Electrochemical olefin reduction hydrogenation or deuteration method

Abstract

The invention discloses an electrochemical olefin reduction hydrogenation or deuteration method, and belongs to the technical field of electrolysis processes for producing compounds. The method comprises the following steps: correspondingly selecting water or deuterium water according to the needs of hydrogenation or deuterium substitution, and mixing the water or deuterium water with an olefin compound, an electrolyte and an organic solvent to obtain an electrochemical reaction solution; the electrochemical reaction liquid is electrolyzed, hydrogen atoms of water or deuterium atoms of deuterium water and olefinic bonds in the olefin compound are subjected to addition, and the saturated alkane compound or the saturated deuterated alkane compound is obtained through recovery. The method has the advantages of simple steps, wide substrate application range and high flexibility, and has a good application prospect in industrial production.

Description

Technical Field

[0001] The invention relates to the technical field of electrolytic process for producing compounds, in particular to a method for electrochemical olefin reduction hydrogenation or deuteration. Background Art

[0002] In the production of industrial raw materials and drug synthesis, olefin reduction reaction can achieve defunctionalization simply and conveniently. It is widely used in the preparation of large-scale industrial raw materials such as fine chemicals, pharmaceuticals, and pesticides, and plays a pivotal role. For the application of olefin reduction reaction, a suitable and efficient catalytic mode is essential.

[0003] Traditional reduction reactions are mainly based on direct use of metal heterogeneous catalytic activation of hydrogen reduction. The most famous catalyst is Raney Ni, which was discovered by American engineer Maury Raney in 1926. Raney nickel is a porous structure catalyst, a fine-grained solid composed of nickel-aluminum alloy, which is widely used in the hydrogenation of various unsaturated groups, such as vegetable oil hydrogenation. In addition to Raney nickel, researchers have also developed many processes that use metal complexes to homogeneously activate hydrogen to achieve hydrogenation reactions. However, the raw material for this type of hydrogenation reaction requires hydrogen. Hydrogen molecules are small in size and difficult to store and transport. As a flammable and explosive gas, improper operation may cause serious safety accidents. Therefore, technicians hope to avoid the large-scale use of hydrogen in current production.

[0004] In order to solve the above-mentioned problems of hydrogen production, various processes based on transfer hydrogenation reactions have emerged. While avoiding the use of hydrogen, these methods have milder reaction conditions. However, they require the introduction of equivalent or excess reducing agents during the hydrogenation process, which results in insufficient atom economy. Therefore, researchers have tried to find new synthetic pathways, and the electrochemical method has received extensive attention and research due to its mild reaction conditions, no need for reducing agents, and high atom utilization.

[0005] For example, the Chinese invention patent with the publication number CN114807983A discloses an electrochemical system for realizing the selective catalytic hydrogenation of unsaturated alkenes and alkynes, which realizes the selective catalytic hydrogenation of unsaturated alkenes and alkynes by electrochemical methods. The system structure consists of four parts: a control and display module, a feed gas control module, an electrochemical work control and reaction module, and an electrolyte control module. The hydrogen atoms produced by electrolysis are directly used for the selective catalytic hydrogenation reaction of unsaturated alkenes and alkynes through the electrochemical technology of electrolysis of water to produce hydrogen, so as to achieve a higher conversion rate and excellent selectivity of gaseous unsaturated alkenes and alkynes. The main advantage of this invention is that it avoids the use of highly dangerous hydrogen, uses electrocatalysis to reduce protons to active hydrogen at room temperature, and controls the hydrogen atom flux by controlling the cathode potential; in the process, the catalytic reaction chemical chamber and the electrochemical chamber catalyzed by the metal film are separated, and the electrochemical and hydrogenation reactions are separated, and the product separation is easy; the metal film used has selective permeability to hydrogen, which can bypass the formation of gaseous hydrogen, and the hydrogen atoms produced by the electrode directly participate in the electrocatalysis. However, the efficiency of this scheme is limited by the flux of hydrogen atoms, resulting in limited production capacity in actual industrial production. In addition, this method is designed based on catalytic hydrogenation, and is not suitable for deuteration reactions similar to hydrogenation, making it difficult to flexibly achieve conversions between hydrogenation and deuteration. And its substrate adaptability is narrow, especially its compatibility with natural multi-substituted olefins is poor. This may be because in natural multi-substituted olefins, as the substituents or chain lengths on the olefins increase, the electron cloud density of the olefins decreases, resulting in a decrease in its electrophilicity and a weakened interaction with the catalytic substance, making the catalytic hydrogenation reaction more difficult; the increase in substituents will increase the steric hindrance of the olefins, making the catalytic hydrogenation reaction more difficult.

