Application of Copper Catalyst in the Selective Hydrogenation of Cyano Group of Organic Nitriles to Prepare Primary Amines by Electrocatalysis

Abstract

The present invention discloses an application of a copper catalyst in the electrocatalytic selective hydrogenation of the cyano group of nitrile organic compounds to prepare primary amines. In this application, the highly selective hydrogenation of the terminal cyano group of nitrile organic compounds to synthesize primary amine organic compounds is realized under an electrochemical system. This method has the characteristics of low cost of the required catalyst, stable performance, mild conditions for hydrogenating to prepare primary amines, simple operation, environmental protection, etc., and has good application prospects.

Description

Technical Field

[0001] The present invention relates to the technical field of electrocatalytic synthesis in organic chemistry. More specifically, it relates to the application of a copper catalyst in the electrocatalytic selective hydrogenation of the cyano group of organic nitriles to prepare primary amines. Background Art

[0002] Primary amines are important industrial intermediates widely used in fine chemical fields such as pharmaceuticals, pesticides, dyes, natural products, and polymers. The hydrogenation reaction of the cyano group of organic nitriles provides an efficient and environmentally friendly method for synthesizing primary amines. However, the products include primary amines, as well as secondary and tertiary amines formed by deamination (NH3) condensation coupling, with poor selectivity. Therefore, how to prevent the condensation reaction during the reduction process and improve the selectivity of primary amines is particularly important. Reported studies have shown that both homogeneous and heterogeneous systems, the catalyst and reaction environment are crucial for improving the selectivity of primary amines. Raney Co, Ni, and other noble metals (Pd, Pt, Ru, and Ir) are commonly used catalysts for the hydrogenation of cyano groups to primary amines in heterogeneous systems, while metal complexes of Ru, Rh, and Fe-, Co-, and Mn-PNP can catalyze the highly selective hydrogenation of various aromatic and aliphatic nitriles to primary amines under homogeneous systems. However, the above methods often need to be carried out under relatively harsh reaction conditions, such as using high concentrations of NH3 or strong bases to inhibit the condensation of primary amines with the imine intermediate of the hydrogenation reaction, and high-temperature and high-pressure H2 as a reducing agent, etc. These all hinder the large-scale application of related catalytic systems.

[0003] The patent document with the publication number CN106582709A discloses a catalyst for the hydrogenation synthesis of aromatic primary amines and its preparation method. The catalyst is composed of Ru and Ni active components supported on an activated carbon carrier. The temperature used in the hydrogenation process of aromatic nitriles is 150°C to 200°C, the pressure is 2 MPa to 10 MPa, and the reducing agent is H2 gas.

[0004] The patent document with the publication number CN110813281A discloses the application of a nano-carbon supported cluster-state palladium-based catalyst in the catalytic hydrogenation of nitrile compounds to prepare primary amines, belonging to the technical field of catalysts for the catalytic hydrogenation of liquid-phase nitrile compounds. Using nano-carbon supported cluster-state palladium as the catalyst, primary amine compounds are highly selectively generated under mild conditions; the catalytic reaction conditions are: reaction temperature 30 - 70°C, and the hydrogen source is ammonia borane.

[0005] The patent document with the publication number CN109651159A discloses a method for selectively reducing nitriles by hydrogen transfer to prepare primary amines. Under mild conditions, using nitrile compounds as raw materials and oxazaborane as a hydrogen transfer reagent, inexpensive metal salts such as copper and iron or readily available iodine are added as additives to further promote the hydrogen transfer reaction, and a series of corresponding primary amines can be selectively synthesized under different conditions. The reaction has high yields and high selectivity.

[0006] The patent document with the publication number CN103965057A discloses a method for preparing primary amines from nitriles. Under the catalysis of a copper compound, the nitrile reacts with potassium borohydride in a solvent. After the reaction is complete, the desired primary amine is obtained through post-treatment. The yield of preparing primary amines is over 80%, and the reaction solvent is easy to purify and recycle, with low cost. The catalyst copper salt is easy to recycle, environmentally friendly, and can be used in industrial production.

