Cu3 (PO4) 2-coated CoOOH / copper foam composite material as well as preparation method and application thereof

Abstract

The invention discloses a Cu3 (PO4) 2-coated CoOOH / copper foam composite material as well as a preparation method and application thereof, and belongs to the technical field of electrochemical catalysis. Three-dimensional porous copper foam is used as a substrate, a Cu3 (PO4) 2 nanosheet array is grown on the surface of the substrate in situ through an electrochemical deposition method, then a Cu3 (PO4) 2 (at) CoOOH heterostructure is constructed through cobalt salt modification, and then the Cu3 (PO4) 2 (at) CoOOH / copper foam composite material is obtained. The preparation method is simple in preparation process, mild in condition, free of high-temperature treatment and easy for large-scale production. The prepared composite material shows excellent bifunctional catalytic performance, on one hand, N-N oxidative coupling reaction of 3, 5-diamino-1H-1, 2, 4-triazole can be efficiently catalyzed, azo compounds with high added value are selectively generated, and meanwhile hydrogen is co-produced; and on the other hand, sulfides (S2-, H2S and the like) in the sulfur-containing wastewater can be efficiently catalyzed and converted into elemental sulfur, so that purification treatment of the wastewater is realized.

Description

Technical Field

[0001] This invention belongs to the field of electrochemical catalysis technology, and particularly relates to a Cu3(PO4)2@CoOOH / copper foam composite material, its preparation method and application. Background Technology

[0002] In the current chemical industry system, organic synthesis processes and environmental remediation technologies have long been separated, and this fragmented development model can no longer meet the needs of green chemistry and sustainable development. High-concentration sulfur- and nitrogen-containing wastewater generated during traditional organic synthesis often requires additional end-of-pipe treatment, which not only increases the complexity of the process but also results in a double waste of resources and energy. Taking the synthesis of nitrogen-containing heterocyclic compounds as an example, its production process consumes large amounts of oxidants, generating pollution, and also emits sulfur-based byproducts with recycling value, which are then treated through end-of-pipe treatment. This linear "pollute first, then treat" model exposes the inherent defects of the traditional chemical industry. Electrocatalysis technology, due to its mild reaction conditions and strong controllability, provides a new approach to achieving synergistic optimization of organic synthesis and pollution control. However, existing catalytic systems cannot simultaneously meet the dual requirements of highly selective conversion of organic matter and efficient degradation of pollutants, necessitating the development of novel multifunctional catalytic materials to overcome this technological barrier.

[0003] In traditional organic synthesis processes, the oxidative coupling reactions of nitrogen-containing heterocyclic compounds typically rely on strong oxidants such as potassium permanganate and persulfate. These methods not only generate large amounts of heavy metal waste but also face the significant challenge of controlling reaction selectivity. Taking the N / N coupling reaction of 3,5-diamino-1H-1,2,4-triazole (DAT) as an example, existing thermocatalytic systems generally suffer from high reaction temperatures (typically 80-120°C) and large amounts of organic solvents, and it is difficult to avoid ring-breaking side reactions caused by excessive oxidation. Although electrocatalytic synthesis technology has shown unique advantages in recent years, existing platinum-based and ruthenium-based noble metal catalysts are expensive, while transition metal-based catalysts generally suffer from technical bottlenecks such as low current efficiency and poor product selectivity.

[0004] In the field of environmental governance, technologies for treating sulfur-containing pollutants face even more severe challenges. The Fenton oxidation method, widely used in industry, carries the risk of secondary pollution from iron sludge, while biological desulfurization technology is limited by low treatment efficiency and poor adaptability of microbial strains. Although electrochemical oxidation technology is theoretically clean and efficient, existing electrode materials lack sufficient ability to regulate the oxidation pathway of sulfides, often resulting in the deposition of elemental sulfur or intermediate products such as sulfites, leading to electrode passivation and unstable treatment effects. Particularly for high-concentration sulfur-containing wastewater (such as produced water from oil and gas fields and refining wastewater), existing electrode materials struggle to achieve complete sulfide conversion while maintaining high current efficiency.

[0005] From a materials science perspective, although copper-based catalysts are inexpensive and possess multiple redox properties, their practical application still faces numerous obstacles. Pure copper electrodes are prone to surface oxidation and reconstruction during electrocatalysis, leading to the loss of active sites; while copper oxides or hydroxides suffer from poor conductivity and insufficient exposure of active sites. Although recent studies have attempted to improve performance by constructing copper-based composite materials, most preparation methods require high-temperature calcination or multi-step modification, which not only consumes a lot of energy but also easily causes agglomeration of active components. Especially under neutral or weakly alkaline conditions, the stability problems of traditional copper-based catalysts are more pronounced, severely restricting their application in practical wastewater treatment.

[0006] In current technologies, the design of multifunctional electrocatalytic materials still lacks systematic research. Most reported catalysts are developed only for single reaction systems, making it difficult to simultaneously meet the different needs of organic synthesis and environmental remediation. Furthermore, traditional powder catalysts require the addition of binders to prepare electrodes, which not only increases process complexity but may also lead to active site embedding and increased mass transfer resistance. Although three-dimensional porous electrode materials have shown certain advantages, how to construct nanostructures with rich active interfaces on macroscopic substrates through controllable preparation methods remains a key technical problem that urgently needs to be solved in the field of materials design. Summary of the Invention

[0007] This invention addresses the problems of disconnect between organic synthesis and pollution control, and the limited functionality of electrocatalytic materials in existing technologies. It proposes a Cu3(PO4)2@CoOOH / copper foam composite material, its preparation method, and its applications. The Cu3(PO4)2@CoOOH / copper foam composite material prepared by this invention exhibits unique bifunctional catalytic performance: in organic electrosynthesis, this composite material can efficiently catalyze the NNN oxidative coupling reaction of DAT under mild conditions (room temperature and pressure), with high DAT selectivity, while simultaneously achieving high-purity hydrogen co-production; in environmental control, it effectively catalyzes various sulfides (S... 2- It exhibits excellent electrocatalytic oxidation performance (such as H2S), with high sulfur conversion rate and can effectively inhibit electrode passivation.

[0008] To achieve the above objectives, the present invention provides the following technical solution:

[0009] This invention provides a method for preparing Cu3(PO4)2@CoOOH / copper foam composite material, comprising the following steps:

[0010] (1) Electrochemical deposition was performed using three-dimensional porous copper foam as the working electrode and phosphate buffer as the electrolyte to obtain Cu3(PO4)2 / three-dimensional porous copper foam.

