CN109082682B - Application of bipolar membrane taking zinc-metal organic framework material as middle interface layer in photoelectrocatalysis nitrogen fixation - Google Patents
Application of bipolar membrane taking zinc-metal organic framework material as middle interface layer in photoelectrocatalysis nitrogen fixation Download PDFInfo
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Abstract
The application of the bipolar membrane with the zinc-metal organic framework material as the middle interface layer in photoelectrocatalysis nitrogen fixation is characterized in that the bipolar membrane with the zinc-metal organic framework material as the middle interface layer is used as a diaphragm of a cathode chamber and an anode chamber, an ionic liquid electrolyte solution is prepared, metal and oxide thereof are used as an anode, a semiconductor material and transition metal oxide are used as a cathode, and nitrogen is fixed and reduced into ammonia under the action of photoelectrocatalysis. The bipolar membrane is applied to nitrogen fixation and reduction, and the nitrogen fixation amount can reach as high as 300-−1h‑1And the water dissociation of the interface layer in the middle of the bipolar membrane provides continuous 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.
Description
Technical Field
The invention relates to an application of a bipolar membrane taking a zinc-metal organic framework material as a middle interface layer in photoelectrocatalysis nitrogen fixation, in particular to a technical scheme of the photoelectrocatalysis bipolar membrane in nitrogen fixation and reduction application.
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, therefore, the improvement of the water dissociation efficiency of the middle interface layer is particularly important, documents and patents report that the bipolar membrane with excellent performance can be prepared by modifying the middle interface layer, and the middle interface layer of the bipolar membrane is modified by metal phthalocyanine derivatives (Chinese patent invention, CN: 101899675B), photosensitizer or semiconductor photocatalytic material (Chinese patent invention, CN: 1011613483B) in the aspects of ageing 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 converted2Can be absorbed and utilized after being converted into a nitrogen-containing compound, and free N is absorbed and utilized through a photoelectrocatalysis technology2The conversion into ammonia is one of the hot spots of current research in the field of photoelectrocatalysis, but the N is relatively large (940 kJ. mol) due to the N bond energy-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
Aiming at the problems of low water dissociation efficiency, large water dissociation voltage and low nitrogen reduction efficiency of a bipolar membrane in the prior art, the invention provides the application of the bipolar membrane taking a zinc-metal organic framework material as a middle interface layer in photoelectrocatalysis nitrogen fixation.
The specific technical scheme is as follows:
the application of the bipolar membrane taking a zinc-metal organic framework material as a middle interface layer in photoelectrocatalysis nitrogen fixation is characterized in that: the application is characterized in that 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, 100-200 g/L ionic liquid electrolyte solution is prepared, N2 with the flow rate of 50-200 mL min < -1 > is adopted for bubbling in the cathode chamber, metal and oxide thereof are used as an anode, a semiconductor material and transition metal oxide are used as a cathode, 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 ammonia under the action of photoelectrocatalysis.
Additional features of the above scheme are as follows.
The ionic liquid electrolyte solution is an ionic liquid prepared by dissolving 1-butyl-3-methylimidazolium chloride salt or 1-butyl-3-methylimidazolium bromide salt in N, N-dimethylformamide.
The metal and its oxide is one of titanium-based oxide, Pt and Pd.
The semiconductor material and the transition metal oxide are one or a plurality of compounds of BiOCl, MoS2, WS2, Cu2O, TiO2 and WO 3.
The zinc-metal organic framework material is a catalyst which is synthesized in ionic liquid by an electrochemical method, has a spherical or flower-shaped morphology structure, is 0.5-5 mu m in diameter and has a molecular formula of Zn4O (BDC)3, wherein BDC = terephthalic acid group.
The preparation method of the zinc-metal organic framework material is carried out according to 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 0.5-5.5h, 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.
The bipolar membrane is prepared by the following steps:
preparation of film 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;
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 synthesized 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 synthesized 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 up to 300-900 mu mol L−1h-1And the water dissociation of the interface layer in the middle of the bipolar membrane provides continuous 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.
Description of the drawings:
FIG. 1 is a diagram of a zinc-metal organic framework material synthesized 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 and a diameter of about 2 μm;
FIG. 2 is a zinc-metal organic framework material synthesized 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
The following further describes the embodiments of the present invention.
Embodiment mode 1
Preparing 100 g/L1-butyl-3-methylimidazolium chloride ionic liquid electrolyte solution by taking a bipolar membrane containing a zinc-metal organic framework material in a middle interface layer as a diaphragm of a cathode chamber and an anode chamber, wherein 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 DC stabilized power supply and 350W is used as a light source, nitrogen is fixed and the nitrogen is also fixed under the action of photoelectrocatalysisOriginally ammonia.
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。
Embodiment mode 2
Preparing 150 g/L1-butyl-3-methylimidazolium bromide ionic liquid electrolyte solution by taking a bipolar membrane containing a zinc-metal organic framework material in a middle interface layer as a diaphragm of a cathode chamber and an anode chamber, wherein 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。
Embodiment 3
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, 200 g/L of 1-butyl-3-methylimidazolium chloride ionic liquid electrolyte solution is prepared, and a solvent is N, N-dimethylformamide. The cathode chamber is 100 mL min-1N of flow velocity2Bubbling with titanium-based oxide as anode, Cu2O is used as a cathode, a direct current stabilized power supply is used for providing an external voltage of 2.0V, a 350W xenon lamp is used as a light source, and nitrogen is fixed and reduced into ammonia under the action of photoelectrocatalysis.
