CN110743399A - Carboxylation-containing g-C3N4Preparation method of calcium alginate antibacterial hydrogel filtering membrane - Google Patents
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Abstract
The invention discloses a carboxylated g-C-containing catalyst3N4The preparation method of the calcium alginate antibacterial hydrogel filtering membrane. Firstly, the mixed aqueous solution of potassium dichromate and sulfuric acid is used for g-C3N4Chemical oxidation is carried out to generate hydroxyl and carboxyl on the basal surface, in order to further increase g-C3N4Carboxyl content of the surface, g-C after chemical oxidation3N4Reaction with chloroacetic acid to give carboxylated g-C3N4. Subsequently carboxylating g-C3N4Fully dispersing the mixture into water, adding sodium alginate, and fully dissolving to obtain the membrane casting solution. Scraping the membrane casting solution into a membrane and soakingFully crosslinking in soluble calcium salt water solution to obtain carboxylated g-C3N4The calcium alginate antibacterial hydrogel filtering membrane. Calcium ion can crosslink and carboxylate g-C at the same time3N4The carboxyl on the calcium alginate hydrogel and the carboxyl on the alginate generate organic and inorganic hybrid materials, thereby improving the strength of the calcium alginate hydrogel and reducing the swelling performance of the calcium alginate hydrogel. g-C3N4Endows calcium alginate hydrogel with good antibacterial performance, thereby leading the calcium alginate hydrogel to contain carboxylated g-C3N4The calcium alginate antibacterial hydrogel filtering membrane can be used for a long time.
Description
Technical Field
The invention relates to a carboxylated g-C-containing catalyst3N4The preparation method of the calcium alginate antibacterial hydrogel filtering membrane belongs to the field of functional materials and membrane separation.
The invention relates to the technical fields of antibiosis, filtering membranes, hydrogel and the like. In particular to a carboxylated g-C-containing catalyst3N4The preparation method of the calcium alginate antibacterial hydrogel filtering membrane.
Background
Membrane separation technology has become an important separation technology with its unique advantages and wide adaptability. With the continuous expansion of the application field of membrane separation and the gradual maturity of the membrane preparation process, the membrane separation technology has been successfully applied to various fields of industrial production, such as energy, mineral products, petrochemical industry, medical treatment, food, water treatment, seawater desalination and the like. Compared with the traditional separation method, the membrane separation has the advantages of small occupied area, simple process, convenient operation, low investment, low pollution and the like, and meets the requirements of energy conservation and emission reduction sustainable development of the current society. The traditional membrane is usually made of inorganic materials (ceramics), organic high molecular materials or inorganic-organic composite materials, and the structure of the traditional membrane is divided into a plurality of types; different materials and structures determine the direction of application and the degree of separation of the membrane, and thus correspond to different applications. Compared with an inorganic membrane, the polymer membrane has the advantages of small size, low energy consumption, simple preparation, low price and the like, but has certain defects, such as acid and alkali resistance, organic solvent resistance of the separation membrane, easy bacterial breeding of the membrane in the application process, poor mechanical strength, poor thermal stability and the like.
The antibacterial methods can be classified into physical methods and chemical methods. The physical method is sterilization by physical means such as temperature, pressure, electromagnetic wave of use environment, electron ray, etc.; the chemical method is to perform gas exchange and water loss isolation of nutrient source by adjusting pH value. The method used in the field of materials at present achieves the antibacterial effect mainly by adding an antibacterial agent, and the method has the characteristics of wide application range, high efficiency and long validity period. The antibacterial agents can be broadly classified into 3 types, inorganic, organic and natural biological; the inorganic antibacterial agent utilizes the antibacterial capacity of metals such as silver, copper, zinc and the like, and the metals such as silver, copper, zinc and the like are fixed on the surface of porous materials such as fluorite, silica gel and the like by methods such as physical adsorption ion exchange and the like to prepare the antibacterial agent, and then the antibacterial agent is added into a corresponding product to obtain the material with the antibacterial capacity, so that bacteria can not generate drug resistance, but the antibacterial effect of the inorganic antibacterial agent is usually obvious in the nanometer size, and is gradually reduced along with the increase of the nanometer size. The inorganic antibacterial agent is easy to agglomerate, and the size of the agglomerated inorganic antibacterial agent is obviously increased, so that the antibacterial effect of the agglomerated inorganic antibacterial agent is greatly reduced.
