CN108866567B - Bipolar membrane with zinc-metal organic framework material as middle interface layer and preparation method thereof - Google Patents
Bipolar membrane with zinc-metal organic framework material as middle interface layer and preparation method thereof Download PDFInfo
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Abstract
A bipolar membrane with zinc-metal organic framework material as a middle interface layer and a preparation method thereof, wherein the middle interface layer of the bipolar membrane is formed by crosslinking or coating zinc-metal organic framework material catalyst on the inner surfaces of an anion exchange membrane layer and a cation exchange membrane layer; the method comprises the steps of adopting a layer-by-layer casting method, firstly casting a cation exchange membrane solution on a clean glass plate, obtaining a cation exchange membrane after air drying at room temperature, then casting an intermediate interface layer membrane solution on the surface of the cation exchange membrane by adopting a chemical crosslinking or physical adsorption method, forming an intermediate interface layer after drying treatment, finally casting an anion exchange membrane solution on the surface of the intermediate interface layer to form an anion exchange membrane layer, and obtaining the bipolar membrane after drying treatment; the bipolar membrane has the advantages of high water dissociation rate, low water dissociation voltage, high working current density, stable performance, long service life and the like, and is favorable for realizing sustainable operation of reducing nitrogen into ammonia.
Description
Technical Field
The invention relates to a bipolar membrane and a preparation method thereof, in particular to a bipolar membrane taking a zinc-metal organic framework material as a middle interface layer and a preparation method thereof.
Background
The bipolar membrane consists of a cation exchange membrane layer, an anion exchange membrane layer and a middle interface layer, and under the action of a direct-current electric field, water in the middle interface layer is dissociated to generate hydrogen ions and hydroxyl ions which respectively enter an anode chamber and a cathode chamber; the size of the water dissociation efficiency of the middle interface layer of the bipolar membrane is one of key factors for measuring the performance superiority of the bipolar membrane, so that the improvement of the water dissociation efficiency of the middle interface layer is particularly important, documents and patent reports can prepare the bipolar membrane with excellent performance by modifying the middle interface layer, and the improvement of the water dissociation efficiency of the middle interface layer of the bipolar membrane by modifying the middle interface layer with a metal phthalocyanine derivative (Chinese patent invention, CN: 101899675B), a photosensitizer or a semiconductor photocatalytic material (Chinese patent invention, CN: 1011613483B) is reported by aging and the like, so that the water dissociation of the middle interface layer of the bipolar membrane is greatly accelerated; the Xubronze language and the like modify the interface layer in the middle of the bipolar membrane by adopting hyperbranched polymers (Chinese patent invention, CN: 101138707B), dendritic polymers or coordination compounds (Chinese patent invention, CN: 1319632C) obtained by adding heavy metal salts into the modified substances of the hyperbranched polymers or the dendritic polymers, and the like, so that the water dissociation is accelerated, and the water dissociation voltage is reduced.
The atmosphere contains rich nitrogen elements, and most of the nitrogen elements are N2The form (2) is difficult to be directly absorbed by living organisms, and N is required to be converted2The nitrogen-containing compound can be absorbed and utilized; free N by photoelectrocatalysis2The conversion into ammonia is one of the hot spots of the research in the field of photoelectrocatalysis at present; but because of the larger N.ident.N bond energy (940 kJ. mol)-1) Difficult to be activated, resulting in very low nitrogen reduction efficiency and large consumption of H in the process of reducing nitrogen to ammonia+So that the electrolyte in the cathode chamber is gradually changed into alkalinity, which on one hand can cause the catalytic activity of the cathode material to be reduced, and is not beneficial to the continuous progress of catalytic reaction; on the other hand, H in the electrolyte+The supply is insufficient, resulting in a decrease in the reduction rate.
Disclosure of Invention
The invention provides a bipolar membrane taking a zinc-metal organic framework material as a middle interface layer and a preparation method thereof, aiming at the problems of low water dissociation efficiency, large water dissociation voltage and low nitrogen reduction efficiency of the bipolar membrane in the prior art.
