CO2 ELECTROCATALYTIC MATERIAL FROM COPPER ANODE SLIME AND PREPARATION METHOD THEREOF

Description

CROSS-REFERENCE TO RELATED APPLICATIONS

This application claims priority to Chinese Patent Application No. 202411914520.3, filed on Dec. 24, 2024, the contents of which are hereby incorporated by reference.

TECHNICAL FIELD

The present disclosure belongs to the technical field of solid waste resource utilization and carbon emission reduction, and particularly relates to a carbon dioxide (CO₂) electrocatalytic material from copper anode slime and a preparation method thereof.

BACKGROUND

Carbon dioxide (CO₂) electrocatalytic conversion is an important technology for achieving the high-value utilization of CO₂, and electrocatalytic materials are the core of this technology. Conventional electrocatalytic materials are generally prepared using chemical reagents as synthetic raw materials. Since elements with CO₂ electrocatalytic activity are generally rare and noble metals, the synthesis cost of CO₂ electrocatalytic materials remains high. Considering that CO₂ emission reduction has become a global consensus, the consumption of rare and noble metal resources by CO₂ electrocatalytic technology will increase day by day in the future.

Copper anode slime is a main type of solid waste generated during the pyrometallurgical process of copper, rich in elements such as silver (Ag), copper (Cu), gold (Au), selenium (Se), tellurium (Te), etc. Among these, Ag, Cu, Se, and Te elements have been widely reported to possess CO₂ electrocatalytic activity. Therefore, preparing CO₂ electrocatalytic materials from anode slime is feasible in terms of chemical element balance of chemical reactions. However, no relevant patent reports have been found currently. Preparing high-end electrocatalytic materials from anode slime may significantly enhance the resource utilization benefits of solid waste. Currently, noble metal elements in anode slime are mostly recovered as high-purity metal single substances, which, although having certain added value, have limited value as bulk industrial products and are greatly affected by market supply and demand.

CN111438373A discloses a preparation method for copper-silver core-shell structured bimetallic spherical nanoparticles. This disclosure uses copper acetylacetonate and silver trifluoroacetate as raw materials, and prepares the material through a two-step method: first heating to prepare copper cores, then injecting an oleylamine solution of a silver organic compound for reaction. The reagents used in this disclosure are expensive, the synthesis process is relatively complex, and the material preparation cost is high.

CN111748828B discloses a method for recovering copper, silver, selenium, and tellurium from copper anode slime by molten salt electrolysis. This disclosure involves pretreating copper anode slime to prepare an electrode, performing electrolysis in a molten salt, and then post-processing the electrochemically deposited metals to obtain metal single substances such as copper, silver, selenium, and tellurium. The obtained products have low added value.

CN116747869A discloses a single-atom catalyst for CO₂ reduction based on waste adsorbent and a preparation method thereof. This disclosure prepares a single-atom catalyst for CO₂ reduction by utilizing carbon-containing solid waste that has adsorbed heavy metals from wastewater. In this disclosure, due to the low content of heavy metals in wastewater and the limited adsorption capacity of the adsorbent for heavy metals, the content of active components in the catalyst is limited, restricting the catalytic performance.

SUMMARY

To solve the above technical problems, the present disclosure proposes a carbon dioxide (CO₂) electrocatalytic material from copper anode slime and a preparation method thereof. By selectively separating and extracting active components such as copper (Cu) and silver (Ag) from copper anode slime that possess CO₂ electrocatalytic reduction activity, a carbon-containing support and a solid acid promoter are introduced into a leachate to enhance electrocatalytic performance, and the CO₂ electrocatalytic material is prepared by in situ reduction precipitation, thereby achieving high-value utilization of solid waste. Meanwhile, the prepared CO₂ electrocatalytic material may be widely used for carbon emission reduction in industrial flue gas. Compared with traditional methods, the preparation cost of the catalytic material is greatly reduced.

To achieve the above objectives, the present disclosure provides the following technical schemes.