g-C3N4Inorganic antibacterial agents have received the general attention of researchers due to their non-toxicity, high safety and good stability. g-C3N4The inorganic nano material can effectively utilize sunlight and is widely applied in the aspects of environmental protection and energy conservation. However, for g-C3N4Inorganic semiconductor materials have been rarely studied as inorganic antibacterial agents for bacteriostasis and sterilization. To explore g-C3N4The application of inorganic semiconductor materials in sterilization and the improvement of the antibacterial performance by cold plasma irradiation treatment also become a new direction of research. As can be seen from the recovery experiments, g-C3N4The inorganic antibacterial agent has stable sterilization performance and can be recycled. Tianjin university general g-C3N4Nanosheets (CNs) and Sodium Alginate (SA)) Composite, a highly selective hybrid membrane with excellent water/ethanol separation performance was prepared [ j.membrane.sci, 2015, 490: 72-83. Due to the strong interfacial interaction between the CNs and the SA chains, the hybrid membrane has high mechanical strength and swelling resistance. In particular, the horizontally arranged layered structure of the CNs within the hybrid membrane may provide ordered channels for water transport, while the nanoporous structure of the CNs may provide an additional sieving effect. Furthermore, the intervention of the CNs on the polymer chain filler leads to a decrease in crystallinity. Thus, the hybrid membrane has good water permeability and selectivity for the separation of water/ethanol mixtures. Especially for the membrane containing 3 wt.% CNs, the permeation flux of the membrane can reach 2469g m at 76 ℃ and 10 wt.% of feed water concentration-2h-1The separation coefficient is up to 1653. At the same time, the hybrid membranes have good long-term stability.
The invention discloses a carboxylated g-C-containing catalyst3N4The preparation method of the calcium alginate antibacterial hydrogel filtering membrane. Firstly, the mixed aqueous solution of potassium dichromate and sulfuric acid is used for g-C3N4Chemical oxidation is carried out to generate hydroxyl and carboxyl on the basal surface, in order to further increase g-C3N4Carboxyl content of the surface, g-C after chemical oxidation3N4Reaction with chloroacetic acid to give carboxylated g-C3N4. Subsequently carboxylating g-C3N4Fully dispersing the mixture into water, adding sodium alginate, and fully dissolving to obtain the membrane casting solution. Scraping the membrane casting solution into a membrane and soaking the membrane casting solution into a soluble calcium salt aqueous solution for full crosslinking to obtain a carboxylated g-C-containing solution3N4The calcium alginate antibacterial hydrogel filtering membrane. Calcium ion can crosslink and carboxylate g-C at the same time3N4The carboxyl on the calcium alginate hydrogel and the carboxyl on the alginate generate organic and inorganic hybrid materials, thereby improving the strength of the calcium alginate hydrogel and reducing the swelling performance of the calcium alginate hydrogel. g-C3N4Endows calcium alginate hydrogel with good antibacterial performance, thereby leading the calcium alginate hydrogel to contain carboxylated g-C3N4The calcium alginate antibacterial hydrogel filtering membrane can be used for a long time.
Disclosure of Invention
Aiming at the defects of the prior art, the invention aims to solve the technical problems that the traditional membrane is not pollution-resistant, has poor hydrophilicity, and the calcium alginate hydrogel filtering membrane has low strength and is easy to degrade by bacteria.
The invention provides a technical scheme for solving the problems that the traditional membrane is not pollution-resistant, has poor hydrophilicity, has low strength of a calcium alginate hydrogel filtering membrane, is easy to degrade by bacteria and the like3N4The preparation method of the calcium alginate antibacterial hydrogel filtering membrane.
