Electrochemical active species diffusion membrane electrode and membrane electrode reactor formed by same
By designing the diffusion membrane electrode of electrochemical active species, adopting a structure without support electrolyte, the gas barrier layer and gas diffusion layer work together to achieve efficient transmission of active species, solving the problems of product pollution and cost increase caused by supporting electrolytes, enhancing reactor stability, and broadening application scenarios.
Patent Information
- Application Number
- CN202510448413.4
- Authority / Receiving Office
- CN · China
- Patent Type
- Applications(China)
- Current Assignee / Owner
- Filing Date
- 2025-04-10
- Publication Date
- 2025-08-15
AI Technical Summary
The use of supporting electrolytes in existing electrochemical reactors results in product contamination and increased cost, and palladium membrane electrode reactors have poor mechanical stability and high cost.
Design an electrochemically active species diffusion membrane electrode, including an electrochemical reaction layer, a gas diffusion layer and a chemical reaction layer, adopt a structure without support electrolytes, and achieve efficient transmission of active species through the synergistic effect of the gas barrier layer and the gas diffusion layer, and react in pure water.
Achieve electrochemical reactions without support electrolytes, reduce production costs, eliminate product pollution, enhance reactor stability and flexibility, compatible with reduction and oxidation reactions, and broaden application scenarios.
Smart Images
Figure CN120485805A_ABST
Abstract
Description
Technical Field
[0001] The invention belongs to the field of electrochemistry, and in particular relates to an electrochemically active species diffusion membrane electrode and a membrane electrode reactor constituted by the same. Background Art
[0002] Green, mild electrochemical technologies are crucial for replacing traditional high-temperature, high-pressure, and highly corrosive thermochemical syntheses. However, the need for supporting electrolytes limits their practical application. These electrolytes not only contaminate the reaction solution, increasing product separation costs and raw material costs, but also increase the cost of raw materials. Reducing or eliminating the use of supporting electrolytes in electrochemical reactions has become a new challenge in the field of electrochemistry.
[0003] To overcome the problem of supporting electrolytes, a common approach currently is to reduce their use, which significantly increases the reactor cell voltage and energy consumption. Another approach is to use palladium membrane electrode reactors, but these suffer from poor mechanical stability and are prohibitively expensive. Therefore, the development of new electrochemical reactors without supporting electrolytes is a pressing task for scientists. Summary of the Invention
[0004] The object of the present invention is to provide an electrochemically active species diffusion membrane electrode and a membrane electrode reactor composed thereof, which can carry out electrochemical reactions without supporting electrolyte.
[0005] In order to solve the above technical problems, the following technical solutions are adopted:
[0006] An electrochemically active species diffusion membrane electrode is characterized by comprising an electrochemical reaction layer, a gas diffusion layer and a chemical reaction layer, wherein the electrochemical reaction layer is connected to the gas diffusion layer, and the gas diffusion layer is connected to the chemical reaction layer; the electrochemical reaction layer generates active species, and the active species pass through the gas diffusion layer to reach the chemical reaction layer for reaction.
[0007] On the one hand, active species include reducing substances such as hydrogen and deuterium.
[0008] On the other hand, active species also include oxidizing substances such as chlorine and bromine.
[0009] Furthermore, the electrode also includes a gas barrier layer, which is connected to the electrochemical reaction layer.
[0010] Furthermore, the chemical reaction layer is composed of a material having catalytic hydrogenation, deuteration or halogenation activity, and is selected from one of platinum, ruthenium, palladium, nickel or iron. The reaction of the chemical reaction layer includes the process of the active species reacting with other reactants.
[0011] Furthermore, the electrochemical reaction layer is composed of a material having electrocatalytic activity in hydrogen evolution reaction, deuterium evolution reaction, or halogen evolution reaction; the material is selected from one of platinum, ruthenium, palladium, copper, iron, or titanium. The electrochemical reaction of the electrochemical reaction layer includes the process of electrolyzing and generating the active species from the electrolyte.
