Electrochemical double hydrogenation three-cell system and application thereof

Abstract

The application discloses an electrochemical double hydrogenation three-cell system, which comprises a chemical cell, an anode cell, a cathode cell, an ion exchange film, a palladium film, and a power supply; the palladium film serves as an anode electrode, and a first nano-porous palladium alloy catalyst is coated on one side of the surface of the palladium film; a cathode electrode is arranged in the cathode cell, and the cathode electrode is a second nano-porous palladium alloy catalyst; the system generates adsorbed hydrogen by electro-oxidation of a second organic substrate in the anode cell on the surface of the palladium film through the anode electrode; the adsorbed hydrogen is transferred to the chemical cell through the characteristics of the palladium film body phase hydrogen transfer, and the hydrogenation of the organic substrate is realized on the surface of the first nano-porous palladium alloy catalyst; meanwhile, the cathode electrode generates adsorbed hydrogen by hydrolysis on the surface of the second nano-porous palladium alloy catalyst to realize the hydrogenation of the organic substrate, and finally the electrochemical double hydrogenation of the organic matter is realized; experimental results show that when the three-cell system is applied to organic hydrogenation, the faraday efficiency is as high as 200%, and meanwhile, the system has excellent stability and ultralow energy consumption.

Description

Technical Field

[0001] This invention relates to the field of electrochemical technology, specifically to an electrochemical double hydrogenation three-cell system and its application. Background Technology

[0002] Organic hydrogenation is one of the most critical technological revolutions in the chemical industry, playing a vital role in the production of fine and pharmaceutical chemicals. However, the high-temperature, high-pressure catalytic conditions and the large-scale use of hydrogen severely limit the large-scale application of thermocatalytic organic hydrogenation. Electrochemical organic hydrogenation has emerged as a promising alternative to traditional thermocatalytic hydrogenation, offering the possibility of generating active hydrogen at ambient temperature and pressure, avoiding the production, storage, transportation, and processing of hydrogen. However, the kinetics of the oxygen evolution reaction at the anode in organic hydrogenation are slow, producing low-value oxygen, which leads to significant energy waste. Thermodynamically, the electrochemical oxidation of organic matter is favorable, producing valuable organic products. However, the adsorbed hydrogen generated by the electrooxidation of organic matter is easily converted into water or coupled to form hydrogen gas at the anode. How to cleverly utilize the adsorbed hydrogen generated at the anode for organic hydrogenation, while simultaneously coupling organic hydrogenation at the cathode to break the Faraday limit, remains a significant challenge. Summary of the Invention

[0003] In view of the technical problems existing in the background art, the purpose of this invention is to provide an electrochemical double hydrogenation three-cell system and its application.

[0004] To achieve the above objectives, the present invention adopts the following technical solution:

[0005] A first aspect of the present invention provides an electrochemical dual hydrogenation three-cell system, comprising a chemical cell, an anode cell, a cathode cell, an ion exchange membrane, a palladium membrane, and a power source. The palladium membrane serves as the anode electrode, separating the chemical cell and the anode cell. A first nanoporous palladium alloy catalyst is coated on one side of the palladium membrane and is connected to the chemical cell. The ion exchange membrane separates the anode cell and the cathode cell. The cathode cell contains a cathode electrode, which is a second nanoporous palladium alloy catalyst. The power source is connected to the anode electrode and the cathode electrode via wires, providing power to both electrodes. The chemical cell and the cathode cell contain a first organic substrate and a first base liquid, and the anode cell contains a second organic substrate and a second base liquid.

[0006] In the three-cell system, the anode electrode uses the second organic substrate in the anode cell to electro-oxidize and generate adsorbed hydrogen on the surface of the palladium film. The adsorbed hydrogen is then transferred to the chemical cell through the hydrogen transfer characteristics of the palladium film in bulk, thus achieving hydrogenation of the organic substrate on the surface of the first nanoporous palladium alloy catalyst. At the same time, the matching cathode electrode generates adsorbed hydrogen on the surface of the second nanoporous palladium alloy catalyst through water dissociation, thereby achieving hydrogenation of the organic substrate. Finally, the electrochemical dual hydrogenation of the organic material is realized.

