A method for preparing organophosphorus oxides by electrolytic oxidation

Abstract

This disclosure relates to a method for preparing organophosphorus oxides by electrolytic oxidation. The method includes: placing organophosphorus in an electrolyte of an electrolytic cell for electrolytic oxidation. The anode in the electrolytic cell is a nickel-based multimetallic catalyst. The electrolyte includes an organic electrolyte, water, and an organic solvent. The nickel-based multimetallic catalyst includes nickel and an active metal selected from one or more of iron, aluminum, manganese, copper, vanadium, and cerium. This method uses a heterogeneous nickel-based multimetallic catalyst as the anode, and through a green electrolytic process, oxidizes organophosphorus in the electrolyte to organophosphorus oxides without requiring a heat source or excitation light source, while simultaneously producing hydrogen at the cathode.

Description

Technical Field

[0001] This disclosure relates to the fields of electrocatalytic organic synthesis and hydrogen production technology, and more specifically, to a method for preparing organophosphorus oxides by electrolytic oxidation. Background Technology

[0002] Phosphorus is one of the most abundant non-metallic elements in the Earth's crust and is also an essential element for the growth and development of living organisms and plants. Therefore, phosphorus plays a crucial role in human life activities and industrial and agricultural production. Among the many phosphorus-containing compounds, organophosphorus oxides have attracted widespread attention from chemists due to their extensive applications in pesticides, pharmaceuticals, chiral catalysts, and materials. Therefore, developing efficient and highly selective methods for the synthesis of phosphorus oxides is of great research significance and application value for drug development and synthetic chemistry, and may even promote the development of more new methodologies. Traditional synthesis of phosphorus oxides involves homogeneous transition metal catalysts, dangerous free radical initiators, or external oxidants (organoalkanes, iodine(III) reagents, AIBN, K2S2O8, etc.). However, these synthetic methods require further product separation and harsh conditions, which seriously hinder their organic synthesis.

[0003] In recent years, organic electrosynthesis, known as a green synthesis technology, has gained increasing attention as a novel and effective chemical synthesis method. Currently, the synthesis of phosphine oxides mainly involves thermocatalysis and photocatalysis. These reactions require heat sources and excitation light sources, and necessitate the addition of reducing or oxidizing agents. The synthesis steps and reaction apparatus are relatively complex, resulting in numerous side reactions and difficulties in catalyst recovery. Summary of the Invention

[0004] The purpose of this disclosure is to provide a method for preparing organophosphorus oxides by electrolytic oxidation. This method uses a heterogeneous nickel-based multimetallic catalyst as the anode and oxidizes organophosphorus in the electrolyte into organophosphorus oxides through a green electrocatalytic process, while simultaneously producing hydrogen at the cathode.

[0005] To achieve the above objectives, this disclosure provides a method for preparing organophosphorus oxides by electrolytic oxidation. The method includes: placing the organophosphorus in the electrolyte of an electrolytic cell for electrolytic oxidation reaction, wherein the anode in the electrolytic cell is a nickel-based multimetallic catalyst, and the electrolyte includes an organic electrolyte, water, and an organic solvent; the nickel-based multimetallic catalyst includes nickel and an active metal, wherein the active metal is selected from one or more of iron, aluminum, manganese, copper, vanadium, and cerium.

[0006] Optionally, the nickel-based multimetal catalyst comprises a conductive substrate and a nickel-based multimetal compound supported on the conductive substrate. The nickel-based multimetal compound comprises one or more of nickel-based multimetal hydroxides, nickel-based multimetal oxides, nickel-based multimetal sulfides, nickel-based multimetal phosphides, nickel-based multimetal borides, nickel-based multimetal nitrides, and nickel-based multimetal carbides; the active metal is iron.

