Revisiting the Electron Transfer Mechanisms in Ru(III)-Mediated Advanced Oxidation Processes with Peroxyacids and Ferrate(VI).

The potential of Ru(III)-mediated advanced oxidation processes has attracted attention due to the recyclable catalysis, high efficiency at circumneutral pHs, and robust resistance against background anions (e.g., phosphate). However, the reactive species in Ru(III)-peracetic acid (PAA) and Ru(III)-ferrate(VI) (FeO42-) systems have not been rigorously examined and were tentatively attributed to organic radicals (CH3C(O)O•/CH3C(O)OO•) and Fe(IV)/Ru(V), representing single electron transfer (SET) and double electron transfer (DET) mechanisms, respectively. Herein, the reaction mechanisms of both systems were investigated by chemical probes, stoichiometry, and electrochemical analysis, revealing different reaction pathways. The negligible contribution of hydroxyl (HO•) and organic (CH3C(O)O•/CH3C(O)OO•) radicals in the Ru(III)-PAA system clearly indicated a DET reaction via oxygen atom transfer (OAT) that produces Ru(V) as the only reactive species. Further, the Ru(III)-performic acid (PFA) system exhibited a similar OAT oxidation mechanism and efficiency. In contrast, the 1:2 stoichiometry and negligible Fe(IV) formation suggested the SET reaction between Ru(III) and ferrate(VI), generating Ru(IV), Ru(V), and Fe(V) as reactive species for micropollutant abatement. Despite the slower oxidation rate constant (kinetically modeled), Ru(V) could contribute comparably as Fe(V) to oxidation due to its higher steady-state concentration. These reaction mechanisms are distinctly different from the previous studies and provide new mechanistic insights into Ru chemistry and Ru(III)-based AOPs.

Chemically Etched Prussian Blue Analog-WS2 Composite as a Precatalyst for Enhanced Electrocatalytic Water Oxidation in Alkaline Media.

The electrochemical water-splitting reaction is a promising source of ecofriendly hydrogen fuel. However, the oxygen evolution reaction (OER) at the anode impedes the overall process due to its four-electron oxidation steps. To address this issue, we developed a highly efficient and cost-effective electrocatalyst by transforming Co-Fe Prussian blue analog nanocubes into hollow nanocages using dimethylformamide as a mild etchant and then anchoring tungsten disulfide (WS2) nanoflowers onto the cages to boost OER efficiency. The resulting hybrid catalyst-derived oxide demonstrated a low overpotential of 290 mV at a current density of 10 mA cm-2 with a Tafel slope of 75 mV dec-1 in 1.0 M KOH and a high faradaic efficiency of 89.4%. These results were achieved through the abundant electrocatalytically active sites, enhanced surface permeability, and high electronic conductivity provided by WS2 nanoflowers and the porous three-dimensional (3D) architecture of the nanocages. Our research work uniquely combines surface etching of Co-Fe PBA with WS2 growth to create a promising OER electrocatalyst. This study provides a potential solution to the challenge of the OER in electrochemical water-splitting, contributing to UN SDG 7: Affordable and clean energy.

Enhanced Oxidation of Antibiotics by Ferrate Mediated with Natural Organic Matter: Role of Phenolic Moieties.

The increasing presence of antibiotics in water sources threatens public health and ecosystems. Various treatments have been previously applied to degrade antibiotics, yet their efficiency is commonly hindered by the presence of natural organic matter (NOM) in water. On the contrary, we show here that nine types of NOM and NOM model compounds improved the removal of trimethoprim and sulfamethoxazole by ferrate(VI) (FeVIO42-, Fe(VI)) under mild alkaline conditions. This is probably associated with the presence of phenolic moieties in NOMs, as suggested by first-order kinetics using NOM, phenol, and hydroquinone. Electron paramagnetic resonance reveals that NOM radicals are generated within milliseconds in the Fe(VI)-NOM system via single-electron transfer from NOM to Fe(VI) with the formation of Fe(V). The dominance of the Fe(V) reaction with antibiotics resulted in their enhanced removal despite concurrent reactions between Fe(V) and NOM moieties, the radicals, and water. Kinetic modeling considering Fe(V) explains the enhanced kinetics of antibiotics abatement at low phenol concentrations. Experiments with humic and fulvic acids of lake and river waters show similar results, thus supporting the enhanced abatement of antibiotics in real water situations.

Enhancing the catalytic OER performance of MoS2via Fe and Co doping.

Enhancing the sluggish kinetics of the electrochemical oxygen evolution reaction (OER) is crucial for many clean-energy production technologies. Although much progress has been made in recent years, developing active, stable, and cost-effective OER electrocatalysts is still challenging. The layered MoS2, based on Earth-abundant elements, is widely explored as a promising hydrogen evolution electrocatalyst but exhibits poor OER activity. Here, we report a facile strategy to improve the sluggish OER of MoS2 through co-doping MoS2 nanosheets with Fe and Co atoms. The synergistic effect obtained by adjusting the Co/Fe ratio in the Fe-Co doped MoS2 induces electronic and structural modifications and a richer active surface area morphology resulting in a relatively low OER overpotential of 380 mV (at 10 mA cm-2). The electronic modulation upon doping was further supported by DFT calculations that show favorable interaction with the OER intermediate species, thus reducing the energy barrier for the OER. This work paves the way for future strategies for tailoring the electronic properties of transition-metal dichalcogenides (TMDCs) to activate the structure for the sluggish OER with the assistance of non-noble-metal materials.

The Role of Common Alcoholic Sacrificial Agents in Photocatalysis: Is It Always Trivial?

Photocatalytic hydrogen production is proposed as a sustainable energy source. Simultaneous reduction and oxidation of water is a complex multistep reaction with high overpotential. Photocatalytic processes involving semiconductors transfer electrons from the valence band to the conduction band. Sacrificial substrates that react with the photochemically formed holes in the valence band are often used to study the mechanism of H2 production, as they scavenge the holes and hinder charge carrier recombination (electron-hole pairs). Here, we show that the desired sacrificial agent is one forming a radical that is a fairly strong reducing agent, and whose oxidized form is not a good electron acceptor that might suppress the hydrogen evolution reaction (HER). In an acidic medium, methanol was found to fulfill both these requirements better than ethanol and propan-2-ol in the TiO2 -(M0 -NPs) (M=Au or Pt) system, whereas in an alkaline medium, the alcohols exhibit a reverse order of activity. Moreover, we report that CH2 (OH)2 is by far the most efficient sacrificial agent in a nontrivial mechanism in acidic media. Our study provides general guidelines for choosing an appropriate sacrificial substrate and helps to explain the variance in the performance of alcohol scavenger-based photocatalytic systems.