Efficient photodegradation of perfluoroalkyl substances under visible light by hexagonal ZnIn2S4 nanosheets.

Perfluoroalkyl substances (PFASs) are typical persistent organic pollutants, and their removal is urgently required but challenging. Photocatalysis has shown potential in PFASs degradation due to the redox capabilities of photoinduced charge carriers in photocatalysts. Herein, hexagonal ZnIn2S4 (ZIS) nanosheets were synthesized by a one-pot oil bath method and were well characterized by a series of techniques. In the degradation of sodium p-perfluorous nonenoxybenzenesulfonate (OBS), one kind of representative PFASs, the as-synthesized ZIS showed activity superior to P25 TiO2 under both simulated sunlight and visible-light irradiation. The good photocatalytic performance was attributed to the enhanced light absorption and facilitated charge separation. The pH conditions were found crucial in the photocatalytic process by influencing the OBS adsorption on the ZIS surface. Photogenerated e- and h+ were the main active species involved in OBS degradation in the ZIS system. This work confirmed the feasibility and could provide mechanistic insights into the degradation and defluorination of PFASs by visible-light photocatalysis.

Novel Insight into the Synergistic Mechanism for Pd and Rh Promoting the Hydro-Defluorination of 4-Fluorophenol over Bimetallic Rh-Pd/C Catalysts.

This study explores the synergistic effect between the Rh and Pd of bimetallic Rh-Pd/C catalysts for the catalytic hydro-defluorination (HDF) of 4-fluorophenol (4-FP). It was found that 4-FP could not be efficiently hydro-defluorinated over 6% Pd/C and 6% Rh/C due to the inherent properties of Pd and Rh species in the dissociation of H2 and the activation of C-F bonds. Compared with 6% Pd/C and 6% Rh/C, bimetallic Rh-Pd/C catalysts, especially 1% Rh-5% Pd/C, exhibited much higher catalytic activity in the HDF of 4-FP, suggesting that the synergistic effect between the Rh and Pd of the catalyst was much more positive. Catalyst characterizations (BET, XRD, TEM, and XPS) were introduced to clarify the mechanism for the synergistic effect between the Rh and Pd of the catalyst in the HDF reaction and revealed that it was mainly attributed to the bifunctional mechanism: Pd species were favorable for the dissociation of H2, and Rh species were beneficial to the activation of C-F bonds in the HDF reaction. Meanwhile, the interaction between Rh and Pd species enabled Rh and Pd to exhibit a more positive synergistic effect, which promoted the migration of atomic H* from Pd to Rh species and thus enhanced the HDF of 4-FP. Furthermore, 1% Rh-5% Pd/C prepared using 20-40 equiv NaBH4 exhibited the best performance in the catalytic HDF of 4-FP. Catalysis characterizations suggested that appropriate Rh3+/Rh0 and Pd2+/Pd0 ratios were beneficial to the dissociation of H2 and the activation of C-F bonds, which caused the more positive synergistic effect between the Rh and Pd of Rh-Pd/C in the HDF reaction. This work offers a valuable strategy for enhancing the performance of catalytic HDF catalysts via promoting synergistic effects.

Enzymatic Degradation of PFAS: Current Status and Ongoing Challenges.

Per- and polyfluoroalkyl substances (PFAS) are often considered the quintessential example of industrial chemical pollution - they are toxic and ubiquitous environmental contaminants that are extremely difficult to degrade. There has been a large research focus on the development of effective and renewable degradation technologies. In comparison to traditional pollutant degradation techniques, such as advanced oxidation processes and electrochemistry, degradation of PFAS using extracellular enzymes offers an eco-friendly solution as enzymes are biodegradable, recyclable and have low energy and chemical requirements. This review outlines the current understanding of extracellular enzymatic degradation of PFAS with a focus on reported results and proposed degradation mechanisms. More importantly, this review highlights limitations that hinder the application of enzymes for PFAS degradation and proposes critical future research that is needed to improve the applicability of this promising remediation strategy.

