引用本文:戴胜,刘鲁英,王致钘,杨苹.具有增强光催化和抗菌活性的TiO2@Ag-GO复合材料[J].中国表面工程,2024,37(1):118~125
DAI Sheng,LIU Luying,WANG Zhi,YANG Ping.TiO2@Ag-GO Composite Materials with Enhanced Photocatalytic and Antimicrobial Activities[J].China Surface Engineering,2024,37(1):118~125
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具有增强光催化和抗菌活性的TiO2@Ag-GO复合材料
戴胜, 刘鲁英, 王致钘, 杨苹
西南交通大学材料科学与工程学院 成都 610036
摘要:
光催化降解环境中的污染物被认为一种理想的清洁方法,其中二氧化钛(TiO2)是目前最有前途的光催化材料之一。 但由于能带宽、光生电子与空穴快速复合等特点,限制了其利用效率和范围,开发一种高效的 TiO2基光催化复合材料具有重要意义。通过简单的溶胶-凝胶法和一步 Marangoni 法,将 TiO2和 Ag 纳米颗粒(AgNPs)和氧化石墨烯(GO)有效结合,制备出显著增强光催化活性和抗菌能力的复合材料 TiO2@Ag-GO。氧化石墨烯(GO)具有多个催化活性中心,可以高效地进行光催化反应降解污染物。同时,还能提高电荷分离程度,抑制光生电子和空穴复合,提高 TiO2 光催化活性。AgNPs 具有存储电子和促进电荷分离的能力,同时释放的 Ag+ ,赋予材料广谱的抗菌性能。光催化试验抑菌试验结果表明,复合材料能高效降解亚甲基蓝染料,2 h 降解率达到 74.5%,同时对金黄色葡萄球菌和铜绿杆菌有较强的杀灭作用。这种简易制备的高催化和杀菌功能的 TiO2 基复合材料在光催化清洁领域有很大的应用潜力。
关键词:  二氧化钛(TiO2)  Ag 纳米颗粒(AgNPs)  氧化石墨烯(GO)  光催化活性  抗菌性能
DOI:10.11933/j.issn.1007-9289.20221115003
分类号:TB332
基金项目:
TiO2@Ag-GO Composite Materials with Enhanced Photocatalytic and Antimicrobial Activities
DAI Sheng, LIU Luying, WANG Zhi, YANG Ping
School of Materials Science and Engineering, Southwest Jiaotong University, Chengdu 610036 , China
Abstract:
Environmental pollution has become an increasingly serious issue. Numerous studies have revealed that the increased incidence of cancer and other diseases can be associated with environmental pollution. Pollutants include not only inorganic matter, but also bacteria and organic matter. Photocatalytic breakdown of contaminants in the environment is considered an ideal cleaning technology, and one of the most promising photocatalytic compounds is titanium dioxide (TiO2). However, their utilization efficiency and range are limited because of their narrow energy bandwidth and the quick recombination of photogenerated electrons and holes. Therefore, developing efficient TiO2-based photocatalytic composites is crucial. A simple sol-gel and one-step Marangoni methods were used to efficiently combine TiO2, Ag nanoparticles (AgNPs), and graphene oxide (GO) to make composites of TiO2@Ag-GO with significantly enhanced photocatalytic activity and antibacterial capabilities. GO has multiple catalytically active centers that can efficiently degrade pollutants via photocatalytic reactions. Simultaneously, it can improve charge separation, restrict the recombination of photogenerated electrons and holes, and boost the photocatalytic activity of TiO2. AgNPs can hold electrons, facilitate charge separation, and release Ag+ , making them a material with diverse antibacterial properties. Ag-doped TiO2 sol-gel was prepared by the sol-gel method, and the prepared sol-gel was then coated on the surface of an Si substrate via spin-coating. An anatase-type Ag-doped TiO2 film (TiO2@Ag) was prepared via heat treatment. Finally, the TiO2@Ag-GO nanocomposite photocatalytic material was effectively prepared by transferring a large-area ultrathin GO film, produced via the single-step Marangoni process, onto its surface. The compositions of the films made of TiO2 and TiO2@Ag were examined using X-ray Diffraction (XRD), Transmission Electron Microscope (TEM), High Resolution Transmission Electron Microscopy (HRTEM), and X-ray Photoelectron Spectroscopy (XPS). the Ag in the TiO2@Ag sample was primarily in the form of Ag2O nanoparticles, and the TiO2 sample was primarily composed of anatase crystals. Ion-release experiments demonstrated that TiO2@Ag-GO could stably release Ag+ from Phosphate Buffered Saline (PBS) for at least 12 d. The rates of TiO2 and TiO2@Ag degradation in a 2 h photocatalytic methylene blue degradation test were 42.4 and 52.5%, respectively. Simultaneously, the degradation rate increased considerably after the addition of GO, reaching 74.5% for TiO2@Ag-GO. These findings suggest that Ag doping and GO loading enhance the photocatalytic activity of TiO2. This is because when TiO2 is modified by AgNPs and GO, TiO2 absorbs UV radiation; the electrons generated by TiO2 are transferred to the AgNPs, which demonstrate electron storage capability, serving as electron traps that promote charge separation. In contrast, GO on the semiconductor surface contains numerous catalytically active centers that can efficiently break down pollutants in a photocatalytic reaction. Furthermore, GO significantly enhances photocatalysis by increasing the degree of charge separation and preventing the recombination of photogenerated electrons and holes in the semiconductor. Seeding assays with Gram-negative (Pseudomonas aeruginosa) and Gram-positive bacteria (Staphylococcus aureus) were used to assess the broad-spectrum antibacterial capabilities of the composites. Scanning Electron Microscope (SEM) images and statistical analyses of bacterial adhesion and proliferation revealed that many bacteria attached to and proliferated on the TiO2 surface, and the bacteria tended to aggregate to form colonies. The wrinkled shape of the GO surface prevented bacterial aggregation, resulting in a more even distribution of the bacteria on the TiO2-GO surface, with significantly fewer bacteria present. The TiO2@Ag and TiO2@Ag-GO surfaces drastically reduced the number of bacteria and severely damaged their morphology, demonstrating significant bactericidal activity. AgNPs and Ag+ can bind to negatively charged bacterial biofilms, disrupting the bacterial membrane potential, and leading to bacterial death. This simple TiO2-based composite, with significant photocatalytic and antibacterial activities, has considerable potential for use in photocatalytic cleaning.
Key words:  titanium dioxide (TiO2)  Ag nanoparticles (AgNPs)  graphene oxide (GO)  photocatalytic activity  antibacterial properties
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