A method for electrochemical synthesis reaction using inorganic solid electrolyte as diaphragm

Abstract

The present invention provides a method for conducting an electrochemical synthesis reaction using an inorganic solid electrolyte as a diaphragm, including the preparation of the inorganic solid electrolyte and the method for conducting the electrochemical synthesis reaction using the inorganic solid electrolyte as a diaphragm. The inorganic solid electrolyte is one or more of a garnet-type electrolyte, a fluorite-type oxide electrolyte, a perovskite-structured oxide electrolyte, and a LAMOX-based electrolyte, forming a layered or uniformly distributed structure, a controllable multi-microporous structure, and resistance to strong acids, strong bases, and various organic solvents. It can block the penetration of reactive molecules, enabling efficient and highly selective oxidation and reduction reactions to occur simultaneously in the anode and cathode chambers. The present invention has a reasonable design, convenient operation, and low cost, and is generally applicable to important synthesis reactions such as water electrolysis, electrochemical oxidation, hydrogenation, halogenation, amination, and coupling.

Description

Technical Field

[0001] The present invention relates to an inorganic solid electrolyte and a method for performing an electrochemical synthesis reaction using the inorganic solid electrolyte as a diaphragm. The method comprises the preparation of the inorganic solid electrolyte and a method for performing an electrochemical synthesis reaction using the inorganic solid electrolyte as a diaphragm. The method belongs to the fields of material synthesis, electrochemical energy conversion and electrosynthetic chemistry. Background Art

[0002] Electrochemistry is a clean and sustainable synthesis technology, central to achieving large-scale green hydrogen production, precise synthesis of high-value-added fine chemicals, efficient carbon dioxide utilization, and low-energy ammonia synthesis (Science 2020, 368,1181-1182; JACS Au 2022, 2, 5, 1054-1070; ACS Catal. 2024, 14, 8, 6045-6061; Acc. Chem. Res. 2020, 53, 3, 545-546). During the electrochemical process, reduction and oxidation reactions occur in the cathode and anode compartments, respectively. The electrolyte membrane, which conducts electricity through ion transport, separates the two compartments, isolating the diffusion and migration of reduction and oxidation products between them. It is an essential component for ensuring the safe, stable, and efficient operation of electrochemical systems.

[0003] Taking water electrolysis as an example, the mainstream technologies for hydrogen production include alkaline water electrolysis (AWE), anion exchange membrane electrolysis (AEM), and proton exchange membrane electrolysis (PEM) (Energy Environ. Sci. 2023, 16, 1384-1430). AWE technology is the most widely used method due to its maturity and affordability. However, in practical engineering applications, AWE faces challenges such as low current density, slow dynamic response, membrane cross-over, and equipment corrosion. To overcome these issues, researchers developed AEM technology (Chem. Rev. 2024, 124, 10, 6393-6443). AEM technology uses a low-cost anion exchange membrane as the diaphragm and pure water or a weak alkaline solution as the electrolyte, which reduces equipment corrosion. It exhibits excellent airtightness, stability, and low electrical resistivity. However, its limitations lie in its low ionic conductivity and insufficient high-temperature stability. PEM technology uses proton exchange membrane as a separator and is known for its high current density and fast responsiveness, but its cost is as high as 3,000 yuan / kilowatt, and voltage fluctuations during operation can lead to reduced electrolysis efficiency (Curr. Opin. Green Sustain. 2024,47: 100932).

[0004] Electrolyte membranes also play a key role in the electrochemical synthesis of fine chemicals. Most reported electrochemical synthesis reactions conducted at room temperature and in liquid phase use membranes with selective ion permeability, such as proton exchange membranes and bipolar membranes (Science 2020, 368, 1228–1233; Nat. Commun. 2022, 13, 3125; Adv. Funct. Mater. 2019, 29, 1904780). However, existing membranes are not tolerant to organic solvents and solutions containing certain specific ions (such as halides). Prolonged contact with these solvents can cause the membrane to dissolve, limiting the types of organic synthesis reactions that can be performed. Damage to the membrane can also lead to direct contact between the polar regions, causing solution exchange and complicating separation and purification.

[0005] The performance of the diaphragm is crucial to the efficiency and safety of the system. Under conditions of high voltage, high current, and strong acid and alkali solutions, diaphragm damage can reduce its permselectivity. In severe cases, this can lead to direct contact between hydrogen and oxygen, increasing the risk of explosion. Existing diaphragms are expensive and have a short service life, making electrolysis equipment cost-effective and requiring frequent disassembly and inspection, limiting their large-scale application. Summary of the Invention

[0006] The present invention provides a method for conducting an electrochemical synthesis reaction using an inorganic solid electrolyte as a separator. The method includes a method for preparing the inorganic solid electrolyte and a method for conducting the electrochemical synthesis reaction using the inorganic solid electrolyte as a separator. The method is suitable for high voltage, high current, organic solution, and normal temperature and pressure conditions. It has the advantages of high Faradaic efficiency, good mass transfer performance, flexible and simple operation, high yield, and a wide range of applications.

[0007] The present invention adopts the following technical solutions.

[0008] The invention discloses an inorganic solid electrolyte diaphragm for electrochemical synthesis reaction.

[0009] The present invention discloses a preparation method of the above-mentioned inorganic solid electrolyte membrane, which includes a sol-gel method, a gel casting method, an electrostatic spinning method, a spray drying method, a hot pressing method, a cold pressing method, a casting method, a chemical vapor deposition method or a physical vapor deposition method.

[0010] The invention discloses a method for performing electrochemical synthesis reaction by using an inorganic solid electrolyte as a diaphragm, wherein the inorganic solid electrolyte diaphragm is used to isolate a cathode chamber and an anode chamber.

[0011] In the present invention, in the electrochemical synthesis reaction, the cathode chamber and the anode chamber respectively undergo a reduction reaction and an oxidation reaction. Preferably, the electrochemical synthesis reaction includes hydrogen production reaction, ammonia synthesis reaction, and organic synthesis reactions such as oxidation reaction, hydrogenation reaction, halogenation reaction, amination reaction, and coupling reaction.

[0012] In the present invention, the inorganic solid electrolyte is one or more of a garnet-type electrolyte, a fluorite-type oxide electrolyte, a perovskite-structured oxide electrolyte, and a LAMOX-based electrolyte.

[0013] The present invention discloses a device for electrochemical synthesis using the above-mentioned inorganic solid electrolyte as a diaphragm, comprising an electrolytic cell and the above-mentioned inorganic solid electrolyte diaphragm. The diaphragm divides the electrolytic cell into independent anode and cathode chambers, which can be used for oxidation and reduction reactions respectively.

[0014] The present invention discloses a membrane electrode assembly for electrochemical synthesis reaction, comprising an inorganic solid electrolyte diaphragm and electrodes on both sides of the inorganic solid electrolyte diaphragm. Furthermore, a catalyst layer may or may not be provided on the outer side of the electrode.

[0015] The present invention discloses the application of the above-mentioned inorganic solid electrolyte membrane, device or membrane electrode assembly for electrochemical synthesis reaction in electrochemical synthesis reaction; wherein, the electrochemical synthesis reaction includes organic synthesis reaction, water electrolysis reaction, and ammonia synthesis reaction; preferably, the organic synthesis reaction includes oxidation reaction, hydrogenation reaction, halogenation reaction, amination reaction or coupling reaction.

[0016] Preferably, electrodes and catalyst coatings can be prepared on both sides of the outer surface of the inorganic solid electrolyte membrane, that is, a membrane electrode assembly. For example, the anode side and the cathode side of the inorganic solid electrolyte membrane are both coated with electrode materials and catalyst materials.

