阅读说明：本技术 一种电解产氯的碳基阳极材料及其应用 (Carbon-based anode material for producing chlorine by electrolysis and application thereof ) 是由 尹华杰 舒亚婕 于 2021-07-26 设计创作，主要内容包括：本发明属于电催化技术领域,具体涉及一种电解产氯的碳基阳极材料及其应用,所述碳基阳极材料所述原材料包括掺杂非金属碳基材料、掺杂非贵金属碳基材料和负载非贵金属氧化物碳基材料中至少一种；通过掺杂不同元素,引入官能团的种类和数量,调控碳基材料中碳原子p轨道在费米能级附近的填充度,达到对电化学产氯反应中间体吸附能的精确调控,最终实现在电解产氯具有高催化活性、高选择性以及在强酸性条件下具有长效稳定性的特点。可广泛应用于氯碱工业、电解海水制氯、电渗析、电解海水盐水防污、污水处理、泳池或饮用水消毒等领域。(The invention belongs to the technical field of electrocatalysis, and particularly relates to a carbon-based anode material for producing chlorine by electrolysis and an application thereof, wherein the raw material of the carbon-based anode material comprises at least one of a non-metal carbon-based material, a non-noble metal carbon-based material and a non-noble metal oxide supported carbon-based material; different elements are doped, the types and the number of functional groups are introduced, the filling degree of a carbon atom p orbit in the carbon-based material near a Fermi level is regulated, the accurate regulation of the adsorption energy of the electrochemical chlorine generation reaction intermediate is achieved, and the characteristics of high catalytic activity, high selectivity and long-acting stability under a strong acid condition in the electrolytic chlorine generation are finally realized. Can be widely applied to the fields of chlor-alkali industry, seawater electrolysis for chlorine production, electrodialysis, seawater brine electrolysis for pollution prevention, sewage treatment, swimming pool or drinking water disinfection and the like.)

1. A carbon-based anode material for producing chlorine by electrolysis is characterized in that the carbon-based anode material comprises at least one of a non-metal-doped carbon-based material, a non-noble metal-doped carbon-based material and a non-noble metal oxide-loaded carbon-based material.

2. The carbon-based anode material according to claim 1, wherein the doping atoms of the doped non-metallic carbon-based material are non-metallic atoms comprising at least one of oxygen, boron, nitrogen and sulfur atoms; the doping atoms of the non-noble metal-doped carbon-based material are non-noble metal atoms, the non-noble metal comprises at least one of cobalt, iron, copper, nickel and manganese, the dopant doped with the non-noble metal oxide is a non-noble metal oxide, and the non-noble metal oxide comprises at least one of cobalt-containing oxide, iron-containing oxide, copper-containing oxide, nickel-containing oxide and manganese-containing oxide.

3. The carbon-based anode material according to claim 2, wherein in the doped non-metal carbon-based material, the molar ratio of non-metal atoms to carbon atoms is greater than 1: 100; in the non-noble metal-doped carbon-based material and the non-noble metal oxide-loaded carbon-based material, the molar ratio of the non-noble metal atoms to the carbon atoms is more than 1: 100.

4. The carbon-based anode material according to claim 1, wherein the carbon-based anode material is a carbon-based material formed with a substrate carbon and dopant atoms, the substrate carbon comprising: at least one of graphite, conductive carbon black powder, carbon nanotubes, activated carbon, carbon gel, carbon nanomolecular sieve, carbon fibers, and carbonized biomass.

5. The carbon-based anode material according to claim 4, wherein the carbon fibers comprise: at least one of carbon paper, carbon velvet, carbon cloth and graphite felt; the carbonized biomass includes: at least one of chitosan, cellulose and lignin.

6. The carbon-based anode material according to claim 1, wherein the carbon-based anode material is formed from a carbon-based material as a raw material and has an oxygen-containing functional group; the oxygen-containing functional group includes: at least one of a hydroxyl group, a carbonyl group, a carboxyl group, and an ester group.

7. The carbon-based anode material according to claim 1, wherein the carbon-based anode material has a specific surface area of more than 500m²/g。

8. The carbon-based anode material according to claim 1, wherein the carbon-based anode material is stable in an environment having a pH of 1-14.