[0007] Optionally, based on the total molar number of all metals in the nickel-based polymetallic compound, the content of nickel is 10-90 mol%, preferably 40-80 mol%; the content of the active metal is 10-90 mol%, preferably 20-50 mol%; the molar ratio of nickel to the active metal is (1-9):1, preferably (1-5):1; wherein all metals, nickel and active metal are calculated as metal elements.

[0008] Optionally, the concentration of the organophosphorus in the electrolyte is 0.01–100 mmol / L, preferably 0.015–30 mmol / L; the concentration of the organic electrolyte is 0.01–3 mol / L, preferably 0.1–1 mol / L; the molar ratio of organophosphorus to organic electrolyte is 1:(1–1000), preferably 1:(10–100); and the concentration of the electrolyte is 0.05–10 mol / L, preferably 0.1–1 mol / L.

[0009] Optionally, the organophosphine is selected from one or more of trimethylphosphine, triethylphosphine, triphenylphosphine, tricyclohexylphosphine, dimethylphenylphosphine, bis(dimethylphosphine)methane, trivinylphosphine, tri-tert-butylphosphine, tri-n-octylphosphine, diphenylcyclohexylphosphine, benzyldiphenylphosphine, tert-butyldiphenylphosphine, and allyldiphenylphosphine; the organic electrolyte is selected from one or more of tetra-n-butylammonium hexafluorophosphate, tetra-n-butylammonium perchlorate, tetra-n-butylammonium sulfate, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium iodide, tetra-n-butylammonium nitrate, tetra-n-butylammonium acetate, and tetra-n-butylammonium hydroxide.

[0010] Optionally, the water is selected from one or more of distilled water, deionized water, and ultrapure water, and the organic solvent is selected from one or more of acetonitrile, ethyl acetate, ethanol, methanol, hexafluoroisopropanol, tetrahydrofuran, dimethyl sulfoxide nitrile, and dimethyl sulfoxide; the volume ratio of water to organic solvent in the electrolyte is (0.01-1):1, preferably (0.1-0.3):1.

[0011] Optionally, the cathode in the electrolytic cell is a platinum sheet, the reference electrode is a silver / silver chloride electrode, the voltage of the electrolytic oxidation reaction is 0.5-50V, preferably 1-10V, and the time is 1-24h, with a duration of 1.5-8h.

[0012] Optionally, the preparation method of the nickel-based multimetal catalyst includes: mixing and stirring a nickel source, an active metal source, a directing agent, and water to obtain a mixed solution; placing a conductive substrate in the mixed solution and subjecting the resulting reaction solution to hydrothermal treatment at a temperature of 70–150°C for 3–12 hours; wherein the nickel source is selected from one or more of nickel nitrate, nickel chloride, and nickel sulfate; the active metal source is selected from one or more of ferric nitrate, ferric chloride, ferrous sulfate, aluminum nitrate, aluminum chloride, manganese nitrate, manganese chloride, copper nitrate, copper chloride, vanadium chloride, and cerium nitrate; the directing agent is selected from one or more of ammonium fluoride, urea, and hexamethylenetetramine; and the conductive substrate is selected from one or more of carbon cloth, carbon paper, nickel foam, nickel sheet, nickel mesh, copper foam, copper sheet, copper mesh, titanium sheet, titanium mesh, stainless steel sheet, stainless steel mesh, ITO conductive glass, and FTO conductive glass.

[0013] Optionally, the active metal source is selected from one or more of ferric nitrate, ferric chloride, and ferrous sulfate, and the conductive substrate is selected from one or more of carbon cloth, nickel foam, nickel sheet, and titanium sheet.

[0014] Optionally, in step (1), the concentration of the nickel source in the mixed solution is 1-50 mg / mL, the concentration of the active metal source is 1-50 mg / mL, and the concentration of the directing agent is 1-30 mg / mL; the molar ratio of the nickel source to the active metal source is (0.1-5):1, preferably (1-3):1.