Biotransformation of 6:2/4:2 fluorotelomer alcohols by Dietzia aurantiaca J3: Enzymes and proteomics.

Per- and polyfluoroalkyl substances (PFAS) are recalcitrant synthetic organohalides known to negatively impact human health. Short-chain fluorotelomer alcohols are considered the precursor of various perfluorocarboxylic acids (PFCAs) in the environment. Their ongoing production and widespread detection motivate investigations of their biological transformation. Dietzia aurantiaca strain J3 was isolated from PFAS-contaminated landfill leachate using 6:2 fluorotelomer sulphonate (6:2 FTS) as a sulphur source. Resting cell experiments were used to test if strain J3 could transform fluorotelomer alcohols (6:2 and 4:2 FTOH). Strain J3 transformed fluorotelomer alcohols into PFCAs, polyfluorocarboxylic acids and transient intermediates. Over 6 days, 80 % and 58 % of 6:2 FTOH (0.1 mM) and 4:2 FTOH (0.12 mM) were degraded with 6.4 % and 14 % fluoride recovery respectively. Fluorotelomer unsaturated carboxylic acid (6:2 FTUCA) was the most abundant metabolite, accounting for 21 to 30 mol% of 6:2 FTOH (0.015 mM) applied on day zero. Glutathione (GSH) conjugates of 6:2/4:2 FTOH and 5:3 FTCA adducts were also structurally identified. Proteomics studies conducted to identify enzymes in the biotransformation pathway have revealed the role of various enzymes involved in ß oxidation. This is the first report of 6:2/4:2 FTOH glutathione conjugates and 5:3 FTCA adducts in prokaryotes, and the first study to explore the biotransformation of 4:2 FTOH by pure bacterial strain.

Removal of mixed pollutants of perfluorooctanoic acid and 2,4,6-trichlorophenol via adsorption-photocatalysis using Ga2O3-Bi4O7 combining with fluorine-doped covalent triazine framework: Role of different active species.

Perfluorooctanoic acid (PFOA) and 2,4,6-trichlorophenol (2,4,6-TCP) are significant pollutants found in textile wastewater, posing severe threats to ecological environments. The construction of an adsorption-photocatalytic system enables the efficient removal of mixed pollutants by harnessing their synergistic effect, thereby overcoming the limitations of removing mixed pollutants with single water treatment technologies. Herein, fluorine-doped covalent triazine framework (F-CTF) was combined with Ga2O3-Bi4O7 heterojunction to obtain Ga2O3-Bi4O7/F-CTF (GaBi/CTF). F-CTF greatly facilitates the adsorption process and provides convenience for photocatalysis. Simultaneously, the excellent conductivity of F-CTF promoted the separation of photoinduced charge carriers in Ga2O3-Bi4O7. GaBi/CTF5 (5 is the mass percentage of F-CTF) showed excellent degradation performance, and the removal rates of PFOA and 2,4,6-TCP reached 93.0 % and 100.0 % within 90 min, respectively. Mechanistic analysis revealed that 2,4,6-TCP and PFOA were attacked by distinct active species because of the disparate characteristics. The presence of phenolic hydroxyl groups makes 2,4,6-TCP more vulnerable to superoxide radicals (·O2-) and hydroxyl radicals (·OH), whereas PFOA is oxidized by holes (h+). The coexistence of mixed pollutants with diverse characteristics enables optimal utilization of active species generated within photocatalytic system. Moreover, the good stability of GaBi/CTF5 provides a feasible solution for efficient treatment of mixed pollutants in textile wastewater.

Effect of electrolyte composition on electrocatalytic transformation of perfluorooctanoic acid (PFOA) in high pH medium.

