CN114284518A - Application of PMSA composite membrane obtained based on interface super-assembly in salt gradient energy conversion - Google Patents
Application of PMSA composite membrane obtained based on interface super-assembly in salt gradient energy conversion Download PDFInfo
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- 239000002131 composite material Substances 0.000 title claims abstract description 82
- JFINOWIINSTUNY-UHFFFAOYSA-N pyrrolidin-3-ylmethanesulfonamide Chemical compound NS(=O)(=O)CC1CCNC1 JFINOWIINSTUNY-UHFFFAOYSA-N 0.000 title claims abstract description 73
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- 239000000377 silicon dioxide Substances 0.000 claims abstract description 24
- 238000000034 method Methods 0.000 claims abstract description 22
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- 238000012360 testing method Methods 0.000 claims abstract description 11
- PNEYBMLMFCGWSK-UHFFFAOYSA-N aluminium oxide Inorganic materials [O-2].[O-2].[O-2].[Al+3].[Al+3] PNEYBMLMFCGWSK-UHFFFAOYSA-N 0.000 claims abstract description 9
- 239000013505 freshwater Substances 0.000 claims abstract description 7
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- 239000000243 solution Substances 0.000 claims description 71
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- 238000004528 spin coating Methods 0.000 claims description 27
- DVKJHBMWWAPEIU-UHFFFAOYSA-N toluene 2,4-diisocyanate Chemical compound CC1=CC=C(N=C=O)C=C1N=C=O DVKJHBMWWAPEIU-UHFFFAOYSA-N 0.000 claims description 23
- 238000001035 drying Methods 0.000 claims description 18
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- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 10
- VEXZGXHMUGYJMC-UHFFFAOYSA-N Hydrochloric acid Chemical compound Cl VEXZGXHMUGYJMC-UHFFFAOYSA-N 0.000 claims description 10
- 239000008367 deionised water Substances 0.000 claims description 10
- 229910021641 deionized water Inorganic materials 0.000 claims description 10
- VLKZOEOYAKHREP-UHFFFAOYSA-N n-Hexane Chemical compound CCCCCC VLKZOEOYAKHREP-UHFFFAOYSA-N 0.000 claims description 10
- 238000003756 stirring Methods 0.000 claims description 10
- 238000012695 Interfacial polymerization Methods 0.000 claims description 8
- BOTDANWDWHJENH-UHFFFAOYSA-N Tetraethyl orthosilicate Chemical compound CCO[Si](OCC)(OCC)OCC BOTDANWDWHJENH-UHFFFAOYSA-N 0.000 claims description 8
- 230000037427 ion transport Effects 0.000 claims description 7
- 239000012948 isocyanate Substances 0.000 claims description 7
- 150000002513 isocyanates Chemical class 0.000 claims description 7
- 239000000178 monomer Substances 0.000 claims description 7
- 239000003921 oil Substances 0.000 claims description 7
- 229920000642 polymer Polymers 0.000 claims description 7
- 239000011148 porous material Substances 0.000 claims description 7
- 229910021607 Silver chloride Inorganic materials 0.000 claims description 5
- 125000003277 amino group Chemical group 0.000 claims description 5
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- 238000004090 dissolution Methods 0.000 claims description 5
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- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 claims description 5
- 230000002194 synthesizing effect Effects 0.000 claims description 5
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- FAPWRFPIFSIZLT-UHFFFAOYSA-M Sodium chloride Chemical compound [Na+].[Cl-] FAPWRFPIFSIZLT-UHFFFAOYSA-M 0.000 description 16
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- VEXZGXHMUGYJMC-UHFFFAOYSA-M Chloride anion Chemical compound [Cl-] VEXZGXHMUGYJMC-UHFFFAOYSA-M 0.000 description 3
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- 239000003795 chemical substances by application Substances 0.000 description 3
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- 229910001414 potassium ion Inorganic materials 0.000 description 3
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- 239000013335 mesoporous material Substances 0.000 description 2
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- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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Abstract
The invention discloses an application of a PMSA composite membrane obtained based on interface super-assembly in salt gradient energy conversion, wherein the PMSA composite membrane is used as an ion transmission membrane for converting salt gradient energy into electric energy, and the PMSA composite membrane is a polyurea/mesoporous silica/anodic alumina composite membrane prepared based on an interface super-assembly strategy. Firstly, preparing a PU/MS/AAO heterojunction membrane by adopting a super-assembly strategy, and then clamping the heterojunction membrane in a self-made two-chamber semi-conductance cell to test the gradient energy conversion performance of the salt. The modification of the PU layer gives the composite membrane very good stability in water, resulting in great potential in applications involving water. In addition, the mesoporous silicon oxide layer contains rich nano-channels with nano-sizes and negative charges, and the nano-channels and the AAO nano-channels with positive charges form an asymmetric heterostructure, so that the concentration polarization phenomenon in the salt gradient energy conversion process is reduced to a great extent. The PMSA captures electric energy from the condition of artificial freshwater seawater, and has potential practical application value in the field of energy conversion.