[0017] The present invention discloses a method for conducting an electrochemical synthesis reaction using the above-mentioned inorganic solid electrolyte membrane as a separator, comprising the following steps: assembling an electrolytic cell and a membrane electrode assembly, connecting a DC power supply, subjecting the raw materials to an electrochemical synthesis reaction, and collecting the product. Specifically, the electrolytic cell and the membrane electrode assembly are assembled, connected to a DC power supply, subjecting the raw materials to an electrochemical synthesis reaction, and collecting the product via a collection bottle.

[0018] Preferably, the membrane electrode assembly is prepared based on an inorganic solid electrolyte membrane; for example, the anode side and the cathode side of the inorganic solid electrolyte membrane are coated with electrode materials and catalyst materials, and the surface of the electrode or catalyst is flat and smooth.

[0019] In the present invention, the preparation methods of the inorganic solid electrolyte membrane specifically include: sol-gel method, gel casting method, electrospinning method, spray drying method, hot pressing method, cold pressing method, casting method, chemical vapor deposition method, and physical vapor deposition method.

[0020] In the present invention, the sol-gel method comprises the following steps: aging a sol containing a metal alkoxide, an acidic catalyst and a solvent to obtain a gel, and then drying, pre-calcining and sintering to obtain an inorganic solid electrolyte membrane.

[0021] In a specific embodiment of the present invention, the sol-gel method for preparing an inorganic solid electrolyte membrane includes: selecting one or more metal alkoxides as precursors and dissolving them in an alcohol solvent to form a uniform solution; then adding an acidic catalyst to the solution to promote the hydrolysis reaction of the metal alkoxide to form a primary sol; then aging the primary sol at ambient temperature to promote the transformation of the sol to a gel; then drying the formed wet gel to remove the residual solvent therein; then pre-calcining the dried gel to remove organic residues, and finally sintering the pre-calcined gel to form an oxide ceramic membrane.

[0022] Preferably, the metal alkoxide includes one or more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl silicate, tetramethyl silicate, trimethyl aluminate, triethyl aluminate, tetrapropyl zirconate, and tetraethyl niobate, and its concentration in the solution is 0.1 to 1 M. Here, the concentration of the metal alkoxide is the sum of the concentrations of all metal alkoxides.

[0023] Preferably, the alcohol solvent is a C1-C4 alcohol reagent, such as ethanol and isopropanol.

[0024] Preferably, the acidic catalyst includes one or more of HF / Al2O3, BF3 / Al2O3, CdS, and ZnS, with a pH value of 1.0 to 4.0; the molar ratio of the acidic catalyst to the metal alkoxide is 0.1 to 5, where the molar weight of the metal alkoxide is the sum of the molar weights of all metal alkoxides.

[0025] Preferably, the hydrolysis reaction temperature is 50-100° C., and the time is 1-12 h.

[0026] Preferably, the drying temperature is 40-100° C. and the drying time is 1-12 h.

[0027] Preferably, the pre-firing temperature is 300-800° C. and the pre-firing time is 1-4 h.

[0028] Preferably, the sintering temperature is 800-1400° C., and the sintering time is 2-8 h.

[0029] In the present invention, the gel casting method includes the following steps: injecting a sol containing a metal alkoxide, a stabilizer, a thickener and a solvent into a mold, letting it stand and age to form a gel; and then drying, pre-firing and sintering to obtain an inorganic solid electrolyte membrane.

[0030] In a specific embodiment of the present invention, the preparation of an inorganic solid electrolyte membrane by a gel injection molding method includes: selecting one or more metal alkoxides as precursors and dissolving them in an alcohol solvent, and adding a stabilizer to prevent aggregation and sedimentation of sol particles, then adding a thickener to the sol and mixing it evenly by stirring, and then injecting it into a mold, standing to form a wet gel, and then solidifying to form a dry gel, followed by aging treatment to improve the structural stability of the gel; then vacuum drying to remove the solvent and moisture in the dry gel, and then pre-calcining the dried gel and finally sintering it to form an oxide ceramic membrane.

[0031] Preferably, the metal alkoxide includes one or more of tetrabutyl titanate, tetraisopropyl titanate, tetraethyl silicate, tetramethyl silicate, trimethyl aluminate, triethyl aluminate, tetrapropyl zirconate, and tetraethyl niobate, and its concentration in the alcohol solvent is 0.1 to 1 M. Here, the concentration of the metal alkoxide is the sum of the concentrations of all metal alkoxides.

[0032] Preferably, the alcohol solvent is a C1-C4 alcohol reagent, such as ethanol and isopropanol.

[0033] Preferably, the stabilizer is a surfactant, such as one or more of sodium dodecyl sulfate, sodium dodecylbenzenesulfonate, ammonium dodecyl sulfate, and dodecyltrimethylammonium bromide, and the molar ratio of the stabilizer to the metal alkoxide is 0.1 to 5, where the molar amount of the metal alkoxide is the sum of the molar amounts of all metal alkoxides.

[0034] Preferably, the thickener is one or more of polyvinyl alcohol and carboxymethyl cellulose, and the molar ratio of the thickener to the metal alkoxide is 0.01 to 1, where the molar weight of the metal alkoxide is the sum of the molar weights of all metal alkoxides.

[0035] Preferably, the curing time is 2 to 12 hours.

[0036] Preferably, the aging treatment is performed at a temperature of 40 to 60° C., a humidity of 60 to 90%, and a time of 1 to 12 hours.

[0037] Preferably, the vacuum drying temperature is 60-80° C., and the time is 1-12 h.

[0038] Preferably, the pre-firing temperature is 300-800° C. and the pre-firing time is 1-4 h.

[0039] Preferably, the sintering temperature is 800-1400° C., and the sintering time is 2-8 h.

[0040] In the present invention, the electrospinning method includes the following steps: using a mixture containing an inorganic precursor, a polymer and a solvent as a spinning solution, electrospinning is performed to obtain a nanofiber membrane; the nanofiber membrane is placed at room temperature to remove residual solvent, and then pre-calcined and finally sintered to form an inorganic solid electrolyte membrane.

[0041] In a specific embodiment of the present invention, the electrospinning method for preparing an inorganic solid electrolyte membrane includes: selecting an inorganic precursor, a polymer and a solvent to mix to form a uniform solution suitable for electrospinning, which is then loaded into a syringe with a metal needle and connected to a high-voltage power supply with adjustable voltage, and the receiver is grounded and kept at an appropriate distance from the syringe needle; then a voltage is applied to form a stable Taylor cone at the needle, the solvent evaporates as the jet flies toward the receiver, the polymer gradually solidifies to form fibers, and is randomly deposited on the receiver to form a nanofiber membrane with a certain thickness; the collected nanofiber membrane is then placed at room temperature to remove residual solvent, and then pre-sintered and finally sintered to form an oxide ceramic membrane.

[0042] Preferably, the inorganic precursor includes one or more of titanium tetrachloride, cesium lead chloride, and cesium lead bromide, and the concentration thereof in the solution is 8 to 12 wt %. Here, the concentration of the inorganic precursor is the sum of the concentrations of all inorganic precursors.

[0043] Preferably, the polymer includes one or more of polyacrylonitrile, polylactic acid, and polycaprolactone, and the concentration of the polymer in the solution is 8 to 12 wt %. Here, the concentration of the polymer is the sum of the concentrations of all polymers.

[0044] Preferably, the solvent is one or more of dimethylformamide and dimethyl sulfoxide.

[0045] Preferably, the diameter of the metal needle is 0.5-0.7 mm.

[0046] Preferably, the appropriate distance between the receiver and the syringe needle is 10 to 30 cm.

[0047] Preferably, the applied voltage is 10-50 kV.

[0048] Preferably, the time of standing at room temperature is 12 to 48 hours.

[0049] Preferably, the pre-firing temperature is 300-800° C. and the pre-firing time is 1-4 h.

[0050] Preferably, the sintering temperature is 800-1400° C., and the sintering time is 2-8 h.

