CN115321581A - Photoresponse type cuprous oxide anti-fouling agent and preparation method thereof - Google Patents

Photoresponse type cuprous oxide anti-fouling agent and preparation method thereof Download PDF

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CN115321581A
CN115321581A CN202211111405.3A CN202211111405A CN115321581A CN 115321581 A CN115321581 A CN 115321581A CN 202211111405 A CN202211111405 A CN 202211111405A CN 115321581 A CN115321581 A CN 115321581A
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cuprous oxide
copper
crystal
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antifouling agent
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王璐
王萌
王晶晶
汤黎容
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725th Research Institute of CSIC
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Abstract

The invention discloses a photoresponse type cuprous oxide antifouling agent and a preparation method thereof, wherein the photoresponse type cuprous oxide antifouling agent comprises cuprous oxide truncated octahedral micro-nano particles with special crystal faces exposed, each cuprous oxide micro-nano particle is formed by closing 6 (100) crystal faces and 8 (111) crystal faces, each (111) crystal face is adjacent to 3 (100) crystal faces, 36 edges and 24 vertexes are formed in total, the particle size distribution is 0.5-2 mu m, and the cuprous oxide micro-nano particles are prepared through a surfactant mediated wet chemical reduction strategy. Under the sunlight irradiation environment, cuprous oxide particles can rapidly separate surface photocarrier pairs (electron-hole, e) by virtue of the energy level difference between the (111) crystal planes and the (100) crystal planes ‑h + ) Not only inhibiting photooxidation reaction of photogenerated cavity, but also continuously catalyzing dissolved oxygen (O) in seawater 2 ) Water (H) 2 O) and hydroxide ion (OH) ) Etc. to generate oxyanion (. O) 2 ) And hydroxyl free radical (HO), and the like, so as to achieve the protection effect of killing fouling organisms.

Description

一种光响应型氧化亚铜防污剂及其制备方法A light-responsive cuprous oxide antifouling agent and preparation method thereof

技术领域technical field

本发明涉及海洋防污技术领域,具体而言,涉及一种光响应型氧化亚铜防污剂及其制备方法。The invention relates to the technical field of marine antifouling, in particular to a light-responsive cuprous oxide antifouling agent and a preparation method thereof.

背景技术Background technique

在船舶表面涂装防污涂料是解决海洋生物污损难题最为有效的技术方案,其一般采用具有广谱杀生活性的氧化亚铜作为主防污剂。船舶轻、重载线之间的水线位置处于日光暴晒且海水干湿交替浸泡-冲刷的恶劣环境下,该部位防污漆中的氧化亚铜防污剂面临着较高氧化失效风险。这主要是因为氧化亚铜在可见光照射下易被自身产生的光生空穴(h+)氧化而发生光腐蚀。这一空穴的生成-传递过程受到氧化亚铜结构形貌的显著影响。常规使用的工业级氧化亚铜防污剂为微米级颗粒,不具备规则形貌,其光生载流子更易在表面富集而导致严重的光腐蚀氧化,使得水线部位防污漆性能严重劣化,并一定程度引发水下部位防污失效风险。Coating antifouling coatings on the surface of ships is the most effective technical solution to solve the problem of marine biofouling. Cuprous oxide, which has broad-spectrum biocidal activity, is generally used as the main antifouling agent. The waterline between the ship's light and heavy load lines is in the harsh environment of sun exposure and sea water alternately soaking and scouring. The cuprous oxide antifouling agent in the antifouling paint at this part faces a high risk of oxidation failure. This is mainly because cuprous oxide is easily oxidized by the photogenerated holes (h + ) generated by itself under visible light irradiation to cause photocorrosion. This hole generation-transfer process is significantly affected by the morphology of the cuprous oxide structure. The conventionally used industrial-grade cuprous oxide antifouling agent is micron-sized particles without regular morphology, and its photogenerated carriers are more likely to be enriched on the surface, resulting in severe photocorrosion and oxidation, which seriously deteriorates the performance of the antifouling paint on the waterline , and to a certain extent lead to the risk of antifouling failure of underwater parts.