9. A gas diffusion electrode comprising a carbon-based anode material according to any one of claims 1 to 8 as a starting material for the electrolytic production of chlorine.

10. Use of a carbon-based anode material according to any one of claims 1 to 8, comprising the use of said carbon-based anode material for electrolysis of seawater for chlorine production, chlor-alkali industry, electrodialysis, capacitive deionization, electrolysis of brine for antifouling, sewage treatment, swimming pool or drinking water disinfection.

Technical Field

The invention belongs to the technical field of electrocatalysis, and particularly relates to a carbon-based anode material for producing chlorine by electrolysis and application thereof.

Background

The electrochemical catalysis for chlorine production is one of the most valuable and widely applied electrochemical reactions at present, and the application fields of the electrochemical catalysis for chlorine production comprise the chlor-alkali industry, the seawater electrolysis for chlorine production, the seawater electrolysis for pollution prevention, the sewage treatment, the chemical synthesis and the like. One of the keys to electrochemical chlorine generation is the anode for electrolysis. Graphite was selected as the chlorine-evolving anode in the chlor-alkali industry in the early days, but the required working voltage is large and the service life is short, so titanium-based metal oxides with high stability are developed, and in the development and application of the next decades, a series of binary composite coating electrodes, namely Dimension Stable Anodes (DSA), are formed step by step, wherein noble metal oxides such as ruthenium, iridium and the like are loaded on a metal titanium plate as active components and titanium dioxide is mixed with the metal titanium plate.

Although the DSA electrode as a chlorine evolution anode shows excellent catalytic activity and stability in the chlor-alkali industry, the needed precious metal is high in price, short in supply and demand, and under an acidic condition, the solid solution structure of the metal oxide is unstable and easy to dissolve out, so that potential environmental risks are caused. Aiming at the seawater or sewage with low chloride ion concentration, the side reaction oxygen evolution activity of the DSA electrode is high, the metal oxide solid solution structure is easy to damage, and meanwhile, various anions and cations exist in the seawater, so that the active components are easy to lose, the titanium matrix is passivated, and the DSA electrode fails. The above disadvantages severely restrict the mass production of the noble metal-based DSA electrode and the expanded application of the technology in various fields.

In recent years, a great deal of research finds that the nonmetallic carbon-based material shows excellent performance comparable to that of a noble metal catalyst in electrochemical oxygen reduction reaction and fuel cells. However, the research on the carbon-based material in the field of chlorine generation by electrolysis is still insufficient. In view of the low cost and high designability of carbon-based materials, the practical development of carbon-based electrolysis chlorine production catalysts and electrode materials undoubtedly has important application value and scientific significance.

Disclosure of Invention

The application provides a carbon-based anode material for producing chlorine by electrolysis and application thereof, which are used for solving the technical problems that in the prior art, a metal oxide solid solution structure in a precious metal-based DSA electrode is unstable, easy to dissolve out and easy to lose effectiveness.

A carbon-based anode material for producing chlorine by electrolysis, the carbon-based anode material comprises at least one of a non-metal-doped carbon-based material, a non-noble-metal-doped carbon-based material and a non-noble-metal-oxide-supported carbon-based material.

Optionally, the doping atoms of the non-metal carbon-based material are non-metal atoms, and the non-metal atoms include at least one of oxygen, boron, nitrogen and sulfur atoms; the doping atoms of the non-noble metal-doped carbon-based material are non-noble metal atoms, the non-noble metal comprises at least one of cobalt, iron, copper, nickel and manganese, the doping matter of the non-noble metal oxide is non-noble metal oxide, and the non-noble metal oxide comprises at least one of cobalt-containing oxide, iron-containing oxide, copper-containing oxide, nickel-containing oxide and manganese-containing oxide.

Optionally, in the doped non-metal carbon-based material, the molar ratio of the non-metal atoms to the carbon atoms is greater than 1: 100; in the non-noble metal doped carbon-based material and the non-noble metal oxide supported carbon-based material, the molar ratio of the non-noble metal atoms to the carbon atoms is more than 1: 100.

Optionally, the carbon-based anode material is a carbon-based material formed by substrate carbon and doping atoms, and the substrate carbon includes: at least one of graphite, conductive carbon black powder, carbon nanotubes, activated carbon, carbon gel, carbon nanomolecular sieve, carbon fibers and carbonized biomass.