A bipolar membrane taking a zinc-metal organic framework material as a middle interface layer comprises a cation exchange membrane layer, an anion exchange membrane layer and the middle interface layer, and is characterized in that: the middle interface layer is a water dissociation catalyst layer which is formed by crosslinking or coating zinc-metal organic framework materials on the inner surfaces of the anion exchange membrane layer and the cation exchange membrane layer;
the water dissociation catalyst layer is prepared by adopting an electrochemical method in ionic liquid and has a molecular formula of Zn4O(BDC)3And is separated from the catalyst layerOf a secondary structural unit Zn4O is a coordination polymer formed by self-assembly, benzene ring bridging with the organic ligand BDC, where BDC = terephthalic acid group.
Wherein the morphology structure of the catalyst layer is spherical or flower-shaped, and the diameter is 0.5-5 mu m.
The preparation method of the bipolar membrane for taking the zinc-metal organic framework material as the intermediate interface layer is characterized in that: the preparation method comprises the following steps:
(1) dissolving dried zinc nitrate and terephthalic acid in N, N-dimethylformamide according to the molar ratio of 4:3, then adding ionic liquid of 1-butyl-3-methylimidazole chlorine salt or 1-butyl-3-methylimidazole bromine salt, and stirring until the ionic liquid is completely dissolved;
(2) adopting a zinc sheet as an anode, a titanium sheet or a copper sheet as a cathode, and the liquid prepared in the step (1) as an electrolyte, wherein the current density is 0.005A cm-2-0.055A cm-2Carrying out the reaction;
(3) after reaction for 0.5-5.5 h, white flocculent precipitate is separated out from the solution, the precipitate is filtered, and then the solution is respectively washed by N, N-dimethylformamide and chloroform for three times and then dried for storage.
Further, the preparation method comprises the following steps:
(1) preparation of membrane liquid
Polyvinyl alcohol or polypropylene imine is prepared into a concentration of 0.05-1.0 mol L-1Adding a zinc-metal organic framework material into the aqueous solution, and uniformly stirring to obtain an intermediate interface layer membrane liquid;
preparing 1.0-5.0% by mass of carboxymethyl cellulose or cellulose acetate aqueous solution and 1.0-5.0% by mass of polyvinyl alcohol or polyvinylpyrrolidone aqueous solution, mixing, continuously stirring to form jelly, standing and defoaming for 60-100 minutes to obtain cation exchange membrane solution;
preparing 1.0-5.0% by mass of aqueous solution of chitosan, polyimide or benzimidazole and 1.0-5.0% by mass of aqueous solution of polyvinyl alcohol or polyvinylpyrrolidone, mixing, continuously stirring to form jelly, standing and defoaming for 60-100 minutes to obtain anion exchange membrane solution;
(2) preparation of bipolar membrane
Preparing a bipolar membrane by adopting a layer-by-layer casting method, namely casting a cation exchange membrane solution on a clean glass plate with a frame, air-drying at room temperature to obtain a cation exchange membrane, casting a middle interface layer membrane solution on the surface of the cation exchange membrane by adopting a chemical crosslinking or physical adsorption method, drying to form a middle interface layer, casting an anion exchange membrane solution on the surface of the middle interface layer to form an anion exchange membrane layer, and drying to obtain the bipolar membrane;
the thickness of the cation exchange membrane is 30-50 nm, the thickness of the anion exchange membrane is 30-60 nm, and the thickness of the middle interface layer is 0.01-5.0 nm.
Compared with the prior art, the invention has the following beneficial effects:
(1) the bipolar membrane prepared by the invention adopts a zinc-metal organic framework material as a catalyst of the middle interface layer, the catalyst has a photocatalytic effect and an electrocatalytic effect at the same time, the water dissociation reaction can be effectively promoted, the activation energy required by the water dissociation reaction of the bipolar membrane is reduced, and the water dissociation efficiency is improved by 5-20%.
(2) The zinc-metal organic framework material is prepared by adopting an electrochemical method in ionic liquid and has a molecular formula of Zn4O(BDC)3The spherical or flower-like catalyst of (2) has characteristics of flexible porosity, large specific surface area, unsaturated coordinate bond and the like, and is capable of proceeding with a water dissociation catalytic reaction.
