{"title":"过渡金属基mof用于类fenton光催化降解有机污染物:性能、稳定性和生物相容性","authors":"S.M. Tikhanova , Yu.A. Tishchenko , E.Yu. Stovpiaga , M. Timofeeva , D.V. Lipin , S.A. Povarov , V.A. Milichko , A.S. Timin , S.A. Shipilovskikh , V.I. Popkov","doi":"10.1016/j.enceco.2025.01.003","DOIUrl":null,"url":null,"abstract":"<div><div>The development of efficient materials for water treatment is crucial to addressing global environmental challenges. In this study, transition metal-based metal-organic frameworks (MeBDC MOFs; Me = Fe, Co, Ni; BDC = benzene dicarboxylic acid) were synthesized via a solvothermal method and considered as dual-function photocatalysts for adsorption and removal of organic pollutant. Comprehensive physicochemical analysis of the developed samples was performed using scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDX), fourier-transform infrared spectroscopy (FTIR), raman spectroscopy, N<sub>2</sub> adsorption-desorption isotherms (BET), and diffuse reflectance spectroscopy (DRS). The materials exhibited a high visible-light absorption with band gap energies of 1.76 eV (FeBDC), 3.08 eV (CoBDC), and 3.73 eV (NiBDC), BET surface areas of 28.2 m<sup>2</sup>/g (FeBDC), 74.3 m<sup>2</sup>/g (CoBDC), and 31.4 m<sup>2</sup>/g (NiBDC). Photocatalytic performance was evaluated using methylene blue (MB) degradation under visible-light irradiation containing both conventional and Fenton-like processes. FeBDC achieved a reaction rate constant of 0.2719 min<sup>−1</sup> with 50 mmol/L H₂O₂, outperforming other materials due to its superior visible-light absorption and catalytic activity, which justified its selection for more detailed mechanistic studies. The proposed mechanism involves ligand-to-metal charge transfer (LMCT) and Fe-driven generation of reactive oxygen species (ROS) such as hydroxyl radicals. <em>In vitro</em> studies conducted on human monocytes (THP-1), murine embryonic fibroblasts (MEF-NF), breast cancer cells (4T1), melanoma cells (B16-F10), and colorectal cancer cells (CT26) demonstrated high biocompatibility of the developed MOFs. By reducing reliance on toxic chemical treatments, this study highlights MeBDC MOFs as highly efficient, biocompatible, and sustainable photocatalysts, with significant potential for industrial and domestic water purification applications.</div></div>","PeriodicalId":100480,"journal":{"name":"Environmental Chemistry and Ecotoxicology","volume":"7 ","pages":"Pages 305-318"},"PeriodicalIF":9.0000,"publicationDate":"2025-01-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Transition metal-based MOFs for Fenton-like photocatalytic degradation of organic pollutants: Performance, stability, and biocompatibility\",\"authors\":\"S.M. Tikhanova , Yu.A. Tishchenko , E.Yu. Stovpiaga , M. Timofeeva , D.V. Lipin , S.A. Povarov , V.A. Milichko , A.S. Timin , S.A. Shipilovskikh , V.I. Popkov\",\"doi\":\"10.1016/j.enceco.2025.01.003\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>The development of efficient materials for water treatment is crucial to addressing global environmental challenges. In this study, transition metal-based metal-organic frameworks (MeBDC MOFs; Me = Fe, Co, Ni; BDC = benzene dicarboxylic acid) were synthesized via a solvothermal method and considered as dual-function photocatalysts for adsorption and removal of organic pollutant. Comprehensive physicochemical analysis of the developed samples was performed using scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDX), fourier-transform infrared spectroscopy (FTIR), raman spectroscopy, N<sub>2</sub> adsorption-desorption isotherms (BET), and diffuse reflectance spectroscopy (DRS). The materials exhibited a high visible-light absorption with band gap energies of 1.76 eV (FeBDC), 3.08 eV (CoBDC), and 3.73 eV (NiBDC), BET surface areas of 28.2 m<sup>2</sup>/g (FeBDC), 74.3 m<sup>2</sup>/g (CoBDC), and 31.4 m<sup>2</sup>/g (NiBDC). Photocatalytic performance was evaluated using methylene blue (MB) degradation under visible-light irradiation containing both conventional and Fenton-like processes. FeBDC achieved a reaction rate constant of 0.2719 min<sup>−1</sup> with 50 mmol/L H₂O₂, outperforming other materials due to its superior visible-light absorption and catalytic activity, which justified its selection for more detailed mechanistic studies. The proposed mechanism involves ligand-to-metal charge transfer (LMCT) and Fe-driven generation of reactive oxygen species (ROS) such as hydroxyl radicals. <em>In vitro</em> studies conducted on human monocytes (THP-1), murine embryonic fibroblasts (MEF-NF), breast cancer cells (4T1), melanoma cells (B16-F10), and colorectal cancer cells (CT26) demonstrated high biocompatibility of the developed MOFs. By reducing reliance on toxic chemical treatments, this study highlights MeBDC MOFs as highly efficient, biocompatible, and sustainable photocatalysts, with significant potential for industrial and domestic water purification applications.