Electrochemical double-hydrogenation three-pool system and application thereof

Abstract

The invention discloses an electrochemical double-hydrogenation three-pool system which comprises a chemical pool, an anode pool, a cathode pool, an ion exchange membrane, a palladium membrane and a power supply, the palladium membrane is used as an anode electrode, one side of the surface of the palladium membrane is coated with a first nano-porous palladium alloy catalyst, a cathode electrode is arranged in the cathode pool, and the cathode electrode is a second nano-porous palladium alloy catalyst; adsorbed hydrogen is generated on the surface of a palladium membrane through electrooxidation of a second organic substrate in an anode pool by means of an anode electrode, the adsorbed hydrogen is transferred into a chemical pool through the characteristic of palladium membrane body phase hydrogen transfer, and organic substrate hydrogenation is achieved on the surface of a first nano-porous palladium alloy catalyst; meanwhile, a cathode electrode generates adsorbed hydrogen on the surface of the second nano-porous palladium alloy catalyst through water dissociation to realize hydrogenation of an organic substrate, electrochemical double hydrogenation of organic matters is finally realized, experimental results show that when the three-pool system is applied to organic hydrogenation, the Faraday efficiency reaches up to 200%, and meanwhile, the three-pool system also has excellent stability and ultralow energy consumption.

Description

Technical Field

[0001] The present invention relates to the field of electrochemical technology, and in particular to an electrochemical double hydrogenation three-cell system and applications thereof. Background Art

[0002] Organic hydrogenation is one of the most critical technological advancements in the chemical industry, playing a vital role in the production of fine chemicals and pharmaceutical chemicals. However, the high-temperature, high-pressure catalytic conditions and the extensive use of hydrogen severely limit the large-scale application of thermal catalytic organic hydrogenation. Electrochemical organic hydrogenation has emerged as a promising alternative to conventional thermal catalytic hydrogenation, offering the possibility of generating active hydrogen at ambient temperature and pressure, avoiding the production, storage, transportation, and handling of hydrogen. However, the kinetics of the oxygen evolution reaction at the anode, which is compatible with organic hydrogenation, are sluggish, resulting in the generation of low-value oxygen, which results in significant energy waste. Electrochemical oxidation of organic matter is thermodynamically favorable, producing valuable organic products. However, the adsorbed hydrogen generated by organic electrooxidation is easily converted to water or coupled to form hydrogen at the anode. Innovatively utilizing the adsorbed hydrogen generated at the anode for organic hydrogenation while simultaneously coupling it to cathodic organic hydrogenation to break the Faraday limit presents a significant challenge. Summary of the Invention

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

[0004] In order to achieve the above object, the present invention adopts the following technical solutions:

[0005] A first aspect of the present invention provides an electrochemical double hydrogenation three-cell system, which includes a chemical cell, an anode cell, a cathode cell, an ion exchange membrane, a palladium membrane, and a power supply. The palladium membrane serves as an anode electrode, which is used to separate the chemical cell and the anode cell. One side of the surface of the palladium membrane is coated with a first nanoporous palladium alloy catalyst, and the first nanoporous palladium alloy catalyst is connected to the chemical cell; the ion exchange membrane is used to separate the anode cell and the cathode cell. The cathode cell is provided with a cathode electrode, and the cathode electrode is a second nanoporous palladium alloy catalyst. The power supply is connected to the anode electrode and the cathode electrode through a wire to provide power to the two electrodes. The chemical cell and the cathode cell are used to accommodate a first organic substrate and a first base liquid, and the anode cell is used to accommodate a second organic substrate and a second base liquid.

[0006] In the three-cell system, the anode electrode utilizes the electro-oxidation of the second organic substrate in the anode cell on the surface of the palladium membrane to generate adsorbed hydrogen, which is transferred to the chemical cell through the bulk hydrogen transfer characteristics of the palladium membrane, thereby achieving hydrogenation of the organic substrate on the surface of the first nanoporous palladium alloy catalyst; simultaneously, the cathode electrode matched therewith generates adsorbed hydrogen on the surface of the second nanoporous palladium alloy catalyst through water dissociation to achieve hydrogenation of the organic substrate, ultimately achieving electrochemical double hydrogenation of the organic matter.