[0011] (2) The Cu3(PO4)2 / three-dimensional porous copper foam is immersed in an ethanol solution containing cobalt salt, ammonium bicarbonate is added and stirred to react, and then washed and vacuum dried to obtain the Cu3(PO4)2@CoOOH / copper foam composite material.

[0012] This invention uses a three-dimensional porous copper foam as a substrate. A vertically aligned array of Cu3(PO4)2 nanosheets is grown in situ on the substrate surface via electrochemical deposition. This array is then modified with cobalt salt to construct a Cu3(PO4)2@CoOOH heterostructure with abundant interfacial effects and strong synergistic effects. This ingenious material architecture not only provides abundant active sites and efficient electron transport pathways but also cleverly combines the intrinsic catalytic activity of Cu3(PO4)2 with the redox properties of CoOOH. Simultaneously, it fully leverages the high conductivity and mechanical stability of the copper foam substrate, ultimately yielding a Cu3(PO4)2@CoOOH / copper foam composite material with unique bifunctional catalytic performance. The preparation method provided by this invention avoids high-temperature processing, saves energy, and is easily scalable for mass production.

[0013] Further, in step (1), the pore size of the three-dimensional porous copper foam is 100-500 μm, and the porosity is ≥90%; and / or,

[0014] The concentration of the phosphate buffer solution is 0.5-1.0 mol / L, and the pH value is 6.5-7.5.

[0015] Further, in step (1), the electrochemical deposition temperature is 25-35℃, the voltage is 0.8-1.2V vs. Ag / AgCl, and the time is 0.5-3 hours.

[0016] Further, in step (2), the ratio of Cu3(PO4)2 / three-dimensional porous copper foam, cobalt salt, and ammonium bicarbonate is (0.2-0.6) g : (0.5-2) mmol : (3-5) mmol; and / or,

[0017] The cobalt salt is at least one of cobalt chloride, cobalt nitrate, and cobalt sulfate.

[0018] Further, in step (2), the temperature of the stirring reaction is 20-30℃, the stirring speed is 200-400rpm, and the time is 8-18 hours; the stirring reaction is carried out in a closed container.

[0019] The present invention also provides a Cu3(PO4)2@CoOOH / copper foam composite material, which is prepared according to the preparation method described in the above technical solution.

[0020] This invention also provides the application of the Cu3(PO4)2@CoOOH / copper foam composite material as described above in the NN oxidative coupling dehydrogenation (OCD) reaction of 3,5-diamino-1H-1,2,4-triazole (DAT), comprising the following steps:

[0021] Using a mixed solution containing 3,5-diamino-1H-1,2,4-triazole (DAT) and KOH as the electrolyte, and the Cu3(PO4)2@CoOOH / copper foam composite material as the working electrode, an electrocatalytic oxidation reaction was carried out to achieve NN oxidative coupling dehydrogenation of 3,5-diamino-1H-1,2,4-triazole.

[0022] This invention also provides an application of the Cu3(PO4)2@CoOOH / copper foam composite material as described above in the electrocatalytic sulfur oxidation reaction (SOR), comprising the following steps:

[0023] Using a mixed solution containing a sulfur source and a supporting electrolyte as the electrolyte, the pH of the electrolyte is adjusted to 7-11, and the Cu3(PO4)2@CoOOH / copper foam composite material is used as the working electrode to carry out a sulfur oxidation reaction to obtain elemental sulfur; the sulfur source includes Na2S or H2S.

[0024] The present invention also provides a coupled reaction system, which includes a Pt / C catalyst electrode, a proton exchange membrane, and the Cu3(PO4)2@CoOOH / copper foam composite material described in the above technical solution;

[0025] The Cu3(PO4)2@CoOOH / copper foam composite material serves as the anode and forms the anode chamber with the proton exchange membrane, while the Pt / C catalyst electrode serves as the cathode and forms the cathode chamber with the proton exchange membrane.

[0026] The electrolytes in both the anode and cathode chambers are mixed solutions containing 3,5-diamino-1H-1,2,4-triazole and KOH.

[0027] The anode chamber undergoes an NN oxidative coupling dehydrogenation reaction to generate an azo compound (DAAT); the cathode chamber undergoes a redox reaction to generate hydrogen gas.

[0028] The present invention also provides a sulfur pollutant treatment device, which includes a reaction tank, an electrolyte circulation system and a gas collection system;

[0029] The reaction tank uses the Cu3(PO4)2@CoOOH / copper foam composite material described in the above technical solution as the anode and a nickel mesh as the cathode;

[0030] The electrolyte in the electrolyte circulation system is a sulfur pollutant; the sulfur pollutant is sulfur-containing wastewater.

[0031] The technical principle of this invention is as follows:

[0032] The working principle of this invention is based on a multi-level synergistic catalysis mechanism, achieving highly efficient catalysis through precisely designed material interface electronic structures and surface coordination environments. In terms of electron transport, a three-dimensional porous copper foam substrate constructs a three-dimensional conductive network, enabling electrons to be rapidly conducted to active sites. The semiconductor properties of Cu3(PO4)2 nanosheets complement the redox activity of CoOOH, generating a synergistic electron transfer path within a potential window of 0.6-1.5V. Experiments have shown that the charge transfer resistance of the composite material is reduced by approximately 60% compared to the single-component composite.

[0033] For the DAT oxidative coupling reaction, the catalytic process exhibits a synergistic effect of multiple active sites. Specifically, Cu... 3+ / Cu 2+ Redox pairs are responsible for the initial activation of amino groups in DAT molecules, effectively reducing the NH bond dissociation energy; Co 3+ / Co 2+ The cycle promotes the coupling process of the generated nitrogen radical intermediates; simultaneously, the phosphate group stabilizes the transition state through hydrogen bonding, significantly improving reaction selectivity. In sulfide oxidation, the highly reactive oxygen species (·OH) provided by CoOOH directly attack S... 2- The lone pair electrons of Cu3(PO4)2 and the lattice oxygen participate in the gradual oxidation process of sulfur. The oxygen vacancies at the heterojunction promote the adsorption and dissociation of H2O molecules, continuously replenishing the active oxygen source and realizing the efficient conversion of sulfides to sulfate.

