CN114774987A - Iron-based bipolar membrane and preparation method and application thereof - Google Patents
Iron-based bipolar membrane and preparation method and application thereof Download PDFInfo
- Publication number
- CN114774987A CN114774987A CN202210247226.6A CN202210247226A CN114774987A CN 114774987 A CN114774987 A CN 114774987A CN 202210247226 A CN202210247226 A CN 202210247226A CN 114774987 A CN114774987 A CN 114774987A
- Authority
- CN
- China
- Prior art keywords
- membrane
- iron
- bipolar membrane
- ferrous
- nafion
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Pending
Links
- 239000012528 membrane Substances 0.000 title claims abstract description 146
- XEEYBQQBJWHFJM-UHFFFAOYSA-N Iron Chemical compound [Fe] XEEYBQQBJWHFJM-UHFFFAOYSA-N 0.000 title claims abstract description 72
- 229910052742 iron Inorganic materials 0.000 title claims abstract description 32
- 238000002360 preparation method Methods 0.000 title claims abstract description 15
- 229920000557 Nafion® Polymers 0.000 claims abstract description 33
- CWYNVVGOOAEACU-UHFFFAOYSA-N Fe2+ Chemical compound [Fe+2] CWYNVVGOOAEACU-UHFFFAOYSA-N 0.000 claims abstract description 19
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 claims abstract description 19
- 230000002378 acidificating effect Effects 0.000 claims abstract description 17
- 229910001448 ferrous ion Inorganic materials 0.000 claims abstract description 15
- 238000003825 pressing Methods 0.000 claims abstract description 13
- 230000009467 reduction Effects 0.000 claims abstract description 11
- 238000007605 air drying Methods 0.000 claims abstract description 7
- 239000002131 composite material Substances 0.000 claims abstract description 7
- 238000005507 spraying Methods 0.000 claims abstract description 7
- 238000005266 casting Methods 0.000 claims abstract description 5
- -1 iron ions Chemical class 0.000 claims abstract description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Chemical compound CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 claims description 52
- CSCPPACGZOOCGX-UHFFFAOYSA-N Acetone Chemical compound CC(C)=O CSCPPACGZOOCGX-UHFFFAOYSA-N 0.000 claims description 38
- 239000000243 solution Substances 0.000 claims description 34
- 239000011550 stock solution Substances 0.000 claims description 7
- MCDLETWIOVSGJT-UHFFFAOYSA-N acetic acid;iron Chemical compound [Fe].CC(O)=O.CC(O)=O MCDLETWIOVSGJT-UHFFFAOYSA-N 0.000 claims description 6
- BAUYGSIQEAFULO-UHFFFAOYSA-L iron(2+) sulfate (anhydrous) Chemical compound [Fe+2].[O-]S([O-])(=O)=O BAUYGSIQEAFULO-UHFFFAOYSA-L 0.000 claims description 6
- 238000000034 method Methods 0.000 claims description 5
- LFKXWKGYHQXRQA-FDGPNNRMSA-N (z)-4-hydroxypent-3-en-2-one;iron Chemical compound [Fe].C\C(O)=C\C(C)=O.C\C(O)=C\C(C)=O LFKXWKGYHQXRQA-FDGPNNRMSA-N 0.000 claims description 2
- 229910002651 NO3 Inorganic materials 0.000 claims description 2
- NHNBFGGVMKEFGY-UHFFFAOYSA-N Nitrate Chemical compound [O-][N+]([O-])=O NHNBFGGVMKEFGY-UHFFFAOYSA-N 0.000 claims description 2
- 239000008367 deionised water Substances 0.000 claims description 2
- 229910021641 deionized water Inorganic materials 0.000 claims description 2
- 238000001035 drying Methods 0.000 claims description 2
- 229960002089 ferrous chloride Drugs 0.000 claims description 2
- 235000003891 ferrous sulphate Nutrition 0.000 claims description 2
- 239000011790 ferrous sulphate Substances 0.000 claims description 2
- NMCUIPGRVMDVDB-UHFFFAOYSA-L iron dichloride Chemical compound Cl[Fe]Cl NMCUIPGRVMDVDB-UHFFFAOYSA-L 0.000 claims description 2
- 229910000359 iron(II) sulfate Inorganic materials 0.000 claims description 2
- 239000011259 mixed solution Substances 0.000 claims description 2
- 238000010494 dissociation reaction Methods 0.000 abstract description 5
- 239000003054 catalyst Substances 0.000 abstract description 4
- 230000003197 catalytic effect Effects 0.000 abstract description 4
- 125000002091 cationic group Chemical group 0.000 abstract description 3
- 208000018459 dissociative disease Diseases 0.000 abstract description 2
- 230000009257 reactivity Effects 0.000 abstract 1
- BDAGIHXWWSANSR-UHFFFAOYSA-N methanoic acid Natural products OC=O BDAGIHXWWSANSR-UHFFFAOYSA-N 0.000 description 38
- 239000010410 layer Substances 0.000 description 27
- OKKJLVBELUTLKV-UHFFFAOYSA-N Methanol Chemical compound OC OKKJLVBELUTLKV-UHFFFAOYSA-N 0.000 description 24
- OSWFIVFLDKOXQC-UHFFFAOYSA-N 4-(3-methoxyphenyl)aniline Chemical compound COC1=CC=CC(C=2C=CC(N)=CC=2)=C1 OSWFIVFLDKOXQC-UHFFFAOYSA-N 0.000 description 19
- 235000019253 formic acid Nutrition 0.000 description 19
- 235000019441 ethanol Nutrition 0.000 description 17
- 239000002253 acid Substances 0.000 description 12
- 239000003792 electrolyte Substances 0.000 description 12
- 239000002184 metal Chemical group 0.000 description 5
- 229910052751 metal Inorganic materials 0.000 description 5
- 239000000047 product Substances 0.000 description 5
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 4
- 230000009471 action Effects 0.000 description 4