A first technical scheme of the present disclosure is:

• • a CO₂ electrocatalytic material from copper anode slime, where raw materials include copper anode slime, a leaching agent, a metal ion stabilizer, a carbon-containing support, a solid acid promoter, and a reducing agent;
  • the dosage ratio of the copper anode slime to the leaching agent is 1 gram (g): 10 milliliters (mL);
  • the dosage ratio of the metal ion stabilizer to the copper anode slime is 10 mL: 1 g;
  • the dosage ratio of the reducing agent to the copper anode slime is 25 mL: 2 g;
  • the mass percentage of the solid acid promoter in the CO₂ electrocatalytic material from copper anode slime is 20-30 percent (%);
  • the mass percentage of the carbon-containing support in the CO₂ electrocatalytic material from copper anode slime is 20-30%.

In an embodiment, the leaching agent includes sulfuric acid (H₂SO₄) and an oxidizing agent, where the oxidizing agent includes but is not limited to one or more of hydrogen peroxide (H₂O₂), potassium permanganate (KMnO₄), nitric acid (HNO₃), oxygen (O₂), and ozone (O₃).

In an embodiment, the concentration of H₂SO₄ in the leaching agent is 1.5 mole per liter (mol/L), and the concentration of the oxidizing agent is 3 mol/L.

In an embodiment, the metal ion stabilizer includes but is not limited to one or more of sodium citrate, polyvinylpyrrolidone (PVP), and polyethylene glycol (PEG).

In an embodiment, the carbon-containing support includes but is not limited to one or more of carbon black particles, carbon nanotubes, and graphene.

In an embodiment, the solid acid promoter includes but is not limited to one or more of molecular sieve, cerium oxide (CeO₂), titanium dioxide (TiO₂), zirconium dioxide (ZrO₂), and tungsten trioxide (WO₃).

In an embodiment, the reducing agent includes but is not limited to one or more of sodium borohydride (NaBH₄), zinc (Zn) powder, ascorbic acid, and formaldehyde.

In an embodiment, the concentration of the metal ion stabilizer is 150 millimoles per liter (mmol·L⁻¹), and the concentration of the reducing agent is 150 mmol·L⁻¹.

A second technical scheme of the present disclosure is:

• • a preparation method for a CO₂ electrocatalytic material from copper anode slime, including: subjecting copper anode slime to oxidative leaching using a leaching agent to obtain a leachate including metal components; then adding the metal ion stabilizer, the carbon-containing support, the solid acid promoter, and the reducing agent to the leachate; stirring; followed by centrifugal washing and vacuum drying to obtain the CO₂ electrocatalytic material from copper anode slime.

The present disclosure subjects copper anode slime to oxidative leaching, thereby transferring metallic components into the leachate. By adding a leaching agent containing an oxidizing agent, the leaching rate of metal elements is enhanced. Metal elements such as Ag and Cu possessing CO₂ electrocatalytic activity from the leachate are selectively extracted. Subsequently, a carbon-containing support and a solid acid promoter is introduced to the system to improve the electrocatalytic performance of the material. Finally, a reducing agent is introduced into the system, and a CO₂ electrocatalytic material is prepared by in-situ reduction precipitation.

In an embodiment, the dropping rate of the reducing agent is 3-4 drops per second, and the temperature for the stirring is 18-30 degrees Celsius (° C.). By controlling the reduction rate and reduction temperature during the addition of the reducing agent, clustering of the catalyst into large particles is prevented.

By way of example, the preparation method for the CO₂ electrocatalytic material from copper anode slime of the present disclosure specifically includes the following steps:

• • oxidative leaching of metal elements in copper anode slime is carried out using a leaching agent (H₂SO₄+oxidizing agent), where the concentration of H₂SO₄ in the leaching agent is 1.5 mol/L, the concentration of the oxidizing agent is 3 mol/L, the dosage of the leaching agent is 20 mL, and the dosage of copper anode slime is 2 g, so that metal components such as Ag, Cu, selenium (Se), and tellurium (Te) in the copper anode slime are transferred into a liquid phase to obtain a leachate; a carbon-containing support and a solid acid promoter are added to the leachate; then 20 mL of a 150 mmol·L⁻¹ metal ion stabilizer is quickly added and stirred for 10 minutes (min); after stabilization, 25 mL of a 30 mmol·L⁻¹ reducing agent is added dropwise to reduce the metal ions, where the dropping rate is 3-4 drops per second, and rapid stirring is performed at 18-30° C. for 2 hours (h); followed by filtration and washing, and vacuum drying at 60° C. for 6 h to obtain the CO₂ electrocatalytic material from copper anode slime.

In an embodiment, the vacuum drying is performed at a temperature of 60° C. for a duration of 6 h.

