A highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites and its electrolytic application

Abstract

This invention relates to the field of electrochemistry and discloses a highly selective chlorine evolution anode with in-situ formed RuCeCl-N6 active sites and its electrolytic application, comprising a conductive substrate and a Ru-Ce heteronuclear diatomic catalyst supported on the conductive substrate; the Ru sites and Ce sites in the Ru-Ce heteronuclear diatomic catalyst are dispersed in an atomically adjacent manner; in Cl-containing... ‑ Under the operating conditions of electrolyte and anolyte bias, the Ru-Ce heteronuclear diatomic catalyst forms an in-situ RuCeCl-N6 active configuration. In this invention, the Ce site acts as an auxiliary chloride ion binding unit, capable of specifically adsorbing Cl. ‑ Increase Cl near the interface ‑ The coverage increases, thereby promoting the enrichment and adsorption of Cl species at Ru-Ce sites. Ru sites, as the main chlorine evolution reaction centers, participate in the Cl-Cl coupling and Cl2 release process. This bifunctional synergistic mechanism makes the RuCeCl-N6 running active configuration nearly thermally neutral for subsequent Cl adsorption, which is conducive to the Cl-Cl coupling reaction and increases the overpotential required for the formation of OOH oxygen-containing intermediates.

Description

Technical Field

[0001] This invention relates to the field of electrochemistry, and more particularly to a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites and its electrolytic application. Background Technology

[0002] Electrochemical chlorine production is widely used in water treatment, chemical synthesis, and the chlor-alkali industry. Its core function is the anodic electrocatalytic oxidation of Cl... - Cl2 is generated. However, the key technical challenges facing the electrochemical chlorine production process are not only improving the chlorine evolution reaction (CER) activity at the anode, but also effectively suppressing the competition from the oxygen evolution reaction (OER) in the aqueous system. In recent years, Ru-based single-atom catalysts have attracted attention due to their high atom utilization.

[0003] In existing technologies, although Ru-based single-atom catalysts can improve atom utilization to some extent, the single Ru site has limited effect on Cl. - The adsorption selectivity of Ru-based nanoparticles is limited, and they are still difficult to effectively suppress OER competition at high overpotentials. Furthermore, although Ru-based nanoparticle catalysts have a high density of active sites, the coordination environment and electronic structure of these sites are difficult to precisely control, and the particles are prone to aggregation and dissolution deactivation under electrochemical conditions. While the introduction of rare earth elements such as Ce into catalyst systems has been reported, current techniques mostly use Ce as a structural aid or support modification element, failing to fully utilize the Ce sites for Cl... - The specific adsorption and enrichment of Ru did not form a heteronuclear diatomic orbital configuration that synergizes with Ru sites.

[0004] Therefore, there is an urgent need for a method that can be used in Cl-containing environments. - Electrodes with highly selective active centers can be formed in situ in the electrolyte, enabling high-efficiency and long-life chlorine production. Summary of the Invention

[0005] To address the shortcomings of existing technologies, this invention provides a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites and its electrolytic application, thus solving the above problems.

[0006] To achieve the above objectives, the present invention provides the following technical solution: a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites, comprising a conductive substrate and a Ru-Ce heteronuclear diatomic catalyst supported on the conductive substrate; wherein the Ru sites and Ce sites in the Ru-Ce heteronuclear diatomic catalyst are dispersed in an atomically adjacent manner; in a Cl-containing... - Under the operating conditions of electrolyte and anolyte bias, the Ru-Ce heteronuclear diatomic catalyst forms an in-situ RuCeCl-N6 active configuration; wherein, the Ce site acts as an auxiliary chloride ion binding unit to enhance the Cl- ion binding near the interface. -This process enriches and promotes the adsorption of Cl species at Ru-Ce sites. Ru sites serve as the primary chlorine evolution reaction centers, participating in Cl-Cl coupling and Cl2 release, while Ce sites act as auxiliary chloride ion binding units, specifically adsorbing Cl. - Increase Cl near the interface - This increased coverage promotes the enrichment and adsorption of Cl species at Ru-Ce sites. Ru sites, as the primary chlorine evolution reaction centers, participate in Cl-Cl coupling and Cl2 release processes. This bifunctional synergistic mechanism makes the RuCeCl-N6 running active configuration nearly thermally neutral for subsequent Cl adsorption, facilitating Cl-Cl coupling reactions and simultaneously increasing OOH coverage. The overpotential required for the formation of oxygen-containing intermediates effectively suppresses competitive oxygen evolution side reactions.