[0015] Through the above technical solution, this disclosure provides an electrolytic oxidation method. This method uses a heterogeneous nickel-based multimetallic catalyst as the anode, and through a green electrolysis process, oxidizes organophosphorus compounds in the electrolyte to organophosphorus oxides without requiring a heat source or excitation light source, while simultaneously producing hydrogen at the cathode. The method of this disclosure achieves a high yield of organophosphorus oxides, avoids the use of other reducing or oxidizing agents, reduces side reactions, greatly simplifies product separation and purification, and features relatively simple synthesis steps and reaction apparatus. It provides a convenient and promising method for low-cost, high-efficiency heterogeneous electrocatalytic synthesis of high-value-added oxides.

[0016] Other features and advantages of this disclosure will be described in detail in the following detailed description section. Attached Figure Description

[0017] The accompanying drawings are provided to further illustrate the present disclosure and form part of the specification. They are used together with the following detailed description to explain the present disclosure, but do not constitute a limitation thereof. In the drawings:

[0018] Figure 1 This is a schematic diagram of the electrolytic oxidation reaction for preparing organophosphorus oxides in Embodiment 1 of this disclosure;

[0019] Figure 2 This is a scanning electron microscope image of the carbon cloth-supported nickel-iron bimetallic hydroxide prepared in Example 1 of this disclosure;

[0020] Figure 3 This is a linear sweep voltammetry (LSV) curve of Example 1 of this disclosure before and after the addition of triphenylphosphine;

[0021] Figure 4 This is the hydrogen nuclear magnetic resonance spectrum of the product obtained in Example 1 of this disclosure. Detailed Implementation

[0022] The specific embodiments of this disclosure will be described in detail below with reference to the accompanying drawings. It should be understood that the specific embodiments described herein are for illustration and explanation only and are not intended to limit this disclosure.

[0023] This disclosure provides a method for preparing organophosphorus oxides by electrolytic oxidation. The method includes: placing the organophosphorus in the electrolyte of an electrolytic cell for electrolytic oxidation reaction, wherein the anode in the electrolytic cell is a nickel-based multimetallic catalyst, the electrolyte includes an organic electrolyte, water and an organic solvent, and the nickel-based multimetallic catalyst includes nickel and an active metal, wherein the active metal is selected from one or more of iron, aluminum, manganese, copper, vanadium and cerium.

[0024] This disclosed method uses a heterogeneous nickel-based multimetallic catalyst as the anode, and through a green electrolysis process, oxidizes organophosphorus compounds in the electrolyte to organophosphorus oxides without the need for a heat source or excitation light source, while simultaneously producing hydrogen at the cathode. This method achieves high yields of organophosphorus oxides, avoids the use of other reducing or oxidizing agents, reduces side reactions, greatly simplifies product separation and purification, and features relatively simple synthesis steps and reaction apparatus. It provides a convenient and promising method for the low-cost, high-efficiency heterogeneous electrocatalytic synthesis of high-value-added oxides.

[0025] In one embodiment of this disclosure, the nickel-based multimetal catalyst includes a conductive substrate and a nickel-based multimetal compound supported on the conductive substrate. The nickel-based multimetal compound includes one or more of nickel-based multimetal hydroxides, nickel-based multimetal oxides, nickel-based multimetal sulfides, nickel-based multimetal phosphides, nickel-based multimetal borides, nickel-based multimetal nitrides, and nickel-based multimetal carbides. In specific embodiments, nickel in nickel-based multimetallic hydroxides exists in the form of nickel hydroxide, and the active metal exists in the form of hydroxide; nickel in nickel-based multimetallic oxides exists in the form of nickel oxide, and the active metal exists in the form of oxide; nickel in nickel-based multimetallic sulfides exists in the form of nickel sulfide, and the active metal exists in the form of sulfide; nickel in nickel-based multimetallic phosphides exists in the form of nickel phosphide, and the active metal exists in the form of phosphide; nickel in nickel-based multimetallic borides exists in the form of nickel boride, and the active metal exists in the form of boride; nickel in nickel-based multimetallic nitrides exists in the form of nickel nitride, and the active metal exists in the form of nitride; nickel in nickel-based multimetallic carbides exists in the form of nickel carbide, and the active metal exists in the form of carbide. In one embodiment, the active metal is iron, and the nickel-based multimetallic catalyst includes a conductive substrate and a nickel-iron bimetallic hydroxide supported on the conductive substrate.