[0034] The stability enhancement mechanism of the Cu3(PO4)2@CoOOH / copper foam composite material in this invention is mainly reflected in the three-dimensional structural design. Specifically, the rigid skeleton of copper foam effectively inhibits the structural reconstruction of Cu3(PO4)2 nanosheets during the electrochemical process, the CoOOH modification layer protects Cu3(PO4)2 from excessive oxidation, and the phosphate matrix maintains the overall structural stability through the strong covalent nature of PO bonds. This multi-level protection strategy enables the composite material to maintain excellent performance stability during long-term operation.

[0035] The dual-effect effect is the core innovation of this invention. During the DAT oxidation process, protons (H+) generated on the surface of the composite material... +The reactive oxygen species (ROS) can migrate to the cathode and be reduced to H2, achieving energy conversion; electrons released from sulfide oxidation are rapidly conducted through the copper substrate, forming a charge balance with the organic oxidation reaction; although the two reactions share the same reactive oxygen species transport pathway, selective control is achieved through precisely regulated steric hindrance effects. This "one material, two effects" design concept provides an important theoretical basis for the development of novel multifunctional electrocatalysts, realizing the dual-functional coupling of organic electrosynthesis (DAT oxidative coupling) and environmental remediation (sulfide oxidation).

[0036] Compared with the prior art, the present invention has the following advantages and technical effects:

[0037] In terms of material architecture, this invention employs a three-dimensional porous copper foam as a conductive substrate. Through a precisely controlled electrochemical deposition process, a vertically aligned array of Cu3(PO4)2 nanosheets is grown in situ on its surface. This unique structural design not only provides abundant active sites but also ensures efficient electron transport pathways. More importantly, through a subsequent cobalt salt modification process, CoOOH active components are uniformly loaded onto the surface of the Cu3(PO4)2 nanosheets, constructing a heterogeneous interface structure with strong synergistic effects. This multi-level composite design cleverly combines the intrinsic catalytic activity of Cu3(PO4)2 with the redox properties of CoOOH, while fully leveraging the high conductivity and mechanical stability advantages of the copper foam substrate. Regarding microstructure control, by optimizing synthesis parameters, the Cu3(PO4)2 nanosheets are ensured to have appropriate thickness and spacing, guaranteeing sufficient exposure of active sites while maintaining good mass transport channels. This meticulously designed electrode material exhibits excellent comprehensive performance. Its unique structural features significantly improve the utilization rate of active sites, greatly reduce interfacial charge transfer resistance, and effectively inhibit structural degradation during the catalytic process, providing an ideal platform for efficient and stable electrocatalytic reactions.

[0038] In terms of catalytic performance, the Cu3(PO4)2@CoOOH / copper foam composite material of this invention exhibits groundbreaking performance: it demonstrates extremely high selectivity for the oxidative coupling reaction of DAT, while simultaneously achieving highly efficient conversion of sulfides, with catalytic activity far exceeding that of conventional copper-based materials. Its unique microstructure design, through optimizing the thickness and spacing of Cu3(PO4)2 nanosheets, ensures sufficient exposure of active sites while maintaining good mass transport channels, significantly improving the utilization rate of active sites, greatly reducing interfacial charge transfer resistance, and effectively inhibiting structural degradation during the catalytic process.

[0039] In terms of economic efficiency and environmental friendliness, the preparation process of this invention significantly reduces production costs and energy consumption. The reaction process requires no chemical oxidants, reducing pollution emissions at the source, and the reaction conditions are mild and safe. The composite material prepared by this invention exhibits excellent stability, maintaining good performance under complex water quality conditions and long-term operation. It has a wide range of applications, can treat wastewater of different concentrations and pH conditions, and has been successfully scaled up industrially.

[0040] This invention integrates material design innovation, performance breakthroughs, and process optimization. Through multi-faceted collaborative innovation, it not only provides an ideal platform for efficient and stable electrocatalytic reactions, but also offers reliable solutions for green chemical manufacturing and environmental pollution control, demonstrating broad application prospects and significant promotional value. Attached Figure Description

[0041] The accompanying drawings, which form part of this invention, are used to provide a further understanding of the invention. The illustrative embodiments of the invention and their descriptions are used to explain the invention and do not constitute an undue limitation of the invention. In the drawings:

[0042] Figure 1 SEM image of Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1;

[0043] Figure 2 The elemental mapping diagram of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1;

[0044] Figure 3 SEM image of Cu3(PO4)2 / copper foam prepared in step (2) of Example 1;

[0045] Figure 4 The EDS results are for the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1;

[0046] Figure 5 XPS full spectrum of Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1;

[0047] Figure 6 The image shows a comparison of the three-electrode linear sweep voltammetry curves of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1 under DAT oxidation and OER in alkaline electrolyte. In the image, 1M KOH+0.2MDAT represents the three-electrode linear sweep voltammetry curve of DAT oxidation, and 1M KOH represents the three-electrode linear sweep voltammetry curve of OER.

[0048] Figure 7The image shows a comparison of the three-electrode linear sweep voltammetry curves of the Cu3(PO4)2 / copper foam composite material prepared in Comparative Example 1 under DAT oxidation and OER in alkaline electrolyte. In the image, 1M KOH+0.2M DAT represents the three-electrode linear sweep voltammetry curve of DAT oxidation, and 1M KOH represents the three-electrode linear sweep voltammetry curve of OER.

[0049] Figure 8 The image shows a comparison of the three-electrode linear sweep voltammetry curves of the CoOOH / copper foam composite material prepared in Comparative Example 2 under DAT oxidation and OER in alkaline electrolyte. In the image, 1M KOH+0.2M DAT represents the three-electrode linear sweep voltammetry curve of DAT oxidation, and 1M KOH represents the three-electrode linear sweep voltammetry curve of OER.

[0050] Figure 9 The image shows a comparison of the three-electrode linear sweep voltammetry curves (SOR and OER) of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1. In the image, 1M Na2S+1M KOH represents the three-electrode linear sweep voltammetry curve of SOR, and 1M KOH represents the three-electrode linear sweep voltammetry curve of OER.

[0051] Figure 10 The image shows a comparison of the three-electrode linear sweep voltammetry curves of the SOR of the copper foam composite materials prepared in Example 2 and Comparative Example 1, where Cu3(PO4)2@CoOOH / CF is Example 2 and Cu3(PO4)2 / CF is Comparative Example 1.

