E tot Total energy E of each model ads Adsorption energy of each model

[0043] 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 initially located in the plane of the lignin-based porous graphene are repelled out of the plane, indicating a strong non-covalent interaction between rhein and lignin-based porous graphene. 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 one where the molecular plane of rhein is parallel to that of the lignin-based porous graphene. Similarly, as... Figure 4 As shown in Table 2:

[0044] Table 2

[0045]

[0046] E tot Total energy E of each model ads Adsorption energy of each model

[0047] Alizarin red exhibits four non-covalent interaction configurations with lignin-based porous graphene. After the non-covalent interaction with alizarin red, all the doped oxygen atoms initially located in the plane of the lignin-based porous graphene are repelled out of the plane, indicating a strong non-covalent interaction between alizarin red and lignin-based porous graphene. 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 one where the molecular plane of alizarin red is parallel to that of the lignin-based porous graphene. The above optimized model confirms that π-π stacking participates in the non-covalent self-assembly process between anthraquinone small molecules and lignin-based porous graphene.

[0048] Biomass gels with different mass ratios exhibited different intermolecular non-covalent interactions. The main non-covalent interactions between anthraquinone small molecules and lignin-based porous graphene were hydrogen bonding between the hydroxyl groups of the anthraquinone small molecules and the oxygen atoms doped in the lignin-based porous graphene, as well as π-π stacking interactions between molecules. In biomass gels with a mass ratio of 2:1–1:3, the non-covalent interactions between anthraquinone small molecules and lignin-based porous graphene were relatively strong; when the mass ratio was 2:1–7:1 or 1:3–1:7, the excess of anthraquinone small molecules or lignin-based porous graphene led to a weakening of the intermolecular non-covalent interactions. Scanning electron microscopy experiments showed that different mass ratios resulted in different microstructures. Figures 5 to 6 Different component ratios are important for the gelation of the mixtures because the presence of different microscopic interactions can lead to different phase states in each mixture. The degree of non-covalent interaction at each different mass ratio will also affect their rheological properties.

[0049] In one embodiment 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°C, or 60°C to 70°C. After ultrasounding at the above temperatures, the ultrasound is naturally cooled to room temperature (25°C), resulting in a faster gelation rate.

[0050] In one embodiment of this example, the ultrasound time can be 0.5 hours, 1 hour, 1.5 hours, 2 hours, 2.5 hours, 3 hours, 3.5 hours, 4 hours, or 4.5 hours, at which time complete gelation can be achieved.

[0051] The following specific embodiments will further explain and illustrate the biomass gel, its preparation method, and its applications provided by the present invention.

[0052] Example 1

[0053] In an air atmosphere, 8.75 g of anthraquinone small molecules and 1.25 g of lignin-based porous graphene (A / P = 7:1 and R / P = 7:1) were added to a reactor containing 0.5 mL of 0.2 M NaHCO3 solution (pH = 8.3), and then stirred to mix evenly. The mixture was then heated to 30 °C and subjected to ultrasonic treatment for 0.5 hours.

[0054] After sonication, the biomass gel is obtained by naturally cooling to room temperature (25°C).

[0055] Example 2

[0056] In an air atmosphere, 8.35 g of anthraquinone small molecules and 1.67 g of lignin-based porous graphene (A / P = 5:1 and R / P = 5:1) were added to a reactor containing 0.5 mL of 0.2 M NaHCO3 solution (pH = 8.3), and then stirred to mix evenly. The mixture was then heated to 35 °C and subjected to ultrasonic treatment for 1.0 hour.

[0057] After sonication, the biomass gel is obtained by naturally cooling to room temperature (25°C).

[0058] Example 3

[0059] In an air atmosphere, 7.5 g of anthraquinone small molecules and 2.5 g of lignin-based porous graphene (A / P = 3:1 and R / P = 3:1) were added to a reactor containing 0.5 mL of 0.2 M NaHCO3 solution (pH = 8.3), and then stirred to mix evenly. The mixture was then heated to 40 °C and subjected to ultrasonic treatment for 1.5 hours.

[0060] After sonication, the biomass gel is obtained by naturally cooling to room temperature (25°C).

[0061] Example 4

[0062] In an air atmosphere, 6.6 g of anthraquinone small molecules and 3.3 g of lignin-based porous graphene (A / P = 2:1 and R / P = 2:1) were added to a reactor containing 0.5 mL of 0.2 M NaHCO3 solution (pH = 8.3), and then stirred to mix evenly. The mixture was then heated to 45 °C and subjected to ultrasonic treatment for 2.0 hours.

[0063] After sonication, the biomass gel is obtained by naturally cooling to room temperature (25°C).

[0064] Example 5

[0065] In an air atmosphere, 5g of anthraquinone small molecules and 5g of lignin-based porous graphene (A / P=1:1 and R / P=1:1) were added to a reactor containing 0.5mL of 0.2M NaHCO3 solution (pH=8.3), and then stirred to mix evenly. The mixture was then heated to 50℃ and subjected to ultrasonic treatment for 2.5 hours.

[0066] After sonication, the biomass gel is obtained by naturally cooling to room temperature (25°C).