[0007] Preferably, the anode pool has openings on both sides, the chemical pool and the cathode pool have openings on one side, and the palladium film has a thickness of 1-100 μm.

[0008] Preferably, the first nanoporous palladium alloy catalyst and the second nanoporous palladium alloy catalyst can be the same or different, and both are selected from any one of PdZn, PdCu, Pd3Sn and Pd3In alloys.

[0009] Preferably, the first and second nanoporous palladium alloy catalysts are prepared by the following steps:

[0010] S1. Preparation of palladium alloy precursor: Pd and one of Zn, Cu, Sn, In are melted in a melting furnace, and then the mixture is rapidly quenched and spun at a speed of 1000-5000 r / min to obtain the precursor alloy.

[0011] S2, Chemical dealloying: The precursor alloy is placed in an etching solution and freely etched to obtain a nanoporous palladium alloy.

[0012] Alternatively, S2', electrochemical dealloying: The precursor alloy is placed in an electrolyte solution and electrochemically corroded at room temperature until the current reaches 0 mA / cm². -2 A nanoporous palladium alloy catalyst was obtained.

[0013] Preferably, in the chemical dealloying process, the etching solution is a 1.0-17.5 mol / L acetic acid solution, a 1.0-5.0 mol / L nitric acid solution, a 1.0-5.0 mol / L ammonium chloride solution, or a 1.0-5.0 mol / L hydrochloric acid solution, the etching temperature is 25-80℃, and the etching time is 10-48 h.

[0014] Preferably, in the electrochemical dealloying process, the electrolyte solution is a 0.1-1.0 mol / L acetic acid solution, a 0.1-1.0 mol / L nitric acid solution, a 0.1-1.0 mol / L ammonium chloride solution, a 0.1-1.0 mol / L hydrochloric acid solution, or a 0.1-1.0 mol / L potassium hydroxide solution.

[0015] Preferably, the first organic substrate is an alkynol, furfural, or quinoxaline, with a concentration of 0.01-1.0 mol / L.

[0016] Preferably, the first base solution is selected from any one of chloroform, ethanol, phosphate buffer, potassium hydroxide solution, hydrochloric acid solution, dichloromethane, and ethyl acetate, with a concentration of 0.1-1.0 mol / L.

[0017] Preferably, the second organic substrate is selected from any one of formaldehyde, furfural, paraformaldehyde, hydrazine hydrate, and 3,5-diamino-1,2,4-triazole.

[0018] Preferably, the second base solution is a potassium hydroxide solution or a sodium hydroxide solution with a concentration of 0.1-6.0 mol / L.

[0019] A second aspect of the present invention provides the application of the above-described electrochemical double hydrogenation three-cell system in organic hydrogenation.

[0020] Preferably, the electrochemical dual hydrogenation three-cell system is used in organic hydrogenation with a two-electrode system or a three-electrode system.

[0021] Preferably, when the electrochemical dual hydrogenation three-cell system is applied to organic hydrogenation using a three-electrode system and the working electrode is a palladium membrane, the reference electrode is an Hg / HgO electrode placed in the anode cell, and the counter electrode is connected to the second nanoporous palladium alloy catalyst in the cathode electrode; when the electrochemical dual hydrogenation three-cell system is applied to organic hydrogenation using a three-electrode system and the working electrode is a second nanoporous palladium alloy catalyst, the reference electrode is an Hg / HgO electrode placed in the cathode cell, and the counter electrode is connected to a palladium membrane.

