LCA of recycling aluminium incineration bottom ash, dross and shavings in a rotary furnace and environmental benefits of salt-slag valorisation.

Recycling aluminium in a rotary furnace with salt-fluxes allows recovering valuable alloys from hard-to-recycle waste/side-streams such as packaging, dross and incinerator bottom ash. However, this recycling route generates large amounts of salt-slag/salt-cake hazardous wastes which can pose critical environmental risks if landfilled. To tackle this issue, the metallurgical industry has developed processes to valorise the salt-slag residues into recyclable salts and aluminium concentrates, while producing by-products such as ammonium sulphate and non-metallic compounds (NMCs), with applications in the construction or chemical industries. This study aims to assess through LCA the environmental impacts of recycling aluminium in rotary furnaces for both salt-slag management routes: valorisation or landfill. It was found that this recycling process brings forth considerable net environmental profits, which increase for all the considered impact categories if the salt-slag is valorised. The main benefits arise from the production of secondary cast aluminium alloys, which is not unexpected due to the high energy intensity of aluminium primary production. However, the LCA results also identify other hotspots which play a significant role, and which should be considered for the optimisation of the process based on its environmental performance, such as the production of by-products, the consumption of energy/fuels and the avoidance of landfilling waste. Additionally, the assessment shows that the indicators for mineral resource scarcity, human carcinogenic toxicity and terrestrial ecotoxicity are particularly benefited by the salt-slag valorisation. Finally, a sensitivity analysis illustrates the criticality of the metal yield assumptions when calculating the global warming potential of aluminium recycling routes.

Janus Electrochemistry: Asymmetric Functionalization in One Step.

Janus structures represent an overwhelming member of materials with adaptable chemical and physical properties. Development of new synthesis routes has allowed the fabrication of Janus architectures with specific characteristics depending on the final applications. In the case of the membranes, the improvement of wet routes has been limited to the capillary effect, in which the solution can gradually penetrate through the membrane, avoiding a double modification different at each face of the membrane. In this work, we propose a new electrochemical methodology to circumvent the capillary limitation and obtain a double electrochemical functionalization in only one step in a controlled way. This innovative methodology has been validated using a tridirectional spectroelectrochemistry setup. Moreover, the information provided by this optical arrangement should be especially useful for the study of the different processes (ion transfer, assisted ion transfer, and electron transfer) that can take place at liquid/liquid interfaces. Janus electrochemistry allows us to modify the two faces of a free-standing single-walled carbon nanotube electrode in a single experiment. As proof of concept, the free-standing films have been functionalized with two different conducting polymers, polyaniline and poly(3-hexylthiophene), in one electrochemical experiment. According to the obtained results, this new electrochemical methodology will open new gates for the design and functionalization of Janus materials.

Magnetic Propulsion of Recyclable Catalytic Nanocleaners for Pollutant Degradation.

Electrochemically fabricated magnetic mesoporous CoNi@Pt nanorods are excellent nanomotors with controlled magnetic propulsion and excellent catalytic properties. The core-shell structure allows a double functionality: (i) controlled motion of the nanorods by applying rotating magnetic fields at different frequencies and field strengths and (ii) effective catalytic activity of the platinum shell for reactions involving sodium borohydride. The structure and magnetic properties of the CoNi core are not modified by the presence of the Pt shell. Nanorods were propelled via a tumbling-like dynamic by a rotating magnetic field. While in absence of NaBH4, nanorods move at constant speed showing a linear path; in the presence of NaBH4, they showed an intermittent trajectory. These catalytic nanorods can be used as nanocleaners with controlled directionality for pollutants degradation in the presence of borohydride. Their magnetic character allows control of the velocity and the direction throughout the contaminated solution by degrading the different pollutants in their path. The magnetic character of nanorods also allows their easy recycling.

Green electrochemical template synthesis of CoPt nanoparticles with tunable size, composition, and magnetism from microemulsions using an ionic liquid (bmimPF6).

Electrodeposition from microemulsions using ionic liquids is revealed as a green method for synthesizing magnetic alloyed nanoparticles, avoiding the use of aggressive reducing agents. Microemulsions containing droplets of aqueous solution (electrolytic solution containing Pt(IV) and Co(II) ions) in an ionic liquid (bmimPF6) define nanoreactors in which the electrochemical reduction takes place. Highly crystalline hcp alloyed CoPt nanoparticles, in the 10-120 nm range with a rather narrow size distribution, have been deposited on a conductive substrate. The relative amount of aqueous solution to ionic liquid determines the size of the nanoreactors, which serve as nanotemplates for the growth of the nanoparticles and hence determine their size and distribution. Further, the stoichiometry (Pt(x)Co(1-x)) of the particles can be tuned by the composition of the electrolytic solution inside the droplets. The control of the size and composition of the particles allows tailoring the room-temperature magnetic behavior of the nanoparticles from superparaparamagnetic to hard magnetic (with a coercivity of HC = 4100 Oe) in the as-obtained state.