为了解决氧化亚铜防污剂在水线部位的失效难题,迫切需要提升氧化亚铜在光照环境下的稳定性,其关键在于通过结构调控来强化氧化亚铜表面光生载流子的分离-传递。对此,学术界达成了一定共识:文献J.Phys.Chem.C2009,113,14448对比了一系列不同形貌氧化亚铜单晶颗粒的稳定性,并指出完全由(111)晶面组成的八面体单晶具有最为优异的光稳定性,得益于其具有能级位置较低的(111)晶面有利于光生空穴快速分离。尽管如此,由单一晶面组成的氧化亚铜颗粒仍面临着光生空穴积累而导致的氧化腐蚀难题。专利CN104591257B公开了一种立方体微纳米氧化亚铜粉末及其制备方法。所得立方体氧化亚铜颗粒由(100)晶面组成,其作为防污剂在可见光照射下易发生光氧化腐蚀,无法有效解决船舶水线位置防污剂失效难题。从根本上说,高效分离氧化亚铜表面光生空穴需要引入能级差。为此,现有技术提出了二元异质结制备策略。文献Nat.Catal.2018,s41929-018-0077-6借助电化学及单原子沉积方法,在氧化亚铜纳米线表面分别沉积氧化镓等异质结复合层;通过交错匹配二者之间的能带结构,促进载流子在氧化亚铜表面分离,从而提升材料在光电催化过程中的稳定性。但上述异质结复合材料的制备方法繁琐且成本高昂,难以进行规模化制备以用于防污领域。因此,制备一种具有本征能级差异的氧化亚铜防污剂材料,是解决船舶水线位置防污剂失效难题的有效策略。In order to solve the failure problem of cuprous oxide antifouling agent on the waterline, it is urgent to improve the stability of cuprous oxide under light environment. The key is to strengthen the separation and transfer of photogenerated carriers on the surface of cuprous oxide through structural regulation. . In this regard, the academic community has reached a certain consensus: the document J.Phys.Chem.C2009, 113, 14448 compared the stability of a series of cuprous oxide single crystal particles with different shapes, and pointed out that the crystal plane is completely composed of (111) Octahedral single crystal has the most excellent photostability, thanks to its (111) crystal face with lower energy level position, which is conducive to the rapid separation of photogenerated holes. Nevertheless, cuprous oxide particles composed of a single crystal face still face the problem of oxidation and corrosion caused by the accumulation of photogenerated holes. Patent CN104591257B discloses a cubic micronano cuprous oxide powder and a preparation method thereof. The obtained cubic cuprous oxide particles are composed of (100) crystal faces, which are prone to photooxidative corrosion as an antifouling agent under visible light irradiation, and cannot effectively solve the problem of failure of the antifouling agent at the ship's waterline. Fundamentally, the efficient separation of photogenerated holes on the surface of cuprous oxide requires the introduction of energy level difference. For this reason, the prior art proposes a binary heterojunction preparation strategy. Literature Nat.Catal.2018, s41929-018-0077-6 uses electrochemical and single-atom deposition methods to deposit gallium oxide and other heterojunction composite layers on the surface of cuprous oxide nanowires; The band structure promotes the separation of carriers on the surface of cuprous oxide, thereby improving the stability of the material in the photoelectrocatalytic process. However, the preparation method of the above-mentioned heterojunction composite materials is cumbersome and costly, and it is difficult to carry out large-scale preparation for the antifouling field. Therefore, the preparation of a cuprous oxide antifouling agent material with intrinsic energy level differences is an effective strategy to solve the problem of antifouling agent failure at the ship's waterline.

目前来说,工业界主要通过复配高毒性杀生剂等配方设计手段来补充、强化氧化亚铜防污剂在船舶水线部位的使用效果:发明专利201210494499.7及201710577196.4均提出以三丁基氟化锡复配氧化亚铜等作为船舶水线漆的防污剂体系。值得注意的是,所采用的有机锡类物质因极高的生物累积毒性,已于2008年被国际海事组织实施全球禁用。综上所述,现有研究未能从根本上解决船舶水线部位氧化亚铜防污剂因光腐蚀氧化而提前失效的瓶颈难题。At present, the industry mainly supplements and strengthens the effect of cuprous oxide antifouling agents on the waterline of ships by compounding highly toxic biocides and other formula design methods: Invention patents 201210494499.7 and 201710577196.4 both propose to use tributyl fluoride Tin compounded with cuprous oxide, etc. as an antifouling agent system for ship waterline paint. It is worth noting that the organotin substances used were banned globally by the International Maritime Organization in 2008 due to their extremely high bioaccumulation toxicity. To sum up, the existing research failed to fundamentally solve the bottleneck problem of premature failure of cuprous oxide antifouling agents on the waterline of ships due to photocorrosion and oxidation.

