Electrochemical Reduction of Perfluorooctanoic Acid (PFOA): An Experimental and Theoretical Approach.

Perfluorooctanoic acid (PFOA) is an artificial chemical of global concern due to its high environmental persistence and potential human health risk. Electrochemical methods are promising technologies for water treatment because they are efficient, cheap, and scalable. The electrochemical reduction of PFOA is one of the current methodologies. This process leads to defluorination of the carbon chain to hydrogenated products. Here, we describe a mechanistic study of the electrochemical reduction of PFOA in gold electrodes. By using linear sweep voltammetry (LSV), an E0' of -1.80 V vs Ag/AgCl was estimated. Using a scan rate diagnosis, we determined an electron-transfer coefficient (αexp) of 0.37, corresponding to a concerted mechanism. The strong adsorption of PFOA into the gold surface is confirmed by the Langmuir-like isotherm in the absence (KA = 1.89 × 1012 cm3 mol-1) and presence of a negative potential (KA = 3.94 × 107 cm3 mol-1, at -1.40 V vs Ag/AgCl). Based on Marcus-Hush's theory, calculations show a solvent reorganization energy (λ0) of 0.9 eV, suggesting a large electrostatic repulsion between the perfluorinated chain and water. The estimated free energy of the transition state of the electron transfer (ΔG‡ = 2.42 eV) suggests that it is thermodynamically the reaction-limiting step. 19F - 1H NMR, UV-vis, and mass spectrometry studies confirm the displacement of fluorine atoms by hydrogen. Density functional theory (DFT) calculations also support the concerted mechanism for the reductive defluorination of PFOA, in agreement with the experimental values.

Rapid, Selective, and Chemical-Free Removal of Dissolved Silica from Water via Electrosorption: Feasibility and Mechanisms.

The unavoidable and detrimental formation of silica scale in engineered processes necessitates the urgent development of effective, economic, and sustainable strategies for dissolved silica removal from water. Herein, we demonstrate a rapid, chemical-free, and selective silica removal method using electrosorption. Specifically, we confirm the feasibility of exploiting local pH dynamics at the electrodes in flow-through electrosorption, achieved through a counterintuitive cell configuration design, to induce ionization and concomitant electrosorption of dissolved silica. In addition, to improve the feasibility of silica electrosorption under high-salinity solutions, we developed a silica-selective anode by functionalizing porous activated carbon cloths with aluminum hydroxide nanoparticles (Al(OH)3-p-ACC). The modification markedly enhances silica sorption capacity (2.8 vs 1.1 mgsilica ganode-1) and reduces the specific energy consumption (13.3 vs 19.8 kWh kgsilica-1). Notably, the modified electrode retains remarkable silica sorption capacity even in the presence of high concentrations of co-occurring ions (up to 100 mM NaCl). The mechanisms underlying the superior silica removal stability and selectivity with the Al(OH)3-p-ACC electrode are also elucidated, revealing a synergistic interaction involving outer-sphere and inner-sphere complexation between dissolved silica and Al(OH)3 nanoparticles on the electrodes. Moreover, we find that effective regeneration of the electrodes may be achieved by applying a reverse potential during discharge, although complete regeneration of the modified electrodes may necessitate alternative materials or process optimization. We recommend the adoption of feedwater-specific designs for the development of future silica-selective electrodes in electrosorption capable of meeting silica removal demands across a wide range of engineered systems.

Bifunctional porphyrin-based metal-organic polymers for electrochemical water splitting.

Electrochemical water splitting offers the potential for environmentally friendly hydrogen and oxygen gas generation. Here, we present the synthesis, characterization, and electrochemical analyses of four organic polymers where metalloporphyrins are the active center nodes. These materials were obtained from the polymerization reaction of poly(p-phenylene terephtalamide) (PPTA) with the respective amino-functionalized metalloporphyrins, where M = Fe, 1; Co, 2; Ni, 3; Cu, 4. Scanning and transmission electron microscopy images (SEM and TEM) show that these polymers exhibit a layer-type morphology, which is attributed to hydrogen bonding and π-π stacking between the metalloporphyrin nodes. The synthesized materials were characterized by X-ray photoelectron spectroscopy (XPS), X-ray powder diffraction (XRD), energy-dispersive X-ray spectroscopy (EDX), UV-Vis spectroscopy, and Fourier-transform infrared spectroscopy (FT-IR). Among the materials studied, the cobalt-based polymer, 2, demonstrates a bifunctional electrocatalytic activity for oxygen (OER) and hydrogen (HER) evolution reactions with overpotentials (η10) of 337 mV and 435 mV, respectively. The Fe, 1, and Ni, 2, polymers are less active for HER with maximum current densities (jmax) of 12.6 and 19.1 mA cm-2 and η10 678 mV, 644 mV. Polymer 2 achieves a jmax of 37.7 mA cm-2 for HER and 133 mA cm-2 for OER. The copper-based material, 4, on the other hand, shows selectivity towards HER with an overpotential (η) of 436 mV and a maximum current density (j) of 45.5 mA cm-2. The bifunctional electrocatalytic performance was tested in the overall water-splitting setup, where polymer 2 requires a cell voltage of 1.64 V at 10 mA cm-2. This work presents a novel approach to heterogenized molecular systems, providing materials with exceptional structural characteristics and enhanced electrocatalytic capabilities.