DataVXACS Energy LettersPaper
journal article·2026-05-08

Enhanced PFAS Defluorination through Control of Radical-Dependent Degradation Pathways

Alexander Nitsche, Haldrian Iriawan, Xiao Wang, Yuriy Román-Leshkov, Yang Shao-Horn

ACS Energy Letters· Volume 11· Issue 5
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Source abstract

Abstract

Per- and polyfluoroalkyl substances (PFAS) are persistent pollutants that are resistant to conventional water treatment. This study investigates the electrochemical degradation of perfluorooctanoic acid (PFOA) in perchlorate and sulfate electrolytes with boron-doped diamond. Quantification of PFOA degradation and fluoride (F – ) and short-chain perfluorocarboxylic acid (PFCA) formation showed similar defluorination efficiency in both electrolytes at 4.0 V RHE but significantly higher PFCA yields with the sulfate electrolyte. Through electrochemistry-mass spectrometry, 19 F and 1 H NMR spectroscopy, potential-dependent investigation, and radical-scavenger experiments, we showed that both electrolytes exhibit similar decarboxylation rates of the carboxylic group to evolve CO 2 . However, HO • primarily drove C–F cleavage, releasing F – and leaving the remaining fluorocarbon backbone hydrogenated, while SO 4 •– promoted C–C cleavage to form fully fluorinated shorter-chain PFCAs. These results highlight the distinct roles of free radicals in PFOA degradation, offering mechanistic insights to design electrolytes to promote complete PFAS defluorination and suppress the formation of short-chain PFAS.
Source: openalex_inverted_index · Quality: baseline

Research context

Energy storage

OpenAlex topics: Per- and polyfluoroalkyl substances research · Fluorine in Organic Chemistry · Metal-Catalyzed Oxygenation Mechanisms

SciVX discovery tags are terminology-based. OpenAlex topics are source-provided classifications.

Affiliations

Department of Chemistry, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States

Department of Materials Science and Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States

Department of Chemical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States

Department of Mechanical Engineering, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States

Research Laboratory of Electronics, Massachusetts Institute of Technology, 77 Massachusetts Avenue, Cambridge, Massachusetts 02139, United States

Funding

Bill and Melinda Gates Foundation · Natural Sciences and Engineering Research Council of Canada · Center for Electrification and Decarbonization of Industry, Massachusetts Institute of Technology

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