Cu / zn synergistic light response composite material and preparation method and application thereof

Abstract

This invention discloses a Cu / Zn synergistic photoresponsive composite material, its preparation method, and its application, belonging to the field of marine antifouling materials technology. The Cu / Zn synergistic photoresponsive composite material comprises, from the inside out, Cu... x Zr y Amorphous alloy substrate, nanoporous copper layer and nano zinc oxide; or Cu x Zr y The invention comprises an amorphous alloy matrix, a nanoporous copper layer, cuprous oxide nanowire clusters, and nano-zinc oxide, wherein x and y are atomic percentages, 30≤x≤50, 50≤y≤70, and y=100-x. Through a dual design of "multi-level pore channel regulation + synergistic mechanism," this invention significantly reduces Cu ion release, avoids secondary pollution, and aligns with the trend of green marine antifouling development.

Description

Technical Field

[0001] This invention relates to the field of marine antifouling materials technology, and in particular to a Cu / Zn synergistic photoresponsive composite material, its preparation method, and its application. Background Technology

[0002] Marine biofouling is a long-standing key challenge in the field of marine engineering. Barnacles, shrimp, jellyfish, seaweed, and other marine organisms attach and grow on the surfaces of facilities such as nuclear power plant cold source outlets, aquaculture cages, and seawater pipeline systems, increasing resource consumption, accelerating equipment corrosion, and severely impacting the service life and operational efficiency of marine engineering facilities. Antifouling materials, as a core means of solving this problem, have become a research hotspot.

[0003] Metal-based antifouling materials have attracted widespread attention due to their highly efficient antibacterial and antifouling properties. Among them, copper-based materials are the most widely used in marine antifouling due to their excellent antibacterial activity. However, most existing antifouling materials adopt micron- or millimeter-scale porous structures, which have problems such as uncontrollable pore size, uneven distribution, and easy aggregation. They also have many technical defects: First, there are significant shortcomings in structural design. The single-scale pore structure is prone to pore blockage and component aggregation, which can hinder ion transport. Second, it is difficult to precisely control the ion release rate, which can easily lead to excessive release in the early stage, causing secondary pollution of the marine environment, or insufficient release in the later stage, resulting in short antifouling time. Third, the antifouling mechanism is singular, mainly relying on the toxic effect of copper ions. It lacks multi-component synergistic design, has a narrow antifouling spectrum, and fails to improve the overall antifouling efficiency by leveraging the complementary effects of different antifouling mechanisms. Relying solely on high copper ion release to ensure antifouling effect will disrupt the marine ecological balance and is inconsistent with the concept of green antifouling.

[0004] The prior art, patent CN121203524A, "A marine antifouling coating with both controllable release and self-healing functions and its preparation method," involves physically blending a modified CuO / AC antifouling agent into a self-healing polyurethane matrix. While this technology attempts to achieve long-term controlled release by utilizing activated carbon adsorption and matrix self-healing, it lacks a multi-level micro / nano pore design, relying solely on a single-scale pore structure. This leads to the antifouling agent's tendency to aggregate, causing pore blockage and hindering ion transport. The ion release essentially still depends on the physical barrier and passive diffusion of the coating, failing to achieve precise quantitative control of ion release or intelligent adjustment in response to the environment. Furthermore, the antifouling mechanism relies solely on a single copper ion, lacking a synergistic design involving multiple components and mechanisms.

[0005] Prior art, patent CN112940555A, entitled "Preparation and Application of an Antifouling Agent with Controllable Release of Cuprous Ions," describes the preparation of graphene-copper composite powder and its use of galvanic corrosion to promote the slow release of copper ions. However, its lack of hierarchical pore structure design leads to easy agglomeration and poor dispersibility of the powder in the organic resin carrier. The release rate is determined by the inherent electrochemical process and cannot be intelligently controlled. This powder material relies on an organic resin carrier, resulting in dispersion and interfacial stability issues. Furthermore, its antifouling mechanism depends entirely on the release of single copper ions, failing to incorporate other synergistic effects such as photocatalysis. Therefore, there is room for improvement in both the antifouling spectrum and environmental friendliness.

[0006] The prior art, publication number CN104403448A, "A Marine Antifouling Coating Based on Nano-Cuprous Oxide Composite with Nano-Silver," focuses on preparing an antifouling coating by mixing and dispersing nano-cuprous oxide and nano-silver sol in a polyacrylic acid resin-chlorinated rubber (or rosin) composite base. This technology has significant drawbacks: firstly, the cost of nano-silver raw materials is high, and the silver ammonia solution reduction preparation process is stringent, limiting its large-scale application; secondly, nano-copper and silver particles are prone to agglomeration, and cuprous oxide is easily oxidized and deactivated, leading to rapid decay of antifouling efficacy; thirdly, the ion release rate lacks a precise control mechanism, easily resulting in excessive initial pollution or insufficient later release. Furthermore, the coating's long-term durability and adaptability to extreme marine environments are poor, making it difficult to meet the requirements for long-term environmentally friendly antifouling.

[0007] Prior art, patent CN120905679A, entitled "A Multifunctional Z-shaped Heterojunction Photoanode with Anti-corrosion, Antifouling, and Antibacterial Properties and its Preparation Method," significantly improves photocatalytic efficiency by constructing a highly efficient Z-shaped heterojunction. It utilizes photogenerated electrons and holes to generate reactive oxygen species for antifouling, representing a green technology direction that does not rely on ion release. However, this "pure photocatalysis" approach has inherent limitations. Its antifouling effectiveness is entirely and instantaneously dependent on light conditions, making it difficult to sustain in darkness or low-light environments. Its mechanism of action primarily targets the oxidative decomposition of microorganisms, and its effectiveness against large fouling organisms such as barnacles and mussels may be limited. More importantly, this technological approach completely avoids ion release systems, failing to construct a long-term storage and intelligent release system for metal ions, and thus cannot address practical engineering scenarios requiring continuous, on-demand antifouling. Summary of the Invention

[0008] The purpose of this invention is to address the technical shortcomings of existing marine antifouling materials, such as rough pore structure, uncontrollable ion release, single antifouling mechanism, and insufficient long-term effectiveness, by providing a Cu / Zn synergistic photoresponsive composite material.

[0009] Another object of the present invention is to provide a method for preparing the above-mentioned composite material.

[0010] Another object of the present invention is to provide the application of the above-mentioned composite material in marine antifouling.