[0026] In one embodiment of this disclosure, based on the total molar number of all metals in the nickel-based polymetallic compound, the nickel content is 10-90 mol%, preferably 40-80 mol%; the active metal content is 10-90 mol%, preferably 20-50 mol%; the molar ratio of nickel to the active metal is (1-9):1, preferably (1-5):1; wherein all metals, nickel, and active metal are calculated as metal elements. In the above embodiment, by selecting a nickel-based polymetallic compound with a preferred composition, it is beneficial to form an active NiOOH intermediate, which has strong oxidizing properties and can oxidize organophosphorus compounds to organophosphorus oxides.

[0027] In one embodiment, a nickel-based multimetallic compound is loaded onto a conductive substrate in the form of layered nanosheets, which have a large specific surface area, thus improving the contact area with organophosphorus compounds.

[0028] In one embodiment of this disclosure, the concentration of the organophosphorus in the electrolyte is 0.01–100 mmol / L, preferably 0.015–30 mmol / L; the concentration of the organic electrolyte is 0.01–3 mol / L, preferably 0.1–1 mol / L; the molar ratio of organophosphorus to organic electrolyte is 1:(1–1000), preferably 1:(10–100); and the concentration of the electrolyte is 0.05–10 mol / L, preferably 0.1–1 mol / L. In the above embodiment, selecting the preferred organic electrolyte is beneficial for increasing the ion content and ionic strength in the system, enhancing the conductivity of the electrolyte, and improving the current density and reaction efficiency. Using this organic electrolyte in combination with organophosphorus is beneficial for improving the solubility of the organophosphorus substrate in the reaction solvent and accelerating the oxidation of the substrate.

[0029] In one embodiment of this disclosure, the organophosphine is selected from one or more of trimethylphosphine, triethylphosphine, triphenylphosphine, tricyclohexylphosphine, dimethylphenylphosphine, bis(dimethylphosphine)methane, trivinylphosphine, tri-tert-butylphosphine, tri-n-octylphosphine, diphenylcyclohexylphosphine, benzyldiphenylphosphine, tert-butyldiphenylphosphine, and allyldiphenylphosphine; the organic electrolyte is selected from one or more of tetra-n-butylammonium hexafluorophosphate, tetra-n-butylammonium perchlorate, tetra-n-butylammonium sulfate, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium iodide, tetra-n-butylammonium nitrate, tetra-n-butylammonium acetate, and tetra-n-butylammonium hydroxide.

[0030] In one embodiment of this disclosure, the water is selected from one or more of distilled water, deionized water, and ultrapure water, and the organic solvent is selected from one or more of acetonitrile, ethyl acetate, ethanol, methanol, hexafluoroisopropanol, tetrahydrofuran, dimethyl sulfoxide nitrile, and dimethyl sulfoxide; the volume ratio of water to organic solvent in the electrolyte is (0.01–10):1, preferably (0.01–1):1, more preferably (0.1–1):1, and even more preferably (0.1–0.3):1. In the above embodiment, using the preferred ratio of water and organic solvent is beneficial for introducing organophosphorus compounds into the electrolyte and improving the dispersibility of the organophosphorus compounds.

[0031] In one embodiment of this disclosure, the cathode in the electrolytic cell is a platinum sheet, the reference electrode is a silver / silver chloride electrode, the voltage of the electrolytic oxidation reaction is 0.5-50V, preferably 1-10V, and the time is 1-24h, with a duration of 1.5-8h.