[0051] In the present invention, the spray drying method includes the following steps: spray drying a solution containing an inorganic precursor and a solvent to obtain a powder, pressing the powder into a film, pre-sintering the film, and finally sintering the film to form an inorganic solid electrolyte membrane.

[0052] In a specific embodiment of the present invention, the spray drying method for preparing an inorganic solid electrolyte membrane includes: selecting an inorganic precursor to dissolve in a solvent to form a uniform solution, then loading it into the feeding system of a spray dryer, setting the temperature and pressure parameters required for drying, and atomizing the solution into fine droplets through a nozzle with the assistance of a high-pressure pump or air flow. The solvent evaporates rapidly when passing through a drying tower, and the generated powder is collected by a cyclone separator, and the consistency of the powder particle size is ensured by screening. The powder is pressed into a thin film, pre-fired, and finally sintered to form an oxide ceramic membrane.

[0053] Preferably, the inorganic precursor includes one or more of carbon metatungstate and lithium dimanganese tetraoxide, and the concentration of the inorganic precursor in the solution is 0.1 to 1 M. Here, the concentration of the inorganic precursor is the sum of the concentrations of all inorganic precursors.

[0054] Preferably, the solvent is one or more of deionized water, ethanol, and isopropanol.

[0055] Preferably, during the spray drying process, the temperature of the hot air is controlled at 200-400° C., and the atomization pressure is controlled at 1-10 bar.

[0056] Preferably, the powder particles collected by the cyclone separator have a particle size of 1 to 10 μm.

[0057] Preferably, the pre-firing temperature is 300-800° C. and the pre-firing time is 1-4 h.

[0058] Preferably, the sintering temperature is 800-1400° C., and the sintering time is 2-8 h.

[0059] In the present invention, the hot pressing method includes the following steps: hot pressing the powdered raw material to form an inorganic solid electrolyte membrane.

[0060] In a specific embodiment of the present invention, the hot pressing method for preparing an inorganic solid electrolyte membrane includes: loading powder raw materials into a mold and filling it evenly; then placing the mold filled with powder into a hot pressing device, and setting the required hot pressing temperature, pressure and holding time.

[0061] Preferably, the powder raw material includes one or more of lithium zirconium oxide, lithium aluminum titanium phosphate, lithium germanium phosphorus sulfur, and lithium tantalum oxide.

[0062] Preferably, the hot pressing temperature is 1000-1500° C., the pressure is 10-50 MPa, and the holding time is 1-4 h.

[0063] In the present invention, the cold pressing method comprises the following steps: cold pressing the powder raw material, and then pre-firing and sintering to form an inorganic solid electrolyte membrane.

[0064] In one specific embodiment of the present invention, the cold pressing method for preparing an inorganic solid electrolyte membrane includes: loading powder raw materials into a mold and filling it evenly, then fixing the mold filled with powder on a cold press, setting the required pressing pressure, and then pre-sintering the resulting film and finally sintering it to form an oxide ceramic membrane.

[0065] Preferably, the powder raw material includes one or more of lithium zirconium oxide, yttrium-stabilized zirconium oxide, lithium aluminum titanium phosphate, lithium germanium phosphorus sulfur, and lithium tantalum oxide.

[0066] Preferably, the cold pressing pressure is 10-50 MPa, and the holding time is 0-2 h.

[0067] Preferably, the pre-firing temperature is 300-800° C. and the pre-firing time is 1-4 h.

[0068] Preferably, the sintering temperature is 800-1400° C., and the sintering time is 2-8 h.

[0069] In the present invention, the tape casting method includes the following steps: casting a slurry containing powder raw materials, a binder and a solvent into a film, and then drying, pre-firing and sintering to form an inorganic solid electrolyte membrane.

[0070] In a specific embodiment of the present invention, the preparation of an inorganic solid electrolyte membrane by a casting method includes: selecting a powder raw material, mixing it with a solvent and a binder to form a slurry, pouring the slurry into the hopper of a casting machine, adjusting the distance between the scraper and the base belt, setting the temperature and wind speed of the drying box, and the slurry flows through the scraper under the action of gravity or pressure, and is evenly spread on the base belt to form a thin film; then drying the formed film to remove the residual solvent therein, and then pre-firing the dried film to remove organic residues, and finally sintering the pre-firing gel to form an oxide ceramic membrane.

[0071] Preferably, the powder raw material includes one or more of lithium zirconium oxide, yttrium-stabilized zirconium oxide, and lithium tantalum oxide.

[0072] Preferably, the solvent includes water and an organic solvent, such as methyl ethyl ketone, toluene, xylene, ethanol, trichloroethylene, and the like.

[0073] Preferably, the binder includes polyvinyl alcohol (PVA), cellulose (MC), polyacrylic acid (PAA), etc.

[0074] Preferably, in the slurry, the concentration of the powder raw materials is 40 to 80 wt %, where the concentration of the powder raw materials is the sum of the concentrations of all the powder raw materials.

[0075] Preferably, the distance between the scraper and the base belt is adjustable to control the thickness of the film.

[0076] Preferably, the drying temperature is 40 to 150° C., the wind speed is conventional, and the drying time is 1 to 12 hours.

[0077] Preferably, the pre-firing temperature is 300-800° C. and the pre-firing time is 1-4 h.

[0078] Preferably, the sintering temperature is 800-1400° C., and the sintering time is 2-8 h.

[0079] In the present invention, the chemical vapor deposition method includes the following steps: depositing a precursor gas and a reaction gas on the surface of a substrate, and causing a chemical reaction to form an inorganic solid electrolyte membrane.

[0080] In a specific embodiment of the present invention, the chemical vapor deposition method for preparing an inorganic solid electrolyte membrane includes: selecting a substrate material for cleaning and decontamination treatment, selecting a precursor gas and a reaction gas; heating a reaction chamber to a specific temperature, and precisely controlling the flow rate of the reaction gas to adjust the growth rate and composition of the film; the precursor gas and the reaction gas chemically react on the surface of the substrate to generate a solid substance and deposit it to form a thin film, and controlling the pressure in the reaction chamber to optimize the film quality; and controlling the growth time according to the desired film thickness.

[0081] Preferably, the substrate comprises a silicon wafer, a metal sheet or other inert materials.

[0082] Preferably, the precursor gas includes trimethylaluminum, zirconium tetrachloride, tetraethoxysilane, etc.

[0083] Preferably, the reaction gas includes water vapor, oxygen, etc.

[0084] Preferably, the temperature of the reaction chamber is 400-1200°C.

[0085] Preferably, the flow rate of the gas is 1 to 1000 sccm.

[0086] Preferably, the pressure in the reaction chamber is controlled at 0.1 to 10 atm.

[0087] In the present invention, the physical vapor deposition method includes the following steps: depositing a target material on the surface of a substrate to form an inorganic solid electrolyte membrane.

[0088] In a specific embodiment of the present invention, the physical vapor deposition method for preparing an inorganic solid electrolyte membrane includes: selecting a substrate material for cleaning and decontamination treatment, selecting a target material, and using a turbomolecular pump and a dry pump combination to evacuate the material; using a DC sputtering source, applying a DC bias to the target material, and introducing a working gas into the sputtering chamber; setting appropriate sputtering parameters and substrate temperature, and allowing the sputtered atoms to condense on the substrate surface to form a uniform oxide film, which is finally annealed.

[0089] Preferably, the substrate material comprises a silicon wafer, a metal sheet or other inert materials.

[0090] Preferably, the target material includes aluminum oxide, silicon carbide, titanium nitride, etc.

[0091] Preferably, the vacuum environment of the reaction chamber is 10-6 Pa.

[0092] Preferably, the DC bias voltage is 200-800 V.

[0093] Preferably, the working gas is argon, nitrogen, etc., and the gas flow rate is 10 to 50 sccm.

