Per- and polyfluorinated alkyl substances (PFAS) are anthropogenic compounds which have recently drawn great attention due to their high biological, chemical and physical stability and lipid/water repelling properties. The present work aims to provide for the first time insights on the thermal behaviour of Ag-exchanged Y zeolite loaded with perfluorooctanoic acid (PFOA, CHFO) and perfluorooctane sulfonate (PFOS, CHFOS) emphasizing the close link between crystal structure and desorption/dehydration processes. Elemental and isotopic abundance of carbon analysis, thermal analysis, and high-temperature synchrotron X-ray powder diffraction were used to evaluate critically if the thermal regeneration affects the initial zeolites structural features. Rietveld refinements revealed that PFAS sites are emptied in the 550-650 °C temperature range, when the thermal degradation of PFOA and PFOS are reached. The crystallinity of the samples is not affected by the adsorption/desorption processes. Upon heating, the removal of both PFAS and coadsorbed water molecules induced a cation migration of the silver ions and changes of initial geometry of the framework. The dimensions of the channels remain comparable to those of the pristine materials thus suggesting the potential re-use of the samples in other adsorption PFAS cycles. Additionally, once regenerated and reloaded Ag-exchanged Y can re-adsorb PFAS in amounts comparable to that adsorbed in the first cycle with clear benefits on the costs of the whole water treatment process.
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http://dx.doi.org/10.1039/d3cp01584j | DOI Listing |
Phys Chem Chem Phys
July 2023
Department of Physics and Earth Sciences, University of Ferrara, Via Saragat 1, I-44121, Ferrara, Italy.
Per- and polyfluorinated alkyl substances (PFAS) are anthropogenic compounds which have recently drawn great attention due to their high biological, chemical and physical stability and lipid/water repelling properties. The present work aims to provide for the first time insights on the thermal behaviour of Ag-exchanged Y zeolite loaded with perfluorooctanoic acid (PFOA, CHFO) and perfluorooctane sulfonate (PFOS, CHFOS) emphasizing the close link between crystal structure and desorption/dehydration processes. Elemental and isotopic abundance of carbon analysis, thermal analysis, and high-temperature synchrotron X-ray powder diffraction were used to evaluate critically if the thermal regeneration affects the initial zeolites structural features.
View Article and Find Full Text PDFNanoscale
June 2018
Department of Physics and Astronomy, Laboratory of Solid State Physics and Magnetism, KU Leuven, Celestijnenlaan 200D, 3001 Leuven, Belgium.
Luminescent silver clusters (AgCLs) stabilized inside partially Ag exchanged Na LTA zeolites show a remarkable reversible on-off switching of their green-yellowish luminescence that is easily tuned by a hydration and dehydration cycle, making them very promising materials for sensing applications. We have used a unique combination of photoluminescence (PL), UV-visible-NIR Diffuse Reflectance (DRS), X-ray absorption fine structure (XAFS), Fourier Transform-Infrared (FTIR) and electron spin resonance (ESR) spectroscopies to unravel the atomic-scale structural changes responsible for the reversible optical behavior of the confined AgCLs in LTA zeolites. Water coordinated, diamagnetic, tetrahedral AgCLs [Ag4(H2O)4]2+ with Ag atoms positioned along the axis of the sodalite six-membered rings are at the origin of the broad and intense green-yellowish luminescence in the hydrated sample.
View Article and Find Full Text PDFPhys Chem Chem Phys
June 2015
Graduate School of Science and Engineering, Tokyo Institute of Technology, 2-12-1 Ookayama, Meguro-ku, Tokyo 152-8550, Japan.
Ag(+)-exchanged zeolites exhibit unique catalytic properties caused by the combination of their redox and acidic properties. Partial reduction of Ag(+) ions in zeolites with hydrogen leads to the formation of acidic protons and silver metal particles, which can be observed using X-ray powder diffraction patterns (XRD). By simply evacuating hydrogen from the system, the silver metal particles are returned back to Ag(+) ions and at the same time, acidic protons are eliminated.
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