[0032] In one embodiment of this disclosure, the preparation method of the nickel-based multimetal catalyst includes: mixing and stirring a nickel source, an active metal source, a directing agent, and water to obtain a mixed solution; placing a conductive substrate in the mixed solution and subjecting the resulting reaction solution to hydrothermal treatment at a temperature of 70–150°C for 3–12 hours; wherein the nickel source is selected from one or more of nickel nitrate, nickel chloride, and nickel sulfate; the active metal source is selected from one or more of ferric nitrate, ferric chloride, ferrous sulfate, aluminum nitrate, aluminum chloride, manganese nitrate, manganese chloride, copper nitrate, copper chloride, vanadium chloride, and cerium nitrate; the directing agent is selected from one or more of ammonium fluoride, urea, and hexamethylenetetramine; and the conductive substrate is selected from one or more of carbon cloth, carbon paper, nickel foam, nickel sheet, nickel mesh, copper foam, copper sheet, copper mesh, titanium sheet, titanium mesh, stainless steel sheet, stainless steel mesh, ITO conductive glass, and FTO conductive glass.

[0033] In a specific embodiment, before placing the conductive substrate in the mixed solution in step (1), the conductive substrate is first subjected to a purification treatment. The purification treatment conditions include: placing the conductive substrate in anhydrous ethanol, acetone and deionized water for ultrasonic treatment to remove surface impurities.

[0034] In one embodiment of this disclosure, the active metal source is selected from one or more of ferric nitrate, ferric chloride, and ferrous sulfate, and the conductive substrate is selected from one or more of carbon cloth, nickel foam, nickel sheet, and titanium sheet.

[0035] In one embodiment of this disclosure, in step (1), the concentration of the nickel source in the mixed solution is 1-50 mg / mL, preferably 5-15 mg / mL; the concentration of the active metal source is 1-50 mg / mL, preferably 1-30 mg / mL; the concentration of the directing agent is 1-30 mg / mL, preferably 2-20 mg / mL; and the molar ratio of the nickel source to the active metal source is (0.1-5):1, preferably (1-3):1.

[0036] The present disclosure is further illustrated by the following examples, but the present disclosure is not limited thereto. Unless otherwise specified, all raw materials used in the examples of the present disclosure are commercially available and are pure reagents.

[0037] The scanning electron microscope (SEM) was tested using a SEM (Zeiss SUPRA55, 20kV).

[0038] The linear sweep voltammetry method was used to test the electrochemical performance of the prepared catalyst in a 10 mL beaker under ambient temperature and pressure using a three-electrode standard system. The three electrodes included a working electrode (nickel-based multimetallic catalyst), a counter electrode (platinum sheet electrode), and a reference electrode (silver / silver chloride electrode). A mixed solution of acetonitrile and water was used as the solvent, and tetrabutylammonium perchlorate was used as the organic electrolyte. The current density curves of the reaction system at different voltages were determined by linear sweep voltammetry at a scan rate of 5 mV / s. -1 The scanning range was 0V–1.8V vs. Ag / AgCl. The testing instrument was an electrochemical workstation (CHI 760E, Shanghai Chenhua Co., Ltd.).

[0039] The method for proton NMR spectroscopy is to use CH2Br2 as an internal standard and CDCl3 as a solvent. 1 HNMR was performed using a 400MHz nuclear magnetic resonance spectrometer (AVANCE III, Bruker Instruments).

[0040] Preparation Example 1

[0041] (1) Prepare a 40 mL aqueous solution containing 0.2 g urea (first directing agent, concentration 5 mg / mL), 0.3 g ammonium fluoride (second directing agent, concentration 7.5 mg / mL), 0.3 g nickel nitrate (nickel source, concentration 7.5 mg / mL), and 0.4 g ferric nitrate (active metal source, concentration 10 mg / mL), denoted as mixed solution. The total concentration of directing agents in the mixed solution is 12.5 mg / mL, and the molar ratio of nickel source to active metal source is 1:1. Cut carbon cloth (conductive substrate) into pieces of 2.5 cm × 4.0 cm, and sonicate them in anhydrous ethanol, acetone, and deionized water for 15 min each to remove surface impurities. Dry them for later use.