[0022] The present invention has the following beneficial effects:

[0023] (1) This invention provides an electrochemical dual-hydrogenation three-cell system. Its working principle is as follows: In this system, the anode electrode generates adsorbed hydrogen on the surface of a palladium film using the electro-oxidation of a second organic substrate in the anolyte. Then, through the hydrogen transfer characteristics of the palladium film bulk phase, the generated adsorbed hydrogen is transferred to the chemical cell, achieving hydrogenation of the organic substrate on the surface of a first nanoporous palladium alloy catalyst. Simultaneously, the matching cathode electrode generates adsorbed hydrogen on the surface of the second nanoporous palladium alloy catalyst through water dissociation, achieving hydrogenation of the organic substrate, ultimately realizing the electrochemical dual hydrogenation of the organic matter. Experimental results show that this electrochemical dual-hydrogenation three-cell system has an ultra-low starting voltage as low as 0V, a Faraday efficiency as high as 200%, and an ultra-low energy consumption as low as 0.19 kWh / kg. -1 .

[0024] (2) The electrochemical double hydrogenation three-cell system provided by the present invention can reduce the reaction potential by utilizing the inherent thermodynamic advantages of organic oxidation over water oxidation; in addition, the oxidation of organic substrates produces value-added products to replace low-value oxygen.

[0025] (3) Compared with the high energy consumption and carbon emissions caused by traditional thermocatalysis which relies on high temperature, high pressure and hydrogen, the electrochemical double hydrogenation three-cell system provided by the present invention can achieve efficient conversion under normal temperature and pressure conditions, and has the advantages of being green and environmentally friendly, low energy consumption and scalable. Attached Figure Description

[0026] To more clearly illustrate the technical solutions in the embodiments of the present invention, the accompanying drawings used in the embodiments will be briefly introduced below. Obviously, the drawings described below are only some embodiments of the present invention. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort.

[0027] Figure 1 This invention provides a schematic diagram of the structure of an electrochemical dual hydrogenation three-cell system;

[0028] Figure 2 A schematic diagram of the process for preparing nanoporous palladium alloy catalysts;

[0029] Figure 3 Characterization results for nanoporous PdZn: (a) XRD pattern; (b) STEM and corresponding elemental distribution map; (c) HAADF-STEM image;

[0030] Figure 4 XRD pattern of nanoporous PdCu;

[0031] Figure 5 SEM image of nanoporous PdCu;

[0032] Figure 6 XRD pattern of nanoporous Pd3Sn;

[0033] Figure 7 SEM image of nanoporous Pd3Sn;

[0034] Figure 8 XRD pattern of nanoporous Pd3In;

[0035] Figure 9 SEM image of nanoporous Pd3In;

[0036] Figure 10 LSV curves for organic oxidation replacing water oxidation in an electrochemical double hydrogenation three-cell system;

[0037] Figure 11 Performance results of the electrochemical double hydrogenation three-cell system for nanoporous PdZn: (a) Conversion, selectivity, and Faradaic efficiency of alkynol hydrogenation to enol in the chemical and cathode cells; (b) Overall Faradaic efficiency; (c) 10 mA cm⁻¹ -2(d) Constant current test curve; (d) Energy consumption diagram of the system;

[0038] Figure 12 The Faraday efficiency of the electrochemical organic double hydrogenation three-cell system of nanoporous PdCu and Pd3Sn.

[0039] Figure 13 The Faraday efficiency of an electrochemical double hydrogenation three-cell system with a cross combination of nanoporous PdCu and Pd3In catalysts. Detailed Implementation

[0040] In the following description, specific details such as particular system architectures and techniques are set forth for illustrative purposes and not for limitation, in order to provide a thorough understanding of the embodiments of the invention. However, those skilled in the art will understand that the invention may be implemented in other embodiments without these specific details.

[0041] like Figure 1 As shown, this invention provides an electrochemical dual hydrogenation three-cell system device. The system includes a chemical cell, an anode cell, a cathode cell, an ion exchange membrane, a palladium membrane, and a power source. The palladium membrane serves as the anode electrode, separating the chemical cell and the anode cell. One side of the palladium membrane is coated with a first nanoporous palladium alloy catalyst, which is connected to the chemical cell. The ion exchange membrane separates the anode cell and the cathode cell. The cathode cell contains a cathode electrode, which is a second nanoporous palladium alloy catalyst. The power source is connected to the anode electrode and the cathode electrode via wires, providing power to both electrodes. The chemical cell and the cathode cell contain a first organic substrate and a first base liquid, while the anode cell contains a second organic substrate and a second base liquid.