[0052] Figure 11 The AC impedance spectra of Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1 and Cu3(PO4)2 / copper foam composite material prepared in Comparative Example 1 in 1M KOH+1M Na2S are shown. Cu3(PO4)2@CoOOH / CF is Example 1 and Cu3(PO4)2 / CF is Comparative Example 1. Detailed Implementation

[0053] The technical solutions of the embodiments of the present invention will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of the present invention, and not all embodiments. Based on the embodiments of the present invention, all other embodiments obtained by those skilled in the art without creative effort are within the scope of protection of the present invention.

[0054] To make the above-mentioned objects, features and advantages of the present invention more apparent and understandable, the present invention will be further described in detail below with reference to the accompanying drawings and specific embodiments.

[0055] This invention provides a method for preparing Cu3(PO4)2@CoOOH / copper foam composite material, comprising the following steps:

[0056] (1) Electrochemical deposition was performed using three-dimensional porous copper foam as the working electrode and phosphate buffer as the electrolyte to obtain Cu3(PO4)2 / three-dimensional porous copper foam.

[0057] (2) The Cu3(PO4)2 / three-dimensional porous copper foam is immersed in an ethanol solution containing cobalt salt, ammonium bicarbonate is added and stirred to react, and then washed and vacuum dried to obtain the Cu3(PO4)2@CoOOH / copper foam composite material.

[0058] In a preferred embodiment, in step (1), the pore size of the three-dimensional porous copper foam is 100-500 μm, and the porosity is ≥90%. The three-dimensional porous copper foam of the present invention has high conductivity and large specific surface area, providing an excellent conductive framework and material transport channel for composite materials, ensuring rapid electron transport and full exposure of active sites.

[0059] In a preferred embodiment, step (1) further includes a pretreatment step for the three-dimensional porous copper foam; the pretreatment process specifically involves: placing the three-dimensional porous copper foam in an acidic solution, acetone and ethanol in sequence for ultrasonic cleaning to remove surface impurities and oxide layers, then rinsing thoroughly with deionized water, and then drying with nitrogen gas; the acidic solution is selected from one of hydrochloric acid aqueous solution, nitric acid aqueous solution and sulfuric acid aqueous solution.

[0060] In a preferred embodiment, in step (1), the concentration of the phosphate buffer is 0.5-1.0 mol / L, and the pH value is 6.5-7.5; the phosphate buffer is a Na2HPO4 / NaH2PO4 buffer solution.

[0061] In a preferred embodiment, in step (1), the electrochemical deposition temperature is 25-35°C, the voltage is 0.8-1.2V vs. Ag / AgCl, and the time is 0.5-3 hours. This invention grows Cu3(PO4)2 nanosheet arrays in situ on the surface of a three-dimensional porous copper foam via electrochemical deposition. By controlling the parameters of the electrochemical deposition, the Cu3(PO4)2 nanosheets are ensured to have appropriate thickness and spacing, guaranteeing sufficient exposure of active sites while maintaining good material transport channels.

[0062] In a preferred embodiment, the thickness of the Cu3(PO4)2 nanosheets in the Cu3(PO4)2 nanosheet array is 20-50 nm, the Cu3(PO4)2 nanosheets are arranged in a vertical orientation, and the inter-sheet spacing is 50-500 nm.

[0063] In a preferred embodiment, in step (1), a platinum sheet is used as the counter electrode during the electrochemical deposition process, and the deposition process employs a constant potential method.

[0064] In a preferred embodiment, in step (2), the ratio of Cu3(PO4)2 / three-dimensional porous copper foam, cobalt salt, and ammonium bicarbonate is (0.2-0.6) g : (0.5-2) mmol : (3-5) mmol, more preferably (0.2-0.4) g : (1-2) mmol : (3-4) mmol. This invention controls the distribution of CoOOH nanoparticles on the surface of Cu3(PO4)2 nanosheets by controlling the amount of cobalt salt. Excessive use of cobalt salt results in a large-area coverage of Cu3(PO4)2 nanosheets by CoOOH nanoparticles, failing to fully utilize the catalytic activity of the Cu3(PO4)2 nanosheets. Conversely, insufficient use of cobalt salt leads to a weak modification effect of the CoOOH nanoparticles, failing to fully realize the strong synergistic effect.

[0065] In a preferred embodiment, in step (2), the cobalt salt is at least one of cobalt chloride, cobalt nitrate and cobalt sulfate, and is more preferably cobalt chloride.

[0066] In a preferred embodiment, in step (2), the temperature of the stirring reaction is 20-30℃, the stirring speed is 200-400 rpm, and the time is 8-18 hours; the stirring reaction is carried out in a closed container. This invention employs a mild solution-phase modification strategy to generate CoOOH active species in situ on the surface of Cu3(PO4)2 nanosheets, achieving uniform modification of CoOOH nanoparticles on the surface of Cu3(PO4)2 nanosheets, forming a heterostructure with a strong synergistic effect. The synergistic effect between Cu3(PO4)2 nanosheets and CoOOH generates new active centers, significantly improving catalytic activity and selectivity. Simultaneously, the stable three-dimensional structure effectively prevents the active components from detaching, greatly extending the material's service life.

[0067] In a preferred embodiment, in step (2), the washing reagent is deionized water; and the washing is performed 3 times.

[0068] In a preferred embodiment, in step (2), the vacuum drying temperature is 60°C and the time is 6 hours.

[0069] The present invention also provides a Cu3(PO4)2@CoOOH / copper foam composite material, which is prepared according to the preparation method described in the above technical solution.

[0070] The Cu3(PO4)2@CoOOH / copper foam composite material provided by this invention exhibits unique bifunctional catalytic properties:

[0071] In the field of organic electrosynthesis, the composite material can efficiently catalyze the NNN oxidative coupling reaction of DAT under mild conditions (room temperature and pressure), with high DAT selectivity, while achieving high-purity hydrogen co-production.

[0072] In terms of environmental remediation, various sulfides (S) 2- It exhibits excellent electrocatalytic oxidation performance (such as H2S), with high sulfur conversion rate and can effectively inhibit electrode passivation.