[0042] (2) The purified carbon was placed in the mixed solution, and the resulting reaction solution was hydrothermally treated at 120℃ for 5 h. The product was washed with deionized water and dried to obtain carbon cloth-supported nickel-iron bimetallic hydroxide, i.e., nickel-based multimetallic catalyst. Based on the total molar amount of all metals in the nickel-iron bimetallic hydroxide, the nickel content was 50 mol%, the iron content was 50 mol%, and the molar ratio of nickel to iron was 1:1.

[0043] The scanning electron microscope (SEM) image of the carbon cloth-loaded nickel-iron bimetallic hydroxide is as follows: Figure 2 As shown, by Figure 2 It is known that the nickel-iron bimetallic hydroxide has a layered nanosheet structure, which provides a large specific surface area and abundant active sites, which is beneficial for catalyzing the oxidation reaction of organophosphorus compounds.

[0044] Preparation Example 2

[0045] Same as in Preparation Example 1, except that in step (1), carbon cloth (conductive substrate) is replaced with nickel foam to obtain nickel-iron bimetallic hydroxide supported on nickel foam, i.e., nickel-based multimetal catalyst.

[0046] Preparation Example 3

[0047] The preparation method is the same as in Example 1, except that in step (1), the active metal source ferric nitrate is replaced with the same molar amount of manganese nitrate to obtain a carbon cloth-supported nickel-manganese bimetallic hydroxide, i.e., a nickel-based multimetallic catalyst. Based on the total molar amount of all metals in the nickel-manganese bimetallic hydroxide, the nickel content is 50 mol%, the manganese content is 50 mol%, and the molar ratio of nickel to manganese is 1:1.

[0048] Preparation Example 4

[0049] The preparation method is the same as in Example 1, except that in step (1), the active metal source ferric nitrate is replaced with the same molar amount of aluminum nitrate to obtain a carbon cloth-supported nickel-aluminum bimetallic hydroxide, i.e., a nickel-based multimetallic catalyst. Based on the total molar amount of all metals in the nickel-aluminum bimetallic hydroxide, the nickel content is 50 mol%, the aluminum content is 50 mol%, and the molar ratio of nickel to aluminum is 1:1.

[0050] Example 1

[0051] 1 mL of deionized water and 7 mL of acetonitrile (organic solvent) were mixed, and triphenylphosphine (organophosphine) and tetrabutylammonium perchlorate (nBu4NClO4, organic electrolyte) were added to prepare 8 mL of electrolyte with a concentration of 0.325 mol / L. The concentration of triphenylphosphine in the electrolyte was 0.025 mol / L, the concentration of tetrabutylammonium perchlorate was 0.3 mol / L, the molar ratio of triphenylphosphine to tetrabutylammonium perchlorate was 1:12, and the volume ratio of water to acetonitrile was 0.14:1. The carbon cloth-supported nickel-iron bimetallic hydroxide prepared in Example 1 was used as the anode, a platinum sheet as the cathode, and a silver / silver chloride electrode as the reference electrode to build a three-electrode system. The reaction was carried out continuously for 2 h at a constant voltage of 1.5 V.

[0052] The reaction diagram is as follows Figure 1 As shown, the linear sweep voltammetry (LSV) curves before and after the addition of triphenylphosphine are as follows: Figure 3 As shown, Figure 3 The results show that the onset potential was 1.51 V before the addition of triphenylphosphine, and decreased to 0.78 V after the addition, indicating that triphenylphosphine participated in the oxidation reaction. The product was quantitatively identified as triphenylphosphine oxide using 1H NMR spectroscopy, as shown in the 1H NMR spectrum. Figure 4 As shown, the results indicate that the yield of triphenylphosphine oxide is 98%.

