3-butene-1-ol prepared based on electro-catalysis of hydrodehydroxylation of 1, 4-butenediol as well as preparation method and application of 3-butene-1-ol

Abstract

The invention discloses 3-butene-1-ol prepared based on electro-catalysis of hydrodehydroxylation of 1, 4-butenediol as well as a preparation method and application of the 3-butene-1-ol, and relates to the technical field of organic synthesis. According to the method, 1, 4-butenediol is added into catholyte by adopting a flow type / H type electrolytic tank, water is taken as a hydrogen source, and high-selectivity preparation of 3-butene-1 alcohol is realized through a three-electrode or two-electrode method under the action of a catalyst. The method is an electro-catalysis mode which is green, safe, low in cost and high in efficiency. Compared with a traditional thermocatalysis route, the method has the advantages of reduction of reaction energy consumption, mild and environment-friendly reaction conditions, low raw material cost, high substrate conversion rate, high product selectivity and low process cost, meets the requirements of green chemical industry, and has great development prospects and strategic significance.

Description

Technical Field

[0001] The present invention relates to the technical field of organic synthesis, and in particular to 3-butene-1-ol prepared by electrocatalytic hydrogenation and dehydroxylation of 1,4-butenediol, and a preparation method and application thereof. Background Art

[0002] 3-Butene-1-ol (BTO) is an unsaturated alcohol compound containing a double bond and a hydroxyl group. It is chemically very active and can participate in many types of reactions such as oxidation, reduction, addition, and esterification. BTO is widely used in fine chemical fields such as medicine, pesticides, plastic lenses, edible flavors, and petroleum processing. For example, as an important pharmaceutical intermediate, BTO can be used to synthesize new heterocyclic derivative drugs, such as anti-AIDS drugs, anti-tumor drugs, and anti-proliferative drugs.

[0003] So far, the methods for synthesizing 3-butene-1-ol in industry mainly include: propylene formaldehyde addition method, 3-butenoic acid reduction method, 3-butyne-1-ol hydrogenation method and 1,4-butanediol selective dehydration method. The propylene formaldehyde addition method uses propylene and formaldehyde as raw materials, and synthesizes them under the catalytic action of ethanol and silica sand at a temperature of 235-350 °C and a pressure of 50-800 bar, with a yield of 27%. However, this method requires high energy consumption and it is difficult to separate the products. The 3-butenoic acid reduction method uses lithium aluminum tetrahydride as a reducing agent for chemical reduction, but the reducing agent is expensive and extremely flammable, which is not conducive to safe and economic production. The 3-butyne-1-ol hydrogenation method uses 3-butyne-1-ol and hydrogen as raw materials, and obtains them by thermal catalytic hydrogenation in an alcohol solvent. However, the raw materials used in this method are expensive, and hydrogen has the risk of explosion. The selective dehydration method of 1,4-butanediol was proposed by Japanese scholars Sato et al. (Catal. Commun., 2003, 4: 77). First, 1,4-butanediol is gasified at high temperature (>300 ℃), and then dehydrated and synthesized under the action of solid oxide catalysts (cerium oxide, indium oxide, etc.). This method is relatively more economical and efficient, but the process will inevitably produce a series of by-products, such as BDO cyclization to produce tetrahydrofuran (THF) or γ-butyrolactone (GBL), or isomerization, hydrogenation, dehydrogenation and other reactions to produce 2-butene-1-ol, 2-butyraldehyde, n-butanol and other by-products, and the reaction requires high temperature.

[0004] Therefore, it is urgent to develop a low-energy, low-cost, and environmentally friendly efficient technology route. Summary of the invention

[0005] In view of the deficiencies in the above-mentioned background technology, the present invention mainly solves the problems that the existing BTO synthesis route still has harsh reaction conditions, high raw material costs, and complex product separation. Most routes require relatively high temperature and pressure driving, resulting in high energy consumption and high carbon dioxide emissions. The present invention provides a method for preparing 3-butene-1-ol based on electrocatalytic 1,4-butenediol hydrodehydroxylation. The method uses electricity driven by renewable energy at room temperature and pressure, with low energy consumption. At the same time, cheap water and 1,4-butenediol are used as raw materials, with low cost and safe reaction.

[0006] The first object of the present invention is to provide a method for preparing 3-butene-1-ol by electrocatalytic hydrodehydroxylation of 1,4-butenediol, comprising the following steps: Adhere cathode or anode powder catalyst to the conductive substrate by in-situ growth method or powder spraying method to obtain cathode or anode; A flow electrolytic cell or an H-type electrolytic cell is assembled using the prepared cathode and anode, and a cathode electrolyte and an anode electrolyte are introduced into the cathode chamber and the anode chamber respectively. At the same time, a raw material 1,4-butenediol is introduced into the cathode chamber. Subsequently, a three-electrode or two-electrode system is used to carry out an electrochemical hydrogenation and dehydroxylation reaction of 1,4-butenediol. After 1 to 2 hours of electrochemical reaction, 3-butene-1-ol is obtained.