Description
Technical Field
The invention belongs to the field of energy conversion, and particularly relates to an application of a PMSA composite membrane obtained based on interface super-assembly in salt gradient energy conversion.
Background
At present, nano-fluidic devices have a wide application value in the fields of salt difference energy conversion, biosensing, logic gating, ion screening and the like because of having nano-sized charge channels. Materials currently used to construct nanochannels include zero-dimensional nanoparticles such as PS spheres, MOF particles, and the like, one-dimensional nanofibers, nanowires, nanotubes, and the like, two-dimensional graphene oxide, Mxenes, and C3N4And the like. However, the nano-channel structure formed by the materials is obtained by randomly stacking the materials, and has the problems of high disorder degree, disordered pore channel structure, uneven pore size distribution and the like. In view of the above problems, it is necessary to search for a membrane material with regular pore structure and pore size. The mesoporous material has a size of 2-50nm, a regular pore channel structure and a high specific surface area, and is widely used for constructing nanofluidic equipment and applying the nanofluidic equipment to capture salt difference energy. However, inorganic-based nanochannel devices such as silica, alumina, and the like, all exhibit poor mechanical properties due to their intrinsic framework inflexibility. In order to solve the problem, a coating with high mechanical property needs to be found to improve the mechanical property of the mesoporous material.
Disclosure of Invention
The invention aims to solve the problems and provide an application of a PMSA composite membrane obtained based on interface super-assembly in salt gradient energy conversion.
The purpose of the invention is realized by the following technical scheme:
the PMSA composite membrane is used as an ion transmission membrane for converting salt gradient energy into electric energy, wherein the PMSA composite membrane is a polyurea/mesoporous silica/anodic alumina composite membrane prepared based on an interface super-assembly strategy.
Further, the PMSA composite membrane is used as an ion transport membrane for converting salt gradient energy between fresh water and seawater into electric energy, for example, 0.5M NaCl and 0.01M NaCl are respectively adopted as test electrolyte solutions to respectively simulate solution environments of seawater and fresh water, and the PMSA composite membrane has very good cation selectivity and can selectively transport cations to generate static current so as to be converted into electric energy. Preferably, the PU side of the PMSA composite membrane is exposed to seawater.
Further, the PMSA composite membrane is prepared by the following method:
(1) growing an ordered mesoporous silicon oxide film on the AAO substrate by adopting an interface super-assembly method;
(2) preparing water-oil phase solution of synthetic polyurea monomer;
(3) dropwise adding PEI onto the surface of the MS/AAO membrane, and volatilizing the water until the water is dry;
(4) and (3) dropwise adding the TDI solution on the surface of MS/AAO containing a PEI polymer chain, and carrying out interfacial polymerization reaction on amino between two phases and isocyanate to generate a compact polyurea film so as to obtain the PMSA composite film.
Further, the step (1) specifically comprises the following steps:
(1-1) adopting polymethyl methacrylate to perform hole plugging treatment on the AAO;
(1-2) spin-coating a polymethylmethacrylate solution onto the AAO substrate;
(1-3) drying the PMMA/AAO film after spin coating to ensure that PMMA permeates into AAO pores;
(1-4) preparing a precursor solution of mesoporous silica, and pre-polymerizing at 60 ℃;
(1-5) preparing an F127 template solution;
(1-6) dropwise adding the prepolymerized mesoporous silica into the F127 template solution, and stirring at room temperature to obtain a final mesoporous silica precursor solution;
(1-7) spin-coating the mesoporous silicon oxide precursor solution on the AAO substrate with the plugged holes;
(1-8) carrying out evaporation induction self-assembly at 40 ℃ for 24h, and carrying out thermal polymerization at 100 ℃ for 24h to obtain the final mesoporous silica/alumina (MS/AAO) composite membrane.
Further, the specific method in the step (1-1) is as follows: dissolving 2.3-2.7g of polymethyl methacrylate (PMMA) into 23-27 ml of acetone solution, heating and stirring at 40-45 ℃ until the PMMA is dissolved;
the spin coating speed of the step (1-2) is 3000 and 3500 revolutions, and the spin coating time is 30-40 seconds;
drying the PMMA/AAO film subjected to spin coating in the step (1-3) in a fume hood for two hours, and then drying in an oven at 200 ℃ for 5-6 hours;
the specific method of the step (1-4) is as follows: preparing a prepolymerized mesoporous silica oligomer, adding 2-2.2g of tetraethyl silicate into a mixed solution of 10-12g of absolute ethanol, 1.0-1.5g of deionized water and 0.5-0.6g of 0.2M hydrochloric acid, and prepolymerizing at 60 ℃ for 1 h;
the specific method for preparing the F127 template solution in the step (1-5) comprises the following steps: dissolving 0.8-1g of F127 into 9-12g of absolute ethyl alcohol, and performing ultrasonic dispersion and dissolution until the solution is clear;
and (1-7) spin-coating 200-.