发明内容Contents of the invention

有鉴于此,本发明旨在提出一种光响应型氧化亚铜防污剂,借助晶面间能级差,高效分离光生空穴以抑制氧化亚铜腐蚀氧化,从而解决船舶水线部位防污剂失效的瓶颈难题。现有技术所采用的氧化亚铜防污剂不具备规则形貌,无法形成晶面间的能级差,因此在可见光照射下表面更易富集光生空穴,从而发生严重的光腐蚀氧化使得水线部位防污漆性能劣化甚至失效。In view of this, the present invention aims to propose a light-responsive cuprous oxide antifouling agent, which efficiently separates photogenerated holes by virtue of the energy level difference between crystal planes to inhibit the corrosion and oxidation of cuprous oxide, thereby solving the problem of antifouling agents on the waterline of ships. Ineffective bottleneck problem. The cuprous oxide antifouling agent used in the prior art does not have a regular morphology and cannot form an energy level difference between crystal planes. Therefore, the surface is more likely to be enriched with photogenerated holes under visible light irradiation, resulting in severe photocorrosion oxidation that makes the waterline The performance of the antifouling paint is degraded or even invalid.

为达到上述目的,本发明的技术方案是这样实现的:In order to achieve the above object, technical solution of the present invention is achieved in that way:

一种光响应型氧化亚铜防污剂,包括具有特殊晶面暴露的氧化亚铜截八面体微纳米颗粒,所述氧化亚铜微纳米颗粒由6个(100)晶面及8个(111)晶面封闭组成,每个(111)晶面与3个(100)晶面相邻,共有36条棱边和24个顶点,粒径分布500nm~2μm,所述氧化亚铜微纳米颗粒通过表面活性剂介导湿化学还原策略制备。A light-responsive cuprous oxide antifouling agent, including cuprous oxide octahedral micro-nanoparticles with special exposed crystal planes, the cuprous oxide micro-nanoparticles are composed of 6 (100) crystal planes and 8 (111 ) crystal plane closed composition, each (111) crystal plane is adjacent to 3 (100) crystal planes, there are 36 edges and 24 vertices in total, the particle size distribution is 500nm~2μm, and the cuprous oxide micro-nano particles pass through Preparation by Surfactant-Mediated Wet Chemical Reduction Strategy.

一种光响应型氧化亚铜防污剂的制备方法,用于制备上述所述的光响应型氧化亚铜防污剂,包括如下步骤:A preparation method of a photoresponsive cuprous oxide antifouling agent, which is used to prepare the above-mentioned photoresponsive cuprous oxide antifouling agent, comprising the following steps:

1)在50~70℃反应温度下,将可溶性二价铜盐溶解于80~4500mL去离子水中,随后加入无机碱、聚乙烯吡咯烷酮表面活性剂,匀速搅拌反应0.5~1.5小时,得到蓝色或蓝绿色的氢氧化铜悬浊液;1) Dissolve soluble divalent copper salt in 80-4500mL deionized water at a reaction temperature of 50-70°C, then add inorganic base and polyvinylpyrrolidone surfactant, and stir at a constant speed for 0.5-1.5 hours to obtain blue or Blue-green copper hydroxide suspension;

2)将还原剂溶解于10~800mL去离子水中,并逐滴加入上述制备的氢氧化铜悬浊液中,在50~70℃温度下还原反应0.5~1小时,随后采用洗涤溶剂进行离心洗涤,真空干燥后得到具有特殊晶面暴露的截八面体氧化亚铜微纳米颗粒。2) Dissolve the reducing agent in 10-800mL deionized water, and add dropwise to the above-prepared copper hydroxide suspension, perform a reduction reaction at a temperature of 50-70°C for 0.5-1 hour, and then use a washing solvent for centrifugal washing , obtained octahedral cuprous oxide micro-nanoparticles with special exposed crystal planes after vacuum drying.

进一步地,步骤1)中的二价铜盐与无机碱的摩尔比为1:30~55。Further, the molar ratio of the divalent copper salt to the inorganic base in step 1) is 1:30-55.

进一步地,步骤1)中的二价铜盐与聚乙烯吡咯烷酮的摩尔比为10~33:1。Further, the molar ratio of divalent copper salt to polyvinylpyrrolidone in step 1) is 10-33:1.

进一步地,步骤2中的氢氧化铜与还原剂的摩尔比为1:3~8。Further, the molar ratio of copper hydroxide to reducing agent in step 2 is 1:3-8.

进一步地,所述二价铜盐为硫酸铜、氯化铜、醋酸铜、硝酸铜中的一种或组合物。Further, the divalent copper salt is one or a combination of copper sulfate, copper chloride, copper acetate and copper nitrate.