The invention provides a carboxylated g-C-containing catalyst3N4The preparation method of the calcium alginate antibacterial hydrogel filtering membrane is characterized by comprising the following steps:
a) using a mixed aqueous solution of potassium dichromate and sulfuric acid for g-C3N4Is subjected to chemical oxidation at g-C3N4Introduction of hydroxyl and carboxyl on basal plane to further increase g-C3N4Carboxyl content of the surface, g-C after chemical oxidation3N4Reaction with chloroacetic acid to form carboxylated g-C3N4Centrifuging, washing to remove residual inorganic salt and acid, and freeze drying to obtain carboxylated g-C3N4A solid powder; controlling the concentration of chloroacetic acid, reaction temperature and reaction time to carboxylation g-C3N4The mass percentage content of the carboxyl is 0.1-10%;
b) carboxylating g-C obtained in step a)3N4Dispersing the solid powder into deionized water, adjusting pH to 9-12, and performing ultrasonic treatment for 5-120min to carboxylate g-C3N4Dispersing solid powder in water uniformly, and controlling carboxylation g-C3N4The mass percentage concentration in water is 0.01-5%;
c) to the mixture obtained in step b) containing homogeneously dispersed carboxylated g-C3N4Adding sodium alginate with the mass percentage of 0.5-5% of the aqueous solution into the water, stirring the mixture while adding the sodium alginate until the sodium alginate is fully dissolved, and standing and defoaming the mixture to obtain a membrane casting solution;
d) preparing a soluble calcium salt water solution with the mass percentage concentration of 0.2-20% as a coagulating bath;
e) pouring the casting solution obtained in the step c) into a drying and cleaning deviceScraping the glass plate with a glass rod with two ends wound with copper wires with the diameter of 20-1500 μm, immediately soaking the glass plate and the scraped film in the coagulating bath obtained in step d) for 5-240min, reacting the soluble calcium salt with sodium alginate to generate calcium alginate hydrogel, and simultaneously reacting with carboxylated g-C3N4The carboxyl groups on the surface are crosslinked to generate an organic-inorganic hybrid structure, and carboxylation g-C is added3N4The physical enhancement function of the calcium alginate hydrogel, thereby improving the mechanical strength of the calcium alginate hydrogel and reducing the swelling performance of the calcium alginate hydrogel;
f) finally, the inorganic salt remained on the membrane neutralization membrane surface is removed by using deionized water for soaking and washing, and the carboxylation g-C-containing3N4The antibacterial rate of the calcium alginate hydrogel filtering membrane to escherichia coli is 80% -100%, and the swelling rate of the filtering membrane in physiological saline is only 20% -50% of that of the calcium alginate hydrogel filtering membrane.
The soluble calcium salt is any one or a mixture of two or more of calcium chloride, calcium nitrate, calcium dihydrogen phosphate and calcium gluconate.
In the present invention, carboxylated g-C3N4Endows the calcium alginate hydrogel filtering membrane with good antibacterial performance, and avoids the calcium alginate hydrogel filtering membrane from being degraded by bacteria in the using process.
Carboxylated g-C-containing compounds obtained according to the invention3N4The calcium alginate antibacterial hydrogel filtering membrane has good pollution resistance and has good application prospect in dye desalination, brown sugar decolorization and protein purification.
Detailed Description
Specific examples of the present invention will be described below, but the present invention is not limited to the examples.
Example 1.
a) Using a mixed aqueous solution of potassium dichromate and sulfuric acid for g-C3N4Is subjected to chemical oxidation at g-C3N4Introduction of hydroxyl and carboxyl on basal plane to further increase g-C3N4Carboxyl content of the surface, g-C after chemical oxidation3N4Reaction with chloroacetic acid to form carboxylated g-C3N4Centrifuging, washing to remove residual inorganic salt and acid, and freeze drying to obtain carboxylated g-C3N4A solid powder; controlling the concentration of chloroacetic acid, reaction temperature and reaction time to carboxylation g-C3N4The mass percentage content of the carboxyl is 0.1 percent;
b) carboxylating g-C obtained in step a)3N4Dispersing the solid powder into deionized water, adjusting pH of the solution to 9, and performing ultrasonic treatment for 5min to carboxylate g-C3N4Dispersing solid powder in water uniformly, and controlling carboxylation g-C3N4The mass percentage concentration in water is 0.01 percent;
c) to the mixture obtained in step b) containing homogeneously dispersed carboxylated g-C3N4Adding sodium alginate with the mass percentage of 0.5 percent of the aqueous solution into the water, stirring the mixture while adding the sodium alginate until the sodium alginate is fully dissolved, and standing the mixture for defoaming to obtain a membrane casting solution;
d) preparing a calcium chloride aqueous solution with the mass percentage concentration of 0.2 percent as a coagulating bath;
e) pouring the casting solution obtained in the step C) on a dry and clean glass plate, strickling the glass plate by a glass rod with copper wires with the diameter of 20 mu m wound at two ends, immediately putting the glass plate and the strickled film into the coagulating bath obtained in the step d) for soaking for 5min, reacting calcium chloride with sodium alginate to generate calcium alginate hydrogel, and simultaneously reacting the calcium chloride with carboxylated g-C3N4The carboxyl groups on the surface are crosslinked to generate an organic-inorganic hybrid structure, and carboxylation g-C is added3N4The physical enhancement function of the calcium alginate hydrogel, thereby improving the mechanical strength of the calcium alginate hydrogel and reducing the swelling performance of the calcium alginate hydrogel;
f) finally, the inorganic salt remained on the membrane neutralization membrane surface is removed by using deionized water for soaking and washing, and the carboxylation g-C-containing3N4The antibacterial rate of the calcium alginate hydrogel filtering membrane to escherichia coli is 80%, and the swelling rate of the filtering membrane in physiological saline is only 50% of that of the calcium alginate hydrogel filtering membrane.