Further, the specific method for preparing the water-oil phase solution for synthesizing the polyurea monomer in the step (2) comprises the following steps: preparing 1.0-1.8 w/v% Polyethyleneimine (PEI) aqueous solution, and dissolving 1.2-2.16mg of 50 wt% PEI solution in 55-65ml of deionized water; then 0.3-0.8 w/v% of 2, 4-Toluene Diisocyanate (TDI) is prepared, about 0.18-0.48mg of TDI is weighed and dissolved in 55-65ml of n-hexane, and the prepared two solutions are placed in an oven at 60 ℃.
Further, 200-250. mu.L of PEI was dropped on the surface of the MS/AAO membrane in the step (3), and the moisture was evaporated to dryness at 60 ℃;
in the step (4), 160-200 μ L of TDI solution is dripped on the surface of MS/AAO containing a PEI polymer chain, and the amino group between the two phases and isocyanate are subjected to interfacial polymerization reaction in an oven at 60 ℃ for 1 min.
Further, the PMSA composite membrane is clamped in a two-chamber semi-conductance cell to test the salt gradient energy conversion performance, an artificial freshwater seawater solution is placed in the two-chamber conductance cell in the testing process, and then ion transmission current under different resistances is detected by a picoammeter.
Further, clamp the PMSA complex film in two room conductometers, adopt Ag/AgCl electrode slice to connect whole circuit, the magnitude of measuring equipment monitoring current is regarded as to the picoammeter, wherein during the resistance box is connected to whole circuit, adopts the picoammeter to detect under the different resistance condition, the magnitude of electric current, calculates energy density according to following formula:
wherein, P is power density, I is absolute value of penetration current, R is external resistance, and S is test area.
The invention adopts polyurea as a waterproof protective layer of mesoporous silica, and adopts interface super-assembly and interface polymerization dual strategies to prepare the PMSA composite membrane, which has a hydrophobic outer surface and very good stability in water compared with MS/AAO. In addition, the ion transmission is slowed down to a certain extent, so that the cation selectivity of the PMSA composite membrane can be increased, and then the salt difference energy conversion performance of the PMSA composite membrane is represented by adopting a self-made two-chamber conductivity cell and an electrochemical method.
The PMSA composite membrane is constructed by adopting the mesoporous silicon oxide as an intermediate material, and the main reason is that the composite membrane not only has a regular nano-channel structure and provides rich ion transmission channels, but also has rich negative charges due to rich silicon hydroxyl groups, and has wide application value in the field of ion transmission. The invention adopts AAO as the substrate of the composite membrane, and has three functions: (1) further spin-coating as a substrate to prepare a mesoporous silicon oxide nano-channel; (2) can provide abundant ion transmission channels with positive charge nanometer size; (3) and the silicon oxide nano-channel form an asymmetric nano-channel, so that the concentration polarization phenomenon can be effectively inhibited.
The self-made two-chamber conductivity cell is adopted to carry out transmembrane ion transmission, so that the salt difference energy existing between the fresh water and the seawater is converted into the electric energy, and the self-made two-chamber conductivity cell has potential practical application value in the field of salt gradient energy conversion.
Drawings
FIG. 1 is a graph of the stability performance of ion transport of a PMSA composite membrane;
FIG. 2 is a graph showing ion transmission performance of PGA composite membranes at different KCl concentrations, wherein FIG. 2(a) is a graph showing I-V curves at different KCl concentrations; FIG. 2(b) is a rectification ratio diagram of the PMSA composite membrane at different concentrations; (c) is an electric conductance graph of the PMSA composite membrane under different electrolyte concentrations;
FIG. 3 is a graph of ion selectivity performance of a PMSA composite membrane prepared according to the present invention;
FIG. 4 is a schematic view of ion transport for PMSA in different concentration directions and voltage directions;
FIG. 5 is a graph comparing salt difference energy capture performance of PMSA composite membranes with different concentration gradient configurations, wherein FIG. 5(a) is an I-V comparison graph of PMSA composite membranes in different concentration directions; (b) is a current density comparison graph under different resistance conditions in different concentration directions; (c) the energy density comparison graph of the PMSA composite film under different resistance conditions in different concentration directions is shown; (d) is a comparison graph of the maximum energy density of the PMSA composite membrane in different concentration directions.
Detailed Description
The invention is described in detail below with reference to the figures and specific embodiments.
