CN113683799B - Preparation method and application of high-strength and high-ion-selectivity film - Google Patents
Preparation method and application of high-strength and high-ion-selectivity film Download PDFInfo
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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
- C08J5/00—Manufacture of articles or shaped materials containing macromolecular substances
- C08J5/18—Manufacture of films or sheets
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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
- C08J3/00—Processes of treating or compounding macromolecular substances
- C08J3/24—Crosslinking, e.g. vulcanising, of macromolecules
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N11/00—Generators or motors not provided for elsewhere; Alleged perpetua mobilia obtained by electric or magnetic means
- H02N11/002—Generators
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- H—ELECTRICITY
- H02—GENERATION; CONVERSION OR DISTRIBUTION OF ELECTRIC POWER
- H02N—ELECTRIC MACHINES NOT OTHERWISE PROVIDED FOR
- H02N3/00—Generators in which thermal or kinetic energy is converted into electrical energy by ionisation of a fluid and removal of the charge therefrom
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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
- C08J2301/00—Characterised by the use of cellulose, modified cellulose or cellulose derivatives
- C08J2301/02—Cellulose; Modified cellulose
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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
- C08J2305/04—Alginic acid; Derivatives thereof
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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
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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
- C08J2397/00—Characterised by the use of lignin-containing materials
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- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08K—Use of inorganic or non-macromolecular organic substances as compounding ingredients
- C08K3/00—Use of inorganic substances as compounding ingredients
- C08K3/01—Use of inorganic substances as compounding ingredients characterized by their specific function
- C08K3/011—Crosslinking or vulcanising agents, e.g. accelerators
Abstract
The invention relates to a high-strength and high-ion selectivity film, a preparation method and application thereof. The film is a biomass-metal ion crosslinked film which is obtained by crosslinking metal ions serving as a crosslinking agent with biomass macromolecules. The method comprises the following steps: 1) Preparing a metal salt solution with a certain concentration and a biomass solution with a certain concentration; 2) Weighing a biomass solution, adding a metal salt solution to crosslink the biomass solution and the metal salt solution, and airing at room temperature to obtain the biomass high-strength crosslinked film. The prepared cross-linked film is applied to salt difference power generation. The invention reduces the problem of environmental pollution and the cost, effectively optimizes the mechanical property of the film, has simple method, and can prepare the cross-linked films with different salt solution concentrations and different thicknesses in a large scale.
Description
Technical Field
The invention relates to a high-strength and high-ion-selectivity film, a preparation method and application, and belongs to the field of preparation of ion-selectivity films.
Background
On the background that non-renewable energy sources such as fossil and the like are rapidly consumed and the environment is increasingly worsened, the exploration of clean and renewable energy sources to meet the requirement of human society on energy sources has important significance on the survival and sustainable development of human civilization. The salt difference energy existing between seawater and fresh water is known as 'blue energy', is clean and sustainable energy, can be regenerated, has no pollution to the environment and zero emission, and compared with wind energy, solar energy and the like, the salt difference energy is not influenced by objective factors such as weather, geographical position and the like, and is more suitable for the development of human beings. But efficiently extracting it as a useful form of energy remains a challenge for current technology. Up to now, the extraction of salts with poor energy based on membrane technology, such as reverse electrodialysis, has attracted much attention due to its remarkable advantages of high safety, simple operation, high flexibility, etc. In the reverse electrodialysis technique, an ion-selective membrane is a key material for converting the salt difference energy into electric energy, the ion selectivity of the membrane determines the performance of the membrane, and the permeability limits the output power density of the membrane. It has become a challenge to balance permeability and selectivity.
