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The activity of monometallic (Pd or Rh) and bimetallic (iron-bearing) catalysts has been tested in the HDC of 4-chlorophenol (4-CP) in aqueous phase. The catalysts were prepared by a simple procedure consisting of incipient wetness impregnation followed by calcination and reduction at different temperatures. This allowed controlling the size, dispersion and oxidation state of the metallic nanoparticles. Increasing the temperature of calcination led to a higher dispersion of the active phase (from 21 to 46% by increasing the calcination temperature from 200 to 400 °C) and a higher ratio of zerovalent to electrodefficient palladium (M 0 /M n + values from 1.15 to 2.17) in the case of the Pd-catalysts. Those calcined in air at 400 °C and reduced with H 2 at 350 °C yielded the highest values of the pseudo-first-order rate constant of 4-CP dechlorination (16.2 L h −1 g cat −1 ). The introduction of iron reduced the metal dispersion of both Pd and Rh but the catalysts maintained their dechlorination activity and showed magnetic properties useful for further separation from the liquid phase. [ABSTRACT FROM AUTHOR]

Abstract Aqueous-phase catalytic hydrodechlorination (HDC) has been scarcely explored in the literature for the removal of chlorinated micropollutants. The aim of this work is to prove the feasibility of this technology for the fast and environmentally-friendly degradation of such kind of compounds. Diclofenac (DCF), a highly consumed anti-inflammatory drug, has been selected as the target pollutant given its toxicity and low biodegradability. The commercial Pd/Al 2 O 3 (1% wt.) catalyst has been used due to its prominent role on this field. Complete degradation of DCF was achieved in a short reaction time (20 min) under ambient conditions (25 °C, 1 atm) at [DCF] 0 = 68 μM; [Pd/Al 2 O 3 ] 0 = 0.5 g L−1 and H 2 flow rate of 50 N mL min−1. Remarkably, the chlorinated intermediate (2-(2-chloroanilino)-phenylacetate (Cl-APA)) generated along reaction was completely removed at the same time, being the chlorine-free compound 2-anilinophenylacetate (APA) the only final product. A reaction scheme based on this consecutive pathway and a pseudo-first-order kinetic model have been proposed. An apparent activation energy of 43 kJ mol−1 was obtained, a comparable value to those previously reported for conventional organochlorinated pollutants. Remarkably, the catalyst exhibited a reasonable stability upon three successive uses, achieving the complete degradation of the drug and obtaining APA as the final product in 30 min. The evolution of ecotoxicity was intimately related to the disappearance of the chlorinated organic compounds and thus, the final HDC effluents were non-toxic. The versatility of the system was finally demonstrated in different environmentally-relevant matrices (wastewater treatment plant effluent and surface water). Graphical abstract Image 1 Highlights • HDC is a fast and environmentally-friendly technology for the removal of diclofenac. • The commercial Pd/Al 2 O 3 catalyst showed a high activity and a reasonable stability. • A kinetic model based on a consecutive reaction pathway fitted the experimental data. • Non-toxic effluents were achieved at the end of reaction. • The versatility of the system was proved in environmentally-relevant water matrices. [ABSTRACT FROM AUTHOR]

The production and application of ionic liquids (ILs) is often associated with the formation of aqueous effluents. Due to the well-known toxicity and poor biodegradability of those compounds, effective treatments for their removal from aqueous solutions are required. In this work, the Fenton oxidation methodology under optimum operating conditions (50 mg L −1 Fe 3+ , stoichiometric dose of H 2 O 2 , 70 °C and pH 0 = 3) was investigated in eleven different ILs, based in the imidazolium, phosphonium, quaternary ammonium, pyridinium and cholinium families, conjugated with various inorganic and organic anions such as chloride, cyanoborate, cyanamide, thiocyanate, dimethylphosphate and tosylate. The efficacy of the process was evaluated by the analysis of the chemical oxygen demand (COD), total organic carbon (TOC), the acids formed by ILs oxidation and the toxicity of the non-treated and treated aqueous effluents towards the Vibrio fischeri bacteria. It was possible to identify the main compounds produced upon Fenton oxidation in the final aqueous effluents (acetic, oxalic and formic acids) and the results seem to suggest that the Fenton oxidation is a good degradation methodology for most of the ILs tested, achieving TOC conversions in the range of 40–80% and 30–40% for aromatic and aliphatic ILs, respectively. Furthermore, non-toxic effluents were obtained at the end of the treatment for all the ILs investigated with the exception of the cyano-based ones due to the release of highly toxic cyanide species to the aqueous medium. [ABSTRACT FROM AUTHOR]

• CWPO of the neonicotinoid pesticides listed in the EU Watch List was investigated. • Fast elimination (20 min) of all pesticides and aromatic by-products was achieved. • Mineralization yields above 50% were reached, being the final products short-chain acids. • The application of CWPO warranted the complete removal of ecotoxicity. • The versatility of the process was demonstrated in different water matrices. Neonicotinoid pesticides family is nowadays identified as the most important type of insecticides in the world. Their consequent widespread occurrence in the environment represents not only a well-known risk for bees but also a significant negative impact in aquatic ecosystems. In this work, the capability of catalytic wet peroxide oxidation (CWPO) (Fe 3 O 4 -R400/H 2 O 2) as a low-cost and environmentally-friendly system for the treatment of the neonicotinoid pesticides listed in the EU Watch List (Decision 2018/840) (acetamiprid (ACT), clothianidin (CLT), imidacloprid (IMD), thiacloprid (THC) and thiamethoxam (THM)) has been investigated. Remarkably, complete elimination of the pollutants (1000 μg L−1) and the aromatic by-products was reached in 20 min reaction time operating at 25 °C, 1 atm, and pH 0 = 5, with the stoichiometric H 2 O 2 amount (~4–5 mg L−1) and 1 g L−1 catalyst load. The reactivity order of the insecticides decreased as follows: THC > IMD > THM > CLT > ACT, being the pseudo-first order rate constant values within the range of 0.26–0.61 min−1. Notably, high mineralization yields were obtained (>50%), being the final effluents non-toxic. As example, the oxidation pathway of ACT was proposed. Finally, the catalytic system was tested in real surface water. [ABSTRACT FROM AUTHOR]