进一步地,所述无机碱为氢氧化钠、氢氧化钾中的一种或组合物。Further, the inorganic base is one or a combination of sodium hydroxide and potassium hydroxide.

进一步地,所述还原剂为抗坏血酸、葡萄糖、亚硫酸钠中的一种或组合物。Further, the reducing agent is one or a combination of ascorbic acid, glucose, and sodium sulfite.

进一步地,所述洗涤溶剂为甲醇、乙醇、异丙醇中的一种或组合物。Further, the washing solvent is one or a combination of methanol, ethanol, and isopropanol.

进一步地,所述真空干燥温度为30~40℃,干燥时间为12~24小时。Further, the vacuum drying temperature is 30-40° C., and the drying time is 12-24 hours.

相对于现有技术,本发明所述的光响应型氧化亚铜防污剂及其制备方法具有以下优势:Compared with the prior art, the photoresponsive cuprous oxide antifouling agent of the present invention and its preparation method have the following advantages:

(1)本发明提出一种光响应型氧化亚铜防污剂,适用于船舶水线位置,基于表面活性剂介导湿化学还原策略,获得一种具有特殊晶面暴露的截八面体氧化亚铜微纳米颗粒。在日光照射下,所述光响应型氧化亚铜颗粒可借助不同晶面间的能级差快速分离表面产生光生载流子(电子-空穴,e--h+),一方面抑制光生空穴的光氧化反应,另一方面催化海水中溶氧(O2)、水(H2O)及氢氧根离子(OH-)等生成氧阴离子(·O2-)、羟基自由基(HO·)等活性物种,以杀灭水线部位附着的海洋污损生物,从而发挥防污活性,除此之外,氧化亚铜由于微粒尺寸小,可以减缓铜离子的释放,起到长效杀菌的作用。(1) The present invention proposes a light-responsive cuprous oxide antifouling agent, which is suitable for the waterline position of the ship. Based on the surfactant-mediated wet chemical reduction strategy, a truncated octahedral cuprous oxide with special exposed crystal faces is obtained. copper micronanoparticles. Under sunlight irradiation, the photoresponsive cuprous oxide particles can quickly separate the surface by virtue of the energy level difference between different crystal planes to generate photogenerated carriers (electron-holes, e - -h + ), on the one hand suppress photogenerated holes On the other hand, it catalyzes dissolved oxygen (O 2 ), water (H 2 O) and hydroxide ions (OH - ) in seawater to generate oxygen anions (·O 2- ), hydroxyl radicals (HO· ) and other active species to kill marine fouling organisms attached to the waterline, thereby exerting antifouling activity. In addition, cuprous oxide can slow down the release of copper ions due to its small particle size and play a long-term bactericidal role effect.

(2)本发明所制备的光响应型氧化亚铜防污剂,适配于现有磨蚀型、自抛光型、污损释放型等多种防污涂料体系,可推广涂装于船舶水线位置。(2) The photoresponsive cuprous oxide antifouling agent prepared by the present invention is suitable for various antifouling coating systems such as the existing abrasive type, self-polishing type, and fouling release type, and can be applied to ship waterlines Location.

(3)本发明提出一种光响应型氧化亚铜防污剂的制备方法,以二价铜盐为铜源,以聚乙烯吡咯烷酮为结构导向剂,在铜盐与强碱反应后,经过还原剂还原制备出具有特殊晶面暴露的氧化亚铜微纳米颗粒,其制备路线明确,反应条件简单,稳定性好,无毒无害,绿色环保,可重复性高,有利于规模放大生产。(3) the present invention proposes a kind of preparation method of photoresponsive cuprous oxide antifouling agent, take divalent cupric salt as copper source, take polyvinylpyrrolidone as structure directing agent, after copper salt reacts with strong base, through reduction Cuprous oxide micro-nanoparticles with special exposed crystal facets were prepared by reduction with reagents. The preparation route is clear, the reaction conditions are simple, the stability is good, non-toxic and harmless, green and environmentally friendly, and the reproducibility is high, which is conducive to large-scale production.