Optionally, the carbon fiber includes: at least one of carbon paper, carbon velvet, carbon cloth and graphite felt; the carbonized biomass includes: at least one of chitosan, cellulose and lignin.

Optionally, the carbon-based anode material is formed by taking a carbon-based material as a raw material and has an oxygen-containing functional group; the oxygen-containing functional group includes: at least one of a hydroxyl group, a carbonyl group, a carboxyl group, and an ester group.

Optionally, the specific surface area of the carbon-based anode material is more than 500m²/g。

The gas diffusion electrode is prepared by taking the carbon-based anode material as a raw material and is used for producing chlorine through electrolysis.

Use of a carbon-based anode material, said use comprising use of said carbon-based anode material for electrolysis of seawater for chlorine production, chlor-alkali industry, electrodialysis, capacitive deionization, electrolytic brine anti-fouling, sewage treatment, swimming pool or drinking water disinfection.

Compared with the prior art, the technical scheme provided by the embodiment of the application has the following advantages:

according to the embodiment of the application, the excellent stability and high conductivity of the carbon-based material are utilized, the filling of the p-orbit of the carbon atom in the carbon-based material near the Fermi level is regulated and controlled by doping different elements and introducing the types and the number of functional groups, so that the accurate regulation and control of the adsorption energy of the electrochemical chlorine generation reaction intermediate are achieved, the characteristics of high catalytic activity and high selectivity in chlorine electrolysis generation and long-acting stability under a strong acid condition are finally realized, and the technical problems that in the prior art, the side reaction oxygen evolution activity in a DSA electrode is high, the structure of a metal oxide solid solution is unstable, the metal oxide solid solution is easy to dissolve out, and the electricity is easy to lose efficacy are solved.

Drawings

The accompanying drawings, which are incorporated in and constitute a part of this specification, illustrate embodiments consistent with the invention and together with the description, serve to explain the principles of the invention.

In order to more clearly illustrate the embodiments of the present invention or the technical solutions in the prior art, the drawings used in the embodiments or the prior art descriptions will be briefly described below, and it is obvious for those skilled in the art to derive other drawings without inventive exercise.

FIG. 1 is a scanning electron micrograph of O-BP synthesized according to an embodiment of the present invention;

FIG. 2 is a transmission electron micrograph of O-BP synthesized according to an embodiment of the present invention;

FIG. 3 is a graph showing polarization curves of O-BP and other carbon-based materials synthesized by examples of the present invention;

FIG. 4 is a polarization curve diagram of the O-BP catalyst prepared by the present invention in a low concentration NaCl solution under a neutral condition;

FIG. 5 is a graph of O-BP polarization curves at different pH conditions;

FIG. 6 is a graph of the stability and Faraday efficiency of O-BP and graphite rods in 4M NaCl, pH 1 electrolyte;

FIG. 7 is a polarization curve of O-BP under conditions of 4M NaCl, pH 1 and normal temperature;

FIG. 8 is a graph showing the polarization of O-BP in 4M NaCl at pH 1 at 70 ℃.

Detailed Description

In order to make the objects, technical solutions and advantages of the embodiments of the present application clearer, the technical solutions in the embodiments of the present application will be clearly and completely described below with reference to the drawings in the embodiments of the present application, and it is obvious that the described embodiments are some embodiments of the present application, but not all embodiments. All other embodiments, which can be derived by a person skilled in the art from the embodiments given herein without making any creative effort, shall fall within the protection scope of the present application.

In a first aspect, the present application provides a carbon-based anode material for the electrolytic production of chlorine, the carbon-based anode material comprising at least one of a non-metal doped carbon-based material, a non-noble metal doped carbon-based material, and a non-noble metal oxide supported carbon-based material.

In the embodiment of the application, a non-metallic carbon-based material is firstly proposed to be used as a chlorine separation anode to replace the traditional DSA electrode taking ruthenium oxide as an active component. The carbon-based anode material has high-efficiency catalytic activity, selectivity and long-acting stability, and meanwhile, the preparation method is simple, low in cost and simple in process, and is suitable for large-scale industrial production. The carbon-based anode material has high catalytic activity and selectivity and long-acting stability under strong acid conditions, and the preparation method is simple and economic and is suitable for large-scale industrial production.