[0011] The technical solution adopted to achieve the purpose of this invention is: A Cu / Zn synergistic photoresponsive composite material, wherein the Cu / Zn synergistic photoresponsive composite material comprises, from the inside out, Cu x Zr y Amorphous alloy substrate, nanoporous copper layer and nano zinc oxide; or Cu x Zr y The composition consists of an amorphous alloy matrix, a nanoporous copper layer, cuprous oxide nanowire clusters, and nano-zinc oxide, where x and y are atomic percentages, 30 ≤ x ≤ 50, 50 ≤ y ≤ 70, and y = 100 - x.

[0012] In the above technical solution, the cuprous oxide nanowire cluster is formed by the aggregation of nanowires with an aspect ratio of 50 to 300, and the length of a single nanowire is 1 to 3 μm and the diameter is 5 to 20 nm.

[0013] In the above technical solution, when Cu is included sequentially from the inside out... x Zr y When an amorphous alloy substrate, a nanoporous copper layer, and nano zinc oxide are used, the nano zinc oxide is in the form of nanoflowers with a gap of 50~200nm between each nanoflower. The nanoflowers are assembled from multiple spindle-shaped nanosheets, and micropores of 5~20nm are formed between adjacent spindle-shaped nanosheets.

[0014] In the above technical solution, when Cu is included sequentially from the inside out... x Zr y When the amorphous alloy matrix, nanoporous copper layer, cuprous oxide nanowire clusters, and nano zinc oxide are used, the nano zinc oxide is in the form of a spindle-shaped nanosheet with a lateral dimension (maximum radial width perpendicular to the length direction) of 20~50nm, a longitudinal dimension (maximum axial length along the length direction) of 50~200nm, and a thickness of 5~10nm.

[0015] Another aspect of the present invention includes a method for preparing the Cu / Zn synergistic photoresponsive composite material, comprising the following steps: Step 1: Clean and melt Cu and Zr to obtain Cu-Zr alloy ingots, then melt and spin the ingots to form Cu. x Zr y Amorphous alloy matrix; Step 2, Cu x Zr y Nanoporous copper is obtained by dealloying an amorphous alloy matrix. Step 3: A three-electrode system is used, with nanoporous copper as the working electrode and zinc nitrate hexahydrate solution containing ammonium nitrate (NH4NO3) as the electrolyte for constant potential electrodeposition treatment. The surface is repeatedly washed to remove residual electrodeposition solution and impurities, and then dried to load nano zinc oxide on the surface of the nanoporous copper layer, thus obtaining Cu / Zn synergistic photoresponsive composite material.

[0016] In the above technical solution, before step 3, the same three-electrode system is used first, with nanoporous copper as the working electrode, to perform constant current in-situ anodic oxidation treatment, drying, and heat treatment to generate cuprous oxide nanowire clusters in-situ on the surface of the nanoporous copper. Then, the process of step 3 is used, with cuprous oxide nanowire clusters as the working electrode, and nano zinc oxide is loaded on the surface of the cuprous oxide nanowire clusters.

[0017] In the above technical solution, the temperature of the heat treatment is 100~250℃ and the time is 0.5~4.0h.

[0018] In the above technical solution, in step 1, the purity of both Cu and Zr is 99.99%.

[0019] In the above technical solution, in step 2, the Cu x Zr y The amorphous alloy matrix is ​​cut into sizes ranging from 2cm×1mm×20μm to 6cm×2.5mm×30μm and then subjected to dealloying treatment.

[0020] In the above technical solution, in step 1, the vacuum degree of the melting and spinning process is 3×10⁻⁶. -4 ~3×10 -3 Pa, the blow casting pressure is 0.5~2.0MPa, Cu x Zr y The amorphous alloy matrix is ​​in the form of thin strips, with a width of 1.5~2mm and a thickness of 20~40μm.

[0021] In the above technical solution, step 2, the dealloying process involves removing the Cu... x Zr y The amorphous alloy matrix was immersed in a mixed solution of ammonium fluoroborate (NH4BF4), trisodium citrate (Na3C6H5O7) and HF acid at 20~30℃ for 0.5~8h.

[0022] In the above technical solution, in step 2, the concentration of the HF acid is 0.01~0.1M, the concentration of the ammonium fluoroborate is 0.001~0.01M, and the concentration of the trisodium citrate is 0.005~0.02M.

[0023] In the above technical solution, in step 3, a platinum mesh is used as the counter electrode and a standard silver / silver chloride electrode (Ag / AgCl) is used as the reference electrode.

[0024] In the above technical solution, in step 3, the concentration of ammonium nitrate in the electrolyte is 0.5~5mM, the concentration of zinc nitrate hexahydrate is 1~20mM, the deposition temperature of the constant potential electrodeposition treatment is 25~80℃, the deposition potential is -0.8~-1.2V, and the deposition time is 1~60min.

[0025] In the above technical solution, in step 3, the drying temperature is 100~250℃ and the drying time is 2~3h.

[0026] Another aspect of the present invention includes the application of the Cu / Zn synergistic photoresponsive composite material in marine antifouling.

[0027] Compared with the prior art, the beneficial effects of the present invention are: (1) The composite material of the present invention has a multi-level micro-nano porous composite structure, comprising: Primary structure: A three-dimensional nanoporous copper (NPC) framework serving as an ion storage and mechanical support. This framework has a three-dimensional network structure with dual continuous ligaments / pores, and the sizes of the ligaments and pores are both at the micro-nano scale (NPC tubular layer thickness 80~120μm, ligament width 10~100nm, pore size 20~80nm). It can store a large amount of copper ion precursors and provide a stable substrate for subsequent structure growth, while also serving as a primary ion transport channel. Secondary structure: Cuprous oxide (Cu₂O) nanowire clusters serving as directional ion transport channels. These nanowire clusters are grown in situ on the surface of a nanoporous copper framework via anodizing. The nanowires are 1–3 μm long and 5–10 nm wide, with 10–30 nanowires clustered together. The gaps between these vertically oriented nanostructures form a regular, high-speed channel for ion transport from the interior of the framework to the surface, allowing for precise control of the ion diffusion path. Alternatively, they serve as gaps between zinc oxide nanoflowers, acting as secondary ion transport channels. The zinc oxide nanoflowers grow densely on the nanoporous copper surface, naturally forming gaps of 50–200 nm between adjacent nanoflowers. These gaps act as secondary ion transport channels, further regulating the ion transport path.