[0007] Preferably, both sides of the anode cell are open, and both the chemical cell and the cathode cell are open on one side, and the thickness of the palladium membrane is 1-100 μm.

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

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

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

[0011] S2. Chemical dealloying: placing the precursor alloy in a corrosive solution and allowing it to corrode freely to obtain a nanoporous palladium alloy;

[0012] Or S2', electrochemical dealloying: Place the precursor alloy in an electrolyte solution and electrochemically corrode it at room temperature until the current is 0 mA cm -2 , and obtain a nanoporous palladium alloy catalyst.

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

[0014] Preferably, in the electrochemical dealloying, the electrolyte solution 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.

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

[0016] Preferably, the first base liquid is selected from any one of chloroform, ethanol, phosphate buffer, potassium hydroxide solution, hydrochloric acid solution, dichloromethane, and ethyl acetate, and the concentration is 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 liquid is a potassium hydroxide solution or a sodium hydroxide solution with a concentration of 0.1-6.0 mol / L.

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

[0020] Preferably, the electrochemical dual hydrogenation three-cell system uses a two-electrode system or a three-electrode system when applied to organic hydrogenation.

[0021] Preferably, when the electrochemical double 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 a Hg / HgO electrode and is 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 double 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 a Hg / HgO electrode and is placed in the cathode cell, and the counter electrode is connected to the palladium membrane.

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

[0023] (1) The present invention provides an electrochemical double hydrogenation three-cell system, the working principle of which is as follows: in this 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 then transfers the generated adsorbed hydrogen to the chemical cell through the characteristics of hydrogen transfer in the bulk phase of the palladium membrane, and realizes hydrogenation of the organic substrate on the surface of the first nanoporous palladium alloy catalyst; at the same time, the cathode electrode matched therewith generates adsorbed hydrogen by water dissociation on the surface of the second nanoporous palladium alloy catalyst to realize hydrogenation of the organic substrate, and finally realizes electrochemical double hydrogenation of organic matter. Experimental results show that the electrochemical double 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 0.19kWh 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, organic substrate oxidation produces value-added products to replace low-value oxygen.

[0025] (3) Compared with traditional thermal catalysis which relies on harsh conditions such as high temperature, high pressure and hydrogen, resulting in high energy consumption and carbon emissions, 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, environmentally friendly, low energy consumption and scalable. BRIEF DESCRIPTION OF THE DRAWINGS

[0026] In order to more clearly illustrate the technical solutions in the embodiments of the present invention, the following briefly introduces the drawings required for use in the embodiments. Obviously, the drawings described below are only some embodiments of the present invention. For ordinary technicians in this field, other drawings can be obtained based on these drawings without paying any creative work.

[0027] Figure 1 A schematic diagram of the structure of an electrochemical double hydrogenation three-cell system provided by the present invention;

[0028] Figure 2 Schematic diagram of the process for preparing nanoporous palladium alloy catalyst;

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

[0030] Figure 4 is the XRD pattern of nanoporous PdCu;

[0031] Figure 5 is the SEM image of nanoporous PdCu;

[0032] Figure 6 is the XRD pattern of nanoporous Pd3Sn;

[0033] Figure 7 is the SEM image of nanoporous Pd3Sn;

[0034] Figure 8 is the XRD pattern of nanoporous Pd3In;

[0035] Figure 9 is the SEM image of nanoporous Pd3In;

[0036] Figure 10 This is the LSV curve of organic matter oxidation replacing water oxidation in the electrochemical double hydrogenation three-cell system;

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

[0038] Figure 12 Faradaic efficiency of a three-cell system for electrochemical organic double hydrogenation using nanoporous PdCu and Pd3Sn;

[0039] Figure 13 Faradaic efficiency of the electrochemical double hydrogenation three-cell system with a cross-combination of nanoporous PdCu and Pd3In catalysts. DETAILED DESCRIPTION

[0040] In the following description, specific details such as specific system structures and technologies are provided for the purpose of illustration rather than limitation to facilitate a thorough understanding of the embodiments of the present invention. However, it should be clear to those skilled in the art that the present invention may also be implemented in other embodiments without these specific details.