Example 2.
a) Using a mixed aqueous solution of potassium dichromate and sulfuric acid for g-C3N4Performing chemical oxidationIn g-C3N4Introduction of hydroxyl and carboxyl on basal plane to further increase g-C3N4Carboxyl content of the surface, g-C after chemical oxidation3N4Reaction with chloroacetic acid to form carboxylated g-C3N4Centrifuging, washing to remove residual inorganic salt and acid, and freeze drying to obtain carboxylated g-C3N4A solid powder; controlling the concentration of chloroacetic acid, reaction temperature and reaction time to carboxylation g-C3N4The mass percentage content of the carboxyl is 10 percent;
b) carboxylating g-C obtained in step a)3N4Dispersing the solid powder into deionized water, adjusting pH of the solution to 12, and performing ultrasonic treatment for 120min to carboxylate g-C3N4Dispersing solid powder in water uniformly, and controlling carboxylation g-C3N4The mass percentage concentration in water is 5 percent;
c) to the mixture obtained in step b) containing homogeneously dispersed carboxylated g-C3N4Adding sodium alginate with the mass percentage of 5 percent of the aqueous solution into the water, stirring the mixture while adding the sodium alginate until the sodium alginate is fully dissolved, and standing the mixture for defoaming to obtain a membrane casting solution;
d) preparing a calcium nitrate water solution with the mass percentage concentration of 20 percent as a coagulating bath;
e) pouring the casting solution obtained in the step C) on a dry and clean glass plate, strickling the glass plate by a glass rod with two ends wound with copper wires with the diameter of 1500 mu m, immediately putting the glass plate and the strickled film into the coagulating bath obtained in the step d), soaking for 240min, reacting calcium nitrate with sodium alginate to generate calcium alginate hydrogel, and simultaneously reacting with carboxylated g-C3N4The carboxyl groups on the surface are crosslinked to generate an organic-inorganic hybrid structure, and carboxylation g-C is added3N4The physical enhancement function of the calcium alginate hydrogel, thereby improving the mechanical strength of the calcium alginate hydrogel and reducing the swelling performance of the calcium alginate hydrogel;
f) finally, the inorganic salt remained on the membrane neutralization membrane surface is removed by using deionized water for soaking and washing, and the carboxylation g-C-containing3N4The antibacterial calcium alginate hydrogel filtering membrane has the bacteriostasis rate of 100 percent on escherichia coli, and the swelling rate of the filtering membrane in physiological saline is onlyIs 20 percent of the calcium alginate hydrogel filtering membrane.