In recent years, polymer-based ion-selective membranes have been developed for salinity gradient-driven power conversion due to their low cost and wide resource availability. For example, the combination of two ionic crosslinked polymers with negative charges, namely hexa-sulfonated polyaryletherketone and polyether sulfone with positive charges, which are designed by Zhu et al, and modified pyridine is subjected to spin coating to obtain a three-dimensional porous structure and an asymmetric membrane nano-channel, and the power density is 2.66W m in a seawater and river water system -2 . Chinese patent with application number CN201910848756.4 adopts ultraviolet irradiation method to prepare high-density hybridization step hole ion selective membrane. The invention designs and synthesizes the ultraviolet broken bond and crosslinked block copolymer, realizes the large-area ordered ultrahigh pore density self-supporting membrane by utilizing the block copolymer assembly, and carries out accurate interface modification on the nanometer pore channel by the polyethyleneimine molecule with a three-dimensional structure. The ion transmission amount and ion selectivity brought by ultra-high pore density and charge density can realize the excellent performance of the electrolyte in the aspect of salt tolerance power generation, and the output power density is up to 22.1Wm under the condition of 500 times of electrolyte concentration gradient -2 . The Chinese patent with the application number of CN201710374911.4 adopts a solvent annealing method to prepare a block copolymer membrane and a functional pore ion selective membrane. The invention leads the random channel in the block copolymer film to be vertically communicated through solvent annealing, thereby reducing the effective distance of ion transmission and impedance on one hand, and increasing the effective distance on the other handThe length of the functional area greatly improves the ion selectivity, and the salt difference power generation power density of the composite ion channel salt difference power generation film is 0.70Wm -2 . However, polymer-based ion-selective mechanical properties are poor, and the properties of the membrane are easily affected by seawater or river water, thereby affecting the practical industrial application of the membrane. In addition, the preparation process of the polymer-based membrane is complex or the raw materials are expensive, so that the large-scale preparation is difficult. Furthermore, energy losses during salt-poor energy conversion may also hinder their use. To maintain economic relevance, the ultimate goal of the industry is to ensure output power densities above 5Wm -2 . Therefore, the development of an ion selective membrane with excellent mechanical properties, high power density and programmable large-scale preparation is the key for realizing the industrial application of the ion selective membrane.
Disclosure of Invention
The invention aims to provide a high-strength and high-ion-selectivity film, a preparation method and application aiming at the problems of the existing ion-selectivity film. The high-strength and high-ion selectivity film is a biomass-metal ion cross-linked film, and the high-efficiency conversion of the salt tolerance is realized. The film can be prepared in a large scale, and has the advantages of low cost, simple process and high mechanical strength. The biomass polymer material comprises one, two or more of cellulose, lignin, chitosan, sodium alginate, catechin and chitin, and the metal ions comprise Al 3+ 、Ca 2+ 、Fe 3+ 、Mg 2+ 、Cu 2+ 、Mn 2+ And Sn 4+ One, two or more.
The purpose of the invention is realized by the following technical scheme:
a high-strength and high-ion selectivity film is a metal ion and biomass cross-linked film. Wherein the metal ion is a cross-linking agent. The weight percentage of the biomass in the crosslinked membrane is 80-98% based on the total weight of the crosslinked membrane.
Further, the metal ion is selected from Al 3+ 、Ca 2+ 、Fe 3+ 、Mg 2+ 、Cu 2+ 、Mn 2+ And Sn 4+ One, two or more.
A method of making a high strength, high ion selectivity membrane as described above, comprising the steps of:
1) Adding the biomass material into water, stirring for 3-6h, and then refrigerating for later use; wherein the biomass material comprises one, two or more of cellulose, lignin, chitosan, sodium alginate, catechin and chitin;
2) Preparing a metal salt solution, and then storing for later use; wherein the metal ion salt comprises one, two or more of aluminum salt, calcium salt, iron salt, magnesium salt, copper salt, manganese salt and tin salt;
3) The method comprises the steps of controlling the ambient temperature to be 20-30 ℃ and the relative humidity to be 20-40%, applying the biomass material to a substrate, and then immersing the substrate with the biomass material into a metal salt solution to enable the substrate to generate a crosslinking reaction. And taking out and airing after 5-30min to obtain the biomass high-strength film.