[0007] Preferably, the cathode powder catalyst includes Cu, CuO, Cu3P, CuS, Cu(OH)2, Co, CoO, CoP, Co(OH)2, copper phthalocyanine, carbene copper or a copper single atom catalyst supported on a nitrogen-doped carbon material.

[0008] Preferably, the anode powder catalyst comprises Ir / C, Ru / C, IrO2, RuO2, nickel hydroxide nanosheets, nickel iron hydroxide nanosheets or nickel cobalt hydroxide nanosheets.

[0009] Preferably, the cathode or anode is prepared by spraying a powder catalyst, comprising: The powder catalyst is evenly dispersed in the solvent, and the Nafion solution is added and mixed evenly to obtain an evenly dispersed slurry; The slurry is sprayed onto a conductive substrate and dried to obtain a cathode or an anode; When the powder catalyst is a cathode powder catalyst, a cathode is obtained; when the powder catalyst is an anode powder catalyst, an anode is obtained; The solvent includes one or more of ultrapure water, ethanol, and isopropanol.

[0010] Preferably, the dosage ratio of the powder catalyst, solvent and Nafion solution is (10 mg~10 g): (2 mL~2L): (30 μL~5 mL); the mass fraction of the Nafion solution is 1-20 wt%.

[0011] Preferably, the conductive substrate comprises carbon paper, carbon cloth, conductive glass or foam metal; The foam metal includes foam copper, foam cobalt or foam nickel.

[0012] Preferably, the cathode or anode powder catalyst is attached to the conductive substrate by an in-situ growth method to prepare the cathode or anode, comprising: Using foamed metal as a conductive substrate, in-situ growing cathode or anode powder catalyst by impregnation, hydrothermal, electrodeposition or calcination, and obtaining the cathode or anode by washing and drying; Preferably, the cathode electrolyte and the anode electrolyte are both 0.01-10 M KOH aqueous solution, 0.01-10 M KHCO3 aqueous solution, 0.01-5 M hydrochloric acid aqueous solution or 0.01-5 M sulfuric acid aqueous solution.

[0013] Preferably, for a flow-type electrolytic cell, the electrolyte flow rate is 5-500 sccm; for an H-type electrolytic cell, the electrolyte stirring speed is 200-1000 rppm; The electrochemical method includes cyclic voltammetry, constant current method or constant voltage method.

[0014] Preferably, the concentration of 1,4-butenediol is 0.001-5M.

[0015] Compared with the prior art, the present invention has the following beneficial effects: The present invention provides 3-butene-1-ol prepared by electrocatalytic 1,4-butenediol hydrogenation and dehydroxylation, and a preparation method and application thereof. The method is carried out at room temperature and pressure, has low energy consumption, and does not emit carbon dioxide during the reaction process, which meets the requirements of green chemical industry. The present invention uses low-priced 1,4-butenediol as a raw material, and uses water as a hydrogen source, and uses non-precious metal catalysts such as copper and cobalt, which greatly reduces the preparation cost of 3-butene-1-ol. The method of the present invention has a simple device and is easy to operate, and can be carried out in a modular manner; experimental results show that its conversion rate, selectivity and yield are better than those under thermal catalytic conditions, and has great application value. BRIEF DESCRIPTION OF THE DRAWINGS

[0016] Figure 1 This is the SEM image of the Cu(OH)2 nanoarray provided in Example 1.

[0017] Figure 2This is a gas chromatogram of Example 1 after electrochemical reaction for 1 hour at -1.0 V.

[0018] Figure 3 This is Example 1, the conversion rate of 1,4-butenediol and the selectivity of 3-butene-1-ol at different voltages.

[0019] Figure 4 Performance comparison of electrocatalytic process and thermal catalytic process. DETAILED DESCRIPTION

[0020] In order to enable those skilled in the art to better understand and implement the technical solution of the present invention, the present invention is further described below in conjunction with specific embodiments and drawings, but the embodiments are not intended to limit the present invention.

[0021] The purpose of the present invention is to provide 3-butene-1-ol prepared by electrocatalytic 1,4-butenediol hydrogenation and dehydroxylation, and a preparation method and application thereof. The present invention adopts electricity driven by renewable energy at room temperature and pressure, and has low energy consumption. At the same time, cheap water and 1,4-butenediol are used as raw materials, so the cost is low and the reaction is safe.