[0042] In this system, the anode electrode on the palladium film surface electro-oxidizes the second organic substrate in the anolyte to generate adsorbed hydrogen. This adsorbed hydrogen is then transferred to the chemical cell via the bulk hydrogen transfer properties of the palladium film, achieving hydrogenation of the organic substrate on the surface of the first nanoporous palladium alloy catalyst. Simultaneously, the matching cathode electrode on the surface of the second nanoporous palladium alloy catalyst generates adsorbed hydrogen through water dissociation, achieving hydrogenation of the organic substrate. This ultimately achieves electrochemical dual hydrogenation of the organic material. The first and second nanoporous palladium alloy catalysts can be the same or different.

[0043] Example 1

[0044] The first and second nanoporous palladium alloy catalysts are the same, specifically nanoporous PdZn, as described above. Figure 2 Preparation of nanoporous PdZn:

[0045] (1) Preparation of Pd4Zn 96Strip: 0.318g Pd and 4.682g Zn were melted in a melting furnace, and then rapidly quenched and spun at 2000 r / min to obtain Pd4Zn. 96 Strips (i.e., precursor alloys);

[0046] (2) Chemical dealloying: The obtained Pd4Zn 96 The precursor alloy was freely etched in 1 mol / L acetic acid at room temperature for 24 h to obtain nanoporous PdZn.

[0047] Alternatively, electrochemical dealloying: Pd4Zn 96 The precursor alloy was placed in an electrolyte solution of 1 mol / L potassium hydroxide at -0.45V. Hg / HgO At room temperature, corrosion is carried out at a potential until the current is 0 mA cm. -2 Nanoporous PdZn was obtained.

[0048] The prepared nanoporous PdZn alloy was characterized, and the results are shown in the figure. Figure 3 .

[0049] Depend on Figure 3 (a) The XRD pattern shows that the nanoporous PdZn alloy has an ordered body-centered tetragonal crystal structure (PDF#97-010-5752); Figure 3 (b) The STEM image and EDX spectrum show that the PdZn alloy has a uniform nanoporous structure with interconnected ligaments and uniform distribution of Pd and Zn elements. Figure 3 In (c), the interplanar spacings of 0.145 nm and 0.22 nm in the HAADF-STEM image correspond to the (200) and (101) crystal planes of the PdZn alloy, respectively.

[0050] Assemble an electrochemical double hydrogenation three-cell system

[0051] (1) The prepared nanoporous PdZn was coated on one side of a palladium film (thickness of 30 μm) used as an anode electrode and coated on the surface of carbon paper as a cathode electrode.

[0052] (2) The chemical cell and the anode cell are separated by a palladium membrane coated with nanoporous PdZn, and one side of the palladium membrane coated with nanoporous PdZn is connected to the chemical cell, and the other side of the palladium membrane is connected to the anode cell.

[0053] (3) Use an anion exchange membrane to separate the anode cell and the cathode cell;

[0054] (4) Carbon paper coated with nanoporous PdZn is placed in the cathode cell as a cathode electrode.

[0055] (5) Dissolve 2 mmol of 2-methyl-3-butyn-2-ol in 20 mL of 1 mol / L phosphate buffer and add it to the chemical cell. Add a mixture of 0.6 mol / L formaldehyde and 1 mol / L potassium hydroxide to the anode cell. Dissolve 2 mmol of 2-methyl-3-butyn-2-ol in 20 mL of 1 mol / L potassium hydroxide and add it to the cathode cell to assemble a three-cell system.

[0056] The assembled three-cell system described above can perform both two-electrode and three-electrode tests. When performing a three-electrode test, the working electrode is connected to a palladium film, the reference electrode is an Hg / HgO electrode placed in the anolyte, and the counter electrode is connected to a nanoporous PdZn catalyst coated on carbon paper. Alternatively, the working electrode can be connected to a nanoporous PdZn catalyst coated on carbon paper, the reference electrode is an Hg / HgO electrode placed in the cathode, and the counter electrode is connected to a palladium film.

