A thin-film anode material with a nanopore confined structure, its preparation method and application

Abstract

A nanoporous confined thin-film anode material, its preparation method, and its application are disclosed. The method is characterized by the preparation of Ti4O7 anode thin-film materials with different pore sizes and lattice structures, specifically divided into two parts: pore construction and doping enhancement. Pore construction involves a secondary anodic oxidation process to refine the surface of a TiO2 foil, forming a porous TiO2 anode integrated with the parent metal. Doping enhancement involves immersing the prepared TiO2 foil film in a specially formulated solution. This invention prepares a double-channel sub-titanium oxide (Ti4O7) anode with a controllable nano-sized pore structure and uses surfactants and transition metal doping to prepare anode materials with different lattice structures. This results in the preparation of electrocatalytic anode materials for deep treatment and detoxification of MCs.

Description

Technical Field

[0001] This application belongs to the field of electrocatalytic anodes, specifically relating to a thin-film anode material with a nanoporous confined structure, its preparation method, and its application. Background Technology

[0002] Current advanced oxidation processes are neither suitable nor meet the processing requirements of MCs.

[0003] Algal toxins (MCs) possess a cyclic heptapeptide structure, exhibiting stable properties and persisting for extended periods at 15–30°C. Studies have shown that MCs can remain intact even at 300°C for extended periods. Current advanced oxidation processes (AOPs) still face significant limitations in practical applications, including: ① catalyst agglomeration, reducing the exposure of active sites; ② low mass transfer efficiency; and ③ the inability of generated reactive oxygen species (ROS) to quickly contact the target pollutant, leading to free radical self-quenching or ineffective oxidation reactions. Furthermore, the intermediate products of incomplete MC degradation may still possess high biotoxicity. Therefore, advanced oxidation processes with higher degradation efficiency and more stable performance are essential.

[0004] Electrocatalysis is a promising approach for sustainable environmental remediation and chemical synthesis. Despite significant progress in developing highly active electrocatalysts, the full potential of electrocatalyst performance is often limited by slow mass transfer processes. To address this issue, electrochemical membranes have been developed as a promising solution. Due to the multi-scale pore network within the electrode, the diffusion layer thickness of electrochemical membranes can be significantly reduced compared to conventional planar electrodes, which helps enhance mass transfer of reactants and utilization of active sites. Although electrochemical membranes have been widely applied in electrochemical systems including water treatment reactors, electrochemical synthesis electrolyzers, and redox flow cells, the design principles for specific applications remain unclear due to the lack of structure-activity relationships. This gap stems from the complexity of mass transfer and electrochemical reactions within spatially confined channels. For example, one of the most critical factors determining the performance of electrochemical membranes is pore size, which directly relates to the mass transfer and electrochemical properties of the channels; however, currently reported electrochemical membranes vary in catalyst and pore geometry, making it nearly impossible to quantitatively assess the impact of pore size. Furthermore, how pore size affects reaction mechanisms remains an unresolved issue. The lack of research on spatially confined electrochemical reactions has hindered the development of high-efficiency electrochemical membranes and electrochemical devices.

[0005] Meanwhile, the spatially confined Fenton-like reaction is difficult to apply to complex surface water environments, and the addition of oxidants can also affect water quality and taste. Therefore, the development of confined and enhanced electrocatalytic oxidation materials and processes is of great significance for ensuring the safety of water sources.

[0006] Since the electrocatalytic anodes currently being developed (BDD, DSA, titanium oxide, etc.) are all based on two-dimensional metal materials, this directly affects the microstructure of the electrode material, limiting the continuous contact with pollutants and enhancing their degradation capabilities. Furthermore, traditional doping and etching modification methods have a random effect on the electrode's micromorphology, making it difficult to propose a precise and controllable adjustment strategy for the pore structure and lattice morphology of the electrocatalytic anode, thus restricting the research on active sites in the ·OH pathway of water electrolysis.

[0007] Therefore, it is of great significance to prepare a double-channel titanium suboxide (Ti4O7) anode with controllable nano-sized pore structure, and to prepare anode materials with different lattice structures by using surfactants and transition metal doping, so as to prepare electrocatalytic anode materials for deep treatment and detoxification of MCs. Summary of the Invention

[0008] This application prepared a double-channel titanium suboxide (Ti4O7) anode with a controllable nano-sized pore structure, and used surfactants and transition metal doping to prepare anode materials with different lattice structures. The specific technical solutions are as follows:

[0009] A thin-film anode material with a nanopore confined structure is a Ti4O7 anode thin film material with different pore and lattice structures, with pore size in the range of 50-350 nm, and doped with La, Cu or Zn metal.