[0022] In order to achieve the above object, the first aspect of the present invention provides a method for preparing 3-butene-1-ol by electrocatalytic hydrodehydroxylation of 1,4-butenediol, comprising the following steps: Adhere cathode or anode powder catalyst to the conductive substrate by in-situ growth method or powder spraying method to obtain cathode or anode; A flow electrolytic cell or an H-type electrolytic cell is assembled using the prepared cathode and anode, and a cathode electrolyte and an anode electrolyte are introduced into the cathode chamber and the anode chamber respectively. At the same time, a raw material 1,4-butenediol is introduced into the cathode chamber. Subsequently, a three-electrode or two-electrode system is used to carry out an electrochemical hydrogenation and dehydroxylation reaction of 1,4-butenediol. After 1 to 2 hours of electrochemical reaction, 3-butene-1-ol is obtained.

[0023] The present invention can be carried out at normal temperature and pressure, can maintain high selectivity at a high conversion rate, and uses water as a hydrogen source in an electrocatalytic manner, thus meeting the needs of green chemical industry.

[0024] Among them, the cathode powder catalyst includes Cu, CuO, Cu3P, CuS, Cu(OH)2, Co, CoO, CoP, Co(OH)2, phthalocyanine copper, carbene copper or copper single atom catalyst supported by nitrogen-doped carbon material.

[0025] The anode powder catalyst includes Ir / C, Ru / C, IrO2, RuO2, nickel hydroxide nanosheets, nickel iron hydroxide nanosheets or nickel cobalt hydroxide nanosheets.

[0026] The cathode or anode is prepared by spraying powder catalyst, including: The powder catalyst is evenly dispersed in the solvent, and the Nafion solution is added and mixed evenly to obtain an evenly dispersed slurry; The slurry is sprayed onto a conductive substrate and dried to obtain a cathode or an anode; When the powder catalyst is a cathode powder catalyst, a cathode is obtained; when the powder catalyst is an anode powder catalyst, an anode is obtained; The solvent includes one or more of ultrapure water, ethanol, and isopropanol.

[0027] The dosage ratio of the powder catalyst, solvent and Nafion solution is (10 mg~10 g): (2 mL~2 L): (30 μL~5 mL); the mass fraction of the Nafion solution is 1-20 wt%.

[0028] The conductive substrate includes carbon paper, carbon cloth, conductive glass or foam metal; The foam metal includes foam copper, foam cobalt or foam nickel.

[0029] According to the present invention, a cathode or anode powder catalyst is attached to a conductive substrate by an in-situ growth method to prepare a cathode or anode, comprising: Using foamed metal as a conductive substrate, in-situ growing cathode or anode powder catalyst by impregnation, hydrothermal, electrodeposition or calcination, and obtaining the cathode or anode by washing and drying; The cathode electrolyte and the anode electrolyte are both 0.01-10 M KOH aqueous solution, 0.01-10 M KHCO3 aqueous solution, 0.01-5 M hydrochloric acid aqueous solution or 0.01-5 M sulfuric acid aqueous solution.

[0030] For a flow-type electrolytic cell, the electrolyte flow rate is 5-500 sccm; for an H-type electrolytic cell, the electrolyte stirring speed is 200-1000 rppm; The electrochemical method includes cyclic voltammetry, constant current method or constant voltage method.

[0031] The concentration of the 1,4-butenediol is 0.001-5M.

[0032] It should be noted that the principle of preparing 3-butene-1-ol by electrocatalytic 1,4-butenediol hydrogenation and dehydroxylation is as follows: in an electrolytic cell, water in the electrolyte is used as a hydrogen source, 1,4-butenediol raw material is added to the cathode chamber, and when power is turned on, the product generated at the cathode is 3-butene-1-ol.

[0033] The reaction equation for electrocatalytic hydrodehydroxylation of 1,4-butenediol is as follows:

[0034] In order to realize the above principle, the following specific steps are adopted: Preparation of cathode and anode The cathode and anode include a conductive foam metal on a conductive substrate sprayed with a powder catalyst or on which a catalyst is grown in situ; The preparation method of the conductive substrate sprayed with powder catalyst is as follows: 10 mg to 10 g of cathode or anode catalyst powder is uniformly dispersed in 2 mL to 2 L of solvent, and 30 μL to 5 mL of Nafion solution is added, and ultrasonic bath is shaken for 10 to 120 min to obtain a uniformly dispersed catalyst slurry, wherein the solvent includes but is not limited to one or more of ultrapure water, ethanol, and isopropanol, and the mass fraction of the Nafion solution is 1-20 wt%; the catalyst slurry is sprayed on the conductive substrate, and a conductive substrate cathode / anode sprayed with powder catalyst is obtained by drying, and the catalyst loading is 0.001 to 10 mg / cm 2 , the conductive substrate includes but is not limited to carbon paper, carbon cloth, conductive glass, and foam metal; The cathode powder catalyst includes but is not limited to nanoparticles such as Cu, CuO, Cu3P, CuS, Cu(OH)2, Co, CoO, CoP, Co(OH)2, etc., molecular catalysts such as phthalocyanine copper and carbene copper, and copper single atom catalysts supported by nitrogen-doped carbon materials; the anode powder catalyst includes but is not limited to Ir / C, Ru / C, IrO2, RuO2, nickel hydroxide nanosheets, nickel iron hydroxide nanosheets, nickel cobalt hydroxide nanosheets, etc.; The preparation method of the conductive foam metal of the in-situ grown catalyst is: using the conductive foam metal as a substrate, in-situ growing the catalyst by an impregnation method, a hydrothermal method, an electrodeposition method or a calcination method, and obtaining the final electrode by a cleaning and drying process, wherein the foam metal includes but is not limited to foam copper, foam cobalt, and foam nickel; taking the growth of Cu(OH)2 on foam copper as a cathode as an example, the specific preparation method is: ultrasonically cleaning the foam copper with 1 M dilute hydrochloric acid, acetone, and anhydrous ethanol in sequence, drying with a nitrogen flow, immersing the treated foam copper in a solution prepared by ammonium persulfate and sodium hydroxide, standing for half an hour, rinsing with ultrapure water and naturally air-drying, wherein the concentration of the ammonium persulfate is 0.04 M, and the concentration of the sodium hydroxide is 0.8 M.

[0035] Assembly of electrolytic cell: The electrolytic cell includes a flow-type electrolytic cell and an H-type electrolytic cell; when the electrolytic cell is a flow-type electrolytic cell, the specific assembly steps are: assemble the electrolytic cell in the order of an end plate, the cathode prepared above, an ion exchange membrane, an anode, and an end plate, wherein the ion exchange membrane includes but is not limited to one of a proton exchange membrane and an anion exchange membrane, an electrolyte is introduced into the cathode chamber and the anode chamber, and a 1,4-butenediol raw material is added to the cathode, and the electrolyte flow rate is 5-500 sccm; When the electrolytic cell is an H-type electrolytic cell, the specific assembly steps are as follows: the cathode chamber and the anode chamber are separated by an ion exchange membrane. The ion exchange membrane includes but is not limited to one of a proton exchange membrane and an anion exchange membrane, an electrolyte is added to the cathode chamber and the anode chamber, and 1,4-butenediol raw material is added to the cathode chamber at the same time, and the mixture is continuously stirred, and the rotation speed is 200-1000rppm; The electrolyte includes, but is not limited to, 0.01 to 10 M KOH aqueous solution, 0.01 to 10 M KHCO3 aqueous solution, 0.01 to 5 M hydrochloric acid aqueous solution, 0.01 to 5 M sulfuric acid aqueous solution, 0.01 to 5 M KCl aqueous solution, 0.01 to 10 M KOH aqueous solution; The concentration of the 1,4-butenediol raw material is 0.001-5M.

[0036] The electrocatalytic hydrogenation dehydroxylation reaction adopts a three-electrode system or a two-electrode system to carry out the electrocatalytic hydrogenation dehydroxylation reaction, operates the electrolytic cell by an electrochemical method, and tests the products after the reaction by a liquid chromatograph to determine the conversion rate of 1,4-butenediol, the selectivity and yield of 3-butene-1-ol, and the electrochemical method includes but is not limited to cyclic voltammetry, constant current method, and constant voltage method.

[0037] It should be noted that the experimental methods used in the present invention are all conventional methods unless otherwise specified; the reagents and materials used are all commercially available unless otherwise specified.

[0038] Example 1 (1) Preparation of in-situ grown Cu(OH)2 nanoarrays on copper foam: a. Ultrasonicate the copper foam with 1 M dilute hydrochloric acid, acetone and anhydrous ethanol solution for 5 min respectively, and blow dry with nitrogen gas; b. Immerse the copper foam in a solution of 0.04 M ammonium persulfate and 0.8 M sodium hydroxide dissolved in deionized water, let it stand for 30 min, then take out the copper foam sample, rinse it with deionized water several times and air dry it naturally. Figure 1 Shown is a SEM image of the Cu(OH)2 nanoarray provided in this embodiment.