[0007] The patent document with the publication number CN101011661 discloses a catalyst for the hydrogenation of aliphatic nitriles to aliphatic primary amines, with a molar ratio composition of nickel∶cobalt∶promoter∶rare earth metal = 100∶0.01 - 2.0∶1 - 15∶0.01 - 1.

[0008] The patent document with the publication number CN1635991A discloses an improvement in the method for preparing primary amines by hydrogenating nitriles. The improvement in this hydrogenation method lies in the use of a hydrogenation catalyst modified in situ with a pre-adsorbed alkali metal carbonate or bicarbonate such as K2CO3 or KHCO3.

[0009] The patent document with the publication number CN1483016A discloses a method for catalytically hydrogenating imines and / or nitriles with a hydrogen-containing gas to prepare amines, in which a shaped Raney catalyst is used as the hydrogenation catalyst, and the catalyst is in the form of a hollow body.

[0010] The patent document with the publication number CN1365965 discloses a method for preparing a mixture of a primary amine of the general formula (I) X-CH2-NH2 (I) and a secondary amine of the general formula (II) by reacting a nitrile of the general formula (III) X-CN (III) with hydrogen in the presence of a Pd-containing catalyst containing 0.1 - 10% (by weight) Pd based on the total weight of the catalyst on a carrier at a temperature of 50 - 250 °C and a pressure of 5 - 350 bar.

[0011] However, the above patents are all proposed in a non-electrochemical system, and most of them use high-temperature and high-pressure hydrogen gas as the hydrogen source. Therefore, it is urgently necessary to design and develop an efficient catalytic system for the selective hydrogenation of cyano groups to primary amines with mild reaction conditions, simple operation, and environmental friendliness.

[0012] Electrochemical hydrogenation is a very attractive method that is expected to replace traditional nitrile hydrogenation to primary amines. In particular, it can be carried out in an aqueous solution under normal conditions (room temperature and atmospheric pressure), directly using water molecules H2O as a proton source. However, at present, the slow kinetics of the hydrogenation reaction, poor functional group tolerance, and unsatisfactory selectivity of primary amines are still the main problems in the electrocatalytic hydrogenation of nitriles to primary amines. Summary of the Invention

[0013] Based on the above problems, the purpose of the present invention is to provide an application of a copper catalyst in the electrocatalytic selective hydrogenation of the cyano group of nitrile organic compounds to prepare primary amines. In this application, the high-selectivity hydrogenation of the terminal cyano group of nitrile organic compounds to synthesize primary amine organic compounds is realized under an electrochemical system. This method has the characteristics of low cost of the required catalyst, stable performance, mild conditions for hydrogenation to prepare primary amines, simple operation, environmental protection, etc., and has good application prospects.

[0014] To achieve the above object, the present invention adopts the following technical solutions:

[0015] Application of a copper catalyst in the electrocatalytic selective hydrogenation of the cyano group of nitrile organic compounds to prepare primary amines.

[0016] Further, the copper catalyst is used as a cathode catalyst in the electrocatalytic selective hydrogenation of the cyano group of nitrile organic compounds to prepare primary amines.

[0017] Further, the structural formula of the nitrile organic compound is: R-CN; wherein, R is selected from substituents of C1~C 12 preferably one of straight-chain or branched alkanes, cycloalkanes, alcohols or carboxylic acids of C1~C 12 In the application of the present invention, the product of the copper catalyst in the electrocatalytic selective hydrogenation of the cyano group of nitrile organic compounds to prepare primary amines is R-CH2-NH2, where the definition of R is the same as that in the structural formula of the nitrile organic compound above.

[0018] In the electrocatalytic reaction, the electrolyte solution in the cathode chamber is saturated with carbon dioxide gas. Introducing CO2 gas into the reaction system, using the reversible reaction between CO2 and primary amine molecules to protect the primary amine product of cyano hydrogenation, so as to improve the reaction selectivity and increase the primary amine yield. In addition, the copper catalyst in the present invention can cooperate with the CO2 molecules dissolved in the solution to jointly inhibit side reactions such as hydrogen production, CO2 reduction, and primary amine imine condensation, and improve the primary amine yield.

