Pablo Martín-Ramos

Rhodamine B removal with activated carbons obtained from lignocellulosic waste

By-products from the wax production process from carnauba palm (leaves), from the extraction of oil from macauba seeds (endocarp) and from pine nut production (shell) have been assessed for activated carbon production, using H3PO4 or CaCl2 for their chemical activation. The resulting activated charcoals have been thoroughly characterized by elemental and thermal analysis, X-ray diffraction, infrared spectroscopy, electron scanning microscopy and N2 adsorption behavior. Subsequently, their adsorption capacity for the removal of rhodamine B (RhB) from aqueous solutions has been evaluated by studying different parameters: contact time, pH, adsorbent dose, initial dye concentration and solution temperature. The adsorption of RhB followed Freundlichs model in all cases. Kinetic studies indicate that the pseudo-second order model can be used for describing the dynamics of the adsorption process. Thermodynamic parameters have also been evaluated, indicating its endothermic and spontaneous nature. Finally, a preliminary analysis of the impact of cellulose content in the carbon precursor materials has been conducted, by using a mixture of native cellulose with one of the lignocellulosic materials.

Novel erbium(III) fluorinated β-diketonate complexes with N,N-donors for optoelectronics: from synthesis to solution-processed devices

Three novel ternary Er3+ complexes emitting in the C band transmission window for fiber optic communications have been synthesised and their structures have been elucidated by single crystal X-ray diffraction. The fluorinated β-diketonate ligand, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, combines a good absorption cross-section in the ultraviolet region with reduction of non-radiative quenching of the Er3+ emission, while the rigidity and bulkiness of the three different N,N-donors (2,2′-bipyridine, bathophenanthroline and 5-nitro-1,10-phenanthroline) have a pronounced impact on the emission intensity of luminescence. Furthermore, the choice of the ancillary ligand also determines the efficiency of the antenna effect, leading to complete quenching of the ligand-associated visible emission for the optimized complex with 5-nitro-1,10-phenanthroline. Solution processed 1.54 μm organic light-emitting diodes have been manufactured and characterized for this complex, confirming the aforementioned complete resonant energy transfer from the ligands to the Er3+ ion. The features of the reported device fabrication show a simple way to obtain large area NIR-OLEDs.

A kinetic study on microwave-assisted conversion of cellulose and lignocellulosic waste into hydroxymethylfurfural/furfural

Native cellulose, lignocellulosic materials from Brazil (carnauba palm leaves and macauba pulp and shell) and pine nut shell from Spain have been studied as substrates for the production of HMF and furfural in a conventional microwave oven. In order to promote the dissolution of native cellulose, several ionic liquids, catalysts, organic solvents and water doses have been assessed. The most suitable mixture (5mL of choline chloride/oxalic acid, 2mL of sulfolane, 2mL of water, 0.02g of TiO2 and 0.1g of substrate) has been chosen to conduct kinetic studies at different reaction times (5-60min) and various temperatures (120-200°C) and to evaluate the best conditions for HMF+furfural production according to Seamans model. The best production yields of HMF+furfural have been attained for native cellulose, with a yield of 53.24% when an ultrasonic pretreatment was used prior to a microwave treatment with stirring.

Novel erbium(III) complexes with 2,6-dimethyl-3,5-heptanedione and different N,N-donor ligands for ormosil and PMMA matrices doping

Three novel complexes, [Er(dmh)3(bipy)], [Er(dmh)3bath] and [Er(dmh)3(5NO2phen)], with 2,6-dimethyl-3,5-heptanedione (Hdmh) as the main sensitizer and either 2,2′-bipyridine (bipy), bathophenanthroline (bath) or 5-nitro-1,10-phenanthroline (5NO2phen) as synergistic ligands were synthesized. Upon excitation at the maximum absorption of the ligands, the complexes show the characteristic near-infrared (NIR) luminescence of the Er3+ ions, due to efficient energy transfer from the ligands to the central Er3+ ion via the antenna effect. Single crystals were grown and their structures were determined showing different Er–N distances. The compound with shorter Er–N distances, [Er(dmh)3(5NO2phen)], was found to be the best light harvester and the best for transferring the energy to the lanthanide among the three studied compounds. Finally, the novel complexes have been assessed for their application in sol–gel and polymer-based waveguides and optical amplifiers through their inclusion into ormosil and polymethylmethacrylate matrices. The dispersion was successful in the bipy and 5NO2phen cases, with the properties of the hybrid materials mimicking those of the pure complexes.