Further, in step 1), the biomass material has a group such as a carboxyl group or the like, and can coordinate with a metal ion.
Further, in step 2), the salt may be, but is not limited to, a sulfate salt and a chloride salt.
Further, the biomass material in the step 1) is added in the following amount by weight: 1-5 parts of biomass material.
Further, the addition amount of the metal salt in the step 2) is calculated by weight parts: 0.05-0.5 part of metal ion salt.
Use of a membrane as described in any one of the above or a high strength, high ion selectivity membrane prepared by a method as described in any one of the above in salt-difference power generation.
The invention has the following advantages:
1) These common biomasses, carrying hydroxyl or carboxyl groups, are highly hydrophilic. 2) Directly chemically cross-linked with metal ions, and stable coordination bonds are formed between the metal ions and the groups instead of being combined by simple electrostatic force. Therefore, the resulting crosslinked film has excellent water stability. The hydrophilicity and the water stability of the membrane lay a foundation for the application of the membrane in salt tolerance power generation. 3) The mechanical property and the salt difference power generation property of the crosslinked membrane can be adjusted through the mass of the crosslinked biomass and the concentration of metal ions. 4) The cross-linked membrane has the advantages of simple preparation method, low cost, excellent mechanical property and large-scale preparation.
Drawings
FIG. 1 shows the mechanical properties of the chitosan-copper ion crosslinked membrane of the present invention.
FIG. 2 shows the salt poor power generation performance of the chitosan-copper ion crosslinked film of the present invention.
Detailed Description
The technical solution of the present invention will be further described with reference to the following examples.
The invention provides a biomass high-strength film which can be prepared in a large scale, is low in cost, simple in process and high in mechanical strength, and a preparation method thereof, and realizes the application of salt tolerance power generation.
The biomass high-strength film comprises the following raw materials in parts by weight:
1-5 parts of biomass and 0.05-0.5 part of metal salt.
The biomass high-strength film provided by the invention is characterized in that the biomass material can be, but not limited to, cellulose, lignin, chitosan, sodium alginate, catechin and chitin.
The biomass high-strength film provided by the invention is characterized in that metal ion salts can be but are not limited to aluminum salt, calcium salt, iron salt, magnesium salt, copper salt, manganese salt and tin salt; the salt can be but not limited to sulfate or chloride, and in practical application, the mixture of 2 or more salts can be used for preparing the biomass high-strength film.
The biomass high-strength film provided by the invention is characterized in that the concentration of the copper chloride solution is 0.1-0.2M, and the copper ion solution can be not limited to copper chloride.
The invention also comprises a preparation method of any biomass high-strength film, which comprises the following steps:
1) Adding the biomass material into water, stirring for 3-6h, and then putting into a refrigerator for refrigeration and preservation for later use;
2) Adding metal salt into water, stirring for 20-30min, and storing for use;
3) The biomass material is applied to a substrate with an ambient temperature of 20-30 ℃ and a relative humidity of 25-40%, and the substrate with the biomass material is then immersed in a metal salt solution to cause a crosslinking reaction. And taking out and airing after 10-20min to obtain the biomass high-strength film.
The invention also provides application of any biomass high-strength film in the field of salt difference power generation.
The invention is described in detail below with reference to the figures and the embodiments. The following examples are only for explaining the present invention, the scope of the present invention shall include the full contents of the claims, and the full contents of the claims of the present invention can be fully realized by those skilled in the art through the following examples.
Example 1:
the preparation method of the chitosan-copper ion film comprises the following steps:
1) Dissolving 2g of chitosan powder in 98g of water to prepare a chitosan solution with the concentration of 2wt%, placing the solution on a magnetic stirrer to stir for 3 hours to ensure that the chitosan powder is completely dissolved to obtain the chitosan solution with certain viscosity, and placing the chitosan solution in a refrigerator to store in a sealed manner for later use.