Recent regulatory actions aim to limit per- and polyfluoroalkyl substances (PFAS) concentrations in drinking water and wastewaters. Regenerable anion exchange resin (AER) is an effective separation process to remove PFAS from water but will require PFAS post-treatment of the regeneration wastestream. Electrocatalytic (EC) processes using chemically boron-doped diamond electrodes, stable in a wide range of chemical compositions show potential to defluorinate PFOA in drinking water and wastewater treatments. Chemical composition and concentration of mineral salts in supporting electrolytes affect AER regeneration efficiency, and play a crucial role in the EC processes. Their impact on PFAS degradation remains understudied. This study investigates the impact of 17 brine electrolytes with different compositions on perfluorooctanoic acid (PFOA) degradation in an alkaline medium and explores the correlation between the rate of PFOA degradation and the solution's conductivity. Results show that higher electrolyte concentrations and conductivity lead to faster PFOA degradation rates. The presence of chloride anions have negligible impact on the degradation rate. However, the presence of nitrate salts reduce PFOA degradation efficiency. Additionally, the use of mixed electrolytes may be a promising approach for reducing the cost of EC operations. PFOA degradation was not influenced by the pH of the bulk solution.

Modulating crystal facets of photoanodes for photoelectrocatalytic scalable degradation of fluorinated pharmaceuticals in wastewater.

Fluorinated pharmaceuticals pollution has become an ever-increasing environmental concern due to its negative impacts. Photoelectrocatalytic (PEC) degradation system is a desirable approach to tackle the pollution problems. However, photogenerated charge separation and interfacial mass transfer are the main bottlenecks for improving the PEC degradation performance. Herein, we report a TiO2 photoanode with tuned (101)/(110) facets in situ grown on a Ti mesh substrate for PEC degradation of fluorinated pharmaceuticals. The exposure of (101) facets facilitates efficient photogenerated charge separation and the desorption of generated •OH radical. Besides, the three-dimensional (3D) architecture of photoanode promotes macroscopic mass transfer. This system performed complete defluorination of 5-fluorouracil and more than 75 % total organic carbon (TOC) removal efficiency. The apparent reaction rate constant of high (101) facet-exposed TiO2 grown on Ti mesh is up to 6.96 h-1, 6‒fold faster than that of photoanode with low (101) facet-exposed TiO2 grown on Ti foil. It is demonstrated that a large-sized PEC system of 1200 cm2 can degrade 100 L of synthetic fluorinated pharmaceutical wastewater with more than 80 % elimination efficiency. This work showcases the facet and substrate modulated strategy of fabricating high-performed photoanode for PEC wastewater purification.

Synergistic material-microbe interface toward deeper anaerobic defluorination.

Per- and polyfluoroalkyl substances (PFAS), particularly the perfluorinated ones, are recalcitrant to biodegradation. By integrating an enrichment culture of reductive defluorination with biocompatible electrodes for the electrochemical process, a deeper defluorination of a C6-perfluorinated unsaturated PFAS was achieved compared to the biological or electrochemical system alone. Two synergies in the bioelectrochemical system were identified: i) The in-series microbial-electrochemical defluorination and ii) the electrochemically enabled microbial defluorination of intermediates. These synergies at the material-microbe interfaces surpassed the limitation of microbial defluorination and further turned the biotransformation end products into less fluorinated products, which could be less toxic and more biodegradable in the environment. This material-microbe hybrid system brings opportunities in the bioremediation of PFAS driven by renewable electricity and warrants future research on mechanistic understanding of defluorinating and electroactive microorganisms at the material-microbe interface for system optimizations.

The action of coenzyme B12-dependent diol dehydratase on 3,3,3-trifluoro-1,2-propanediol results in elimination of all the fluorides with formation of acetaldehyde.