Embodiment 4
The intermediate interface layer contains zinc-metal organic framework materialBipolar membranes of the materials are used as diaphragms of a cathode chamber and an anode chamber, 150 g/L of 1-butyl-3-methylimidazolium bromide ionic liquid electrolyte solution is prepared, and a solvent is N, N-dimethylformamide. The cathode chamber is 50 mL min-1N of flow velocity2Bubbling with Pd as anode, MoS2/WS2The composite material is used as a cathode, a direct-current stabilized power supply is used for providing an external voltage of 1.0V, a 350W xenon lamp is used as a light source, and nitrogen is fixed and reduced into ammonia under the action of photoelectrocatalysis.
In the embodiments 1 to 4 described above, the bipolar membrane with a zinc-metal organic framework material as a middle interface layer is applied to photoelectrocatalytic nitrogen fixation, and the preparation method of the bipolar membrane with a zinc-metal organic framework material as a middle interface layer is as follows:
preparation of film liquid
Polyvinyl alcohol or polypropylene imine is prepared into a concentration of 0.05-1.0 mol L-1Then adding zinc-metal organic framework material into the aqueous solution, and uniformly stirring to obtain the intermediate interface layer membrane liquid.
Preparing 1.0-5.0% carboxymethyl cellulose or cellulose acetate aqueous solution and 1.0-5.0% polyvinyl alcohol or polyvinylpyrrolidone aqueous solution, mixing, continuously stirring to form jelly, standing and defoaming for 60-100 minutes to obtain the cation exchange membrane solution.
Preparing 1.0-5.0% of aqueous solution of chitosan, polyimide or benzimidazole and 1.0-5.0% of aqueous solution of polyvinyl alcohol or polyvinylpyrrolidone, mixing, continuously stirring to form jelly, standing and defoaming for 60-100 minutes to obtain the anion exchange membrane solution.
Preparation of bipolar membrane
Preparing the bipolar membrane by adopting a layer-by-layer tape casting method. The preparation method comprises the steps of firstly, casting a cation exchange membrane solution on a clean glass plate with a frame, 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 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.
The bipolar membrane with the zinc-metal organic framework material as the middle interface layer is applied to photoelectrocatalysis nitrogen fixation, wherein the zinc-metal organic framework material is synthesized in ionic liquid by adopting an electrochemical method, the shape and structure of the zinc-metal organic framework material are spherical or flower-shaped, the diameter of the zinc-metal organic framework material is 0.5-5 mu m, and the molecular formula of the zinc-metal organic framework material is Zn4O(BDC)3Wherein BDC = terephthalic acid group, is prepared by the following steps:
(1) 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 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-2The reaction was carried out as follows.
(3) After reaction for 0.5-5.5h, 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.
Claims (5)
1. The application of the bipolar membrane taking a zinc-metal organic framework material as a middle interface layer in photoelectrocatalysis nitrogen fixation is characterized in that: the application is that a bipolar membrane with an intermediate interface layer containing a zinc-metal organic framework material is used as a diaphragm of a cathode chamber and an anode chamber to prepare 100-200 g/L ionic liquid electrolyte solution, and the cathode chamber is used for 50-200 mL min-1N of flow velocity2Bubbling is carried out, metal or metal oxide is used as an anode, semiconductor material or transition metal oxide is used as a cathode, a direct current stabilized voltage power 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 ammonia under the action of photoelectrocatalysis;
the preparation method of the zinc-metal organic framework material is carried out according to 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 the reaction is carried out for 0.5-5.5h, 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;
the preparation method of the bipolar membrane comprises the following steps:
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;
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. The use of the bipolar membrane with a zinc-metal organic framework material as an intermediate interface layer in photoelectrocatalytic nitrogen fixation according to claim 1, wherein: the ionic liquid electrolyte solution is an ionic liquid prepared by dissolving 1-butyl-3-methylimidazolium chloride salt or 1-butyl-3-methylimidazolium bromide salt in N, N-dimethylformamide.
3. The use of the bipolar membrane with a zinc-metal organic framework material as an intermediate interface layer in photoelectrocatalytic nitrogen fixation according to claim 1, wherein: the metal or metal oxide is one of titanium-based oxide, Pt and Pd.
4. The use of the bipolar membrane with a zinc-metal organic framework material as an intermediate interface layer in photoelectrocatalytic nitrogen fixation according to claim 1, wherein: the semiconductor material or transition metal oxide is BiOCl or MoS2、WS2、Cu2O、TiO2And WO3One or more of the above components are compounded.
5. The use of the bipolar membrane with a zinc-metal organic framework material as an intermediate interface layer in photoelectrocatalytic nitrogen fixation according to claim 1, wherein: the zinc-metal organic framework material is synthesized in ionic liquid by adopting an electrochemical method, has a spherical or flower-shaped morphology structure, a diameter of 0.5-5 mu m and a molecular formula of Zn4O(BDC)3Wherein BDC = terephthalic acid group.
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| CN110079816B (en) * | 2019-04-30 | 2020-06-19 | 太原师范学院 | Device and method for synthesizing ammonia by photoelectrocatalysis nitrogen fixation |
| CN110426440B (en) * | 2019-07-16 | 2022-02-01 | 曲阜师范大学 | Photoelectrochemistry biosensor and detection method of photoelectrochemistry biosensor for BLM |
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| CN102912374B (en) * | 2012-10-24 | 2015-04-22 | 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 |
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