Nanoparticle-embedded hydrogel synthesized electrodes for electrochemical oxidation of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS).

In this study, sliver (Ag) and gold (Au) nanoparticles (NPs) were embedded on poly (acrylic acid) (PAA)/poly (allylamine) hydrochloride (PAH) hydrogel fibers for improved electrochemical oxidation (EO) of perfluorooctanoic acid (PFOA) and perfluorooctanesulfonic acid (PFOS) removal. The NPs-loaded PAA/PAHs shows the better charge transport compared to the ceramic nanofiber membranes (CNM) electrodes. At 10 mA cm-2 of current density, the Ag-PAA/PAH electrodes showed a faster removal of PFAS compared to the Ag-CNM electrode probably due to large surface area-volume ratio and high porosity from the hydrogel. Among NPs-loaded PAA/PAH electrodes, the Ag/Au-PAA/PAH electrodes showed the highest removal of PFOA (72%) and PFOS (91%) in 2 h with the maximum removal rate of PFOA (0.0046 min-1) and PFOS (0.0093 min-1). The rapid PFOS removal is possibly due to the high activity of electron transfer with a higher redox potential of SO4•- than •OH. The highly stable F- generation was obtained from each electrode during reproducibility (n = 3). The net energy consumption from Ag/Au-PAA/PAH electrode was 164.9 kWh m-3 for 72% PFOA removal and 90 kWh m-3 for 91% PFOS removal, respectively. The developed Au-PAA/PAH electrodes were applied to lake water samples and showed acceptable PFOS removal (65%) with relative standard deviations (RSD) of 10.2% (n = 3) at 10 mA cm-2 of current density. Overall, the NP-embedded hydrogel nanofibers were proven to be a promising sustainable catalyst for the electrochemical PFAS oxidation in water.

Light-Modulated Cationic and Anionic Transport across Protein Biopolymers*.

Light is a convenient source of energy and the heart of light-harvesting natural systems and devices. Here, we show light-modulation of both the chemical nature and ionic charge carrier concentration within a protein-based biopolymer that was covalently functionalized with photoacids or photobases. We explore the capability of the biopolymer-tethered photoacids and photobases to undergo excited-state proton transfer and capture, respectively. Electrical measurements show that both the photoacid- and photobase-functionalized biopolymers exhibit an impressive light-modulated increase in ionic conductivity. Whereas cationic protons are the charge carriers for the photoacid-functionalized biopolymer, water-derived anionic hydroxides are the suggested charge carriers for the photobase-functionalized biopolymer. Our work introduces a versatile toolbox to photomodulate both protons and hydroxides as charge carriers in polymers, which can be of interest for a variety of applications.

Use of Photoacids and Photobases To Control Dynamic Self-Assembly of Gold Nanoparticles in Aqueous and Nonaqueous Solutions.

Dynamic self-assembly of nanoparticles (NPs) for the formation of aggregates takes place out of thermodynamic equilibrium and is sustained by external energy supply. Herein, we present light energy driven dynamic self-assembly process of AuNPs, decorated with pH sensitive ligands. The process is being controlled by the use of photoacids and photobases that undergo excited state proton or hydroxide transfer, respectively, due to their large p Ka change between their ground and excited electronic states. The unique design is underlined by record subsecond conversion rates between the assembled and disassembled AuNPs states, and the ability to control the process using only light of different wavelengths. Measurements in both aqueous and nonaqueous solutions resulted in different self-assembly mechanisms, hence showing the wide versatility of photoacids and photobases for dynamic processes.

Modular Design of Fluorescent Dibenzo- and Naphtho-Fluoranthenes: Structural Rearrangements and Electronic Properties.

A library of 12 dibenzo- and naphtho-fluoranthene polycyclic aromatic hydrocarbons (PAHs) with MW = 302 (C24H14) was synthesized via a Pd-catalyzed fluoranthene ring-closing reaction. By understanding the various modes by which the palladium migrates during the transformation, structural rearrangements were bypassed, obtaining pure PAHs in high yields. Spectroscopic and electrochemical characterization demonstrated the profound diversity in the electronic structures between isomers. Highlighting the significant differences in emission of visible light, this library of PAHs will enable their standardization for toxicological assessment and potential use as optoelectronic materials.