[0019] Further, during the reaction, carbon dioxide gas is continuously introduced into the electrolyte solution at a flow rate of 10~60 mL / min, preferably 30 mL / min.

[0020]

[0021] ​Furthermore, the reaction potential of the electrocatalytic reaction is -0.3 to -1.3 V relative to the reversible hydrogen electrode, and the reaction time is 15 minutes to 5 hours. Preferably, the reaction potential of the electrocatalytic reaction is -0.3 to -0.9 V relative to the reversible hydrogen electrode, more preferably -0.3 to -0.7 V, and even more preferably -0.5 to -0.7 V, at which time the selectivity for primary amines is higher.

[0022] Furthermore, the electrocatalytic reaction is one or more of a constant potential method, a constant current method, or a linear sweep voltammetry method.

[0023] Furthermore, in the electrocatalytic reaction, the anode catalyst is a ruthenium-iridium oxide catalyst.

[0024] Furthermore, in the electrocatalytic reaction, in the electrolyte solutions used in the cathode chamber and the anode chamber, the electrolyte is a soluble salt of a metal, and the solvent is water or a mixed solution of water and an alcohol. Among them, the solvent water serves both as the electrolyte solvent and directly as the proton source for nitrile hydrogenation under cathode polarization.

[0025] Furthermore, the soluble salt of the metal is one or more of a soluble carbonate, bicarbonate, sulfate, nitrate, phosphate, or hydroxide of the metal.

[0026] Furthermore, the metal is selected from one of potassium and sodium.

[0027] Furthermore, in the electrocatalytic reaction, the electrolytic cell adopts an "H"-type cathode and anode isolation structure.

[0028] Furthermore, the cathode chamber and the anode chamber are isolated by a proton exchange membrane.

[0029] Furthermore, in the reaction, the concentration of the nitrile organic compound in the electrolyte is 0.01 to 10 mol / L, preferably 0.1 to 2.5 mol / L, and more preferably 0.1 to 1.0 mol / L. At this time, the selectivity for primary amines is higher.

[0030] Furthermore, the reaction is carried out under normal temperature and normal pressure conditions. Exemplarily, the temperature of the reaction includes but is not limited to 15 to 30 °C, below 100 °C, etc. Exemplarily, the pressure of the reaction includes but is not limited to 100 kPa, 80 kPa to 5 MPa, etc.

[0031] Furthermore, in the electrocatalytic reaction, the copper catalyst is metallic copper particles, preferably one or more of copper nanosheets, copper nanowires, nano- and micro-sized copper powders.

[0032] Further, the copper catalyst is nano - copper, and the structure of the nano - copper includes a copper foil substrate and a copper nanosheet array formed in - situ on the copper foil substrate. Exemplarily, the nano - copper can be prepared by referring to the following method:

[0033] 1) Immerse the cleaned copper sheet into a mixed solution of ammonium persulfate and sodium hydroxide, and let it react at room temperature and stand still. Prepare an array of copper oxide nanosheets directly on the surface of the copper sheet;

[0034] 2) Wash and dry the obtained sample above, and then perform annealing treatment;

[0035] 3) The annealed sample is further reduced at a constant potential in an electrochemical system to in - situ reduce copper oxide to metallic copper.

[0036] Preferably, in step 1) above, the size of the cleaned copper sheet is: 1.0 cm × 2.5 cm × 0.15 mm.

[0037] Preferably, in step 1) above, in the mixed solution, the concentration of ammonium persulfate ((NH4)2S2O8) is 0.133 mol / L, and the concentration of sodium hydroxide (NaOH) is 2.667 mol / L.

[0038] Preferably, in step 1) above, the reaction time is 4 hours.

[0039] Preferably, in step 2) above, the washing method is washing with deionized water and / or ethanol.

[0040] Preferably, in step 2) above, the drying method is natural drying in air.

[0041] Preferably, in step 2) above, the annealing temperature is: 250 °C, the time is 2 hours, and the annealing atmosphere is air.