As an alternative embodiment, the doping atoms of the doped non-metallic carbon-based material are non-metallic atoms including at least one of oxygen, boron, nitrogen and sulfur atoms; the doping atoms of the non-noble metal-doped carbon-based material are non-noble metal atoms, the non-noble metal comprises at least one of cobalt, iron, copper, nickel and manganese, the dopant doped with the non-noble metal oxide is a non-noble metal oxide, and the non-noble metal oxide comprises at least one of cobalt-containing oxide, iron-containing oxide, copper-containing oxide, nickel-containing oxide and manganese-containing oxide.

In the embodiment of the application, the doping atoms or dopants are non-noble metal oxides, and can participate in the subsequent reaction, so that the carbon-based material obtains oxygen-containing functional groups to perform electrolysis to generate chlorine.

In an alternative embodiment, the non-metallic carbon-based material is doped in a molar ratio of non-metallic atoms to carbon atoms of greater than 1: 100; in the non-noble metal-doped carbon-based material and the non-noble metal oxide-loaded carbon-based material, the molar ratio of the non-noble metal atoms to the carbon atoms is more than 1: 100.

As an alternative embodiment, the carbon-based anode material is a carbon-based material formed by base carbon and doping atoms, the base carbon including: at least one of graphite, conductive carbon black powder, carbon nanotubes, activated carbon, carbon gel, carbon nanomolecular sieve, carbon fibers, and carbonized biomass.

Any one of the substrate carbons in the embodiments of the present application can achieve the object of the embodiments of the present invention, and can be used for chlorine production by electrolysis in a laboratory or chlorine production by electrolysis in an industrial large scale.

In the embodiment of the application, the substrate carbon is subjected to non-metal atom doping or non-noble metal oxide loading treatment, and then subjected to first treatment to obtain the carbon-based anode material.

As an alternative embodiment, the carbon fiber comprises: at least one of carbon paper, carbon velvet, carbon cloth and graphite felt; the carbonized biomass includes: at least one of chitosan, cellulose and lignin.

In the examples of the present application, the carbon black powder may be acetylene black, or a commercially available carbon black powder of the type Vulcan XC-72R or BP2000, or Ketjen carbon black.

As an alternative embodiment, the carbon-based anode material has a specific surface area of more than 500m²The higher specific surface area can effectively adsorb chlorine and is beneficial toIn the chlorine generating reaction.

As an alternative embodiment, the carbon-based anode material is a carbon-based anode material having an oxygen-containing functional group formed using a carbon-based material as a raw material; the oxygen-containing functional group includes: at least one of a hydroxyl group, a carbonyl group, a carboxyl group, and an ester group.

In the embodiment of the application, hydroxyl, carbonyl, carboxyl and ester groups in the oxygen-containing functional group can participate in the reaction in the subsequent electrolytic chlorine production process, and the accurate regulation and control of the adsorption energy of the electrochemical chlorine production reaction intermediate is achieved by changing the filling degree of the p orbit of the carbon atom in the carbon-based material near the Fermi level.

In the embodiment of the present application, the carbon-based anode material may be any one of the following chemical formulas:

in the examples of the present application, the carbon-based anode material is stable in an environment of pH 1 to 14. Preferably, it is stable under acidic conditions (pH < 3).

In an embodiment of the present application, a method for preparing a carbon-based anode material is provided, which includes the following steps:

obtaining the carbon-based raw material;

carrying out first treatment on the carbon-based raw material to obtain a carbon-based anode material;

the first treatment includes at least one of an electrochemical treatment, a hydrothermal treatment, a chemical treatment, and a thermal treatment.

In the embodiment of the application, the heat treatment comprises heating the raw materials at 300-1000 ℃ for 1-4 hours under a protective atmosphere.

In the embodiment of the present application, the heat treatment is co-baking, and the chemical treatment may be acid treatment.

A gas diffusion electrode is prepared from the carbon-based anode material through electrolysis to generate chlorine.

Use of a carbon-based anode material, said use comprising use of said carbon-based anode material for electrolysis of seawater for chlorine production, chlor-alkali industry, electrodialysis, capacitive deionization, electrolytic brine anti-fouling, sewage treatment, swimming pool or drinking water disinfection.