[0012] Furthermore, the gas diffusion layer is a porous, hydrophobic material, isolating the active species from contact with the reaction solutions on both sides of the membrane electrode, allowing the electrochemical reaction to occur in pure water without a supporting electrolyte. Specifically, one of the materials used is a polytetrafluoroethylene membrane, hydrophobic carbon paper, or hydrophobic carbon cloth.
[0013] Furthermore, the gas barrier layer is composed of a lyophilic porous material, and is selected from one of hydrophilic nano-carbon powder, hydrophilic silicon dioxide or hydrophilic aluminum oxide.
[0014] A reactor equipped with an electrochemically active species diffusion membrane electrode, characterized in that: the electrochemical reactor is used for reduction reaction and oxidation reaction, includes a chemical chamber and an electrochemical chamber, the chemical chamber and the electrochemical chamber are separated by the electrochemically active species diffusion membrane electrode, and the electrochemically active species diffusion membrane electrode can serve as an anode, a cathode, or both a cathode and an anode.
[0015] Furthermore, the electrochemical chamber can be a membrane-less electrochemical chamber or an ion exchange membrane electrochemical chamber.
[0016] Furthermore, the chemical chamber can be a single chemical chamber or a double chemical chamber. The single chemical chamber is constructed by one electrochemically active species diffusion membrane electrode, and the double chemical chamber is constructed by two electrochemically active species diffusion membrane electrodes.
[0017] The above technical solution has the following beneficial effects:
[0018] 1. Realize electrochemical reaction synthesis without supporting electrolyte: Overcoming the need to add supporting electrolyte in traditional reactors, reducing production costs and eliminating product contamination; the gas barrier layer and gas diffusion layer work synergistically to ensure the efficient transmission of active species in gas form.
[0019] 2. Enhanced reactor stability and flexibility: The reactor supports an electrochemical chamber with a diaphragm-free structure or an ion exchange membrane and a single chemical chamber, or a dual chemical chamber constructed by two electrochemically active species diffusion membrane electrodes, which is compatible with reduction and oxidation reactions and broadens application scenarios. BRIEF DESCRIPTION OF THE DRAWINGS
[0020] The present invention will be further described below in conjunction with the accompanying drawings:
[0021] Figure 1 Schematic diagram of the electrochemically active species diffusion membrane electrode of the present invention;
[0022] Figure 2Schematic diagram of the electrochemically active species diffusion membrane electrode reactor of the present invention;
[0023] Figure 3 Schematic diagram of the dual-chemical chamber electrochemically active species diffusion membrane electrode reactor of the present invention.
[0024] The reference numerals in the drawings are: power supply 1 , chemical chamber 2 , electrochemical chamber 3 , electrochemically active species diffusion membrane electrode 4 , ion exchange membrane 5 , electrode 6 . DETAILED DESCRIPTION
[0025] like Figure 1 The electrochemically active species diffusion membrane electrode of the present invention is manufactured by stacking and assembling a gas barrier layer, an electrochemical reaction layer, a gas diffusion layer and a chemical reaction layer in sequence.
[0026] like Figure 2 The electrochemically active species diffusion membrane electrode reactor of the present invention is manufactured by installing an electrochemically active species diffusion membrane electrode 4, a counter electrode 6, and an ion exchange membrane 5 into an electrolytic cell, and includes a chemical chamber 2 and two electrochemical chambers 3 separated by an ion exchange membrane 5.
[0027] like Figure 3 The dual-chemical chamber electrochemically active species diffusion membrane electrode reactor of the present invention is manufactured by installing two electrochemically active species diffusion membrane electrodes 4 and an ion exchange membrane 5 into an electrolytic cell. It includes two chemical chambers 2 and two electrochemical chambers 3 separated by an ion exchange membrane 5.