[0010] The preparation method of Ti4O7 anode thin film materials with different pore structures and crystal lattice structures is divided into two parts: pore construction and doping enhancement.

[0011] Furthermore, the pore structure is constructed by using a secondary anodizing method to refine the surface of the TiO2 foil, forming a porous TiO2 anode that is integrated with the parent metal.

[0012] Furthermore, the specific steps for constructing the channel are as follows:

[0013] S1. Polish and clean the cut TiO2 foil, and place it in an acidic electrolytic solution of 0.3 mol / L H3PO4 and 0.3 mol / L H2C2O4. The electrolyte temperature is 5℃, and the oxidation time is set to 1.5h.

[0014] S2. Immerse the substrate in H3PO4 and H2C2O4 solutions at constant temperature. The second electrolysis is performed under the same conditions as the first electrolysis, and the time is set to 6 hours.

[0015] S3. Demolding is performed using a pressure reduction method, followed by washing with distilled water, drying, and pore enlargement. By controlling the current intensity, double-pass TiO2 foils with different pore sizes are produced.

[0016] Furthermore, the doping enhancement involves immersing the prepared TiO2 foil film in a special solution.

[0017] Furthermore, the specific steps of the doping enhancement are as follows:

[0018] S4. The surfactant is sodium lauryl laurate, and the doping metals are La, Cu, and Zn.

[0019] S5. TiO2 foils with different pore sizes were fully impregnated in solution S1 and then calcined at 800°C for 2 hours in an atmosphere of hydrogen:helium = 2:1.

[0020] S6. After taking out TiO2 foils with different pore sizes, they were immersed in the mixed solution and calcined again. This process was repeated three times to prepare Ti4O7 anode films with different pore and lattice structures.

[0021] Application of thin-film anode materials in the treatment of algal toxins (MCs).

[0022] The advantages and effects of this application are as follows:

[0023] 1. This application prepared a double-pass titanium suboxide (Ti4O7) anode with a controllable nano-sized pore structure, and used surfactants and transition metal doping to prepare anode materials with different lattice structures.

[0024] 2. This application has prepared an electrocatalytic anode material capable of deep treatment and detoxification of MCs.

[0025] 3. The material prepared in this application can be applied to complex surface water environments, reducing the use of oxidants and playing an important role in ensuring the safety of water sources.

[0026] The above description is only an overview of the technical solution of this application. In order to better understand the technical means of this application and implement it in accordance with the contents of the specification, and to make the above and other objects, features and advantages of this application more obvious and understandable, the preferred embodiments of this application are described in detail below with reference to the accompanying drawings.

[0027] The above and other objects, advantages and features of this application will become more apparent to those skilled in the art from the following detailed description of specific embodiments in conjunction with the accompanying drawings. Attached Figure Description

[0028] To more clearly illustrate the technical solutions in the embodiments of this application or the prior art, the drawings used in the description of the embodiments or the prior art will be briefly introduced below. Obviously, the drawings described below are some embodiments of this application. For those skilled in the art, other drawings can be obtained based on these drawings without creative effort. In all drawings, similar elements or parts are generally identified by similar reference numerals. In the drawings, the elements or parts are not necessarily drawn to scale.

[0029] Figure 1. SEM images of TiO2 thin films with pore sizes of 160 nm, 150 nm, and 300 nm.

[0030] Figure 2 Design of a multi-stage purification reactor based on confined anode thin film materials

[0031] Figure 3 EDS characterization analysis of confined pore structure Ti4O7 electrode

[0032] Figure 4 XRD characterization analysis of Ti4O7 electrodes with confined pore structure

[0033] Figure 5 Oxygen evolution potential (LSV curves) under different doping elements

[0034] Figure 6 CV curves of electrodes with different aperture sizes

[0035] Figure 7 Removal rate of algal toxin MC-LR by electrodes with different pore sizes

[0036] Figure 8 Removal rate of algal toxin MC-LR by different doped electrodes Specific Implementation

[0037] To make the objectives, technical solutions, and advantages of the embodiments of this application clearer, the technical solutions of the embodiments of this application will be clearly and completely described below with reference to the accompanying drawings. Obviously, the described embodiments are only some embodiments of this application, not all embodiments. In the following description, specific details such as specific configurations and components are provided merely to help fully understand the embodiments of this application. Therefore, those skilled in the art should understand that various changes and modifications can be made to the embodiments described herein without departing from the scope and spirit of this application. In addition, for clarity and brevity, descriptions of known functions and structures are omitted in the embodiments.