[0073] This invention also provides the application of the Cu3(PO4)2@CoOOH / copper foam composite material as described above in the NN oxidative coupling dehydrogenation reaction of 3,5-diamino-1H-1,2,4-triazole, comprising the following steps:

[0074] Using a mixed solution containing 3,5-diamino-1H-1,2,4-triazole and KOH as the electrolyte and the Cu3(PO4)2@CoOOH / copper foam composite material as the working electrode, an electrocatalytic oxidation reaction was carried out to achieve NN oxidative coupling dehydrogenation of 3,5-diamino-1H-1,2,4-triazole.

[0075] In a preferred embodiment, the concentration of 3,5-diamino-1H-1,2,4-triazole in the mixed solution containing 3,5-diamino-1H-1,2,4-triazole is 0.1-0.5 mol / L, and the concentration of KOH is 0.1-1.0 mol / L.

[0076] In a preferred embodiment, the temperature of the electrocatalytic oxidation reaction is controlled at 25-35°C, and the reaction duration is 2-6 hours, which can realize the efficient oxidative coupling reaction of DAT.

[0077] This invention also provides an application of the Cu3(PO4)2@CoOOH / copper foam composite material as described above in the electrocatalytic sulfur oxidation reaction, comprising the following steps:

[0078] Using a mixed solution containing a sulfur source and a supporting electrolyte as the electrolyte, the pH of the electrolyte is adjusted to 7-11, and the Cu3(PO4)2@CoOOH / copper foam composite material is used as the working electrode to carry out a sulfur oxidation reaction to obtain elemental sulfur; the sulfur source includes Na2S or H2S.

[0079] In a preferred embodiment, the concentration of the sulfur source in the mixed solution containing the sulfur source and the supporting electrolyte is 0.05-0.3 mol / L, and the concentration of the supporting electrolyte is 0.1-0.5 mol / L; the supporting electrolyte is selected from KOH.

[0080] In a preferred embodiment, the sulfur oxidation reaction operates at a potential of 1.0-1.2V (vs. RHE) and takes 1-3 hours, enabling efficient conversion of sulfides to sulfate.

[0081] In a preferred embodiment, NaOH is used to adjust the pH of the electrolyte to 7-11, more preferably 8.5-9.5.

[0082] The present invention also provides a coupled reaction system, which includes a Pt / C catalyst electrode, a proton exchange membrane, and the Cu3(PO4)2@CoOOH / copper foam composite material described in the above technical solution;

[0083] The Cu3(PO4)2@CoOOH / copper foam composite material serves as the anode and forms the anode chamber with the proton exchange membrane, while the Pt / C catalyst electrode serves as the cathode and forms the cathode chamber with the proton exchange membrane.

[0084] The electrolytes in both the anode and cathode chambers are mixed solutions containing 3,5-diamino-1H-1,2,4-triazole and KOH.

[0085] The anode chamber undergoes an NN oxidative coupling dehydrogenation reaction to generate an azo compound (DAAT); the cathode chamber undergoes a redox reaction to generate hydrogen gas.

[0086] In a preferred embodiment, the size of the Cu3(PO4)2@CoOOH / copper foam composite material is 2.5cm × 2.5cm.

[0087] In a preferred embodiment, the concentration of 3,5-diamino-1H-1,2,4-triazole in the mixed solution containing 3,5-diamino-1H-1,2,4-triazole is 0.1-0.5 mol / L, and the concentration of KOH is 0.1-1.0 mol / L.

[0088] In a preferred embodiment, the proton exchange membrane is selected from the Nafion series of proton exchange membranes, and more preferably the Nafion 117 proton exchange membrane.

[0089] In a preferred embodiment, the volume of electrolyte in both the anode chamber and the cathode chamber is 50 mL.

[0090] The present invention also provides a sulfur pollutant treatment device, which includes a reaction tank, an electrolyte circulation system and a gas collection system;

[0091] The reaction tank uses the Cu3(PO4)2@CoOOH / copper foam composite material described in the above technical solution as the anode and a nickel mesh as the cathode;

[0092] The electrolyte in the electrolyte circulation system is a sulfur pollutant; the sulfur pollutant is sulfur-containing wastewater.

[0093] In a preferred embodiment, the sulfur in the sulfur-containing wastewater 2- The concentration is 0.1-1000 ppm. The electrolyte circulation system in this invention is used for the continuous treatment of sulfur-containing wastewater, and the gas collection system is used to collect the hydrogen gas generated during the reaction.

[0094] Unless otherwise specified, all raw materials used in the embodiments of this invention were purchased through commercial channels.

[0095] Example 1

[0096] A method for preparing Cu3(PO4)2@CoOOH / copper foam composite material, comprising the following steps:

[0097] (1) Three-dimensional porous copper foam with a pore size of 100-500μm and a porosity of ≥90% was ultrasonically cleaned in hydrochloric acid aqueous solution, acetone and ethanol for 10 minutes each, rinsed with deionized water 3 times and dried with nitrogen to obtain pretreated three-dimensional porous copper foam.

[0098] (2) Using the pretreated three-dimensional porous copper foam in step (1) as the working electrode, a platinum sheet as the counter electrode, and a 0.8M Na2HPO4 / NaH2PO4 buffer solution with pH=7 as the electrolyte, electrochemical deposition was carried out under a constant potential of 1.0V (vs. Ag / AgCl) for 0.5 hours. The entire deposition process was carried out in a constant temperature environment of 25℃ to ensure uniform nucleation and growth. After the electrochemical deposition was completed, Cu3(PO4)2 / copper foam was obtained.

[0099] (3) Soak 0.2g of the Cu3(PO4)2 / copper foam obtained in step (2) in an ethanol solution containing 1mM CoCl2·6H2O and 3mM NH4HCO3 (i.e., the ratio of Cu3(PO4)2 / copper foam, CoCl2·6H2O and NH4HCO3 is 0.2g∶1mmol∶3mmol), and magnetically stir the reaction at 200rpm for 12 hours at 25℃. The magnetic stirring reaction is carried out in a closed container to allow Co to... 2+ The material is converted to CoOOH in situ on the surface of the material. After the reaction is complete, the resulting material is washed three times with deionized water and vacuum dried at 60°C for 6 hours to obtain Cu3(PO4)2@CoOOH / copper foam composite material.

[0100] Figure 1 SEM image of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1. Figure 1As can be seen, CoOOH is uniformly distributed on Cu3(PO4)2 nanosheets, resulting in a three-dimensional self-supporting porous structure. This structure greatly increases the specific surface area of ​​the catalyst, which is beneficial for mass transfer.