[0039] (2) Assembly of flow electrolytic cell: The Cu(OH)2 grown in situ on copper foam was used as the cathode of the electrolytic cell, nickel foam was used as the anode of the electrolytic cell, Hg / HgO was used as the reference electrode of the electrolytic cell, 1 M KOH solution was used as the cathode electrolyte and the anode electrolyte, the flow rate was 100 sccm, and the cathode chamber and the anode chamber were separated by a Fumasep FAB-PK-130 anion exchange membrane. 0.5 M of the reactant 1,4-butenediol was added to the cathode electrolyte.

[0040] (3) Electrochemical hydrogenation and dehydroxylation performance reaction: The electrochemical performance test was carried out using a three-electrode system. The catalytic activity of the Cu(OH)2 catalyst was tested using a constant potential method. After one hour of reaction, the product 3-butene-1-ol was analyzed by liquid chromatography.

[0041] Example 2 (1) Preparation of Cu nanoparticle catalyst sprayed on carbon fiber paper: 80 mg of Cu nanoparticle catalyst powder was dispersed in 20 mL of ethanol, and then 100 μL of Nafion solution (5 wt%) was added, ultrasonically dispersed for 60 min, and then sprayed onto the carbon fiber paper.

[0042] (2) Assembly of a flow-type electrolytic cell: The carbon fiber paper sprayed with Cu nanoparticle catalyst was used as the cathode of the electrolytic cell, nickel foam was used as the anode of the electrolytic cell, Hg / HgO was used as the reference electrode of the electrolytic cell, and the cathode and anode electrolytes were both 1 M KOH solutions with a flow rate of 100 sccm. The cathode chamber and the anode chamber were separated by a Fumasep FAB-PK-130 anion exchange membrane. 0.5 M of the reactant 1,4-butenediol was added to the cathode electrolyte.

[0043] (3) Electrochemical hydrogenation and dehydroxylation performance reaction: The electrochemical performance test was carried out using a three-electrode system. The catalytic activity of the carbon fiber paper sprayed Cu nanoparticle catalyst was tested using a constant potential method. After one hour of reaction, the product 3-butene-1-ol was analyzed by liquid chromatography.

[0044] Example 3 (1) Preparation of in situ grown Cu nanowire arrays on copper foam: a. Ultrasonicate the copper foam with 1 M dilute hydrochloric acid, acetone and anhydrous ethanol solutions for 5 min respectively, and blow dry with nitrogen flow; b. Immerse the copper foam in a solution of 0.04 M ammonium persulfate and 0.8 M sodium hydroxide dissolved in deionized water. After standing for 30 min, take out the copper foam sample, rinse it with deionized water several times and air-dry it to obtain Cu(OH)2 nanowire arrays; c. Reduce it in a tubular furnace at 300 °C in an atmosphere of H2 / Ar mixed gas (4:96) to obtain in situ grown Cu nanowire arrays on copper foam.

[0045] (2) Assembly of flow electrolytic cell: The in-situ grown Cu nanowire array on copper foam was used as the cathode of the electrolytic cell, Hg / HgO was used as the reference electrode of the electrolytic cell, nickel foam was used as the anode of the electrolytic cell, the electrolytes for the cathode and cathode were both 1 M KOH solution, the flow rate was 100 sccm, and they were separated by a Fumasep FAB-PK-130 anion exchange membrane. 0.5 M of the reactant 1,4-butenediol was added to the cathode electrolyte.

[0046] (3) Electrochemical hydrogenation and dehydroxylation performance reaction: The electrochemical performance test was carried out using a three-electrode system. The catalytic activity of the in-situ grown Cu nanowire array on copper foam was tested using a constant potential method. After one hour of reaction, the product 3-butene-1-ol was analyzed by liquid chromatography.

[0047] Example 4 (1) Preparation of CuO nanoparticle catalyst sprayed on carbon cloth: 80 mg of CuO nanoparticle catalyst powder was dispersed in 40 mL of isopropanol, and then 100 μL of Nafion solution (5%) was added. The mixture was stirred and ultrasonically dispersed for 60 min and then sprayed onto the carbon cloth.

[0048] (2) Assembly of a flow-type electrolytic cell: A CuO nanoparticle catalyst was sprayed onto a carbon cloth as the cathode of the electrolytic cell, and nickel foam was used as the anode. The cathode and anode electrolytes were both 1 M KHCO3 solutions with a flow rate of 100 sccm. The cathode and anode chambers were separated by a Nafion 117 proton exchange membrane. 0.5 M of the reactant 1,4-butenediol was added to the cathode electrolyte.