- 239000007864 aqueous solution Substances 0.000 description 4
- 229910052799 carbon Inorganic materials 0.000 description 4
- 238000006243 chemical reaction Methods 0.000 description 4
- 238000001816 cooling Methods 0.000 description 4
- 230000000694 effects Effects 0.000 description 4
- 239000011521 glass Substances 0.000 description 4
- 238000010438 heat treatment Methods 0.000 description 4
- 239000012263 liquid product Substances 0.000 description 4
- 239000007921 spray Substances 0.000 description 4
- 238000012360 testing method Methods 0.000 description 4
- 238000010586 diagram Methods 0.000 description 3
- 230000005593 dissociations Effects 0.000 description 3
- 230000005684 electric field Effects 0.000 description 3
- RAXXELZNTBOGNW-UHFFFAOYSA-N imidazole Chemical group C1=CNC=N1 RAXXELZNTBOGNW-UHFFFAOYSA-N 0.000 description 3
- 238000004519 manufacturing process Methods 0.000 description 3
- 239000011736 potassium bicarbonate Substances 0.000 description 3
- 229910000028 potassium bicarbonate Inorganic materials 0.000 description 3
- 238000012876 topography Methods 0.000 description 3
- 238000005516 engineering process Methods 0.000 description 2
- 150000002500 ions Chemical class 0.000 description 2
- 238000001000 micrograph Methods 0.000 description 2
- 230000035515 penetration Effects 0.000 description 2
- 238000011160 research Methods 0.000 description 2
- 239000004215 Carbon black (E152) Substances 0.000 description 1
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical compound [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 1
- 229910021607 Silver chloride Inorganic materials 0.000 description 1
- 238000007792 addition Methods 0.000 description 1
- 239000003513 alkali Substances 0.000 description 1
- 238000005349 anion exchange Methods 0.000 description 1
- 239000003011 anion exchange membrane Substances 0.000 description 1
- 239000003125 aqueous solvent Substances 0.000 description 1
- 230000009286 beneficial effect Effects 0.000 description 1
- 230000015572 biosynthetic process Effects 0.000 description 1
- 239000000969 carrier Substances 0.000 description 1
- 238000005341 cation exchange Methods 0.000 description 1
- 238000013461 design Methods 0.000 description 1
- 238000011161 development Methods 0.000 description 1
- 230000005611 electricity Effects 0.000 description 1
- 239000010411 electrocatalyst Substances 0.000 description 1
- 238000004070 electrodeposition Methods 0.000 description 1
- 239000008151 electrolyte solution Substances 0.000 description 1
- 229940021013 electrolyte solution Drugs 0.000 description 1
- 238000002474 experimental method Methods 0.000 description 1
- 239000000446 fuel Substances 0.000 description 1
- 239000007789 gas Substances 0.000 description 1
- 238000000227 grinding Methods 0.000 description 1
- 125000002795 guanidino group Chemical group C(N)(=N)N* 0.000 description 1
- 150000002391 heterocyclic compounds Chemical group 0.000 description 1
- 229930195733 hydrocarbon Natural products 0.000 description 1
- 150000002430 hydrocarbons Chemical class 0.000 description 1
- 229910052739 hydrogen Inorganic materials 0.000 description 1
- 239000001257 hydrogen Substances 0.000 description 1
- 239000012535 impurity Substances 0.000 description 1
- 230000002401 inhibitory effect Effects 0.000 description 1
- 239000011229 interlayer Substances 0.000 description 1
- 150000002506 iron compounds Chemical class 0.000 description 1
- 230000007246 mechanism Effects 0.000 description 1
- 230000000116 mitigating effect Effects 0.000 description 1
- 239000000203 mixture Substances 0.000 description 1
- 238000012986 modification Methods 0.000 description 1
- 230000004048 modification Effects 0.000 description 1
- 230000020477 pH reduction Effects 0.000 description 1
- 238000011056 performance test Methods 0.000 description 1
- 229920006254 polymer film Polymers 0.000 description 1
- 229920005597 polymer membrane Polymers 0.000 description 1
- 230000008569 process Effects 0.000 description 1
- 150000003242 quaternary ammonium salts Chemical group 0.000 description 1
- 238000011946 reduction process Methods 0.000 description 1
- HKZLPVFGJNLROG-UHFFFAOYSA-M silver monochloride Chemical compound [Cl-].[Ag+] HKZLPVFGJNLROG-UHFFFAOYSA-M 0.000 description 1
- 239000002356 single layer Substances 0.000 description 1
- 230000003595 spectral effect Effects 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
Images
Classifications
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/02—Diaphragms; Spacing elements characterised by shape or form
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B13/00—Diaphragms; Spacing elements
- C25B13/04—Diaphragms; Spacing elements characterised by the material
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/01—Products
- C25B3/07—Oxygen containing compounds
-
- C—CHEMISTRY; METALLURGY
- C25—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES; APPARATUS THEREFOR
- C25B—ELECTROLYTIC OR ELECTROPHORETIC PROCESSES FOR THE PRODUCTION OF COMPOUNDS OR NON-METALS; APPARATUS THEREFOR