(3) The zinc-metal organic framework material catalyst is electrochemically prepared in the ionic liquid, part of zinc is electrochemically oxidized into ZnO and is doped into the metal organic framework material, so that a new energy band structure is formed, the photoelectric conversion efficiency is improved, and the water dissociation reaction is promoted.
(4) The bipolar membrane prepared by the invention and taking the zinc-metal organic framework material as the middle interface layer is applied to the fixation and reduction of nitrogen, and the nitrogen fixation amount can be as high as 300-900 mu mol L−1h-1And the water dissociation of the intermediate interface layer of the bipolar membrane provides continuous non-contactBroken H+The method provides a raw material for reducing the nitrogen into the ammonia, and is favorable for realizing the sustainable operation of reducing the nitrogen into the ammonia.
Drawings
FIG. 1 shows a zinc-metal organic framework material prepared in an ionic liquid 1-butyl-3-methylimidazolium chloride system by an electrochemical method in embodiment 1 of the present invention, which has a spherical structure with a diameter of about 2 μm.
FIG. 2 shows a zinc-metal organic framework material prepared in an ionic liquid 1-butyl-3-methylimidazolium bromide system by an electrochemical method in embodiment 2 of the present invention, which has a flower-like structure and a diameter of about 2 μm.
Fig. 3 is a schematic diagram showing the photoelectrocatalytic fixation of nitrogen and reduction to ammonia in the case where a bipolar membrane in which a zinc-metal organic skeleton material is contained in an intermediate interface layer is used as a separator in embodiment 1 of the present invention.
Detailed Description
Example 1
Preparation of zinc-metal organic framework material:
dissolving dried zinc nitrate and terephthalic acid in N, N-dimethylformamide according to the molar ratio of 4:3, adding ionic liquid of 1-butyl-3-methylimidazolium chloride, and stirring until the ionic liquid is completely dissolved to serve as electrolyte; inserting zinc sheet as anode and titanium sheet as cathode, and heating at current density of 0.025A cm-2Carrying out the reaction; after reacting for 2.5 h, white flocculent precipitate is separated out from the solution, the precipitate is filtered, then the solution is washed by N, N-dimethylformamide and chloroform for three times respectively and dried for storage, and the morphological structure of the solution is shown in figure 1.
Preparing a bipolar membrane:
preparing a 2.5 percent carboxymethyl cellulose aqueous solution and a 2.5 percent polyvinyl alcohol aqueous solution by mass fraction, mixing and continuously stirring to form a jelly, standing and defoaming for 90 minutes to prepare a cation exchange membrane solution, casting the cation exchange membrane solution on a clean glass plate with a frame, and air-drying at room temperature to obtain the cation exchange membrane with the thickness of 37 nm.
Polyvinyl alcohol is prepared into a concentration of 0.5 mol L-1Then adding the zinc-metalAnd (3) uniformly stirring the organic framework material to obtain an intermediate interface layer membrane solution, then casting the intermediate interface layer membrane solution on the surface of the cation exchange membrane, and drying to form an intermediate interface layer with the thickness of 2.0 nm.
Preparing a chitosan aqueous solution with the mass fraction of 2.5% and a polyvinyl alcohol aqueous solution with the mass fraction of 2.5%, mixing and continuously stirring to form a jelly, standing and defoaming for 90 minutes to prepare an anion exchange membrane solution, casting the anion exchange membrane solution on the surface of an intermediate interface layer to form an anion exchange membrane layer with the thickness of 40 nm, and drying to obtain the bipolar membrane.