附图说明Description of drawings

图1为常规工业级的氧化亚铜的电子扫描显微镜图;Fig. 1 is the scanning electron microscope picture of the cuprous oxide of conventional industrial grade;

图2为实施例1所制备的光响应型氧化亚铜的电子扫描显微镜图;Fig. 2 is the scanning electron micrograph of the photoresponsive cuprous oxide prepared in embodiment 1;

图3为实施例1所制备的光响应型氧化亚铜的X射线衍射谱图;Fig. 3 is the X-ray diffraction spectrogram of the photoresponsive cuprous oxide prepared in embodiment 1;

图4为实施例2所制备的光响应型氧化亚铜的红外光谱图;Fig. 4 is the infrared spectrogram of the photoresponsive cuprous oxide prepared in embodiment 2;

图5为实施例3所制备的光响应型氧化亚铜与常规工业级氧化亚铜的稳态荧光发光光谱;Fig. 5 is the steady-state fluorescence emission spectrum of photoresponsive cuprous oxide and conventional industrial grade cuprous oxide prepared in embodiment 3;

图6为实施例1所制备的光响应型氧化亚铜加入活性物种捕捉剂前、后的细菌抑制活性对比图;Fig. 6 is the comparison diagram of the antibacterial activity before and after the light-responsive cuprous oxide prepared in Example 1 is added to the active species capture agent;

图7为常规工业级的氧化亚铜加入活性物种捕捉剂前、后的细菌抑制活性对比图;Fig. 7 is the comparison chart of the antibacterial activity before and after the cuprous oxide of conventional industrial grade is added active species capture agent;

图8为实施例1所制备的光响应型氧化亚铜的光响应防污机理示意图。8 is a schematic diagram of the light-responsive antifouling mechanism of the light-responsive cuprous oxide prepared in Example 1.

具体实施方式Detailed ways

为使本发明的上述目的、特征和优点能够更为明显易懂,下面结合附图对本发明的具体实施例做详细的说明。In order to make the above objects, features and advantages of the present invention more comprehensible, specific embodiments of the present invention will be described in detail below in conjunction with the accompanying drawings.

实施例1Example 1

称取0.25g五水合硫酸铜、2.75g聚乙烯吡咯烷酮,55℃下搅拌溶于80mL去离子水中,称取1.68g氢氧化钠加入反应液中,得到蓝色或蓝绿色的氢氧化铜悬浊液;随后,称取0.85g抗坏血酸并溶于10mL去离子水中,再逐滴加入上述氢氧化铜悬浊液中,在55℃下还原反应0.5小时;最后,采用乙醇对还原产物进行洗涤-离心分离,并在真空条件下30℃干燥12小时,制备出具有特殊晶面暴露的光响应型氧化亚铜防污剂。Weigh 0.25g copper sulfate pentahydrate and 2.75g polyvinylpyrrolidone, stir and dissolve in 80mL deionized water at 55°C, weigh 1.68g sodium hydroxide and add to the reaction solution to obtain blue or blue-green copper hydroxide suspension solution; then, weigh 0.85g of ascorbic acid and dissolve it in 10mL of deionized water, then add it dropwise to the above copper hydroxide suspension, and perform a reduction reaction at 55°C for 0.5 hours; finally, use ethanol to wash the reduced product-centrifuge Separated and dried under vacuum at 30°C for 12 hours, a photoresponsive cuprous oxide antifouling agent with special exposed crystal faces was prepared.

实施例2Example 2

称取6.7g氯化铜、145.0g聚乙烯吡咯烷酮,70℃下搅拌溶于4500mL去离子水中,称取75.0g氢氧化钠加入反应液中,得到蓝色或蓝绿色的氢氧化铜悬浊液;随后,称取45.0g葡萄糖并溶于800mL去离子水中,再逐滴加入上述氢氧化铜悬浊液中,在70℃下还原反应1小时;最后,采用异丙醇对还原产物进行洗涤-离心分离,并在真空条件下40℃干燥24小时,制备出具有特殊晶面暴露的光响应型氧化亚铜防污剂。Weigh 6.7g copper chloride and 145.0g polyvinylpyrrolidone, stir and dissolve in 4500mL deionized water at 70°C, weigh 75.0g sodium hydroxide and add to the reaction solution to obtain a blue or blue-green copper hydroxide suspension ; Subsequently, weigh 45.0g of glucose and dissolve it in 800mL of deionized water, then add it dropwise to the above-mentioned copper hydroxide suspension, and perform a reduction reaction at 70°C for 1 hour; finally, use isopropanol to wash the reduced product- After centrifugation and drying at 40°C for 24 hours under vacuum, a photoresponsive cuprous oxide antifouling agent with special exposed crystal planes was prepared.