[0028] The present invention will be described in detail below in conjunction with specific embodiments:
[0029] Example 1
[0030] Preparation of an electrochemically active species diffusion membrane electrode. Using hydrophobic carbon paper as the gas diffusion layer, 20 mg of Pt / C catalyst was coated on the side of the gas diffusion layer facing the electrochemical chamber to form a Pt / C electrochemical reaction layer. Next, 20 mg of hydrophilic nanocarbon powder was coated on the electrochemical reaction layer to form a gas barrier layer. Finally, 20 mg of Pt / C catalyst was coated on the side of the gas diffusion layer facing the chemical chamber to form a chemical reaction layer, completing the preparation of the membrane electrode. The electrode area was 5 cm 2 .
[0031] Electrochemically active species diffusion membrane electrode reactor is assembled. The electrochemically active species diffusion membrane is used as the cathode, the platinum electrode is used as the anode, and the cation exchange membrane is used as the ion exchange membrane. The electrolytic cell has a cathode chemical chamber, a cathode electrochemical chamber, and an anode electrochemical chamber. The volume of each reaction chamber is 50 cm 3 .
[0032] Application of an electrochemically active species diffusion membrane electrode reactor in electrochemical reactions; electrochemical hydrogenation reaction. 30 mL of a 10 mM aqueous phenol solution was added to the cathode chamber, and 30 mL of a 0.5 M aqueous sulfuric acid solution was added to the cathode and anode chambers, respectively. A voltage of 2 V was applied. After 5 hours of reaction, the solution in the cathode chamber was converted into a cyclohexanol solution, with a reaction conversion rate exceeding 98% and a cyclohexanol yield exceeding 98%. No sulfate ions were detected in the chamber solutions.
[0033] Example 2
[0034] Preparation of an electrochemically active species diffusion membrane electrode. Using hydrophobic carbon paper as the gas diffusion layer, 20 mg of Pt / C catalyst was coated on the side of the gas diffusion layer facing the electrochemical chamber to form a Pt / C electrochemical reaction layer. Next, 20 mg of hydrophilic nanocarbon powder was coated on the electrochemical reaction layer to form a gas barrier layer. Finally, 20 mg of Pd / C catalyst was coated on the side of the gas diffusion layer facing the chemical chamber to form a chemical reaction layer, completing the preparation of the membrane electrode. The electrode area was 5 cm 2 .
[0035] Electrochemically active species diffusion membrane electrode reactor is assembled. The electrochemically active species diffusion membrane is used as the cathode, the platinum electrode is used as the anode, and the cation exchange membrane is used as the ion exchange membrane. The electrolytic cell has a cathode chemical chamber, a cathode electrochemical chamber, and an anode electrochemical chamber. The volume of each reaction chamber is 50 cm 3 .
[0036] Application of an electrochemically active species diffusion membrane electrode reactor in electrochemical reactions; electrochemical deuterium addition reaction. 30 mL of a 10 mM aqueous solution of 4-chloroaniline was added to the cathode chamber, and 30 mL of a 0.5 M aqueous solution of deuterium deuterated sulfate was added to the cathode chamber and the anode chamber, respectively. A voltage of 2 V was applied. After 6 hours of reaction, the solution in the cathode chamber was converted into an aqueous solution of 4-deuterated aniline, with a reaction conversion rate exceeding 98% and a 4-deuterated aniline yield exceeding 98%. No sulfate ions were detected in the solution in the chambers.
[0037] Example 3
[0038] Preparation of an electrochemically active species diffusion membrane electrode. Using hydrophobic carbon paper as the gas diffusion layer, 20 mg of RuO2 catalyst was coated on the side of the gas diffusion layer facing the electrochemical chamber to form a RuO2 electrochemical reaction layer. Next, 20 mg of hydrophilic nanocarbon powder was coated on the electrochemical reaction layer to form a gas barrier layer. Finally, 20 mg of PTFE was coated on the side of the gas diffusion layer facing the chemical chamber to form a chemical reaction layer, completing the membrane electrode preparation. The electrode area was 5 cm 2 .
