Chem. J. Chinese Universities ›› 2022, Vol. 43 ›› Issue (10): 20220216.doi: 10.7503/cjcu20220216
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TIAN Xiaokang1,2, ZHANG Qingsong1,2(), YANG Shulin1,2, BAI Jie3, CHEN Bingjie1,2, PAN Jie4, CHEN Li1,2, WEI Yen5
Received:
2022-04-06
Online:
2022-10-10
Published:
2022-06-11
Contact:
ZHANG Qingsong
E-mail:zqs8011@163.com
Supported by:
CLC Number:
TrendMD:
TIAN Xiaokang, ZHANG Qingsong, YANG Shulin, BAI Jie, CHEN Bingjie, PAN Jie, CHEN Li, WEI Yen. Porous Materials Inspired by Microbial Fermentation: Preparation Method and Application[J]. Chem. J. Chinese Universities, 2022, 43(10): 20220216.
Methods | Mechanism | Advantage | Disadvantage |
---|---|---|---|
Freeze? drying[ | The well?free gel absorbs water after deep freezing, followed by vacuum drying to sublimate the solvent, thus leaving the hole. | Wide application, convenient operation, without any chemical solvent or heating, safety and green. | The size of holes depends on the growth form and growth rate of ice crystals at different temperatures, which is not easy to control. |
Phase separation[ | Different temperatures cause phase transformation, so that a polymer?rich phase and a polymer?poor phase are generated in the reaction solution, and phase separation occurs. The pores of the gel appear after the solvent is removed. | Compared with the traditional non?porous gel, the swelling rate is improved by 5 to 6 times, thereby providing advantages for the application of drug transmission, water absorption and sensor. | Poor universality; higher or lower heating rate will result in a closed pore structure, and it is difficult to control the pore size and porosity. |
Supercritical fluids[ | Supercritical carbon dioxide(SC?CO2) was used to replace organic foaming agent, and foaming was carried out under a certain pressure and temperature. | The gas is non?toxic, stable, cheap and easy to obtain and many other advantages. | The unit is relatively complex and the melt temperature is relatively high (155—170 ℃). The cell size distribution is uniform only when the approp? riate melt temperature is reached. |
Templating method[ | Regular template was added into the prepolymer solution for polymerization, and the pore size was determined by the template. | Porous gel with uniform distribution can be prepared. The pore size can be adjusted according to the content of surfactant in the emulsion. | When removing the template, a large number of organic solvents need to be used, which will pollute and cause solvent residue, so it is not widely used. |
Pore?foaming agent[ | In the process of polymerization, the pore forming agent is added, and the gel is soaked in water or acid solution to dissolve the pore forming agent, leaving holes in its original position. | It can improve gel swelling and deswelling properties and improve product mechanical strength. | Processes such as dissolution, water washing, soaking, and removal of porogens are time?consuming and have problems with porogen residues. |
Foaming[ | Adding gaseous substances to the polymer solution during the reaction, producing gases during gelation and leaving holes in the polymer after the reaction is completed. | The samples are diverse in size, low cost, pollution free and energy efficient. | Gelation was required to be synchronized with the addition of foaming agents to obtain well porous hydrogels, and the reaction conditions had an important influence on the gelation process. |
3D printing[ | Using CAD of 3D digital models, printing using adhesible materials, and many ways such as crosslinking by photocuring or regulation of environmental conditions, achieve rapid shaping of hydrogels. | Quick prototyping greatly reduces the difficulty of forming hydrogels with 3D complex structure. No special moulds and tools are required for the process. | High cost, low manufacturing efficiency, limited scale production, relatively poor accuracy, physical and chemical performance, limited use in actual projects. |
Method induced by microorganism | The MIH constructed by in?situ free radical polymerization and freeze?induced phase separation using CO2 generated from fermentation of microorganism and carbon source as foaming agent. | The microorganism has the advanta?ges of quick reaction, mild conditions, wide sources and low price. | The reproductive capacity of yeast is too strong for yeast to be completely remove from that porous hydrogel. |
Table 1 Comparison of preparation methods of Porous hydrogel
Methods | Mechanism | Advantage | Disadvantage |
---|---|---|---|
Freeze? drying[ | The well?free gel absorbs water after deep freezing, followed by vacuum drying to sublimate the solvent, thus leaving the hole. | Wide application, convenient operation, without any chemical solvent or heating, safety and green. | The size of holes depends on the growth form and growth rate of ice crystals at different temperatures, which is not easy to control. |
Phase separation[ | Different temperatures cause phase transformation, so that a polymer?rich phase and a polymer?poor phase are generated in the reaction solution, and phase separation occurs. The pores of the gel appear after the solvent is removed. | Compared with the traditional non?porous gel, the swelling rate is improved by 5 to 6 times, thereby providing advantages for the application of drug transmission, water absorption and sensor. | Poor universality; higher or lower heating rate will result in a closed pore structure, and it is difficult to control the pore size and porosity. |