[0028] The tertiary structure consists of a zinc-containing photocatalytic layer that serves as both a smart release gate and a synergistic antifouling component. This layer is electrochemically deposited onto the surface of a cuprous oxide nanowire array via an ammonium nitrate-containing zinc nitrate system. Zinc oxide and the underlying cuprous oxide layer form a heterojunction, constituting the material's "smart response unit." Under illumination, the built-in electric field of the heterojunction drives photogenerated charge separation, achieving photocatalytic antifouling through the generation of reactive oxygen species from zinc oxide, while also regulating the directional release rate of copper ions. Simultaneously, zinc ions possess bactericidal properties, synergizing with the copper ion's toxicity and photocatalytic antifouling effects to construct a highly efficient and green antifouling system. Alternatively, it can serve as a fine-tuning layer and the pores between the nanosheets within the zinc oxide nanoflowers, forming a synergistic antifouling component. The nanosheets constituting the zinc oxide nanoflowers are arranged in an interlaced pattern, forming micropores of approximately 5–20 nm. These micropores act as tertiary channels for ion transport, working in conjunction with primary pores and secondary gaps to form a multi-level, precise ion transport system, enabling precise control of the ion release rate.

[0029] Furthermore, zinc oxide and the underlying nanoporous copper form a pn heterojunction, constituting the material's "intelligent response unit." Under illumination, the built-in electric field of the heterojunction drives photogenerated charge separation, achieving photocatalytic antifouling through the generation of reactive oxygen species from zinc oxide, while also regulating the directional release rate of copper ions. Simultaneously, zinc ions themselves possess bactericidal properties, synergizing with the toxic and photocatalytic antifouling effects of copper ions to construct a highly efficient and green antifouling system.

[0030] (2) Uniqueness of the preparation method: This invention employs a two-step continuous process of "dealloying for pore formation - electrodeposition for flower formation" or a three-step in-situ continuous process of "dealloying for pore formation - anodic oxidation for wire formation - electrodeposition for coating." In the dealloying step, an innovative ammonium fluoroborate-trisodium citrate composite additive system is introduced, and in the electrodeposition step, ammonium nitrate is introduced to optimize the zinc nitrate deposition system, eliminating the need for complex intermediate processing steps. The preceding structure provides active anchoring points for the subsequent growth, forming a chemically bonded integrated structure without physical interface gaps, thus avoiding the risks of poor interfacial compatibility and performance degradation caused by physical composites. The process is simple and controllable. By adjusting process parameters, the storage capacity of the nanoporous copper, the transport efficiency of the cuprous oxide nanowires, and the photoresponse and controllability of the zinc oxide nanosheets (or the conductivity of the zinc oxide nanoflowers and the fine controllability of the micropores within the nanoflowers) can be customized, precisely tailoring the material structure and ion release rate to adapt to different marine environments and antifouling requirements.

[0031] (3) Structural Innovation: This invention constructs a multi-level micro-nano porous composite structure of Cu / Zn synergistic zinc oxide shuttle nanosheets @ cuprous oxide nanowire clusters. The ligament width, pore size, and thickness of the porous matrix are precisely controlled through a dealloying process, and the ion transport channels are optimized by anodizing or by combining the multi-level pores of the zinc oxide nanoflowers themselves. The channels at each scale are interconnected, which not only solves the problems of easy aggregation, blockage, and ion transport obstruction in single-scale pore structures, but also achieves slow and stable release of Cu ions and prolongs the antifouling effect by utilizing the pore size restriction effect of the micro-nano porous structure and the optimized ion transport uniformity. At the same time, the multi-level micro-nano porous structure significantly increases the specific surface area of ​​the material, optimizes the ion transport efficiency and light capture performance, and provides a structural basis for light response regulation and synergistic antifouling. Compared with the micron-level uncontrollable pores of the foamed copper matrix, the multi-level micro-nano porous structure of this invention fundamentally solves the technical bottleneck of the difficulty in controlling the ion release rate of existing antifouling materials.

[0032] (4) Synergistic Mechanism Innovation: This invention achieves a triple synergistic effect of Cu ion toxicity, Zn ion sterilization, and ZnO / Cu2O heterojunction photocatalytic antifouling, effectively broadening the antifouling spectrum. Compared with the single "pure photocatalysis" path in the prior art, ZnO and Cu2O (or Cu substrate) in this invention can form a heterojunction, enhancing light capture capability, efficiently separating photogenerated charges and generating active oxygen, inhibiting the attachment of microorganisms such as algae and bacteria, and realizing intelligent regulation of ion release based on the photoresponse characteristics of the heterojunction; Cu ions exert a toxic effect on large fouling organisms such as barnacles and mussels; while Zn ions have a bactericidal effect on a variety of microorganisms, which can reduce the marine bioaccumulation of Cu ions, achieving complementary effects between ions. The synergistic effect of the three solves the defect of narrow antifouling spectrum of traditional single-mechanism antifouling materials. In addition, the active oxygen generated by photocatalysis can directly replace part of the toxic effect of Cu ions, which also reduces the dependence on Cu ion release, reducing marine environmental pollution from the source, and taking into account both antifouling effect and environmental protection.

[0033] (5) Green and environmentally friendly advantages: This invention significantly reduces Cu ion release (by 40% to 60% compared to traditional copper-based materials) through a dual design of "multi-level pore channel regulation + synergistic mechanism," avoiding secondary pollution and conforming to the development trend of green marine antifouling. Existing Cu-based antifouling materials do not involve photocatalysis and synergistic design of complementary different ions, still requiring a relatively high Cu ion release to ensure antifouling effect, which is not environmentally friendly enough and cannot meet the current application requirements of green antifouling. At the same time, the multi-level micro-nano pore structure of the material of this invention has excellent anti-clogging and anti-agglomeration properties, ensuring long-term cycle antifouling stability from a structural level, further reducing marine pollution caused by material replacement.

[0034] (6) Advantages of the preparation process: The process adopts a combination of "dealloying + anodizing + electrodeposition" or a combination of "dealloying + electrodeposition". The dealloying step innovatively introduces ammonium fluoroborate-trisodium citrate composite additive, and the electrodeposition step introduces ammonium nitrate to optimize the zinc nitrate homologous deposition system. This combination process has not been publicly reported. The overall operation is simple and highly controllable. The material structure and ion release rate can be customized by adjusting the process parameters to meet the needs of different marine environments. Compared with the physical blending-curing process, it does not require complex loading and cross-linking steps, resulting in higher preparation efficiency and lower cost. The raw materials are inexpensive and readily available. The in-situ growth of each structure forms a chemically bonded integrated structure without physical interfaces, which is tightly bonded and effectively ensures long-term service stability in harsh marine environments. Attached Figure Description

[0035] Figure 1 This is a SEM image of the nanoporous copper prepared in Example 1.