- C25B3/00—Electrolytic production of organic compounds
- C25B3/20—Processes
- C25B3/25—Reduction
- C25B3/26—Reduction of carbon dioxide
Abstract
The invention discloses an iron-based bipolar membrane and a preparation method and application thereof. The iron-based bipolar membrane is a composite membrane comprising a commercial alkaline membrane layer, a ferrous ion intermediate layer and a Nafion acidic membrane layer. The bipolar membrane is prepared by sequentially spraying a ferrous ion solution and casting a Nafion membrane solution on a commercial alkaline membrane, and then carrying out air drying and cold pressing. The commercial alkaline membrane in the iron-based bipolar membrane prepared by the invention has cationic groups and can realize OH‑Conduction in alkaline membranes; the Nafion series membrane has high proton conductivity and can realize H+Conduction in acidic membranes; the iron ions as the intermediate catalyst layer can perform catalytic water dissociation reaction with water molecules to improve water qualityThe reactivity of (3) weakens the bond of water molecules; therefore, the iron-based bipolar membrane can realize efficient reduction of CO2And has good application prospect.
Description
Technical Field
The invention relates to an iron-based bipolar membrane, a preparation method and application thereof, and belongs to electrochemical reduction of CO2The technical field is as follows.
Background
Electrochemical CO2Reduction (CO)2RR) is before an itemA widely recognized technology for the production of CO from human production activities2Production of high value-added fuels and chemicals as a carbon source while effectively mitigating CO2Discharge in the atmosphere [ chem. Soc. Rev.2014,45,631-675]. Electricity and CO generated by renewable energy sources such as wind energy, solar energy, tidal energy and geothermal energy2Can be converted into a plurality of products in the electrochemical reactor, such as acid, alcohol, hydrocarbon, synthesis gas and the like [ Joule.2018,2,825-]. The selectivity of different products depends on a number of influencing factors, including: the type of catalyst and its morphology, the type and concentration of the electrolyte and the pH, the flow characteristics of the electrolyte, the aqueous or non-aqueous solvent, the temperature, pressure, potential and current density, and the impurities present in the electrolyte and the design of the cell [ ACS Catal.2017,7,4822-]。
Usually, to prevent CO2The products obtained by reduction are diffused to the anode to be oxidized, and the types of electrolytes used by the anode and the cathode are different due to different reactions. Therefore, a polymer film is often required to be added between the cathode and the anode for separating the cathode and the anode [ Ind]. There are currently three main types of polymer membranes, which are: alkaline anion exchange membranes, acidic membranes, and bipolar membranes, wherein acidic membranes have been shown to increase the evolution of hydrogen from competing reactions due to the conduction of large quantities of protons to the cathode, while alkaline membranes have been shown to have a higher formic acid "penetration" resulting in CO2Loss of reduced liquid product [ adv. sustatin. Syst.2018,2,1700187]。
Unlike the two membranes described above, the composition of the bipolar membrane comprises a positively charged Anion Exchange Layer (AEL), an intermediate catalytic layer, and a negatively charged Cation Exchange Layer (CEL) [ ChemUSChem.2014, 7,3017-]It can operate in two modes, (a) forward bias (V)>0) With the membrane's CEL towards the anode, (b) reverse bias (V)<0) With CEL facing the cathode. In forward bias mode, the electric field causes mobile ions to migrate to the Interface Region (IR), where they accumulate to compensate for the charge in the layer, thereby reducing the selectivity of the film. In contrast, in the reverse bias mode, when the applied voltage reaches a certain value, the voltage is applied to the substrateSeparation of water molecules will occur at the interface of AEL and CEL and there is an OnSager's Law of enhanced electric field, the second Diyan Effect [ Electrochim. acta.1986,31,1175-1177, in the interior of the membrane]In the presence of an applied electric field, H+Will migrate through CEL to the cathode, OH-Migrate to the anode by AEL. Electrochemical reduction of CO with bipolar membranes as compared to single-layer alkaline or acidic membranes2Has the outstanding advantages that: (a) when the bipolar membrane is used as a diaphragm, two electrolyte solutions with different pH values can be used for the anode and the cathode, and the pH values of the electrolytes on the two sides can be maintained in the using process; (b) the "breakthrough" (crossover) of the liquid product from cathode to anode was negligible; (c) when the electrolyte of the cathode and the anode is pure water, the acidification and the alkalization of the electrolyte do not need to add extra acid and alkali.