[0094] Preferably, the sputtering power is set to 1-20 W / cm 2 , the sputtering time is 1 to 6 h.

[0095] Preferably, the substrate temperature is set to 80-150°C.

[0096] Preferably, the pressure in the reaction chamber is controlled at 0.1 to 10 atm.

[0097] Preferably, the annealing temperature is 600-1400° C., and the time is 2-8 h.

[0098] As a preferred technical solution, all the above preparation methods can select appropriate porogens when feeding according to the pore size and porosity required for the diaphragm, and can be finally removed by ultrasonic cleaning after sintering.

[0099] Preferably, the pore-forming agent includes sodium carbonate, calcium carbonate, sodium chloride, starch, etc., and the mass ratio of the pore-forming agent to the inorganic material is 1: (2-20), where the mass of the inorganic material is the sum of the masses of all inorganic materials.

[0100] The present invention discloses for the first time a method for conducting electrochemical synthesis reactions using an inorganic solid electrolyte as a diaphragm, including a method for preparing the inorganic solid electrolyte and a method for conducting electrochemical synthesis reactions using the inorganic solid electrolyte as a diaphragm. The solid electrolyte diaphragm is low-cost, has good chemical stability, a long service life, and is generally suitable for electrochemical synthesis reactions. In this method, both the cathode and anode of the electrolytic cell are simultaneously utilized, resulting in high device efficiency. Furthermore, different heterogeneous electrocatalysts can be easily replaced by coating, expanding the types of reactions applicable to the invented device. By increasing the size of the electrolytic cell, the synthesis scale can be increased, and the operation is simple and suitable for industrial application. In particular, the present invention overcomes the prior art's technical prejudice that inorganic solid electrolyte diaphragms are difficult to apply due to their poor electrical conductivity at low temperatures, especially at room temperature. By using an inorganic solid electrolyte as a diaphragm for the first time, electrochemical synthesis reactions are conducted, unexpectedly achieving efficient electrochemical reactions including organic synthesis, hydrogen production from water electrolysis, and ammonia synthesis. BRIEF DESCRIPTION OF THE DRAWINGS

[0101] Figure 1 This is a schematic structural diagram of the device for performing electrochemical synthesis reactions using a solid electrolyte as a diaphragm, provided in Example 1, wherein: 1-H-type electrolytic cell, 2-electrode / catalyst coating, 3-diaphragm, 4-DC power supply.

[0102] Figure 2 These are SEM plan views of the solid electrolyte membrane in Example 1, wherein (a) is a SEM plan view and (b) is a SEM cross-sectional view.

[0103] Figure 3 Schematic diagram of the structure of the device for electrochemical synthesis reaction using a solid electrolyte as a diaphragm provided in Example 7, wherein: 5-injection device, 6-electrolyzer, 7-membrane electrode assembly, 8-end plate, 9-anode / cathode chamber, 10-solid electrolyte diaphragm, 11-cathode electrode / catalyst coating, 12-anode electrode / catalyst coating, 13-peristaltic pump, 14-electrode ear, 15-injection bottle, 16-collecting bottle, 17-DC power supply.

[0104] Figure 4 These are SEM plan views of the solid electrolyte membrane in Example 7, where (a) is a SEM plan view and (b) is a SEM cross-sectional view.

[0105] Figure 5 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after reaction for 8 hours in Example 1, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after reaction for 8 hours of the cathode mixed solution.

[0106] Figure 6The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after reaction for 8 hours in Example 2, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after reaction of the cathode mixed solution.

[0107] Figure 7 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 3, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the cathode mixed solution after the reaction.

[0108] Figure 8 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 4, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0109] Figure 9 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 5, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the cathode mixed solution after the reaction.

[0110] Figure 10 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 6, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0111] Figure 11 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 7, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0112] Figure 12 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 8, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0113] Figure 13 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 9, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0114] Figure 14The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 10, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0115] Figure 15 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database after the reaction of the anode mixed solution in Comparative Example 1, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution. DETAILED DESCRIPTION

[0116] The present invention discloses a method for performing an electrochemical synthesis reaction using an inorganic solid electrolyte as a diaphragm. The method includes a method for preparing the inorganic solid electrolyte and a method for performing an electrochemical synthesis reaction using the inorganic solid electrolyte as a diaphragm. The method for preparing the inorganic solid electrolyte specifically includes: a sol-gel method, a gel casting method, an electrospinning method, a spray drying method, a hot pressing method, a cold pressing method, a casting method, a chemical vapor deposition method, and a physical vapor deposition method.

[0117] In the present invention, the inorganic solid electrolyte membrane is a layered structure or a uniformly distributed structure composed of one or more of a garnet-type electrolyte, a fluorite-type oxide electrolyte, a perovskite-structured oxide electrolyte, and a LAMOX-based electrolyte. It has a multi-microporous structure, is resistant to strong acids and alkalis and a variety of organic solvents, can block the penetration of reaction molecules, and realize efficient and highly selective oxidation and reduction reactions in the anode chamber and the cathode chamber at the same time.

[0118] The method of the present invention for performing electrochemical synthesis reactions using an inorganic solid electrolyte as a diaphragm is based on an electrolytic cell, achieving efficient and highly selective oxidation and reduction reactions in the anode chamber and the cathode chamber simultaneously, and is generally applicable to important synthesis reactions such as electrolysis of water, electrochemical oxidation, hydrogenation, halogenation, amination, and coupling.

[0119] In the present invention, the solid electrolyte material needs to block the penetration of organic molecules while preventing the exchange of solutions between the anode and cathode. At the same time, the solid electrolyte material maintains a certain chemical stability in the solution required for the reaction and a certain mechanical toughness in the reaction container.

[0120] The present invention provides an apparatus for electrochemical synthesis using a solid electrolyte as a diaphragm, comprising an electrolytic cell and the aforementioned inorganic solid electrolyte diaphragm. The diaphragm divides the electrolytic cell into independent anode and cathode chambers, respectively used for oxidation and reduction reactions. The diaphragm is an inorganic solid electrolyte diaphragm prepared according to the aforementioned method, such as a garnet-type electrolyte, a fluorite-type oxide electrolyte diaphragm, a perovskite-structured oxide electrolyte diaphragm, or a LAMOX-based electrolyte diaphragm. The pores of the solid electrolyte are sized to prevent the penetration of organic molecules.

[0121] Preferably, electrodes and catalyst coatings can be prepared on both sides of the outer surface of the inorganic solid electrolyte membrane, that is, a membrane electrode assembly. For example, the anode side and the cathode side of the inorganic solid electrolyte membrane are both coated with electrode materials and catalyst materials.

[0122] The present invention discloses a method for electrochemical synthesis reaction using an inorganic solid electrolyte membrane as a membrane, comprising the following steps: assembling an electrolytic cell and a membrane electrode assembly, connecting a DC power supply, and collecting the product through a collection bottle after the raw materials undergo an electrochemical synthesis reaction.

[0123] Preferably, the membrane electrode assembly is prepared based on an inorganic solid electrolyte membrane; for example, the anode side and the cathode side of the inorganic solid electrolyte membrane are coated with electrode materials and catalyst materials, and the surface of the electrode or catalyst is flat and smooth.

[0124] Preferably, the electrolytic cell can be a flow-type electrolytic cell, and is connected to a sampling device and a collecting device, which can be communicated through a peristaltic pump device, specifically a conventional technology.

[0125] In the present invention, the inorganic solid electrolyte membrane has a pore size of 0.1 to 100 nm and a thickness of 0.01 to 5 mm. Preferably, the inorganic solid electrolyte membrane has a pore size of 1 to 50 nm and a thickness of 1 to 5 mm. More preferably, the inorganic solid electrolyte membrane has a pore size of 1 to 20 nm and a thickness of 1 to 2 mm. It should be noted that the present invention does not impose specific requirements or special limitations on the shape and size of the inorganic solid electrolyte membrane. The role of the inorganic solid electrolyte membrane in the present invention is to divide the electrolytic cell into independent anode and cathode chambers. Therefore, those skilled in the art can adapt the size of the solid electrolyte membrane according to the usage scenario and test conditions.

