CN111040234A - Novel preparation method of hierarchical pore chitin material - Google Patents
Novel preparation method of hierarchical pore chitin material Download PDFInfo
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- CN111040234A CN111040234A CN201911292154.1A CN201911292154A CN111040234A CN 111040234 A CN111040234 A CN 111040234A CN 201911292154 A CN201911292154 A CN 201911292154A CN 111040234 A CN111040234 A CN 111040234A
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- chitin
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J9/00—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof
- C08J9/28—Working-up of macromolecular substances to porous or cellular articles or materials; After-treatment thereof by elimination of a liquid phase from a macromolecular composition or article, e.g. drying of coagulum
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2201/00—Foams characterised by the foaming process
- C08J2201/04—Foams characterised by the foaming process characterised by the elimination of a liquid or solid component, e.g. precipitation, leaching out, evaporation
- C08J2201/048—Elimination of a frozen liquid phase
- C08J2201/0484—Elimination of a frozen liquid phase the liquid phase being aqueous
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2205/00—Foams characterised by their properties
- C08J2205/04—Foams characterised by their properties characterised by the foam pores
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08J—WORKING-UP; GENERAL PROCESSES OF COMPOUNDING; AFTER-TREATMENT NOT COVERED BY SUBCLASSES C08B, C08C, C08F, C08G or C08H
- C08J2305/00—Characterised by the use of polysaccharides or of their derivatives not provided for in groups C08J2301/00 or C08J2303/00
- C08J2305/08—Chitin; Chondroitin sulfate; Hyaluronic acid; Derivatives thereof
Abstract
The invention relates to a novel preparation method of a porous chitin material, belonging to the technical field of materials. The invention adopts natural polysaccharide chitin as a material substrate, calcium carbonate and chitosan are respectively used as a super-macroporous template and a microporous-mesoporous template, and the template is removed by acid treatment after the three are mixed and formed, so that the hierarchical porous chitin material is finally obtained. The chitin material prepared by the preparation method has the structure of ultra-large pores, mesopores and micropores, wherein the mesopores and the micropores can provide larger surface area, and the ultra-large pores and the macropores can promote the medium to rapidly enter the inner pore passage of the chitin material, promote mass transfer and improve efficiency. Meanwhile, the method has the advantages of simple process, easy industrial production, wide raw material source, easy degradation, no toxicity, good biocompatibility and huge application potential in the fields of separation, catalysis, medicine, energy and the like.
Description
Technical Field
The invention belongs to the technical field of materials, and relates to a novel preparation method of a hierarchical pore chitin material.
Background
Chitin is one of the most abundant biomass resources in the nature, mainly exists in shrimp, crab shell, cell walls of fungi and algae and shells of arthropod, and the annual output can reach 1010-1011Ton, low price, good biocompatibility, easy degradation, no toxicity and the like, and simultaneously, the biomass material is an ideal biomass material easy to functionalize due to a large amount of hydroxyl groups, and shows great application in the fields of chemistry, biology, medicine, adsorption, separation and the likeAnd therefore attract the attention of a large number of researchers.
The hierarchical porous material has a porous structure with multiple scales, so that the material has the advantages of high specific surface area, high contact area, low density and the like, and has obvious improvement effects on light absorption, ion and electron transfer, mass load and transmission, so that the hierarchical porous material has unusual application potential in the fields of energy storage and conversion, catalysis, adsorption, separation, biological medicine and the like. The invention takes chitin which is an abundant biomass resource as a research object and adopts a double-template method to prepare the hierarchical pore chitin material. The key points of the preparation method are as follows: the method comprises the steps of adopting natural polysaccharide chitin as a material substrate, respectively adopting calcium carbonate and chitosan as ultra-macroporous and microporous-mesoporous pore-forming agents, removing a template through acid treatment after the material is formed, and finally obtaining the multi-level pore chitin material.
Disclosure of Invention
The invention utilizes chitin which is an abundant natural biomass resource, and adopts calcium carbonate and chitosan as template agents to prepare the hierarchical pore chitin material. The chitin material prepared by the method has the structure of super-macropores, mesopores and micropores, wherein the mesopores and the micropores provide larger surface area, and the super-macropores and the macropores can be used for allowing a medium to rapidly enter an inner pore channel of the chitin material, so that the absorption of the chitin material to light, the transmission of ionic electrons, the mass load and the transmission performance are improved.