[0057] Example 2

[0058] The first and second nanoporous palladium alloy catalysts are the same, specifically nanoporous PdCu, refer to... Figure 2 Preparation of nanoporous PdCu:

[0059] (1) Preparation of Pd4Cu 96 Strip: 0.326 g Pd and 4.674 g Cu were melted in a melting furnace, and then rapidly quenched and spun at 3000 r / min to obtain Pd4Cu. 96 Strips (i.e., precursor alloys);

[0060] (2) Chemical dealloying: Pd4Cu 96 The precursor alloy was freely etched in 1 mol / L ammonium chloride at room temperature for 48 h to obtain nanoporous PdCu;

[0061] Or (3) Chemical dealloying: Pd4Cu 96 The precursor alloy was placed in an electrolyte solution of 0.1 mol / L nitric acid at a voltage of 0.5 V. AgCl At room temperature, corrosion occurs at a potential of 0 mA / cm². -2 Nanoporous PdCu was obtained;

[0062] The prepared nanoporous PdCu alloy was characterized, and the results are shown in the figure. Figure 4 and Figure 5 .

[0063] Depend on Figure 4 and Figure 5 The results show that the PdCu alloy has a nanoporous structure with uniform element distribution and a face-centered cubic crystal structure.

[0064] Assemble an electrochemical double hydrogenation three-cell system

[0065] (1) The prepared nanoporous PdCu was coated on one side of the palladium film as the anode, and the nanoporous PdCu catalyst was coated on the surface of carbon paper as the cathode.

[0066] (2) The chemical cell and the anode cell are separated by a palladium membrane coated with nanoporous PdCu, and the side of the anode coated with nanoporous PdCu is connected to the chemical cell, and the side of the palladium membrane is connected to the anode cell.

[0067] (3) Separate the anode cell and the cathode cell with anion exchange membrane;

[0068] (4) Carbon paper coated with nanoporous PdCu was placed in the cathode cell as a cathode.

[0069] (5) Dissolve 2 mmol of quinoxaline in 20 mL of 1 mol / L phosphate buffer and add it to the chemical cell. Add a mixture of 1 mol / L hydrazine hydrate and 1 mol / L potassium hydroxide to the anode cell. Dissolve 2 mmol of quinoxaline in 20 mL of 1 mol / L potassium hydroxide and add it to the cathode cell to form a three-cell system.

[0070] The assembled three-cell system described above can perform both two-electrode and three-electrode tests. When performing a three-electrode test, the working electrode is connected to a palladium film, the reference electrode is an Hg / HgO electrode placed in the anolyte, and the counter electrode is connected to a nanoporous PdCu catalyst coated on carbon paper. Alternatively, the working electrode can be connected to a nanoporous PdCu catalyst coated on carbon paper, the reference electrode is an Hg / HgO electrode placed in the cathode, and the counter electrode is connected to a palladium film.

[0071] Example 3

[0072] The first and second nanoporous palladium alloy catalysts are the same, specifically nanoporous Pd3Sn, as described above. Figure 2 Preparation of nanoporous Pd3Sn:

[0073] (1) Preparation of Pd4Sn 96 Strip: 0.180 g Pd and 4.820 g Sn were melted in a melting furnace, and then rapidly quenched and spun at 4000 r / min to obtain Pd4Sn. 96 Strips (i.e., precursor alloys);

[0074] (2) Chemical dealloying: Pd4Sn 96 The precursor alloy was freely etched in 1.0 mol / L nitric acid at room temperature for 10 h to obtain nanoporous Pd3Sn;

[0075] Or (3) Electrochemical dealloying: Pd4Sn96 The precursor alloy was placed in an electrolyte solution of 0.1 mol / L nitric acid at 0.3 V. AgCl At room temperature, corrosion occurs at a potential of 0 mA / cm². -2 Nanoporous Pd3Sn was obtained;

[0076] The prepared nanoporous Pd3Sn was characterized, and the results are shown in the figure. Figure 6 and Figure 7 .

[0077] Depend on Figure 6 and Figure 7 The results show that the prepared Pd3Sn has a nanoporous structure and a face-centered cubic crystal structure.