[0101] Figure 2 The elemental mapping diagram is shown for the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1. From... Figure 2 It can be seen that copper, cobalt, phosphorus and oxygen elements are evenly distributed on the sample surface.

[0102] Figure 3 SEM image of the Cu3(PO4)2 / copper foam prepared in step (2) of Example 1. From Figure 3 It can be seen that the thickness of the nanosheets in the Cu3(PO4)2 nanosheet array in Cu3(PO4)2 / copper foam is 20-50 nm, the Cu3(PO4)2 nanosheets are arranged in a vertical orientation, and the inter-sheet spacing is 50-500 nm.

[0103] Figure 4 EDS results for the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1. From... Figure 4 It can be seen that the sample contains copper, cobalt, phosphorus and oxygen.

[0104] Figure 5 The XPS full spectrum of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1 is shown below. Figure 5 It can be seen that the sample contains copper, cobalt, phosphorus and oxygen.

[0105] Example 2

[0106] A method for preparing Cu3(PO4)2@CoOOH / copper foam composite material, comprising the following steps:

[0107] (1) Three-dimensional porous copper foam with a pore size of 100-500μm and a porosity of ≥90% was ultrasonically cleaned in nitric acid aqueous solution, acetone and ethanol for 10 minutes each, rinsed with deionized water 3 times and dried with nitrogen to obtain pretreated three-dimensional porous copper foam.

[0108] (2) Using the pretreated three-dimensional porous copper foam in step (1) as the working electrode, a platinum sheet as the counter electrode, and a 0.8M, pH=7 Na2HPO4 / NaH2PO4 buffer solution as the electrolyte, electrochemical deposition was carried out under a constant potential of 1.2V (vs. Ag / AgCl) for 2 hours. The entire deposition process was carried out in a constant temperature environment of 25℃ to ensure uniform nucleation and growth. After the electrochemical deposition was completed, Cu3(PO4)2 / copper foam was obtained.

[0109] (3) Soak 0.3g of the Cu3(PO4)2 / copper foam obtained in step (2) in an ethanol solution containing 1mM CoCl2·6H2O and 3mM NH4HCO3 (i.e., the ratio of Cu3(PO4)2 / copper foam, CoCl2·6H2O and NH4HCO3 is 0.3g∶1mmol∶3mmol), and magnetically stir the reaction at 400rpm for 18 hours at 25℃. The magnetic stirring reaction is carried out in a closed container to allow Co to... 2+ The material is converted to CoOOH in situ on the surface of the material. After the reaction is complete, the resulting material is washed three times with deionized water and vacuum dried at 60°C for 6 hours to obtain Cu3(PO4)2@CoOOH / copper foam composite material.

[0110] Example 3

[0111] A method for preparing Cu3(PO4)2@CoOOH / copper foam composite material, comprising the following steps:

[0112] (1) Three-dimensional porous copper foam with a pore size of 100-500μm and a porosity of ≥90% was ultrasonically cleaned in sulfuric acid aqueous solution, acetone and ethanol for 10 minutes each, rinsed with deionized water 3 times and dried with nitrogen to obtain pretreated three-dimensional porous copper foam.

[0113] (2) Using the pretreated three-dimensional porous copper foam in step (1) as the working electrode, a platinum sheet as the counter electrode, and a 0.8M, pH=7 Na2HPO4 / NaH2PO4 buffer solution as the electrolyte, electrochemical deposition was carried out under a constant potential of 0.8V (vs. Ag / AgCl) for 1 hour. The entire deposition process was carried out in a constant temperature environment of 25℃ to ensure uniform nucleation and growth. After the electrochemical deposition was completed, Cu3(PO4)2 / copper foam was obtained.

[0114] (3) Soak 0.4g of the Cu3(PO4)2 / copper foam obtained in step (2) in an ethanol solution containing 2mM CoCl2·6H2O and 4mM NH4HCO3 (i.e., the ratio of Cu3(PO4)2 / copper foam, CoCl2·6H2O and NH4HCO3 is 0.4g∶2mmol∶4mmol), and magnetically stir the reaction at 200rpm for 12 hours at 30℃. The magnetic stirring reaction is carried out in a closed container to allow Co to... 2+ The material is converted to CoOOH in situ on the surface of the material. After the reaction is complete, the resulting material is washed three times with deionized water and vacuum dried at 60°C for 6 hours to finally obtain Cu3(PO4)2@CoOOH / copper foam composite material.

[0115] Example 4

[0116] A method for preparing Cu3(PO4)2@CoOOH / copper foam composite material, comprising the following steps:

[0117] (1) Three-dimensional porous copper foam with a pore size of 100-500μm and a porosity of ≥90% was ultrasonically cleaned in hydrochloric acid aqueous solution, acetone and ethanol for 10 minutes each, rinsed with deionized water 3 times and dried with nitrogen to obtain pretreated three-dimensional porous copper foam.

[0118] (2) Using the pretreated three-dimensional porous copper foam in step (1) as the working electrode, a platinum sheet as the counter electrode, and a 0.8M Na2HPO4 / NaH2PO4 buffer solution with pH=7 as the electrolyte, electrochemical deposition was carried out under a constant potential of 1.0V (vs. Ag / AgCl) for 2 hours. The entire deposition process was carried out in a constant temperature environment of 25℃ to ensure uniform nucleation and growth. After the electrochemical deposition was completed, Cu3(PO4)2 / copper foam was obtained.

[0119] (3) 0.6 g of the Cu3(PO4)2 / copper foam obtained in step (2) was soaked in an ethanol solution containing 2 mM CoCl2·6H2O and 4 mM NH4HCO3 (i.e., the ratio of Cu3(PO4)2 / copper foam, CoCl2·6H2O and NH4HCO3 was 0.6 g : 2 mmol : 3 mmol). The reaction was carried out at 25 °C with magnetic stirring at 300 rpm for 12 hours. The magnetic stirring reaction was carried out in a closed container to allow Co to... 2+ The material is converted to CoOOH in situ on the surface of the material. After the reaction is complete, the resulting material is washed three times with deionized water and vacuum dried at 60°C for 6 hours to finally obtain Cu3(PO4)2@CoOOH / copper foam composite material.