Example 1
The ion transmission performance of the PMSA composite membrane is tested by an electrochemical method, and the specific operation steps are as follows:
the method comprises the following steps: firstly, growing an ordered mesoporous silicon oxide film on an AAO substrate by adopting an interface super-assembly method;
(1) before preparing MS, firstly adopting polymethyl methacrylate to perform hole plugging treatment on AAO, specifically dissolving 2.5g of polymethyl methacrylate (PMMA) into 25ml of acetone solution, and heating and stirring at 40-45 ℃ until the PMMA is dissolved;
(2) then spin-coating the polymethyl methacrylate solution on the AAO substrate at 3500 rpm for 30 seconds;
(3) drying the PMMA/AAO film subjected to spin coating in a fume hood for two hours, and then drying in an oven at 200 ℃ for 6 hours to ensure that PMMA can penetrate into AAO holes, thereby playing a role in blocking the holes;
(4) then preparing a precursor solution of the mesoporous silica, firstly preparing a prepolymerized mesoporous silica oligomer, adding 2.08g of tetraethyl silicate into a mixed solution of 12g of absolute ethanol, 1.0g of deionized water and 0.5g of 0.2M hydrochloric acid, and prepolymerizing for 1h at 60 ℃;
(5) preparing F127 template agent solution, namely dissolving 0.9g of F127 into 10g of absolute ethyl alcohol, and performing ultrasonic dispersion and dissolution until the solution is clear;
(6) slowly dripping 8g of pre-polymerized tetraethyl silicate into the F127 template solution, and stirring for 1h at room temperature to obtain a final mesoporous silicon oxide precursor solution;
(7) then, 200 mul of mesoporous silicon oxide precursor solution is spin-coated on the AAO substrate with the hole being plugged, the spin-coating speed is 3000 revolutions, and the spin-coating time is 40 seconds;
(8) then evaporating at 40 ℃ to induce self-assembly for 24h, and carrying out thermal polymerization at 100 ℃ for 24h to obtain a final mesoporous silica/alumina (MS/AAO) composite membrane;
step two: then preparing water-oil phase solution for synthesizing polyurea monomer: firstly, preparing 1.5 w/v% of Polyethyleneimine (PEI) aqueous solution, and dissolving 1.8mg of 50 wt% PEI solution in 60ml of deionized water; then 0.5 w/v% of 2, 4-Toluene Diisocyanate (TDI) is prepared, about 0.3mg of TDI is weighed and dissolved in 60ml of n-hexane, and the prepared two solutions are placed in a drying oven at the temperature of 60 ℃;
step three: then, 200 μ L of PEI was first dropped on the MS/AAO membrane surface, and it was left to evaporate the water to dryness at 60 ℃;
step four: then, 200 mu L of TDI solution is dripped on the surface of MS/AAO containing a PEI polymer chain, the amino group between the two phases and isocyanate are subjected to interfacial polymerization reaction in a drying oven at 60 ℃, the reaction time is 1min, and a compact polyurea film is generated;
step five: the final PMSA composite film with high mechanical performance is obtained.
Step six: and then, establishing an ion transmission device: the PMSA composite membrane is clamped in a self-made two-chamber conductivity cell, then an Ag/AgCl electrode plate is adopted to connect a whole circuit, a Peak meter is used as detection equipment for monitoring the current, a resistance box is connected to the whole circuit, electrolyte solution is 0.5M and 0.01M sodium chloride respectively, the 0.5M sodium chloride is arranged on one side of polyurea, the Peak meter is adopted to detect the current under the conditions of different resistances, the external voltage value is 0, and the energy density is calculated according to the following formula:
example 2
The ion transmission performance of the PMSA composite membrane is tested by an electrochemical method, and the specific operation steps are as follows:
the method comprises the following steps: firstly, growing an ordered mesoporous silicon oxide film on an AAO substrate by adopting an interface super-assembly method;
(1) before preparing MS, firstly adopting polymethyl methacrylate to perform hole plugging treatment on AAO, specifically dissolving 2.3g of polymethyl methacrylate (PMMA) into 23ml of acetone solution, and heating and stirring at 40-45 ℃ until the PMMA is dissolved;
(2) then spin-coating the polymethyl methacrylate solution on the AAO substrate at the rotating speed of 3000 revolutions for 35 seconds;
(3) drying the PMMA/AAO film subjected to spin coating in a fume hood for two hours, and then drying the PMMA/AAO film in an oven at the temperature of 200 ℃ for 5 hours to ensure that PMMA can penetrate into AAO holes, so that the effect of blocking the holes is achieved;
(4) then preparing a precursor solution of the mesoporous silica, firstly preparing a prepolymerized mesoporous silica oligomer, adding 2.08g of tetraethyl silicate into a mixed solution of 12g of absolute ethanol, 1.0g of deionized water and 0.5g of 0.2M hydrochloric acid, and prepolymerizing for 1h at 60 ℃;
(5) preparing F127 template agent solution, namely dissolving 0.8g of F127 into 9g of absolute ethyl alcohol, and performing ultrasonic dispersion and dissolution until the solution is clear;