[0078] Assemble an electrochemical double hydrogenation three-cell system

[0079] (1) The prepared nanoporous Pd3Sn was coated on one side of the palladium film as the anode, and the nanoporous Pd3Sn was coated on the surface of carbon paper as the cathode.

[0080] (2) The chemical cell and the anode cell are separated by a palladium membrane coated with nanoporous Pd3Sn, and the side of the anode coated with nanoporous Pd3Sn is connected to the chemical cell, while the side of the palladium membrane is connected to the anode cell.

[0081] (3) Separate the anode cell and the cathode cell with anion exchange membrane;

[0082] (4) Carbon paper coated with nanoporous Pd3Sn is placed in the cathode cell as a cathode.

[0083] (5) Dissolve 2 mmol of furfural in 20 mL of 1 mol / L phosphate buffer and add it to the chemical cell. Add a mixture of 0.5 mol / L 3,5-diamino-1,2,4-triazole and 1 mol / L potassium hydroxide to the anode cell. Dissolve 2 mmol of furfural in 20 mL of 1 mol / L phosphate buffer and add it to the cathode cell to form a three-cell system.

[0084] The assembled three-cell system described above can perform both two-electrode and three-electrode tests. When performing a three-electrode test, the working electrode is connected to a palladium film, the reference electrode is an Hg / HgO electrode placed in the anolyte, and the counter electrode is connected to a nanoporous Pd3Sn catalyst coated on carbon paper. Alternatively, the working electrode can be connected to a nanoporous Pd3Sn catalyst coated on carbon paper, the reference electrode is an Hg / HgO electrode placed in the cathode, and the counter electrode is connected to a palladium film.

[0085] Example 4

[0086] The first nanoporous palladium alloy catalyst and the second nanoporous palladium alloy catalyst are different.

[0087] Reference Figure 2 Preparation of nanoporous Pd3In:

[0088] (1) Preparation of Pd4In 96 Strip: 0.186g Pd and 4.814g In were melted in a melting furnace, and then rapidly quenched and spun at 5000r / min to obtain Pd4In. 96 Strips (i.e., precursor alloys);

[0089] (2) Chemical dealloying: Pd4In 96 The precursor alloy was freely etched in 1.0 mol / L hydrochloric acid at 40 °C for 10 h to obtain nanoporous Pd3In;

[0090] Or (3) Electrochemical dealloying: Pd4In 96 The precursor alloy was placed in an electrolyte solution of 0.1M hydrochloric acid at 0.3V. AgCl At room temperature, corrosion occurs at a potential of 0 mA / cm². -2 Nanoporous Pd3In was obtained;

[0091] The prepared nanoporous Pd3In was characterized, and the results are shown in the figure. Figure 8 and Figure 9 .

[0092] Depend on Figure 8 and Figure 9 The results show that the prepared Pd3In has a nanoporous structure and a face-centered cubic crystal structure.

[0093] Assemble an electrochemical double hydrogenation three-cell system

[0094] (1) The prepared nanoporous Pd3In was coated on one side of the palladium film as the anode, and the nanoporous PdCu was coated on the carbon paper as the cathode.

[0095] (2) The chemical cell and the anode cell are separated by a palladium membrane coated with nanoporous Pd3In, and the side of the anode coated with nanoporous Pd3In is connected to the chemical cell, while the side of the palladium membrane is connected to the anode cell.

[0096] (3) Separate the anode cell and the cathode cell with anion exchange membrane;

[0097] (4) Carbon paper coated with nanoporous PdCu was placed in the cathode cell as a cathode.

[0098] (5) Dissolve 2 mmol of quinoxaline in 20 mL of ethyl acetate and add it to the chemical cell. Add a mixture of 0.5 mol / L 3,5-diamino-1,2,4-triazole and 1 mol / L potassium hydroxide to the anode cell. Dissolve 2 mmol of quinoxaline in 20 mL of 1 mol / L sodium hydroxide solution and add it to the cathode cell to form a three-cell system.