[0006] In summary, a method is provided which has simple steps, wide applicability to multi-substituted substrates, and can be used for olefin reduction hydrogenation or deuteration, which is of great significance to the fields of industrial raw material production and drug synthesis. Summary of the invention

[0007] In view of the above-mentioned defects of the prior art, in a first aspect of the present invention, a method for electrochemical olefin reduction hydrogenation or deuteration with simple steps, wide substrate applicability and high flexibility is provided, comprising the following steps: Selecting water or deuterated water according to the requirements of hydrogenation or deuteration, mixing water or deuterated water with an olefin compound, an electrolyte, and an organic solvent to obtain an electrochemical reaction solution; electrolyzing the electrochemical reaction solution to allow hydrogen atoms of water or deuterium atoms of deuterated water to add to olefin bonds in the olefin compound, and recovering a saturated alkane compound or a saturated deuterated alkane compound; The cathode electrode of electrolysis is nitrogen-doped carbon felt loaded with metal, and its preparation method comprises the following steps: Step (1), mixing carbon felt, melamine and ethanol and subjecting the mixture to a reflux reaction to obtain pretreated carbon felt; Step (2), immersing the pretreated carbon felt in a mixed solution to carry out a polymerization reaction to obtain a polymer-coated carbon felt; wherein the mixed solution is prepared by mixing melamine, paraformaldehyde and a solvent; Step (3), calcining the polymer-coated carbon felt in a protective gas atmosphere to obtain nitrogen-doped carbon felt; Step (4), immersing the nitrogen-doped carbon felt in a metal salt solution for adsorption, thereby obtaining nitrogen-doped carbon felt adsorbing the metal salt; wherein the metal salt solution is prepared by dissolving a metal salt in a solvent, and the metal salt is selected from at least one of rhodium octanoate and rhodium chloride; Step (5), using the nitrogen-doped carbon felt adsorbing the metal salt as a cathode, and electrodepositing to obtain the nitrogen-doped carbon felt loaded with metal.

[0008] Preferably, the olefin compound includes monosubstituted olefins and polysubstituted olefins; Wherein, the structural formula of the monosubstituted olefin is as follows: ; In the formula, R is selected from one of acetanilide, methyl decanoate, decanoyl, carbazolyl, octadecyloxy, tetradecyl, naphthyl, biphenyl, methyl naphthyl, and 3,5-dichlorophenyl; The multi-substituted olefin includes at least one of squalene, terpineol, linalool, caryophyllene, progesterone, adrenosterone, boldenone, idebenone, and N-acetyl-1-(4-methoxyphenyl)-1-propenamine.

[0009] The electrolyte is used to improve the conductivity of the electrolyte and provide a conductive path for the movement of ions. Those skilled in the art can use common electrolyte types, such as halide salts, organic ammonium salts, etc.

[0010] Preferably, the electrolyte includes at least one of sodium fluoride, sodium chloride, sodium bromide, sodium iodide, tetrabutylammonium tetrafluoroborate, tetrabutylammonium fluoride, tetrabutylammonium chloride, tetrabutylammonium bromide, and tetrabutylammonium iodide.

[0011] Organic solvents are used to dissolve raw materials in the electrolyte, promote the dispersion of various substances and create a suitable reaction environment for electrolysis. The selection of organic solvents affects the ionic conductivity, electrochemical stability and compatibility with electrode materials of the electrolyte. It should promote the dissolution and migration of ions, and should have a lower viscosity to reduce the resistance to ion migration. In addition, the solvent should also have a suitable boiling point and chemical stability to ensure safety and reliability during the electrolysis operation. Under the above principles, methanol, ethanol, isopropanol, tert-butyl alcohol, tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, etc. are all suitable solvents for the present invention.

[0012] Preferably, the organic solvent includes at least one of methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, and N,N-dimethylformamide.

[0013] The above organic solvent types are all suitable for hydrogenation or deuteration reaction processes. When the raw material is deuterated water, in order to further optimize the deuteration effect of electrolysis, deuterated organic solvents can also be used as solvents. In saturated deuterated alkane compounds, the source of deuterium atoms is deuterated water.

[0014] More preferably, when the raw material is deuterated water, a deuterated substance of the organic solvent is used.

[0015] Controlling the ratio of raw materials within a suitable range not only helps to reduce waste and control production costs, but also helps to reduce the generation of by-products and obtain the target product with high efficiency. In addition, the electrolysis of the present invention can be carried out in a wide temperature range, the electrolysis reaction has high atomic utilization and reactivity, and hydrogenation or deuteration can be achieved without inputting a large current.

[0016] Preferably, the molar ratio of the water or deuterated water to the olefin compound is 1:140-1400.

[0017] Preferably, the molar ratio of the electrolyte to the olefin compound is 1:0.1-20.

[0018] Preferably, the volume ratio of the organic solvent to the water or deuterated water is 1:0.1-10.

[0019] Preferably, the electrolysis temperature is 10-80°C.

[0020] Preferably, the direct current of the electrolysis is 2-40 mA, and the electrolysis time is 1-36 h.

[0021] Preferably, in step (1), the mass ratio of carbon felt, melamine and ethanol is 1:1-6:20; the temperature of the reflux reaction is 70-90°C, and the time is 12-36 h.

[0022] Preferably, in step (2), the mass ratio of the pretreated carbon felt, melamine, paraformaldehyde and solvent is 1:1-20:1-20:10-50; the polymerization step is first reacting at 100-130°C for 1-4 h, and then reacting at 150-180°C for 12-72 h.

[0023] Preferably, in step (3), the calcination temperature is 600-900°C and the calcination time is 1-3 h.

[0024] Preferably, in step (4), the mass ratio of nitrogen-doped carbon felt, metal salt and solvent is 1:0.05-0.5:40-60; the adsorption is carried out at room temperature for 1-12 h.