A bipolar membrane containing a zinc-metal organic framework material in an intermediate interface layer is used as a diaphragm of a cathode chamber and an anode chamber to prepare 100 g/L of 1-butyl-3-methylimidazolium chloride ionic liquid electrolyte solution, and a solvent is N, N-dimethylformamide. The cathode chamber is 50 mL min-1N of flow velocity2Bubbling is carried out, titanium-based oxide is used as an anode, Bi2O2CO3As a cathode, a xenon lamp with the voltage of 1.0V applied by a direct-current stabilized power supply is used as a light source, and nitrogen is fixed and reduced into ammonia under the action of photoelectrocatalysis, and the specific principle is shown in figure 3. The experimental results show that the current density is 90 mA cm-2Compared with the bipolar membrane without the zinc-metal organic framework material, the bipolar membrane with the zinc-metal organic framework material on the middle interface layer has the advantages that the cell voltage is reduced by 0.4V, and the water dissociation efficiency is improved by 12.6%. In a continuous 48-hour experiment, the average nitrogen fixation amount is up to 675 mu mol L−1h-1。
Example 2
Preparation of zinc-metal organic framework material:
dissolving dried zinc nitrate and terephthalic acid in N, N-dimethylformamide according to the molar ratio of 4:3, adding ionic liquid of 1-butyl-3-methylimidazolium bromide, and stirring until the ionic liquid is completely dissolved to serve as electrolyte; inserting zinc foil as anode and copper foil as cathode, and measuring current density at 0.035A cm-2Carrying out the reaction; after reacting for 1.5 h, white flocculent precipitate is separated out from the solution, the precipitate is filtered and then washed by N, N-dimethylformamide and chloroform respectivelyAnd (4) drying and storing after three times, wherein the shape and structure of the product are shown in figure 2.
Preparing a bipolar membrane:
preparing 1.5 percent of cellulose acetate aqueous solution and 1.5 percent of polyvinylpyrrolidone aqueous solution by mass fraction, mixing and continuously stirring to form jelly, standing and defoaming for 60 minutes to prepare cation exchange membrane solution, casting the cation exchange membrane solution on a clean glass plate with a frame, and air-drying at room temperature to obtain the cation exchange membrane with the thickness of 33 nm.
The polypropylene imine is prepared into 0.1 mol L-1Adding a zinc-metal organic framework material into the aqueous solution, uniformly stirring to obtain an intermediate interface layer membrane solution, casting the intermediate interface layer membrane solution on the surface of a cation exchange membrane, and drying to form an intermediate interface layer with the thickness of 1.0 nm.
Preparing a 1.5% chitosan aqueous solution and a 1.5% polyvinylpyrrolidone aqueous solution, mixing, continuously stirring to form a jelly, standing and defoaming for 60 minutes to obtain an anion exchange membrane solution, casting the anion exchange membrane solution on the surface of an intermediate interface layer to form an anion exchange membrane layer with the thickness of 38 nm, and drying to obtain the bipolar membrane.
A bipolar membrane containing a zinc-metal organic framework material in an intermediate interface layer is used as a diaphragm of a cathode chamber and an anode chamber to prepare 150 g/L of 1-butyl-3-methylimidazolium bromide ionic liquid electrolyte solution, and a solvent is N, N-dimethylformamide. The cathode chamber is 80 mL min-1N of flow velocity2Bubbling with Pt as anode, MoS2As a cathode, a direct-current stabilized power supply is adopted to provide an external voltage of 1.5V, a 350W xenon lamp is adopted as a light source, and nitrogen is fixed and reduced into ammonia under the action of photoelectrocatalysis. The experimental results show that the current density is 90 mA cm-2Compared with the bipolar membrane without the zinc-metal organic framework material, the bipolar membrane with the zinc-metal organic framework material on the middle interface layer has the advantages that the cell voltage is reduced by 0.7V, and the water dissociation efficiency is improved by 17.2%. In a continuous 48-hour experiment, the average nitrogen fixation amount is up to 735 mu mol L−1h-1。
Example 3
Preparation of zinc-metal organic framework material:
dissolving dried zinc nitrate and terephthalic acid in N, N-dimethylformamide according to the molar ratio of 4:3, adding ionic liquid of 1-butyl-3-methylimidazolium chloride, and stirring until the ionic liquid is completely dissolved to serve as electrolyte; inserting a zinc sheet as an anode and a titanium sheet as a cathode, and controlling the current density at 0.015A cm-2Carrying out the reaction; after reacting for 3.5 h, white flocculent precipitate is separated out from the solution, the precipitate is filtered, and then the solution is respectively washed by N, N-dimethylformamide and chloroform for three times and then dried and stored.
