Soluble metal porphyrins - Zero-valent zinc system for effective reductive defluorination of branched per and polyfluoroalkyl substances (PFASs).

Autor: Sun J; School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia., Yu TT; School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia., Mirabediny M; School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia., Lee M; School of Civil and Environmental Engineering, Water Research Centre, The University of New South Wales, Sydney, NSW 2052, Australia., Jones A; School of Civil and Environmental Engineering, Water Research Centre, The University of New South Wales, Sydney, NSW 2052, Australia., O'Carroll DM; School of Civil and Environmental Engineering, Water Research Centre, The University of New South Wales, Sydney, NSW 2052, Australia. Electronic address: d.ocarroll@unsw.edu.au., Manefield MJ; School of Civil and Environmental Engineering, Water Research Centre, The University of New South Wales, Sydney, NSW 2052, Australia., Kumar PV; School of Chemical Engineering, The University of New South Wales, Sydney, NSW 2052, Australia., Pickford R; Bioanalytical Mass Spectrometry Facility, Mark Wainwright Analytical Centre, The University of New South Wales, Sydney, NSW 2052, Australia., Ramadhan ZR; Electron Microscope Unit, Mark Wainwright Analytical Centre, The University of New South Wales, Sydney, NSW 2052, Australia., Bhattacharyya SK; Solid State and Elemental Analysis Unit, Mark Wainwright Analytical Centre, UNSW Sydney, Sydney, NSW, 2052 Australia., Åkermark B; Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Svante Arrhenius väg 16C, SE-10691 Stockholm, Sweden., Das B; Department of Organic Chemistry, Arrhenius Laboratory, Stockholm University, Svante Arrhenius väg 16C, SE-10691 Stockholm, Sweden. Electronic address: biswanath.das@su.se., Kumar N; School of Chemistry, The University of New South Wales, Sydney, NSW 2052, Australia. Electronic address: n.kumar@unsw.edu.au.
Jazyk: angličtina
Zdroj: Water research [Water Res] 2024 Jul 01; Vol. 258, pp. 121803. Date of Electronic Publication: 2024 May 19.
DOI: 10.1016/j.watres.2024.121803
Abstrakt: Nano zero-valent metals (nZVMs) have been extensively utilized for decades in the reductive remediation of groundwater contaminated with chlorinated organic compounds, owing to their robust reducing capabilities, simple application, and cost-effectiveness. Nevertheless, there remains a dearth of information regarding the efficient reductive defluorination of linear or branched per- and polyfluoroalkyl substances (PFASs) using nZVMs as reductants, largely due to the absence of appropriate catalysts. In this work, various soluble porphyrin ligands [[meso‑tetra(4-carboxyphenyl)porphyrinato]cobalt(III)]Cl·7H 2 O (CoTCPP), [[meso‑tetra(4-sulfonatophenyl) porphyrinato]cobalt(III)]·9H 2 O (CoTPPS), and [[meso‑tetra(4-N-methylpyridyl) porphyrinato]cobalt(II)](I) 4 ·4H 2 O (CoTMpyP) have been explored for defluorination of PFASs in the presence of the nZn 0 as reductant. Among these, the cationic CoTMpyP showed best defluorination efficiencies for br-perfluorooctane sulfonate (PFOS) (94%), br-perfluorooctanoic acid (PFOA) (89%), and 3,7-Perfluorodecanoic acid (PFDA) (60%) after 1 day at 70 °C. The defluorination rate constant of this system (CoTMpyP-nZn 0 ) is 88-164 times higher than the VB 12 -nZn 0 system for the investigated br-PFASs. The CoTMpyP-nZn 0 also performed effectively at room temperature (55% for br-PFOS, 55% for br-PFOA and 25% for 3,7-PFDA after 1day), demonstrating the great potential of in-situ application. The effect of various solubilizing substituents, electron transfer flow and corresponding PFASs defluorination pathways in the CoTMpyP-nZn 0 system were investigated by both experiments and density functional theory (DFT) calculations. SYNOPSIS: Due to the unavailability of active catalysts, available information on reductive remediation of PFAS by zero-valent metals (ZVMs) is still inadequate. This study explores the effective defluorination of various branched PFASs using soluble porphyrin-ZVM systems and offers a systematic approach for designing the next generation of catalysts for PFAS remediation.
Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.
(Copyright © 2024 The Authors. Published by Elsevier Ltd.. All rights reserved.)
Databáze: MEDLINE
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