Enhancing Magneto-Ionic Effects in Magnetic Nanostructured Films via Conformal Deposition of Nanolayers with Oxygen Acceptor/Donor Capabilities.

Effective manipulation of the magnetic properties of nanostructured metallic alloys, exhibiting intergrain porosity (i.e., channels) and conformally coated with insulating oxide nanolayers, with an electric field is demonstrated. Nanostructured Co-Pt films are grown by electrodeposition (ED) and subsequently coated with either AlOx or HfOx by atomic layer deposition (ALD) to promote magneto-ionic effects (i.e., voltage-driven ion migration) during electrolyte gating. Pronounced variations in coercivity (HC) and magnetic moment at saturation (mS) are found at room temperature after biasing the heterostructures. The application of a negative voltage results in a decrease of HC and an increase of mS, whereas the opposite trend is achieved for positive voltages. Although magneto-ionic phenomena are already observed in uncoated Co-Pt films (because of the inherent presence of oxygen), the ALD oxide nanocoatings serve to drastically enhance the magneto-ionic effects because of partially reversible oxygen migration, driven by voltage, across the interface between AlOx or HfOx and the nanostructured Co-Pt film. Co-Pt/HfOx heterostructures exhibit the most significant magneto-electric response at negative voltages, with an increase of mS up to 76% and a decrease of HC by 58%. The combination of a nanostructured magnetic alloy and a skinlike insulating oxide nanocoating is shown to be appealing to enhance magneto-ionic effects, potentially enabling electrolyte-gated magneto-ionic technology.

Large Magnetoelectric Effects in Electrodeposited Nanoporous Microdisks Driven by Effective Surface Charging and Magneto-Ionics.

A synergetic approach to enhance magnetoelectric effects (i.e., control of magnetism with voltage) and improve energy efficiency in magnetically actuated devices is presented. The investigated material consists of an ordered array of Co-Pt microdisks, in which nanoporosity and partial oxidation are introduced during the synthetic procedure to synergetically boost the effects of electric field. The microdisks are grown by electrodeposition from an electrolyte containing an amphiphilic polymeric surfactant. The bath formulation is designed to favor the incorporation of oxygen in the form of cobalt oxide. A pronounced reduction of coercivity (88%) and a remarkable increase of Kerr signal amplitude (60%) are observed at room temperature upon subjecting the microdisks to negative voltages through an electrical double layer. These large voltage-induced changes in the magnetic properties of the microdisks are due to (i) the high surface-area-to-volume ratio with ultranarrow pore walls (sub-10 nm) that promote enhanced electric charge accumulation and (ii) magneto-ionic effects, where voltage-driven O2- migration promotes a partial reduction of CoO to Co at room temperature. This simple and versatile procedure to fabricate patterned "nano-in-micro" magnetic motifs with adjustable voltage-driven magnetic properties is very appealing for energy-efficient magnetic recording systems and other magnetoelectronic devices.

Tunable Magnetism in Nanoporous CuNi Alloys by Reversible Voltage-Driven Element-Selective Redox Processes.

Voltage-driven manipulation of magnetism in electrodeposited 200 nm thick nanoporous single-phase solid solution Cu20 Ni80 (at%) alloy films (with sub 10 nm pore size) is accomplished by controlled reduction-oxidation (i.e., redox) processes in a protic solvent, namely 1 m NaOH aqueous solution. Owing to the selectivity of the electrochemical processes, the oxidation of the CuNi film mainly occurs on the Cu counterpart of the solid solution, resulting in a Ni-enriched alloy. As a consequence, the magnetic moment at saturation significantly increases (up to 33% enhancement with respect to the as-prepared sample), while only slight changes in coercivity are observed. Conversely, the reduction process brings Cu back to its metallic state and, remarkably, it becomes alloyed to Ni again. The reported phenomenon is fully reversible, thus allowing for the precise adjustment of the magnetic properties of this system through the sign and amplitude of the applied voltage.

