科普 | 高度耐用的Ag-CuO异质结构装饰网格用于高效的油/水分离以及原位光催化染料降解

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含油污水的大量排放和海上原油泄漏事故的频繁发生严重威胁着生态环境和人类健康。如何快速高效的处理溢油和纯化含油污水已成为关系人民生活、经济发展与环境安全的重要课题。近日,Energy & Environmental Materials上发表了题为“Highly Durable Ag‐CuO Heterostructure‐Decorated Mesh for Efficient Oil/Water Separation and In Situ Photocatalytic Dye Degradation”的研究论文。在这项工作中,通过碱蚀刻煅烧和光电方法制造Ag-CuO异质结构装饰网。其具有超级水性和水下超级渗透性,在油/水混合物显示出高分离效率(> 99.998%)。此外,贵金属 - 半导体异质结构上的强烈可见光收集和有效的电子孔分离使得它在染料降解中显示比单纯的CuO纳米结构涂覆材料更优异的光催化性能。且Cu基材具有较好的韧度以及能够增强结构稳定性,使得该装饰网格在光催化降解试验10个循环后表现出高度可靠的耐久性。更重要的是,在可见光照射下的油/水分离期间,该网状物能够原位催化降解水溶性有机染料。这项策略可为构建实际污水净化的双功能和预耐料材料提供一种新的途径。

The massive discharge of oily sewage and the frequent occurrence of offshore crude oil spills seriously threaten the ecological environment and human health. How to quickly and efficiently treat oil spills and purify oily wastewater has become an important issue related to people’s life, economic development and environmental safety. Recently, a paper entitled “Highly Durable Ag-CuO Heterostructure-Decorated Mesh for Efficient Oil/Water Separation” was published in Energy & Environmental Materials. In this work, a Ag-CuO heterostructure-decorated mesh was fabricated via facile alkali etching-calcination and photoreduction approaches. The as-synthesized mesh with superhydrophilicity and underwater superoleophobicity displayed high separation efficiency (>99.998%) for diverse oil/water mixtures. Besides, it demonstrated more superior photocatalytic performance in dye degradation than those of bare CuO nanostructure-coated materials, which is primarily attributed to the intensive visible light harvesting and efficient electron-holes separation occurred on noble metal-semiconductor heterostructures. Furthermore, on account of the tenacity of Cu substrate as well as enhanced structural stability, this binary composite-decorated mesh exhibited highly reliable durability and robustness after 10 cycles of photocatalytic degradation tests, and even being ultrasonic worn for 30 min. More importantly, our developed mesh was capable of in situ catalytic degrading water-soluble organic dyes during oil/water separation under visible light irradiation. Therefore, such a dexterous and feasible strategy may afford a new route to construct bifunctional and predurable materials for actual sewage purification.


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 文章简读

由于水资源稀缺和环境污染危机的威胁不断增长,水净化引起了很多全球关注。难去除和降解困难的不溶性油和有机染料是臭名昭著的污染物。迄今为止,制备超亲水和水下超疏油材料的几种重要方法已被用于从海洋溢油排放的含油废水、原油开采以及工业和生活污水中获取可行的清洁水资源。然而,大多数制造涉及有毒溶剂,抑或是材料结构稳定性差和单一功能,特别是对于染料化合物消除的情况,限制大规模生产和长期应用。

Water purification has attracted a lot of global attention because of the ever-growing threats of water scarcity and environmental pollution crisis. Among them, insoluble oils and organic dyes are notorious contaminants due to the difficulties of removal and degradation. To date, several important methods for preparing superhydrophilic and underwater superoleophobic materials have been adopted to acquire viable clean water resources from oily wastewater discharged by marine oil spill, crude oil exploitation, and industrial and domestic sewage. Nevertheless, most of the fabrications involve noxious solvents, poor structural stability, and single functionality especially for the case of dye compounds elimination, restricting the large-scale production and prolonged application.

铜(Cu)网格,具有低成本,柔韧性和高孔隙度是制造油/水分离材料的理想基材。金属纳米颗粒可以根据表面等离子体共振来促进浅品相互作用效果有助于可见光的延伸吸收范围,且独特的贵金属 - 半导体界面有助于形成肖特基屏障的形成,从而提高光激发电子孔对的分离。本文设计了一种高度耐用的Ag-CuO异质结构(HS) - 致铜网状物,其在一种材料中同时具有油/水分离和光催化染料降解性能。这里,CuO纳米薄膜(NFS)通过碱蚀刻煅烧处理原位生长在Cu网状物基质上,然后进行简单的光电识别方法。Ag纳米材料在插入的CuO NF上的装饰显着增加了Cu网眼的表面粗糙度。将Ag-CuO复合材料的亲水性与分层结构相结合,所得网格具有超亲水性和水下疏水性,因此表现出油/水混合物的优异分离。另外,金属Ag充当表面电子捕获陷阱,其可以捕获来自CuO的传导带的电子并最小化电子孔对的重组,制备的网格表现出更高的光催化性能。此外,由于Cu基底的韧度以及增强的结构稳定性,这种异质结构装饰网格表现出高度可靠的耐久性,即使在超声波磨损30分钟后也是高度可靠的耐久性。更重要的是,在可见光照射下的油/水分离期间,该网状物能够原位降解水溶性染料污染物。