[0036] Figure 2 This is an EDS image of the nanoporous copper prepared in Example 1.

[0037] Figure 3 This is a SEM image of the nano-zinc oxide prepared in Example 1.

[0038] Figure 4 This is a high-magnification SEM image of the nano-zinc oxide prepared in Example 1.

[0039] Figure 5 This is an EDS image of the nano-zinc oxide flowers prepared in Example 1.

[0040] Figure 6 This is a SEM image of the cuprous oxide nanowire clusters prepared in Example 4.

[0041] Figure 7 This is an EDS image of the cuprous oxide nanowire clusters prepared in Example 4.

[0042] Figure 8 The image shows the XRD pattern of the cuprous oxide nanowire clusters prepared in Example 4.

[0043] Figure 9 This is a SEM image of the composite material prepared in Example 4.

[0044] Figure 10 This is the EDS diagram of the composite material prepared in Example 4. Detailed Implementation

[0045] The present invention will be further described in detail below with reference to specific embodiments. It should be understood that the specific embodiments described herein are merely illustrative of the invention and are not intended to limit the invention.

[0046] Example 1 A method for preparing a Cu / Zn synergistic photoresponsive composite material includes the following steps: Step 1: After cleaning, Cu and Zr with an atomic ratio of 50:50 are placed in a vacuum arc melting furnace for melting to obtain Cu-Zr alloy ingots. Induction melting is then performed in a vacuum strip spinning machine under high-purity argon protection. The molten metal is then blown and cast to form Cu. 50 Zr 50 Amorphous alloy matrix.

[0047] Step 2, Cu 50 Zr 50 After the amorphous alloy substrate was cut to a length of 4cm, a width of 1.5mm, and a thickness of approximately 20μm, it was ultrasonically cleaned with anhydrous ethanol, then immersed in a mixed solution of 0.005M ammonium fluoroborate (NH4BF4), 0.01M trisodium citrate (Na3C6H5O7), and 0.05M HF acid for dealloying treatment for 4h. After cleaning with deionized water, it was dried in a vacuum drying oven at 60℃ to obtain nanoporous copper with uniform pore structure. Step 3: Five nanoporous copper sheets with dimensions of 4cm×1.5mm×20μm were used as working electrodes, a platinum mesh as the counter electrode, and a standard silver / silver chloride electrode (Ag / AgCl) as the reference electrode. A constant potential electrodeposition treatment was performed using a 100ml mixed solution of 2mM ammonium nitrate (NH4NO3) and 5mM zinc nitrate hexahydrate as the electrolyte. The deposition potential was -1V, the deposition time was 20min, and the deposition temperature was 60℃. After removal, the sample was repeatedly washed with deionized water and dried in a vacuum drying oven at 200℃ for 2h to load nano-zinc oxide onto the surface of the nanoporous copper, thus obtaining a Cu / Zn synergistic photoresponsive composite material.

[0048] like Figure 1 As shown, nanoporous copper exhibits a three-dimensional bicontinuous ligament / pore structure with a nanoporous morphology. The ligament width is 25 nm, and the pore size is 20 nm, making it suitable as a copper ion storage and mechanical support. Figure 2 As shown, the nanoporous copper mainly contains Cu, with extremely low Zr content, confirming that the dealloying process effectively removes Zr and yields nanoporous copper.

[0049] like Figures 3-4 As shown, nano zinc oxide is composed of a large number of ultrathin nanosheets interlaced and assembled. The nanosheet structure detected three elements: Cu, O, and Zn, confirming that nano zinc oxide has been loaded onto the nanoporous copper surface.

[0050] Example 2 A method for preparing a Cu / Zn synergistic photoresponsive composite material includes the following steps: Step 1: After cleaning, Cu and Zr with an atomic ratio of 40:60 are placed in a vacuum arc melting furnace for melting to obtain Cu-Zr alloy ingots. Induction melting is then performed in a vacuum strip spinning machine under high-purity argon protection. The molten metal is then blown and cast to form Cu. 40 Zr 60 Amorphous alloy matrix.

[0051] Step 2, Cu 40 Zr 60 An amorphous alloy substrate was cut to a length of 4 cm, a width of 1.5 mm, and a thickness of approximately 20 μm. It was then ultrasonically cleaned with anhydrous ethanol for 10 min (to remove surface oil). Afterward, it was immersed in a mixed solution of 0.008 M ammonium fluoroborate (NH4BF4), 0.015 M trisodium citrate (Na3C6H5O7), and 0.08 M HF acid for 3 h of dealloying treatment. It was then washed three times with deionized water and dried in a vacuum drying oven at 60 °C for 2 h to obtain a nanoporous copper with a uniform pore structure. This nanoporous copper exhibits a three-dimensional bicontinuous ligament / pore structure with a ligament width of 30 nm and a pore size of 40 nm, making it suitable as a copper ion storage and mechanical support.

[0052] Step 3: Five nanoporous copper sheets with dimensions of 4cm×1.5mm×20μm were used as working electrodes, a platinum mesh as the counter electrode, and a standard silver / silver chloride electrode (Ag / AgCl) as the reference electrode. A constant potential electrodeposition treatment was performed using a 100ml mixed solution of 2.5mM ammonium nitrate (NH4NO3) and 5mM zinc nitrate hexahydrate as the electrolyte. The deposition potential was -1.2V, the deposition time was 30min, and the deposition temperature was 55℃. After removal, the sample was repeatedly washed with deionized water and dried in a vacuum drying oven at 200℃ for 2h to load nano-zinc oxide onto the surface of the nanoporous copper, thus obtaining a Cu / Zn synergistic photoresponsive composite material.

[0053] Example 3 A method for preparing a Cu / Zn synergistic photoresponsive composite material includes the following steps: Step 1: After cleaning, Cu and Zr with an atomic ratio of 30:70 are placed in a vacuum arc melting furnace for melting to obtain Cu-Zr alloy ingots. Induction melting is then performed in a vacuum strip spinning machine under high-purity argon protection. The molten metal is then blown and cast to form Cu. 30 Zr 70 Amorphous alloy matrix.