实施例3Example 3

称取0.9g醋酸铜、7.5g聚乙烯吡咯烷酮,60℃下搅拌溶于500mL去离子水中,称取18.5g氢氧化钾加入反应液中,得到蓝色或蓝绿色的氢氧化铜悬浊液;随后,称取26.3g抗坏血酸并溶于50mL去离子水中,再逐滴加入上述氢氧化铜悬浊液中,在60℃下还原反应40分钟;最后,采用甲醇对还原产物进行洗涤-离心分离,并在真空条件下35℃干燥12小时,制备出具有特殊晶面暴露的光响应型氧化亚铜防污剂。Weigh 0.9g copper acetate and 7.5g polyvinylpyrrolidone, stir and dissolve in 500mL deionized water at 60°C, weigh 18.5g potassium hydroxide and add it to the reaction solution to obtain a blue or blue-green copper hydroxide suspension; Subsequently, 26.3 g of ascorbic acid was weighed and dissolved in 50 mL of deionized water, and then added dropwise to the above-mentioned copper hydroxide suspension, and reduced for 40 minutes at 60° C.; finally, the reduced product was washed and centrifuged with methanol, And drying at 35°C for 12 hours under vacuum conditions, a photoresponsive cuprous oxide antifouling agent with special exposed crystal planes was prepared.

本申请中常规工业级的氧化亚铜购买于泰兴冶炼。In this application, conventional industrial-grade cuprous oxide was purchased from Taixing Smelting.

性能测试Performance Testing

图1和图2分别为常规工业级的氧化亚铜和实施例1所制备的光响应型氧化亚铜的电子扫描显微镜图。从图1可以看出,常规工业级所制备的氧化亚铜粒径相差较大,单个氧化亚铜颗粒不具备规则形貌,因而无法形成特殊暴露晶面及晶面能级差,因此易发生光氧化腐蚀,在船舶水线部位的防污效果较差。从图2可以看出,实施例1所制备的氧化亚铜的平均粒径为0.5-2μm,棱角清晰、形状规则、尺寸均一,且具有特殊晶面暴露,即该氧化亚铜呈截八面体形貌,由6个(100)晶面及8个(111)晶面封闭组成,每个(111)晶面与3个(100)晶面相邻,共有36条棱边和24个顶点,其形貌结构显著区别于现有常规工业级氧化亚铜。Figure 1 and Figure 2 are scanning electron microscope images of conventional industrial-grade cuprous oxide and photoresponsive cuprous oxide prepared in Example 1, respectively. It can be seen from Figure 1 that the particle size of cuprous oxide prepared by conventional industrial grades varies greatly, and a single cuprous oxide particle does not have a regular shape, so it cannot form a special exposed crystal plane and a difference in the energy level of the crystal plane, so it is prone to light Oxidation and corrosion, the antifouling effect on the waterline of the ship is poor. It can be seen from Figure 2 that the average particle size of the cuprous oxide prepared in Example 1 is 0.5-2 μm, with clear edges and corners, regular shape, uniform size, and special crystal surface exposure, that is, the cuprous oxide is octahedral The morphology is composed of 6 (100) crystal planes and 8 (111) crystal planes closed, each (111) crystal plane is adjacent to 3 (100) crystal planes, with a total of 36 edges and 24 vertices. Its morphology and structure are significantly different from the existing conventional industrial grade cuprous oxide.

图3为本实施例1所制备的光响应型氧化亚铜的X射线衍射谱图。从图3可以看出,经过X射线衍射表征,所制备氧化亚铜的(111)/(100)晶面比例显著提升,表现出特殊暴露晶面。FIG. 3 is an X-ray diffraction spectrum of the photoresponsive cuprous oxide prepared in Example 1. FIG. It can be seen from Figure 3 that the (111)/(100) crystal plane ratio of the prepared cuprous oxide is significantly improved after X-ray diffraction characterization, showing a special exposed crystal plane.

图4为实施例2所制备的光响应型氧化亚铜的红外光谱图。从图4可以看出,所述光响应型氧化亚铜防污剂表现出Cu(I)-O伸缩振动峰(628cm-1)。FIG. 4 is an infrared spectrogram of the photoresponsive cuprous oxide prepared in Example 2. It can be seen from Fig. 4 that the photoresponsive cuprous oxide antifouling agent exhibits a Cu(I)-O stretching vibration peak (628cm -1 ).