[0025] Preferably, in step (5), the current density of the electrodeposition is 1-40 mA / cm 2 , time is 1-20h; a separate electrolytic cell is used, and the electrodeposition electrolyte used in the cathode chamber and the anode chamber is prepared by electrodeposition electrolyte, electrodeposition organic solvent and water.

[0026] Further preferably, in the electrodeposition electrolyte, the electrodeposition electrolyte includes at least one of sodium fluoride, tetrabutylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium iodide; and the electrodeposition organic solvent includes at least one of tetrahydrofuran, 1,4-dioxane, methanol, ethanol, isopropanol, and tert-butanol.

[0027] Further preferably, in the electrodeposition electrolyte, the concentration of the electrodeposition electrolyte is 0.05-0.2 mol / L; and the mass ratio of the electrodeposition organic solvent to water is 0-9:1.

[0028] The anode electrode can be any common electrode in the art, including a metal electrode and a carbon electrode. The type of electrode can be flexibly changed with the shape of the electrolytic cell. For example, under the conditions of a separation cell, the carbon electrode can be carbon felt, carbon paper, carbon cloth, etc.

[0029] Preferably, the anode electrode for electrolysis is selected from an aluminum electrode, a copper electrode, a lead electrode, a platinum electrode, and a carbon electrode.

[0030] Further preferably, the carbon electrode comprises one of carbon felt, carbon paper and carbon cloth.

[0031] Those skilled in the art can select a suitable type of solvent as a mixed solution or a metal salt solution, and the selected types include methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, N,N-dimethylformamide, etc. and mixtures thereof. After the electrolysis is completed, the technician can adopt a recovery method commonly used in the art according to actual conditions. For example, under small and medium-scale electrolysis conditions such as laboratory preparation, the target product can be easily obtained by extraction, silica gel dry loading, gradient elution, etc. Under the conditions of scaled-up production, other forms of industrial-scale recovery methods can also achieve the above purpose.

[0032] Based on the above technical solution, taking monosubstituted olefin as an example, the reaction formula of electrolysis of the present invention is as follows: When using water for electrolysis: ; When using deuterium water for electrolysis: .

[0033] The conditions of this reaction system are mild, and the cathode electrode is used as a catalytic electrode in electrolysis. The reaction is efficient and has a long life. The device has good applicability, is compatible with a variety of electrochemical devices, is suitable for flow reactors, and has good room for expansion in the industrial field. The present invention adopts electrolysis to prepare the target product, without generating additional waste, and has the advantages of high current efficiency and green economy. The present invention introduces a highly active small-sized metal catalyst into the nitrogen-doped carbon felt by making a homemade cathode. Compared with other existing cathode forms, the metal-loaded nitrogen-doped carbon felt can enhance the activity of hydrogen produced by electrolysis and can contact and add to large sterically hindered olefins. Through metal catalytic guidance, it can be compatible with complex substituted groups and other easily reduced functional groups, and the metal active species are small in size, and can also reduce multi-substituted natural olefin molecules to add hydrogen atoms or deuterium atoms to olefin bonds with high selectivity. The reaction system has fewer types of raw materials, does not require additional reducing agents, has good electrochemical properties, generates less waste, is convenient for post-processing, and has good flexibility.

[0034] Compared with the prior art, the present invention has the following advantages and beneficial effects: The present invention provides a method for electrochemical olefin reduction hydrogenation or deuteration, which has the advantages of simple steps, wide substrate applicability and high flexibility, and has good application prospects in industrial production. DETAILED DESCRIPTION

[0035] The present invention is further described below by way of examples, but the present invention is not limited to the scope of the examples. The experimental methods in the following examples without specifying specific conditions are carried out according to conventional methods and conditions, or selected according to the product specifications.

[0036] Example 1 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0037] 0.4 mmol acrylanilide (59.6 mg) and 0.8 mmol sodium chloride (46.8 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL methanol and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 1 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. Gradient elution with petroleum ether and ethyl acetate was used to separate the corresponding saturated alkane compounds with a yield of 99%.

[0038] In this embodiment, the nitrogen-doped carbon felt loaded with rhodium is prepared by the following method: Step (1), mixing carbon felt, melamine and ethanol, reflux reacting at 80°C and drying to obtain pretreated carbon felt for adsorbing melamine; wherein the mass ratio of carbon felt, melamine and ethanol is 1:4:20; Step (2), dissolving melamine and paraformaldehyde in dimethyl sulfoxide to obtain a mixed solution, and then immersing the carbon felt adsorbed with melamine in the mixed solution; wherein the mass ratio of the pretreated carbon felt, melamine, paraformaldehyde and dimethyl sulfoxide is 1:3.5:1.75:30; first heating at 110°C for 1 h, and then heating to 160°C for 12 h to prepare a polymer-coated carbon felt; Step (3), calcining the polymer-coated carbon felt at 800° C. for 1 h in an argon atmosphere to prepare nitrogen-doped carbon felt; Step (4), immersing the nitrogen-doped carbon felt in an isopropanol solution of rhodium octanoate, stirring at room temperature for 12 h for adsorption, and then taking out and drying to obtain the nitrogen-doped carbon felt adsorbed with rhodium octanoate; wherein the mass ratio of the nitrogen-doped carbon felt, rhodium octanoate and isopropanol is 1:0.1:50; Step (5), using the nitrogen-doped carbon felt adsorbing the metal salt as a cathode, and electrodepositing to obtain the nitrogen-doped carbon felt loaded with metal.