[0042] Preferably, in step 3) above, the electrolyte solution in the electrochemical system is: 0.5 mol / L aqueous solution of potassium bicarbonate KHCO3.

[0043] Preferably, in step 3) above, the method for reducing copper oxide is: the constant - potential method.

[0044] Preferably, in step 3) above, the polarization potential of the constant - potential method is: - 0.7 V (relative to the reversible hydrogen electrode).

[0045] Preferably, in step 3) above, the constant - potential reduction time is: 2 - 15 minutes.

[0046] Unless otherwise specified, any range recorded in the present invention includes the end values and any numerical value between the end values, as well as any sub - range constituted by any numerical value between the end values or the end values.

[0047] The beneficial effects of the present invention are as follows:

[0048] In the application provided by the present invention, a reaction system for the selective hydrogenation of organic nitriles to primary amines on a nano-copper catalyst in a pH-neutral liquid water phase electrolyte at ambient temperature and pressure is provided. In a normal temperature and pressure liquid water phase electrolyte, the highly selective hydrogenation of the terminal cyano group of organic nitriles to primary amines is realized. This reaction system has the advantages of high selectivity and conversion rate, low cost, no need for high temperature and high pressure, and no need for organic solvents to participate in the reaction, which is conducive to the application of green chemistry. Description of the Drawings

[0049] The following further details the specific embodiments of the present invention with reference to the drawings.

[0050] Figure 1 Scanning electron microscope image showing the microscopic morphology of the self-supporting copper nanosheet catalyst prepared in Example 1.

[0051] Figure 2 Transmission electron microscope image showing the microscopic morphology and structure of the self-supporting copper nanosheet catalyst prepared in Example 1.

[0052] Figure 3 Glancing-incidence X-ray powder diffraction pattern showing the self-supporting copper nanosheet catalyst prepared in Example 1.

[0053] Figure 4 Electrochemical characterization results of the potentiodynamic scan and potentiostatic reduction of the terminal cyano group hydrogenation reaction in Example 2. The solution is a 0.5 mol / L potassium bicarbonate aqueous solution saturated with CO2 gas, and 0.5 mol / L acetonitrile (CH3CN) is added thereto.

[0054] Figure 5 Nuclear magnetic resonance spectroscopy (1H NMR) characterization results of the product under the preferred conditions in Example 2 and current efficiency and liquid phase selectivity analysis of the products (ethylamine EtNH2, diethylamine Et2NH, triethylamine Et3N).

[0055] Figure 6 Electrochemical characterization results of the potentiodynamic scan of the effect of acetonitrile concentration on the terminal cyano group hydrogenation reaction in Example 3. The solution is a 0.5 mol / L potassium bicarbonate aqueous solution saturated with CO2 gas, and 0.05 - 5.0 mol / L acetonitrile (CH3CN) is added thereto.

[0056] Figure 7 Scanning electron microscope image showing the microscopic morphology of the electrodeposited copper nano- and micro-particle catalysts prepared in Example 5.

[0057] Figure 8 Scanning electron microscope image showing the microscopic morphology of the self-supporting copper nanowire catalyst prepared in Example 6. Detailed implementation mode

[0058] To more clearly illustrate the present invention, the present invention will be further described below in conjunction with preferred embodiments and the accompanying drawings. Similar components in the drawings are denoted by the same reference numerals. Those skilled in the art should understand that the content specifically described below is illustrative rather than restrictive, and should not be used to limit the protection scope of the present invention.

[0059] The catalytic hydrogenation of the cyano group of organic nitriles is an efficient method for synthesizing primary amines, but it is still relatively difficult to achieve high selectivity for primary amines. High concentrations of NH3 or strong bases are often required to inhibit side reactions, as well as harsh reaction conditions such as high-temperature and high-pressure H2 as a reducing agent. The present invention provides an electrocatalytic method that realizes the highly selective hydrogenation of the terminal cyano group of organic nitriles to prepare primary amines in an aqueous electrolyte at room temperature and atmospheric pressure.