However, electrochemical reduction of CO is performed domestically2The field, whether colleges or scientific research institutions, is still focused on the development of electrocatalysts. The research on reaction devices and electrolytes has been started, but no one is concerned about bipolar membranes.
Disclosure of Invention
The technical problem to be solved by the invention is as follows: how to prepare a catalyst for efficient electrochemical reduction of CO by using a commercial alkaline membrane2The technical problem of the bipolar membrane of (3).
In order to solve the above technical problems, the present invention provides an iron-based bipolar membrane which is a composite membrane comprising a commercial alkaline membrane layer, a divalent iron ion intermediate layer and a Nafion acidic membrane layer, which are connected in this order.
Preferably, the bipolar membrane is prepared by spraying a ferrous ion solution and a Nafion membrane casting solution on a commercial alkaline membrane in sequence, and then performing air drying and cold pressing.
The invention also provides a preparation method of the iron-based bipolar membrane, which comprises the following steps:
step 1: preparing a Nafion stock solution into a Nafion acetone solution;
and 2, step: spraying a ferrous ion solution on the commercial alkaline membrane to obtain a ferrous ion salt intermediate layer;
and step 3: and (3) casting the Nafion acetone solution prepared in the step (1) on the ferrous ion intermediate layer, and then sequentially carrying out air drying and cold pressing to obtain the iron-based bipolar membrane.
Preferably, the concentration of the Nafion acetone solution in the step 1 is 20-40 wt%.
Preferably, the spraying amount of the ferrous ion solution in the step 2 is 3-10 mL; the ferrous ion solution is a mixed solution obtained by dispersing soluble ferrous salt in absolute ethyl alcohol and deionized water in a volume ratio of 1: 1; the concentration of the ferrous ion solution is 0.005-0.02M.
Preferably, the ferrous salt is at least one of ferrous nitrate, ferrous chloride, ferrous sulfate, ferrous acetate and ferrous acetylacetonate.
Preferably, the air drying conditions in the step 3 are as follows: drying for 1-3 h in a flowing air atmosphere at 30-60 ℃; the cold pressing conditions are as follows: cold pressing for 5-30 s at room temperature under the condition of 1-10 MPa.
The invention also provides the iron-based bipolar membrane for electrochemical reduction of CO2The use of (1).
Compared with the prior art, the invention has the beneficial effects that:
(1) the iron-based bipolar membrane prepared by the invention comprises a commercial alkaline membrane layer, a middle ferrous ion layer and a Nafion acidic membrane layer; wherein the commercial alkaline membrane is provided with cationic groups, such as quaternary ammonium salt, heterocyclic compound, imidazole, guanidino, metal group and the like, so that OH-can be conducted in the alkaline membrane under the action of the cationic groups; nafion series membrane has high proton conductivity and can realize H+Conduction in acidic membranes; iron ions serving as an intermediate catalyst layer can perform catalytic water dissociation reaction with water molecules, so that the reaction activity of water is improved, and water molecular bonds are weakened; therefore, the iron-based bipolar membrane of the invention is applied to CO2In the reduction process, the water dissociation of the middle layer into H can be accelerated+And OH-And transfers them to the cathode and the anode under the action of reverse bias voltage, respectively, thereby efficiently reducing CO2；
(2) Test experiments prove that the bipolar membrane prepared by the invention can effectively inhibit ionsThe penetration of the ions between the cathode and the anode can effectively inhibit the CO on the cathode side2The reduction liquid product is conducted to the anode to be oxidized, so that the loss of the cathode product is reduced, and the method has a good application prospect.