[0067] Example 6

[0068] In an air atmosphere, 3.3 g of anthraquinone small molecules and 6.6 g of lignin-based porous graphene (A / P = 1:2 and R / P = 1:2) were added to a reactor containing 0.5 mL of 0.2 M NaHCO3 solution (pH = 8.3), and then stirred to mix evenly. The mixture was then heated to 55 °C and subjected to ultrasonic treatment for 3.0 hours.

[0069] After sonication, the biomass gel is obtained by naturally cooling to room temperature (25°C).

[0070] Example 7

[0071] In an air atmosphere, 2.5 g of anthraquinone small molecules and 7.5 g of lignin-based porous graphene (A / P = 1:3 and R / P = 1:3) were added to a reactor containing 0.5 mL of 0.2 M NaHCO3 solution (pH = 8.3), and then stirred to mix evenly. The mixture was then heated to 60 °C and subjected to ultrasonic treatment for 3.5 hours.

[0072] After sonication, the biomass gel is obtained by naturally cooling to room temperature (25°C).

[0073] Example 8

[0074] In an air atmosphere, 1.67 g of anthraquinone molecules and 8.35 g of lignin-based porous graphene (A / P = 1:5 and R / P = 1:5) were added to a reactor containing 0.5 mL of 0.2 M NaHCO3 solution (pH = 8.3), and then stirred to mix evenly. The mixture was then heated to 65 °C and subjected to ultrasonic treatment for 4.0 hours.

[0075] After sonication, the biomass gel is obtained by naturally cooling to room temperature (25°C).

[0076] Example 9

[0077] In an air atmosphere, 1.25 g of anthraquinone small molecules and 8.75 g of lignin-based porous graphene (A / P = 1:7 and R / P = 1:7) were added to a reactor containing 0.5 mL of 0.2 M NaHCO3 solution (pH = 8.3), and then stirred to mix evenly. The mixture was then heated to 70 °C and subjected to ultrasonic treatment for 4.5 hours.

[0078] After sonication, the biomass gel is obtained by naturally cooling to room temperature (25°C).

[0079] like Figures 7 to 8 As shown, the biomass gels prepared in Examples 1 to 9 exhibit different phase states. Among them, the biomass gels prepared in Examples 4 to 7 exhibit a gel-like state. Experimental verification was conducted on these gels, and the results are as follows:

[0080] like Figures 9 to 10 As shown, the biomass gel prepared in Example 6 (R / P = 1:2 and A / P = 1:2) has a high specific capacity and is formulated into ink based on the above Example 6.

[0081] like Figure 11 As shown, the specific capacitance of the supercapacitor made by screen printing with biomass gel ink at a mass ratio of 1:2 is about 5 times that of the supercapacitor made with lignin-based porous graphene ink. This indicates that the anthraquinone small molecules in the prepared biomass gel and the lignin-based porous graphene have a synergistic effect in improving the specific capacitance, thereby enabling the large-area and high-precision utilization of biomass materials in the field of printed electronics and increasing the added value of biomass materials.

[0082] In summary, this invention provides a biomass gel, its preparation method, and its applications. Using anthraquinone small molecules and lignin-based porous graphene as main raw materials, the biomass gel is prepared through self-assembly via non-covalent intermolecular interactions in a weakly alkaline system. The biomass gel is a room-temperature gel with good temperature responsiveness. Testing shows that the biomass gel possesses excellent specific capacity, significant shear-thinning properties, large shear strain, self-healing characteristics, non-frequency dependence, 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 used to prepare high-performance patterned energy storage electrodes or integrated devices.

[0083] It should be understood that the application of the present invention is not limited to the examples above. Those skilled in the art can make improvements or modifications based on the above description, and all such improvements and modifications should fall within the protection scope of the appended claims.

Claims

1. A method for preparing a biomass gel, characterized in that, Includes the following 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 the porous graphene is 1:0.14-7; the pH value of the mixture is 8-10; The mixture was sonicated at 30-70°C and then cooled to obtain a biomass gel. The anthraquinone small molecules are selected from one of the following: rhein, emodin, chrysophanol, alizarin, hydroxyalizarin, and alizarin red; The porous graphene is lignin-based porous graphene; The biomass gel is in a gel state at room temperature; The step of sonicating the mixture at 30-70℃ and then cooling it to obtain a biomass gel specifically includes: sonicating the mixture at 40-60℃ and then naturally cooling it to 25℃, and then self-assembling the biomass gel through the non-covalent interaction between anthraquinone small molecules and lignin-based porous graphene. The total mass fraction of the anthraquinone small molecules and porous graphene in the mixture is 1.8-2.3%; The sodium bicarbonate solution has a molar concentration of 0.16-0.22 mol / L; the phosphate buffer solution has a molar concentration of 0.1-0.15 mol / L; and the ultrasonication time is 0.5-4.5 hours.

2. The method for preparing biomass gel according to claim 1, characterized in that, The mass ratio of the anthraquinone small molecules to the porous graphene is 2:1 to 1:

3.

3. A biomass gel, characterized in that, The biomass gel was prepared using the preparation method described in any one of claims 1-2.

4. The application of the biomass gel as described in claim 3 as a material for printing ink formulation.

Images