[0099] The assembled three-cell system described above can perform both two-electrode and three-electrode tests. When performing a three-electrode test, the working electrode is connected to a palladium film, the reference electrode is an Hg / HgO electrode placed in the anolyte, and the counter electrode is connected to a nanoporous PdCu coated on carbon paper. Alternatively, the working electrode can be connected to a nanoporous PdCu coated on carbon paper, the reference electrode is an Hg / HgO electrode placed in the cathode, and the counter electrode is connected to a palladium film.

[0100] The three-cell system can also be assembled by exchanging the positions of Pd3In and PdCu catalysts, that is, nanoporous PdCu is coated on one side of the palladium film as the anode, and nanoporous Pd3In is coated on the carbon paper surface as the cathode.

[0101] The assembled three-cell system described above can perform both two-electrode and three-electrode tests. When performing a three-electrode test, the working electrode is connected to a palladium film, the reference electrode is an Hg / HgO electrode placed in the anolyte, and the counter electrode is connected to a nanoporous Pd3In coated on carbon paper. Alternatively, the working electrode can be connected to a nanoporous Pd3In coated on carbon paper, the reference electrode is an Hg / HgO electrode placed in the cathode, and the counter electrode is connected to a palladium film.

[0102] Hydrogenation performance test

[0103] The electrochemical dual-hydrogenation three-cell system assembled in Examples 1-4 was used to test the hydrogenation performance. The reaction solution was added to a dichloromethane extract to extract the liquid product. After sonication for 5 minutes, the lower layer of extract was collected and injected into a gas chromatograph equipped with an ionization flame detector for testing. The results are shown in [Figure 1]. Figure 10-13 .

[0104] Depend on Figure 10-11 The results show that the electrochemical dual-hydrogenation three-cell system assembled in Example 1, equipped with a nanoporous PdZn catalyst, has a lower potential compared to the traditional two-cell water oxidation system, thanks to the thermodynamic advantages of organic oxidation. Furthermore, it maintains high conversion rates and Faradaic efficiencies in both the chemical and cathode cells. This is attributed to the generation of adsorbed hydrogen through anodic electrooxidation, which is then transferred from the anodic cell to the chemical cell for organic hydrogenation, coupled with the electrohydrogenation of organic matter in the cathode chamber. Moreover, the selectivity is not affected by increasing current density. Under optimal conditions, the overall Faradaic efficiency of the electrochemical dual-half-hydrogenation of 2-methyl-3-butyn-2-ol reaches 170%, exhibiting excellent stability and ultra-low energy consumption.

[0105] Depend on Figure 12 The results show that the electrochemical dual-hydrogenation three-cell system assembled in Example 2 maintains high Faradaic efficiency for the hydrogenation of quinoxaline in both the chemical and cathode regions of nanoporous PdCu. The electrochemical organic dual-hydrogenation three-cell system assembled in Example 3 maintains high Faradaic efficiency for the hydrogenation of furfural in both the chemical and cathode regions of nanoporous Pd3Sn. This is attributed to the generation of adsorbed hydrogen through anodic electro-oxidation, which simultaneously transfers the adsorbed hydrogen from the anodic cell to the chemical cell for organic hydrogenation, coupled with the organic electro-hydrogenation in the cathode chamber.

[0106] Depend on Figure 13 The results show that the electrochemical dual-hydrogenation three-cell system assembled in Example 4 maintains high Faradaic efficiencies for the hydrogenation of quinoxaline using cross-catalysts with nanoporous PdCu in the cathode cell and Pd3In in the chemical zone, as well as with nanoporous Pd3In in the cathode cell and PdCu in the chemical zone. This is attributed to the design of the dual-hydrogenation three-cell system, which provides a platform for diverse catalyst combinations.

[0107] This invention is not limited to the specific embodiments described above. Any modifications made by those skilled in the art based on the above concept without creative effort are within the scope of protection of this invention.