[0007] Preferably, the conductive substrate is carbon paper or a gas diffusion electrode substrate; the loading of the Ru-Ce heteronuclear diatomic catalyst is 0.08~0.15 mg cm⁻¹. - ².

[0008] Preferably, the Ru-Ce heteronuclear diatomic catalyst is loaded onto the conductive substrate by an ionic conductive binder, wherein the ionic conductive binder is a Nafion solution.

[0009] Preferably, the RuCeCl-N6 operating-state active configuration is nearly thermally neutral for subsequent Cl adsorption, and makes OOH... The increased overpotential required for the formation of oxygen-containing intermediates inhibits the oxygen evolution side reaction.

[0010] A method for preparing a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites includes the following steps: S1: Tu-COF is prepared by polycondensation reaction of PTABPY and ETTA; S2: Anchor RuCl2(Bpy)(Bpym) to the Tu-COF; S3: Introduce Ce(NO3)3·6H2O to form a heteronuclear diatomic precursor between Ce ions and Ru ions on the Tu-COF; S4: Pyrolysis at 850℃~950℃ for 1.5~2.5 h in an inert gas atmosphere yields a Ru-Ce heteronuclear diatomic catalyst; S5: The Ru-Ce heteronuclear diatomic catalyst is dispersed in a mixed solution containing an ionic conductive binder to form a catalyst ink. The catalyst ink is coated on a conductive substrate and dried to obtain the highly selective chlorine evolution anode.

[0011] Specifically, using Tu-COF as a precursor template, RuCl2(Bpy)(Bpym) and Ce(NO3)3·6H2O were stepwise anchored, and then a Ru-Ce heteronuclear diatomic catalyst was prepared by high-temperature pyrolysis. This method achieved precise adjacency dispersion of Ru sites and Ce sites at the atomic level. The preparation method utilizes the regular pore structure and abundant coordination sites of COF material to effectively inhibit the migration and aggregation of metal atoms, ensuring the formation of the heteronuclear diatomic structure.

[0012] Preferably, in step S5, the mixed solution is prepared by mixing 5% Nafion solution, ethanol, and deionized water in a volume ratio of (15~25):(350~450):(550~650); the concentration of Ru-Ce heteronuclear diatomic catalyst in the catalyst ink is 2~3 mg / mL. - ¹.

[0013] Preferably, the highly selective chlorine evolution anode as described in any one of claims 1 to 4 is used as the anode, in a Cl-containing environment... - Electrolysis is performed by applying an anodic bias voltage to the electrolyte, causing the Ru-Ce heteronuclear diatomic catalyst to form the RuCeCl-N6 operating active configuration in situ and catalyze Cl. - It is oxidized to produce Cl2.

[0014] Preferably, the electrolysis is carried out in a flowing electrolytic cell, the highly selective chlorine evolution anode is a gas diffusion electrode supported on a Ru-Ce heteronuclear diatomic catalyst, the cathode is carbon paper supported on Pt / C, the anode chamber and the cathode chamber are separated by a Nafion membrane, and the anode side contains Cl. - The electrolyte flow rate is 5-15 mL / min. - ¹.

[0015] Preferably, the Cl-containing - The electrolyte is an acidic NaCl electrolyte with a pH of 0.5–2 and a NaCl concentration of 0.5–2 M; the electrolysis current density is 10–200 mA cm⁻¹. - ².

[0016] Preferably, the formation of the active configuration of RuCeCl-N6 in the operating state is monitored and confirmed by one of the following methods: open-circuit potential change monitoring, in-situ Raman spectroscopy analysis, and cyclic voltammetry of Cl2 / Cl. - Redox peak identification, electrochemical impedance spectroscopy analysis, or online chlorine production detection.