[0039] A separate electrolytic cell was set up, in which the electrolyte in the cathode chamber was prepared by 0.8 mmol tetrabutylammonium bromide, 5 mL tert-butyl alcohol and 5 mL water, and the electrolyte in the anode chamber was prepared by 0.8 mmol sodium fluoride and 10 mL water; the nitrogen-doped carbon felt adsorbed with rhodium octanoate was inserted into the cathode chamber as the cathode, and a carbon rod was used as the anode, and a power supply was connected at 5 mA / cm 2 The rhodium-loaded nitrogen-doped carbon felt was obtained by deposition at a current density of 100 nm for 3 h.

[0040] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.52 – 7.45 (m, 2H), 7.29(t, J = 7.6 Hz, 2H), 7.08 (t, J = 7.2 Hz, 1H), 2.38 (q, J = 7.2 Hz, 2H), 1.23(t, J = 7.6 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 172.3, 138.0, 129.0, 124.2,119.9, 30.7, 9.7. Example 2 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0041] 0.4 mmol of methyl undecenoate (79.2 mg) and 0.8 mmol of sodium chloride (46.8 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL of methanol and 2.5 mL of water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 4 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. Gradient elution with petroleum ether and ethyl acetate was used to separate the corresponding alkane product with a yield of 99%.

[0042] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0043] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 3.68 (s, 3H), 2.32 (t, J= 7.6 Hz, 2H), 1.66 - 1.60 (m, 2H), 1.31 - 1.28 (m, 14H), 0.89 (t, J = 6.8Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 174.3, 51.4, 34.1, 31.9, 29.6, 29.5, 29.3,29.3, 29.2, 25.0, 24.9, 22.7, 14.1. Example 3 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0044] 0.4 mmol undecylenic acid (73.6 mg) and 0.8 mmol sodium bromide (82.3 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL methanol and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. The electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 2 h at 60 °C. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, and the yield was 60%.

[0045] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0046] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 2.38 (t, J = 7.4 Hz, 2H), 1.69 - 1.62 (m, 2H), 1.33 - 1.29 (m, 14H), 0.91 (t, J = 6.6 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 180.5, 34.1, 31.9, 29.6, 29.5, 29.5, 29.3, 29.3, 29.1,29.1, 24.7, 22.7, 14.1. Example 4 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0047] 0.4 mmol N-vinylcarbazole (77.2 mg) and 0.8 mmol sodium bromide (82.3 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL methanol and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. The electrochemical reaction solution was stirred and electrolyzed at 10 mA DC for 5 h at 60°C. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, with a yield of 75%.

[0048] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0049] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.18 (d, J = 8.0 Hz, 2H), 7.56 - 7.47 (m, 4H), 7.32 - 7.29 (m, 2H), 4.43 (q, J = 7.2 Hz, 2H), 1.49 (t,J = 7.4 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 140.0, 125.6, 123.0, 120.5, 118.8,108.5, 37.5, 13.9. Example 5 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0050] 0.4 mmol octadecyl vinyl ether (118.4 mg) and 0.8 mmol tetrabutylammonium bromide (257.9 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL tert-butanol and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 5 mA direct current for 10 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, and the yield was 87%.

[0051] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0052] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 3.52 - 3.41 (m, 4H), 1.61- 1.56 (m, 2H), 1.28 - 1.21 (m, 33H), 0.91 (t, J = 6.6 Hz, 3H); 13 C NMR (101MHz, CDCl3) δ 70.8, 66.1, 32.0, 29.9, 29.7, 29.7, 29.6, 29.6, 29.4, 26.2,22.7, 15.3, 14.1. Example 6 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0053] 0.4 mmol hexadecene (89.6 mg) and 0.8 mmol tetrabutylammonium iodide (295.5 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL dimethyl sulfoxide and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 3 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, and the yield was 95%.

[0054] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0055] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 1.30 (s, 28H), 0.93 (t, J= 6.4 Hz, 6H); 13 C NMR (101 MHz, CDCl3) δ 32.0, 29.8, 29.7, 29.4, 22.7, 14.1. Example 7 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0056] 0.4 mmol 2-naphthylethylene (61.6 mg) and 0.8 mmol tetrabutylammonium iodide (295.5 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL ethanol and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 5 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, and the yield was 99%.

[0057] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0058] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.90 - 7.85 (m, 3H), 7.72 (s, 1H), 7.56 - 7.43 (m, 3H), 2.91 (q, J = 7.6 Hz, 2H), 1.43 (t, J = 7.6 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 141.8, 133.8, 132.0, 127.9, 127.7, 127.5,127.2, 125.9, 125.6, 125.08, 29.1, 15.6. Example 8 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0059] 0.4 mmol p-vinylbiphenyl (72.0 mg) and 0.8 mmol tetrabutylammonium iodide (295.5 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet. 2.5 mL tetrahydrofuran and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. The electrochemical reaction solution was stirred and electrolyzed at 10 mA DC for 6 h at 10 °C. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, with a yield of 99%.