图5为实施例3所制备的光响应型氧化亚铜与常规工业级氧化亚铜的稳态荧光发光光谱图。从图5中可以看出,所述光响应型氧化亚铜防污剂表现出更优的光生载流子分离效果。具体地,稳态荧光发光光谱用于表征材料受到光源激发产生的光生载流子对(电子-空穴)的复合发光现象。相比于常规工业级氧化亚铜,本实施例3所述的氧化亚铜表现出明显降低的荧光发射强度,说明光生空穴及电子可以快速转移,分离效果加强。Fig. 5 is a steady-state fluorescence emission spectrum diagram of photoresponsive cuprous oxide prepared in Example 3 and conventional industrial grade cuprous oxide. It can be seen from FIG. 5 that the photoresponsive cuprous oxide antifouling agent exhibits a better separation effect of photogenerated carriers. Specifically, the steady-state fluorescence emission spectrum is used to characterize the recombination luminescence phenomenon of photogenerated carrier pairs (electron-holes) generated by materials excited by a light source. Compared with the conventional industrial-grade cuprous oxide, the cuprous oxide described in Example 3 exhibits significantly lower fluorescence emission intensity, indicating that photogenerated holes and electrons can be transferred rapidly, and the separation effect is enhanced.

图6和图7分别为实施例1所制备的光响应型氧化亚铜和常规工业级的氧化亚铜加入活性物种捕捉剂前、后的细菌抑制活性对比图。从图6中可以看出,所述光响应型氧化亚铜防污剂在可见光照射下光生空穴(h+)快速分离消耗,并生成羟基自由基(HO·)、氧阴离子(·O2-)等防污活性物种。具体地,活性物种捕捉试验用于表征材料受到可见光激发后生成的活性物种类别及数量。分别采用草酸钠、异丙醇、对苯醌作为光生空穴(h+)、羟基自由基(OH·)、氧阴离子(·O2-)等活性物种的捕捉剂,并将上述各捕捉剂加入到含有不同类型氧化亚铜材料的细菌(大肠杆菌E.coil)培养基中;通过对比细菌抑制活性的下降趋势,来甄别氧化亚铜表面主要光生活性物种的种类。相比于图7的常规工业级氧化亚铜,本实施例1所制备的氧化亚铜在加入空穴捕捉剂后的细菌抑制活性下降程度较小,表明特殊晶面暴露形成晶面能级差有助于快速分离-传输氧化亚铜表面生成的光生空穴;同时,所制备光响应型氧化亚铜在加入羟基自由基以及氧阴离子捕捉剂后的细菌抑制活性明显下降,表明特殊晶面暴露有助于氧化亚铜表面生成羟基自由基及氧阴离子等活性物种。Figure 6 and Figure 7 are the comparison charts of the antibacterial activity of the light-responsive cuprous oxide prepared in Example 1 and the conventional industrial grade cuprous oxide before and after adding the active species capture agent, respectively. It can be seen from Figure 6 that the photoresponsive cuprous oxide antifouling agent rapidly separates and consumes photogenerated holes (h+) under visible light irradiation, and generates hydroxyl radicals (HO·), oxygen anions (·O 2- ) and other antifouling active species. Specifically, the active species capture test is used to characterize the type and quantity of active species generated after the material is excited by visible light. Sodium oxalate, isopropanol, and p-benzoquinone were used as traps for photogenerated holes (h + ), hydroxyl radicals (OH·), oxygen anions (·O 2- ) and other active species, and the above traps Added to bacterial (Escherichia coli E.coil) culture medium containing different types of cuprous oxide materials; by comparing the downward trend of bacterial inhibitory activity, the types of main photoactive species on the surface of cuprous oxide were identified. Compared with the conventional industrial-grade cuprous oxide shown in Figure 7, the bacterial inhibitory activity of the cuprous oxide prepared in Example 1 after adding a hole-scavenging agent decreased to a lesser extent, indicating that the exposure of the special crystal plane formed a crystal plane energy level difference. Helps to quickly separate and transport the photogenerated holes generated on the surface of cuprous oxide; at the same time, the antibacterial activity of the prepared photoresponsive cuprous oxide was significantly decreased after adding hydroxyl radicals and oxygen anion traps, indicating that the exposure of special crystal faces Helps to generate active species such as hydroxyl radicals and oxygen anions on the surface of cuprous oxide.