[0041] like Figure 1 As shown, the present invention provides an electrochemical double hydrogenation three-cell system device, which includes a chemical cell, an anode cell, a cathode cell, an ion exchange membrane, a palladium membrane, and a power supply. The palladium membrane serves as an anode electrode, which is used to separate the chemical cell and the anode cell. One side of the surface of the palladium membrane is coated with a first nanoporous palladium alloy catalyst, and the first nanoporous palladium alloy catalyst is connected to the chemical cell; the ion exchange membrane is used to separate the anode cell and the cathode cell. The cathode cell is provided with a cathode electrode, which is a second nanoporous palladium alloy catalyst. The power supply is connected to the anode electrode and the cathode electrode through a wire to provide power to the two electrodes. The chemical cell and the cathode cell are used to accommodate a first organic substrate and a first base liquid, and the anode cell is used to accommodate a second organic substrate and a second base liquid.

[0042] In this system, the anode electrode on the palladium membrane surface electrooxidizes the second organic substrate in the anode cell to produce adsorbed hydrogen. This adsorbed hydrogen is then transferred to the chemical cell via the bulk hydrogen transfer properties of the palladium membrane, hydrogenating the organic substrate on the surface of the first nanoporous palladium alloy catalyst. Simultaneously, the matching cathode electrode produces adsorbed hydrogen on the surface of the second nanoporous palladium alloy catalyst through water dissociation, ultimately achieving electrochemical dual hydrogenation of the organic compound. The first and second nanoporous palladium alloy catalysts can be the same or different.

[0043] Example 1

[0044] The first nanoporous palladium alloy catalyst and the second nanoporous palladium alloy catalyst are the same, specifically nanoporous PdZn, 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 at 2000r / min to obtain Pd4Zn 96 Strip (i.e., precursor alloy);

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

[0047] Or electrochemical dealloying: Pd4Zn 96 The precursor alloy was placed in a 1 mol / L potassium hydroxide electrolyte solution at -0.45 V Hg / HgO The corrosion potential was 0 mA cm at room temperature. -2 , nanoporous PdZn was obtained.

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

[0049] Depend on Figure 3 (a) The XRD spectrum 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 the uniform nanoporous structure of the PdZn alloy with interconnected ligaments and uniform distribution of Pd and Zn elements; Figure 3 The interplanar spacings of 0.145 nm and 0.22 nm in the HAADF-STEM image in (c) correspond to the (200) and (101) planes of the PdZn alloy, respectively.

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

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

[0052] (2) separating the chemical cell and the anode cell by a palladium membrane coated with nanoporous PdZn, with one side coated with nanoporous PdZn connected to the chemical cell and the other side of the palladium membrane connected to the anode cell;

[0053] (3) separating the anode pool and cathode pool with an anion exchange membrane;

[0054] (4) placing carbon paper coated with nanoporous PdZn as a cathode electrode in a cathode cell;

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

[0056] In addition to two-electrode testing, the three-cell system can also perform three-electrode testing. In this test, the working electrode is connected to the palladium membrane, the reference electrode is a Hg / HgO electrode placed in the anode cell, and the counter electrode is connected to a nanoporous PdZn catalyst coated on carbon paper. Alternatively, the working electrode is connected to the nanoporous PdZn catalyst coated on carbon paper, the reference electrode is a Hg / HgO electrode placed in the cathode cell, and the counter electrode is connected to the palladium membrane.