[0054] Step 2, Cu 30 Zr 70An amorphous alloy substrate was cut to a length of 4 cm, a width of 1.5 mm, and a thickness of approximately 20 μm. It was then ultrasonically cleaned with anhydrous ethanol and immersed in a mixed solution of 0.008 M ammonium fluoroborate (NH4BF4), 0.03 M trisodium citrate (Na3C6H5O7), and 0.05 M HF acid for 5 hours for dealloying. After washing three times with deionized water, it was dried in a vacuum drying oven at 60 °C for 2 hours, thus obtaining a nanoporous copper with a uniform pore structure. This nanoporous morphology exhibits a three-dimensional bicontinuous ligament / pore structure, with a ligament width of 20 nm and a pore size of 30 nm. It can serve as a copper ion storage and mechanical support. The finer ligaments, more uniform pore distribution, and larger specific surface area facilitate ion storage and transport.

[0055] Step 3: Five nanoporous copper nanosheets (4cm × 1.5mm × 20μm) were used as working electrodes, a platinum mesh as the counter electrode, and a standard silver / silver chloride electrode (Ag / AgCl) as the reference electrode. A constant potential electrodeposition process was performed using a 100ml mixed solution containing 1.5mM ammonium nitrate (NH4NO3) and 5mM zinc nitrate hexahydrate as the electrolyte. The deposition potential was -0.8V, the deposition time was 10min, and the deposition temperature was 65℃. After removal, the nanosheets were repeatedly washed with deionized water and dried in a vacuum drying oven at 200℃ for 2h to load nano-zinc oxide onto the nanoporous copper surface, obtaining a Cu / Zn synergistic photoresponsive composite material. The nano-zinc oxide is in the form of nanoflowers, each composed of nanosheets. The nanosheets have a lateral dimension of approximately 35nm, a longitudinal dimension of approximately 120nm, and a layer thickness of approximately 9nm. The interlaced nanosheets form micropores, constituting a hierarchical porous structure.

[0056] Example 4 A method for preparing a Cu / Zn synergistic photoresponsive composite material is disclosed in this embodiment. Compared with Example 1, before step 3 of Example 1, a three-electrode system is used, with a platinum mesh as the cathode, a nanoporous copper strip as the anode, and a standard silver / silver chloride electrode (Ag / AgCl) as the reference electrode, for in-situ anodic oxidation under a DC power supply. The electrolyte is a 1M KOH solution, and the current density is 10 mA / cm². 2 The reaction time was 600 s and the reaction temperature was 25 ℃. After removal, it was washed with deionized water and dried in a vacuum drying oven at 200 ℃ for 3 h to obtain a nanoporous copper-supported cuprous oxide nanowire cluster composite material.

[0057] In step 3 of this embodiment, compared with that of embodiment 1, a nanoporous copper-supported cuprous oxide nanowire cluster composite material is used as the working electrode, while the rest of the process is the same, to obtain a Cu / Zn synergistic photoresponsive composite material.

[0058] like Figure 6As shown, the cuprous oxide nanowire cluster is composed of multiple ultrafine nanowires, each 2 μm long and 15 nm in diameter, with nanoscale pores on each nanowire, which can serve as directional ion transport channels. Figure 7 The image shown is the EDS spectrum of the cuprous oxide nanowire clusters prepared in this embodiment, where only Cu and O elements were detected. Figure 8 As shown, it is the XRD pattern of the cuprous oxide nanowire clusters prepared in this embodiment, which confirms the formation of the pure phase of cuprous oxide without impurity peaks.

[0059] like Figure 9 As shown, this is a SEM image of the Cu / Zn synergistic photoresponsive composite material prepared in this embodiment. Figure 10 As shown, this is the EDS image of the composite material prepared in this embodiment. Cu, O and Zn elements were detected, confirming that the nano zinc oxide was uniformly loaded on the surface of the cuprous oxide nanowire cluster.

[0060] Example 5 A method for preparing a Cu / Zn synergistic photoresponsive composite material is disclosed in this embodiment. Compared with Embodiment 2, the method in this embodiment employs a three-electrode system before step 3 of Embodiment 2, using a platinum mesh as the cathode, a nanoporous copper strip as the anode, and a standard silver / silver chloride electrode (Ag / AgCl) as the reference electrode, for in-situ anodic oxidation under a DC power supply. The electrolyte is a 1.2M KOH solution, and the current density is 15 mA / cm². 2 The reaction time was 500 s, and the reaction temperature was 25 °C. After removal, the mixture was washed with deionized water and dried in a vacuum drying oven at 200 °C for 3 h to obtain a nanoporous copper-supported cuprous oxide nanowire cluster composite material. The prepared cuprous oxide nanowire clusters consist of multiple ultrafine nanowires, each nanowire being 1.5 μm long and 10 nm in diameter. Approximately 20 nanowires are clustered together, and each nanowire has nanoscale pores that can serve as directional ion transport channels.

[0061] In step 3 of this embodiment, compared with that of embodiment 2, a nanoporous copper-supported cuprous oxide nanowire cluster composite material is used as the working electrode, while the rest of the process is the same, to obtain a Cu / Zn synergistic photoresponsive composite material.

[0062] Example 6 A method for preparing a Cu / Zn synergistic photoresponsive composite material is disclosed in this embodiment. Compared with Example 3, the method in this embodiment employs a three-electrode system before step 3 of Example 3, using a platinum mesh as the cathode, a nanoporous copper strip as the anode, and a standard silver / silver chloride electrode (Ag / AgCl) as the reference electrode, for in-situ anodic oxidation under a DC power supply. The electrolyte is a 0.8M KOH solution, and the current density is 8 mA / cm². 2The reaction time was 700 s, and the reaction temperature was 25 °C. After removal, the mixture was washed with deionized water and dried in a vacuum drying oven at 200 °C for 3 h to obtain a nanoporous copper-supported cuprous oxide nanowire cluster composite material. The prepared cuprous oxide nanowire clusters consist of multiple ultrafine nanowires, each nanowire being 1.5 μm long and 10 nm in diameter. Approximately 20 nanowires are clustered together, and each nanowire has nanoscale pores, which can serve as directional ion transport channels.

[0063] In step 3 of this embodiment, compared with that of embodiment 3, a nanoporous copper-supported cuprous oxide nanowire cluster composite material is used as the working electrode, while the rest of the process is the same, to obtain a Cu / Zn synergistic photoresponsive composite material.