图8为实施例1所制备的光响应型氧化亚铜的光响应防污机理示意图。从图8可以看出,在可见光照射下,氧化亚铜表面产生光生载流子,借助其(111)与(100)晶面之间的能级差,一方面高效分离-传输光生空穴,从根本上抑制氧化亚铜光腐蚀;另一方面快速传输光生载流子至防污界面,催化生成如氧阴离子(·O2-)、过氧化氢(H2O2)、羟基自由基(OH·)等活性物种,以杀灭船舶水线部位附着的污损生物,从而长效发挥光响应防污活性。8 is a schematic diagram of the light-responsive antifouling mechanism of the light-responsive cuprous oxide prepared in Example 1. It can be seen from Figure 8 that under the irradiation of visible light, photogenerated carriers are generated on the surface of cuprous oxide. With the help of the energy level difference between the (111) and (100) crystal planes, on the one hand, the photogenerated holes are efficiently separated and transported. It fundamentally inhibits the photocorrosion of cuprous oxide; on the other hand, it quickly transports photogenerated carriers to the antifouling interface, and catalyzes the generation of oxygen anions (·O 2- ), hydrogen peroxide (H 2 O 2 ), hydroxyl radicals (OH ) and other active species to kill the fouling organisms attached to the waterline of the ship, so as to exert light-responsive antifouling activity for a long time.

综上,本发明所涉及的具有特殊晶面暴露的光响应型氧化亚铜作为防污剂,合成工艺简单,适配于现有防污涂料配方体系,适合处于日光暴晒且干湿交替环境下船舶水线位置的防污应用。In summary, the light-responsive cuprous oxide with special crystal surface exposure involved in the present invention is used as an antifouling agent, the synthesis process is simple, it is suitable for the existing antifouling paint formulation system, and it is suitable for exposure to sunlight and alternating dry and wet environments Antifouling applications at the waterline of ships.

虽然本发明披露如上,但本发明并非限定于此。任何本领域技术人员,在不脱离本发明的精神和范围内,均可作各种更动与修改,因此本发明的保护范围应当以权利要求所限定的范围为准。Although the present invention is disclosed above, the present invention is not limited thereto. Any person skilled in the art can make various changes and modifications without departing from the spirit and scope of the present invention, so the protection scope of the present invention should be based on the scope defined in the claims.

Claims (10)

1. A photoresponse type cuprous oxide antifouling agent comprises cuprous oxide truncated octahedral micro-nano particles with special crystal faces exposed, and is characterized in that the cuprous oxide micro-nano particles are formed by closing 6 (100) crystal faces and 8 (111) crystal faces, each (111) crystal face is adjacent to 3 (100) crystal faces, 36 edges and 24 vertexes are formed in total, the particle size distribution is 0.5-2 mu m, and the cuprous oxide micro-nano particles are prepared through a surfactant mediated wet chemical reduction strategy.
2. A method for preparing a photoresponsive cuprous oxide antifouling agent, which is used for preparing the photoresponsive cuprous oxide antifouling agent according to claim 1, and is characterized by comprising the following steps:
1) Dissolving soluble divalent copper salt in 80-4500 mL deionized water at the reaction temperature of 50-70 ℃, then adding inorganic base and polyvinylpyrrolidone surfactant, and stirring at a constant speed for reaction for 0.5-1.5 hours to obtain blue or blue-green copper hydroxide suspension;
2) Dissolving a reducing agent in 10-800 mL of deionized water, dropwise adding the solution into the copper hydroxide suspension prepared in the step 1), carrying out reduction reaction for 0.5-1 h at the temperature of 50-70 ℃, then carrying out centrifugal washing by using a washing solvent, and carrying out vacuum drying to obtain the cuprous oxide truncated octahedral micro-nano particles with special crystal face exposure.
3. The method according to claim 2, wherein the molar ratio of the divalent copper salt to the inorganic base in step 1) is 1.
4. The method according to claim 2, wherein the molar ratio of the divalent copper salt to the polyvinylpyrrolidone in step 1) is 10 to 33.
5. The method according to claim 2, wherein the molar ratio of the copper hydroxide to the reducing agent in step 2 is 1.
6. The method of claim 2, wherein the cupric salt is one or a combination of copper sulfate, copper chloride, copper acetate and copper nitrate.
7. The preparation method according to claim 2, wherein the inorganic base is one or a combination of sodium hydroxide and potassium hydroxide.
8. The method of claim 2, wherein the reducing agent is one or a combination of ascorbic acid, glucose or sodium sulfite.
9. The method according to claim 2, wherein the washing solvent is one or a combination of methanol, ethanol and isopropanol.
10. The method according to claim 2, wherein the vacuum drying temperature is 30 to 40 ℃ and the drying time is 12 to 24 hours.
CN202211111405.3A 2022-09-13 2022-09-13 Photoresponse type cuprous oxide anti-fouling agent and preparation method thereof Pending CN115321581A (en)

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