Compared with the prior art, the present disclosure has the following advantages and technical effects.

The present disclosure enables high-value utilization of copper anode slime solid waste, and the prepared CO₂ electrocatalytic material may be widely used for carbon emission reduction in industrial flue gas. Compared with conventional methods, the preparation cost of the catalytic material is greatly reduced. In addition, by introducing a carbon-containing support and a solid acid promoter to enhance electrocatalytic performance, significant advantages in environmental protection and economy are achieved.

BRIEF DESCRIPTION OF THE DRAWING

The drawing, which forms a part of the present disclosure, is intended to provide a further understanding of the present disclosure. The schematic embodiments of the present disclosure and their descriptions are used to explain the present disclosure and do not constitute an undue limitation of the present disclosure. In the drawing:

the FIGURE is a schematic flowchart of a preparation method of the carbon dioxide (CO₂) electrocatalytic material from copper anode slime according to the present disclosure.

DETAILED DESCRIPTION OF THE EMBODIMENTS

Various exemplary embodiments of the present disclosure are now described in detail. This detailed description is required not to be construed as limiting the present disclosure, but is required to be understood as a more detailed description of certain aspects, characteristics, and implementation schemes of the present disclosure.

It is required to be understood that the terms used in the present disclosure are merely for describing specific embodiments and are not intended to limit the disclosure. In addition, for numerical ranges in the present disclosure, it is required to be understood that each intermediate value between the upper and lower limits of the range is specifically disclosed. Every smaller range between any stated value or intermediate value within a stated range and any other stated value or intermediate value within said range is also included in the present disclosure. The upper and lower limits of these smaller ranges may independently be included or excluded in the range.

Unless otherwise stated, all technical and scientific terms used herein have the same meanings as commonly understood by one of ordinary skill in the art to which this disclosure belongs. Although only preferred methods and materials are described herein, any methods and materials similar or equivalent to those described herein may be used in the practice or testing of the present disclosure. All documents mentioned in this specification are incorporated by reference to disclose and describe the methods and/or materials related to the documents. In case of conflict with any incorporated document, the content of this specification shall prevail.

Without departing from the scope or spirit of the present disclosure, various improvements and changes may be made to the specific embodiments of the description of the present disclosure, which will be apparent to those skilled in the art. Other embodiments obtained from the description of the present disclosure will be apparent to those skilled in the art. The description and embodiments of the present disclosure are exemplary only.

As used herein, the terms “comprising”, “including”, “having”, “containing”, etc. are all open-ended terms, meaning including but not limited to.

An embodiment of the present disclosure provides a carbon dioxide (CO₂) electrocatalytic material from copper anode slime, where raw materials include the copper anode slime, a leaching agent, a metal ion stabilizer, a carbon-containing support, a solid acid promoter, and a reducing agent;

• • the dosage ratio of the copper anode slime to the leaching agent is 1 gram (g): 10 milliliters (mL);
  • the dosage ratio of the metal ion stabilizer to the copper anode slime is 10 mL: 1 g;
  • the dosage ratio of the reducing agent to the copper anode slime is 25 mL: 2 g;
  • the mass percentage of the solid acid promoter in the CO₂ electrocatalytic material from copper anode slime is 20-30 percent (%);
  • the mass percentage of the carbon-containing support in the CO₂ electrocatalytic material from copper anode slime is 20-30%.

In an embodiment of the present disclosure, the leaching agent includes sulfuric acid (H₂SO₄) and an oxidizing agent, where the oxidizing agent includes but is not limited to one or more of hydrogen peroxide (H₂O₂), potassium permanganate (KMnO₄), nitric acid (HNO₃), oxygen (O₂), and ozone (O₃). By way of example, the leaching agent used in the embodiments of the present disclosure includes H₂SO₄ and H₂O₂.

In an embodiment of the present disclosure, the concentration of H₂SO₄ in the leaching agent is 1.5 mole per liter (mol/L), and the concentration of the oxidizing agent is 3 mol/L.

In an embodiment of the present disclosure, the metal ion stabilizer includes but is not limited to one or more of sodium citrate, polyvinylpyrrolidone (PVP), and polyethylene glycol (PEG). By way of example, the metal ion stabilizer used in the embodiments of the present disclosure is sodium citrate, and the concentration of the sodium citrate is 150 millimoles per liter (mmol·L⁻¹).