[0064] Comparative Example 1 A method for preparing a composite material is provided in this comparative example. Compared with Example 1, the method directly uses ordinary foamed copper as the working electrode and follows step 3 of Example 1 to obtain the composite material. Marine antifouling tests show that under light and dark conditions, the surface biofouling coverage is 25% and 32% within 60 minutes, respectively, and the copper ion release rate is uneven (fluctuation range 0.5~2.2 μg / (cm³)). 2 •h)), which cannot achieve controlled release, and the material does not bond tightly to the substrate. It is easy to fall off after long-term immersion. After three cycles of testing, the adhesion coverage increased to 40%, which cannot meet the long-term antifouling requirements.

[0065] Comparative Example 2 A method for preparing a composite material, which, compared with the method in Example 1, only includes steps 1 and 3 to obtain the composite material.

[0066] Marine antifouling tests showed that the adhesion coverage rates were 15% and 23% respectively within 60 minutes, and the copper ion release rate was uneven (fluctuation range 0.5~2.2μg / (cm³)). 2 The material cannot achieve controlled release, and the material does not bond tightly to the substrate. It is easy to fall off after long-term immersion. After three cycles of testing, the adhesion coverage increased to 40%, which cannot meet the long-term antifouling requirements.

[0067] Comparative Example 3 A method for preparing a composite material, which, compared with Example 4, uses ordinary copper foam as the anode to prepare the composite material, and the remaining steps are the same as in Example 4.

[0068] Nanoporous copper was prepared without a dealloying process, using ordinary foamed copper directly as the substrate, with no changes to subsequent processes. Marine antifouling tests showed that the adhesion coverage was 16% and 25% within 60 minutes, respectively, with uneven copper ion release rates (fluctuating between 0.7 and 2.4 μg / (cm³)). 2•h)), which cannot achieve controlled release, and the material is not tightly bonded to the substrate, making it prone to detachment after long-term immersion.

[0069] Comparative Example 4 A method for preparing a composite material, which, compared to the method in Example 4, includes only steps 1 and 3 to obtain the composite material. Marine antifouling tests showed that the adhesion coverage was 22% and 30% within 60 minutes, respectively, and the copper ion release rate was approximately 0.3–0.8 μg / (cm³). 2 •h)), after 3 cycles of testing, the surface nanosheets detached severely, resulting in poor structural stability.

[0070] Application Example 1 The Cu / Zn synergistic photoresponsive composite materials obtained in Examples 1, 2, 3, 4, 5, or 6 were cut into 1cm × 1cm samples and fixed onto the surface of a quartz carrier as the experimental group. Simultaneously, equal amounts of the nanoporous copper substrate material obtained in Examples 1, 2, or 3 (or the nanoporous copper-supported cuprous oxide nanowire cluster composite material obtained in Examples 4, 5, or 6) were cut into the same size and fixed onto the same quartz carrier surface as the blank control group. Similarly, equal amounts of the composite materials obtained in Comparative Examples 1, 2, 3, or 4 were cut into the same size and fixed onto the same quartz carrier surface as the control group. Two sets of samples were placed simultaneously in a simulated marine environment system (simulated seawater composition: NaCl: 35g / L, MgCl2: 7.5g / L, CaCl2: 1.5g / L, containing common marine microorganisms (Escherichia coli, Vibrio vulnificus), algal spores (diatoms, dinoflagellates) and fouling organism larvae (barnacle larvae, mussel larvae), simulating the normal temperature and pressure environment of the ocean).

[0071] In the dark and under a 300W xenon lamp source (λ≥420nm, illuminance of 50mW / cm²), respectively. 2 Under the irradiation condition (the vertical distance between the light source and the sample is 10cm), the antifouling performance test was carried out continuously for 60min. Every 10min, the adhesion of microorganisms and algae on the surface of the two groups of samples and the release rate of copper ions were observed and recorded.

[0072] The test results show that: (1) Attachment condition: In Example 1, under light conditions, the surface coverage of the experimental group was less than 3% with microorganisms and algae within 60 minutes, and no barnacle or mussel larvae were attached. Under dark conditions, the coverage was less than 8%, with no obvious fouling organisms attached. In the blank control group of Example 1, under light and dark conditions, the surface coverage was 30% and 38% within 60 minutes, respectively, with obvious microorganisms, algae, and a small number of barnacle larvae attached.

[0073] In Example 2, under light conditions, the surface coverage of the experimental group was less than 4% with microorganisms and algae within 60 minutes, and no barnacle or mussel larvae were attached. Under dark conditions, the coverage was less than 9%, with no obvious fouling organisms attached. In the blank control group of Example 2, under light and dark conditions, the surface coverage was 29% and 36% within 60 minutes, respectively, with obvious microorganisms, algae, and a small number of barnacle larvae attached.

[0074] In Example 3, under light conditions, the surface coverage of the experimental group was less than 2.5% with microorganisms and algae attached within 60 minutes, and no barnacle larvae or mussel larvae were attached. Under dark conditions, the coverage was less than 7%, with no obvious fouling organisms attached. In the blank control group of Example 3, under light and dark conditions, the surface coverage was 27% and 34% respectively within 60 minutes, with obvious microorganisms and algae attached, and a small number of barnacle larvae attached.

[0075] In Example 4, under light conditions, the surface coverage of the experimental group was less than 3% with microorganisms and algae within 60 minutes, and no barnacle or mussel larvae were attached. Under dark conditions, the coverage was less than 8%, with no obvious fouling organisms attached. In the blank control group of Example 4, under light and dark conditions, the surface coverage was 28% and 35% within 60 minutes, respectively, with obvious microorganisms, algae, and a small number of barnacle larvae attached.

[0076] In Example 5, under light conditions, the surface coverage of the experimental group was less than 2% with microorganisms and algae within 60 minutes, and no barnacle or mussel larvae were attached. Under darkness conditions, the coverage was less than 7%, with no obvious fouling organisms attached. In the blank control group of Example 5, under light and darkness conditions, the surface coverage was 27% and 33% respectively within 60 minutes, with obvious microorganisms, algae, and a small number of barnacle larvae attached.

[0077] In Example 6, under light conditions, the surface coverage of the experimental group was less than 2.5% with microorganisms and algae attached within 60 minutes, and no barnacle larvae or mussel larvae were attached. Under dark conditions, the coverage was less than 7%, with no obvious fouling organisms attached. In the blank control group of Example 6, under light and dark conditions, the surface coverage was 27% and 34% respectively within 60 minutes, with obvious microorganisms and algae attached, and a small number of barnacle larvae attached.