3,3,3-Trifluoro-1,2-propanediol undergoes complete defluorination in two distinct steps: first, the conversion into 3,3,3-trifluoropropionaldehyde catalyzed by adenosylcobalamin (coenzyme B12)-dependent diol dehydratase; second, non-enzymatic elimination of all three fluorides from this aldehyde to afford malonic semialdehyde (3-oxopropanoic acid), which is decarboxylated to acetaldehyde. Diol dehydratase accepts 3,3,3-trifluoro-1,2-propanediol as a relatively poor substrate, albeit without significant mechanism-based inactivation of the enzyme during catalysis. Optical and electron paramagnetic resonance (EPR) spectra revealed the steady-state formation of cob(II)alamin and a substrate-derived intermediate organic radical (3,3,3-trifluoro-1,2-dihydroxyprop-1-yl). The coenzyme undergoes Co-C bond homolysis initiating a sequence of reaction by the generally accepted pathway via intermediate radicals. However, the greater steric size of trifluoromethyl and especially its negative impact on the stability of an adjacent radical centre compared to a methyl group has implications for the mechanism of the diol dehydratase reaction. Nevertheless, 3,3,3-trifluoropropionaldehyde is formed by the normal diol dehydratase pathway, but then undergoes non-enzymatic conversion into acetaldehyde, probably via 3,3-difluoropropenal and malonic semialdehyde.

Direct Defluorination and Amination of Polytetrafluoroethylene and Other Fluoropolymers by Lithium Alkylamides.

Polytetrafluoroethylene (PTFE) and, by extension, fluoropolymers are ubiquitous in science, life, and the environment as perfluoroalkyl pollutants (PFAS). In all cases, it is difficult to transform these materials due to their chemical inertness. Herein, we report a direct amination process of PTFE and some fluoropolymers such as polyvinylidene fluoride (PVDF) and Nafion by lithium alkylamide salts. Synthesizing these reactants extemporaneously between lithium metal and an aliphatic primary di- or triamine that also serves as a solvent leads to the rapid nucleophilic substitution of fluoride by an alkylamide moiety when in contact with the fluoropolymer. Moreover, lithium alkylamides dissolved in suitable solvents other than amines can react with fluoropolymers. This highly efficient one-pot process opens the way for further surface or bulk modification if needed, providing an easy, inexpensive, and fast experiment protocol on large scales.

Influence of chemical structures on reduction rates and defluorination of fluoroarenes during catalytic reduction using a rhodium-based catalyst.

Continuous growth in fluoroarene production has led to environmental pollution and health concerns owing to their persistence, which is attributed to the stable C-F bond in their structures. Herein, we investigated fluoroarene decomposition via hydrodefluorination using a rhodium-based catalyst, focusing on the effects of the chemical structure and functional group on the defluorination yield. Most compounds, except (pentafluoroethyl)benzene, exhibited full or partial reduction with pseudo-first-order rate constants in the range of 0.002-0.396 min-1 and defluorination yields of 0%-100%. Fluoroarenes with hydroxyl, methyl, and carboxylate groups were selected to elucidate how hydrocarbon and oxygen-containing functional groups influence the reaction rate and defluorination. Inhibition of the reaction rate and defluorination yield based on functional groups increased in the order of hydroxyl < methyl < carboxylate, which was identical to the order of the electron-withdrawing effect. Fluoroarenes with polyfluoro groups were also assessed; polyfluoro groups demonstrated a different influence on catalyst activity than non-fluorine functional groups because of fluorine atoms in the substituents undergoing defluorination. The reaction kinetics of (difluoromethyl)fluorobenzenes and their intermediates suggested that hydrogenation and defluorination occurred during degradation. Finally, the effects of the type and position of functional groups on the reaction rate and defluorination yield were investigated via multivariable linear regression analysis. Notably, the electron-withdrawing nature of functional groups appeared to have a greater impact on the defluorination yield of fluoroarenes than the calculated C-F bond dissociation energy.

Enhanced perfluorooctanoic acid (PFOA) degradation by electrochemical activation of peroxydisulfate (PDS) during electrooxidation for water treatment.