Drawings
FIG. 1 is a scanning electron microscope image of the bipolar membrane prepared in example 1, wherein (a) and (b) are surface topography maps of the acidic membrane side and the alkaline membrane side of the bipolar membrane, respectively; (c) respectively showing the cross sections of the acid membrane side and the alkaline membrane side of the bipolar membrane;
FIG. 2 is a graph of the formic acid Faraday efficiencies at different potentials using a Cu-coped-Bi electrode as the working electrode and the intermediate membranes commercial alkaline membrane A201, commercial acidic membrane Nafion 212 and the bipolar membrane prepared in example 1, respectively;
FIG. 3 shows CO when a Cu-doped-Bi electrode is used as a working electrode and the intermediate membranes are a commercial alkaline membrane A201, a commercial acidic membrane Nafion 212 and the bipolar membrane prepared in example 12The "cross-over" rate of reduction product (formic acid) from cathode to anode;
FIG. 4 shows the results of a two-electrode test using carbon paper as the working and counter electrodes, with 0.5M KHCO as the electrolyte on the anode side3The solution and the catholyte are 0.5M KHCO containing formic acid, methanol and ethanol (0.02M) in sequence3When the solution and the intermediate membrane respectively adopt the commercial alkaline membrane A201, the commercial acidic membrane Nafion 212 and the bipolar membrane prepared in the example 1, the concentration is 50mA/cm2The current density of the anode chamber is measured, and the contents of formic acid, methanol and ethanol in the anode chamber are sequentially measured;
FIG. 5 is a pictorial view of the bipolar membrane prepared in example 1;
FIG. 6 is a diagram showing the operation of the bipolar membrane prepared in example 1, in which the iron in the intermediate layer promotes dissociation of water under the action of reverse bias, resulting in H+OH passes through the acid membrane to the cathode compartment-Across the alkaline membrane to the anode compartment.
Detailed Description
In order to make the invention more comprehensible, preferred embodiments are described in detail below with reference to the accompanying drawings.
The commercial alkaline membrane used in the following examples was purchased from Tokuyama, Japan, iron compounds, absolute ethanol, acetone, Shanghai Aladdin Biochemical technologies, Inc., and Nafion solution (stock solution) was purchased from Sigma-Aldrich, Inc.
Example 1
The embodiment provides a preparation method of an iron-based bipolar membrane, which comprises the following specific preparation processes:
heating 50mL of the stock solution (30 wt%) in water bath at 85 ℃ for 5h, cooling to room temperature, metering to 50mL by using acetone, and repeating for three times to obtain a 30 wt% Nafion acetone solution. Commercial alkaline membranes were mounted between two glass plates to achieve 2 x 2cm2Is placed on a 45 ℃ hot plate, and 5mL of 0.01M aqueous solution of Fe (II) (iron acetate) in ethanol (ethanol: H) is sprayed using a spray gun2O1: 1 volume ratio) was sprayed uniformly onto commercial alkaline membranes. 2.5mL of the above 30 wt% Nafion acetone solution was cast on the Fe (II) -containing intermediate layer film and dried under an air flowing atmosphere at 30 ℃ for 2 h. And then, cold pressing the commercial alkaline membrane, the Fe (II) middle layer and the acid membrane composite layer for 10s at room temperature of 3MPa to obtain the bipolar membrane.
Example 2
The embodiment provides a preparation method of an iron-based bipolar membrane, which comprises the following specific preparation processes:
heating 50mL of the stock solution (30 wt%) in water bath at 85 ℃ for 5h, cooling to room temperature, metering to 50mL by using acetone, and repeating for three times to obtain a 30 wt% Nafion acetone solution. Commercial alkaline membranes were mounted between two glass plates to achieve 2 x 2cm2Is placed on a 45 ℃ hot plate, and 5mL of a 0.01M aqueous solution of Fe (II) (iron acetate) in ethanol (ethanol: H) is sprayed using a spray gun2O1: 1 volume ratio) was uniformly sprayed on commercial alkaline membranes. 5mL of the above 30 wt% Nafion acetone solution was cast on the Fe (II) -containing intermediate layer film and dried under an air flowing atmosphere at 30 ℃ for 2 h. And then, cold pressing the commercial alkaline membrane, the Fe (II) middle layer and the acid membrane composite layer for 10s at room temperature of 3MPa to obtain the bipolar membrane.