Structure and NIR-luminescence of ytterbium(III) beta-diketonate complexes with 5-nitro-1,10-phenanthroline ancillary ligand: assessment of chain length and fluorination impact

Seven new tris(β-diketonear-nate)ytterbium(III) complexes with the general formula [Yb(β-diketonate)3(5NO2phen)] (where the β-diketone is either 4,4,4-trifluoro-1-(2-naphthyl)-1,3-butanedione, 4,4,4-trifluoro-1-(2-furyl)-1,3-butanedione, 1,1,1-trifluoro-2,4-pentanedione, 1,1,1-trifluoro-5,5-dimethyl-2,4-hexanedione, 1,1,1,5,5,6,6,7,7,7-decafluoro-2,4-heptanedione, 2,4-hexanedione or 2,6-dimethyl-3,5-heptanedione, and 5NO2phen = 5-nitro-1,10-phenanthroline) were synthesized and characterized by elemental analysis, attenuated total reflectance Fourier transform infrared spectroscopy and photoluminescence spectroscopy. Single crystal X-ray structures have been determined for three fluorinated complexes and ground state geometries of the other four complexes have been predicted using the Sparkle/PM6 model. These experimental structures and those designed by semi-empirical models reveal octacoordination around the Yb(3+) ion. Photoluminescence studies and lifetime measurements show that the increase in the fluorinated β-diketonate chain length is associated with a decrease in Yb(3+) luminescence intensity of the (2)F5/2→(2)F7/2 transition at around 980 nm and the (2)F5/2 excited state lifetime, while the ligand lifetime value remains almost unaffected. Finally, fluorination of the ligands is only advised when the complexes are to be used for co-doping with isostructural Er(3+) complexes for optical amplifiers, since it leads to a slight decrease in luminescence intensity for the same β-diketonate chain length.

Polymeric Carbon Nitride Nanosheets

Polymeric carbon nitride was synthesized by polycondensation in a nitrogen flux using melamine cyanurate as a reagent and sulfuric acid as a catalyst. The product was polymeric-graphitic carbon nitride based on heptazine units. The carbon nitride was composed of nanosheet flakes. This synthesis method seems to be a suitable pathway toward carbon nitride graphene formation.

Synthesis of Chitosan Oligomers/Propolis/Silver Nanoparticles Composite Systems and Study of Their Activity against Diplodia seriata

The synthesis and characterization of composites of oligomeric chitosan with propolis extract which allow the incorporation of a third component (silver nanoparticles) are reported, together with their application in aqueous or hydroalcoholic solutions with a view to the formation of adhesive substances or nanofilms for the protection of vineyards against harmful xylophagous fungi. The antimicrobial properties of the association of the two biological products or those resulting from the incorporation of silver nanoparticles (NPs) are studied and discussed. The efficacy of the chitosan oligomers/propolis/silver NPs ternary system is assessed in vitro for Diplodia fungi. A preliminary study on the convenience of replacing propolis with gentisic acid is also presented.

Slow magnetic relaxation and photoluminescent properties of a highly coordinated erbium(III) complex with dibenzoylmethane and 2,2′-bipyridine

A new Er(III) β-diketonate complex, tris(dibenzoylmethanate)mono(2,2′-bipyridine) erbium(III) or [Er(dbm)3(bipy)], has been synthesized and its structural, thermal, photophysical and low temperature magnetic properties have been characterized. In the new complex, Er(III) ions are coordinated by six O atoms and two N atoms in a distorted square antiprismatic geometry. The Er(III) complex exhibits out-of-phase (χM′′) ac susceptibility signals, when a static magnetic field is applied, signaling that at zero field a quantum tunneling regime occurs. The nearly semi-circular and symmetrical shape of the Cole–Cole plots sustains the existence of a single magnetic relaxation process. The solid state luminescent studies show an intense, sharp and narrow emission band in the near infrared region. The combined results demonstrate the ability of dbm and bipy to provide an environment that yields both interesting magnetic and optical properties.

Organic MEMS/NEMS-based high-efficiency 3D ITO-less flexible photovoltaic cells

A novel approach based on three-dimensional (3D) architecture for polymeric photovoltaic cells made up of an array of sub-micron and nano-pillars which not only increase the area of the light absorbing surface, but also improve the carrier collection efficiency of bulk-heterojunction organic solar cells is presented. The approach also introduces coating of 3D anodes with a new solution-processable highly conductive transparent polymer (Orgacon™) that replaces expensive vacuum-deposited ITO (indium tin oxide) as well as the additional hole-collecting layer of conventional PEDOT:PSS (poly(3,4-ethylenedioxythiophene) poly(styrenesulfonate)). In addition, the described procedure is well suited to roll-to-roll high-throughput manufacturing. The high aspect-ratio 3D pillars which form the basis for this new architecture are patterned through micro-electromechanical-system- and nano-electromechanical-system-based processes. For the particular case of P3HT (poly(3-hexylthiophene)) and PCBM (phenyl-C61-butyric acid methyl ester) active material, efficiencies in excess of 6% have been achieved for these photovoltaic cells of 3D architecture using ITO-less flexible PET (polyethylene terephthalate) substrates. This increase in efficiency turns out to be more than twice higher than those achieved for their 2D counterparts.

Structure, luminescence and magnetic properties of an erbium(III) β-diketonate homodinuclear complex

The photoluminescence properties and field-induced single-molecule-magnetic behavior of a novel erbium(III) β-diketonate homodinuclear complex, [Er2(nd)6(μ-bpm)] (nd = 2,4-nonanedione and bpm = 2,2′-bipyrimidine), are presented. On the basis of structural data, ab initio calculations using the SO-CASSCF method have been performed so as to gain insight into the spin-relaxation mechanism, giving evidence of the nature of the mJ ground state and the orientation of the related magnetic anisotropy axis. The overlap integrals between the natural spin orbitals (NSOs) of the mononuclear fragments, related to the magnitude of the antiferromagnetic exchange, show that the two fragments have no magnetic interaction.