In an embodiment of the present disclosure, the carbon-containing support includes but is not limited to one or more of carbon black particles, carbon nanotubes, and graphene. By way of example, the carbon-containing support used in the embodiments of the present disclosure is carbon black particles.

In an embodiment of the present disclosure, the solid acid promoter includes but is not limited to one or more of molecular sieve, cerium oxide (CeO₂), titanium dioxide (TiO₂), zirconium dioxide (ZrO₂), and tungsten trioxide (WO₃). By way of example, the solid acid promoter used in the embodiments of the present disclosure is CeO₂ or TiO₂.

In an embodiment of the present disclosure, the reducing agent includes but is not limited to one or more of NaBH₄ (sodium borohydride), zinc (Zn) powder, ascorbic acid, and formaldehyde. By way of example, the reducing agent used in the embodiments of the present disclosure is sodium borohydride (NaBH₄), and the concentration of the reducing agent is 150 mmol·L⁻¹.

An embodiment of the present disclosure also provides a preparation method for a CO₂ electrocatalytic material from copper anode slime (a schematic flowchart is shown in the FIGURE), including: subjecting copper anode slime to oxidative leaching using a leaching agent to obtain a leachate containing metal components; then adding a metal ion stabilizer, a carbon-containing support, a solid acid promoter, and a reducing agent to the leachate; stirring; followed by centrifugal washing and vacuum drying to obtain the CO₂ electrocatalytic material from copper anode slime.

In an embodiment of the present disclosure, the dropping rate of the reducing agent is 3-4 drops per second, and the temperature for the stirring reaction is 18-30 degrees Celsius (° C.). By controlling the reduction rate and reduction temperature during the addition of the reducing agent, clustering of the catalyst into large particles is prevented. By way of example, in the embodiments of the present disclosure, the dropping rate of the reducing agent is 4 drops per second, and the temperature for the stirring reaction is 25° C.

In an embodiment of the present disclosure, the vacuum drying is performed at a temperature of 60° C. for a duration of 6 hours (h).

The present disclosure uses H₂SO₄ and an oxidizing agent as the leaching agent to oxidize and dissolve metal elements (such as silver (Ag), copper (Cu), selenium (Se), tellurium (Te), etc.) from copper anode slime into a solution. H₂SO₄ provides an acidic environment to facilitate the dissolution of metals. Under acidic conditions, an oxidizing agent such as hydrogen peroxide may oxidize metals to higher valence states. For example, Ag may be oxidized to silver ion (Ag⁺), Cu may be oxidized to copper ion (Cu²⁺), Se may be oxidized to selenate ion (SeO₄²⁻), tellurium (Te) may be oxidized to tellurate ion (TeO₄²⁻), etc. As a support, carbon black particles provide a physical surface to facilitate the adsorption of metal ions and subsequent reduction. The solid acid promoter serves a catalytic role, promoting the reduction process of the metal ions. Under the action of the metal ion stabilizer, the reducing agent may reduce the metal ions to metal single substances. In this process, the reducing agent is oxidized, and the metal ions are reduced. After the reduction reaction is completed, the solid catalyst and the liquid are separated by stirring and filtration, and drying is performed to remove excess moisture, thereby obtaining the dried catalyst material. Throughout the process, the oxidation and reduction of metal ions are key steps. By controlling the reaction conditions and adding appropriate promoters, effective leaching and reduction of metal elements may be achieved, ultimately obtaining the desired CO₂ electrocatalytic material from copper anode slime.

The materials used in the embodiments of the present disclosure are all commercially available. The copper anode slime used is sourced from a copper smelting enterprise in Yunnan Province, and its initial parameters are shown in Table 1.

The technical scheme of the present disclosure is further illustrated below by means of embodiments.