[0039] Electrochemically active species diffusion membrane electrode reactor is assembled. The electrochemically active species diffusion membrane is used as the anode, the platinum electrode is used as the cathode, and the cation exchange membrane is used as the ion exchange membrane. The electrolytic cell has an anode chemical chamber, an anode electrochemical chamber, and a cathode electrochemical chamber. The volume of each reaction chamber is 50 cm 3 .
[0040] Application of electrochemically active species diffusion membrane electrode reactors in electrochemical reactions; chlorination reaction in electrochemical halogenation reactions. 30 mL of 10 mM phenoxyacetic acid aqueous solution was added to the anodic electrochemical chamber, and 30 mL of 3 M sodium chloride aqueous solution was added to the anodic electrochemical chamber and the cathodic chamber, respectively. A voltage of 2 V was applied. After 2 hours of reaction, the solution in the anodic electrochemical chamber was converted into 4-chlorophenoxyacetic acid aqueous solution, with a reaction conversion rate exceeding 99% and a 4-chlorophenoxyacetic acid yield exceeding 90%. No sodium ions were detected in the electrochemical chamber solution.
[0041] Example 4
[0042] Preparation of an electrochemically active species diffusion membrane electrode. Using hydrophobic carbon paper as the gas diffusion layer, 20 mg of RuO2 catalyst was coated on the side of the gas diffusion layer facing the electrochemical chamber to form a RuO2 electrochemical reaction layer. Next, 20 mg of hydrophilic nanocarbon powder was coated on the electrochemical reaction layer to form a gas barrier layer. Finally, 20 mg of PTFE was coated on the side of the gas diffusion layer facing the chemical chamber to form a chemical reaction layer, completing the membrane electrode preparation. The electrode area was 5 cm 2 .
[0043] Electrochemically active species diffusion membrane electrode reactor is assembled. The electrochemically active species diffusion membrane is used as the anode, the platinum electrode is used as the cathode, and the cation exchange membrane is used as the ion exchange membrane. The electrolytic cell has an anode chemical chamber, an anode electrochemical chamber, and a cathode electrochemical chamber. The volume of each reaction chamber is 50 cm 3 .
[0044] Application of an electrochemically active species diffusion membrane electrode reactor in electrochemical reactions; bromination reaction in electrochemical halogenation reactions. 30 mL of a 10 mM phenoxyacetic acid aqueous solution was added to the anodic electrochemical chamber, and 30 mL of an aqueous solution consisting of 3 M sodium bromide and 0.5 M sulfuric acid was added to the anodic electrochemical chamber and the cathodic chamber, respectively. A voltage of 2 V was applied. After 2 hours of reaction, the solution in the anodic electrochemical chamber was converted into a 4-bromophenoxyacetic acid aqueous solution, with a reaction conversion rate exceeding 99% and a 4-bromophenoxyacetic acid yield exceeding 95%. No sodium ions were detected in the electrochemical chamber solution.
[0045] Example 5
[0046] Preparation of two electrochemically active species diffusion membrane electrodes. Using hydrophobic carbon paper as the gas diffusion layer, 20 mg of Pt / C catalyst was coated on the side of the gas diffusion layer facing the electrochemical chamber to obtain a Pt / C electrochemical reaction layer. Then, 20 mg of hydrophilic nanocarbon powder was coated on the electrochemical reaction layer to obtain a gas barrier layer. Finally, 20 mg of Pt / C catalyst was coated on the side of the gas diffusion layer facing the chemical chamber to obtain a chemical reaction layer, completing the preparation of membrane electrode A. The electrode area was 5 cm 2 . Using hydrophobic carbon paper as the gas diffusion layer, 20 mg of RuO2 catalyst was coated on the side of the gas diffusion layer facing the electrochemical chamber to obtain a RuO2 electrochemical reaction layer. Then, 20 mg of hydrophilic nanocarbon powder was coated on the electrochemical reaction layer to obtain a gas barrier layer. Finally, 20 mg of Pt / C catalyst was coated on the side of the gas diffusion layer facing the chemical chamber to obtain a chemical reaction layer, completing the preparation of membrane electrode B with an electrode area of 5 cm 2 .