[0057] Example 2

[0058] The first nanoporous palladium alloy catalyst and the second nanoporous palladium alloy catalyst are the same, specifically nanoporous PdCu, Figure 2 , preparation of nanoporous PdCu:

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

[0060] (2) Chemical dealloying: Pd4Cu 96 The precursor alloy was free-corroded 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 a 0.1 mol / L nitric acid electrolyte solution at 0.5 V. AgCl The corrosion current is 0 mA cm at room temperature. -2 , nanoporous PdCu was obtained;

[0062] The prepared nanoporous PdCu alloy was characterized and the results are shown in 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] Assembling an electrochemical double hydrogenation three-cell system

[0065] (1) The prepared nanoporous PdCu is coated on one side of the palladium membrane as an anode, and the nanoporous PdCu catalyst is coated on the surface of carbon paper as a cathode;

[0066] (2) separating the chemical cell and the anode cell by a palladium membrane coated with nanoporous PdCu, and connecting the side of the anode coated with nanoporous PdCu to the chemical cell, and connecting the side of the palladium membrane to the anode cell;

[0067] (3) separating the anode pool and cathode pool with an anion exchange membrane;

[0068] (4) placing carbon paper coated with nanoporous PdCu as a cathode in a cathode cell;

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

[0070] In addition to two-electrode testing, the three-cell system can also perform three-electrode testing. In this test, the working electrode is connected to the palladium membrane, the reference electrode is a Hg / HgO electrode placed in the anode cell, and the counter electrode is connected to a nanoporous PdCu catalyst coated on carbon paper. Alternatively, the working electrode is connected to the nanoporous PdCu catalyst coated on carbon paper, the reference electrode is a Hg / HgO electrode placed in the cathode cell, and the counter electrode is connected to the palladium membrane.

[0071] Example 3

[0072] The first nanoporous palladium alloy catalyst and the second nanoporous palladium alloy catalyst are the same, specifically nanoporous Pd3Sn, Figure 2 , preparation of nanoporous Pd3Sn:

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

[0074] (2) Chemical dealloying: Pd4Sn 96 The precursor alloy was free-corroded 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 a 0.1 mol / L nitric acid electrolyte solution at 0.3 V. AgCl The corrosion current is 0 mA cm at room temperature. -2 , nanoporous Pd3Sn was obtained;

[0076] The prepared nanoporous Pd3Sn was characterized and the results are shown in 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] Assembling an electrochemical double hydrogenation three-cell system

[0079] (1) The prepared nanoporous Pd3Sn is coated on one side of the palladium membrane as an anode, and the nanoporous Pd3Sn is coated on the surface of carbon paper as a cathode;

[0080] (2) separating the chemical cell and the anode cell by a palladium membrane coated with nanoporous Pd3Sn, and connecting the side of the anode coated with nanoporous Pd3Sn to the chemical cell, and connecting the side of the palladium membrane to the anode cell;

[0081] (3) separating the anode pool and cathode pool with an anion exchange membrane;

[0082] (4) placing carbon paper coated with nanoporous Pd3Sn as a cathode in a cathode cell;

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

[0084] In addition to two-electrode testing, the three-cell system can also perform three-electrode testing. In this test, the working electrode is connected to the palladium membrane, the reference electrode is a Hg / HgO electrode placed in the anode cell, and the counter electrode is connected to a nanoporous Pd3Sn catalyst coated on carbon paper. Alternatively, the working electrode is connected to the nanoporous Pd3Sn catalyst coated on carbon paper, the reference electrode is a Hg / HgO electrode placed in the cathode cell, and the counter electrode is connected to the palladium membrane.