[0060] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0061] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.70 - 7.68 (m, 2H), 7.63 (d, J = 8.0 Hz, 2H), 7.53 (t, J = 7.6 Hz, 2H), 7.44 - 7.37 (m, 3H), 2.80 (q,J = 7.6 Hz, 2H), 1.39 (t, J = 7.6 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 143.5,141.3, 138.7, 128.8, 128.4, 127.2, 127.1, 127.0, 28.6, 15.7. Example 9 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0062] 0.4 mmol 1-propenylnaphthalene (67.2 mg) and 0.8 mmol tetrabutylammonium tetrafluoroborate (263.4 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL 1,4-dioxane and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. The electrochemical reaction solution was stirred and electrolyzed at 1 mA direct current for 40 h at 10 °C. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, and the yield was 95%.

[0063] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0064] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 8.15 (d, J = 8.0 Hz, 1H), 7.95 (d, J = 7.6 Hz, 1H), 7.81 (d, J = 7.6 Hz, 1H), 7.62-7.54 (m, 2H), 7.49(m, 1H), 7.42 (d, J = 6.8 Hz, 1H), 3.15 (dt, J = 7.6, 1.6 Hz, 2H), 1.94-1.85(m, 2H), 1.14 (dt, J = 7.4, 2.0 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 138.8,133.9, 132.0, 128.8, 126.5, 126.0, 125.6, 125.5, 125.4, 124.0, 35.2, 24.0,14.3. Example 10 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0065] 0.4 mmol 3,5-dichlorostyrene (68.4 mg) and 0.8 mmol tetrabutylammonium tetrafluoroborate (263.4 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL 1,4-dioxane and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. The electrochemical reaction solution was stirred and electrolyzed at 3 mA DC for 10 h at 40 °C. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, and the yield was 95%.

[0066] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0067] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 1H NMR (400 MHz, CDCl3) δ7.21 (t, J = 2.0 Hz, 1H), 7.11 (d, J = 2.0 Hz, 2H), 2.64 (q, J = 7.6 Hz, 2H), 1.26 (t, J = 7.6 Hz, 3H); 13 C NMR (101 MHz, CDCl3) δ 147.5, 134.7, 126.5,125.9, 28.5, 15.1. Embodiment 11 The method for electrochemical olefin deuteration reduction comprises the following steps:

[0068] 0.2 mmol acrylanilide (29.8 mg) and 0.8 mmol sodium chloride (46.8 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL deuterated methanol and 2.5 mL deuterated water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 1 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, and the yield was 99%.

[0069] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0070] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 7.71 (S, 1H), 7.56 (d, J= 7.2 Hz, 2H), 7.32 (t, J = 8.0 Hz, 2H), 7.12 (t, J = 7.6 Hz, 1H), 2.44-2.37(m, 1.40H), 1.29-1.22 (m, 2.09H); 13 C NMR (101 MHz, CDCl3) δ 172.5, 138.1,128.9, 124.2, 120.0, 77.3, 30.7-30.5 (m), 9.8-9.2 (m). Example 12 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0071] 0.2 mmol squalene (82.0 mg) and 0.8 mmol sodium chloride (46.8 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL methanol and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution; nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 1 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading, and petroleum ether and ethyl acetate were used for gradient elution to separate the corresponding alkane product with a yield of 86%.

[0072] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0073] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 1.60-1.52 (m, 2H), 1.41-1.1- (m, 36H), 0.92-0.88 (m, 24H); 13 C NMR (101 MHz, CDCl3) δ 39.4, 37.5, 37.5,37.4, 37.4, 37.3, 37.3, 37.2, 37.2, 32.8, 32.8, 28.0, 27.5, 27.5, 24.9, 24.5,22.8, 22.7, 22.7, 19.8, 19.8, 19.7, 19.7. Example 13 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0074] 0.4 mmol pineol (61.6 mg) and 0.8 mmol sodium chloride (46.8 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL methanol and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 4 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. Gradient elution with petroleum ether and ethyl acetate was used to separate the corresponding alkane product with a yield of 91%.

[0075] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0076] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 1.84-1.75 (m, 2.5H), 1.59-1.52 (m, 2.5H), 1.27-1.24 (m, 2H), 1.18 (m, 6H), 1.11-1.01 (m, 1.5H), 0.98-0.89 (m, 4.5H); 13 C NMR (101 MHz, CDCl3) δ 73.0, 72.9, 49.6, 48.9, 35.4,32.7, 32.0, 27.4, 27.0, 26.9, 26.8, 22.6, 21.4, 17.4. Embodiment 14 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0077] 0.4 mmol linalool (61.6 mg) and 0.8 mmol sodium bromide (82.3 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL methanol and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. The electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 2 h at 60 °C. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with a gradient of petroleum ether and ethyl acetate with a yield of 99%.

[0078] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0079] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 1.62-1.48 (m, 3H), 1.46-1.40 (m, 2H), 1.38-1.28 (m, 3H) 1.23-1.17 (m, 5H), 0.93-0.89 (m, 9H); 13 C NMR (101 MHz, CDCl3) δ 73.0, 41.6, 39.6, 34.2, 28.0, 26.4, 22.6, 21.6, 8.2. Embodiment 15 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0080] 0.4 mmol caryophyllene (81.6 mg) and 0.8 mmol sodium bromide (82.3 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL methanol and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. The electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 5 h at 60 °C. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, and the yield was 68%.