[0047] Electrochemically active species diffusion membrane electrode reactor is assembled. Electrochemically active species diffusion membrane A is used as cathode, electrochemically active species diffusion membrane B is used as anode, and cation exchange membrane is used as ion exchange membrane and installed in the electrolytic cell. The electrolytic cell has a cathode chemical chamber, a cathode electrochemical chamber, an anode electrochemical chamber, and an anode chemical chamber. The volume of each reaction chamber is 50 cm 3 .
[0048] Application of an electrochemically active species diffusion membrane electrode reactor in electrochemical reactions; paired electrochemical hydrogenation and halogenation reactions. 30 mL of a 10 mM aqueous phenol solution was added to the cathode chemical chamber, and 30 mL of a 0.5 M aqueous sulfuric acid solution was added to the cathode electrochemical chamber. 30 mL of a 30 mM aqueous phenoxyacetic acid solution was added to the anode chemical chamber, and 30 mL of a 3 M aqueous sodium chloride solution was added to the anode electrochemical chamber. After a 5-hour reaction with a 40 mA current, the solution in the cathode chemical chamber was converted into a cyclohexanol solution with a reaction conversion rate exceeding 98% and a cyclohexanol yield exceeding 98%. The solution in the anode chemical chamber was converted into a 4-chlorophenoxyacetic acid solution with a reaction conversion rate exceeding 99% and a 4-chlorophenoxyacetic acid yield exceeding 85%. No sodium ions were detected in the chemical chamber solutions.
[0049] Comparative Example 1
[0050] Preparation of an electrochemically active species diffusion membrane electrode. Using hydrophobic carbon paper as the gas diffusion layer, 20 mg of RuO2 catalyst was coated on the side of the gas diffusion layer facing the electrochemical chamber to create the RuO2 electrochemical reaction layer. Next, 20 mg of Pt / C was coated on the side of the gas diffusion layer facing the chemical chamber to create the chemical reaction layer, completing the membrane preparation.
[0051] Electrochemically active species diffusion membrane electrode reactor is assembled. The electrochemically active species diffusion membrane is used as the anode, the platinum electrode is used as the cathode, and the cation exchange membrane is used as the ion exchange membrane. The electrolytic cell has a cathode chemical chamber, a cathode electrochemical chamber, and an anode electrochemical chamber. The volume of each reaction chamber is 50 cm 3 .
[0052] 30 mL of a 10 mM aqueous phenol solution was added to the cathode electrochemical chamber, and 30 mL of a 0.5 M aqueous sulfuric acid solution was added to the cathode electrochemical chamber and the anode electrochemical chamber, respectively. After a 2 V voltage was applied and the reaction lasted for 5 hours, the solution in the cathode electrochemical chamber was converted into a cyclohexanol solution, with a conversion rate of 67%. No sulfate ions were detected in the electrochemical chamber solution.
[0053] Comparative Example 2
[0054] Preparation of an electrochemically active species diffusion membrane electrode. Using hydrophilic carbon paper as the gas diffusion layer, 20 mg of Pt / C catalyst was coated on the side of the gas diffusion layer facing the electrochemical chamber to form the Pt / C electrochemical reaction layer. Next, 20 mg of hydrophilic nanocarbon powder was coated on the electrochemical reaction layer to form the gas barrier layer. Finally, 20 mg of Pt / C catalyst was coated on the side of the gas diffusion layer facing the chemical chamber to form the chemical reaction layer, completing the membrane preparation.