Preparing a bipolar membrane:
preparing a cellulose acetate aqueous solution with the mass fraction of 3.5% and a polyvinyl alcohol aqueous solution with the mass fraction of 3.5%, mixing and continuously stirring to form a jelly, standing and defoaming for 80 minutes to prepare a cation exchange membrane solution, casting the cation exchange membrane solution on a clean glass plate with a frame, and air-drying at room temperature to obtain the cation exchange membrane with the thickness of 41 nm.
Polyvinyl alcohol is prepared into the solution with the concentration of 0.8 mol L-1Adding a zinc-metal organic framework material into the aqueous solution, uniformly stirring to obtain an intermediate interface layer membrane solution, casting the intermediate interface layer membrane solution on the surface of a cation exchange membrane, and drying to form an intermediate interface layer with the thickness of 2.5 nm.
Preparing a polyimide aqueous solution with the mass fraction of 3.5% and a polyvinyl alcohol aqueous solution with the mass fraction of 3.5%, mixing and continuously stirring to form a jelly, standing and defoaming for 80 minutes to prepare an anion exchange membrane solution, casting the anion exchange membrane solution on the surface of an intermediate interface layer to form an anion exchange membrane layer with the thickness of 45 nm, and drying to obtain the bipolar membrane.
Example 4
Preparation of zinc-metal organic framework material:
dissolving dried zinc nitrate and terephthalic acid in N, N-dimethylformamide according to a molar ratio of 4:3, adding ionic liquid of 1-butyl-3-methylimidazolium bromide, and stirring until the ionic liquid is completely dissolved to serve as electrolyte; inserting zinc foil as anode and copper as cathode, in electric currentThe density was 0.045A cm-2Carrying out the reaction; after the reaction is carried out for 0.5 h, white flocculent precipitate is separated out in the solution, the precipitate is filtered, and then the solution is respectively washed by N, N-dimethylformamide and chloroform for three times and then is dried and stored.
Preparing a bipolar membrane:
preparing 4.5 percent of carboxymethyl cellulose aqueous solution and 4.5 percent of polyvinyl alcohol aqueous solution by mass fraction, mixing and continuously stirring to form jelly, standing and defoaming for 90 minutes to prepare cation exchange membrane liquid, casting the cation exchange membrane liquid on a clean glass plate with a frame, and air-drying at room temperature to obtain the cation exchange membrane with the thickness of 43 nm.
The polypropylene imine is prepared into the solution with the concentration of 1.0 mol L-1Adding a zinc-metal organic framework material into the aqueous solution, uniformly stirring to obtain an intermediate interface layer membrane solution, casting the intermediate interface layer membrane solution on the surface of a cation exchange membrane, and drying to form an intermediate interface layer with the thickness of 2.5 nm.
Preparing a benzimidazole aqueous solution with the mass fraction of 4.5% and a polyvinyl alcohol aqueous solution with the mass fraction of 4.5%, mixing and continuously stirring to form a jelly, standing and defoaming for 90 minutes to prepare an anion exchange membrane solution, casting the anion exchange membrane solution on the surface of an intermediate interface layer to form an anion exchange membrane layer with the thickness of 47 nm, and drying to obtain the bipolar membrane.
In the embodiments 1 to 4 of the present invention, the bipolar membrane with a zinc-metal organic framework material as an intermediate interface layer is used as a separator, and nitrogen is fixed and reduced under the action of photoelectricity, and the preparation method comprises: preparing 100-200 g/L ionic liquid electrolyte solution by using a bipolar membrane containing a zinc-metal organic framework material in an intermediate interface layer as a diaphragm of a cathode chamber and an anode chamber, wherein the cathode chamber adopts N with the flow rate of 50-200 mL min < -1 >2Bubbling is carried out, metal and oxide thereof are used as anodes, semiconductor material and transition metal oxide are used as cathodes, a direct current stabilized voltage supply is adopted to provide an external voltage of 0.5-2.0V, a 350W xenon lamp is used as a light source, and nitrogen is fixed and reduced into nitrogen under the action of photoelectrocatalysisAmmonia.
