{"title":"金属杂原子大大提高了二氧化钛纳米材料促进有机磷水解的功效:对减轻塑料添加剂污染的影响。","authors":"Xule Pei, Weichao Wang, Zaihao Chen, Keman Liu, Zongsheng Liang, Chuanjia Jiang, Tong Zhang, Wei Chen","doi":"10.1016/j.scitotenv.2024.177548","DOIUrl":null,"url":null,"abstract":"<p><p>Organophosphate esters (OPEs) are prevalent pollutants in the aquatic environment. OPEs are released from many sources, particularly, from the breakdown and weathering of plastic wastes, as OPEs are commonly used plastic additives. Metal oxide mineral nanoparticles play critical roles in the hydrolytic transformation of OPEs. While natural minerals often contain metal impurities, it is unclear how metal heteroatoms affect the efficiency of mineral nanoparticles in mediating hydrolysis reactions. Herein, we show that transition metal-doped anatase titanium dioxide (TiO<sub>2</sub>) nanomaterials are more effective in catalyzing the hydrolysis of 4-nitrophenyl phosphate (pNPP), a model OPE compound, with the relative effects of the heteroatoms following the order of Fe > Cr > Mn ≈ Ni > Co > Cu. With multiple lines of evidence based on spectroscopic analysis, kinetics modeling, and theoretical calculations, we show that metal doping increases the Lewis acidity of the TiO<sub>2</sub> nanomaterials by increasing the oxidation state of surface Ti atoms, inducing oxygen vacancies, and creating additional Lewis acid sites with stronger acidities. Moreover, the increased amounts of surface hydroxyl groups due to metal doping enhance inner-sphere complexation of pNPP through ligand exchange. The interesting observation that Fe-doped TiO<sub>2</sub> exhibited the highest catalytic efficiency may have important implications for reducing the risks of organophosphate plastic additives, as iron is the most common heteroatom of naturally occurring TiO<sub>2</sub> (nano)materials.</p>","PeriodicalId":422,"journal":{"name":"Science of the Total Environment","volume":" ","pages":"177548"},"PeriodicalIF":8.2000,"publicationDate":"2024-12-20","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Metal heteroatoms significantly enhance efficacy of TiO<sub>2</sub> nanomaterials in promoting hydrolysis of organophosphates: Implications for mitigating pollution of plastic additives.\",\"authors\":\"Xule Pei, Weichao Wang, Zaihao Chen, Keman Liu, Zongsheng Liang, Chuanjia Jiang, Tong Zhang, Wei Chen\",\"doi\":\"10.1016/j.scitotenv.2024.177548\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p><p>Organophosphate esters (OPEs) are prevalent pollutants in the aquatic environment. OPEs are released from many sources, particularly, from the breakdown and weathering of plastic wastes, as OPEs are commonly used plastic additives. Metal oxide mineral nanoparticles play critical roles in the hydrolytic transformation of OPEs. While natural minerals often contain metal impurities, it is unclear how metal heteroatoms affect the efficiency of mineral nanoparticles in mediating hydrolysis reactions. Herein, we show that transition metal-doped anatase titanium dioxide (TiO<sub>2</sub>) nanomaterials are more effective in catalyzing the hydrolysis of 4-nitrophenyl phosphate (pNPP), a model OPE compound, with the relative effects of the heteroatoms following the order of Fe > Cr > Mn ≈ Ni > Co > Cu. With multiple lines of evidence based on spectroscopic analysis, kinetics modeling, and theoretical calculations, we show that metal doping increases the Lewis acidity of the TiO<sub>2</sub> nanomaterials by increasing the oxidation state of surface Ti atoms, inducing oxygen vacancies, and creating additional Lewis acid sites with stronger acidities. Moreover, the increased amounts of surface hydroxyl groups due to metal doping enhance inner-sphere complexation of pNPP through ligand exchange. The interesting observation that Fe-doped TiO<sub>2</sub> exhibited the highest catalytic efficiency may have important implications for reducing the risks of organophosphate plastic additives, as iron is the most common heteroatom of naturally occurring TiO<sub>2</sub> (nano)materials.