[0053] Example 2

[0054] Same as Example 1, except that: triphenylphosphine was replaced with the same amount of tricyclohexylphosphine, and nickel-iron bimetallic hydroxide supported on nickel foam prepared in Example 2 was used as the anode. The product obtained from the reaction was quantitatively identified by 1H NMR spectroscopy, and the yield of tricyclohexylphosphine oxide was 95%.

[0055] Example 3

[0056] Same as Example 1, except that: the nickel-manganese bimetallic hydroxide supported on carbon cloth prepared in Example 3 was used as the anode, and the product obtained from the reaction was quantitatively identified by 1H NMR spectroscopy, with a yield of 93% for triphenylphosphine oxide.

[0057] Example 4

[0058] Same as Example 1, except that: the nickel-aluminum bimetallic hydroxide supported on carbon cloth prepared in Example 4 was used as the anode, and the product obtained from the reaction was quantitatively identified by 1H NMR spectroscopy, with a yield of 87% for triphenylphosphine oxide.

[0059] When nickel-based polymetallic catalysts are used as anodes in Examples 1-4, organophosphorus oxides with high yields can be obtained. Moreover, no heat source or excitation light source is required during the reaction process. The synthesis steps and reaction apparatus are relatively simple. At the same time, the use of other reducing agents or oxidizing agents is avoided, side reactions are reduced, and product separation and purification are simplified.

[0060] The preferred embodiments of this disclosure have been described in detail above with reference to the accompanying drawings. However, this disclosure is not limited to the specific details of the above embodiments. Within the scope of the technical concept of this disclosure, various simple modifications can be made to the technical solutions of this disclosure, and these simple modifications all fall within the protection scope of this disclosure.

[0061] It should also be noted that the various specific technical features described in the above specific embodiments can be combined in any suitable manner without contradiction. In order to avoid unnecessary repetition, this disclosure will not describe the various possible combinations separately.

[0062] Furthermore, various different embodiments of this disclosure can be combined in any way, as long as they do not violate the spirit of this disclosure, they should also be regarded as the content disclosed in this disclosure.

Claims

1. A method for preparing organophosphorus oxides by electrolytic oxidation, characterized in that, The method includes: placing an organophosphorus in the electrolyte of an electrolytic cell for an electrolytic oxidation reaction, wherein the anode in the electrolytic cell is a nickel-based multimetallic catalyst, and the electrolyte includes an organic electrolyte, water, and an organic solvent; The nickel-based multimetallic catalyst comprises a conductive substrate and a nickel-based multimetallic compound supported on the conductive substrate. The nickel-based multimetallic compound includes one or more of nickel-based multimetallic hydroxides, nickel-based multimetallic oxides, nickel-based multimetallic sulfides, nickel-based multimetallic phosphides, nickel-based multimetallic borides, nickel-based multimetallic nitrides, and nickel-based multimetallic carbides. The nickel-based multimetallic catalyst comprises nickel and an active metal selected from one or more of iron, aluminum, manganese, copper, vanadium, and cerium.

2. The method according to claim 1, characterized in that, The active metal is iron.

3. The method according to claim 2, characterized in that, Based on the total number of moles of all metals in the nickel-based polymetallic compound, the content of nickel is 10-90 mol%, the content of active metal is 10-90 mol%, and the molar ratio of nickel to active metal is (1-9):1; wherein, all metals, nickel and active metal are calculated as metal elements.

4. The method according to claim 3, characterized in that, Based on the total number of moles of all metals in the nickel-based polymetallic compound, the nickel content is 40-80 mol%, the active metal content is 20-50 mol%, and the molar ratio of nickel to the active metal is (1-5):

1.

5. The method according to claim 1, characterized in that, The concentration of organophosphorus in the electrolyte is 0.01~100 mmol / L, the concentration of organic electrolyte is 0.01~3 mol / L, and the molar ratio of organophosphorus to organic electrolyte is 1:(1~1000).