(6) slowly dripping 8g of pre-polymerized tetraethyl silicate into the F127 template solution, and stirring for 1h at room temperature to obtain a final mesoporous silicon oxide precursor solution;
(7) then, 200 mul of mesoporous silicon oxide precursor solution is spin-coated on the AAO substrate with the hole being plugged, the spin-coating speed is 3000 revolutions, and the spin-coating time is 40 seconds;
(8) then evaporating at 40 ℃ to induce self-assembly for 24h, and carrying out thermal polymerization at 100 ℃ for 24h to obtain a final mesoporous silica/alumina (MS/AAO) composite membrane;
step two: then preparing water-oil phase solution for synthesizing polyurea monomer: firstly, preparing 1.5 w/v% of Polyethyleneimine (PEI) aqueous solution, and dissolving 1.8mg of 50 wt% PEI solution in 60ml of deionized water; then 0.5 w/v% of 2, 4-Toluene Diisocyanate (TDI) is prepared, about 0.3mg of TDI is weighed and dissolved in 60ml of n-hexane, and the prepared two solutions are placed in a drying oven at the temperature of 60 ℃;
step three: then, 200 μ L of PEI was first dropped on the MS/AAO membrane surface, and it was left to evaporate the water to dryness at 60 ℃;
step four: then, 200 mu L of TDI solution is dripped on the surface of MS/AAO containing a PEI polymer chain, the amino group between the two phases and isocyanate are subjected to interfacial polymerization reaction in a drying oven at 60 ℃, the reaction time is 1min, and a compact polyurea film is generated;
step five: the final PMSA composite film with high mechanical performance is obtained.
Step six: and then, establishing an ion transmission device: the PMSA composite membrane is clamped in a self-made two-chamber conductivity cell, then an Ag/AgCl electrode plate is adopted to connect the whole circuit, a Peak meter is used as detection equipment for monitoring the magnitude of current, a resistance box is connected to the whole circuit, electrolyte solutions are respectively 1M and 0.01M sodium chloride, 0.5M sodium chloride is arranged on one side of polyurea, the Peak meter is adopted to detect the magnitude of current under the condition of different resistances, wherein the value of an external voltage is 0, and the energy density is calculated according to a formula.
Example 3
The ion transmission performance of the PMSA composite membrane is tested by an electrochemical method, and the specific operation steps are as follows:
the method comprises the following steps: firstly, growing an ordered mesoporous silicon oxide film on an AAO substrate by adopting an interface super-assembly method;
(1) before preparing MS, firstly adopting polymethyl methacrylate to perform hole plugging treatment on AAO, specifically dissolving 2.7g of polymethyl methacrylate (PMMA) into 27ml of acetone solution, and heating and stirring at 40-45 ℃ until the PMMA is dissolved;
(2) then spin-coating the polymethyl methacrylate solution on the AAO substrate at 3500 rpm for 30 seconds;
(3) drying the PMMA/AAO film subjected to spin coating in a fume hood for two hours, and then drying the PMMA/AAO film in an oven at the temperature of 200 ℃ for 5 hours to ensure that PMMA can penetrate into AAO holes, so that the effect of blocking the holes is achieved;
(4) then preparing a precursor solution of the mesoporous silica, firstly preparing a prepolymerized mesoporous silica oligomer, adding 2.2g of tetraethyl silicate into a mixed solution of 12g of absolute ethyl alcohol, 1.0g of deionized water and 0.5g of 0.2M hydrochloric acid, and prepolymerizing for 1h at 60 ℃;
(5) preparing F127 template agent solution, namely dissolving 0.9g of F127 into 10g of absolute ethyl alcohol, and performing ultrasonic dispersion and dissolution until the solution is clear;
(6) slowly dripping 8g of pre-polymerized tetraethyl silicate into the F127 template solution, and stirring for 1h at room temperature to obtain a final mesoporous silicon oxide precursor solution;
(7) then, 200 mul of mesoporous silicon oxide precursor solution is spin-coated on the AAO substrate with the hole being plugged, the spin-coating speed is 3000 revolutions, and the spin-coating time is 40 seconds;
(8) then evaporating at 40 ℃ to induce self-assembly for 24h, and carrying out thermal polymerization at 100 ℃ for 24h to obtain a final mesoporous silica/alumina (MS/AAO) composite membrane;
step two: then preparing water-oil phase solution for synthesizing polyurea monomer: firstly, preparing 1.5 w/v% of Polyethyleneimine (PEI) aqueous solution, and dissolving 1.8mg of 50 wt% PEI solution in 60ml of deionized water; then 0.5 w/v% of 2, 4-Toluene Diisocyanate (TDI) is prepared, about 0.3mg of TDI is weighed and dissolved in 60ml of n-hexane, and the prepared two solutions are placed in a drying oven at the temperature of 60 ℃;
step three: then, 200 μ L of PEI was first dropped on the MS/AAO membrane surface, and it was left to evaporate the water to dryness at 60 ℃;
step four: then, 200 mu L of TDI solution is dripped on the surface of MS/AAO containing a PEI polymer chain, the amino group between the two phases and isocyanate are subjected to interfacial polymerization reaction in a drying oven at 60 ℃, the reaction time is 1min, and a compact polyurea film is generated;
step five: the final PMSA composite film with high mechanical performance is obtained.