[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 at 5000r / min to obtain Pd4In 96 Strip (i.e., precursor alloy);

[0089] (2) Chemical dealloying: Pd4In 96 The precursor alloy was free-corroded 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 a 0.1M hydrochloric acid electrolyte solution at 0.3V AgCl The corrosion current is 0 mA cm at room temperature. -2 , nanoporous Pd3In was obtained;

[0091] The prepared nanoporous Pd3In was characterized and the results are shown in 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] Assembling an electrochemical double hydrogenation three-cell system

[0094] (1) The prepared nanoporous Pd3In was coated on one side of the palladium membrane as an anode, and the nanoporous PdCu was coated on the surface of carbon paper as a cathode;

[0095] (2) separating the chemical cell and the anode cell by a palladium membrane coated with nanoporous Pd3In, and connecting the side of the anode coated with nanoporous Pd3In to the chemical cell, and connecting the side of the palladium membrane to the anode cell;

[0096] (3) separating the anode pool and cathode pool with an anion exchange membrane;

[0097] (4) placing carbon paper coated with nanoporous PdCu as a cathode in a cathode cell;

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

[0099] In addition to two-electrode testing, the three-cell system can also perform three-electrode testing. In this test, the working electrode is connected to the palladium membrane, the reference electrode is a Hg / HgO electrode placed in the anode cell, and the counter electrode is connected to a nanoporous PdCu coated on a carbon paper surface. Alternatively, the working electrode is connected to the nanoporous PdCu coated on a carbon paper surface, the reference electrode is a Hg / HgO electrode placed in the cathode cell, and the counter electrode is connected to the palladium membrane.

[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 membrane as the anode, and nanoporous Pd3In is coated on the carbon paper surface as the cathode.

[0101] In addition to two-electrode testing, the three-cell system can also perform three-electrode testing. In this test, the working electrode is connected to the palladium membrane, the reference electrode is a Hg / HgO electrode placed in the anode cell, and the counter electrode is connected to nanoporous Pd3In coated on carbon paper. Alternatively, the working electrode is connected to nanoporous Pd3In coated on carbon paper, the reference electrode is a Hg / HgO electrode placed in the cathode cell, and the counter electrode is connected to the palladium membrane.

[0102] Hydrogenation performance test

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

[0104] Depend on Figure 10-11 As can be seen from the results, the electrochemical double hydrogenation three-cell system assembled in Example 1 is equipped with a nanoporous PdZn catalyst, which has a lower potential than the traditional water oxidation two-cell system, thanks to the thermodynamic advantages of organic oxidation. In addition, a high conversion rate and Faraday efficiency are maintained in both the chemical cell and the cathode cell. This is attributed to the production of adsorbed hydrogen by anode electrooxidation, and the transfer of adsorbed hydrogen from the anode cell to the chemical cell for hydrogenation of organic matter, coupled with the electrohydrogenation of organic matter in the cathode chamber, and as the current density increases, the selectivity is not affected by the increase in current density. Under optimal conditions, the total Faraday efficiency of the electrochemical double half hydrogenation of 2-methyl-3-butyn-2-ol reaches 170%, and it has 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 enables nanoporous PdCu to maintain high Faradaic efficiencies for quinoxaline hydrogenation in both the chemical and cathode zones. The electrochemical organic dual hydrogenation three-cell system assembled in Example 3 enables nanoporous Pd3Sn to maintain high Faradaic efficiencies for furfural hydrogenation in both the chemical and cathode zones. This is attributed to the production of adsorbed hydrogen by anodic electrooxidation, which is then transferred from the anodic cell to the chemical cell for organic hydrogenation, coupled with the organic electrohydrogenation 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 quinoxaline hydrogenation using both nanoporous PdCu in the cathode cell and Pd3In in the chemical zone, as well as a crossover catalyst using nanoporous Pd3In in the cathode cell and PdCu in the chemical zone. This is due to the design of the dual hydrogenation three-cell system, which provides a platform for diverse catalyst combinations.

[0107] The present invention is not limited to the above-mentioned specific implementation methods. Various changes made by ordinary technicians in this field based on the above-mentioned concept without creative work are all within the scope of protection of the present invention.

