CN111040234B - Preparation method of hierarchical pore chitin material - Google Patents
Preparation method of hierarchical pore chitin material Download PDFInfo
- Publication number
- CN111040234B CN111040234B CN201911292154.1A CN201911292154A CN111040234B CN 111040234 B CN111040234 B CN 111040234B CN 201911292154 A CN201911292154 A CN 201911292154A CN 111040234 B CN111040234 B CN 111040234B
- Authority
- CN
- China
- Prior art keywords
- chitin
- solution
- chitosan
- preparation
- template
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Active
Links
Images
Classifications
-
- 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
-
- 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
-
- 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
-
- 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 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 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 1010-1011The biomass material has the characteristics of low price, good biocompatibility, easy degradation, no toxicity and the like, is an ideal biomass material easy to functionalize due to a large amount of hydroxyl groups, and shows great application potential in the fields of chemistry, biology, medicine, adsorption, separation and the like, thereby attracting 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 preparation method of a 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 and the chitosan solution obtained in the last step by the mass ratio of more than 50%, and uniformly stirring the mixed solution to form a transparent chitin/chitosan solution;
(3) 8 g 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 non-chitin/chitosan solvent is used as a regeneration bath in the step (4), and the regeneration bath is acid, alcohol, ester or alkane;
preferably, the drying step (5) is supercritical drying, freeze drying or displacement drying.
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 the chitin as the raw material, has low cost, no pollution to the 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 4 wt% transparent chitin solution, and dissolving 4 g chitosan in 96 g 8 wt% LiOH/7 wt% KOH/8 wt% urea/77 wt% H2Forming a 4 wt% transparent chitosan solution in the O solution; mixing the chitin solution and the chitosan solution obtained in the last step 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. By scanning the electricityThe mirror picture shows that the surface of the obtained chitin material presents micron-sized super-large holes; 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 (4)
1. A preparation method of a 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 and the chitosan solution obtained in the last step by the mass ratio of more than 50%, and uniformly stirring the mixed solution to form a transparent chitin/chitosan solution;
(3) 8 g of CaCO3Adding the powder into the obtained chitin/chitosan solution, and uniformly stirring to form uniform suspension;
(4) the solution was spread on a petri dish, regenerated with 5wt% sulfuric acid and the chitosan and CaCO removed3Template to obtain chitin hydrogel;
(5) and drying the obtained hydrogel to obtain the hierarchical pore chitin material.
2. The process according to claim 1, wherein the type of said chitin material in step (1) is in the form of film, spheres, or blocks.
3. The method of claim 1, wherein the concentrations of the chitin solution and the chitosan solution formed in step (1) are 0.5 wt% to 6 wt%.
4. The process according to claim 1, wherein the drying method used in step (5) is supercritical drying, freeze drying or displacement drying to remove the liquid from the gel.
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911292154.1A CN111040234B (en) | 2019-12-16 | 2019-12-16 | Preparation method of hierarchical pore chitin material |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN201911292154.1A CN111040234B (en) | 2019-12-16 | 2019-12-16 | Preparation method of hierarchical pore chitin material |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CN111040234A CN111040234A (en) | 2020-04-21 |
| CN111040234B true CN111040234B (en) | 2021-09-14 |
Family
ID=70236496
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN201911292154.1A Active CN111040234B (en) | 2019-12-16 | 2019-12-16 | Preparation method of hierarchical pore chitin material |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN111040234B (en) |
Families Citing this family (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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 |
Family Cites Families (1)
| 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 |
-
2019
- 2019-12-16 CN CN201911292154.1A patent/CN111040234B/en active Active
Patent Citations (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| 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)
| Title |
|---|
| 超声法制备α-甲壳素纳米纤维及气凝胶;卢芸等;《科技导报》;20141231;第32卷;第61-64页 * |
Also Published As
| Publication number | Publication date |
|---|---|
| CN111040234A (en) | 2020-04-21 |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| CN104722281B (en) | A kind of nano titanium oxide/chitosan three-dimensional is composite porous and preparation method thereof | |
| CN111040234B (en) | Preparation method of hierarchical pore chitin material | |
| Zhu et al. | Lignin-derived sulfonated porous carbon from cornstalk for efficient and selective removal of cationic dyes | |
| CN106853296A (en) | A kind of oil water separation type sodium alginate/graphene oxide composite aerogel and preparation method thereof | |
| KR100954539B1 (en) | The sorbent composition which contains chitosan for water treatment and a method of preparing thereof | |
| CN106076272A (en) | A kind of preparation method of adsorbent for heavy metal | |
| CN107628597B (en) | By using SiO2Method for preparing biomass carbon material with micropore and mesopore structure by coating method | |
| CN111318254A (en) | Preparation method of high-efficiency regenerated activated carbon | |
| CN102641727A (en) | Chitosan collagen biological adsorbent prepared based on ionic liquid serving as solvent | |
| CN113980341B (en) | Preparation method of calcium alginate gel balls | |
| CN109759132A (en) | The preparation method and composite photocatalyst gel ball of composite photocatalyst gel ball | |
| CN106395802B (en) | Preparation method of graphene porous membrane | |
| He et al. | Liquefiable biomass-derived porous carbons and their applications in CO 2 capture and conversion | |
| CN110652962A (en) | Three-dimensional porous graphene/attapulgite composite aerogel and preparation method thereof | |
| CN106215881A (en) | A kind of preparation method of cyanurotriamide modified porous magnetic dextran microspheres | |
| CN105566689B (en) | It is a kind of for starch based aquagel expanded material of sewage disposal and preparation method thereof | |
| CN105195099A (en) | Preparation method of beta-cyclodextrin modified macroporous amino glucan adsorbent | |
| CN114023980B (en) | Preparation method of nitrogen-doped porous carbon material based on furfural residues and electrocatalytic oxygen reduction performance of nitrogen-doped porous carbon material | |
| CN104355311A (en) | Method capable of preparing active carbon by doping surfactant | |
| CN111908443A (en) | Preparation method of self-doped porous carbon | |
| CN112619612A (en) | Preparation method of high-strength cellulose/agarose composite microspheres | |
| CN111530436A (en) | Method for modifying shells | |
| CN1884323A (en) | Cross-linked anion polymer containing tetramethylguanidine cation and its preparation method and uses | |
| CN109569543A (en) | A kind of compressible adsorbent material of 3D printing and preparation method thereof | |
| CN107308986A (en) | A kind of preparation method with photocatalytic activity aerogel microball |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination | ||
| GR01 | Patent grant | ||
| GR01 | Patent grant |