[0120] Comparative Example 1

[0121] A method for preparing a Cu3(PO4)2 / copper foam composite material, comprising the following steps:

[0122] (1) Three-dimensional porous copper foam with a pore size of 100-500μm and a porosity of ≥90% was ultrasonically cleaned in hydrochloric acid aqueous solution, acetone and ethanol for 10 minutes each, rinsed with deionized water 3 times and dried with nitrogen to obtain pretreated three-dimensional porous copper foam.

[0123] (2) Using the pretreated three-dimensional porous copper foam in step (1) as the working electrode, a platinum sheet as the counter electrode, and a 0.8M Na2HPO4 / NaH2PO4 buffer solution with pH=7 as the electrolyte, electrochemical deposition was carried out under a constant potential of 1.0V (vs. Ag / AgCl) for 0.5 hours. The entire deposition process was carried out in a constant temperature environment of 25℃ to ensure uniform nucleation and growth. After the electrochemical deposition was completed, Cu3(PO4)2 / copper foam composite material was obtained.

[0124] Comparative Example 2

[0125] A method for preparing a CoOOH / copper foam composite material, comprising the following steps:

[0126] (1) Three-dimensional porous copper foam with a pore size of 100-500μm and a porosity of ≥90% was ultrasonically cleaned in hydrochloric acid aqueous solution, acetone and ethanol for 10 minutes each, rinsed with deionized water 3 times and dried with nitrogen to obtain pretreated three-dimensional porous copper foam.

[0127] (2) Immerse 0.2g of the pretreated three-dimensional porous copper foam from step (1) in an ethanol solution containing 1mM CoCl2·6H2O and 3mM NH4HCO3 (i.e., the ratio of pretreated three-dimensional porous copper foam, CoCl2·6H2O, and NH4HCO3 is 0.2g∶1mmol∶3mmol). At 25°C, magnetically stir the reaction at 300rpm for 12 hours. The magnetic stirring reaction is carried out in a closed container to allow the Co... 2+ The material is converted to CoOOH in situ on the surface. After the reaction is complete, the resulting material is washed three times with deionized water and vacuum dried at 60°C for 6 hours to obtain a CoOOH / copper foam composite material.

[0128] Performance testing:

[0129] (1) DAT oxidation reactivity

[0130] DAT oxidation reaction: The copper foam composite materials prepared in Example 1, Comparative Example 1, and Comparative Example 2 were used as working electrodes, platinum electrodes as counter electrodes, and Hg / HgO as reference electrodes. An aqueous solution containing 1 M KOH and 0.2 M DAT was used as the electrolyte for the DAT oxidation reaction. Simultaneously, linear sweep voltammetry curves of DAT were measured at a scan rate of 5 mV / s. The results are shown in [Figure number missing]. Figure 6-8 .

[0131] Figure 6This is a comparison of the three-electrode linear sweep voltammetric curves of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1 under alkaline electrolyte conditions for DAT oxidation and OER. In the figure, 1M KOH + 0.2MDAT represents the three-electrode linear sweep voltammetric curve for DAT oxidation, and 1M KOH represents the three-electrode linear sweep voltammetric curve for OER. Figure 6 It can be seen that the DAT oxidation potential of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1 is much higher than that of OER.

[0132] Figure 7 This is a comparison of the three-electrode linear sweep voltammetric curves of the Cu3(PO4)2 / copper foam composite material prepared in Comparative Example 1 under DAT oxidation and OER in alkaline electrolyte. In the figure, 1M KOH + 0.2M DAT represents the three-electrode linear sweep voltammetric curve for DAT oxidation, and 1M KOH represents the three-electrode linear sweep voltammetric curve for OER. Figure 7 It can be seen that the DAT oxidation potential of Cu3(PO4)2 / copper foam composite material is much higher than that of OER.

[0133] contrast Figure 6 and Figure 7 It can be seen that the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1 has better electrochemical activity than the Cu3(PO4)2 / copper foam composite material prepared in Comparative Example 1. This is because, compared with copper phosphate, the Cu3(PO4)2@CoOOH heterostructure can maximize the exposure of active sites, significantly enhance electronic conductivity, maximize adsorption energy, and improve charge transfer ability, thus exhibiting excellent electrochemical activity.

[0134] Figure 8 This is a comparison of the three-electrode linear sweep voltammetric curves of the CoOOH / copper foam composite material prepared in Comparative Example 2 in alkaline electrolyte for DAT oxidation and OER. In the figure, 1M KOH + 0.2M DAT represents the three-electrode linear sweep voltammetric curve for DAT oxidation, and 1M KOH represents the three-electrode linear sweep voltammetric curve for OER. Figure 8 It can be seen that the DAT oxidation potential of the CoOOH / copper foam composite material is much higher than that of the OER.

[0135] contrast Figure 6 and Figure 8 It can be seen that the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1 has better electrochemical activity than the CoOOH / copper foam composite material prepared in Comparative Example 2. This is because the Cu3(PO4)2@CoOOH heterostructure can maximize the exposure of active sites, significantly enhance electronic conductivity, maximize adsorption energy, and improve charge transfer ability, thus exhibiting excellent electrochemical activity.

[0136] (2) Sulfur oxidation reactivity

[0137] Sulfur oxidation reaction: The copper foam composite materials prepared in Examples 1-2 and Comparative Example 1 were used as working electrodes, a platinum electrode as the counter electrode, and Hg / HgO as the reference electrode. An aqueous solution containing 1M KOH and 1M Na₂S was used as the electrolyte for the sulfur oxidation reaction. Linear sweep voltammetry was performed at a scan rate of 5 mV / s. The results are shown in [Figure number missing]. Figure 9-11 .

[0138] Figure 9 This is a comparison of the three-electrode linear sweep voltammetric curves (SOR and OER) of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1. In the figure, 1M Na2S + 1M KOH represents the three-electrode linear sweep voltammetric curve of SOR, and 1M KOH represents the three-electrode linear sweep voltammetric curve of OER. Figure 9 It can be seen that the sulfur oxidation potential of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1 is much higher than that of OER.

[0139] Figure 10 The image shows a comparison of the three-electrode linear sweep voltammetry curves of the SOR (Self-Organic Oxygen Regulator) of the copper foam composite materials prepared in Example 2 and Comparative Example 1, where Cu3(PO4)2@CoOOH / CF is from Example 2 and Cu3(PO4)2 / CF is from Comparative Example 1. Figure 10 It can be seen that the sulfur oxidation reaction activity of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 2 is better than that of the Cu3(PO4)2 / copper foam composite material prepared in Comparative Example 1. This is because, compared with copper phosphate, the Cu3(PO4)2@CoOOH heterostructure can maximize the exposure of active sites, significantly enhance electronic conductivity, maximize adsorption energy, and improve charge transfer ability, thus exhibiting excellent electrochemical activity.