6. The method according to claim 5, characterized in that, The concentration of organophosphorus in the electrolyte is 0.015~30 mmol / L, the concentration of organic electrolyte is 0.1~1 mol / L, and the molar ratio of organophosphorus to organic electrolyte is 1:(10~100).

7. The method according to claim 1, characterized in that, The organophosphine is selected from one or more of trimethylphosphine, triethylphosphine, triphenylphosphine, tricyclohexylphosphine, dimethylphenylphosphine, bis(dimethylphosphine)methane, trivinylphosphine, tri-tert-butylphosphine, tri-n-octylphosphine, diphenylcyclohexylphosphine, benzyl diphenylphosphine, tert-butyl diphenylphosphine, and allyl diphenylphosphine; The organic electrolyte is selected from one or more of tetra-n-butylammonium hexafluorophosphate, tetra-n-butylammonium perchlorate, tetra-n-butylammonium sulfate, tetra-n-butylammonium bromide, tetra-n-butylammonium chloride, tetra-n-butylammonium iodide, tetra-n-butylammonium nitrate, tetra-n-butylammonium acetate, and tetra-n-butylammonium hydroxide.

8. The method according to claim 1, characterized in that, The water is selected from one or more of distilled water, deionized water, and ultrapure water, and the organic solvent is selected from one or more of acetonitrile, ethyl acetate, ethanol, methanol, hexafluoroisopropanol, tetrahydrofuran, dimethyl sulfoxide nitrile, and dimethyl sulfoxide. The volume ratio of water to organic solvent in the electrolyte is (0.01~1):

1.

9. The method according to claim 8, characterized in that, The volume ratio of water to organic solvent in the electrolyte is (0.1~0.3):

1.

10. The method according to claim 1, characterized in that, The cathode in the electrolytic cell is a platinum sheet, the reference electrode is a silver / silver chloride electrode, and the voltage of the electrolytic oxidation reaction is 0.5~50V, and the time is 1~24h.

11. The method according to claim 10, characterized in that, The voltage of the electrolytic oxidation reaction is 1~10V, and the time is 1.5~8h.

12. The method according to claim 1, characterized in that, The preparation method of the nickel-based multimetal catalyst includes: mixing and stirring a nickel source, an active metal source, a directing agent, and water to obtain a mixed solution; placing a conductive substrate in the mixed solution and subjecting the resulting reaction solution to hydrothermal treatment at a temperature of 70~150℃ for 3~12h. The nickel source is selected from one or more of nickel nitrate, nickel chloride, and nickel sulfate; the active metal source is selected from one or more of ferric nitrate, ferric chloride, ferrous sulfate, aluminum nitrate, aluminum chloride, manganese nitrate, manganese chloride, copper nitrate, copper chloride, vanadium chloride, and cerium nitrate; the guiding agent is selected from one or more of ammonium fluoride, urea, and hexamethylenetetramine; and the conductive substrate is selected from one or more of carbon cloth, carbon paper, nickel foam, nickel sheet, nickel mesh, copper foam, copper sheet, copper mesh, titanium sheet, titanium mesh, stainless steel sheet, stainless steel mesh, ITO conductive glass, and FTO conductive glass.

13. The method according to claim 12, characterized in that, The active metal source is selected from one or more of ferric nitrate, ferric chloride, and ferrous sulfate, and the conductive substrate is selected from one or more of carbon cloth, nickel foam, nickel sheet, and titanium sheet.

14. The method according to claim 12, characterized in that, In step (1), the concentration of the nickel source in the mixed solution is 1~50 mg / mL, the concentration of the active metal source is 1~50 mg / mL, and the concentration of the directing agent is 1~30 mg / mL; The molar ratio of the nickel source to the active metal source is (0.1~5):

1.

15. The method according to claim 14, characterized in that, The molar ratio of the nickel source to the active metal source is (1~3):1.

Images