Embodiment 1

Oxidative leaching of metal elements in copper anode slime is carried out using a leaching agent (H₂SO₄+H₂O₂ solution), where the concentration of H₂SO₄ in the leaching agent is 1.5 mol/L, the concentration of the H₂O₂ solution is 3 mol/L, the dosage of the leaching agent used is 20 mL, and the dosage of the anode slime used is 2 g, so that metal components such as Ag, Cu, Se, and Te in the copper anode slime are transferred into a liquid phase to obtain a leachate; a carbon-containing support (carbon black particles) and a solid acid promoter (CeO₂) are added to the leachate, such that the mass percentage of the carbon black particles in the CO₂ electrocatalytic material from copper anode slime is 20%, and the mass percentage of CeO₂ is 30%; then 20 mL of a 150 mmol·L⁻¹ metal ion stabilizer (sodium citrate solution) is quickly added and stirred for 10 minutes (min); after stabilization, 25 mL of a 30 mmol·L⁻¹ reducing agent (sodium borohydride solution) is added dropwise to reduce the metal ions, where the dropping rate is 4 drops per second, and rapid stirring is performed at 25° C. for 2 h; followed by filtration and washing, and vacuum drying at 60° C. for 6 h to obtain the CO₂ electrocatalytic material from copper anode slime.

Embodiment 2

This embodiment is the same as Embodiment 1, except that the solid acid promoter CeO₂ is replaced with TiO₂, specifically including the following steps:

oxidative leaching of metal elements in copper anode slime is carried out using a leaching agent (H₂SO₄+H₂O₂ aqueous solution), where the concentration of H₂SO₄ in the leaching agent is 1.5 mol/L, the concentration of the H₂O₂ aqueous solution is 3 mol/L, the dosage of the leaching agent used is 20 mL, and the dosage of the anode slime used is 2 g, so that metal components such as Ag, Cu, Se, and Te in the copper anode slime are transferred into a liquid phase to obtain a leachate; a carbon-containing support (carbon black particles) and a solid acid promoter (TiO₂) are added to the leachate, such that the mass percentage of the carbon black particles in the CO₂ electrocatalytic material from copper anode slime is 20%, and the mass percentage of TiO₂ is 30%; then 20 mL of a 150 mmol·L⁻¹ metal ion stabilizer (sodium citrate solution) is quickly added and stirred for 10 min; after stabilization, 25 mL of a 30 mmol·L⁻¹ reducing agent (sodium borohydride solution) is added dropwise to reduce the metal ions, where the dropping rate is 4 drops per second, and rapid stirring is performed at 25° C. for 2 h; followed by filtration and washing, and vacuum drying at 60° C. for 6 h to obtain the CO₂ electrocatalytic material from copper anode slime.

Embodiment 3

This embodiment is the same as Embodiment 1, except that the mass percentages of the carbon-containing support (carbon black particles) and the solid acid promoter (CeO₂) in the CO₂ electrocatalytic material from copper anode slime are changed, specifically including the following steps:

oxidative leaching of metal elements in copper anode slime is carried out using a leaching agent (H₂SO₄+H₂O₂ aqueous solution), where the concentration of H₂SO₄ in the leaching agent is 1.5 mol/L, the concentration of the H₂O₂ aqueous solution is 3 mol/L, the dosage of the leaching agent used is 20 mL, and the dosage of the anode slime used is 2 g, so that metal components such as Ag, Cu, Se, and Te in the copper anode slime are transferred into a liquid phase to obtain a leachate; a carbon-containing support (carbon black particles) and a solid acid promoter (CeO₂) are added to the leachate, such that the mass percentage of the carbon black particles in the CO₂ electrocatalytic material from copper anode slime is 30%, and the mass percentage of CeO₂ is 20%; then 20 mL of a 150 mmol·L⁻¹ metal ion stabilizer (sodium citrate solution) is quickly added and stirred for 10 min; after stabilization, 25 mL of a 30 mmol·L⁻¹ reducing agent (sodium borohydride solution) is added dropwise to reduce the metal ions, where the dropping rate is 4 drops per second, and rapid stirring is performed at 25° C. for 2 h; followed by filtration and washing, and vacuum drying at 60° C. for 6 h to obtain the CO₂ electrocatalytic material from copper anode slime.