[0126] The following specific experiments illustrate the technological advancement of the present invention. The raw materials involved are conventional products that meet the conventional requirements of electrolytes. The specific experimental operations and testing methods are conventional techniques; the testing methods for product characterization, conversion rate, and selectivity are all conventional techniques. Unless otherwise specified, the operations are carried out in air. Example 1

[0127] This embodiment provides a paired electrochemical synthesis reaction, which is Figure 1 The device shown is completed, where 1 is an H-type electrolytic cell, 2 is an electrode, 3 is a diaphragm, and 4 is a DC power supply. The specific steps are as follows:

[0128] The sol-gel method was used to prepare an inorganic solid electrolyte as a diaphragm. Specifically, 0.1 mol of trimethyl aluminate was used as a precursor and dissolved in 10 mL of isopropanol solvent to form a uniform solution. 0.05 mol of CdS catalyst and 0.005 mol of starch pore-forming agent were then added. The mixture was stirred at 60°C for 4 h, transferred to a conventional mold and allowed to stand to obtain a gel. The mixture was then dried at 80°C in a vacuum drying oven for 8 h, transferred to a tube furnace, heated from room temperature to 600°C at 5°C / min, pre-calcined for 2 h, and then heated to 1100°C at 1°C / min and sintered for 4 h to obtain a solid oxide diaphragm.

[0129] The pore size of the inorganic solid electrolyte membrane prepared in this example is concentrated in the range of 2 to 11 nm, and the membrane thickness is about 1 mm;

[0130] According to conventional methods, hydrophilic carbon paper is selected as the anode electrode and a Pt sheet is selected as the cathode electrode; during use, a catalyst may be coated on the electrodes as needed.

[0131] Toluene was added to a 1 M HBr and acetonitrile mixture to prepare a 200 mM anode reaction solution, and furfural was added to a 1 M HBr and acetonitrile mixture to prepare a 200 mM cathode reaction solution; these were added to the corresponding tanks respectively;

[0132] In CA mode, the voltage was set to 5 V. After 4 hours of reaction, gas chromatography and gas chromatography-mass spectrometry analysis showed that bromomethylbenzene was obtained at the anode with a conversion of 49% and a selectivity of 97%, while furfuryl alcohol was obtained at the cathode with a conversion of 53% and a selectivity of 99%. After 8 hours of reaction, gas chromatography and gas chromatography-mass spectrometry analysis showed that bromomethylbenzene was obtained at the anode with a conversion of 95% and a selectivity of 99%, while furfuryl alcohol was obtained at the cathode with a conversion of 99% and a selectivity of 99%.

[0133] Figure 2 (a) is a SEM plan view of the solid electrolyte membrane in this embodiment; Figure 2 (b) is a SEM cross-sectional view of the solid electrolyte membrane in this example. Example 2

[0134] This example provides a paired electrochemical synthesis reaction, which is basically the same as that in Example 1, except that styrene is added to a 1 M HBr and acetonitrile mixed solution to prepare a 200 mM anode reaction solution, and styrene is added to a 1 M HBr and acetonitrile mixed solution to prepare a 200 mM cathode reaction solution; the voltage is set to 5.5 V in CA mode, and after 8 hours of reaction, gas chromatography and gas chromatography-mass spectrometry analysis show that 2-bromoacetophenone is obtained at the anode with a conversion rate of 97% and a selectivity of 96%; and ethylbenzene is obtained at the cathode with a conversion rate of 97% and a selectivity of 99%. Example 3

[0135] This embodiment provides a paired electrochemical synthesis reaction, which is basically the same as that in Example 1, except that the solid electrolyte membrane is prepared by electrospinning using titanium tetrachloride as a precursor, as follows:

[0136] An electrospinning method was employed, using titanium tetrachloride as the precursor and polyacrylonitrile as the polymer. Both were dissolved in dimethylformamide at a concentration of 10 wt%, and the mixture was stirred to produce a spinning solution. A 0.5 mm metal needle was used, with the receiver and syringe needle positioned 20 cm apart. A voltage of 40 kV was applied, and the electrospinning instrument was operated for three 20-minute deposition cycles. After deposition, the nanofiber membrane was collected and allowed to stand at room temperature for 20 hours. The membrane was then transferred to a tube furnace, pre-calcined at 5°C / min from room temperature to 600°C for 2 hours, and then sintered at 1°C / min to 1100°C for 4 hours to produce a solid oxide membrane.

[0137] Toluene was added to a 1 M HBr and acetonitrile mixed solution to prepare a 200 mM anode reaction solution, and furfural was added to a 1 M HBr and acetonitrile mixed solution to prepare a 200 mM cathode reaction solution, which were added to the corresponding cells respectively; the voltage was set to 5 V in CA mode, and after 8 h of reaction, the results were tested and analyzed by gas chromatography and gas chromatography-mass spectrometry. The results showed that bromomethylbenzene was obtained at the anode with a conversion rate of 97% and a selectivity of 96%, and furfuryl alcohol was obtained at the cathode with a conversion rate of 95% and a selectivity of 99%. Example 4

[0138] This example provides a paired electrochemical synthesis reaction, which is basically the same as that in Example 3, except that benzyl alcohol is added to a mixed solution of ammonia and acetonitrile to prepare a 200 mM anode reaction solution, and benzaldehyde is added to a mixed solution of 1 M KOH and acetonitrile to prepare a 200 mM cathode reaction solution. In CA mode, the voltage is set to 6 V. After 24 hours of reaction, gas chromatography and gas chromatography-mass spectrometry analysis show that benzonitrile is obtained at the anode with a conversion rate of 98% and a selectivity of 86%, and benzyl alcohol is obtained at the cathode with a conversion rate of 91% and a selectivity of 97%. Example 5

[0139] This embodiment provides a paired electrochemical synthesis reaction, which is basically the same as that in Example 1, except that: the solid electrolyte membrane is prepared by hot pressing using lithium lanthanum zirconium oxide as a precursor, specifically as follows: the hot pressing method is selected, lithium lanthanum zirconium oxide is used as a precursor, 1 g of powder sample is weighed, mixed with 0.05 g of starch pore-forming agent, and after conventional ball milling, it is loaded into a cylindrical tablet mold, and uniform filling of the powder is achieved by vibration; then the mold filled with the powder is placed in a hot pressing device, and the pressure is maintained at 1300°C and 40 MPa for 4 hours to prepare a solid oxide membrane.