Example 3
The embodiment provides a preparation method of an iron-based bipolar membrane, which comprises the following specific preparation processes:
heating 50mL of the Afion stock solution (30 wt%) in a water bath at 85 ℃ for 5h, cooling to room temperature, metering to 50mL by using acetone, and repeating for three times to obtain a 30 wt% Nafion acetone solution. Commercial alkaline membranes were mounted between two glass plates to achieve 2 x 2cm2Is placed on a 45 ℃ hot plate, and 5mL of 0.01M aqueous solution of Fe (II) (iron acetate) in ethanol (ethanol: H) is sprayed using a spray gun2O1: 1 volume ratio) was sprayed uniformly onto commercial alkaline membranes. 7.5mL of the above 30 wt% Nafion acetone solution was cast on the Fe (II) -containing interlayer film and dried under an air flowing atmosphere at 30 ℃ for 2 h. And then, cold pressing the commercial alkaline membrane, the Fe (II) middle layer and the acid membrane composite layer for 10s at room temperature of 3MPa to obtain the bipolar membrane.
Example 4
The embodiment provides a preparation method of an iron-based bipolar membrane, which comprises the following specific preparation processes:
heating 50mL of the Afion stock solution (30 wt%) in a water bath at 85 ℃ for 5h, cooling to room temperature, metering to 50mL by using acetone, and repeating for three times to obtain a 30 wt% Nafion acetone solution. Commercial alkaline membranes were mounted between two glass plates to achieve 2 x 2cm2Is placed on a 45 ℃ hot plate, and 5mL of 0.01M aqueous solution of Fe (II) (iron acetate) in ethanol (ethanol: H) is sprayed using a spray gun2O1: 1 volume ratio) was uniformly sprayed on commercial alkaline membranes. 10mL of the above 30 wt% Nafion acetone solution was cast on the intermediate layer film containing Fe (II), and dried under an air flowing atmosphere at 30 ℃ for 2 h. And then, cold pressing the commercial alkaline membrane, the Fe (II) middle layer and the acid membrane composite layer for 10s at room temperature of 3MPa to obtain the bipolar membrane.
The electrochemical performance test was performed on an electrochemical workstation of Shanghai Chenhua corporation CHI760e, using a three-electrode system. Cu-dot-Bi metal electrode prepared by electrodeposition is used as a working electrode [ appl.Catal.B.288,120003(2021)]Ag/AgCl electrode as reference electrode, spectral fossil grinding rod as counter electrode, and electrolyte of 0.5M KHCO3And (3) solution. Cu-doped-Bi metal electrodes have been shown to efficiently convert CO2The formic acid is prepared by electrochemical reduction, so the liquid product A is researched by utilizing the catalytic electrodeThe "breakthrough" effect of the acid from the cathode to the anode. In the two-electrode test, carbon paper is used as a working electrode and a counter electrode respectively, and the electrolyte at the anode side is 0.5M KHCO3The solution and the catholyte are 0.5M KHCO containing formic acid, methanol and ethanol (0.02M) in sequence3And (3) solution.
FIG. 1 is a scanning electron microscope image of the bipolar membrane of example 1, wherein FIGS. 1(a) and 1(b) are surface topography images of the acidic membrane side and the alkaline membrane side of the bipolar membrane, respectively, and it can be seen that both surfaces are relatively smooth, which can effectively increase contact with the catholyte. FIGS. 1(c) and 1(d) are cross-sectional topography of the acidic membrane side and the alkaline membrane side of the bipolar membrane, respectively, and it can be seen that the cross-section of the acidic membrane side shows a dense microstructure, while the cross-section of the alkaline membrane side shows a layered porous structure, and the microstructure inside the alkaline membrane helps to improve the movement of carriers and accelerate OH-Of the network element.
As shown in FIG. 2, the Faraday efficiencies of formic acid when a Cu-doped-Bi metal electrode is used as a working electrode, Nafion 212 acidic membrane (DuPont corporation, USA), A201 alkaline membrane (Tokuyama corporation, Japan) and a bipolar membrane (bipolar membrane) in example 1 are used as a separator, respectively. It can be seen that the formic acid faradaic efficiency using the bipolar membrane prepared in example 1 as a separator is significantly higher than that using Nafion 212 acid membrane and a201 alkaline membrane, and particularly the formic acid faradaic efficiency reaches the highest (98%) at-0.97V.
FIG. 3 shows the "breakthrough" effect on formic acid from cathode to anode under three membrane operating conditions when the Cu-doped-Bi metal electrode is used as the working electrode. As can be seen, the formic acid "breakthrough" rate of the alkaline membrane (a201) is 22.92%, which is much higher than the Nafion 212 acid membrane in the united states. However, the bipolar membrane prepared in example 1 was used, and the presence of formic acid was not detected at the anode, which indicates that the bipolar membrane prepared in example 1 can effectively inhibit the "breakthrough" of formic acid from the cathode to the anode.