[0049] (3) Electrochemical hydrogenation and dehydroxylation performance reaction: The electrochemical performance test was carried out using a two-electrode system. The catalytic activity of the CuO nanoparticles was tested using a constant potential method. After one hour of reaction, the product 3-butene-1-ol was analyzed by liquid chromatography.

[0050] Example 5 (1) Preparation of carbene copper nanoparticle catalyst sprayed on copper foam: Carbene copper nanoparticles were prepared by dispersing 80 mg of carbene copper nanoparticle catalyst powder in 20 mL of isopropanol, then adding 100 μL of Nafion solution (5%), stirring and ultrasonically dispersing for 60 min and spraying it onto copper foam.

[0051] (2) Assembly of flow-type electrolytic cell: Carbene copper nanoparticle catalyst was sprayed on copper foam as the cathode of the electrolytic cell, Hg / HgO was used as the reference electrode of the electrolytic cell, nickel foam was used as the anode of the electrolytic cell, and the electrolytes of the cathode and cathode were both 1 M KOH solution with a flow rate of 100 sccm. Fumasep FAB-PK-130 anion exchange membrane was used to separate them. 0.5 M of the reactant 1,4-butenediol was added to the cathode electrolyte.

[0052] (3) Electrochemical hydrogenation and dehydroxylation performance reaction: The electrochemical performance test was carried out using a three-electrode system. The catalytic activity of the carbene copper catalyst was tested using a constant potential method. After one hour of reaction, the product 3-butene-1-ol was analyzed by liquid chromatography.

[0053] Example 6 (1) Preparation of copper phthalocyanine nanoparticle catalyst sprayed on carbon cloth: 80 mg of copper phthalocyanine nanoparticle catalyst powder was dispersed in 20 mL of isopropanol, and then 100 μL of Nafion solution (5%) was added. The mixture was stirred and ultrasonically dispersed for 60 min and then sprayed onto the copper foam.

[0054] (2) Assembly of flow-type electrolytic cell: Copper phthalocyanine nanoparticle catalyst was sprayed on carbon cloth as the cathode of the electrolytic cell, Hg / HgO was used as the reference electrode of the electrolytic cell, nickel foam was used as the anode of the electrolytic cell, and the electrolytes of the cathode and cathode were both 1 M KOH solution with a flow rate of 100 sccm. Fumasep FAB-PK-130 anion exchange membrane was used to separate them. 0.5 M of the reactant 1,4-butenediol was added to the cathode electrolyte.

[0055] (3) Electrochemical hydrogenation and dehydroxylation performance reaction: The electrochemical performance test was carried out using a three-electrode system. The catalytic activity of the copper phthalocyanine catalyst was tested using a constant potential method. After one hour of reaction, the product 3-butene-1-ol was analyzed by liquid chromatography.

[0056] Example 7 (1) Preparation of in situ grown Cu(OH)2 nanowire arrays on copper foam: a. Ultrasonicate the copper foam with 1 M dilute hydrochloric acid, acetone and anhydrous ethanol solutions for 5 min respectively, and blow dry with nitrogen gas; b. Immerse the copper foam in a solution of 0.04 ammonium persulfate and 0.8 M sodium hydroxide dissolved in deionized water. After standing for 30 min, take out the copper foam sample, rinse it with deionized water several times and air-dry it naturally.

[0057] (2) Assembly of H-type electrolytic cell: Cu(OH)2 grown in situ on copper foam was used as the cathode of the electrolytic cell, nickel foam was used as the anode of the electrolytic cell, Hg / HgO was used as the reference electrode of the electrolytic cell, 1 M KOH solution was used for both the cathode electrolyte and the anode electrolyte, the stirring speed was 300 rppm, and the cathode chamber and the anode chamber were separated by a Fumasep FAB-PK-130 anion exchange membrane. 0.5 M of the reactant 1,4-butenediol was added to the cathode electrolyte.

[0058] (3) Electrochemical hydrogenation and dehydroxylation performance reaction: The electrochemical performance test was carried out using a three-electrode system. The catalytic activity of the copper hydroxide catalyst was tested using a constant potential method. After one hour of reaction, the product 3-butene-1-ol was analyzed by liquid chromatography.

[0059] Example 8 (1) Preparation of cobalt foam sprayed with cobalt nanoparticle catalyst: 80 mg of cobalt nanoparticle catalyst powder was dispersed in 20 mL of isopropanol, and then 100 μL of Nafion solution (5%) was added. The mixture was stirred and ultrasonically dispersed for 60 min and then sprayed onto the cobalt foam.