[0140] Toluene was added to a 1 M HBr and acetonitrile mixture to prepare a 200 mM anode reaction solution, and furfural was added to a 1 M HBr and acetonitrile mixture to prepare a 200 mM cathode reaction solution; these were added to the corresponding tanks respectively;

[0141] In CA mode, the voltage was set to 5 V. After 8 h of reaction, the results were analyzed by gas chromatograph and gas chromatography-mass spectrometry. The results showed that bromomethylbenzene was obtained at the anode with a conversion rate of 98% and a selectivity of 97%, while furfuryl alcohol was obtained at the cathode with a conversion rate of 96% and a selectivity of 99%. Example 6

[0142] This example provides a paired electrochemical synthesis reaction, which is basically the same as that in Example 5, except that benzyl bromide and butyl bromide are added to a 1 M KOH tetrahydrofuran mixed solution to prepare a 200 mM anode reaction solution, and styrene is added to a 1 M HBr and acetonitrile mixed solution to prepare a cathode reaction solution; in CA mode, the voltage is set to 5.5 V, and after 8 hours of reaction, gas chromatography and gas chromatography-mass spectrometry analysis show that pentylbenzene is obtained at the anode with a conversion rate of 99% and a selectivity of 86%; and ethylbenzene is obtained at the cathode with a conversion rate of 96% and a selectivity of 95%. Example 7

[0143] This embodiment provides a paired electrochemical synthesis reaction, which is Figure 3 The device shown is completed, where 1 is the sample injection device, 2 is the electrolytic cell, 3 is the membrane electrode assembly, 4 is the end plate, 5 is the anode / cathode chamber, 6 is the solid electrolyte membrane, 7 is the cathode electrode, 8 is the anode electrode, 9 is the peristaltic pump, 10 is the electrode ear, 11 is the sample injection bottle, 12 is the collection bottle, and 13 is the DC power supply. The specific steps are as follows:

[0144] The cold pressing method was selected, with 5% yttrium-stabilized zirconia as the precursor. 1 g of powder sample was weighed, mixed with 0.05 g of starch pore-forming agent, and loaded into a square tablet mold after conventional ball milling. Uniform filling of the powder was achieved by vibration. The mold containing the powder was then placed in a cold pressing device, the required pressure was set to 40 MPa, and the holding time was 2 h. The resulting film was then transferred to a tubular furnace, heated from room temperature to 600 °C at 5 °C / min, pre-sintered for 2 h, and then heated to 1300 °C at 1 °C / min and sintered for 4 h to obtain a solid oxide diaphragm.

[0145] A platinum target with a mass fraction of 80% was magnetron sputtered directly onto the cathode side of a cold-pressed solid electrolyte YSZ diaphragm made of yttrium-stabilized zirconia for 30 minutes, resulting in a nanoscale thin film electrode. The cut carbon paper was then attached to the anode side of the solid electrolyte diaphragm to form a membrane electrode assembly.

[0146] When in use, a catalyst can also be coated on the electrode as needed.

[0147] An electrolytic cell chamber with a cathode and anode cavities of 2 cm × 2 cm × 1 cm was selected, and the prepared membrane electrode assembly was fixed between the cavities to assemble the electrolytic cell;

[0148] Styrene was added to 1 M HBr solution to prepare a 200 mM anode reaction solution, and furfural was added to 1 M HBr solution to prepare a cathode reaction solution; these were added to the corresponding tanks respectively;

[0149] In CA mode, the voltage is set to 4 V;

[0150] The peristaltic pump was started and the flow rate was adjusted to 5 mL / min. The mixture after the electrochemical synthesis reaction continuously flowed into the collection bottle. After 6 hours of reaction, the mixture was tested and analyzed by gas chromatograph and gas chromatography-mass spectrometry. The results showed that 1-phenyl-2-bromoethanol was obtained at the anode with a conversion rate of 99% and a selectivity of 96%. Furfuryl alcohol was obtained at the cathode with a conversion rate of 99% and a selectivity of 82%.

[0151] Figure 4 (a) is a SEM plan view of the solid electrolyte membrane YSZ in this embodiment; Figure 4 (b) is a SEM cross-sectional view of the solid electrolyte membrane YSZ in this example. Example 8

[0152] This embodiment provides a paired electrochemical synthesis reaction, which is basically the same as that in Example 7, except that: the solid electrolyte membrane is prepared by gel casting using tetrabutyl titanate as a precursor: the gel casting method is selected, tetrabutyl titanate is used as a precursor and dissolved in an ethanol solution to form a 0.5 M tetrabutyl titanate-ethanol solution, and 0.1 M sodium dodecyl sulfate is added as a stabilizer and 0.05 M polyvinyl alcohol is added as a thickener. After stirring evenly, it is injected into a mold and allowed to stand to form a wet gel. After curing for 8 hours, a dry gel is formed. Subsequently, an aging treatment is performed at a temperature of 60°C, a humidity of 80%, and a time of 8 hours. The aging treatment is then carried out at 80°C under vacuum for 12 hours. The resulting film is then transferred to a tube furnace and heated from room temperature to 600°C at 5°C / min for pre-calcination for 2 hours, and then heated to 1300°C at 1°C / min for sintering for 4 hours to obtain a solid oxide membrane.

[0153] Styrene was added to a 1 M HBr solution to prepare a 200 mM anode reaction solution, and furfural was added to a 1 M HBr solution to prepare a cathode reaction solution, which were added to the corresponding cells respectively. The voltage was set to 4 V in CA mode. After 6 h of reaction, the reaction was analyzed by gas chromatography and gas chromatography-mass spectrometry. The results showed that 1-phenyl-2-bromoethanol was obtained at the anode with a conversion rate of 99% and a selectivity of 97%, and furfuryl alcohol was obtained at the cathode with a conversion rate of 96% and a selectivity of 98%. Example 9

[0154] This embodiment provides a paired electrochemical synthesis reaction, which is basically the same as that in Example 7, except that: the solid electrolyte membrane is prepared by chemical vapor deposition using trimethylaluminum as a precursor; a silicon wafer is selected as the substrate material for cleaning and decontamination treatment, trimethylaluminum is selected as the precursor gas, and oxygen is selected as the reaction gas; the reaction chamber is heated to 1100°C, and the flow rate of the reaction gas is precisely controlled at 200 sccm to adjust the growth rate and composition of the film; the precursor gas and the reaction gas chemically react on the substrate surface to generate a solid substance that is deposited to form a thin film, and the pressure in the reaction chamber is controlled to 1 atm to optimize the film quality; and the growth time is controlled according to the desired film thickness.

[0155] Styrene was added to a 1 M HBr solution to prepare a 200 mM anode reaction solution, and furfural was added to a 1 M HBr solution to prepare a cathode reaction solution, which were added to the corresponding cells respectively. The voltage was set to 4 V in CA mode. After 6 h of reaction, the reaction was analyzed by gas chromatography and gas chromatography-mass spectrometry. The results showed that 1-phenyl-2-bromoethanol was obtained at the anode with a conversion rate of 96% and a selectivity of 97%, and furfuryl alcohol was obtained at the cathode with a conversion rate of 97% and a selectivity of 96%. Example 10

[0156] This embodiment provides a paired electrochemical synthesis reaction, which is basically the same as that in Example 7, except that: the solid electrolyte membrane is prepared by physical vapor deposition using aluminum oxide as a precursor: physical vapor deposition is selected, a corundum sintered plate is selected, the base material is subjected to conventional cleaning and decontamination treatment, aluminum oxide is used as a precursor target, and is placed in a magnetron sputtering coating machine, evacuated to 10 Pa, a DC sputtering source is used, a DC bias of 600 V is applied to the target, argon gas is introduced into the sputtering chamber, the gas flow rate is 30 sccm, and the sputtering parameters are set to 10 W / cm 2 , the sputtering time was 6 h, the substrate temperature was 120 o C, the pressure in the reaction chamber was controlled at 1 atm, and then the prepared film was transferred to a tube furnace and heated from room temperature to 1400°C at 5°C / min and sintered for 4 h to obtain a solid oxide membrane.

[0157] Styrene was added to a 1 M HBr solution to prepare a 200 mM anode reaction solution, and furfural was added to a 1 M HBr solution to prepare a cathode reaction solution, which were added to the corresponding cells respectively. The voltage was set to 4 V in CA mode. After 6 h of reaction, the reaction was analyzed by gas chromatography and gas chromatography-mass spectrometry. The results showed that 1-phenyl-2-bromoethanol was obtained at the anode with a conversion rate of 98% and a selectivity of 97%. Furfuryl alcohol was obtained at the cathode with a conversion rate of 97% and a selectivity of 99%. Example 11

[0158] This embodiment provides the application of the diaphragm in the electrolysis of water reaction, which is achieved by Figure 3 The device shown is completed. The specific steps are as follows:

[0159] The cold pressing method was selected, and 5% yttrium-stabilized zirconia was used as the precursor and placed in a vacuum drying oven at a constant temperature of 80°C for 12 h. After thorough grinding, 1 g of powder sample was weighed, mixed with 0.05 g of starch pore-forming agent, and fully ball-milled before being loaded into a square tablet mold. Uniform filling of the powder was achieved by vibration. The mold containing the powder was then placed in a cold pressing device, the required pressure was set to 40 MPa, and the holding time was 2 h. The resulting film was then transferred to a tubular furnace, heated from room temperature to 600°C at 5°C / min, pre-sintered for 2 h, and then heated to 1300°C at 1°C / min and sintered for 4 h to obtain a solid oxide diaphragm.