Improved treatment of per- and polyfluoroalkyl substances (PFAS) in water is critically important in light of the proposed United States Environmental Protection Agency (USEPA) drinking water regulations at ng L-1 levels. The addition of peroxymonosulfate (PMS) during electrooxidation (EO) can remove and destroy PFAS, but ng L-1 levels have not been tested, and PMS itself can be toxic. The objective of this research was to test peroxydisulfate (PDS, an alternative to PMS) activation by boron-doped diamond (BDD) electrodes for perfluorooctanoic acid (PFOA) degradation. The influence of PDS concentration, temperature, and environmental water matrix effects, and PFOA concentration on PDS-EO performance were systematically examined. Batch reactor experiments revealed that 99 % of PFOA was degraded and 69 % defluorination was achieved, confirming PFOA mineralization. Scavenging experiments implied that sulfate radicals (SO4-) and hydroxyl radicals (HO) played a more important role for PFOA degradation than 1O2 or electrons (e-). Further identification of PFOA degradation and transformation products by liquid chromatography-mass spectrometry (LC-MS) analysis established plausible PFOA degradation pathways. The analysis corroborates that direct electron transfers at the electrode initiate PFOA oxidation and SO4- improves overall treatment by cleaving the CC bond between the C7F15 and COOH moieties in PFOA, leading to possible products such as C7F15 and F-. The perfluoroalkyl radicals can be oxidized by SO4- and HO, resulting in the formation of shorter chain perfluorocarboxylic acids (e.g., perfluorobutanoic acid [PFBA]), with eventual mineralization to CO2 and F-. At an environmentally relevant low initial concentration of 100 ng L-1 PFOA, 99 % degradation was achieved. The degradation of PFOA was slightly affected by the water matrix as less removal was observed in an environmental river water sample (91 %) compared to tests conducted in Milli-Q water (99 %). Overall, EO with PDS provided a destructive approach for the elimination of PFOA.

Detection of volatile hydroperfluoroalkanes during hydrothermal liquefaction of perfluoroalkyl carboxylic acids at circumneutral pH.

Hydrothermal liquefaction (HTL) is a promising technology for converting wet organic waste such as sewage sludge into biocrude oil while simultaneously destroying per- and polyfluoroalkyl substances (PFAS). This study tracked the fate and degradation of six representative PFAS in water to address the effect of perfluoroalkyl chain length on degradation rates and the formation of volatile transformation products at 300-350 °C. While perfluorosulfonic acids were recalcitrant, perfluoroalkyl carboxylic acids (PFCAs) were rapidly and completely decarboxylated to hydroperfluoroalkanes (1 H-perfluoroheptane in the case of perfluorooctanoic acid). The volatile hydroperfluoroalkane was subsequently defluorinated without detectable fluorocarbon intermediates yielding 30-60 % defluorination for ammonium perfluoro(2-methyl-3-oxahexanoate), perfluorobutanoic acid and perfluorooctanoic acid after 2 h at 350 °C. Increasing temperature (especially at 350 °C) and longer perfluoroalkyl chains substantially enhanced the defluorination. This is the first study to report volatile hydroperfluoroalkanes from PFCAs in HTL, raising concern about the potential emission of long-lived greenhouse gasses into the atmosphere, but also opening new avenues for PFAS destruction through HTL.

Defluorination of monofluorinated alkane by Rhodococcus sp. NJF-7 isolated from soil.

Microbial degradation of fluorinated compounds raised significant attention because of their widespread distribution and potential environmental impacts. Here, we report a bacterial isolate, Rhodococcus sp. NJF-7 capable of defluorinating monofluorinated medium-chain length alkanes. This isolate consumed 2.29 ± 0.13 mmol L- 1 of 1-fluorodecane (FD) during a 52 h incubation period, resulting in a significant release of inorganic fluoride amounting to 2.16 ± 0.03 mmol L- 1. The defluorination process was strongly affected by the initial FD concentration and pH conditions, with lower pH increasing fluoride toxicity to bacterial cells and inhibiting enzymatic defluorination activity. Stoichiometric conversion of FD to fluoride was observed at neutral pH with resting cells, while defluorination was significantly lower at reduced pH (6.5). The discovery of the metabolites decanoic acid and methyl decanoate suggests that the initial attack by monooxygenases may be responsible for the biological defluorination of FD. The findings here provide new insights into microbial defluorination processes, specifically aiding in understanding the environmental fate of organic semi-fluorinated alkane chemicals.

Degradation of Perfluorododecyl-Iodide Self-Assembled Monolayers upon Exposure to Ambient Light.