Comparative Example 1

This comparative example is the same as Embodiment 1, except that the addition of the solid acid promoter CeO₂ is omitted, specifically including the following steps:

oxidative leaching of metal elements in copper anode slime is carried out using a leaching agent (H₂SO₄+H₂O₂ aqueous solution), where the concentration of H₂SO₄ in the leaching agent is 1.5 mol/L, the concentration of the H₂O₂ aqueous solution is 3 mol/L, the dosage of the leaching agent used is 20 mL, and the dosage of the anode slime used is 2 g, so that metal components such as Ag, Cu, Se, and Te in the copper anode slime are transferred into a liquid phase to obtain a leachate; a carbon-containing support (carbon black particles) is added to the leachate, such that the mass percentage of the carbon black particles in the CO₂ electrocatalytic material from copper anode slime is 20%; then 20 mL of a 150 mmol·L⁻¹ metal ion stabilizer (sodium citrate solution) is quickly added and stirred for 10 min; after stabilization, 25 mL of a 30 mmol·L⁻¹ reducing agent (sodium borohydride solution) is added dropwise to reduce the metal ions, where the dropping rate is 4 drops per second, and rapid stirring is performed at 25° C. for 2 h; followed by filtration and washing, and vacuum drying at 60° C. for 6 h to obtain the CO₂ electrocatalytic material from copper anode slime.

Comparative Example 2

This comparative example is the same as Embodiment 1, except that the addition of the metal ion stabilizer (sodium citrate solution) is omitted. Due to the lack of the metal ion stabilizer, Ag and Cu ions undergo large-scale aggregation during the reduction process, resulting in failure to successfully prepare the CO₂ electrocatalytic material from copper anode slime.

Comparative Example 3

This comparative example is the same as Embodiment 1, except that the addition of the reducing agent (sodium borohydride solution) is omitted. Due to the lack of the reducing agent, Ag and Cu ions are not able to be reduced to generate electrocatalytically active elemental Ag and Cu, resulting in failure to successfully prepare the CO₂ electrocatalytic material from copper anode slime.

Comparative Example 4

This comparative example is the same as Embodiment 1, except that the mass percentages of the carbon-containing support (carbon black particles) and the solid acid promoter (CeO₂) in the CO₂ electrocatalytic material from copper anode slime are changed, specifically including the following steps:

oxidative leaching of metal elements in copper anode slime is carried out using a leaching agent (H₂SO₄+H₂O₂ aqueous solution), where the concentration of H₂SO₄ in the leaching agent is 1.5 mol/L, the concentration of the H₂O₂ aqueous solution is 3 mol/L, the dosage of the leaching agent used is 20 mL, and the dosage of the anode slime used is 2 g, so that metal components such as Ag, Cu, Se, and Te in the copper anode slime are transferred into a liquid phase to obtain a leachate; a carbon-containing support (carbon black particles) and a solid acid promoter (CeO₂) are added to the leachate, such that the mass percentage of the carbon black particles in the CO₂ electrocatalytic material from copper anode slime is 10%, and the mass percentage of CeO₂ is 40%; then 20 mL of a 150 mmol·L⁻¹ metal ion stabilizer (sodium citrate solution) is quickly added and stirred for 10 min; after stabilization, 25 mL of a 30 mmol·L⁻¹ reducing agent (sodium borohydride solution) is added dropwise to reduce the metal ions, where the dropping rate is 4 drops per second, and rapid stirring is performed at 25° C. for 2 h; followed by filtration and washing, and vacuum drying at 60° C. for 6 h to obtain the CO₂ electrocatalytic material from copper anode slime.

Electrocatalytic Performance Test

The electrocatalytic performance of the CO₂ electrocatalytic materials from copper anode slime prepared in Embodiment 1, Embodiment 2, Embodiment 3, Comparative Example 1, Comparative Example 2, Comparative Example 3, and Comparative Example 4 is determined by linear sweep voltammetry (LSV) and galvanostatic electrolysis i-t test, respectively, and the results are shown in Table 2.

As may be seen from Table 2, Comparative Example 2 and Comparative Example 3 have no electrocatalytic performance, which is because the catalyst product is not able to be successfully prepared by omitting the stabilizer or reducing agent. The performance of Comparative Example 4 is superior to that of Embodiment 2, which is because the promoting effect of the promoter TiO₂ in Embodiment 2 on the catalytic performance is not as good as that of CeO₂. The performance of the comparative examples is lower than that of Embodiment 1, which is because the component ratio in Embodiment 1 is optimal, and the content of the carbon-containing support in Comparative Example 4 is too low, affecting the conductivity of the catalyst.

The above are only optional specific embodiments of the present disclosure, but the protection scope of the present disclosure is not limited thereto. Any changes or substitutions that may be easily conceived by any person skilled in the art within the technical scope disclosed in the present disclosure shall fall within the protection scope of the present disclosure. Therefore, the protection scope of the present disclosure shall be subject to the protection scope of the claims.