Step six: and then, establishing an ion transmission device: clamping the PMSA composite membrane in a self-made two-chamber conductivity cell, then adopting an Ag/AgCl electrode plate to connect the whole circuit, taking a Peak to Meter as the size of detection equipment monitoring current, wherein a resistance box is connected to the whole circuit, electrolyte solution is 2M and 0.01M sodium chloride respectively, wherein 0.5M sodium chloride is on one side of polyurea, adopting the Peak to meter to detect under different resistance conditions, the size of current, wherein the value of applied voltage is 0, and then calculating the energy density according to the following formula:
the performance of PMSA composite membranes was tested as follows, taking example 1 as an example
Fig. 1 is a graph of ion transport stability performance of a PMSA composite membrane prepared by interfacial super-assembly and interfacial polymerization methods in example 1. Firstly, the PMSA composite membrane is clamped between two self-made conductance cells, then 0.1MKCl solution is added into two ends of the PMSA composite membrane, electric potentials in different directions are respectively applied, then currents in different electric potential directions are tested, and the PMSA composite membrane can still keep very good current stability under the condition of positive and negative electric potentials of different cycles, which is caused by the fact that the mechanical stability of the PMSA composite membrane is improved due to the existence of PU.
FIG. 2 is a graph showing ion transport properties of the PMSA composite membrane prepared in example 1, in which FIG. 2(a) is an I-V curve of the PMSA composite membrane at different concentrations of KCl, and (b) isA rectification contrast diagram at different electrolyte concentrations, wherein the rectification ratio is represented by the formula f ═ I+1.4V/I-1.4VAnd (4) calculating. (c) The conductivity values of the PMSA composite membrane under different concentrations are specifically implemented by adding KCl solutions with different concentrations into two conductance cells respectively, testing I-V curves under KCl with different concentrations, and calculating the slope to obtain the final conductivity of the PMSA composite membrane under different concentrations.
Cation selectivity test of PMSA composite membrane
Clamping the PMSA composite membrane in two-chamber conductance cell, respectively adding different 10-4KCl of M and electrolyte solution of KCl concentration of 1M, followed by scanning the I-V curve at +2V and-2V. When the PU side is exposed to 1M KCl, under the concentration condition, the electrolyte solution is mainly transported from the polyurea end to the AAO end, the current generated under the voltage of +2V is mainly attributed to the transport of potassium ions, and the current generated under the voltage of-2V is attributed to the transport of chloride ions, as shown in the red curve of FIG. 3. It can be seen that the voltage of +2V is much higher than that of-2V, indicating that more potassium ions are transported from the PU side to the AAO side compared to chloride ions, indicating that the membrane is cation selective. When the direction of concentration difference is changed, the transmission of chloride ions is mainly attributed to the voltage condition of +2V, the transmission of potassium ions is attributed to the voltage condition of-2V, and the current of-2V is far higher than +2V, so that the PMSA composite membrane integrally shows very good cation selectivity is further illustrated. Wherein figure 4 depicts a schematic ion transport diagram at different concentration and different voltage conditions.
Salt difference energy conversion performance test of PMSA composite membrane
Fig. 5 is a graph of the salt difference energy conversion performance of the PMSA composite membrane. The salt difference energy conversion capability of the PMSA composite membrane is mainly tested under the condition of fresh seawater. The test was conducted under two different concentration configurations, one with PU facing the seawater (0.5MNaCl) and one with AAO facing the seawater, and the salt difference energy conversion performance of the PMSA composite membrane was recorded under two concentration conditions. FIG. 5a is a graph of I-V at two concentrations, and it can be seen that I-V has a higher slope when one side of the PU is exposed to seawater, which indicates that more ion flow can occur at such concentrations; FIG. 5b is a graph comparing the current densities at different external resistances for two concentrations, consistent with 5a, with the higher current density when one side of the PU is facing the seawater; the corresponding FIG. 5c shows that higher energy density is also achieved when the PU is exposed to seawater; fig. 5d finally summarizes that the PMSA composite membrane can achieve the highest energy density with the highest salt difference energy conversion performance when PU is exposed to seawater.
