Feng Xiao

Two ordered microporous carbons (0.83 nm and 1.55 nm) were synthesized for the first time via a modified silica template method, enabling the adjustment of the carbon microporous structure. A pore-size dependent dye removal was observed.

Recent regulations on perfluorinated compounds in drinking water underscore the need for a deeper understanding of the formation of perfluorinated compounds from polyfluoroalkyl substances during chlorine disinfection. Among the compounds investigated in this study, N-(3-(dimethylaminopropan-1-yl)perfluoro-1-hexanesulfonamide (N-AP-FHxSA) underwent rapid transformation during chlorination. Within an hour, it produced quantitative yields of various poly- and per-fluorinated products, including perfluorohexanoic acid (PFHxA). Sixteen reactions involving chlorine with N-AP-FHxSA and its quaternary ammonium analog were investigated; seven were confirmed, while the remainder were either disproved or found to be insignificant. The quaternary ammonium moiety did not determine a polyfluoroalkyl substance's reactivity toward chlorine. For example, while 6:2 fluorotelomer sulfonamide betaine transformed rapidly to PFHxA, other quaternary-ammonium-containing polyfluoroalkyl substances, such as 5:1:2 and 5:3 fluorotelomer betaines, showed significant resistance to chlorination. Further investigation identified potential sites for electrophilic attacks near the amine region by examining the highest occupied molecular orbitals of the polyfluoroalkyl substances. Visualization techniques helped pinpoint electron-deficient and electron-rich sites as potential targets for nucleophilic and electrophilic attacks, respectively. Increasing the solution pH from 6 to 10 did not diminish the apparent degradation of the studied polyfluoroalkyl substances, likely due to the greater reactivity of the deprotonated forms compared to the conjugate acids. Finally, we also examined the hydrolysis of polyfluoroalkyl substances at pH 6 to 11 in the absence of chlorine.

The thermal decomposition of per- and poly fluoroalkyl substances (PFAS) is poorly understood. Here, we present an innovative, comprehensive analytical method to investigate their thermal decomposition, including perfluorocarboxylic acids (PFCAs), alcohol, sulfonates, and GenX (acid dimer), focusing on identifying their breakdown products. In this study, evolved gas analysis-mass spectrometry (EGA-MS) was used for fast real-time screening to determine the significant temperatures to be investigated with the thermal desorption-pyrolysis coupled with gas chromatography-mass spectrometry (TD-Py-GC-MS), which provided detailed information about evolved PFAS and their breakdown products. This approach enabled a systematic study of perfluorocarboxylic acids (PFCAs) ranging from C₃ to C₉ and GenX showing volatilization, followed by degradation and formation of respective perfluorinated-1-alkenes and C₅F₁₀O perfluorinated ether (from GenX). At elevated temperatures (e.g., 600 °C), the products observed included perfluorinated butene and higher molecular-weight products, likely formed by pyrolytic polymerization of perfluorinated radicals. 1H,1H,2H,2H-perfluoro-1-decanol, i.e., 8:2 FTOH, volatilized at 100 °C; however, at higher temperatures, several novel decomposition products were observed, including perfluoro-1-decene and perfluorinated compounds suggesting the presence of the hydroxylic group. Our method offers an alternative approach to studying the thermal behavior of currently regulated and emerging PFAS with a focus on application to a wide range of matrices (laboratory grade standards or environmental samples).

The products of incomplete destruction (PIDs) of per- and polyfluoroalkyl substances (PFAS) represent a substantial ambiguity when employing thermal treatments to remediate PFAS-contaminated materials. In this study, we present new information on PIDs produced in both inert and oxidative environments from five long-chain PFAS, including three now regulated under the U.S. Safe Drinking Water Act, one cationic precursor compound, and one C10 PFAS. The data did not support the generation of tetrafluoromethane from any of the studied PFAS, and carbonyl fluoride was found only from potassium perfluorooctanesulfonate (K-PFOS) when heated in air in a narrow temperature range. Oxidative conditions (air) were observed to facilitate PFAS thermal degradation and accelerate the mineralization of K-PFOS. Spectroscopic data suggest that PFAS thermal degradation is initiated by the cleavage of bonds that form perfluoroalkyl radicals, leading to organofluorine PIDs (e.g., perfluoroalkenes). In air, perfluoroalkyl radicals react with oxygen to form oxygen-containing PIDs. The mineralization of PFAS was enhanced by adding solid additives, which were categorized as highly effective (e.g., granular activated carbon (GAC) and certain noble metals), moderately effective, and noneffective. Remarkably, simply by adding GAC, we achieved >90% mineralization of perfluorooctanoic acid at 300 °C and ∼1.9 atm within just 60 min without using water or solvents.