Example 3.
a) Using a mixed aqueous solution of potassium dichromate and sulfuric acid for g-C3N4Is subjected to chemical oxidation at g-C3N4Introduction of hydroxyl and carboxyl on basal plane to further increase g-C3N4Carboxyl content of the surface, g-C after chemical oxidation3N4Reaction with chloroacetic acid to form carboxylated g-C3N4Centrifuging, washing to remove residual inorganic salt and acid, and freeze drying to obtain carboxylated g-C3N4A solid powder; controlling the concentration of chloroacetic acid, reaction temperature and reaction time to carboxylation g-C3N4The mass percentage content of the carboxyl is 5 percent;
b) carboxylating g-C obtained in step a)3N4Dispersing the solid powder into deionized water, adjusting pH of the solution to 10, and performing ultrasonic treatment for 60min to carboxylate g-C3N4Dispersing solid powder in water uniformly, and controlling carboxylation g-C3N4The mass percentage concentration in water is 2 percent;
c) to the mixture obtained in step b) containing homogeneously dispersed carboxylated g-C3N4Adding sodium alginate with the mass percentage of 2 percent of the aqueous solution into the water, stirring the mixture while adding the sodium alginate until the sodium alginate is fully dissolved, and standing the mixture for defoaming to obtain a membrane casting solution;
d) preparing a calcium dihydrogen phosphate water solution with the mass percentage concentration of 2 percent as a coagulating bath;
e) pouring the casting solution obtained in the step C) on a dry and clean glass plate, strickling the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 500 mu m, immediately putting the glass plate and the strickled film into the coagulating bath obtained in the step d), soaking for 40min, reacting calcium dihydrogen phosphate with sodium alginate to generate calcium alginate hydrogel, and simultaneously reacting with carboxylated g-C3N4The carboxyl groups on the surface are crosslinked to generate an organic-inorganic hybrid structure, and carboxylation g-C is added3N4The physical enhancement function of the calcium alginate hydrogel, thereby improving the mechanical strength of the calcium alginate hydrogel and reducing the swelling performance of the calcium alginate hydrogel;
f) finally soaking and washing with deionized waterRemoving inorganic salt remaining on the membrane neutralization membrane surface to obtain a carboxylated g-C-containing3N4The antibacterial rate of the calcium alginate hydrogel filtering membrane to escherichia coli is 96%, and the swelling rate of the filtering membrane in physiological saline is only 30% of that of the calcium alginate hydrogel filtering membrane.
Example 4.
a) Using a mixed aqueous solution of potassium dichromate and sulfuric acid for g-C3N4Is subjected to chemical oxidation at g-C3N4Introduction of hydroxyl and carboxyl on basal plane to further increase g-C3N4Carboxyl content of the surface, g-C after chemical oxidation3N4Reaction with chloroacetic acid to form carboxylated g-C3N4Centrifuging, washing to remove residual inorganic salt and acid, and freeze drying to obtain carboxylated g-C3N4A solid powder; controlling the concentration of chloroacetic acid, reaction temperature and reaction time to carboxylation g-C3N4The mass percentage content of the carboxyl is 1 percent;
b) carboxylating g-C obtained in step a)3N4Dispersing the solid powder into deionized water, adjusting pH of the solution to 11, and performing ultrasonic treatment for 110min to carboxylate g-C3N4Dispersing solid powder in water uniformly, and controlling carboxylation g-C3N4The mass percentage concentration in water is 1 percent;
c) to the mixture obtained in step b) containing homogeneously dispersed carboxylated g-C3N4Adding sodium alginate with the mass percentage of 3 percent of the aqueous solution into the water, stirring the mixture while adding the sodium alginate until the sodium alginate is fully dissolved, and standing the mixture for defoaming to obtain a membrane casting solution;
d) preparing a calcium gluconate aqueous solution with the mass percentage concentration of 2 percent as a coagulating bath;
e) pouring the casting solution obtained in the step C) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 800 mu m, immediately putting the glass plate and the scraped film into the coagulating bath obtained in the step d) for soaking for 120min, reacting calcium gluconate with sodium alginate to generate calcium alginate hydrogel, and simultaneously reacting the calcium alginate hydrogel with carboxylated g-C3N4Crosslinking of carboxyl groups on to give organic-inorganic hybridsStructure, plus carboxylation g-C3N4The physical enhancement function of the calcium alginate hydrogel, thereby improving the mechanical strength of the calcium alginate hydrogel and reducing the swelling performance of the calcium alginate hydrogel;
f) finally, the inorganic salt remained on the membrane neutralization membrane surface is removed by using deionized water for soaking and washing, and the carboxylation g-C-containing3N4The antibacterial rate of the calcium alginate hydrogel filtering membrane to escherichia coli is 97%, and the swelling rate of the filtering membrane in physiological saline is only 33% of that of the calcium alginate hydrogel filtering membrane.