[0038] It should be understood that the phrase "an embodiment" or "this embodiment" throughout the specification means that a specific feature, structure, or characteristic related to the embodiment is included in at least one embodiment of this application. Therefore, "an embodiment" or "this embodiment" appearing throughout the specification does not necessarily refer to the same embodiment. Furthermore, these specific features, structures, or characteristics can be combined in any suitable manner in one or more embodiments.

[0039] Furthermore, reference numerals and / or letters may be repeated in different examples within this application. Such repetition is for the purpose of simplification and clarity and does not in itself indicate a relationship between the various embodiments and / or settings discussed.

[0040] In this article, the term "and / or" is merely a description of the relationship between related objects, indicating that three relationships can exist. For example, A and / or B can mean: A exists alone, B exists alone, and A and B exist simultaneously. The term " / and" in this article describes another type of relationship between related objects, indicating that two relationships can exist. For example, A / and B can mean: A exists alone, and A and B exist alone. In addition, the character " / " in this article generally indicates that the related objects before and after it are in an "or" relationship.

[0041] In this article, the term "at least one" is merely a description of the relationship between related objects, indicating that there can be three relationships. For example, "at least one of A and B" can mean: A exists alone, A and B exist simultaneously, or B exists alone.

[0042] It should also be noted that, in this document, relational terms such as "first" and "second" are used only to distinguish one entity or operation from another, and do not necessarily require or imply any such actual relationship or order between these entities or operations. Furthermore, the terms "comprising," "including," or any other variations thereof are intended to cover non-exclusive inclusion.

[0043] Example 1

[0044] This embodiment introduces a thin film anode material with a nanopore confined structure, which is a Ti4O7 anode thin film material with different pore and lattice structures, with pore size in the range of 50-350 nm, and doped with La, Cu or Zn metal.

[0045] The preparation method of Ti4O7 anode thin film materials with different pore structures and crystal lattice structures is divided into two parts: pore construction and doping enhancement.

[0046] Preferably, the pore structure is constructed by using a secondary anodizing method to refine the surface of the TiO2 foil, forming a porous TiO2 anode that is integrated with the parent metal.

[0047] Preferably, the specific steps for constructing the channel are as follows:

[0048] S1. Polish and clean the cut TiO2 foil, and place it in an acidic electrolytic solution of 0.3 mol / L H3PO4 and 0.3 mol / L H2C2O4. The electrolyte temperature is 5℃, and the oxidation time is set to 1.5h.

[0049] S2. Immerse the substrate in H3PO4 and H2C2O4 solutions at constant temperature. The second electrolysis is performed under the same conditions as the first electrolysis, and the time is set to 6 hours.

[0050] S3. Demolding is performed using a pressure reduction method, followed by washing with distilled water, drying, and pore enlargement. By controlling the current intensity, double-pass TiO2 foils with different pore sizes are produced.

[0051] Combination Figure 1 , Figure 1 SEM images of TiO2 thin films with pore sizes of 60 nm, 150 nm, and 300 nm.

[0052] Preferably, the doping enhancement is achieved by immersing the prepared TiO2 foil in a special solution.

[0053] Preferably, the specific steps of the doping enhancement are as follows:

[0054] S4. The surfactant is sodium lauryl laurate, and the doping metals are La, Cu, and Zn.

[0055] S5. TiO2 foils with different pore sizes were fully impregnated in solution S1 and then calcined at 800°C for 2 hours in an atmosphere of hydrogen:helium = 2:1.

[0056] S6. After taking out TiO2 foils with different pore sizes, they were immersed in the mixed solution and calcined again. This process was repeated three times to prepare Ti4O7 anode films with different pore and lattice structures.

[0057] Example 2

[0058] This embodiment introduces a reactor design for a confined anode based on the above embodiments, combined with... Figure 2 , Figure 2 This is a multi-stage purification reactor based on confined anode thin film material, which contains multiple electrode pairs consisting of confined anodes and mesh cathodes.

[0059] The process of purifying water using confined anode materials, such as Figure 2 As shown, when pollutants pass through the porous structure of the anode material, they come into full contact with oxidants such as hydroxyl radicals generated at the anode under nanoscale confinement conditions, degrading into small-molecule organic matter, inorganic matter, or CO2. This reactor can be designed with multi-stage purification units according to water quality conditions.