2) Controlling the ambient temperature at 25 ℃ and the relative humidity at 30%, weighing 3g of the chitosan solution obtained in the step 1) into a culture dish, and uniformly spreading. 5mL of 0.2M CuSO 4 Adding the solution into a culture dish containing chitosan solution, taking out the cross-linked membrane after 10min, sufficiently washing with deionized water to remove residual metal ions on the surface of the membrane, and naturally evaporating water to obtain the chitosan-copper ion thin film. In the chitosan-copper ion film, the weight percentage of biomass is 85%.
Example 2:
the preparation method of the chitin-aluminum ion film comprises the following steps:
1) Dissolving 2g of chitin powder in 98g of water to prepare a chitin solution with the concentration of 2wt%, placing the solution on a magnetic stirrer to stir for 3 hours to ensure that the chitin powder is completely dissolved to obtain the chitin solution with certain viscosity, and placing the chitin solution in a refrigerator to store in a sealed manner for later use.
2) Controlling the environmental temperature at 25 ℃ and the relative humidity at 30%, weighing 3g of the chitin solution obtained in the step 1) in a culture dish, and uniformly spreading. 5mL of 0.2M AlCl 3 Adding the solution into a culture dish containing chitin solution, taking out the cross-linked membrane after 10min, sufficiently washing with deionized water to remove residual metal ions on the surface of the membrane, and naturally evaporating water to obtain the chitin-aluminum ion film. In the chitin-aluminum ion film, the weight percentage of biomass is 90%.
Example 3:
the preparation method of the cellulose-iron ion film comprises the following steps:
1) Dissolving 2g of cellulose powder in 98g of water to prepare a 2wt% cellulose solution, placing the solution on a magnetic stirrer, stirring for 3 hours to ensure that the cellulose powder is completely dissolved to obtain a cellulose solution with certain viscosity, and placing the cellulose solution in a refrigerator to store in a sealed manner for later use.
2) Controlling the ambient temperature at 25 ℃ and the relative humidity at 30%, weighing 3g of the cellulose solution obtained in the step 1) in a culture dish, and uniformly spreading. 5mL of 0.15M FeCl 3 Adding the solution into a culture dish containing a cellulose solution, taking out the crosslinked membrane after 10min, sufficiently washing with deionized water to remove residual metal ions on the surface of the crosslinked membrane, and naturally evaporating water to obtain the cellulose-iron ion film. In the cellulose-iron ion film, the weight percentage of biomass is 98%.
Example 4:
the preparation method of the lignin-calcium ion film comprises the following steps:
1) Dissolving 2g of lignin powder in 98g of water to prepare a lignin solution with the weight percent of 2, placing the solution on a magnetic stirrer to stir for 3 hours to ensure that the lignin powder is completely dissolved to obtain the lignin solution with certain viscosity, and placing the lignin solution in a refrigerator to store in a sealed manner for later use.
2) Controlling the ambient temperature at 25 ℃ and the relative humidity at 30%, weighing 3g of the lignin solution obtained in the step 1) in a culture dish, and uniformly spreading. Adding 5mL of 0.2M CaCl 2 Adding the solution into a culture dish containing lignin solution, taking out the crosslinked membrane after 10min, and fully washing with deionized water to removeAnd (3) naturally evaporating water by using residual metal ions on the surface of the film to obtain the lignin-calcium ion film. In the lignin-calcium ion film, the weight percentage of biomass is 80%.
Example 5:
the preparation method of the sodium alginate-manganese ion film comprises the following steps:
1) Dissolving 3g of sodium alginate in 97g of water to prepare a 3wt% sodium alginate solution, placing the solution on a magnetic stirrer to stir for 3h to ensure that the sodium alginate is completely dissolved to obtain a sodium alginate solution with a certain viscosity, and placing the sodium alginate solution in a refrigerator to store in a refrigerating chamber in a sealed manner for later use.