[0017] Beneficial effects This invention provides a highly selective chlorine evolution anode with in-situ formed RuCeCl-N6 active sites and its electrolytic application. Compared with the prior art, it has the following advantages: 1. In this invention, a Ru-Ce heteronuclear diatomic catalyst is loaded onto a conductive substrate, in a Cl-containing environment... - Under the operating conditions of electrolyte and anolyte bias, an in-situ RuCeCl-N6 active configuration is formed, achieving highly selective chlorine evolution. The Ce site, as an auxiliary chloride ion binding unit, can specifically adsorb Cl. - Increase Cl near the interface - This increased coverage promotes the enrichment and adsorption of Cl species at Ru-Ce sites. Ru sites, as the primary chlorine evolution reaction centers, participate in Cl-Cl coupling and Cl2 release processes. This bifunctional synergistic mechanism makes the RuCeCl-N6 running active configuration nearly thermally neutral for subsequent Cl adsorption, facilitating Cl-Cl coupling reactions and simultaneously increasing OOH coverage. The overpotential required for the formation of oxygen-containing intermediates effectively suppresses the competitive oxygen evolution side reaction. Experimental verification shows that the Ru-Ce DAC carbon paper anode prepared in this invention, in acidic 1 M NaCl electrolyte, at 10 mA cm⁻¹ - ² and 100 mA cm - The required overpotentials at the current densities are approximately 20 mV and 70 mV, respectively, and the Tafel slope is approximately 42 mV dec. - ¹, Cl2 has a Faraday efficiency close to 100%, which is significantly better than traditional DSA anodes and single Ru-based catalysts; 2. In this invention, Tu-COF is used as a precursor template. RuCl2(Bpy)(Bpym) and Ce(NO3)3·6H2O are anchored stepwise, followed by high-temperature pyrolysis to prepare a Ru-Ce heteronuclear diatomic catalyst. This achieves precise atomic-level adjacency dispersion of Ru and Ce sites. The preparation method utilizes the regular pore structure and abundant coordination sites of the COF material to effectively inhibit the migration and aggregation of metal atoms, ensuring the formation of the heteronuclear diatomic structure. Experimental verification shows that loading the Ru-Ce DAC catalyst onto a gas diffusion layer to prepare a gas diffusion anode, and assembling it with a Pt / C carbon paper cathode and a Nafion 324 membrane to form a flow electrolyzer, with a NaCl solution flow rate of 10 mL / min on the anode side... - ¹, Current density is 100 mA cm⁻¹ - Under these conditions, the anode can operate stably for 500 hours with a voltage decay rate of approximately 0.04 mV / h. - ¹, Cl2 Faraday efficiency remains above 98%. Attached Figure Description

[0018] Figure 1 This is a flowchart of a highly selective chlorine evolution anode for in-situ formation of RuCeCl-N6 active sites and its electrolytic application, as proposed in this invention. Detailed Implementation

[0019] 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.

[0020] Please see Figure 1 The present invention provides two technical solutions, specifically including the following embodiments: Example 1: A highly selective chlorine evolution anode with in-situ formed RuCeCl-N6 active sites includes a conductive substrate and a Ru-Ce heteronuclear diatomic catalyst supported on the conductive substrate; the Ru sites and Ce sites in the Ru-Ce heteronuclear diatomic catalyst are dispersed in an atomically adjacent manner; in Cl-containing... - Under the operating conditions of electrolyte and anolyte bias, the Ru-Ce heteronuclear diatomic catalyst forms an in-situ RuCeCl-N6 active configuration; in this configuration, the Ce site acts as an auxiliary chloride ion binding unit to enhance the Cl-g bond near the interface. - The catalyst enriches and promotes the adsorption of Cl species at Ru-Ce sites, with Ru sites serving as the main chlorine evolution reaction centers for Cl-Cl coupling and Cl2 release. The conductive substrate is carbon paper or a gas diffusion electrode substrate. The loading of the Ru-Ce heteronuclear diatomic catalyst is 0.08–0.15 mg cm⁻¹. - ², the Ru-Ce heteronuclear diatomic catalyst is supported on a conductive substrate via an ion-conductive binder, which is a Nafion solution. The RuCeCl-N6 operating configuration is nearly thermally neutral for subsequent Cl adsorption and allows OOH to be generated. The increased overpotential required for the formation of oxygen-containing intermediates inhibits the oxygen evolution side reaction.