Claims (4)
1. Carboxylation-containing g-C3N4The preparation method of the calcium alginate antibacterial hydrogel filtering membrane is characterized by comprising the following steps:
a) using a mixed aqueous solution of potassium dichromate and sulfuric acid for g-C3N4Is subjected to chemical oxidation at g-C3N4Introduction of hydroxyl and carboxyl on basal plane to further increase g-C3N4Carboxyl content of the surface, g-C after chemical oxidation3N4Reaction with chloroacetic acid to form carboxylated g-C3N4Centrifuging, washing to remove residual inorganic salt and acid, and freeze drying to obtain carboxylated g-C3N4A solid powder; controlling the concentration of chloroacetic acid, reaction temperature and reaction time to carboxylation g-C3N4The mass percentage content of the carboxyl is 0.1-10%;
b) carboxylating g-C obtained in step a)3N4Dispersing the solid powder into deionized water, adjusting pH to 9-12, and performing ultrasonic treatment for 5-120min to carboxylate g-C3N4Dispersing solid powder in water uniformly, and controlling carboxylation g-C3N4The mass percentage concentration in water is 0.01-5%;
c) to the mixture obtained in step b) containing homogeneously dispersed carboxylated g-C3N4Adding sodium alginate with the mass percentage of 0.5-5% of the aqueous solution into the water, stirring the mixture while adding the sodium alginate until the sodium alginate is fully dissolved, and standing and defoaming the mixture to obtain a membrane casting solution;
d) preparing a soluble calcium salt water solution with the mass percentage concentration of 0.2-20% as a coagulating bath;
e) pouring the casting solution obtained in the step C) on a dry and clean glass plate, scraping the glass plate by using a glass rod with two ends wound with copper wires with the diameter of 20-1500 mu m, immediately putting the glass plate and the scraped film into the coagulating bath obtained in the step d) for soaking for 5-240min, and reacting soluble calcium salt with sodium alginate to generate calcium alginate hydrogel and simultaneously reacting with carboxylated g-C3N4The carboxyl groups on the surface are crosslinked to generate an organic-inorganic hybrid structure, and carboxylation g-C is added3N4The physical enhancement function of the calcium alginate hydrogel, thereby improving the mechanical strength of the calcium alginate hydrogel and reducing the swelling performance of the calcium alginate hydrogel;
f) finally, the inorganic salt remained on the membrane neutralization membrane surface is removed by using deionized water for soaking and washing, and the carboxylation g-C-containing3N4The antibacterial rate of the calcium alginate hydrogel filtering membrane to escherichia coli is 80% -100%, and the swelling rate of the filtering membrane in physiological saline is only 20% -50% of that of the calcium alginate hydrogel filtering membrane.
2. A carboxylated g-C containing composition according to claim 13N4The preparation method of the calcium alginate antibacterial hydrogel filtering membrane is characterized in that the soluble calcium salt is any one or a mixture of two or more of calcium chloride, calcium nitrate, calcium dihydrogen phosphate and calcium gluconate.
3. A carboxylated g-C containing composition according to claim 13N4The preparation method of the calcium alginate antibacterial hydrogel filtering membrane is characterized in that the calcium alginate antibacterial hydrogel filtering membrane is carboxylated g-C3N4Endows the calcium alginate hydrogel filtering membrane with good antibacterial performance, and avoids the calcium alginate hydrogel filtering membrane from being degraded by bacteria in the using process.
4. A carboxylated g-C containing composition according to claim 13N4The preparation method of the calcium alginate antibacterial hydrogel filtering membrane is characterized by simple preparation method and capability of obtaining the product containing carboxylation g-C3N4The calcium alginate antibacterial hydrogel filtering membrane has good pollution resistanceHas good application prospect in dye desalination, brown sugar decolorization and protein purification.
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| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN112121644A (en) * | 2020-10-19 | 2020-12-25 | 天津工业大学 | Preparation method of oxalic acid cross-linked alginate hydrogel filtering membrane and application of filtering membrane in molecular ion separation |
| CN112121644B (en) * | 2020-10-19 | 2022-12-06 | 天津工业大学 | Preparation method of oxalic acid cross-linked alginate hydrogel filtering membrane and application of filtering membrane in molecular ion separation |
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