The present invention will be described in detail below with reference to examples and experimental data.

Example 1

In the present embodiment, the non-metal atom is an oxygen atom, and the base carbon is highly conductive carbon black powder BP 2000. The carbon-based anode material, namely the carbon-based catalyst, with at least one of oxygen-containing functional groups of hydroxyl, carbonyl, carboxyl and ester is prepared by a high-temperature heat treatment method, and is named as O-BP.

The specific preparation steps of the O-BP2000 are as follows: weighing a certain amount of BP2000 in a corundum crucible, placing the corundum crucible in a muffle furnace, raising the temperature from room temperature to 400-600 ℃ at the speed of 5-10 ℃/min, keeping the temperature for 2-3 hours, and then naturally cooling to obtain powder, namely O-BP which can be used as an anode material for electrochemical chlorine generation.

FIGS. 1 and 2 show scanning electron micrographs and transmission electron micrographs of the synthesized O-BP, which is seen to exhibit an irregular "onion carbon" structure with rough surfaces and amorphous edges.

Example 2

In this embodiment, a carbon-based material doped with at least one non-metal atom selected from boron atoms, nitrogen atoms, and sulfur atoms is used as the carbon-based anode material. The non-metal atoms are oxygen atoms, and the substrate carbon is carbon fiber. A carbon-based anode material having at least one of an oxygen-containing functional group of hydroxyl, carbonyl, carboxyl and ester, namely a carbon-based catalyst, named O — CF, is prepared by a high-temperature heat treatment method.

The preparation method comprises the following specific steps: and (3) carrying out continuous anodic oxidation treatment on the surface of the carbon fiber by taking the carbon fiber as an oxidation anode and a graphite rod as a cathode. 5-10% of ammonium bicarbonate is taken as electrolyte, the electrolysis time is 50 seconds to 5 minutes, the electrolysis temperature is 22 to 80 ℃, the control of the oxidation process is realized by adjusting the current intensity to be 50mA to 5A in the anodic oxidation process, in order to ensure that the electrolyte solution remained on the surface of the carbon fiber, the carbon fiber after the anodic oxidation treatment is washed to be neutral by deionized water, and then is put into an oven at 80 to 120 ℃ to be dried for 2 to 8 hours. The O-CF carbon-based material can be used as an anode material for electrochemically generating chlorine.

Example 3

In this embodiment, a carbon-based material doped with at least one non-metal atom selected from boron atoms, nitrogen atoms, and sulfur atoms is used as the carbon-based anode material. In this embodiment, the non-metal atoms are nitrogen atoms and the carbon-based material is selected from carbon nanotubes.

The preparation method comprises the following specific steps: weighing a certain amount of carbon nano tubes, placing the carbon nano tubes and melamine in an agate mortar, and fully grinding for 20 minutes to uniformly mix the carbon nano tubes and the melamine; transferring the ground sample to a porcelain boat, placing the porcelain boat in a tube furnace, introducing nitrogen into the tube furnace for 30 minutes to ensure that air is exhausted, setting the heating rate to be 5-10 ℃/minute, maintaining the temperature at 400-700 ℃ for 2-3 hours, and continuously introducing nitrogen after the reaction is finished until the temperature is reduced to room temperature to obtain a nitrogen-doped carbon nano tube material, wherein the atomic percentage of nitrogen atoms to carbon atoms is more than 1%, so as to obtain the carbon-based anode material for electrochemically generating chlorine.

Example 4

In this embodiment, a carbon-based material supporting an oxide containing at least one non-noble metal of cobalt, iron, copper, nickel, and manganese is selected as the anode material. In the embodiment, the non-noble metal element is manganese, the carbon-based material is carbon cloth, and the prepared carbon cloth is made.

The preparation method comprises the following specific steps: weighing 2mmol of CoSO₄·7H₂Dissolving O in 50mL deionized water, stirring for 30min, adding 0.2g carbon nanotube, stirring, soaking for 10 hr, washing with deionized water for 2-3 times to remove Co adsorbed on surface²⁺And drying for 10-12 hours, placing the dried sample in a tube furnace, introducing argon, heating to 600-900 ℃, and pyrolyzing at constant temperature for 2-3 hours to obtain the cobalt-doped carbon nanotube material which can be used as an anode material for electrochemically generating chlorine.