[0078] In the control group of Comparative Example 1, the surface biofouling coverage was 25% and 32% under light and dark conditions, respectively, within 60 minutes.

[0079] In the control group of Comparative Example 2, the surface biofouling coverage was 15% and 23% under light and dark conditions, respectively, within 60 minutes.

[0080] In the control group of Comparative Example 3, the surface biofouling coverage was 18% and 25% under light and dark conditions, respectively, within 60 minutes.

[0081] In Comparative Example 4, the control group showed surface biofouling coverage of 15% and 23% under light and dark conditions, respectively, within 60 minutes. (2) Ion release rate: In the experimental group of Example 1, the copper ion release rate under light irradiation was approximately 0.8 μg / (cm³). 2 The zinc ion release rate is approximately 0.3 μg / (cm³) (·h). 2 Under dark conditions, the copper ion release rate decreased to 0.4 μg / (cm³). 2 The zinc ion release rate decreased to 0.1 μg / (cm·h). 2 •h), achieving controlled ion release. In the blank control group of Example 1, the copper ion release rate remained at 1.8 μg / (cm²) regardless of whether under light or dark conditions. 2 Around 10 h, there was no significant change and no zinc ion release.

[0082] In Example 2, the copper ion release rate of the experimental group under light irradiation was approximately 0.9 μg / (cm²). 2 The zinc ion release rate is approximately 0.3 μg / (cm³) (·h). 2 Under dark conditions, the copper ion release rate decreased to 0.4 μg / (cm³). 2 The zinc ion release rate decreased to 0.1 μg / (cm·h). 2 •h), achieving controlled ion release. In the blank control group of Example 2, the copper ion release rate remained at 2.0 μg / (cm²) regardless of whether under light or dark conditions. 2 Around 10 h, there was no significant change and no zinc ion release.

[0083] In Example 3, the copper ion release rate of the experimental group under light irradiation was approximately 0.7 μg / (cm²). 2 The zinc ion release rate is approximately 0.3 μg / (cm³) (·h). 2 Under dark conditions, the copper ion release rate decreased to 0.25 μg / (cm³). 2 The zinc ion release rate decreased to 0.1 μg / (cm·h). 2 •h), the controlled release of ions is even more effective. In the blank control group of Example 3, the copper ion release rate remained at 1.7 μg / (cm²) under both light and dark conditions. 2 Around 10 h, there was no significant change and no zinc ion release.

[0084] In Example 4, the copper ion release rate of the experimental group under light irradiation was approximately 0.8 μg / (cm²).2 The zinc ion release rate is approximately 0.3 μg / (cm³) (·h). 2 Under dark conditions, the copper ion release rate decreased to 0.3 μg / (cm³). 2 The zinc ion release rate decreased to 0.1 μg / (cm·h). 2 •h), achieving controlled ion release. In the blank control group of Example 4, the copper ion release rate remained at 1.8 μg / (cm²) regardless of whether under light or dark conditions. 2 Around 10 h, there was no significant change and no zinc ion release.

[0085] In Example 5, the copper ion release rate of the experimental group under light irradiation was approximately 0.9 μg / (cm²). 2 The zinc ion release rate is approximately 0.3 μg / (cm³) (·h). 2 Under dark conditions, the copper ion release rate decreased to 0.4 μg / (cm³). 2 The zinc ion release rate decreased to 0.1 μg / (cm·h). 2 •h), achieving controlled ion release. In the blank control group of Example 5, the copper ion release rate remained at 2.0 μg / (cm²) regardless of whether under light or dark conditions. 2 Around 10 h, there was no significant change and no zinc ion release.

[0086] In Example 6, the copper ion release rate of the experimental group under light irradiation was approximately 0.7 μg / (cm²). 2 The zinc ion release rate is approximately 0.3 μg / (cm³) (·h). 2 Under dark conditions, the copper ion release rate decreased to 0.25 μg / (cm³). 2 The zinc ion release rate decreased to 0.1 μg / (cm·h). 2 •h), the controlled release of ions is even more effective. In the blank control group of Example 6, the copper ion release rate remained at 1.7 μg / (cm²) under both light and dark conditions. 2 Around 10 h, there was no significant change and no zinc ion release.

[0087] Compared with the control group of Example 1, there was no significant difference in the copper ion release rate (approximately 1.7 μg / (cm²)). 2 (·h)), without photocatalytic synergistic antifouling effect, the release of copper ions was not reduced, and the environmental friendliness was insufficient.

[0088] In the control group of Comparative Example 2, the copper ion release rate was uneven (fluctuating range 0.5~2.2 μg / (cm²)). 2 ·h)), which cannot achieve controlled release, and the material is not tightly bonded to the substrate, making it prone to detachment after long-term immersion.

[0089] Compared to the control group in Example 3, the copper ion release rate was higher (approximately 1.3–1.5 μg / (cm²)). 2 ·h), and there is no obvious light response modulation phenomenon.

[0090] Compared to the control group in Example 4, the copper ion release rate was uneven (fluctuating between 0.5 and 2.2 μg / (cm²)). 2 ·h)), which cannot achieve controlled release, and the material is not tightly bonded to the substrate, making it prone to detachment after long-term immersion.

[0091] (3) Cyclic antifouling stability test: The experimental group samples of Example 1 were subjected to five repeated cyclic antifouling tests (after each test, the surface was gently rinsed with deionized water, dried, and the above simulated marine environment test procedure was repeated). The test results showed that after five cycles, the biofouling coverage of the sample surface remained below 10%, and the copper ion release rate did not fluctuate significantly. This indicates that the composite material has excellent cyclic antifouling stability, and its multi-level porous structure has outstanding anti-clogging and anti-agglomeration properties, which can meet the long-term antifouling requirements of the marine environment.

[0092] The experimental group samples of Example 2 were subjected to five repeated cyclic antifouling tests. After five cycles, the biofouling coverage of the sample surface remained below 11%, and the copper ion release rate did not fluctuate significantly, demonstrating good cyclic antifouling stability. The amount of copper ion released was reduced by about 50% compared with traditional copper-based antifouling materials, showing significant green antifouling effect.

[0093] The experimental group samples of Example 3 were subjected to five repeated cyclic antifouling tests. After five cycles, the biofouling coverage of the sample surface remained below 9%, the copper ion release rate did not fluctuate significantly, the cyclic antifouling stability was excellent, and the copper ion release was reduced by about 60% compared with traditional copper-based antifouling materials. The green and environmentally friendly advantages were more prominent, and it was more suitable for harsh marine antifouling scenarios.