2) Controlling the ambient temperature at 25 ℃ and the relative humidity at 30%, weighing 3g of the sodium alginate solution obtained in the step 1) on a culture dish, and uniformly spreading. 5mL of 0.1M MnCl 2 Adding the solution into a culture dish containing a sodium alginate solution, taking out the crosslinked membrane after 10min, sufficiently washing with deionized water to remove residual metal ions on the surface of the crosslinked membrane, and naturally evaporating water to obtain the sodium alginate-manganese ion thin film. In the sodium alginate-manganese ion film, the weight percentage of biomass is 88%.
Example 6:
the preparation method of the catechin-magnesium ion film comprises the following steps:
1) Dissolving 3g catechin in 97g water to obtain 3wt% catechin solution, stirring the solution for 3 hr with a magnetic stirrer to obtain catechin solution with certain viscosity, and storing in refrigerator for sealed storage.
2) Controlling the ambient temperature at 25 ℃ and the relative humidity at 30%, weighing 3g of the catechin solution obtained in the step 1) in a culture dish, and uniformly spreading. 5mL of 0.1M MgSO 4 Adding the solution into a culture dish containing catechin solution, taking out the cross-linked membrane after 10min, sufficiently washing with deionized water to remove residual metal ions on the surface of the membrane, and naturally evaporating water to obtain the catechin magnesium ion film. In the catechin-magnesium ion film, the weight percentage of biomass is 86%.
Example 7:
the preparation method of the catechin-tin ion film comprises the following steps:
1) Dissolving 3g catechin in 97g water to obtain 3wt% catechin solution, stirring the solution for 3 hr with a magnetic stirrer to obtain catechin solution with certain viscosity, and storing in refrigerator for sealed storage.
2) Controlling the ambient temperature at 25 ℃ and the relative humidity at 30%, weighing 3g of the catechin solution obtained in the step 1) in a culture dish, and uniformly spreading. 5mL of 0.1M SnCl 4 Adding the solution into a culture dish containing catechin solution, taking out the cross-linked membrane after 10min, sufficiently washing with deionized water to remove residual metal ions on the surface of the membrane, and naturally evaporating water to obtain the catechin magnesium ion film. In the catechin-magnesium ion film, the weight percentage of biomass is 95%.
Example 8:
application of chitosan-copper ion film in salt difference power generation
The chitosan-copper ion membrane prepared in example 1 was sandwiched between 0.5M/0.01M NaCl solutions and tested for salt difference energy conversion by the method comprising:
the salt tolerance power generation testing device is a Keithley 6487 Piano meter of Beijing Han Lei science and technology Limited company and a megohmmeter standard resistor of Shanghai Xu Ji electric Limited company, and the testing conditions are as follows: two-electrode solution pool, 0.5M and 0.01M NaCl solution as electrolyte, ag/AgCl as electrode, test area 3X 10 -8 m 2 And changing the load resistance to perform current test. The test results are shown in fig. 2. When the thickness of the prepared chitosan-copper ion film cross-linked membrane is 30 mu m and the concentration gradient in the concentration of sodium chloride solution is 50 times, the output power density is 5.27Wm -2 。
FIG. 1 shows the mechanical property diagram of the chitosan-copper ion film crosslinked film (model number AGS-X1KN, stretching area 1 cm) 2 ) The abscissa represents the strain of the membrane and represents the relative deformation degree of the membrane under the action of an external force, and the ordinate represents the stress borne by the membrane and represents the internal force per unit area generated by the deformation of the membrane under the action of a tensile force. FIG. 2 is a graph showing the salt-poor power generation performance of the chitosan-copper ion thin film crosslinked film,the composite membrane is fixed between two solution pools, a pair of Ag/AgCl electrodes is used for providing transmembrane potential for testing performance, the abscissa represents a load resistance value and represents an external resistance value in a test circuit, and the ordinate represents output power density and represents power density generated by a salt difference device under different load resistances.