[0140] Figure 11 The AC impedance spectra of the Cu3(PO4)2@CoOOH / copper foam composite material prepared in Example 1 and the Cu3(PO4)2 / copper foam composite material prepared in Comparative Example 1 in 1M KOH + 1M Na2S are shown. Cu3(PO4)2@CoOOH / CF is from Example 1, and Cu3(PO4)2 / CF is from Comparative Example 1. Figure 11 It can be seen that the resistance of Cu3(PO4)2@CoOOH / copper foam composite material is smaller than that of Cu3(PO4)2 / copper foam composite material, indicating that it has a faster kinetic process for sulfur oxidation reaction.

[0141] The Cu3(PO4)2@CoOOH / copper foam composite materials prepared in Examples 3-4 were used as working electrodes, platinum electrodes as counter electrodes, and Hg / HgO as reference electrodes. DAT oxidation reaction was carried out with an aqueous solution containing 1 M KOH and 0.2 M DAT as electrolyte. The results are shown in Table 1.

[0142] The Cu3(PO4)2@CoOOH / copper foam composite materials prepared in Examples 3-4 were used as working electrodes, platinum electrodes as counter electrodes, and Hg / HgO as reference electrodes. Sulfur oxidation reaction was carried out with an aqueous solution containing 1 M KOH and 1 M Na2S as electrolyte. The results are shown in Table 1.

[0143] Table 1

[0144]

[0145] As can be seen from the results in Table 1, the composite material prepared in this invention exhibits good catalytic activity for both DAT oxidation and sulfur oxidation.

[0146] The above are merely preferred embodiments of the present invention, but the scope of protection of the present invention is not limited thereto. Any variations or substitutions that can be easily conceived by those skilled in the art within the scope of the technology disclosed in the present invention should be included within the scope of protection of the present invention. Therefore, the scope of protection of the present invention should be determined by the scope of the claims.

Claims

1. A method for preparing a Cu3(PO4)2@CoOOH / copper foam composite material, characterized in that, Includes the following steps: (1) Electrochemical deposition was performed using three-dimensional porous copper foam as the working electrode and phosphate buffer as the electrolyte to obtain Cu3(PO4)2 / three-dimensional porous copper foam. (2) The Cu3(PO4)2 / three-dimensional porous copper foam is immersed in an ethanol solution containing cobalt salt, ammonium bicarbonate is added and stirred to react, and then washed and vacuum dried to obtain the Cu3(PO4)2@CoOOH / copper foam composite material.

2. The preparation method according to claim 1, characterized in that, In step (1), the pore size of the three-dimensional porous copper foam is 100-500 μm, and the porosity is ≥90%; and / or, The concentration of the phosphate buffer solution is 0.5-1.0 mol / L, and the pH value is 6.5-7.

5.

3. The preparation method according to claim 1, characterized in that, In step (1), the electrochemical deposition temperature is 25-35℃, the voltage is 0.8-1.2V vs. Ag / AgCl, and the time is 0.5-3 hours.

4. The preparation method according to claim 1, characterized in that, In step (2), the ratio of Cu3(PO4)2 / three-dimensional porous copper foam, cobalt salt, and ammonium bicarbonate is (0.2-0.6) g : (0.5-2) mmol : (3-5) mmol; and / or, The cobalt salt is at least one of cobalt chloride, cobalt nitrate, and cobalt sulfate.

5. The preparation method according to claim 1, characterized in that, In step (2), the temperature of the stirring reaction is 20-30℃, the stirring speed is 200-400rpm, and the time is 8-18 hours; the stirring reaction is carried out in a closed container.

6. A Cu3(PO4)2@CoOOH / copper foam composite material, characterized in that, It is prepared according to any one of claims 1-5.

7. The application of the Cu3(PO4)2@CoOOH / copper foam composite material as described in claim 6 in the NN oxidative coupling dehydrogenation reaction of 3,5-diamino-1H-1,2,4-triazole, characterized in that, Includes the following steps: Using a mixed solution containing 3,5-diamino-1H-1,2,4-triazole and KOH as the electrolyte and the Cu3(PO4)2@CoOOH / copper foam composite material as the working electrode, an electrocatalytic oxidation reaction was carried out to achieve NN oxidative coupling dehydrogenation of 3,5-diamino-1H-1,2,4-triazole.

8. The application of the Cu3(PO4)2@CoOOH / copper foam composite material as described in claim 6 in the electrocatalytic sulfur oxidation reaction, characterized in that, Includes the following steps: Using a mixed solution containing a sulfur source and a supporting electrolyte as the electrolyte, the pH of the electrolyte is adjusted to 7-11, and the Cu3(PO4)2@CoOOH / copper foam composite material is used as the working electrode to carry out a sulfur oxidation reaction to obtain elemental sulfur; the sulfur source includes Na2S or H2S.

9. A coupled reaction system, characterized in that, The coupled reaction system includes a Pt / C catalyst electrode, a proton exchange membrane, and the Cu3(PO4)2@CoOOH / copper foam composite material as described in claim 6; The Cu3(PO4)2@CoOOH / copper foam composite material serves as the anode and forms the anode chamber with the proton exchange membrane, while the Pt / C catalyst electrode serves as the cathode and forms the cathode chamber with the proton exchange membrane. The electrolytes in both the anode and cathode chambers are mixed solutions containing 3,5-diamino-1H-1,2,4-triazole and KOH. The anode chamber undergoes an N-N oxidative coupling dehydrogenation reaction to generate an azo compound; the cathode chamber undergoes a redox reaction to generate hydrogen gas.

10. A sulfur pollutant treatment device, characterized in that, The sulfur pollutant treatment device includes a reaction tank, an electrolyte circulation system, and a gas collection system; The reaction tank uses the Cu3(PO4)2@CoOOH / copper foam composite material as the anode and a nickel mesh as the cathode as described in claim 6. The electrolyte in the electrolyte circulation system is a sulfur pollutant; the sulfur pollutant is sulfur-containing wastewater.

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