[0081] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0082] The NMR data of the product are as follows: 1 H NMR (400 MHz, CDCl3) δ 1.83-1.16 (m, 16H), 1.02-0.78 (m, 12H); 13 C NMR (101 MHz, CDCl3) δ 53.1, 52.8, 47.1, 46.7, 45.4, 44.0,41.7, 41.5, 41.2, 41.0, 40.8, 40.6, 36.9, 36.8, 35.9, 35.1, 35.0, 34.6, 34.5,34.5, 34.5, 34.2, 34.2, 33.8, 33.8, 33.6, 33.5, 33.5, 33.4, 33.4, 33.1, 32.8,32.5, 32.3, 32.2, 30.3, 30.2, 29.7, 29.6, 28.3, 24.0, 23.5, 23.1, 23.0, 22.7,22.7, 22.6, 22.5, 22.5, 22.3, 21.3, 19.6, 19.0, 15.5, 15.0. Example 16 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0083] 0.4 mmol progesterone (125.6 mg) and 0.8 mmol tetrabutylammonium bromide (257.9 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL tert-butanol and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 5 mA direct current for 10 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. Gradient elution with petroleum ether and ethyl acetate was used to separate the corresponding alkane product with a yield of 76%.

[0084] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0085] The NMR data of the product are as follows: 1H NMR (400 MHz, CDCl3) δ 2.69 (dd, J = 13.2, 15.2Hz, 1H), 2.58 - 2.51 (m, 1H), 2.40 - 2.01 (m, 9H), 1.94 - 1.80 (m, 2H), 1.74- 1.32 (m, 9H), 1.29 - 1.09 (m, 4H), 1.02 - 1.00 (m, 3H), 0.63 - 0.63 (m, 3H); 13 C NMR (101 MHz, CDCl3) δ 213.2, 212.0, 209.6, 209.5, 63.7, 63.7, 56.6,56.4, 53.6, 46.6, 44.6, 44.3, 44.2, 42.3, 40.7, 39.1, 38.9, 38.5, 38.1, 37.2,37.0, 35.7, 35.5, 35.3, 34.9, 31.6, 31.6, 28.8, 26.5, 25.7, 24.4, 24.4, 22.9,22.8, 22.6, 21.4, 21.2, 13.5, 11.5. Embodiment 17 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0086] 0.4 mmol adrenosterone (120.0 mg) and 0.8 mmol tetrabutylammonium iodide (295.5 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL of dimethyl sulfoxide and 2.5 mL of water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 3 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. Gradient elution with petroleum ether and ethyl acetate was used to separate the corresponding alkane product with a yield of 80%.

[0087] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0088] The NMR data of the product are as follows: 1H NMR (400 MHz, CDCl3) δ 2.81 - 2.74 (m, 1H), 2.61- 2.09 (m, 9H), 2.07 - 1.76 (m, 5H), 1.71 - 1.62 (m, 1H), 1.57 - 1.48 (m,1H), 1.44 - 1.37 (m, 2H), 1.27 - 1.19 (m, 4H), 0.86 - 0.86 (m, 3H); 13 C NMR (101 MHz, CDCl3) δ 217.3, 212.2, 211.2, 208.6, 64.3, 52.6, 50.6, 50.4, 50.3,50.3, 46.9, 44.8, 44.2, 42.2, 37.9, 37.4, 36.9, 36.2, 36.2, 36.0, 36.0, 35.4,34.6, 31.0, 28.0, 25.8, 25.3, 22.5, 21.6, 21.6, 14.8, 14.7, 11.2. Embodiment 18 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0089] 0.4 mmol of boldenone (114.4 mg) and 0.8 mmol of tetrabutylammonium iodide (295.5 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL of ethanol and 2.5 mL of water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the electrochemical reaction solution was stirred and electrolyzed at 10 mA direct current for 5 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. Gradient elution with petroleum ether and ethyl acetate was used to separate the corresponding alkane product with a yield of 96%.

[0090] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0091] The NMR data of the product are as follows: 1H NMR (400 MHz, CDCl3) 1H NMR (400 MHz, CDCl3) δ3.69 (t, J = 8.6 Hz, 1H), 2.70 (t, J = 14.2 Hz, 1H), 2.40 - 2.31 (m, 1H), 2.22 - 2.02 (m, 4H), 1.95 - 1.82 (m, 3H), 1.67 - 1.25 (m, 10H), 1.19 - 1.04 (m, 6H), 0.78 (s, 3H); 13 C NMR (101 MHz, CDCl3) δ 213.4, 81.8, 51.0, 44.3,43.1, 42.3, 40.9, 37.2, 37.0, 36.8, 35.6, 35.0, 30.6, 26.5, 25.4, 23.4, 22.7,20.8,11.2. Embodiment 19 The method for electrochemical olefin reduction hydrogenation comprises the following steps:

[0092] 0.2 mmol idebenone (67.6 mg) and 0.8 mmol tetrabutylammonium iodide (295.5 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL tetrahydrofuran and 2.5 mL water were added to the system and mixed to obtain an electrochemical reaction solution. Nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. The electrochemical reaction solution was stirred and electrolyzed at 10 mA DC for 6 h at 10°C. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading. The corresponding alkane product was separated and eluted with petroleum ether and ethyl acetate gradient, with a yield of 30%.