[0055] Electrochemically active species diffusion membrane electrode reactor is assembled. The electrochemically active species diffusion membrane is used as the cathode, the platinum electrode is used as the anode, and the cation exchange membrane is used as the ion exchange membrane. The electrolytic cell has a cathode chemical chamber, a cathode electrochemical chamber, and an anode electrochemical chamber. The volume of each reaction chamber is 50 cm 3 .
[0056] Application of an electrochemically active species diffusion membrane electrode reactor in electrochemical reactions; electrochemical hydrogenation reaction. 30 mL of a 10 mM aqueous phenol solution was added to the cathode electrochemical chamber, and 30 mL of a 0.5 M aqueous sulfuric acid solution was added to the cathode and anodic electrochemical chambers, respectively. A voltage of 2 V was applied. After 5 hours of reaction, the solution in the cathode electrochemical chamber was converted into a cyclohexanol aqueous solution. The reaction conversion rate was less than 62%, and the cyclohexanol yield was less than 40%. The solution in the chemical chamber was contaminated with sulfuric acid, and a large amount of sulfate ions was detected.
[0057] The above are only specific embodiments of the present invention, but the technical features of the present invention are not limited thereto. Any simple changes, equivalent substitutions, or modifications based on the present invention to solve substantially the same technical problems and achieve substantially the same technical effects are included within the scope of protection of the present invention.
Claims
1. An electrochemically active species diffusion membrane electrode, characterized in that: It includes an electrochemical reaction layer, a gas diffusion layer and a chemical reaction layer. The electrochemical reaction layer is connected to the gas diffusion layer, and the gas diffusion layer is connected to the chemical reaction layer. The electrochemical reaction layer generates active species, and the active species pass through the gas diffusion layer to reach the chemical reaction layer for reaction.
2. The electrochemically active species diffusion membrane electrode according to claim 1, characterized in that: The electrode further comprises a gas barrier layer, wherein the gas barrier layer is connected to the electrochemical reaction layer.
3. The electrochemically active species diffusion membrane electrode according to claim 1, characterized in that: The chemical reaction layer is made of a material having catalytic hydrogenation, deuteration or halogenation reaction activity; one of platinum, ruthenium, palladium, nickel or iron is selected.
4. The electrochemically active species diffusion membrane electrode according to claim 1, characterized in that: The electrochemical reaction layer is composed of a material having electrocatalytic activity for hydrogen evolution reaction, deuterium evolution reaction or halogen evolution reaction; and is selected from one of platinum, ruthenium, palladium, copper, iron or titanium.
5. The electrochemically active species diffusion membrane electrode according to claim 1, characterized in that: The gas diffusion layer is a porous hydrophobic material, and is selected from one of polytetrafluoroethylene membrane, hydrophobic carbon paper or hydrophobic carbon cloth.
6. The electrochemically active species diffusion membrane electrode according to claim 1, characterized in that: The gas barrier layer is composed of a hydrophilic porous material, and is selected from one of hydrophilic nano carbon powder, hydrophilic silicon dioxide or hydrophilic aluminum oxide.
7. An electrochemically active species diffusion membrane electrode reactor, characterized in that: The invention comprises a chemical chamber and an electrochemical chamber, wherein the chemical chamber and the electrochemical chamber are separated by an electrochemically active species diffusion membrane electrode. The electrochemical reactor is used for reduction reaction and oxidation reaction.
8. The electrochemically active species diffusion membrane electrode reactor according to claim 7, characterized in that: The electrochemical chamber may be a membrane-less electrochemical chamber or an ion exchange membrane electrochemical chamber.
9. The electrochemically active species diffusion membrane electrode reactor according to claim 7, characterized in that: The chemical chamber may be a single chemical chamber or a double chemical chamber. The single chemical chamber is constructed by one electrochemically active species diffusion membrane electrode, and the double chemical chamber is constructed by two electrochemically active species diffusion membrane electrodes.