The purpose of the invention is realized by the following technical scheme.
A novel preparation method of hierarchical pore chitin material is characterized by comprising the following steps:
(1) dissolving chitin in 11 wt% NaOH/4 wt% urea solution to form transparent chitin solution; dissolving chitosan in 8 wt% LiOH/7 wt% KOH/8 wt% urea/77 wt% H2Forming a transparent chitosan solution in the O solution;
(2) mixing the chitin solution obtained in the last step with chitosan according to a certain mass ratio, and uniformly stirring the mixed solution to form a transparent chitin/chitosan solution;
(3) adding appropriate amount of CaCO3Adding the powder into the obtained chitin/chitosan solution, and uniformly stirring to form uniform suspension;
(4) spreading the solution in culture dish, regenerating with non-chitin/chitosan solvent, and acid treating to remove chitosan and CaCO3Template to obtain chitin hydrogel;
(5) and drying the obtained hydrogel to obtain the hierarchical pore chitin material.
Preferably, the concentration of the chitin and chitosan solution in the step (1) is 0.5-6.0 wt%;
preferably, the mass ratio of the chitin/chitosan solution in the step (2) is more than 50%;
preferably, the non-chitin/chitosan solvent used in step (4) is a regeneration bath, and the regeneration bath can be a non-chitin/chitosan solvent such as acid, salt, alcohol, ester, alkane, and the like;
preferably, the drying step in step (5) may be supercritical drying, freeze drying, displacement drying, etc. to remove the liquid in the gel.
Compared with the prior art, the invention has the following advantages:
(1) the method has the advantages of simple operation, easily obtained raw materials and easy large-scale industrial production.
(2) The invention takes chitin as raw material, has low cost, no pollution to environment, easy degradation and good biocompatibility.
(3) The chitin material prepared by the invention has a structure of ultra-large pores, mesopores and micropores, wherein the micropores and the mesopores provide larger surface areas, and the ultra-large pores and the macropores provide wide pore channels to promote mass transfer, so that the chitin material has unusual application potential in the fields of separation, catalysis, energy and the like.
Drawings
FIG. 1 is a scanning electron micrograph of a product of example 1 of the present invention.
FIG. 2 is a nitrogen adsorption/desorption diagram of the product of example 1 of the present invention.
Detailed Description
For a better understanding of the invention, it will be explained further below with reference to the embodiment examples and the accompanying drawings. It should be noted that the embodiments are only used for further explaining the invention, and the scope of the invention to be claimed is not limited to the scope shown in the embodiments.
Examples 1
Dissolving 4 g chitin in 96 g 11 wt% NaOH/4 wt% urea solution to form 4wt% transparent chitin solution, and dissolving 4 g chitosan in 96 g 8 wt% LiOH/7 wt% KOH/8 wt% urea/77 wt% H2Forming a 4wt% transparent chitosan solution in the O solution; mixing the chitin solution obtained in the last step with chitosan according to the mass ratio of 85%, and uniformly stirring the mixed solution to form a transparent chitin/chitosan solution; an appropriate amount of 8 g CaCO3Adding the powder into the obtained 47 mL chitin/chitosan solution, and uniformly stirring to form uniform suspension; the solution was spread on a petri dish, regenerated with 5wt% sulfuric acid and the chitosan and CaCO removed3Template to obtain chitin hydrogel; and (3) freeze-drying the obtained hydrogel to obtain the hierarchical pore chitin material. Scanning electron microscope pictures show that the surfaces of the obtained chitin materials present micron-sized super-large pores; further combining with a nitrogen adsorption/desorption diagram, the material shows an IV-type curve, which indicates that the material has abundant micropores and mesopores; meanwhile, in a high-pressure area, the curve also shows a remarkable rising trend, which indicates that the material also has a macroporous structure. In conclusion, the hierarchical pore chitin material can be prepared by the double-template method.