[0093] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0094] The NMR data of the product are as follows: 1H NMR (400 MHz, CDCl3) δ 4.00 (s, 3.9H), 3.89 (s,1.7H), 3.65 (t, J = 7.2 Hz, 2.0H), 2.60 (t, J = 8.0 Hz, 0.6H), 2.46 (t, J =7.6 Hz, 1.4H), 2.16 (s, 0.9H), 2.02 (s, 2.3H), 1.61-1.54 (m, 2.2H), 1.37-1.26 (m, 14.5H). 13 C NMR (101 MHz, CDCl3) δ 184.7, 184.2, 144.3, 144.2, 143.1,140.0, 139.8, 138.7, 136.7, 136.7, 123.3, 117.7, 63.0, 63.0, 61.2, 60.8,60.7, 32.8, 29.8, 29.8, 29.7, 29.6, 29.5, 29.5, 29.4, 29.4, 29.4, 29.3, 28.7,26.4, 26.3, 25.7, 11.9, 11.2. Embodiment 20 The method for electrochemical olefin deuteration reduction comprises the following steps:

[0095] 0.2 mmol N-acetyl-1-(4-methoxyphenyl)-1-propenamine (41.0 mg) and 0.8 mmol sodium chloride (46.8 mg) were added to a dry three-necked flask (15 mL) equipped with a magnet, and 2.5 mL deuterated methanol and 2.5 mL deuterated water were added to the system and mixed to obtain an electrochemical reaction solution; nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with rhodium and an aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as cathode and anode, respectively. Under room temperature, the reaction system was stirred and electrolyzed at 10 mA direct current for 1 h. After the reaction, the reaction solution was extracted with ethyl acetate, the organic phase was spin-dried, and 200-300 mesh silica gel was used for dry loading, and petroleum ether and ethyl acetate were used for gradient elution to separate the corresponding alkane product with a yield of 93%.

[0096] Wherein, the preparation method of nitrogen-doped carbon felt loaded with rhodium is the same as that in Example 1.

[0097] The NMR data of the product are as follows: 1H NMR (400 MHz, CDCl3) δ 7.24-7.21 (m, 2H), 6.90-6.87 (m, 2H), 5.88 (s, 1H), 4.86-4.82 (m, 0.13H), 3.81 (s, 3H), 1.98 (s, 3H),1.86-1.75 (m, 0.9H), 0.92-0.87 (m, 3H); 13 C NMR (101 MHz, CDCl3) δ 169.3,158.8, 134.2, 127.8, 114.0, 55.3, 54.3-53.7 (m), 28.8-27.9 (m), 23.5, 10.7,10.6. Comparative Example 1 This comparative example uses the nitrogen-doped carbon felt loaded with ruthenium prepared by the inventor in Example 1 in CN118756156A as a comparison:

[0098] The nitrogen-doped carbon felt (1.5 cm×1.5 cm×0.3 cm) loaded with ruthenium and the aluminum sheet electrode (1.5 cm×1.5 cm×0.03 cm) were inserted below the liquid surface as the cathode and anode, respectively. The electrochemical reaction solution was stirred and electrolyzed at 10 mA DC for 6 h at 40 °C. After the reaction, the reaction solution was extracted with ethyl acetate. The product composition was analyzed by gas chromatography-mass spectrometry. The obtained product contained 26% 3,5-dichloroethylbenzene, 42% 3-chlorostyrene, 18% 3-chloroethylbenzene, 7% ethylbenzene, and 5% ethylcyclohexane. Compared with Example 10, the reaction results of this comparative example show that the nitrogen-doped carbon felt electrode loaded with ruthenium does not have the selective reduction ability of the present invention. In the process of olefin reduction, the raw materials will undergo side reactions such as dehalogenation and aromatic ring reduction, which proves the olefin selective reduction advantage of the present invention.

[0099] In summary, the present invention prepares the target product with high current efficiency, generates no additional waste, has the advantage of green economy, and is compatible with monosubstituted olefins or polysubstituted olefin molecules with complex substituent groups and other easily reducible functional groups, so as to selectively add hydrogen atoms or deuterium atoms to olefinic bonds. The reaction system has fewer types of raw materials, does not require additional reducing agents, has good electrochemical properties, generates less waste, is convenient for post-processing, and has good flexibility.

[0100] The preferred specific embodiments of the present invention are described in detail above. It should be understood that a person skilled in the art can make many modifications and changes based on the concept of the present invention without creative work. Therefore, any technical solution that can be obtained by a person skilled in the art through logical analysis, reasoning or limited experiments based on the concept of the present invention on the basis of the prior art should be within the scope of protection determined by the claims.