Example 5

In the embodiment, at least one non-metal atom doped with boron atom, nitrogen atom and sulfur atom and a load bag are selectedThe carbon-based anode material is a carbon-based material containing at least one non-noble metal oxide of cobalt, iron, copper, nickel and manganese elements. In this embodiment, the non-metal atoms are nitrogen atoms, the non-noble metal element is cobalt, and the carbon-based material is carbon nanotubes. The specific implementation steps are as follows: weighing 2mmol of CoSO₄·7H₂O，2mmol NH₄And F and 5mmol of urea are dissolved in 50mL of deionized water, 0.5g of the nitrogen-doped carbon nano tube in the embodiment 3 is added after the mixture is fully stirred for 30 minutes, the mixture is added into a hydrothermal kettle after the mixture is stirred for 10 minutes to carry out hydrothermal reaction, the hydrothermal temperature is 80-180 ℃, and the reaction time is 8-24 hours. After the reaction is finished and the natural cooling is carried out, the obtained sample is washed and dried, and the dried sample is placed in a tubular furnace argon atmosphere to be calcined for 3-5 hours at the temperature of 200-₃O₄The nitrogen-doped carbon nanotube material can be used as an anode material for electrochemically generating chlorine.

Example 6

Use of the O-BP catalyst prepared in example 1 in electrochemical chlorine production reactions (CER) with the background of the chlor-alkali industry:

the electrochemical chlorine generation performance of the O-BP electrocatalyst was tested on a CHI 760D electrochemical workstation (shanghai chenhua) using a three electrode system with an electrolyte solution of 4M NaCl at pH 1, with a silver/silver chloride (Ag/AgCl, 3M) electrode and a graphite rod as reference and counter electrodes, respectively. The prepared O-BP catalyst and 5 wt% Nafion solution were dispersed in 1mL of isopropanol and subjected to water bath sonication for 30min to form a uniform suspension. For the test of the rotary disc electrode, 30-50uL of catalyst dispersion liquid is uniformly dripped on a glassy carbon electrode with the diameter of 5mm, and the glassy carbon electrode is dried at room temperature; for stability testing, 100-150uL of catalyst dispersion was uniformly dropped on a catalyst with a diameter of 0.5X 0.5cm²Dried at room temperature. The test potentials applied by all working electrodes (vs. ag/AgCl) were converted to the standard hydrogen potential (vs. rhe): e (rhe) ═ E (Ag/AgCl) +0.059 × pH + 0.197.

Linear Sweep Voltammetry (LSV) at a sweep rate of 10.0mV · s^-1The test was performed. The stability test adopts an H-type electrolytic cell, wherein a cation exchange membrane N424 is selected to separate two cavitiesA chamber. Stability at current density of j-100 mA cm^-2The measurement was carried out for 264 hours. The cation exchange membrane and electrolyte are periodically replaced to maintain the electrolyte concentration and pH in the anode chamber. The Faraday efficiency of the reaction is determined by a DPD color method to determine the concentration of the solution and gas after the reaction, as shown in figure 6, the O-BP has good stability, and the Faraday efficiency is about 100 percent, which indicates that the O-BP has high selectivity for generating chlorine.

FIG. 3 is a graph showing the polarization curve of O-BP prepared by the present invention in 4M NaCl; RuO₂Polarization plots in 4M NaCl; polarization curve diagram of BP in 4M NaCl; graph Rod polarization plot in 4M NaCl; O-BP (4M NaClO)₄) In 4M NaClO₄Polarization curve in environment, it can be seen that the catalyst has more excellent CER activity relative to other materials.