Micelle-Assisted Electrodeposition of Mesoporous Fe-Pt Smooth Thin Films and their Electrocatalytic Activity towards the Hydrogen Evolution Reaction.

Mesoporous Fe-Pt thin films are obtained by micelle-assisted electrodeposition onto metallic substrates with dissimilar activity (namely, gold, copper, and aluminum seed layers evaporated on Si/Ti) under constant applied potential (E=-1.1 V vs. Ag/AgCl) and deposition time (600 s). The amphiphilic triblock copolymer Pluronic P-123 is used as a soft template to guide the formation of mesopores. The occurrence of pores (ca. 7 nm in diameter) with narrow size distribution, distributed evenly over the surface, is observed in all cases. Despite the applied conditions being the same, the roughness and the amount of Fe incorporated in the films are influenced by the nature of the substrate. In particular, ultra-smooth films containing a larger amount of Fe (21 wt %) are obtained when deposition takes place on the Au surface. X-ray diffraction analyses reveal that Pt and Fe are alloyed to a certain extent, although some iron oxides/hydroxides also unavoidably form. The resulting films have been tested as electrocatalysts in the hydrogen evolution reaction (HER) in alkaline media. The mesoporous Fe-rich Fe-Pt films on Au show excellent HER activity and cyclability.

Micelle-assisted electrodeposition of highly mesoporous Fe-Pt nodular films with soft magnetic and electrocatalytic properties.

Mesoporous Fe-Pt nodular films (with a regular spatial arrangement of sub-15 nm pores) are grown onto evaporated Au, Cu and Al conductive layers by micelle-assisted electrodeposition from metal chloride salts in the presence of Pluronic P123 tri-block copolymer dissolved in the aqueous electrolytic bath. This synthetic approach constitutes a simple, one-step, versatile procedure to grow multifunctional mesoporous layers appealing for diverse applications that take advantage of materials with an ultra-high surface area-to-volume ratio. The films exhibit tuneable composition with relative Fe/Pt weight ratios, disregarding oxygen, varying from 4/96 to 52/48. All the mesoporous alloys show a soft magnetic behaviour with tuneable saturation magnetization and coercivity values (the latter ranging from ca. 5 Oe to 40 Oe). In addition, the Au/Fe-Pt deposits (even the ones with higher Fe content) exhibit good performance towards hydrogen evolution reaction in both alkaline and acidic media due to the inherent mesoporosity, with excellent stability after running 50 cycles. The interest of alloying Fe with Pt is thus two-fold: (i) to confer magnetic properties to the mesoporous alloys and (ii) to reduce the amount of the costly noble metal in the electrocatalyst in an environmentally sustainable manner.

Degradation of pharmaceutical beta-blockers by electrochemical advanced oxidation processes using a flow plant with a solar compound parabolic collector.

The degradation of the beta-blockers atenolol, metoprolol tartrate and propranolol hydrochloride was studied by electro-Fenton (EF) and solar photoelectro-Fenton (SPEF). Solutions of 10 L of 100 mg L⁻¹ of total organic carbon of each drug in 0.1 M Na2SO4 with 0.5 mM Fe²âº of pH 3.0 were treated in a recirculation flow plant with an electrochemical reactor coupled with a solar compound parabolic collector. Single Pt/carbon felt (CF) and boron-doped diamond (BDD)/air-diffusion electrode (ADE) cells and combined Pt/ADE-Pt/CF and BDD/ADE-Pt/CF cells were used. SPEF treatments were more potent with the latter cell, yielding 95-97% mineralization with 100% of maximum current efficiency and energy consumptions of about 0.250 kWh g TOC⁻¹. However, the Pt/ADE-Pt/CF cell gave much lower energy consumptions of about 0.080 kWh g TOC⁻¹ with slightly lower mineralization of 88-93%, then being more useful for its possible application at industrial level. The EF method led to a poorer mineralization and was more potent using the combined cells by the additional production of hydroxyl radicals (•OH) from Fenton's reaction from the fast Fe²âº regeneration at the CF cathode. Organics were also more rapidly destroyed at BDD than at Pt anode. The decay kinetics of beta-blockers always followed a pseudo first-order reaction, although in SPEF, it was accelerated by the additional production of •OH from the action of UV light of solar irradiation. Aromatic intermediates were also destroyed by hydroxyl radicals. Ultimate carboxylic acids like oxalic and oxamic remained in the treated solutions by EF, but their Fe(III) complexes were photolyzed by solar irradiation in SPEF, thus explaining its higher oxidation power. NO3⁻ was the predominant inorganic ion lost in EF, whereas the SPEF process favored the production of NH4⁺ ion and volatile N-derivatives.