The embodiments described above are described to facilitate an understanding and use of the invention by those skilled in the art. It will be readily apparent to those skilled in the art that various modifications to these embodiments may be made, and the generic principles described herein may be applied to other embodiments without the use of the inventive faculty. Therefore, the present invention is not limited to the above embodiments, and those skilled in the art should make improvements and modifications within the scope of the present invention based on the disclosure of the present invention.
Claims (9)
1. The application of the PMSA composite membrane obtained based on interface super-assembly in salt gradient energy conversion is characterized in that the PMSA composite membrane is used as an ion transmission membrane for converting salt gradient energy into electric energy, wherein the PMSA composite membrane is a polyurea/mesoporous silica/anodic alumina composite membrane prepared based on an interface super-assembly strategy.
2. The use of the PMSA composite membrane obtained based on interfacial super assembly in salt gradient energy conversion according to claim 1, wherein the PMSA composite membrane is used as an ion transport membrane for converting salt gradient energy between fresh water and seawater into electrical energy.
3. The use of an interfacial super assembly based PMSA composite membrane in salt gradient energy conversion according to claim 1, wherein said PMSA composite membrane is prepared by a method comprising:
(1) growing an ordered mesoporous silicon oxide film on the AAO substrate by adopting an interface super-assembly method;
(2) preparing water-oil phase solution of synthetic polyurea monomer;
(3) dropwise adding PEI onto the surface of the MS/AAO membrane, and volatilizing the water until the water is dry;
(4) and (3) dropwise adding the TDI solution on the surface of MS/AAO containing a PEI polymer chain, and carrying out interfacial polymerization reaction on amino between two phases and isocyanate to generate a compact polyurea film so as to obtain the PMSA composite film.
4. The application of the PMSA composite membrane obtained based on the interfacial super-assembly in the salt gradient energy conversion is characterized in that the step (1) specifically comprises the following steps:
(1-1) adopting polymethyl methacrylate to perform hole plugging treatment on the AAO;
(1-2) spin-coating a polymethylmethacrylate solution onto the AAO substrate;
(1-3) drying the PMMA/AAO film after spin coating to ensure that PMMA permeates into AAO pores;
(1-4) preparing a precursor solution of mesoporous silica, and pre-polymerizing at 60 ℃;
(1-5) preparing an F127 template solution;
(1-6) dropwise adding the prepolymerized mesoporous silica into the F127 template solution, and stirring at room temperature to obtain a final mesoporous silica precursor solution;
(1-7) spin-coating the mesoporous silicon oxide precursor solution on the AAO substrate with the plugged holes;
(1-8) carrying out evaporation induction self-assembly at 40 ℃ for 24h, and carrying out thermal polymerization at 100 ℃ for 24h to obtain the final mesoporous silica/alumina (MS/AAO) composite membrane.
5. Use of the interface super assembly based PMSA composite membrane according to claim 4 in salt gradient energy conversion,
the specific method in the step (1-1) is as follows: dissolving 2.3-2.7g of polymethyl methacrylate (PMMA) into 23-27 ml of acetone solution, heating and stirring at 40-45 ℃ until the PMMA is dissolved;
the spin coating speed of the step (1-2) is 3000 and 3500 revolutions, and the spin coating time is 30-40 seconds;
drying the PMMA/AAO film subjected to spin coating in the step (1-3) in a fume hood for two hours, and then drying in an oven at 200 ℃ for 5-6 hours;
the specific method of the step (1-4) is as follows: preparing a prepolymerized mesoporous silica oligomer, adding 2-2.2g of tetraethyl silicate into a mixed solution of 10-12g of absolute ethanol, 1.0-1.5g of deionized water and 0.5-0.6g of 0.2M hydrochloric acid, and prepolymerizing at 60 ℃ for 1 h;
the specific method for preparing the F127 template solution in the step (1-5) comprises the following steps: dissolving 0.8-1g of F127 into 9-12g of absolute ethyl alcohol, and performing ultrasonic dispersion and dissolution until the solution is clear;
and (1-7) spin-coating 200-.
6. The application of the PMSA composite membrane obtained based on interfacial super-assembly in salt gradient energy conversion according to claim 3, wherein the specific method for preparing the water-oil phase solution for synthesizing the polyurea monomer in the step (2) comprises the following steps: preparing 1.0-1.8 w/v% of Polyethyleneimine (PEI) aqueous solution, and dissolving the PEI solution in deionized water; then preparing 2, 4-Toluene Diisocyanate (TDI), weighing TDI, dissolving the TDI in n-hexane, and placing the prepared two solutions in an oven at 60 ℃.