Claims

1. An electrochemical double hydrogenation three-cell system, comprising a chemical cell, an anode cell, a cathode cell, an ion exchange membrane, a palladium membrane, and a power supply, characterized in that: The palladium membrane serves as an anode electrode, and is used to separate the chemical cell and the anode cell. One side of the surface of the palladium membrane is coated with a first nanoporous palladium alloy catalyst, and the first nanoporous palladium alloy catalyst is connected to the chemical cell. The ion exchange membrane is used to separate the anode cell and the cathode cell. The cathode cell is provided with a cathode electrode, and the cathode electrode is a second nanoporous palladium alloy catalyst. The power supply is connected to the anode electrode and the cathode electrode through a wire to provide power to the two electrodes. The chemical cell and the cathode cell are used to accommodate a first organic substrate and a first base liquid, and the anode cell is used to accommodate a second organic substrate and a second base liquid. In the electrochemical double hydrogenation three-cell system, the anode electrode utilizes the electro-oxidation of the second organic substrate in the anode cell on the surface of the palladium membrane to generate adsorbed hydrogen, which is transferred to the chemical cell through the bulk hydrogen transfer characteristics of the palladium membrane to achieve hydrogenation of the organic substrate on the surface of the first nanoporous palladium alloy catalyst; simultaneously, the cathode electrode matched therewith generates adsorbed hydrogen on the surface of the second nanoporous palladium alloy catalyst through water dissociation to achieve hydrogenation of the organic substrate, ultimately achieving electrochemical double hydrogenation of organic matter.

2. The electrochemical double hydrogenation three-cell system according to claim 1, characterized in that: Both sides of the anode cell are open, and both sides of the chemical cell and the cathode cell are open. The thickness of the palladium film is 1 to 100 μm.

3. The electrochemical double hydrogenation three-cell system according to claim 1, characterized in that: The first nanoporous palladium alloy catalyst and the second nanoporous palladium alloy catalyst are the same or different, and are both selected from any one of PdZn, PdCu, Pd3Sn and Pd3In alloys.

4. The electrochemical double hydrogenation three-cell system according to claim 3, characterized in that: The first nanoporous palladium alloy catalyst is prepared by the following steps: S1. Preparation of a palladium alloy precursor: Pd and one of Zn, Cu, Sn, and In are melted in a melting furnace, and then rapidly quenched at a speed of 1000-5000 r / min to obtain a precursor alloy; S2, chemical dealloying: placing the precursor alloy in a corrosive solution and allowing it to corrode freely to obtain a nanoporous palladium alloy catalyst; Or S2', electrochemical dealloying: Place the precursor alloy in an electrolyte solution and electrochemically corrode it at room temperature until the current is 0 mA cm -2 , and obtain a nanoporous palladium alloy catalyst.

5. The electrochemical double hydrogenation three-cell system according to claim 4, characterized in that: In the chemical dealloying, the etching solution is 1.0-17.5 mol / L acetic acid solution, 1.0-5.0 mol / L nitric acid solution, 1.0-5.0 mol / L ammonium chloride solution or 1.0-5.0 mol / L hydrochloric acid solution, the etching temperature is 25-80° C., and the etching time is 10-48 h.

6. The electrochemical double hydrogenation three-cell system according to claim 4, characterized in that: In the electrochemical dealloying, the electrolyte solution 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.

7. The electrochemical double hydrogenation three-cell system according to claim 1, characterized in that: The first organic substrate is selected from alkynol, furfural or quinoxaline, with a concentration of 0.01-1.0 mol / L; the first base liquid 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.

8. The electrochemical double hydrogenation three-cell system according to claim 1, characterized in that: The second organic substrate is selected from any one of formaldehyde, furfural, paraformaldehyde, hydrazine hydrate, and 3,5-diamino-1,2,4-triazole; and the second base liquid is a 0.1-6.0 mol / L potassium hydroxide solution or a sodium hydroxide solution.

9. Use of the electrochemical dual hydrogenation three-cell system according to any one of claims 1 to 8 in organic hydrogenation.

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