[0060] Example 3

[0061] This embodiment describes the composition of the confined anode of this application based on the above embodiments, combined with... Figure 3 and Figure 4 , Figure 3 EDS characterization analysis of the confined pore structure Ti4O7 electrode was performed. Figure 4 XRD characterization analysis of the confined pore structure Ti4O7 electrode.

[0062] according to Figure 3 EDS and XRD analyses of the elemental composition show that the confined Ti4O7 anode thin film material is mainly composed of Ti and O elements, accounting for 43% and 57% of the atoms, respectively, which is basically consistent with the atomic ratio of Ti4O7.

[0063] Based on the XRD characterization of the confined Ti4O7 anode thin film ( Figure 4 ), preferentially growing the (121), (123) and (013) crystal planes in Ti4O7.

[0064] Example 4

[0065] This embodiment describes the electrochemical properties of the materials in this application based on the above embodiments, combined with... Figure 5 and Figure 6 , Figure 5 The oxygen evolution potential (LSV curve) is shown for different doping elements. Figure 6 The CV curves are for electrodes with different aperture sizes.

[0066] Depend on Figure 5 As shown, Cu doping can achieve the highest oxygen evolution potential, approximately 1.6V, which has a significant effect on improving the yield of hydroxyl radicals.

[0067] Depend on Figure 6 As shown, the confined Ti4O7 anode with a pore size of 300 nm has the largest CV curve area, indicating that it has the largest electrochemical specific surface area, while the original Ti4O7 anode has the smallest area.

[0068] Example 5

[0069] This embodiment, based on the above embodiments, describes the degradation effect of the material manufactured in this application on algal toxins, combined with... Figure 7 and Figure 8 , Figure 7 The removal rates of algal toxin MC-LR by electrodes with different pore sizes were studied. Figure 8 The removal rates of algal toxin MC-LR by different doped electrodes are shown.

[0070] MC-LR, a type of algal toxin, was selected as the target pollutant. With an initial concentration of 200 ng / L, the electrode with a 150 nm pore structure exhibited the highest removal rate, indicating that 150 nm is the optimal confinement size. Figure 7 Meanwhile, Cu doping also exhibits the highest removal rate, indicating that the highest oxygen evolution potential obtained through Cu doping promotes the removal of algal toxins. Figure 8 ).

[0071] The above description is merely a preferred embodiment of the present invention and does not limit the scope of protection of the present invention. For those skilled in the art, the present invention can have various modifications and variations. Any changes, modifications, substitutions, integrations, and parameter alterations to these embodiments within the spirit and principles of the present invention, achieved through conventional substitutions or by achieving the same function without departing from the principles and spirit of the present invention, fall within the scope of protection of the present invention.

Claims

1. A method for preparing a thin-film anode material with a nanoporous confined structure, characterized in that, The preparation methods of Ti4O7 anode thin film materials with different pore structures and lattice structures are divided into two parts: pore construction and doping enhancement. The pore structure is constructed by using a secondary anodic oxidation method to refine the surface of the TiO2 foil, forming a porous TiO2 anode that is integrated with the parent metal. The specific steps for constructing the channel are as follows: S1. Polish and clean the cut TiO2 foil, and place it in an acidic electrolytic solution of 0.3 mol / L H3PO4 and 0.3 mol / L H2C2O4. The electrolyte temperature is 5℃, and the oxidation time is set to 1.5h. S2. Immerse the substrate in H3PO4 and H2C2O4 solutions at constant temperature. The second electrolysis is performed under the same conditions as the first electrolysis, and the time is set to 6 hours. S3. Demolding is performed using a pressure reduction method, followed by washing with distilled water, drying, and pore enlargement. By controlling the current intensity, double-pass TiO2 foils with different pore sizes are produced. The specific steps of the doping enhancement are as follows: S4. The surfactant is sodium lauryl laurate, and the doping metal is La, Cu, or Zn. S5. TiO2 foils with different pore sizes were fully impregnated in solution S1 and then calcined at 800°C for 2 hours in an atmosphere of hydrogen:helium = 2:

1. S6. After taking out TiO2 foils with different pore sizes, they were immersed in S1 solution and calcined again. This process was repeated 3 times to prepare Ti4O7 anode films with different pore and lattice structures. The prepared anode material is a Ti4O7 anode thin film material with different pore and lattice structures, with pore size in the range of 50-350 nm, and the doped metal is La, Cu or Zn.

2. The application of a thin-film anode material prepared by the method described in claim 1 in the treatment of microcystins (MCs).

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