[0021] A method for preparing a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites includes the following steps: S1: Tu-COF was prepared by polycondensation of PTABPY and ETTA. 0.4–0.6 mmol PTABPY and 0.5–0.7 mmol ETTA were added to a mixture of 20–25 mL mesitylene, 5–8 mL 1,4-dioxane, and 2–3 mL 6 M acetic acid aqueous solution. After ultrasonic dispersion for 10–20 min, the mixture was placed in a pressure-resistant reactor and subjected to polycondensation at 120–130 °C for 72–96 h. After natural cooling to room temperature, the solid product was collected and washed 2–3 times each with N,N-dimethylformamide, tetrahydrofuran, and acetone. The product was then vacuum dried at 70–90 °C for 10–14 h to obtain Tu-COF. S2: Anchor RuCl2(Bpy)(Bpym) onto Tu-COF; disperse 80-120 mg Tu-COF in 40-60 mL of anhydrous ethanol, sonicate for 20-40 min to ensure uniform dispersion, add 15-25 mg RuCl2(Bpy)(Bpym), stir at room temperature for 20-28 h, collect the solid by centrifugation, wash 2-4 times with anhydrous ethanol, and vacuum dry at 50-70 ℃ for 6-10 h to obtain Ru-SAC / Tu-COF; S3: Introduce Ce(NO3)3·6H2O to form a heteronuclear diatomic precursor of Ce ions and Ru ions on Tu-COF; disperse 80~120 mg Ru-SAC / Tu-COF in 25~35 mL of deionized water, sonicate for 10~20 min to make it uniformly dispersed, add 20~30 mg Ce(NO3)3·6H2O, stir at room temperature for 10~14 h, collect the solid by centrifugation, wash with deionized water 2~4 times, and vacuum dry at 50~70 ℃ for 10~14 h to obtain Ru-Ce heteronuclear diatomic precursor; S4: Pyrolysis at 850℃~950℃ for 1.5~2.5 h in an inert gas atmosphere yields a Ru-Ce heteronuclear diatomic catalyst; the Ru-Ce heteronuclear diatomic precursor is placed in a tube furnace and pyrolyzed at 4~6℃ min in an argon atmosphere. - The temperature was increased to 880~920 °C at a heating rate of ¹, and pyrolysis was carried out at this temperature for 1.8~2.2 h. The mixture was then naturally cooled to room temperature to obtain the Ru-Ce heteronuclear diatomic catalyst. S5: A Ru-Ce heteronuclear diatomic catalyst is dispersed in a mixed solution containing an ion-conductive binder to form a catalyst ink. The catalyst ink is coated onto a conductive substrate and dried to obtain a highly selective chlorine evolution anode. The mixed solution is prepared by mixing 5% Nafion solution, ethanol, and deionized water in a volume ratio of (15~25):(350~450):(550~650); the concentration of Ru-Ce heteronuclear diatomic catalyst in the catalyst ink is 2~3 mg / mL.- ¹, 1.5–2.5 mg Ru-Ce heteronuclear diatomic catalyst was dispersed in a mixed solution of 15–25 μL 5% Nafion solution, 350–420 μL ethanol and 550–650 μL deionized water, and sonicated for 25–35 min to form a uniform catalyst ink. 50–70 μL of the catalyst ink was coated onto a 1 cm × 1 cm conductive substrate and vacuum dried at room temperature for 1.5–2.5 h to obtain a highly selective chlorine evolution anode.

[0022] Preferably, in the presence of Cl - Electrolysis is performed by applying an anodic bias voltage to the electrolyte, causing the Ru-Ce heteronuclear diatomic catalyst to form the RuCeCl-N6 operating active configuration in situ and catalyze Cl. - Oxidation produces Cl2, and electrolysis is carried out in a flowing electrolyzer. The highly selective chlorine evolution anode is a gas diffusion electrode supported on a Ru-Ce heteronuclear diatomic catalyst, and the cathode is carbon paper supported on Pt / C. The anode and cathode chambers are separated by a Nafion membrane. The anode side contains Cl2. - The electrolyte flow rate is 5-15 mL / min. - ¹, containing Cl - The electrolyte is an acidic NaCl electrolyte with a pH of 0.5–2 and a NaCl concentration of 0.5–2 M; the electrolysis current density is 10–200 mA cm⁻¹. - ².