[0060] (2) H-type electrolytic cell assembly: Cobalt foam sprayed with cobalt nanoparticle catalyst was used as the cathode of the electrolytic cell, nickel foam was used as the anode of the electrolytic cell, the cathode electrolyte was 1 M KOH solution, the stirring speed was 300 rppm, and the two were separated by Fumasep FAB-PK-130 anion exchange membrane. 0.5 M of the reactant 1,4-butenediol was added to the cathode electrolyte.

[0061] (3) Electrochemical hydrogenation and dehydroxylation performance reaction: The electrochemical performance test was carried out using a two-electrode system. The catalytic activity of the cobalt nanoparticle catalyst was tested using a constant potential method. After one hour of reaction, the product 3-butene-1-ol was analyzed by liquid chromatography.

[0062] Example 9 (1) Preparation of in situ grown CuS on copper foam: a. Ultrasonicate the copper foam with 1 M dilute hydrochloric acid, acetone and anhydrous ethanol solutions for 5 min respectively, and blow dry with nitrogen flow; b. Immerse the copper foam in a solution of 0.04 M ammonium persulfate and 0.8 M sodium hydroxide dissolved in deionized water. After standing for 30 min, take out the copper foam sample, rinse it with deionized water several times and air-dry it naturally; c. Sulfidize it in a tubular furnace at 300 °C for 2 h to obtain in situ grown CuS on copper foam.

[0063] (2) H-type electrolytic cell assembly: CuS in situ grown on copper foam was used as the cathode of the electrolytic cell, nickel foam was used as the anode of the electrolytic cell, the cathode electrolyte was 1 M KOH solution, the stirring speed was 300 rppm, and the two were separated by a Fumasep FAB-PK-130 anion exchange membrane. 0.5 M of the reactant 1,4-butenediol was added to the cathode electrolyte.

[0064] (3) Electrochemical hydrogenation and dehydroxylation performance reaction: The electrochemical performance test was carried out using a two-electrode system. The catalytic activity of the CuS catalyst was tested using a constant potential method. After one hour of reaction, the product 3-butene-1-ol was analyzed by liquid chromatography.

[0065] In order to illustrate the performance of the catalyst used in the method provided by the present invention for preparing 3-butene-1-ol, the specific evaluation results of the catalyst are shown in Table 1.

[0066] Table 1 Catalyst specific evaluation results

[0067] As can be seen from Table 1, both copper-based materials and cobalt-based materials can obtain a 1,4-butenediol conversion rate of more than 84% and a 3-butene-1-ol selectivity of more than 80%, proving that 3-butene-1-ol can be prepared by hydrogenation and dehydroxylation of 1,4-butenediol.

[0068] Figure 1 The SEM image of the Cu(OH)2 nanoarray provided in Example 1; Figure 1 It can be seen that the Cu(OH)2 nanowire array is uniformly loaded on the copper foam, with a diameter of about 100-200 nm.

[0069] Figure 2 This is a gas chromatogram of Example 1 after 1 hour of electrochemical reaction at -1.0 V. It can be seen from the figure that after the electrochemical reaction, the peak of 1,4-butenediol decreases, and peaks of 3-butene-1-ol, 1,4-butanediol and n-butanol appear, and the peak of 3-butene-1-ol accounts for the largest proportion, proving the feasibility of preparing 3-butene-1-ol by hydrodehydroxylation of 1,4-butenediol.

[0070] Figure 3 For Example 1, the conversion rate of 1,4-butenediol and the selectivity of 3-butene-1-ol at different voltages; it can be seen from the figure that at -0.5 V to -1.1 V, the conversion rate of 1,4-butenediol increased from 20.7% to 98.0%, and in the entire voltage application window, the selectivity of 3-butene-1-ol was greater than 61.6%.

[0071] Figure 4The performance comparison of the electrocatalytic process and the thermal catalytic process is shown in the figure; the electrocatalytic process is Example 1, the thermal catalytic process is the 1,4-butanediol dehydration process, the reaction temperature is 360-600°C, and the catalysts are shown in the figure. It can be seen from the figure that the yield of 3-butene-1-ol in the electrocatalytic process is higher than that of the catalysts listed in the thermal catalytic process, showing the advantages of electrocatalysis.

[0072] In summary, the present invention uses 1,4-butenediol as a reactant, and efficiently prepares 3-butene-1-ol through a hydrogenation dehydroxylation reaction at room temperature and pressure in an electrocatalytic manner, thereby solving the key problems faced by the traditional synthesis route, such as high temperature, high pressure, complex process flow, and many by-products.

[0073] The present invention describes preferred embodiments and their effects. However, those skilled in the art may make additional changes and modifications to these embodiments once they are aware of the basic creative concept. Therefore, the appended claims are intended to be interpreted as including the preferred embodiments and all changes and modifications that fall within the scope of the present invention.