[0060] Specifically, the present invention provides an electrocatalytic method for preparing primary amines from nitriles. The catalyst is a simple and easily available metal-state nano-copper powder. The preferred reaction system is an aqueous electrolyte at room temperature and atmospheric pressure and neutral. The electrolyte composition is potassium bicarbonate saturated with CO2 gas and the general formula (1) (R-CN; wherein, R is selected from C1 to C 12 substituent, preferably C1 to C 12 a straight-chain or branched-chain alkane, cycloalkane, alcohol or carboxylic acid.

[0061] Example 1

[0062] Preparation of a self-supporting metal-state copper nanosheet array electrode. This method is a reported conventional method, and the present invention has no limitation on it. It mainly includes the following steps:

[0063] Clean the copper sheet: Electrochemical polishing or cleaning with deionized water. Specifically, for electrochemical polishing: Constant potential (3.0V, the reference electrode is a saturated Ag / AgCl electrode) in 85% concentrated phosphoric acid H3PO4 for 5 minutes of electrochemical polishing, and then wash with ultrapure water and dry with high-purity N2 gas.

[0064] Immerse the above-mentioned cleaned copper sheet with dimensions of 1.0 cm × 2.5 cm × 0.15 mm into a mixed solution of ammonium persulfate and sodium hydroxide (wherein, in this mixed solution, the concentration of ammonium persulfate (NH4)2S2O8 is 0.133 mol / L, and the concentration of sodium hydroxide is 2.667 mol / L), and let it stand at room temperature for 4 hours to directly prepare a copper oxide CuO nanosheet array on the surface of the copper sheet. After washing and drying the obtained sample, anneal it in an air atmosphere (annealing conditions: temperature is 250 °C, annealing time is 2 hours, annealing atmosphere is air, and the cooling method after annealing is natural cooling). The annealed sample is then subjected to constant potential reduction in an electrochemical system to in-situ reduce the copper oxide to metal-state copper.

[0065] Among them, the constant potential reaction conditions for the electrochemical reduction of copper oxide to prepare metallic copper include: the electrolyte solution is an aqueous solution of potassium bicarbonate with a concentration of 0.5 mol / L, the polarization potential is -0.7 V (relative to the reversible hydrogen electrode), the constant potential reduction time is 2 to 15 minutes (taking a copper sheet with dimensions of 1.0 cm × 2.5 cm × 0.15 mm as an example), and after the reaction is completed, it also includes the steps of washing with deionized water and natural drying in an air atmosphere.

[0066] Figure 1 Scanning electron microscopy image showing the microscopic morphology of the self-supporting copper nanosheet catalyst prepared in this example.

[0067] Figure 2 Transmission electron microscopy image showing the microscopic morphology and structure of the self-supporting copper nanosheet catalyst prepared in this example.

[0068] Figure 3 Slightly incident X-ray powder diffraction pattern showing the self-supporting copper nanosheet catalyst prepared in this example. The diffraction peaks of the self-supporting copper nanosheet catalyst in the obtained spectrum exhibit the characteristic diffraction peaks of complete metallic copper, indicating that the obtained material is a metallic state nanocopper catalyst.

[0069] Example 2

[0070] A synthesis method for electrocatalytic hydrogenation of nitriles to primary amines based on nanocopper, taking the hydrogenation of acetonitrile to prepare ethylamine as an example, includes the following steps:

[0071] In the cathode chamber, the substrate acetonitrile (0.5 mol / L) is dissolved in an aqueous solution of potassium bicarbonate (0.5 mol / L), CO2 gas is introduced until saturated, and the CO2 gas is continuously introduced into the reaction solution with a flow rate of 30 mL / min; the cathode is polarized at -0.7 V (relative to the reversible hydrogen electrode) for 2 hours by the constant potential method to complete the hydrogenation reaction to primary amines. Among them, in the electrocatalytic reaction, the electrolytic cell adopts an "H"-type cathode and anode isolation structure, and the isolation medium is a proton exchange membrane; the cathode catalyst is the catalyst prepared in Example 1. The analysis of the hydrogenation reaction product is carried out by nuclear magnetic resonance spectroscopy (proton spectrum), and the chemical shift peak area of the hydrogen on the methylene CH2 obtained by the hydrogenation of the cyano CN is selected as the basis for quantitative analysis of the product. The total current efficiency of the product primary amine (i.e., ethylamine) is 94%, and the liquid phase selectivity is 99%.