[0023] Preferably, the formation of the active configuration of RuCeCl-N6 in the operating state is monitored and confirmed by one of the following methods: open-circuit potential change monitoring, in-situ Raman spectroscopy analysis, and cyclic voltammetry of Cl2 / Cl... - Redox peak identification, electrochemical impedance spectroscopy analysis, or online chlorine production detection.

[0024] Example 2: Based on Example 1, this example uses the highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites prepared by the method steps in Example 1 to conduct a specific verification experiment; The preparation method is as follows: S1: Tu-COF was prepared by polycondensation of PTABPY and ETTA. 0.4–0.6 mmol PTABPY and 0.5–0.7 mmol ETTA were added to a mixture of 20–25 mL mesitylene, 5–8 mL 1,4-dioxane, and 2–3 mL 6 M acetic acid aqueous solution. After ultrasonic dispersion for 10–20 min, the mixture was placed in a pressure-resistant reactor and subjected to polycondensation at 120–130 °C for 72–96 h. After natural cooling to room temperature, the solid product was collected and washed 2–3 times each with N,N-dimethylformamide, tetrahydrofuran, and acetone. The product was then vacuum dried at 70–90 °C for 10–14 h to obtain Tu-COF. S2: Anchor RuCl2(Bpy)(Bpym) onto Tu-COF; disperse 80-120 mg Tu-COF in 40-60 mL of anhydrous ethanol, sonicate for 20-40 min to ensure uniform dispersion, add 15-25 mg RuCl2(Bpy)(Bpym), stir at room temperature for 20-28 h, collect the solid by centrifugation, wash 2-4 times with anhydrous ethanol, and vacuum dry at 50-70 ℃ for 6-10 h to obtain Ru-SAC / Tu-COF; S3: Introduce Ce(NO3)3·6H2O to form a heteronuclear diatomic precursor of Ce ions and Ru ions on Tu-COF; disperse 80~120 mg Ru-SAC / Tu-COF in 25~35 mL of deionized water, sonicate for 10~20 min to make it uniformly dispersed, add 20~30 mg Ce(NO3)3·6H2O, stir at room temperature for 10~14 h, collect the solid by centrifugation, wash with deionized water 2~4 times, and vacuum dry at 50~70 ℃ for 10~14 h to obtain Ru-Ce heteronuclear diatomic precursor; S4: Pyrolysis at 850℃~950℃ for 1.5~2.5 h in an inert gas atmosphere yields a Ru-Ce heteronuclear diatomic catalyst; the Ru-Ce heteronuclear diatomic precursor is placed in a tube furnace and pyrolyzed at 4~6℃ min in an argon atmosphere. - The temperature was increased to 880~920 °C at a heating rate of ¹, and pyrolysis was carried out at this temperature for 1.8~2.2 h. The mixture was then naturally cooled to room temperature to obtain the Ru-Ce heteronuclear diatomic catalyst. S5: A Ru-Ce heteronuclear diatomic catalyst is dispersed in a mixed solution containing an ion-conductive binder to form a catalyst ink. The catalyst ink is coated onto a conductive substrate and dried to obtain a highly selective chlorine evolution anode. The mixed solution is prepared by mixing 5% Nafion solution, ethanol, and deionized water in a volume ratio of (15~25):(350~450):(550~650); the concentration of Ru-Ce heteronuclear diatomic catalyst in the catalyst ink is 2~3 mg / mL.- ¹, 1.5–2.5 mg Ru-Ce heteronuclear diatomic catalyst was dispersed in a mixed solution of 15–25 μL 5% Nafion solution, 350–420 μL ethanol and 550–650 μL deionized water, and sonicated for 25–35 min to form a uniform catalyst ink. 50–70 μL of the catalyst ink was coated onto a 1 cm × 1 cm conductive substrate and vacuum dried at room temperature for 1.5–2.5 h to obtain a highly selective chlorine evolution anode.