[0074] Although embodiments of the present invention have been shown and described, it will be appreciated by those skilled in the art that various changes, modifications, substitutions and variations may be made to the embodiments without departing from the principles and spirit of the present invention, and that the scope of the present invention is defined by the appended claims and their equivalents.

Claims

1. A method for preparing 3-butene-1-ol by electrocatalytic hydrodehydroxylation of 1,4-butenediol, characterized in that: The following steps are involved: Adhere cathode or anode powder catalyst to the conductive substrate by in-situ growth method or powder spraying method to obtain cathode or anode; A flow electrolytic cell or an H-type electrolytic cell is assembled using the prepared cathode and anode, and a cathode electrolyte and an anode electrolyte are introduced into the cathode chamber and the anode chamber respectively. At the same time, a raw material 1,4-butenediol is introduced into the cathode chamber. Subsequently, a three-electrode or two-electrode system is used to carry out an electrochemical hydrogenation and dehydroxylation reaction of 1,4-butenediol. After 1 to 2 hours of electrochemical reaction, 3-butene-1-ol is obtained.

2. The method for preparing 3-butene-1-ol by electrocatalytic hydrodehydroxylation of 1,4-butenediol according to claim 1, characterized in that: The cathode powder catalyst includes Cu, CuO, Cu3P, CuS, Cu(OH)2, Co, CoO, CoP, Co(OH)2, copper phthalocyanine, carbene copper or copper single atom catalyst supported on nitrogen-doped carbon material.

3. The method for preparing 3-butene-1-ol by electrocatalytic hydrodehydroxylation of 1,4-butenediol according to claim 1, characterized in that: The anode powder catalyst includes Ir / C, Ru / C, IrO2, RuO2, nickel hydroxide nanosheets, nickel iron hydroxide nanosheets or nickel cobalt hydroxide nanosheets.

4. The method for preparing 3-butene-1-ol by electrocatalytic hydrodehydroxylation of 1,4-butenediol according to claim 1, characterized in that: The cathode or anode is prepared by spraying powder catalyst, including: The powder catalyst is evenly dispersed in the solvent, and the Nafion solution is added and mixed evenly to obtain an evenly dispersed slurry; The slurry is sprayed onto a conductive substrate and dried to obtain a cathode or an anode; When the powder catalyst is a cathode powder catalyst, a cathode is obtained; when the powder catalyst is an anode powder catalyst, an anode is obtained; The solvent includes one or more of ultrapure water, ethanol, and isopropanol; The conductive substrate includes carbon paper, carbon cloth, conductive glass or foam metal; The foam metal includes foam copper, foam cobalt or foam nickel.

5. The method for preparing 3-butene-1-ol by electrocatalytic hydrodehydroxylation of 1,4-butenediol according to claim 4, characterized in that: The dosage ratio of the powder catalyst, solvent and Nafion solution is (10 mg~10 g): (2 mL~2 L): (30 μL~5 mL); the mass fraction of the Nafion solution is 1-20 wt%.

6. The method for preparing 3-butene-1-ol by electrocatalytic hydrodehydroxylation of 1,4-butenediol according to claim 4, characterized in that: The cathode or anode powder catalyst is attached to the conductive substrate by an in-situ growth method to obtain the cathode or anode, including: Using foamed metal as a conductive substrate, cathode or anode powder catalyst is grown in situ by impregnation, hydrothermal, electrodeposition or calcination, and the cathode or anode is obtained by washing and drying.

7. The method for preparing 3-butene-1-ol by electrocatalytic hydrodehydroxylation of 1,4-butenediol according to claim 1, characterized in that: The cathode electrolyte and the anode electrolyte are both 0.01-10 M KOH aqueous solution, 0.01-10 M KHCO3 aqueous solution, 0.01-5 M hydrochloric acid aqueous solution or 0.01-5 M sulfuric acid aqueous solution; the concentration of the 1,4-butenediol is 0.001-5 M.

8. The method for preparing 3-butene-1-ol by electrocatalytic hydrodehydroxylation of 1,4-butenediol according to claim 1, characterized in that: For a flow-type electrolytic cell, the electrolyte flow rate is 5-500 sccm; for an H-type electrolytic cell, the electrolyte stirring speed is 200-1000 rppm; The electrochemical method includes cyclic voltammetry, constant current method or constant voltage method.

9. 3-Butene-1-ol obtained by the method according to any one of claims 1 to 8.

10. Use of the 3-butene-1-ol according to claim 9 in the field of fine chemicals.

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