{"title":"Fluorinated Metal–Organic Frameworks: Hydrophobic Nanospaces with High Fluorine Density and Proton Conductivity","authors":"Ryota Akai, Hitoshi Kasai, Kouki Oka","doi":"10.1039/d5nr00342c","DOIUrl":null,"url":null,"abstract":"The current work revealed the relationship between the fluorine density of organic-based porous materials and water dynamics (proton conduction) in the hydrophobic nanospace. In detail, focusing on UiO-66 with structural durability at high temperature/humidity based on strong Zr–O bonds, we prepared UiO-66-CF<small><sub>3</sub></small> and UiO-66-(CF<small><sub>3</sub></small>)<small><sub>2</sub></small> with different fluorine densities. The activation energies for proton conduction of UiO-66-CF<small><sub>3</sub></small> (0.91 eV) and UiO-66-(CF<small><sub>3</sub></small>)<small><sub>2</sub></small> (1.38 eV) were significantly larger than in UiO-66 (0.47 eV) depending on their fluorine density. Introducing fluorine into organic-based porous materials allowed hydrophobic nanospace to interact with protons, yielding a larger energy for proton conduction (activation energy). The fluorine density and activation energy were proportional. We clarified that the activation energy of proton conduction increased proportionally with the fluorine density in the nanospace. This indicated the possibility that the state of proton/water in the nanospace could be freely controlled by the fluorine density.","PeriodicalId":92,"journal":{"name":"Nanoscale","volume":"35 1","pages":""},"PeriodicalIF":5.8000,"publicationDate":"2025-03-14","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Nanoscale","FirstCategoryId":"88","ListUrlMain":"https://doi.org/10.1039/d5nr00342c","RegionNum":3,"RegionCategory":"材料科学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
The current work revealed the relationship between the fluorine density of organic-based porous materials and water dynamics (proton conduction) in the hydrophobic nanospace. In detail, focusing on UiO-66 with structural durability at high temperature/humidity based on strong Zr–O bonds, we prepared UiO-66-CF3 and UiO-66-(CF3)2 with different fluorine densities. The activation energies for proton conduction of UiO-66-CF3 (0.91 eV) and UiO-66-(CF3)2 (1.38 eV) were significantly larger than in UiO-66 (0.47 eV) depending on their fluorine density. Introducing fluorine into organic-based porous materials allowed hydrophobic nanospace to interact with protons, yielding a larger energy for proton conduction (activation energy). The fluorine density and activation energy were proportional. We clarified that the activation energy of proton conduction increased proportionally with the fluorine density in the nanospace. This indicated the possibility that the state of proton/water in the nanospace could be freely controlled by the fluorine density.
期刊介绍:
Nanoscale is a high-impact international journal, publishing high-quality research across nanoscience and nanotechnology. Nanoscale publishes a full mix of research articles on experimental and theoretical work, including reviews, communications, and full papers.Highly interdisciplinary, this journal appeals to scientists, researchers and professionals interested in nanoscience and nanotechnology, quantum materials and quantum technology, including the areas of physics, chemistry, biology, medicine, materials, energy/environment, information technology, detection science, healthcare and drug discovery, and electronics.