Copper (Cu) meshes, a commonly used material in daily life with advantages of low cost, flexibility and high porosity, are considered as desirable substrates for fabricating oil/water separation materials. Metallic nanoparticles can promote light-matter interactions depending on the surface plasmon resonance effect, which contributes to the extended absorption range of visible light. Furthermore, the unique noble metal-semiconductor interfaces facilitate the formation of Schottky barriers and thus boost the separation of photo-excited electron-hole pairs. In the light of the aforementioned issues, researchers designed a highly durable Ag-CuO heterostructure (HS)-decorated Cu mesh which combined oil/water separation and photocatalytic dye degradation performance in one material. Herein, CuO nanoflakes (NFs) were in situ grown on the Cu mesh substrate via alkali etching-calcination treatments, followed by a facile photoreduction method. The decoration of Ag nanomaterials onto intercalated CuO NFs significantly increased the surface roughness of Cu mesh. Integrating the hydrophilicity of Ag-CuO composites with hierarchical structure, the resultant mesh possessed superhydrophilicity and underwater superoleophobicity, and thus manifested excellent separation of oil/water mixtures. Additionally, metallic Ag acted as surface traps that could capture the electrons from the conduction band of CuO and minimize the recombination of electron-hole pairs. The as-prepared mesh exhibited much higher photocatalytic performance for degrading organic dyes than those of bare CuO nanostructure-coated materials. Furthermore, on account of the tenacity of Cu base as well as enhanced structural stability, this heterostructure-decorated mesh not only exhibited superior cyclability, but also presented highly reliable durability even after being ultrasonic worn for 30 min. More importantly, the developed mesh was capable of in situ degrading water-soluble dye pollutants during oil/water separation under visible light irradiation.


图文简介

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图1. Ag-CuO 异质结构修饰的网格的制造过程的示意图

Figure 1 Schematic illustration of the fabrication process of Ag-CuO HS-decorated mesh.

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图2. a,b) 金属Ag沉积前后CuO纳米从生长滤网的SEM图。c,d) 金属Ag沉积前后CuO纳米薄片生长滤网的SEM图

Figure 2 a, b) SEM images of CuO NB-grown mesh before and after deposition of metallic Ag. c, d) SEM images of CuO NF-grown mesh before and after deposition of metallic Ag.

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图3. a) CuO 纳米薄片生长网格和Ag-CuO 异质结构修饰网的XPS光谱。b) Ag 3d, c) Cu 2p和d) O 1s Cu 2p的高分辨率光谱。

Figure 3 a) XPS spectra of CuO NF-grown mesh and Ag-CuO HS-decorated mesh. High-resolution spectra of b) Ag 3d, c) Cu 2p, and d) O 1s peaks.

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图4. a) Ag-CuO润湿性图。b) 用于各种油/水混合物的Ag-CuO 异质结构网格的分离效率和相应的渗透通量。

Figure 4 a) Wettability behavior of Ag-CuO HS-decorated mesh. b) Separation efficiency and corresponding permeation flux of the as-prepared mesh for various oil/water mixtures.

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图5. a-c) CuO与Ag纳米材料沉积前后CuO 纳米薄片生长滤网的UV-Vis反射反射光谱和Tauc图

Figure 5 a-c) UV-vis diffuse reflectance spectra and Tauc plots of CuO NF-grown mesh before and after deposition of Ag nanomaterials.

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图6. a) CR溶液的UV-Vis吸收光谱通过在可见光照射下每5分钟时的降解,在不同的时间间隔下,插图显示了CR溶液相应的拍摄图像。b) 三种染料与网状物的时间依赖性光催化降解效率。c) Ln(C0 / C)的相应图与照射时间。d) CR溶液使用网状循环10次的光降解效率

Figure 6 a) UV-vis absorption spectra of CR solution degraded by the as-prepared mesh at every 5 min under visible light irradiation, the inset showed the corresponding photographic image of CR solution at different time intervals. b) Time-dependent photocatalytic degradation efficiency of three dyes with the mesh. c) The corresponding graph of ln(C0/C) versus irradiation time. d) Photodegradation efficiency of CR solution for 10 cycles using the mesh.

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撰稿 | 李佳凯

审核导师 | 肖秀娟

排版 | 覃艳菊

审核 | 邓群




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