[0072] When the CO2 gas is replaced with argon gas Ar and other conditions remain unchanged, the total current efficiency of the product primary amine drops to 40%, and the liquid phase selectivity drops to 48%.

[0073] Figure 4Show the electrochemical characterization results of potentiodynamic scanning and potentiostatic reduction of the terminal cyano hydrogenation reaction in this example. The solution is a 0.5 mol / L potassium bicarbonate aqueous solution saturated with CO2 gas, and 0.5 mol / L acetonitrile (CH3CN) is added thereto.

[0074] Figure 5 Show the characterization results of nuclear magnetic resonance spectroscopy (1H NMR) of the product under the preferred conditions in this example and the current efficiency and liquid-phase selectivity analysis of the products (ethylamine EtNH2, diethylamine Et2NH, triethylamine Et3N).

[0075] Example 3

[0076] Repeat Example 2, except that the reaction conditions are changed as described in Table 1, and the other conditions remain unchanged. The change results of the primary amine selectivity in the product are shown in Table 1.

[0077]

[0078] Table 1

[0079] Serial number <![CDATA[Acetonitrile concentration (mol.L -1 )]]> Total current efficiency (%) Liquid phase selectivity (%) 1 0.05 88 95 2 0.1 91 94 3 1.0 93 94 4 2.5 87 88 5 5.0 64 64 Hydrogenation polarization potential (V vs RHE) 6 -0.3 88 99 7 -0.5 94 98 8 -0.9 81 94 9 -1.1 79 93 Electrolyte 10 <![CDATA[0.5M PBS (pH: 6.8), CO2]]> 32 98 11 <![CDATA[0.5M PBS (pH: 8.0), CO2]]> 43 97 12 <![CDATA[0.1M KOH,CO2]]> 76 76

[0080] Figure 6 Show the potentiodynamic scanning electrochemical characterization results of the effect of acetonitrile concentration on the terminal cyano hydrogenation reaction in this example. The solution is a 0.5 mol / L potassium bicarbonate aqueous solution saturated with CO2 gas, and 0.05 - 5.0 mol / L acetonitrile (CH3CN) is added thereto.

[0081] Example 4

[0082] Results when the reaction substrate is changed to the organic nitrile R-CN (I) of the general formula (1), where R is selected from one of straight-chain or branched alkanes, cycloalkanes, alcohols or carboxylic acids having C1 - C 12 The method steps are the same as those in Example 2, and the primary amine selectivity is shown in Table 2.

[0083]

[0084] Table 2

[0085]

[0086]

[0087] Example 5

[0088] Repeat Example 2, except that the cathode catalyst is electrodeposited copper nano- and micro-particles, and the particle size distribution is as described in Table 1, and the other conditions remain unchanged. The change results of the primary amine selectivity in the product are shown in Table 1.

[0089] Preparation method of electro-deposited copper nano- and micro-particles: Immerse a cleaned copper sheet (with the same size specifications and cleaning method as in Example 2) into a mixed solution of 0.5 mol / L H2SO4 and 0.1 mol / L CuSO4, and reduce and grow at a constant potential of -0.5 V (relative to the Ag / AgCl reference electrode) for different times (such as: 1, 2, 5, 7.5, 10 minutes) to prepare Cu particles with different particle sizes. The morphologies are successively as Figure 7 shown in a - e of

[0090] Table 3

[0091] Serial number Particle size distribution of electrodeposited copper particles Total current efficiency (%) Liquid phase selectivity (%) 1 637.3 ± 190.7 nm 93 99 2 790.7 ± 182.3 nm 92 99 3 1.462 ± 0.292 μm 92 98 4 1.796 ± 0.341 μm 92 96 5 2.591 ± 0.579 μm 91 95

[0092] Example 6

[0093] Repeat Example 2, with the difference that the cathode catalyst is electro-deposited copper nanowires, and the morphology is as Figure 8 shown. With the remaining conditions unchanged, the total current efficiency of the primary amine product (i.e., ethylamine) of acetonitrile hydrogenation still reaches 94%, and the liquid-phase selectivity is 99%.