Claims

1. An electrochemical dual hydrogenation triple cell system comprising a chemical cell, an anode cell, a cathode cell, an ion exchange membrane, a palladium membrane, a power source, characterized in that, The palladium membrane is used as an anode electrode for separating a chemical cell and an anode cell, a surface side of the palladium membrane is coated with a first nano-porous palladium alloy catalyst, and the first nano-porous palladium alloy catalyst is connected with the chemical cell; the ion exchange membrane is used for separating the anode cell and a cathode cell, the cathode cell is provided with a cathode electrode which is a second nano-porous palladium alloy catalyst, a power supply is connected with the anode electrode and the cathode electrode through wires to provide power to the two electrodes, the chemical cell and the cathode cell are used for containing a first organic substrate and a first base solution, and the anode cell is used for containing a second organic substrate and a second base solution; In the electrochemical double hydrogenation three-cell system, the anode electrode generates adsorbed hydrogen by electro-oxidation of the second organic substrate in the anode cell on the surface of the palladium membrane, and the adsorbed hydrogen is transferred to the chemical cell through the characteristics of the bulk phase hydrogen transfer of the palladium membrane to realize the hydrogenation of the organic substrate on the surface of the first nano-porous palladium alloy catalyst; at the same time, the matching cathode electrode generates adsorbed hydrogen by water dissociation on the surface of the second nano-porous palladium alloy catalyst to realize the hydrogenation of the organic substrate, and finally realizes the electrochemical double hydrogenation of the organic matter. The first nano-porous palladium alloy catalyst and the second nano-porous palladium alloy catalyst are the same or different, and are selected from any one of PdZn, PdCu, Pd3Sn and Pd3In alloys; The first organic substrate is selected from any one of acetylene alcohol, furfural or quinoline, and the concentration is 0.01-1.0 mol / L; the first base solution is selected from any one of chloroform, ethanol, phosphate buffer solution, potassium hydroxide solution, hydrochloric acid solution, dichloromethane and ethyl acetate, and the concentration is 0.1-1.0 mol / L; The second organic substrate is selected from any one of formaldehyde, furfural, polyformaldehyde, hydrazine hydrate and 3,5-diamino-1,2,4-triazole; and the second base solution is a 0.1-6.0 mol / L potassium hydroxide solution or a sodium hydroxide solution.

2. An electrochemical dual hydroboration triple cell system according to claim 1, wherein, The anode cell is open on both sides, the chemical cell and the cathode cell are open on one side, and the thickness of the palladium membrane is 1-100 µm.

3. An electrochemical dual hydroboration triple cell system according to claim 1, wherein, The first nano-porous palladium alloy catalyst is prepared by the following steps: S1, preparing a palladium alloy precursor: melting Pd and one of Zn, Cu, Sn and In in a smelting furnace, and then rapidly quenching the strip at a rotation speed of 1000-5000 r / min to obtain a precursor alloy; S2, chemical dealloying: placing the precursor alloy in a corrosion solution for free corrosion to obtain a nano-porous palladium alloy catalyst; or S2', electrochemical dealloying: placing the precursor alloy in an electrolyte solution and electrochemically etching at room temperature to a current of 0 mA cm -2 , to obtain a nanoporous palladium alloy catalyst.

4. An electrochemical dual hydroboration triple cell system according to claim 3, wherein, In the chemical dealloying, the corrosion solution is a 1.0-17.5 mol / L acetic acid solution, a 1.0-5.0 mol / L nitric acid solution, a 1.0-5.0 mol / L ammonium chloride solution or a 1.0-5.0 mol / L hydrochloric acid solution, the corrosion temperature is 25-80 ℃, and the corrosion time is 10-48 h.

5. An electrochemical dual hydroboration triple cell system according to claim 3, wherein, The electrolyte solution in the electrochemical dealloying is 0.1-1.0 mol / L acetic acid solution, 0.1-1.0 mol / L nitric acid solution, 0.1-1.0 mol / L ammonium chloride solution, 0.1-1.0 mol / L hydrochloric acid solution or 0.1-1.0 mol / L potassium hydroxide solution.

6. Use of an electrochemical dual hydrogenation triple cell system according to any one of claims 1 to 5 in the hydrogenation of organic compounds.

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