[0094] The experimental group samples of Example 4 were subjected to five repeated cyclic antifouling tests (after each test, the surface was gently rinsed with deionized water, dried, and the above simulated marine environment test procedure was repeated). The test results showed that after five cycles, the biofouling coverage of the sample surface remained below 10%, and the copper ion release rate did not fluctuate significantly. This indicates that the composite material has excellent cyclic antifouling stability, and the multi-level micro-nano pore structure has outstanding anti-clogging and anti-agglomeration performance, which can meet the long-term antifouling requirements of the marine environment.

[0095] The experimental group samples of Example 5 were subjected to five repeated cyclic antifouling tests. After five cycles, the biofouling coverage of the sample surface remained below 10%, and the copper ion release rate did not fluctuate significantly, demonstrating good cyclic antifouling stability. The amount of copper ion released was reduced by about 50% compared with traditional copper-based antifouling materials, showing significant green antifouling effect.

[0096] The experimental group samples of Example 6 were subjected to five repeated cyclic antifouling tests. After five cycles, the biofouling coverage of the sample surface remained below 9%, the copper ion release rate did not fluctuate significantly, the cyclic antifouling stability was excellent, and the copper ion release was reduced by about 60% compared with traditional copper-based antifouling materials. The green and environmentally friendly advantages were more prominent, and it was more suitable for harsh marine antifouling scenarios.

[0097] Compared to the control group in Example 2, the adhesion coverage increased to 40% after three cycles of antifouling testing, which could not meet the long-term antifouling requirements.

[0098] Compared with the control group of Comparative Example 3, the nanoflowers on the surface were severely detached after 3 cycles of antifouling test, indicating poor structural stability.

[0099] The above description is only a preferred embodiment of the present invention. It should be noted that, for those skilled in the art, several improvements and modifications can be made without departing from the principle of the present invention, and these improvements and modifications should also be considered within the scope of protection of the present invention.

Claims

1. A Cu / Zn synergistic photoresponsive composite material, characterized in that, The Cu / Zn synergistic photoresponsive composite material comprises, from the inside out, Cu... x Zr y Amorphous alloy substrate, nanoporous copper layer and nano zinc oxide; or Cu x Zr y The composition consists of an amorphous alloy matrix, a nanoporous copper layer, cuprous oxide nanowire clusters, and nano-zinc oxide, where x and y are atomic percentages, 30≤x≤50, 50≤y≤70, and y=100-x.

2. The Cu / Zn synergistic photoresponsive composite material according to claim 1, characterized in that, The cuprous oxide nanowire clusters are composed of nanowires with an aspect ratio of 50 to 300, with each nanowire having a length of 1 to 3 μm and a diameter of 5 to 20 nm.

3. The Cu / Zn synergistic photoresponsive composite material according to claim 1, characterized in that, When Cu is included sequentially from the inside out x Zr y When an amorphous alloy substrate, a nanoporous copper layer, and nano zinc oxide are used, the nano zinc oxide is in the form of nanoflowers with a gap of 50~200nm between each nanoflower. The nanoflowers are assembled from multiple spindle-shaped nanosheets, and micropores of 5~20nm are formed between adjacent spindle-shaped nanosheets.

4. The Cu / Zn synergistic photoresponsive composite material according to claim 1, characterized in that, When Cu is included sequentially from the inside out x Zr y When the amorphous alloy matrix, nanoporous copper layer, cuprous oxide nanowire clusters, and nano zinc oxide are used, the nano zinc oxide is in the form of spindle-shaped nanosheets with a lateral dimension of 20~50nm, a longitudinal dimension of 50~200nm, and a thickness of 5~10nm.

5. The method for preparing the Cu / Zn synergistic photoresponsive composite material as described in claim 1, characterized in that, Includes the following steps: Step 1: Clean and melt Cu and Zr to obtain Cu-Zr alloy ingots, then melt and spin the ingots to form Cu. x Zr y Amorphous alloy matrix; Step 2, Cu x Zr y Nanoporous copper is obtained by dealloying an amorphous alloy matrix. Step 3: A three-electrode system is used, with nanoporous copper as the working electrode and zinc nitrate hexahydrate solution containing ammonium nitrate as the electrolyte for constant potential electrodeposition treatment. After repeated washing and drying, nano-zinc oxide is loaded on the surface of the nanoporous copper layer to obtain Cu / Zn synergistic photoresponsive composite material.

6. The preparation method according to claim 5, characterized in that, Before proceeding to step 3, the same three-electrode system is used, with nanoporous copper as the working electrode, to perform constant current in-situ anodic oxidation, drying, and heat treatment to generate cuprous oxide nanowire clusters in-situ on the surface of the nanoporous copper. Then, the process of step 3 is used, with the cuprous oxide nanowire clusters as the working electrode, and nano-zinc oxide is loaded on the surface of the cuprous oxide nanowire clusters. The heat treatment temperature is 100~250℃ and the time is 0.5~4.0h.

7. The preparation method according to claim 5, characterized in that, In step 1, the vacuum degree of the smelting strip casting is 3×10⁻⁶. -4 ~3×10 -3 Pa, the blow casting pressure is 0.5~2.0MPa, Cu x Zr y The amorphous alloy matrix is ​​in the form of thin strips, with a width of 1.5~2mm and a thickness of 20~40μm.

8. The preparation method according to claim 5, characterized in that, In step 2, the dealloying process involves taking the Cu... x Zr y The amorphous alloy matrix is ​​immersed in a mixed solution of ammonium fluoroborate, trisodium citrate and HF acid at 20~30℃ for 0.5~8h; the concentration of HF acid is 0.01~0.1M, the concentration of ammonium fluoroborate is 0.001~0.01M, and the concentration of trisodium citrate is 0.005~0.02M.

9. The preparation method according to claim 5, characterized in that, In step 3, the concentration of ammonium nitrate in the electrolyte is 0.5~5mM, the concentration of zinc nitrate hexahydrate is 1~20mM, the deposition temperature of the constant potential electrodeposition treatment is 25~80℃, the deposition potential is -0.8~-1.2V, and the deposition time is 1~60min; the drying temperature is 100~250℃, and the drying time is 2~3h.

10. The application of Cu / Zn synergistic photoresponsive composite material as described in any one of claims 1 to 4 in marine antifouling.

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