</div></div>\",\"PeriodicalId\":100480,\"journal\":{\"name\":\"Environmental Chemistry and Ecotoxicology\",\"volume\":\"7 \",\"pages\":\"Pages 305-318\"},\"PeriodicalIF\":9.0000,\"publicationDate\":\"2025-01-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Environmental Chemistry and Ecotoxicology\",\"FirstCategoryId\":\"1085\",\"ListUrlMain\":\"https://www.sciencedirect.com/science/article/pii/S2590182625000037\",\"RegionNum\":0,\"RegionCategory\":null,\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"ENVIRONMENTAL SCIENCES\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Environmental Chemistry and Ecotoxicology","FirstCategoryId":"1085","ListUrlMain":"https://www.sciencedirect.com/science/article/pii/S2590182625000037","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"ENVIRONMENTAL SCIENCES","Score":null,"Total":0}
引用次数: 0
摘要
开发高效的水处理材料对于解决全球环境挑战至关重要。在本研究中,过渡金属基金属有机骨架(MeBDC mof;Me = Fe, Co, Ni;采用溶剂热法合成了苯二甲酸(BDC),并将其作为吸附和去除有机污染物的双功能光催化剂。利用扫描电镜(SEM)、粉末x射线衍射(PXRD)、能量色散x射线能谱(EDX)、傅里叶变换红外光谱(FTIR)、拉曼光谱、N2吸附-脱附等温线(BET)和漫反射光谱(DRS)对样品进行了全面的理化分析。该材料具有较高的可见光吸收能力,能带能分别为1.76 eV (FeBDC)、3.08 eV (CoBDC)和3.73 eV (NiBDC), BET表面积分别为28.2 m2/g (FeBDC)、74.3 m2/g (CoBDC)和31.4 m2/g (NiBDC)。在可见光照射下,对亚甲基蓝(MB)降解进行了光催化性能评价,包括常规工艺和类芬顿工艺。FeBDC在50 mmol/L H₂O₂下的反应速率常数为0.2719 min−1,由于其优越的可见光吸收和催化活性,优于其他材料,这证明了选择FeBDC进行更详细的机理研究是合理的。提出的机制包括配体到金属的电荷转移(LMCT)和铁驱动的活性氧(ROS)的产生,如羟基自由基。在体外对人单核细胞(THP-1)、小鼠胚胎成纤维细胞(MEF-NF)、乳腺癌细胞(4T1)、黑色素瘤细胞(B16-F10)和结直肠癌细胞(CT26)进行的研究表明,所开发的MOFs具有很高的生物相容性。通过减少对有毒化学处理的依赖,本研究强调了MeBDC mof作为高效、生物相容性和可持续的光催化剂,在工业和家庭水净化应用中具有巨大的潜力。
Transition metal-based MOFs for Fenton-like photocatalytic degradation of organic pollutants: Performance, stability, and biocompatibility
The development of efficient materials for water treatment is crucial to addressing global environmental challenges. In this study, transition metal-based metal-organic frameworks (MeBDC MOFs; Me = Fe, Co, Ni; BDC = benzene dicarboxylic acid) were synthesized via a solvothermal method and considered as dual-function photocatalysts for adsorption and removal of organic pollutant. Comprehensive physicochemical analysis of the developed samples was performed using scanning electron microscopy (SEM), powder X-ray diffraction (PXRD), energy-dispersive X-ray spectroscopy (EDX), fourier-transform infrared spectroscopy (FTIR), raman spectroscopy, N2 adsorption-desorption isotherms (BET), and diffuse reflectance spectroscopy (DRS). The materials exhibited a high visible-light absorption with band gap energies of 1.76 eV (FeBDC), 3.08 eV (CoBDC), and 3.73 eV (NiBDC), BET surface areas of 28.2 m2/g (FeBDC), 74.3 m2/g (CoBDC), and 31.4 m2/g (NiBDC). Photocatalytic performance was evaluated using methylene blue (MB) degradation under visible-light irradiation containing both conventional and Fenton-like processes. FeBDC achieved a reaction rate constant of 0.2719 min−1 with 50 mmol/L H₂O₂, outperforming other materials due to its superior visible-light absorption and catalytic activity, which justified its selection for more detailed mechanistic studies. The proposed mechanism involves ligand-to-metal charge transfer (LMCT) and Fe-driven generation of reactive oxygen species (ROS) such as hydroxyl radicals. In vitro studies conducted on human monocytes (THP-1), murine embryonic fibroblasts (MEF-NF), breast cancer cells (4T1), melanoma cells (B16-F10), and colorectal cancer cells (CT26) demonstrated high biocompatibility of the developed MOFs. By reducing reliance on toxic chemical treatments, this study highlights MeBDC MOFs as highly efficient, biocompatible, and sustainable photocatalysts, with significant potential for industrial and domestic water purification applications.