Claims (6)
1. A novel preparation method of hierarchical pore chitin material is characterized by comprising the following steps:
(1) dissolving chitin in 11 wt% NaOH/4 wt% urea solution to form transparent chitin solution; dissolving chitosan in 8 wt% LiOH/7 wt% KOH/8 wt% urea/77 wt% H2Forming a transparent chitosan solution in the O solution;
(2) mixing the chitin solution obtained in the last step with chitosan according to a certain mass ratio, and uniformly stirring the mixed solution to form a transparent chitin/chitosan solution;
(3) adding appropriate amount of CaCO3Adding the powder into the obtained chitin/chitosan solution, and uniformly stirring to form uniform suspension;
(4) spreading the solution in culture dish, regenerating with non-chitin/chitosan solvent, and acid treating to remove chitosan and CaCO3Template to obtain chitin hydrogel;
(5) and drying the obtained hydrogel to obtain the hierarchical pore chitin material.
2. The novel process for preparing a hierarchical pore chitosan material as claimed in claim 1, wherein said chitosan material in step (1) can be in the form of film, spheres, blocks, etc.
3. The novel method for preparing a hierarchical pore chitin material according to claim 1, wherein the concentration of the chitin solution and the concentration of the chitosan solution formed in step (1) are both 0.5 wt% to 6 wt%.
4. The method of claim 1, wherein the mass ratio of chitin to chitosan in step (2) is greater than 50%.
5. The method of claim 1, wherein the non-chitin/chitosan solvent used in step (4) is selected from non-chitin and chitosan solvents such as acid, salt, alcohol, ester, alkane, etc.
6. The method for preparing ultra-large pore cellulose microsphere as claimed in claim 1, wherein the drying method adopted in step (5) is supercritical drying, freeze drying, displacement drying, etc. to remove the liquid in the gel.
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Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113697796A (en) * | 2021-07-09 | 2021-11-26 | 中山大学 | Three-dimensional communicated carbon nanosheet with ultrahigh specific surface area and preparation method and application thereof |
| CN115536896A (en) * | 2022-10-20 | 2022-12-30 | 南昌大学 | Chitin-chitosan-based double-crosslinked aerogel and preparation method thereof |
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| US20070148770A1 (en) * | 2000-11-30 | 2007-06-28 | Korea Institute Of Science And Technology | Macroporous chitosan beads and preparation method thereof |
| CN105566674A (en) * | 2016-01-27 | 2016-05-11 | 中国林业科学研究院木材工业研究所 | Chitin-nanometer-fiber aerogel with high specific surface area and preparing method thereof |
| CN106924090A (en) * | 2017-03-22 | 2017-07-07 | 吉林大学 | A kind of preparation and application of the immobilized lysozyme toothpaste of multistage hole bioactive glass |
| CN109092276A (en) * | 2018-09-12 | 2018-12-28 | 北京化工大学 | A kind of preparation of the spherical gel chromatographic media of multi-layer pore size distribution |
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- 2019-12-16 CN CN201911292154.1A patent/CN111040234B/en active Active
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US20070148770A1 (en) * | 2000-11-30 | 2007-06-28 | Korea Institute Of Science And Technology | Macroporous chitosan beads and preparation method thereof |
| CN105566674A (en) * | 2016-01-27 | 2016-05-11 | 中国林业科学研究院木材工业研究所 | Chitin-nanometer-fiber aerogel with high specific surface area and preparing method thereof |
| CN106924090A (en) * | 2017-03-22 | 2017-07-07 | 吉林大学 | A kind of preparation and application of the immobilized lysozyme toothpaste of multistage hole bioactive glass |
| CN109092276A (en) * | 2018-09-12 | 2018-12-28 | 北京化工大学 | A kind of preparation of the spherical gel chromatographic media of multi-layer pore size distribution |
Non-Patent Citations (1)
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| 卢芸等: "超声法制备α-甲壳素纳米纤维及气凝胶", 《科技导报》 * |
Cited By (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN113697796A (en) * | 2021-07-09 | 2021-11-26 | 中山大学 | Three-dimensional communicated carbon nanosheet with ultrahigh specific surface area and preparation method and application thereof |
| CN113697796B (en) * | 2021-07-09 | 2023-01-20 | 中山大学 | Three-dimensionally communicated carbon nanosheet with ultrahigh specific surface area, and preparation method and application thereof |
| CN115536896A (en) * | 2022-10-20 | 2022-12-30 | 南昌大学 | Chitin-chitosan-based double-crosslinked aerogel and preparation method thereof |
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| CN111040234B (en) | 2021-09-14 |
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