Electrochemical Synthesis of Mesoporous CoPt Nanowires for Methanol Oxidation.

A new electrochemical method to synthesize mesoporous nanowires of alloys has been developed. Electrochemical deposition in ionic liquid-in-water (IL/W) microemulsion has been successful to grow mesoporous CoPt nanowires in the interior of polycarbonate membranes. The viscosity of the medium was high, but it did not avoid the entrance of the microemulsion in the interior of the membrane's channels. The structure of the IL/W microemulsions, with droplets of ionic liquid (4 nm average diameter) dispersed in CoPt aqueous solution, defined the structure of the nanowires, with pores of a few nanometers, because CoPt alloy deposited only from the aqueous component of the microemulsion. The electrodeposition in IL/W microemulsion allows obtaining mesoporous structures in which the small pores must correspond to the size of the droplets of the electrolytic aqueous component of the microemulsion. The IL main phase is like a template for the confined electrodeposition. The comparison of the electrocatalytic behaviours towards methanol oxidation of mesoporous and compact CoPt nanowires of the same composition, demonstrated the porosity of the material. For the same material mass, the CoPt mesoporous nanowires present a surface area 16 times greater than compact ones, and comparable to that observed for commercial carbon-supported platinum nanoparticles.

Conductive microemulsions for template CoNi electrodeposition.

Microemulsions have been revealed as feasible templates to grow magnetic nanostructures using an electrodeposition method. Reducing agents are not required and the applied potential has been used as driving force of the nanostructure growth. A systematic study of conductive microemulsion systems to allow the CoNi electrodeposition process has been performed. Different surfactants and organic components have been tested to form microemulsions with a CoNi electrolytic bath as an aqueous component in order to define the microemulsions showing enough conductivity to perform an electrodeposition process from the aqueous component. By using microemulsions of the aqueous electrolyte solution-Triton X-100-diisopropyl adipate system, CoNi electrodeposition has been achieved, the structure of the deposits being dependent on the composition and structure of the microemulsion, which can act as a soft-template to obtain different discontinuous deposits. The magnetic properties of the CoNi deposits vary with their structure.

Measurement of the giant magnetoresistance effect in cobalt-silver magnetic nanostructures: nanoparticles.

Cobalt-silver (Co-Ag) core-shell nanoparticles with different silver thicknesses were prepared by the microemulsion method in a two-step reduction process. Transmission electron microscopy (TEM) characterization revealed the almost monodispersity and nanometric size (in the range 3-5 nm depending on the shell thickness) of the synthesized nanoparticles. However, it was the use of high-resolution TEM that revealed the correct core-shell formation of the nanometric material. The selected area electron diffraction pattern indicated the fcc (face-centered cubic) and hcp (hexagonal close packed) nature for silver and cobalt, respectively. Cyclic voltammetry also allowed the correct core-shell formation to be assured. The magnetic properties revealed the presence of both superparamagnetic and ferromagnetic contributions. Because of the lack of methodology, it was necessary to develop a method to measure the magnetotransport properties of the prepared nanoparticles. The strategy which followed was successful as it was possible to measure these properties: giant magnetoresistance values of 0.1% at room temperature were obtained. The numerical analysis of magnetic and magnetoresistance data indicated the presence of superparamagnetic particles showing interaction among the magnetic moments.

Photo-controllable electronic switches based on azopyridine derivatives.

Stable photo-controllable electronic switches based on new light-sensitive azopyridines are reported herein. Such systems produce notable variations in the cathodic current density on working at low reduction potentials when UV light falls on them. The appropriate design of the azopyridine chromophore allows modulating the response time of the final opto-electronic switch.

Electrodeposition of Co-Ag films and compositional determination by electrochemical methods.

An electrolytic bath containing silver(I), cobalt(II) and different complexing agents to electrodeposit Co-Ag coatings over vitreous carbon and silicon/seed-layer substrates is proposed. In situ electrochemical characterization of thin deposits is performed by means of stripping (potentiodynamic or galvanostatic) methods. These techniques allow detecting the heterogeneous codeposition of cobalt and silver. Electrochemical ex situ methods (polarographic and voltammetric methods) are implemented to quantify the silver and cobalt percentage in the coatings. Optimal analytical parameters for voltammetric method are established.