As shown in FIG. 4, in the two-electrode test, carbon paper was used as the working electrode and the counter electrode, and the electrolyte at the anode side was 0.5M KHCO3The solution and the catholyte are 0.5M KHCO containing formic acid, methanol and ethanol (0.02M) in sequence3And (3) solution. At 50mA/cm2Electricity (D) fromElectrolyzing for one hour under the current density, and respectively detecting the contents of formic acid, methanol and ethanol in the anode chamber. The results show that the formic acid, methanol and ethanol "breakthrough" (cross-over) rates of the Nafion 212 membrane are all less than that of the a201 membrane; whereas, with the bipolar membrane prepared in example 1, the presence of formic acid, methanol and ethanol was not detected at the anode (and thus not shown in fig. 4), indicating that the bipolar membrane is effective in inhibiting "breakthrough" of formic acid, methanol and ethanol from the cathode to the anode;
FIG. 5 is a schematic diagram showing the bipolar membrane prepared in example 1;
as shown in FIG. 6, which is a working mechanism diagram of the bipolar membrane prepared in example 1, under the action of reverse bias, the iron of the intermediate layer will promote the dissociation of water, resulting in H+Across the acid membrane to the cathode compartment, OH-Across the alkaline membrane to the anode compartment.
The above-described embodiments are intended to be preferred embodiments of the present invention only, and not to limit the invention in any way and in any way, it being noted that those skilled in the art will be able to make modifications and additions without departing from the scope of the invention, which shall be deemed to also encompass the scope of the invention.
Claims (8)
1. An iron-based bipolar membrane, characterized in that the bipolar membrane is a composite membrane comprising a commercial alkaline membrane layer, a divalent iron ion intermediate layer and a Nafion acidic membrane layer which are connected in sequence.
2. The iron-based bipolar membrane of claim 1, wherein said bipolar membrane is prepared by spraying a solution of ferrous ions and casting a solution of Nafion membrane on a commercial alkaline membrane in sequence, followed by air drying and cold pressing.
3. The preparation method of the iron-based bipolar membrane of claim 1 or 2, characterized by comprising the following steps:
step 1: preparing a Nafion stock solution into a Nafion acetone solution;
step 2: spraying a ferrous ion solution on the commercial alkaline membrane to obtain a ferrous ion salt intermediate layer;
and step 3: and (3) casting the Nafion acetone solution prepared in the step (1) on the ferrous ion intermediate layer, and then sequentially carrying out air drying and cold pressing to obtain the iron-based bipolar membrane.
4. The method for preparing an iron-based bipolar membrane according to claim 3, wherein the concentration of the Nafion acetone solution in step 1 is 20-40 wt%.
5. The method for preparing an iron-based bipolar membrane according to claim 3, wherein the spraying amount of the ferrous ion solution in the step 2 is 3-10 mL; the ferrous ion solution is a mixed solution obtained by dispersing soluble ferrous salt in absolute ethyl alcohol and deionized water in a volume ratio of 1: 1; the concentration of the ferrous ion solution is 0.005-0.02M.
6. The method for preparing an iron-based bipolar membrane according to claim 5, wherein said ferrous salt is at least one of ferrous nitrate, ferrous chloride, ferrous sulfate, ferrous acetate and ferrous acetylacetonate.
7. The preparation method of the iron-based bipolar membrane according to claim 3, wherein the air-drying conditions in the step 3 are as follows: drying for 1-3 h in a flowing air atmosphere at 30-60 ℃; the cold pressing conditions are as follows: cold pressing for 5-30 s at room temperature under the condition of 1-10 MPa.