[0025] 1. Three-electrode testing: The prepared Ru-Ce DAC-supported carbon paper was used as the working electrode, a graphite rod as the counter electrode, and an Ag / AgCl electrode as the reference electrode to assemble a three-electrode electrolysis system. The electrolyte was an acidic 1 M NaCl solution. Before testing, an inert gas was introduced to remove dissolved oxygen, and the electrolyte was kept thoroughly stirred or circulated. The chlorine evolution polarization curve of the Ru-Ce DAC carbon paper anode was tested using linear sweep voltammetry. The overpotential η in the corresponding current density range of the polarization curve was plotted against log j, and the Tafel slope was fitted to evaluate the chlorine evolution kinetics of the electrode. To determine the Cl2 Faraday efficiency, electrolysis was carried out under constant potential or constant current conditions. The Cl2 generated at the anode was introduced into a KI solution or other chlorine absorbent through a closed gas path to ensure complete absorption of the generated Cl2. The Cl2 / available chlorine content in the absorbent was then determined by iodometric titration, and the Cl2 Faraday efficiency was calculated based on the amount of Cl2 detected and the total charge passing through during electrolysis.

[0026] Test results show that the Ru-Ce DAC carbon paper anode exhibits low chloride evolution overpotential, low Tafel slope, and close to 100% Cl2 Faraday efficiency in acidic 1 M NaCl electrolyte.

[0027] 2. Continuous Chlorine Evolution Test in a Flow Electrolyzer: A Ru-Ce DAC catalyst is loaded onto a gas diffusion layer or conductive carbon paper to prepare a Ru-Ce DAC gas diffusion anode, which is then assembled with a cathode, diaphragm, or ion exchange membrane to form a flow electrolyzer. Acidic 1 M NaCl electrolyte is introduced to the anode side, and a corresponding cathode electrolyte is introduced to the cathode side. The electrolytes on both sides are continuously circulated at a set flow rate. The flow electrolyzer is operated in constant current mode with a current density set to 100 mA cm^-2, and the cell voltage change over time is continuously recorded to evaluate the operational stability of the electrodes and the electrolyzer. During operation, the anode outlet gas or gas-liquid mixture is introduced into a chlorine absorption device, and samples are periodically taken to detect the Cl2 / available chlorine content in the absorption liquid. Based on the amount of Cl2 generated per unit time and the amount of charge passing through in the same time period, the Cl2 Faradaic efficiency at different operating times is calculated. Simultaneously, the cell voltage change of the flow electrolyzer during long-term operation is recorded to determine whether significant electrode deactivation has occurred.

[0028] Test results show that the Ru-Ce DAC gas diffusion anode can continuously generate Cl2 in a flowing electrolyzer and operate stably for 500 h at 100 mA cm^-2, during which the Cl2 Faradaic efficiency remains above 98%, indicating that the anode is suitable for continuous flow electrolytic chlorine applications.

[0029] 3. In-situ formation and monitoring of active sites: The Ru-Ce DAC carbon paper anode was immersed in a 1 M NaCl electrolyte at pH=1. Without applying an external current, the change in open-circuit potential over time was continuously recorded. The initial open-circuit potential was approximately 0.82 V (vs. RHE). With prolonged immersion time, the open-circuit potential gradually shifted positively, stabilizing at around 0.91 V (vs. RHE) after approximately 30 min, with a positive shift of approximately 90 mV. This positive shift in open-circuit potential indicates that the Ce sites are active sites for Cl... - Specific adsorption occurs, causing Cl near the surface of RuCe-N6 to be adsorbed. - Increased coverage leads to Cl formation at the interface. - Enrichment Test results confirm that Ru-Ce DAC works in Cl-containing compounds. - Under working conditions, it has Cl - The specific adsorption and RuCeCl-N6 chlorination operating state characteristics indicate that this configuration is conducive to Cl-Cl coupling and inhibits the oxygen evolution competition pathway.

[0030] The above description is merely a preferred embodiment of this application and is not intended to limit this application. Any modifications, equivalent substitutions, and improvements made within the spirit and principles of this application should be included within the protection scope of this application.