[0160] A platinum target with a mass fraction of 80% was selected and magnetron sputtered directly on the cathode side of a solid electrolyte YSZ diaphragm made by cold pressing with 5% yttrium-stabilized zirconia. The sputtering time was 30 minutes, resulting in a nano-scale thin film electrode. A nickel target with a mass fraction of 80% was selected and magnetron sputtered directly on the anode side of a solid electrolyte YSZ diaphragm made by cold pressing with lithium lanthanum zirconium oxide. The sputtering time was 30 minutes, resulting in a nano-scale thin film electrode.

[0161] An electrolytic cell chamber with a cathode and anode cavities of 2 cm × 2 cm × 1 cm was selected, and the prepared membrane electrode assembly was fixed between the cavities to assemble the electrolytic cell;

[0162] 3 M KOH was prepared as the reaction solution for the anode and cathode and added to the corresponding tanks respectively; the current was set to 40 mA in CC mode; the peristaltic pump was started and the flow rate was adjusted to 2 mL / min; by replenishing the solution, the device could observe the continuous and stable generation of bubbles at the anode and cathode, achieving continuous water electrolysis operation for more than 500 h. Example 12

[0163] This embodiment provides a paired electrochemical synthesis reaction, which is basically the same as that in Example 11, except that: the solid electrolyte membrane is prepared by a tape casting method using lithium lanthanum zirconium oxide as a precursor: the tape casting method is selected, and lithium zirconium oxide is used as a precursor, which is placed in a vacuum drying oven and dried at a constant temperature of 80°C for 12 h. After sufficient grinding, the powder sample is weighed, mixed with 1 wt% starch pore-forming agent, and xylene is added as a solvent and PVA as a binder to obtain a slurry with a powder raw material concentration of 75 wt%. The slurry is poured into the hopper of the tape casting machine, the distance between the scraper and the base belt is adjusted to 1 mm, the temperature of the drying oven is set to 150°C, and the time is 4 h to obtain a thin film. The obtained film is then transferred to a tubular furnace and heated from room temperature to 600°C at 5°C / min for pre-calcination for 2 h, and then heated to 1300°C at 1°C / min for sintering for 4 h to obtain a solid oxide membrane.

[0164] 3 M KOH was prepared as the reaction solution for the anode and cathode and added to the corresponding tanks respectively; the current was set to 40 mA in CC mode; the peristaltic pump was started and the flow rate was adjusted to 2 mL / min; by replenishing the solution, the device could observe the continuous and stable generation of bubbles at the anode and cathode, achieving continuous water electrolysis operation for more than 500 h.

[0165] Comparative Example 1

[0166] This comparative example provides an apparatus for electrochemical synthesis using a Nafion 117 membrane as a diaphragm. Unlike Example 1, diaphragm 3 was replaced with a Nafion 117 membrane. All other parameters and experimental conditions remained the same as those in Example 1. After 4 hours of reaction, analysis by gas chromatography and gas chromatography-mass spectrometry revealed that bromomethylbenzene was obtained at the anode with a conversion of 43% and a selectivity of 95%, and furfuryl alcohol was obtained at the cathode with a conversion of 47% and a selectivity of 99%. After 8 hours of reaction, analysis by gas chromatography and gas chromatography-mass spectrometry revealed that the Nafion 117 membrane had lost its permselectivity, and the solution in the bipolar region had mixed with the substance. However, the present invention showed no loss of permselectivity after 8 hours or even longer reaction times, and no mixing of the solution in the bipolar region with the substance.

[0167] Comparative Example 2

[0168] This comparative example provides an apparatus for electrochemical synthesis using an anion exchange membrane (Fumasep FAA-3-50) as a separator. Unlike Example 1, separator 3 is replaced with an anion exchange membrane. All other parameters and experimental conditions remain the same as those in Example 1. After one hour of reaction, the anion exchange membrane dissolves, and the solutions in the two polar regions mix with the substance.

[0169] Comparative Example 3

[0170] This comparative example provides an apparatus for electrochemical synthesis using a bipolar membrane (Fumasep FBM-PK) as a separator. Unlike Example 1, separator 3 is replaced with a bipolar membrane. All other parameters and experimental conditions remain the same as those in Example 1. After 2 hours of reaction, the bipolar membrane dissolves, and the bipolar solution mixes with the substance.

[0171] Comparative Example 4

[0172] This comparison provides a LAGP (Li 1.5 Al 0.5 Ge 1.5 The device used a (PO4)3) electrolyte as a separator for the electrochemical synthesis reaction. The difference from Example 1 was that separator 3 was replaced with an LAGP electrolyte. The remaining parameters and experimental conditions were the same as those in Example 1. After 1 hour of reaction, the LAGP electrolyte dissolved, and the solutions in the two polar regions mixed with the substances.

[0173] The present invention performs conventional characterization on the above experimental products, which is as follows:

[0174] Figure 5 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after reaction for 8 hours in Example 1, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after reaction for 8 hours of the cathode mixed solution.

[0175] Figure 6 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after reaction for 8 hours in Example 2, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after reaction of the cathode mixed solution.

[0176] Figure 7 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 3, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the cathode mixed solution after the reaction.

[0177] Figure 8 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 4, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0178] Figure 9 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 5, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the cathode mixed solution after the reaction.

[0179] Figure 10 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 6, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0180] Figure 11 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 7, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0181] Figure 12 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 8, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0182] Figure 13 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 9, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0183] Figure 14 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database of the anode mixed solution after the reaction in Example 10, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0184] Figure 15 The gas chromatography, mass spectrum and standard mass spectrum of the National Institute of Standards and Technology (NIST) database after the reaction of the anode mixed solution in Comparative Example 1, and the gas chromatography, mass spectrum and standard mass spectrum of the NIST database after the reaction of the cathode mixed solution.

[0185] By comparison, the device of the present invention using a solid electrolyte as a diaphragm for electrochemical synthesis reaction has similar reaction conversion rate and selectivity when applied to toluene halogenation and furfural hydrogenation reactions. In addition, the physical and chemical properties of the solid electrolyte diaphragm are relatively stable, and it will not be corroded and damaged after the reaction. It still has selective permeability and high efficiency, and the solutions and substances in the two polar regions are still isolated.

[0186] Existing electrochemical synthesis reactions all use membranes that are selectively permeable to ions. However, their resistance to organic solvents and solutions containing some special ions (such as halide ions) is poor. Therefore, the industrial application of water electrolysis and electrochemical organic reactions urgently needs to find alternatives to electrolyte membranes. Inorganic solid electrolyte membranes have higher chemical and thermal stability and can remain stable in a wider range of pH values ​​and chemical environments. At the same time, they have high performance under room temperature liquid phase reaction conditions, effectively isolating the two polar regions to adapt to various types of reactions, extending the service life of the electrochemical system, and reducing operating costs. In summary, the research on methods for electrochemical synthesis reactions using inorganic solid electrolytes as membranes is of great value. It helps to achieve more efficient, safer, and more economical electrolysis processes, meets the requirements of green chemistry and sustainable development, and promotes the development of clean energy technologies.