It should be noted that, according to the above embodiments of the present invention, those skilled in the art can fully implement the full scope of the present invention as defined by the independent claims and the dependent claims, and implement the processes and methods as the above embodiments; and the invention has not been described in detail so as not to obscure the present invention.
The above description is only a part of the embodiments of the present invention, but the scope of the present invention is not limited thereto, and any changes or substitutions that can be easily conceived by those skilled in the art within the technical scope of the present invention are included in the scope of the present invention.
Claims (3)
1. The application of the high-strength and high-ion selectivity film in the salt tolerance power generation is characterized in that the film is a metal ion and biomass cross-linked film; wherein, the metal ions are used as a cross-linking agent, and the weight percentage of the biomass in the cross-linked membrane is 80-98 percent based on the total weight of the cross-linked membrane; the metal ions are selected from Al 3+ 、Ca 2+ 、Fe 3+ 、Mg 2+ 、Cu 2+ 、Mn 2+ And Sn 4+ One or more of; the method for preparing the high-strength and high-ion selectivity film comprises the following steps of:
1) Adding the biomass material into water, stirring for 3-6h, and then refrigerating for later use; wherein the biomass material is one or more of cellulose, lignin, chitosan, catechin and chitin;
2) Preparing a metal salt solution, and then storing for later use; wherein the metal salt is one or more of aluminum salt, calcium salt, iron salt, magnesium salt, copper salt, manganese salt and tin salt;
3) Controlling the environmental temperature to be 20-30 ℃ and the relative humidity to be 20-40%, applying the biomass material to a substrate, immersing the substrate with the biomass material into a metal salt solution to perform a cross-linking reaction, and taking out and drying the substrate after 5-30min to obtain the biomass high-strength film.
2. Use according to claim 1, wherein in step 2) the salt is a sulphate or chloride salt.
3. The use according to claim 1, wherein the biomass material in step 1) is added in an amount of, in parts by weight: 1-5 parts of biomass material; the addition amount of the metal salt in the step 2) is calculated by weight parts: 0.05-0.5 part of metal ion salt.
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| CN1481907A (en) * | 2003-08-19 | 2004-03-17 | ��������ҽ�ò�������˾ | Carboxymethyl chitosan / carboxymethyl cellulose operative antiblocking film and method for making the same |
| CN113045528A (en) * | 2021-03-18 | 2021-06-29 | 山东大学 | Metal-catechin composite nano material and preparation method and application thereof |
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| JP2000281805A (en) * | 1999-03-31 | 2000-10-10 | Daicel Chem Ind Ltd | Ion-crosslinking film and its production |
| CN102430391B (en) * | 2011-09-11 | 2013-06-19 | 大连理工大学 | Preparation method of metal ion imprinted chitosan crosslinked membrane adsorbent and application thereof |
| CN103446897B (en) * | 2013-09-13 | 2015-03-11 | 天津工业大学 | Chemical and ionic cross-linked alginate hydrogel flat membrane for filtration and preparation method thereof |
| CN104262667A (en) * | 2014-09-18 | 2015-01-07 | 哈尔滨工业大学 | Alginate-based material external controllable ionic crosslinked method |
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| CN1481907A (en) * | 2003-08-19 | 2004-03-17 | ��������ҽ�ò�������˾ | Carboxymethyl chitosan / carboxymethyl cellulose operative antiblocking film and method for making the same |
| CN113045528A (en) * | 2021-03-18 | 2021-06-29 | 山东大学 | Metal-catechin composite nano material and preparation method and application thereof |
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| "Developments and future prospects of reverse electrodialysis for salinity gradient power generation: Influence of ion exchange membranes and electrodes";Jaewon Jang等;《Desalination》;20201001;第491卷;第1-15页 * |
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