Claims

1. A highly selective chlorine evolution anode that forms RuCeCl-N6 active sites in situ, characterized in that: The catalyst includes a conductive substrate and a Ru-Ce heteronuclear diatomic catalyst supported on the conductive substrate; the Ru sites and Ce sites in the Ru-Ce heteronuclear diatomic catalyst are dispersed in an atomically adjacent manner; in the presence of Cl... - Under the operating conditions of electrolyte and anolyte bias, the Ru-Ce heteronuclear diatomic catalyst forms an in-situ RuCeCl-N6 active configuration; wherein, the Ce site acts as an auxiliary chloride ion binding unit to enhance the Cl- ion binding near the interface. - It enriches and promotes the adsorption of Cl species on Ru-Ce sites, with Ru sites serving as the main chlorine evolution reaction centers for participating in Cl-Cl coupling and Cl2 release.

2. The highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites as described in claim 1, characterized in that: The conductive substrate is carbon paper or a gas diffusion electrode substrate; the loading of the Ru-Ce heteronuclear diatomic catalyst is 0.08~0.15 mg cm⁻¹. - ².

3. The highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites as described in claim 1, characterized in that: The Ru-Ce heteronuclear diatomic catalyst is loaded onto the conductive substrate by an ionic conductive binder, wherein the ionic conductive binder is a Nafion solution.

4. The highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites as described in claim 1, characterized in that: The RuCeCl-N6 operating active configuration is nearly thermally neutral for subsequent Cl adsorption and makes OOH The increased overpotential required for the formation of oxygen-containing intermediates inhibits the oxygen evolution side reaction.

5. A method for preparing a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites, characterized in that: Includes the following steps: S1: Tu-COF is prepared by polycondensation reaction of PTABPY and ETTA; S2: Anchor RuCl2(Bpy)(Bpym) to the Tu-COF; S3: Introduce Ce(NO3)3·6H2O to form a heteronuclear diatomic precursor between Ce ions and Ru ions on the Tu-COF; S4: Pyrolysis at 850℃~950℃ for 1.5~2.5 h in an inert gas atmosphere yields a Ru-Ce heteronuclear diatomic catalyst; S5: The Ru-Ce heteronuclear diatomic catalyst is dispersed in a mixed solution containing an ionic conductive binder to form a catalyst ink. The catalyst ink is coated on a conductive substrate and dried to obtain the highly selective chlorine evolution anode.

6. The method for preparing a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites according to claim 5, characterized in that: In step S5, the mixed solution is prepared by mixing 5% Nafion solution, ethanol, and deionized water in a volume ratio of (15~25):(350~450):(550~650); the concentration of Ru-Ce heteronuclear diatomic catalyst in the catalyst ink is 2~3 mg / mL. - ¹.

7. An electrolytic application of a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites, wherein the highly selective chlorine evolution anode as described in any one of claims 1 to 4 is used as the anode, characterized in that: In the presence of Cl - Electrolysis is performed by applying an anodic bias voltage to the electrolyte, causing the Ru-Ce heteronuclear diatomic catalyst to form the RuCeCl-N6 operating active configuration in situ and catalyze Cl. - It is oxidized to produce Cl2.

8. The electrolytic application of a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites as described in claim 7, characterized in that: The electrolysis is carried out in a flowing electrolytic cell. The highly selective chlorine evolution anode is a gas diffusion electrode supported on a Ru-Ce heteronuclear diatomic catalyst, and the cathode is carbon paper supported on Pt / C. The anode chamber and cathode chamber are separated by a Nafion membrane. The anode side contains Cl. - The electrolyte flow rate is 5-15 mL / min. - ¹.

9. The electrolytic application of a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites as described in claim 8, characterized in that: The Cl-containing - The electrolyte is an acidic NaCl electrolyte with a pH of 0.5-2 and a NaCl concentration of 0.5-2M. Electrolysis current density is 10~200 mA cm⁻¹ - ².

10. The electrolytic application of a highly selective chlorine evolution anode with in-situ RuCeCl-N6 active sites as described in claim 7, characterized in that: This also includes monitoring and confirming the formation of the operating active configuration of RuCeCl-N6 using one of the following methods: open-circuit potential change monitoring, in-situ Raman spectroscopy analysis, and cyclic voltammetry of Cl2 / Cl. - Redox peak identification, electrochemical impedance spectroscopy analysis, or online chlorine production detection.

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