[0187] The above embodiments are intended only to illustrate the technical concepts and features of the present invention. Their purpose is to enable those skilled in the art to understand the contents of the present invention and implement them accordingly. They are not intended to limit the scope of protection of the present invention. Any equivalent changes or modifications made in accordance with the spirit of the present invention are intended to be covered by the scope of protection of the present invention.

Claims

1. A method for electrochemical synthesis reaction using an inorganic solid electrolyte as a diaphragm, characterized in that: The cathode chamber and the anode chamber are separated by the inorganic solid electrolyte membrane; the inorganic solid electrolyte is one or more of a garnet-type electrolyte, a fluorite-type oxide electrolyte, a perovskite structure oxide electrolyte, and a LAMOX-based electrolyte; during the electrochemical synthesis reaction, a reduction reaction and an oxidation reaction occur in the cathode chamber and the anode chamber, respectively; the solvent of the electrochemical synthesis reaction contains an organic solvent; and the electrochemical synthesis reaction is one of the following reactions: ① Add toluene to a mixed solution of HBr and acetonitrile to prepare an anode reaction solution, and add furfural to a mixed solution of HBr and acetonitrile to prepare a cathode reaction solution; Add them into the corresponding tanks respectively, bromomethylbenzene is obtained at the anode and furfuryl alcohol is obtained at the cathode; ② Add styrene to a mixed solution of HBr and acetonitrile to prepare an anode reaction solution, and add styrene to a mixed solution of HBr and acetonitrile to prepare a cathode reaction solution; Add them to the corresponding tanks respectively, 2-bromoacetophenone is obtained at the anode and ethylbenzene is obtained at the cathode; ③ Add benzyl alcohol to a mixed solution of ammonia and acetonitrile to prepare an anode reaction solution, and add benzaldehyde to a mixed solution of KOH and acetonitrile to prepare a cathode reaction solution; Add them to the corresponding tanks respectively, benzonitrile is obtained at the anode and benzyl alcohol is obtained at the cathode; ④ Add benzyl bromide and butyl bromide to a KOH tetrahydrofuran mixed solution to prepare an anode reaction solution, and add styrene to a HBr and acetonitrile mixed solution to prepare a cathode reaction solution; Add them into the corresponding tanks respectively, pentylbenzene is obtained at the anode and ethylbenzene is obtained at the cathode; ⑤ Add styrene to HBr solution to prepare the anode reaction solution, and add furfural to HBr solution to prepare the cathode reaction solution; add them to the corresponding tanks respectively, and 1-phenyl-2-bromoethanol will be obtained at the anode and furfural will be obtained at the cathode.

2. The method for electrochemical synthesis reaction using an inorganic solid electrolyte as a diaphragm according to claim 1, characterized in that: Preparation methods of inorganic solid electrolytes include sol-gel method, gel casting method, electrospinning method, spray drying method, hot pressing method, cold pressing method, casting method, chemical vapor deposition method or physical vapor deposition method.

3. An inorganic solid electrolyte membrane, an apparatus for performing an electrochemical synthesis reaction using an inorganic solid electrolyte membrane, or a membrane electrode assembly for an electrochemical synthesis reaction, characterized in that: The device for performing electrochemical synthesis reaction using an inorganic solid electrolyte membrane comprises an electrolytic cell and the inorganic solid electrolyte membrane; The membrane electrode assembly for electrochemical synthesis reaction comprises an inorganic solid electrolyte membrane and electrodes on both sides of the inorganic solid electrolyte membrane; the outer sides of the electrodes may or may not be provided with a catalyst layer; The inorganic solid electrolyte is one or more of a garnet-type electrolyte, a fluorite-type oxide electrolyte, a perovskite-structured oxide electrolyte, and a LAMOX-based electrolyte; in the electrochemical synthesis reaction, a reduction reaction and an oxidation reaction occur in the cathode chamber and the anode chamber, respectively; the solvent of the electrochemical synthesis reaction contains an organic solvent; and the electrochemical synthesis reaction is one of the following reactions: ① Add toluene to a mixed solution of HBr and acetonitrile to prepare an anode reaction solution, and add furfural to a mixed solution of HBr and acetonitrile to prepare a cathode reaction solution; Add them into the corresponding tanks respectively, bromomethylbenzene is obtained at the anode and furfuryl alcohol is obtained at the cathode; ② Add styrene to a mixed solution of HBr and acetonitrile to prepare an anode reaction solution, and add styrene to a mixed solution of HBr and acetonitrile to prepare a cathode reaction solution; Add them to the corresponding tanks respectively, 2-bromoacetophenone is obtained at the anode and ethylbenzene is obtained at the cathode; ③ Add benzyl alcohol to a mixed solution of ammonia and acetonitrile to prepare an anode reaction solution, and add benzaldehyde to a mixed solution of KOH and acetonitrile to prepare a cathode reaction solution; Add them to the corresponding tanks respectively, benzonitrile is obtained at the anode and benzyl alcohol is obtained at the cathode; ④ Add benzyl bromide and butyl bromide to a KOH tetrahydrofuran mixed solution to prepare an anode reaction solution, and add styrene to a HBr and acetonitrile mixed solution to prepare a cathode reaction solution; Add them into the corresponding tanks respectively, pentylbenzene is obtained at the anode and ethylbenzene is obtained at the cathode; ⑤ Add styrene to HBr solution to prepare the anode reaction solution, and add furfural to HBr solution to prepare the cathode reaction solution; add them to the corresponding tanks respectively, and 1-phenyl-2-bromoethanol will be obtained at the anode and furfural will be obtained at the cathode.

4. A method for electrochemical synthesis reaction using an inorganic solid electrolyte membrane as a separator, characterized in that: The following steps are involved: Assemble an electrolytic cell with the inorganic solid electrolyte membrane as a diaphragm, connect a power supply, and collect the product after the raw materials undergo an electrochemical synthesis reaction; the inorganic solid electrolyte is one or more of a garnet-type electrolyte, a fluorite-type oxide electrolyte, a perovskite structure oxide electrolyte, and a LAMOX-based electrolyte; the electrochemical synthesis reaction is an organic synthesis reaction; the solvent of the electrochemical synthesis reaction contains an organic solvent; the electrochemical synthesis reaction is one of the following reactions: ① Add toluene to a mixed solution of HBr and acetonitrile to prepare an anode reaction solution, and add furfural to a mixed solution of HBr and acetonitrile to prepare a cathode reaction solution; Add them into the corresponding tanks respectively, bromomethylbenzene is obtained at the anode and furfuryl alcohol is obtained at the cathode; ② Add styrene to a mixed solution of HBr and acetonitrile to prepare an anode reaction solution, and add styrene to a mixed solution of HBr and acetonitrile to prepare a cathode reaction solution; Add them to the corresponding tanks respectively, 2-bromoacetophenone is obtained at the anode and ethylbenzene is obtained at the cathode; ③ Add benzyl alcohol to a mixed solution of ammonia and acetonitrile to prepare an anode reaction solution, and add benzaldehyde to a mixed solution of KOH and acetonitrile to prepare a cathode reaction solution; Add them to the corresponding tanks respectively, benzonitrile is obtained at the anode and benzyl alcohol is obtained at the cathode; ④ Add benzyl bromide and butyl bromide to a KOH tetrahydrofuran mixed solution to prepare an anode reaction solution, and add styrene to a HBr and acetonitrile mixed solution to prepare a cathode reaction solution; Add them into the corresponding tanks respectively, pentylbenzene is obtained at the anode and ethylbenzene is obtained at the cathode; ⑤ Add styrene to HBr solution to prepare the anode reaction solution, and add furfural to HBr solution to prepare the cathode reaction solution; add them to the corresponding tanks respectively, and 1-phenyl-2-bromoethanol will be obtained at the anode and furfural will be obtained at the cathode.

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