Wherein, the metal and the oxide thereof are one of titanium-based oxide, Pt and Pd; the ionic liquid electrolyte solution is an ionic liquid prepared by dissolving 1-butyl-3-methylimidazole chloride salt or 1-butyl-3-methylimidazole bromide salt in N, N-dimethylformamide; the semiconductor material and the transition metal oxide are BiOCl, Bi2O2CO3, BiOBr，MoS2, MoSe2,WS2, WSe2, ZnO，Cu2O，CuO，TiO2, WO3One or more of the above components are compounded.
Claims (3)
1. A preparation method of a bipolar membrane taking a zinc-metal organic framework material as an intermediate interface layer is characterized in that: the preparation method comprises the following steps:
preparation of zinc-metal organic framework material
(1) Dissolving dried zinc nitrate and terephthalic acid in N, N-dimethylformamide according to the molar ratio of 4:3, then adding ionic liquid of 1-butyl-3-methylimidazolium chloride salt or 1-butyl-3-methylimidazolium bromide salt, and stirring until the ionic liquid is completely dissolved;
(2) adopting a zinc sheet as an anode, a titanium sheet or a copper sheet as a cathode, and the liquid prepared in the step (1) as an electrolyte, wherein the current density is 0.005A cm-2-0.055A cm-2Carrying out the reaction;
(3) after the reaction is carried out for 0.5-5.5 h, white flocculent precipitate is separated out from the solution, the precipitate is filtered, and then the solution is respectively washed by N, N-dimethylformamide and chloroform for three times and then is dried and stored;
preparation of bipolar membrane
Polyvinyl alcohol or polypropylene imine is prepared into the solution with the concentration of 0.05-1.0 mol L-1Adding a zinc-metal organic framework material into the aqueous solution, and uniformly stirring to obtain an intermediate interface layer membrane liquid;
preparing 1.0-5.0% by mass of carboxymethyl cellulose or cellulose acetate aqueous solution and 1.0-5.0% by mass of polyvinyl alcohol or polyvinylpyrrolidone aqueous solution, mixing, continuously stirring to form jelly, standing and defoaming for 60-100 minutes to obtain cation exchange membrane solution;
preparing 1.0-5.0% by mass of aqueous solution of chitosan, polyimide or benzimidazole and 1.0-5.0% by mass of aqueous solution of polyvinyl alcohol or polyvinylpyrrolidone, mixing, continuously stirring to form jelly, standing and defoaming for 60-100 minutes to obtain anion exchange membrane solution;
preparing a bipolar membrane by adopting a layer-by-layer casting method, namely casting a cation exchange membrane solution on a clean glass plate with a frame, air-drying at room temperature to obtain a cation exchange membrane, casting a middle interface layer membrane solution on the surface of the cation exchange membrane by adopting a chemical crosslinking or physical adsorption method, drying to form a middle interface layer, casting an anion exchange membrane solution on the surface of the middle interface layer to form an anion exchange membrane layer, and drying to obtain the bipolar membrane;
the thickness of the cation exchange membrane is 30-50 nm, the thickness of the anion exchange membrane is 30-60 nm, and the thickness of the middle interface layer is 0.01-5.0 nm.
2. A bipolar membrane prepared by the preparation method of the bipolar membrane with the zinc-metal organic framework material as the intermediate interface layer according to claim 1, which comprises a cation exchange membrane layer, an anion exchange membrane layer and the intermediate interface layer, and is characterized in that: the middle interface layer is a water dissociation catalyst layer which is formed by crosslinking or coating zinc-metal organic framework materials on the inner surfaces of the anion exchange membrane layer and the cation exchange membrane layer;
the water dissociation catalyst layer is prepared by adopting an electrochemical method in ionic liquid and has a molecular formula of Zn4O(BDC)3And from a separate secondary structural unit Zn4O is a coordination polymer formed by self-assembly, benzene ring bridging with the organic ligand BDC, where BDC = terephthalic acid group.
3. The bipolar membrane having a zinc-metal organic framework material as an intermediate interface layer according to claim 2, wherein: the morphology structure of the catalyst layer is spherical or flower-shaped, and the diameter of the catalyst layer is 0.5-5 mu m.
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