Shaping gold nanocomposites with tunable optical properties

We report the synthesis of morphological uniform composites using miniemulsions of poly(tert-butyl acrylate) or poly(styrene) containing organically capped gold nanocrystals (NCs). The optical features of such hybrid structures are dominated by plasmonic effects and depend critically on the morphology of the resulting nanocomposite. In particular, we demonstrate the ability to tune the overall optical response in the visible spectral region by varying the Au NCs arrangement within the polymer matrix, and therefore the interparticle plasmon coupling, using Au NCs resulting from the same batch of synthesis. This is a consequence of two well-known effects on the optical properties of Au particles: the variation of the surrounding dielectric refractive index and interparticle plasmonic coupling. The research reported here shows a general strategy to produce optical responsive nanocomposites via control of the morphology of submicrometric polymer particles containing metal nanocrystals and thus is an alternative to the more common strategy of size tuning metal nanoparticles used as nanofillers

Mechanistic insights into the reversible lithium storage in an open porous carbon via metal cluster formation in all solid-state batteries

Porous carbons are promising anode materials for next generation lithium batteries due to their large lithium storage capacities. However, their high voltage slope during lithiation and delithiation as well as capacity fading due to intense formation of solid electrolyte interphase (SEI) limit their gravimetric and volumetric energy densities. Herein we compare a microporous carbide-derived carbon material (MPC) as promising future anode for all solid-state batteries with a commercial high-performance hard carbon anode. The MPC obtains high and reversible lithiation capacities of 1000 mAh g−1carbon in half-cells exhibiting an extended plateau region near 0 V vs. Li/Li+ preferable for full-cell application. The well-defined micro porosity of the MPC with a specific surface area of >1500 m2 g−1 combines well with the argyrodite-type electrolyte (Li6PS5Cl) suppressing extensive SEI formation to deliver high coulombic efficiencies. Preliminary full-cell measurements vs. nickel-rich NMC-cathodes (LiNi0.9Co0.05Mn0.05O2) provide a considerably improved average potential of 3.76 V leading to a projected energy density as high as 449 Wh kg−1 and reversible cycling for more than 60 cycles. 7Li Nuclear Magnetic Resonance spectroscopy was combined with ex-situ Small Angle X-ray Scattering to elucidate the storage mechanism of lithium inside the carbon matrix. The formation of extended quasi-metallic lithium clusters after electrochemical lithiation was revealed

Multifunctional hybrid materials based on transparent poly(methyl methacrylate) reinforced by lanthanoid hydroxo clusters

Three pentanuclear lanthanoid hydroxo clusters of composition [Ln(OH)5(abzm)10], where Ln = Eu, Tb,Ho and abzm = di(4-allyloxy)benzoylmethanide, have been prepared. The structures have beencharacterised by means of IR, Raman, elemental analyses and X-ray diffraction, showing a pyramidalsquare-based cluster core. The clusters (Tb and Ho) exhibit Curie?Weiss Law behaviour, displayingantiferromagnetic ordering at low temperatures. The emission properties of the Eu cluster demonstratethe abzm- ligand is an efficient antenna (lex = 420 nm) only for the sensitisation of Eu luminescence inthe visible range, via energy transfer to the 5D0 state of the trivalent metal. The clusters have beenreacted in the presence of methyl methacrylate and azobisisobutyronitrile to prepare reinforcedpolymers via radical polymerisation. The obtained materials exhibit swelling upon immersion intoorganic solvents up to 110% of their original size, in agreement with the presence of cluster-crosslinked polymeric chains. Also, no loss of transparency was observed in the preparation of the materials. The characteristic red emission of the Eu cluster in also retained in the polymeric material