Claims

1. A method for electrochemical olefin reduction hydrogenation or deuteration, characterized in that: The steps include: Selecting water or deuterated water according to the requirements of hydrogenation or deuteration, mixing water or deuterated water with an olefin compound, an electrolyte, and an organic solvent to obtain an electrochemical reaction solution; electrolyzing the electrochemical reaction solution to allow hydrogen atoms of water or deuterium atoms of deuterated water to add to olefin bonds in the olefin compound, and recovering a saturated alkane compound or a saturated deuterated alkane compound; The cathode electrode of electrolysis is nitrogen-doped carbon felt loaded with metal, and its preparation method comprises the following steps: Step (1), mixing carbon felt, melamine and ethanol and subjecting the mixture to a reflux reaction to obtain pretreated carbon felt; Step (2), immersing the pretreated carbon felt in a mixed solution to carry out a polymerization reaction to obtain a polymer-coated carbon felt; wherein the mixed solution is prepared by mixing melamine, paraformaldehyde and a solvent; Step (3), calcining the polymer-coated carbon felt in a protective gas atmosphere to obtain nitrogen-doped carbon felt; Step (4), immersing the nitrogen-doped carbon felt in a metal salt solution for adsorption, thereby obtaining nitrogen-doped carbon felt adsorbing the metal salt; wherein the metal salt solution is prepared by dissolving a metal salt in a solvent, and the metal salt is selected from at least one of rhodium octanoate and rhodium chloride; Step (5), using the nitrogen-doped carbon felt adsorbing the metal salt as a cathode, and electrodepositing to obtain the nitrogen-doped carbon felt loaded with the metal; The olefin compounds include monosubstituted olefins and polysubstituted olefins; Wherein, the structural formula of the monosubstituted olefin is as follows: ； In the formula, R is selected from one of acetanilide, methyl decanoate, decanoyl, carbazolyl, octadecyloxy, tetradecyl, naphthyl, biphenyl, methyl naphthyl, and 3,5-dichlorophenyl; The multi-substituted olefin includes at least one of squalene, terpineol, linalool, caryophyllene, progesterone, adrenosterone, boldenone, idebenone, and N-acetyl-1-(4-methoxyphenyl)-1-propenamine.

2. The method for electrochemical olefin reduction hydrogenation or deuteration according to claim 1, characterized in that: When the raw material is water, the organic solvent includes at least one of methanol, ethanol, isopropanol, tert-butanol, tetrahydrofuran, 1,4-dioxane, dimethyl sulfoxide, and N,N-dimethylformamide; when the raw material is deuterated water, the deuterated substance of the organic solvent is used accordingly.

3. The method for electrochemical olefin reduction hydrogenation or deuteration according to claim 1, characterized in that: The molar ratio of the water or deuterated water to the olefin compound is 1:140-1400; the molar ratio of the electrolyte to the olefin compound is 1:0.1-20; the volume ratio of the organic solvent to the water or deuterated water is 1:0.1-10; the temperature of the electrolysis is 10-80°C; the direct current current of the electrolysis is 2-40 mA, and the electrolysis time is 1-36 h.

4. The method for electrochemical olefin reduction hydrogenation or deuteration according to claim 1, characterized in that: In the step (1), the mass ratio of carbon felt, melamine and ethanol is 1:1-6:20; the temperature of the reflux reaction is 70-90°C and the time is 12-36 hours.

5. The method for electrochemical olefin reduction hydrogenation or deuteration according to claim 1, characterized in that: In the step (2), the mass ratio of the pretreated carbon felt, melamine, paraformaldehyde and solvent is 1:1-20:1-20:10-50; the polymerization step is first reacting at 100-130°C for 1-4 h, and then reacting at 150-180°C for 12-72 h.

6. The method for electrochemical olefin reduction hydrogenation or deuteration according to claim 1, characterized in that: In the step (3), the calcination temperature is 600-900°C and the calcination time is 1-3 h.

7. The method for electrochemical olefin reduction hydrogenation or deuteration according to claim 1, characterized in that: In the step (4), the mass ratio of nitrogen-doped carbon felt, metal salt and solvent is 1:0.05-0.5:40-60; the adsorption is carried out at room temperature for 1-12 h.

8. The method for electrochemical olefin reduction hydrogenation or deuteration according to claim 1, characterized in that: In the step (5), the current density of the electrodeposition is 1-40 mA / cm 2 , time is 1-20h; a separate electrolytic cell is used, and the electrodeposition electrolyte used in the cathode chamber and the anode chamber is prepared by an electrodeposition electrolyte, an electrodeposition organic solvent and water; in the electrodeposition electrolyte, the concentration of the electrodeposition electrolyte is 0.05-0.2 mol / L, and the electrodeposition electrolyte includes at least one of sodium fluoride, tetrabutylammonium bromide, tetrabutylammonium chloride, and tetrabutylammonium iodide; the mass ratio of the electrodeposition organic solvent to water is 0-9:1, and the electrodeposition organic solvent includes at least one of tetrahydrofuran, 1,4-dioxane, methanol, ethanol, isopropanol, and tert-butanol.

9. The method for electrochemical olefin reduction hydrogenation or deuteration according to claim 1, characterized in that: The anode electrode of the electrolysis is selected from an aluminum electrode, a copper electrode, a lead electrode, a platinum electrode, and a carbon electrode; the carbon electrode includes one of carbon felt, carbon paper, and carbon cloth.

Images