</p>\",\"PeriodicalId\":422,\"journal\":{\"name\":\"Science of the Total Environment\",\"volume\":\" \",\"pages\":\"177548\"},\"PeriodicalIF\":8.2000,\"publicationDate\":\"2024-12-20\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Science of the Total Environment\",\"FirstCategoryId\":\"93\",\"ListUrlMain\":\"https://doi.org/10.1016/j.scitotenv.2024.177548\",\"RegionNum\":1,\"RegionCategory\":\"环境科学与生态学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"2024/11/18 0:00:00\",\"PubModel\":\"Epub\",\"JCR\":\"Q1\",\"JCRName\":\"ENVIRONMENTAL SCIENCES\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Science of the Total Environment","FirstCategoryId":"93","ListUrlMain":"https://doi.org/10.1016/j.scitotenv.2024.177548","RegionNum":1,"RegionCategory":"环境科学与生态学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"2024/11/18 0:00:00","PubModel":"Epub","JCR":"Q1","JCRName":"ENVIRONMENTAL SCIENCES","Score":null,"Total":0}
引用次数: 0
摘要
有机磷酸酯(OPE)是水生环境中普遍存在的污染物。由于 OPE 是常用的塑料添加剂,OPE 的释放来源很多,特别是塑料废物的分解和风化。金属氧化物矿物纳米粒子在 OPE 的水解转化过程中发挥着关键作用。虽然天然矿物通常含有金属杂质,但目前还不清楚金属杂原子如何影响矿物纳米粒子介导水解反应的效率。在本文中,我们发现掺杂过渡金属的锐钛型二氧化钛(TiO2)纳米材料在催化模型 OPE 化合物 4-硝基苯磷酸酯(pNPP)的水解过程中更为有效,杂原子的相对影响顺序为 Fe > Cr > Mn ≈ Ni > Co > Cu。通过基于光谱分析、动力学建模和理论计算的多重证据,我们证明了金属掺杂可通过提高表面 Ti 原子的氧化态、诱导氧空位和创建酸性更强的额外 Lewis 酸位点来增加 TiO2 纳米材料的 Lewis 酸性。此外,金属掺杂导致的表面羟基数量增加,通过配体交换增强了 pNPP 的内球络合。由于铁是天然 TiO2(纳米)材料中最常见的杂原子,因此掺杂铁的 TiO2 表现出最高的催化效率,这一有趣的观察结果可能对降低有机磷塑料添加剂的风险具有重要意义。
Metal heteroatoms significantly enhance efficacy of TiO2 nanomaterials in promoting hydrolysis of organophosphates: Implications for mitigating pollution of plastic additives.
Organophosphate esters (OPEs) are prevalent pollutants in the aquatic environment. OPEs are released from many sources, particularly, from the breakdown and weathering of plastic wastes, as OPEs are commonly used plastic additives. Metal oxide mineral nanoparticles play critical roles in the hydrolytic transformation of OPEs. While natural minerals often contain metal impurities, it is unclear how metal heteroatoms affect the efficiency of mineral nanoparticles in mediating hydrolysis reactions. Herein, we show that transition metal-doped anatase titanium dioxide (TiO2) nanomaterials are more effective in catalyzing the hydrolysis of 4-nitrophenyl phosphate (pNPP), a model OPE compound, with the relative effects of the heteroatoms following the order of Fe > Cr > Mn ≈ Ni > Co > Cu. With multiple lines of evidence based on spectroscopic analysis, kinetics modeling, and theoretical calculations, we show that metal doping increases the Lewis acidity of the TiO2 nanomaterials by increasing the oxidation state of surface Ti atoms, inducing oxygen vacancies, and creating additional Lewis acid sites with stronger acidities. Moreover, the increased amounts of surface hydroxyl groups due to metal doping enhance inner-sphere complexation of pNPP through ligand exchange. The interesting observation that Fe-doped TiO2 exhibited the highest catalytic efficiency may have important implications for reducing the risks of organophosphate plastic additives, as iron is the most common heteroatom of naturally occurring TiO2 (nano)materials.
期刊介绍:
The Science of the Total Environment is an international journal dedicated to scientific research on the environment and its interaction with humanity. It covers a wide range of disciplines and seeks to publish innovative, hypothesis-driven, and impactful research that explores the entire environment, including the atmosphere, lithosphere, hydrosphere, biosphere, and anthroposphere.
The journal's updated Aims & Scope emphasizes the importance of interdisciplinary environmental research with broad impact. Priority is given to studies that advance fundamental understanding and explore the interconnectedness of multiple environmental spheres. Field studies are preferred, while laboratory experiments must demonstrate significant methodological advancements or mechanistic insights with direct relevance to the environment.