Perfluorododecyl iodide (I-PFC12) is of interest for area-selective deposition (ASD) applications as it exhibits intriguing properties such as ultralow surface energy, the ability to modify silicon's band gap, low surface friction, and suitability for micro-contact patterning. Traditional photolithography is struggling to reach the required critical dimensions. This study investigates the potential of using I-PFC12 as a way to produce contrast between the growth area and non-growth areas of a surface subsequent to extreme ultraviolet (EUV) exposure. Once exposed to EUV, the I-PFC12 molecule should degrade with the help of the photocatalytic substrate, allowing for the subsequent selective deposition of the hard mask. The stability of a vapor-deposited I-PFC12 self-assembled monolayer (SAM) was examined when exposed to ambient light for extended periods of time by using X-ray photoelectron spectroscopy (XPS). Two substrates, SiO2 and TiO2, are investigated to ascertain the suitability of using TiO2 as a photocatalytic active substrate. Following one month of exposure to light, the atomic concentrations showed a more substantial fluorine loss of 10.2% on the TiO2 in comparison to a 6.2% loss on the SiO2 substrate. This more pronounced defluorination seen on the TiO2 is attributed to its photocatalytic nature. Interestingly, different routes to degradation were observed for each substrate. Reference samples preserved in dark conditions with no light exposure for up to three months show little degradation on the SiO2 substrate, while no change is observed on the TiO2 substrate. The results reveal that the I-PFC12 SAM is an ideal candidate for resistless EUV lithography.

Overlooked Activation Role of Sulfite in Accelerating Hydrated Electron Treatment of Perfluorosulfonates.

Photoexcitation of sulfite (SO32-) is often used to generate hydrated electrons (eaq-) in processes to degrade perfluoroalkyl and polyfluoroalkyl substances (PFASs). Conventional consensus discourages the utilization of SO32- concentrations exceeding 10 mM for effective defluorination. This has hindered our understanding of SO32- chemistry beyond its electron photogeneration properties. In contrast, the radiation-chemical study presented here, directly producing eaq- through water radiolysis, suggests that SO32- plays a previously overlooked activation role in the defluorination. Quantitative 60Co gamma irradiation experiments indicate that the increased SO32- concentration from 0.1 to 1 M enhances the defluorination rate by a remarkable 15-fold, especially for short-chain perfluoroalkyl sulfonate (PFSA). Furthermore, during the treatment of long-chain PFSA (C8F17-SO3-) with a higher concentration of SO32-, the intermediates of C8H17-SO3- and C3F7-COO- were observed, which are absent without SO32-. These observations highlight that a higher concentration of SO32- facilitates both reaction pathways: chain shortening and H/F exchange. Pulse radiolysis measurements show that elevated SO32- concentrations accelerate the bimolecular reaction between eaq- and PFSA by 2 orders of magnitude. 19F NMR measurements and theoretical simulations reveal the noncovalent interactions between SO32- and F atoms, which exceptionally reduce the C-F bond dissociation energy by nearly 40%. As a result, our study offers a more effective strategy for degrading highly persistent PFSA contaminants.

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

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 [[meso­tetra(4-carboxyphenyl)porphyrinato]cobalt(III)]Cl·7H2O (CoTCPP), [[meso­tetra(4-sulfonatophenyl) porphyrinato]cobalt(III)]·9H2O (CoTPPS), and [[meso­tetra(4-N-methylpyridyl) porphyrinato]cobalt(II)](I)4·4H2O (CoTMpyP) have been explored for defluorination of PFASs in the presence of the nZn0 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-nZn0) is 88-164 times higher than the VB12-nZn0 system for the investigated br-PFASs. The CoTMpyP-nZn0 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-nZn0 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.

Promotive Effects of Chloride and Sulfate on the Near-Complete Destruction of Perfluorocarboxylates (PFCAs) in Brine via Hydrogen-tuned 185-nm UV Photolysis: Mechanisms and Kinetics.