8. The iron-based bipolar membrane of claim 1 or 2 in electrochemical reduction of CO2The use of (1).
Priority Applications (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210247226.6A CN114774987A (en) | 2022-03-14 | 2022-03-14 | Iron-based bipolar membrane and preparation method and application thereof |
Applications Claiming Priority (1)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| CN202210247226.6A CN114774987A (en) | 2022-03-14 | 2022-03-14 | Iron-based bipolar membrane and preparation method and application thereof |
Publications (1)
| Publication Number | Publication Date |
|---|---|
| CN114774987A true CN114774987A (en) | 2022-07-22 |
Family
ID=82422824
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CN202210247226.6A Pending CN114774987A (en) | 2022-03-14 | 2022-03-14 | Iron-based bipolar membrane and preparation method and application thereof |
Country Status (1)
| Country | Link |
|---|---|
| CN (1) | CN114774987A (en) |
Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227040A (en) * | 1987-07-30 | 1993-07-13 | Unisearch Limited | High performance bipolar membranes |
| CN102912374A (en) * | 2012-10-24 | 2013-02-06 | 中国科学院大连化学物理研究所 | Electrochemical reduction CO2 electrolytic tank using bipolar membrane as diaphragm and application of electrochemical reduction CO2 electrolytic tank |
| KR101746591B1 (en) * | 2016-02-29 | 2017-06-14 | 주식회사 이노켐텍 | Bipolar ion exchange composite membrane and method of manufacturing the same |
| KR102062737B1 (en) * | 2019-10-14 | 2020-01-06 | 상명대학교 천안산학협력단 | Bipolar membrane for water dissociation |
-
2022
- 2022-03-14 CN CN202210247226.6A patent/CN114774987A/en active Pending
Patent Citations (4)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US5227040A (en) * | 1987-07-30 | 1993-07-13 | Unisearch Limited | High performance bipolar membranes |
| CN102912374A (en) * | 2012-10-24 | 2013-02-06 | 中国科学院大连化学物理研究所 | Electrochemical reduction CO2 electrolytic tank using bipolar membrane as diaphragm and application of electrochemical reduction CO2 electrolytic tank |
| KR101746591B1 (en) * | 2016-02-29 | 2017-06-14 | 주식회사 이노켐텍 | Bipolar ion exchange composite membrane and method of manufacturing the same |
| KR102062737B1 (en) * | 2019-10-14 | 2020-01-06 | 상명대학교 천안산학협력단 | Bipolar membrane for water dissociation |
Non-Patent Citations (1)
| Title |
|---|
| 陈强等: "二茂铁改性双极膜技术制备3-甲基-2-吡啶甲酰胺", 高分子材料科学与工程, vol. 11, no. 3, pages 132 - 135 * |
Similar Documents
| Publication | Publication Date | Title |
|---|---|---|
| Chen et al. | Address the “alkalinity problem” in CO2 electrolysis with catalyst design and translation | |
| Bodner et al. | H2 generation from alkaline electrolyzer | |
| Lobyntseva et al. | Electrochemical synthesis of hydrogen peroxide: Rotating disk electrode and fuel cell studies | |
| An et al. | Performance of an alkaline-acid direct ethanol fuel cell | |
| CN109321936B (en) | Device and method for producing hydrogen by electrolyzing water step by step based on liquid flow redox medium | |
| JP6501141B2 (en) | Organic hydride manufacturing apparatus and method of manufacturing organic hydride using the same | |
| CN109560310B (en) | Fuel cell ultra-low platinum loading self-humidifying membrane electrode and preparation method thereof | |
| CN111088504B (en) | Practical carbon dioxide reduction membrane electrolyzer and preparation method thereof | |
| JP6189327B2 (en) | Regenerative fuel cell | |
| CN108579818B (en) | Preparation method of solid polymer electrolyte water electrolysis membrane electrode catalyst slurry | |
| JP2018537838A (en) | Regenerative fuel cell | |
| WO2023231481A1 (en) | Membrane electrode assembly comprising acidic cation exchange membrane, and application | |
| Li et al. | Performance degradation of a direct borohydride fuel cell | |
| Liu et al. | A High-Performance Continuous-Flow MEA Reactor for Electroreduction CO 2 to Formate | |
| CN110791773A (en) | Method and device for producing hydrogen by electrolyzing water | |
| CN110416553B (en) | Proton membrane fuel cell catalyst, preparation method thereof and fuel cell system | |
| CN113416971B (en) | Device and method for producing hydrogen by electrolyzing hydrogen peroxide | |
| US20220018033A1 (en) | Method for preparing a catalytic material of an electrode for electrochemical reduction reactions prepared by electroreduction | |
| CN113549942A (en) | Method and device for improving hydrogen production efficiency by electrolyzing water | |
| Adilbish et al. | Effect of the deposition time on the electrocatalytic activity of Pt/C catalyst electrodes prepared by pulsed electrophoresis deposition method | |
| CN113937328A (en) | Membrane electrode for reducing metal ion pollution of catalyst layer | |
| CN115697553A (en) | Anion exchange membrane electrolyzer with self-supporting oxygen evolution electrodes free of platinum group metals | |
| JP2015534607A (en) | Electrolytic electrode catalyst | |
| CN1683596A (en) | Method for producing hydrogen and storaging hydrogen integrately | |
| CN114774987A (en) | Iron-based bipolar membrane and preparation method and application thereof |
Legal Events
| Date | Code | Title | Description |
|---|---|---|---|
| PB01 | Publication | ||
| PB01 | Publication | ||
| SE01 | Entry into force of request for substantive examination | ||
| SE01 | Entry into force of request for substantive examination |