7. The use of the PMSA composite membrane obtained based on interfacial super-assembly in salt gradient energy conversion according to claim 3, wherein 200-250 μ L of PEI is dropped on the surface of the MS/AAO membrane in the step (3), and the PEI is evaporated to dryness at 60 ℃;
in the step (4), 160-200 μ L of TDI solution is dripped on the surface of MS/AAO containing a PEI polymer chain, and the amino group between the two phases and isocyanate are subjected to interfacial polymerization reaction in an oven at 60 ℃ for 1 min.
8. The application of the PMSA composite membrane obtained based on the interfacial super-assembly in salt gradient energy conversion is characterized in that the PMSA composite membrane is clamped in a two-chamber semi-conductivity cell to test the salt gradient energy conversion performance, an artificial freshwater seawater solution is placed in the two-chamber conductivity cell in the testing process, and then ion transmission current under different resistances is detected by using a picoammeter.
9. The application of the PMSA composite membrane obtained based on the interfacial super-assembly in the salt gradient energy conversion is characterized in that the PMSA composite membrane is clamped in a two-chamber conductivity cell, an Ag/AgCl electrode plate is adopted to connect the whole circuit, a picometer is used as detection equipment to monitor the magnitude of current, a resistance box is connected into the whole circuit, the picometer is adopted to detect the magnitude of the current under different resistance conditions, and the energy density is calculated according to the following formula:
wherein, P is power density, I is absolute value of penetration current, R is external resistance, and S is test area.
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Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063502A (en) * | 1990-07-16 | 1992-08-12 | 泰咖克萨科开发公司 | The process for purification that contains the mixture of pressed oil and dewaxing solvent |
| CN1132108A (en) * | 1994-10-12 | 1996-10-02 | 东丽株式会社 | Reverse osmosis separating unit and its method |
| CN1213985A (en) * | 1996-03-18 | 1999-04-14 | 日东电工株式会社 | Composite reverse osmosis membrane and method of reverse osmotic treatment of water using same |
| CN109157986A (en) * | 2018-10-16 | 2019-01-08 | 中国石油大学(华东) | Osmosis vaporizing compound membrane and preparation method thereof with " ladder " degree of cross linking |
| CN111729512A (en) * | 2020-07-06 | 2020-10-02 | 复旦大学 | Mesoporous carbon-silicon/anodic aluminum oxide composite membrane, super-assembly preparation method and application thereof |
| CN111729517A (en) * | 2020-07-06 | 2020-10-02 | 复旦大学 | Asymmetric composite membrane based on ordered mesoporous carbon, super-assembly preparation method and application thereof |
| CN111748803A (en) * | 2020-07-06 | 2020-10-09 | 复旦大学 | Mesoporous silica/anodic alumina heterojunction film, super-assembly preparation method and application thereof |
-
2021
- 2021-12-31 CN CN202111667908.4A patent/CN114284518A/en active Pending
Patent Citations (7)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN1063502A (en) * | 1990-07-16 | 1992-08-12 | 泰咖克萨科开发公司 | The process for purification that contains the mixture of pressed oil and dewaxing solvent |
| CN1132108A (en) * | 1994-10-12 | 1996-10-02 | 东丽株式会社 | Reverse osmosis separating unit and its method |
| CN1213985A (en) * | 1996-03-18 | 1999-04-14 | 日东电工株式会社 | Composite reverse osmosis membrane and method of reverse osmotic treatment of water using same |
| CN109157986A (en) * | 2018-10-16 | 2019-01-08 | 中国石油大学(华东) | Osmosis vaporizing compound membrane and preparation method thereof with " ladder " degree of cross linking |
| CN111729512A (en) * | 2020-07-06 | 2020-10-02 | 复旦大学 | Mesoporous carbon-silicon/anodic aluminum oxide composite membrane, super-assembly preparation method and application thereof |
| CN111729517A (en) * | 2020-07-06 | 2020-10-02 | 复旦大学 | Asymmetric composite membrane based on ordered mesoporous carbon, super-assembly preparation method and application thereof |
| CN111748803A (en) * | 2020-07-06 | 2020-10-09 | 复旦大学 | Mesoporous silica/anodic alumina heterojunction film, super-assembly preparation method and application thereof |
Non-Patent Citations (1)
| Title |
|---|
| 邹宁宇 等主编, 中国石化出版社 * |
Cited By (2)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| CN115138223A (en) * | 2022-05-20 | 2022-10-04 | 复旦大学 | Super-assembled nanowire-porous alumina heterostructure film device and preparation method thereof |
| CN115138223B (en) * | 2022-05-20 | 2024-05-03 | 复旦大学 | Super-assembled nanowire-porous alumina heterostructure film device and preparation method thereof |
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