[0094] Preparation of the above self-supporting metallic copper nanowire electrode. This method is similar to Example 1, with the difference that the copper sheet (size: 1.0 cm × 2.5 cm × 0.15 mm) is replaced by copper foam (with the same size), and in addition, the soaking time of the copper foam in the mixed solution of ammonium persulfate and sodium hydroxide is shortened to 15 - 30 minutes, with the remaining conditions unchanged.

[0095] Obviously, the above embodiments of the present invention are merely examples for clearly illustrating the present invention, rather than limitations on the implementation manners of the present invention. For those of ordinary skill in the art, other different forms of changes or modifications can be made based on the above description. It is impossible to list all the implementation manners here. Any obvious changes or modifications derived from the technical solutions of the present invention still fall within the protection scope of the present invention.

Claims

1. Application of a copper catalyst in the reaction of electrocatalytic selective hydrogenation of nitrile organic compounds to prepare primary amines, characterized in that, The copper catalyst is used as a cathode catalyst in the electrocatalytic selective hydrogenation of the cyano group of nitrile organic compounds to prepare primary amines; In the electrocatalytic reaction, the electrolyte solution in the cathode chamber is saturated with carbon dioxide gas; During the reaction, carbon dioxide gas is continuously introduced into the electrolyte solution at a flow rate of 10 - 60 mL / min; In the electrocatalytic reaction, the copper catalyst is metallic copper particles; In the electrocatalytic reaction, the anode catalyst is a ruthenium-iridium oxide catalyst; In the electrocatalytic reaction, in the electrolyte solutions used in the cathode chamber and the anode chamber, the electrolyte is a soluble salt of a metal; In the electrocatalytic reaction, the solvent in the electrolyte solution is water or a mixed solution of water and alcohol.

2. The application according to claim 1, wherein The structural formula of the nitrile organic compound is: R-CN; wherein, R is selected from C1 to C 12 substituent.

3. The application according to claim 2, characterized in that The R is selected from one of straight-chain or branched-chain alkanes, cycloalkanes, alcohols or carboxylic acids having C1 to C 12 and having a straight-chain or branched-chain structure, cycloalkane, alcohol or carboxylic acid.

4. The application according to claim 1, wherein The reaction potential of the electrocatalytic reaction is -0.3 to -1.3 V relative to the reversible hydrogen electrode, and the reaction time is 15 minutes to 5 hours.

5. The application according to claim 4, characterized in that The electrocatalytic reaction is one or more of the constant potential method, the constant current method, or the potential sweep method.

6. The application according to claim 1, wherein The soluble salt of the metal is one or more of the soluble carbonate, bicarbonate, sulfate, nitrate, phosphate, and hydroxide of the metal.

7. The application according to claim 6, characterized in that, The metal is selected from one of potassium and sodium.

8. The application according to claim 1, characterized in that, In the electrocatalytic reaction, the electrolytic cell adopts an "H"-type cathode and anode isolation structure.

9. The application according to claim 8, wherein, The cathode chamber and the anode chamber are isolated by a proton exchange membrane.

10. The application according to claim 1, characterized in that, In the reaction, the concentration of the nitrile organic compound in the electrolyte solution is 0.01 - 10 mol / L.

11. The application according to claim 1, wherein In the reaction, the concentration of the nitrile organic compound in the electrolyte solution is 0.1 - 1.0 mol / L.

12. The application according to claim 1, characterized in that The reaction is carried out under normal temperature and pressure conditions.

13. The application according to claim 1, wherein In the electrocatalytic reaction, the copper catalyst is one or more of copper nanosheets, copper nanowires, nano- and micro-copper powders.

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