Example 7

The application of the O-BP catalyst prepared in the example 2 in the electrochemical chlorine generating reaction (CER) with the background of water with low concentration salinity, such as seawater, is as follows:

the electrochemical chlorine generation performance of the O-BP electrocatalyst was tested on a CHI 760D electrochemical workstation (shanghai chenhua) using a three electrode system with an electrolyte solution of 0.33M NaCl at a pH of 7-8, with a silver/silver chloride (Ag/AgCl, 3M) electrode and a graphite rod as reference and counter electrodes, respectively. The prepared O-BP catalyst and 5 wt% Nafion solution were dispersed in 1mL of isopropanol and a homogeneous suspension was formed after 30 minutes of water bath sonication. For the test of the rotary disc electrode, 30-50uL of catalyst dispersion liquid is uniformly dripped on a glassy carbon electrode with the diameter of 5mm, and the glassy carbon electrode is dried at room temperature; for stability test, 100-150uL of catalyst dispersion was uniformly dropped on a catalyst with a diameter of 0.5X 0.5cm²Dried at room temperature. The test potential (vs. ag/AgCl) applied by all working electrodes was converted to the standard hydrogen potential (vs. rhe): e (rhe) ═ E (Ag/AgCl) +0.059 × pH + 0.197.

FIG. 4 is a graph showing the polarization of O-BP prepared according to the present invention in a low concentration of 0.33M NaCl at pH 7-8; it can be seen from the figure that O-BP still has good chlorine generating performance.

Linear Sweep Voltammetry (LSV) at a sweep rate of 10.0mV · s^-1The test was performed. The stability test selects an H-type electrolytic cell, wherein a cation exchange membrane N424 is selected to separate two chambers. Stability at current density of j-100 mA cm^-2The measurement was carried out for 264 hours. The cation exchange membrane and electrolyte are periodically replaced to maintain the electrolyte concentration and pH in the anode chamber. Faradaic efficiency of reaction the solution and gas concentrations after the reaction were determined by DPD chromogenic method.

Detailed explanation of the drawings:

FIG. 5 is a polarization curve diagram of O-BP under different pH conditions, showing that O-BP has higher CER activity under different pH conditions, and H⁺Has little influence on the CER performance of O-BP, and can be stably used as a carbon-based anode material under different pH conditions.

FIG. 6 is a graph of O-BP vs. chronopotentiometric curve of a conventional graphite rod at 100mA cm^-2The Faraday efficiency of the O-BP electrode is about 100 percent when the experiment is measured under the condition that the pH value is 1 under the strong acid condition, which shows that the material has high selectivity for producing chlorine; at a current density of 100mA cm^-2In comparison with the conventional graphite rod, the O-BP (the lower line of the transverse line) has the disadvantages of large voltage required by the conventional graphite electrode, poor stability and high consumption speed, and the voltage of the O-BP electrode is stabilized at about 1.5V in a long time (264 hours), which indicates that the O-BP electrode has high stability and high chlorine selectivity.

In FIG. 7, panel A is a polarization curve plot of O-BP under 4M NaCl, pH 1 and normal temperature conditions, one is a 95% iR corrected O-BP curve and the other is a conventional O-BP polarization curve; the graph B shows the potential of O-BP under different current densities, and the graph shows that the O-BP still has low over potential and stable current potential under high current density and can be used as an anode material for electrochemical chlorine generation.

FIG. 8 is a graph showing the polarization curve of O-BP at 4M Nacl, pH 1 and 70 ℃ with a further decrease in the required overpotential as the temperature increases and a current density of 1Acm^-2When the overvoltage is higher than the overvoltage, the overvoltage is only 113mV, which indicates that the overvoltage of O-BP in the industrial environment of chlor-alkali at 70 ℃ is low, and the overvoltage can be reducedThe material can be used as an anode material for electrochemical chlorine generation, and the current potential is stable.

It is noted that, in this document, relational terms such as "first" and "second," and the like, may be used solely to distinguish one entity or action from another entity or action without necessarily requiring or implying any actual such relationship or order between such entities or actions. Also, the terms "comprises," "comprising," or any other variation thereof, are intended to cover a non-exclusive inclusion, such that a process, method, article, or apparatus that comprises a list of elements does not include only those elements but may include other elements not expressly listed or inherent to such process, method, article, or apparatus. Without further limitation, an element defined by the phrase "comprising an … …" does not exclude the presence of other identical elements in a process, method, article, or apparatus that comprises the element.

The foregoing are merely exemplary embodiments of the present invention, which enable those skilled in the art to understand or practice the present invention. Various modifications to these embodiments will be readily apparent to those skilled in the art, and the generic principles defined herein may be applied to other embodiments without departing from the spirit or scope of the invention. Thus, the present invention is not intended to be limited to the embodiments shown herein but is to be accorded the widest scope consistent with the principles and novel features disclosed herein.