Supercritical fluids[ | Supercritical carbon dioxide(SC?CO2) was used to replace organic foaming agent, and foaming was carried out under a certain pressure and temperature. | The gas is non?toxic, stable, cheap and easy to obtain and many other advantages. | The unit is relatively complex and the melt temperature is relatively high (155—170 ℃). The cell size distribution is uniform only when the approp? riate melt temperature is reached. |
Templating method[ | Regular template was added into the prepolymer solution for polymerization, and the pore size was determined by the template. | Porous gel with uniform distribution can be prepared. The pore size can be adjusted according to the content of surfactant in the emulsion. | When removing the template, a large number of organic solvents need to be used, which will pollute and cause solvent residue, so it is not widely used. |
Pore?foaming agent[ | In the process of polymerization, the pore forming agent is added, and the gel is soaked in water or acid solution to dissolve the pore forming agent, leaving holes in its original position. | It can improve gel swelling and deswelling properties and improve product mechanical strength. | Processes such as dissolution, water washing, soaking, and removal of porogens are time?consuming and have problems with porogen residues. |
Foaming[ | Adding gaseous substances to the polymer solution during the reaction, producing gases during gelation and leaving holes in the polymer after the reaction is completed. | The samples are diverse in size, low cost, pollution free and energy efficient. | Gelation was required to be synchronized with the addition of foaming agents to obtain well porous hydrogels, and the reaction conditions had an important influence on the gelation process. |
3D printing[ | Using CAD of 3D digital models, printing using adhesible materials, and many ways such as crosslinking by photocuring or regulation of environmental conditions, achieve rapid shaping of hydrogels. | Quick prototyping greatly reduces the difficulty of forming hydrogels with 3D complex structure. No special moulds and tools are required for the process. | High cost, low manufacturing efficiency, limited scale production, relatively poor accuracy, physical and chemical performance, limited use in actual projects. |
Method induced by microorganism | The MIH constructed by in?situ free radical polymerization and freeze?induced phase separation using CO2 generated from fermentation of microorganism and carbon source as foaming agent. | The microorganism has the advanta?ges of quick reaction, mild conditions, wide sources and low price. | The reproductive capacity of yeast is too strong for yeast to be completely remove from that porous hydrogel. |
Type | Pore structure parameter | Ref. | |||
---|---|---|---|---|---|
Porosity(%) | Density/(g?cm?3) | Specific surface area/(m2?g?1) | Pore size/μm | ||
GO/CS/PVA composite sponge | 67.72—78.31 | 0.215—0.319 | — | — | [ |
P(AAEA?co?AMPS) hydrogel | — | — | — | 30—120 | [ |
Polyacrylamide(PAM) hydrogel | — | 0.33—0.76 | — | 1.04—2.48 | [ |
Chitosan and alginate scaffolds | ~90 | — | — | 60—150 | [ |
PEG?grafted SPH | — | — | — | 100—250 | [ |
3D Porous graphene oxide | — | 0.01—0.028 | ~206.8 | — | [ |
Air?dryable graphene hydrogels | — | 0.0063—0.063 | — | 18—95 | [ |
PVA/C porous hydrogels | ~54.1 | 0.3—0.85 | — | ~21.34 | [ |
Chitosan?agarose cryogels | 80—85 | — | — | 85—100 | [ |
PEG hydrogel scaffolds | 55—84 | — | — | 53—180 | [ |
Supermacroporous cryogel | — | — | 84.9—194.9 | 10—200 | [ |
Cryogels | — | — | ~192 | 10—100 | [ |
Carbon aerogels | — | ~0.225 | 550—660 | 0.03—0.05 | [ |
Hierarchical porous chitosan?carbon | 80—94 | — | 667—1743 | 0.00268—0.00358 | [ |
Nanocomposite gels | — | — | ~17.7 | ~0.0033 | [ |
Lightweight ceramic foam | 74.1—82.4 | 0.38—0.56 | — | 1500—5600 | [ |
Table 2 Pore structure parameters(porosity, density, specific surface area and pore size) of porous hydrogel
Type | Pore structure parameter | Ref. | |||
---|---|---|---|---|---|
Porosity(%) | Density/(g?cm?3) | Specific surface area/(m2?g?1) | Pore size/μm | ||
GO/CS/PVA composite sponge | 67.72—78.31 | 0.215—0.319 | — | — | [ |
P(AAEA?co?AMPS) hydrogel | — | — | — | 30—120 | [ |
Polyacrylamide(PAM) hydrogel | — | 0.33—0.76 | — | 1.04—2.48 | [ |
Chitosan and alginate scaffolds | ~90 | — | — | 60—150 | [ |
PEG?grafted SPH | — | — | — | 100—250 | [ |
3D Porous graphene oxide | — | 0.01—0.028 | ~206.8 | — | [ |
Air?dryable graphene hydrogels | — | 0.0063—0.063 | — | 18—95 | [ |
PVA/C porous hydrogels | ~54.1 | 0.3—0.85 | — | ~21.34 | [ |
Chitosan?agarose cryogels | 80—85 | — | — | 85—100 | [ |
PEG hydrogel scaffolds | 55—84 | — | — | 53—180 | [ |
Supermacroporous cryogel | — | — | 84.9—194.9 | 10—200 | [ |
Cryogels | — | — | ~192 | 10—100 | [ |
Carbon aerogels | — | ~0.225 | 550—660 | 0.03—0.05 | [ |
Hierarchical porous chitosan?carbon | 80—94 | — | 667—1743 | 0.00268—0.00358 | [ |
Nanocomposite gels | — | — | ~17.7 | ~0.0033 | [ |
Lightweight ceramic foam | 74.1—82.4 | 0.38—0.56 | — | 1500—5600 | [ |
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