Hydrogen-tuned 185 nm vacuum ultraviolet (VUV/H2) photolysis is an emerging technology to destroy per- and polyfluoroalkyl substance (PFAS) in brine. This study discovered the promotive effects of two major brine anions, i.e., chloride and sulfate in VUV/H2 photolysis on the hydrated electron (eaq-) generation and perfluorocarboxylates (PFCAs) destruction and established a kinetics model to elucidate the promotive effects on the steady-state concentration of eaq- ([eaq-]ss). Results showed that VUV/H2 achieved near-complete defluorination of perfluorooctanoic acid (PFOA) in the presence of up to 1000 mM chloride or sulfate at pH 12. The defluorination rate constant (kdeF) of PFOA peaked with a chloride concentration at 100 mM and with a sulfate concentration at 500 mM. The promotive effects of chloride and sulfate were attributed to an enhanced generation of eaq- via their direct VUV photolysis and conversion of additionally generated hydroxyl radical to eaq- by H2, which was supported by a linear correlation between the predicted [eaq-]ss and experimentally observed kdeF. The kdeF value increased from pH 9 to 12, which was attributed to the speciation of the H·/eaq- pair. Furthermore, the VUV system achieved >95% defluorination and ≥99% parent compound degradation of a concentrated PFCAs mixture in a synthetic brine, without generating any toxic perchlorate or chlorate.

High-Level Disordered Metal-Organic Frameworks Synthesized by Interference-Oriented Attachment for Electrochemical Anion Sieve.

Disordered MOFs seamlessly amalgamate the robust stability and pore tunability inherent in crystalline MOFs with the advantages derived from abundant defects and active sites present in amorphous structures. This study pioneers the use of the interference-oriented attachment (IOA) mechanism to meticulously craft the morphology and crystal growth of MIL-101(Cr) (Cr-MOF), resulting in the successful synthesis of a high-level disordered Cr-MOF boasting an enhanced array of active sites and exceptional electrochemical properties. The correlation between disordered structures and the electrochemical properties of MOFs are elucidated using the lattice distortion index and fractal dimension. The high-level disordered MOF electrode showcases a remarkable fluoride sieving effect, outperforming conventional fluoride removal materials with a remarkable fluoride adsorption capacity of 41.04 mgNaF gelectrodes -1. First-principles calculations, in conjunction with relevant experiments, provided further validation that the disordered structure significantly enhances the defluorination performance of the material. This study introduces a novel approach for the direct bottom-up synthesis of high-level disordered MOFs, showcasing their potential for applications in electrochemical water treatment.

Efficient photocatalytic degradation of perfluorooctanoic acid by bismuth nanoparticle modified titanium dioxide.

Perfluorooctanoic acid (PFOA) is potentially toxic and exceptionally stable attributed to its robust CF bond, which is hard to be removed by UV/TiO2 systems. In this research, bismuth nanoparticle (Bi NP) modified titanium oxides (Bi/TiO2) were synthesized by a simple photochemical deposition-calcination method and were applied as photocatalysts for the first time to degrade PFOA. The removal rate of 50 mg/L PFOA reached 99.3 % with 58.6 % defluorination rate after 30 min of irradiation via a mercury lamp. Bi/TiO2 exhibited superior performance in PFOA degradation compared to commercial photocatalysts (TiO2, Ga2O3, Bi2O3 and In2O3). In addition, Bi/TiO2 showed high degradation activity under actual sunlight, achieved 100 % removal rate and 59.3 % defluorination rate within 2 h. Bi NPs increase the light trapping ability of Bi/TiO2 and promote the separation of photogenerated electron-hole pairs via local surface plasmon resonance (LSPR) effect, which results in more photogenerated holes (h+) and hydroxyl radicals (OH). Combined with DFT calculations and intermediate detections, the degradation reaction is initiated from the oxidation of the PFOA carboxyl group via h+, followed by the loss of the CF2 unit step by step with the participation of OH. This work presents a novel approach for the practical implementation of TiO2-based photocatalysts to achieve highly efficient photocatalytic degradation of perfluorocarboxylic acids (PFCAs).