Mineralization of metoprolol by electro-Fenton and photoelectro-Fenton processes.

Solutions of about 0.25 mM of the ß-blocker metoprolol tartrate (100 mg L(-1) total organic carbon) with 0.5 mM Fe(2+) in the presence and absence of 0.1 mM Cu(2+) of pH 3.0 have been comparatively degraded under electro-Fenton (EF) and photoelectro-Fenton (PEF) conditions. The electrolyses were carried out with two systems: (i) a single cell with a boron-doped diamond (BDD) anode and an air-diffusion cathode (ADE) for H(2)O(2) electrogeneration and (ii) a combined cell with a BDD/ADE pair coupled with a Pt/carbon felt (CF) cell. Overall mineralization was reached in all PEF treatments using both systems due to the efficient production of hydroxyl radical ((•)OH) from Fenton's reaction induced by UVA light and the quick photolysis of Fe(III) carboxylate complexes formed. In EF, the combined cell was much more potent than the single one by the larger (•)OH generation from the continuous Fe(2+) regeneration at the CF cathode, accelerating the oxidation of organics. However, almost total mineralization in EF was feasible using the combined cell in the presence of 0.1 mM Cu(2+), because of the parallel quick oxidation of Cu(II) carboxylate complexes by (•)OH. Metoprolol decay always followed a pseudo-first-order reaction. Aromatic products related to consecutive hydroxylation/oxidation reactions of metoprolol were detected by gas chromatography-mass spectrometry. The evolution of the aromatic 4-(2-methoxyethyl)phenol and generated carboxylic acids was followed by HPLC. The degradation rate and mineralization degree of metoprolol tartrate were limited by the removal of Fe(III) and Cu(II) complexes of ultimate carboxylic acids such as formic, oxalic, and oxamic. NH(4)(+) ion and to a lesser extent NO(3)(-) ion were released in all treatments, being quantified by ionic chromatography.

Electro-Fenton and photoelectro-Fenton degradations of the drug beta-blocker propranolol using a Pt anode: identification and evolution of oxidation products.

The beta-blocker propranolol hydrochloride has been degraded by electrochemical advanced oxidation processes like electro-Fenton (EF) and photoelectro-Fenton (PEF) using a single cell with a Pt anode and an air diffusion cathode (ADE) for H(2)O(2) electrogeneration and a combined system containing the above Pt/ADE pair coupled in parallel to a Pt/carbon-felt (CF) cell. Organics are mainly oxidized with hydroxyl radical (OH) formed from Fenton's reaction between added Fe(2+) and electrogenerated H(2)O(2). The PEF treatment in Pt/ADE-Pt/CF system yields almost total mineralization because OH production is enhanced by Fe(2+) regeneration from Fe(3+) reduction at the CF cathode and Fe(III) complexes with generated carboxylic acids are rapidly photodecarboxylated under UVA irradiation. Lower mineralization degree is found for PEF in Pt/ADE cell due to the little influence of UVA light on Fe(2+) regeneration. The homologous EF processes are much less potent as a result of the persistence of Fe(III)-carboxylate complexes. Aromatic intermediates such as 1-naphthol, 1,4-naphthoquinone and phthalic acid and generated carboxylic acids such as pyruvic, glycolic, malonic, maleic, oxamic, oxalic and formic are identified. While chloride ion remains stable, NH(4)(+) and NO(3)(-) ions are released to the medium. A reaction sequence for propranolol hydrochloride mineralization is proposed.