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Surface activation of catalysts is known to be an efficient process to enhance their activity in catalytic processes. The activation process includes the generation of oxygen vacancies, changing the nature of the catalyst surface from acidic to basic and vice versa, and the reduction of catalyst surface by H2. On the other hand, magnetically separable catalysts are highly beneficial for their utilization in water or biological fluid-based catalytic processes, as they can be easily guided to the target site and recovered. Here, we present the fabrication of CoFe2O4 and composites of Co3O4/CoFe2O4/α-Fe2O3 and Co/CoFe2O4/α-Fe2O3 through solution combustion process to utilize them as catalysts for 4-nitrophenol (4-NP) reduction. Although none of the as-prepared CoFe2O4 and Co3O4/CoFe2O4 was seen to be active in 4-NP reduction reaction, the surface of the composite gets activated by borohydride (NaBH4) treatment to act as a highly active catalyst for 4-NP reduction. X-ray photoelectron spectroscopy of the composite revealed the formation of metal-hydroxide (M–O–H) species of both Co and Fe at its surface due to borohydride treatment. The mechanism of the surface activation and the dynamics of 4-NP reduction of the surface-activated composite have been studied, proposing a possible pathway for the reduction of 4-NP.

International audience; This work reports the effects of four organic compounds (referred to as levelers) on the electrodeposition of Zn on steel from alkaline free-cyanide electrolytes. The additives tested included polyvinylalcohol (PVA) and the condensation products of epichlorhydrin with amines, called polyamines (PAs), that were synthesized using an aliphatic amine (PA-I, from diethylamine and PA-II from diethylamine-triethylamine), and a heterocyclic quaternary imidazolium molecule (PA-Imid, from imidazole). These compounds were evaluated in the absence and in addition to a quaternary ammonium brightener, N-benzyl-3-carboxylpyridinium chloride (3NCP). The imidazole derivative-based polyamine (PA-Imid) causes greater inhibition of the zinc reduction process than the aliphatic polyamine, and more cathodic overpotential is necessary to promote massive metal deposition. The morphology of the deposits is modified when polyamines are added to the bath; more compact and smaller crystals are obtained with PVA as well as with polyamine PA-I. The addition of PA-II as well as PA-Imid yields crystals growing perpendicular to the substrate. The addition of 3NCP with PVA, PA, or PA-Imid increased the deposition overpotential and modified the morphology by diminishing the grain size. In the absence of additives, crystallographic orientation favored the basal Zn(002) with high atomic packing. The addition of the levelers favored the high-angle pyramidal Zn(101) with low atomic packing. The combination of the levelers with (3NCP) favored the prismatic Zn(100) crystallographic orientation. Additives decrease the size of zinc crystals and tend to increase the energy of lattice favoring the growth of pyramidal and prismatic planes.

International audience; The effects of several quaternary ammonium compounds on electrodeposition of zinc onto AISI 1018 carbon steel were studied in an alkaline zincate electrolyte. Tetraethylammonium, tetrabutylammonium, N-benzyltriethylammonium and N-benzyl-3-carboxyl pyridinium cations were examined. The electrochemical behavior and the inhibition of dendrite formation are related to the structure of the ammonium compounds. The presence of either long-chain aliphatic groups or aromatic groups, i.e., with tetrabutylammonium hydroxide (TBAOH) or N-benzyltriethylammonium chloride (NBT) exerts a more effective inhibition of dendrite formation. N-benzyl-3-carboxylpyridinium (3NCP) and tetraethylammonium hydroxide (TEAOH) additives lead to slightly deformed deposit morphology. Crystallographic measurements of the zinc deposits revealed a highly oriented deposit formed in the presence of 3NCP, which favors the dense atomic packing basal plane (002). The presence of TEAOH diminishes slightly the peak of plane (002) and introduces some pyramidal (101) orientation. Addition of NBT or TBAOH favors the formation of low-atomic packing prismatic planes. Additives that increase the overpotential for Zn(II) reduction tend to promote the formation of high-energy low-atomic packing crystallographic planes. Comparison of the effects of these ammonium compounds indicates that the observed effects are related to the hydrophobic and steric interactions introduced to the interface by the size and structure of the ammonium compounds.

Phosphate esters are employed in some agrochemical formulations and have long life time in the Environment. They are neurotoxic to mammals and it is very difficult to hydrolyze them. It is easy to find papers in the literature dealing with transition metal complexes used in the hydrolysis processes of organophosphorous compounds. However, there are few reports related with degradation of phosphate esters with inorganic nanoparticles. In this work bis-4-nitrophenyl phosphate (BNPP) was used as an agrochemical agent model. The BNPP interaction with zero-valent iron nanoparticles (ZVI NPs), in aqueous media, was searched. The concentration of BNPP was 1000 times higher than the ZVI NPs concentration. The average size of the used iron nanoparticles was 10.2 ± 3.2 nm. The BNPP degradation process was monitored by means of UV-visible method. Initially, the BNPP hydrolysis happens through the P-O bonds breaking-off under the action of the ZVI NPs. Subsequently, the nitro groups were reduced to amine groups. The overall process takes place in 10 minutes. The reaction products were identified employing standard substances in adequate concentrations. The iron by-products were isolated and characterized by X-RD. These iron derivatives were identified as magnetite (Fe3O4) and/or maghemite (γ-Fe2O3) and lepidocrocite (γ-FeOOH). A suggested BNPP degradation mechanism will be discussed.

International audience; The effects of vanillin and anisaldehyde on electrodeposition of zinc–cobalt alloys onto AISI 1018 carbon steel were studied in an alkaline gluconate zincate electrolyte. The influence of an additive on the metal discharge depends on the structure of the added molecule and on the nature of the substrate. The composition of the deposit varies during the electrodeposition process. Maximum cobalt content is observed close to the steel–ZnCo interface for ZnCo formed with or without vanillin, but the composition profile becomes more uniform when anisaldehyde is added to the bath. The morphology of Zn-rich Co-alloy coatings was evaluated: Cobalt ions produce porous ZnCo alloys; vanillin induces slightly porous deposits, whereas uniform and more compact deposits were observed with anisaldehyde. Furthermore, a crystallographic study showed that the orientation of the lattice planes changes, with highly oriented deposits produced in the presence of anisaldehyde.