Search Results
Controlling palladium morphology in electrodeposition from nanoparticles to dendrites via the use of mixed solvents
By changing the mole fraction of water (χwater) in the solvent acetonitrile (MeCN), we report a simple procedure to control nanostructure morphology during electrodeposition. We focus on the electrodeposition of palladium (Pd) on electron beam transparent boron-doped diamond (BDD) electrodes. Three solutions are employed, MeCN rich (90% v/v MeCN, χwater = 0.246), equal volumes (50% v/v MeCN, χwater = 0.743) and water rich (10% v/v MeCN, χwater = 0.963), with electrodeposition carried out under a constant, and high overpotential (−1.0 V), for fixed time periods (50, 150 and 300 s). Scanning transmission electron microscopy (STEM) reveals that in MeCN rich solution, Pd atoms, amorphous atom clusters and (majority) nanoparticles (NPs) result. As water content is increased, NPs are again evident but also elongated and defected nanostructures which grow in prominence with time. In the water rich environment, NPs and branched, concave and star-like Pd nanostructures are now seen, which with time translate to aggregated porous structures and ultimately dendrites. We attribute these observations to the role MeCN adsorption on Pd surfaces plays in retarding metal nucleation and growth.
Nanorattles with tailored electric field enhancement
Nanorattles are metallic core-shell particles with core and shell separated by a dielectric spacer. These nanorattles have been identified as a promising class of nanoparticles, due to their extraordinary high electric-field enhancement inside the cavity. Limiting factors are reproducibility and loss of axial symmetry owing to the movable metal core; movement of the core results in fluctuation of the nanocavity dimensions and commensurate variations in enhancement factor. We present a novel synthetic approach for the robust fixation of the central gold rod within a well-defined box, which results in an axisymmetric nanorattle. We determine the structure of the resulting axisymmetric nanorattles by advanced transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS). Optical absorption and scattering cross-sections obtained from UV-vis-NIR spectroscopy quantitatively agree with finite-difference time-domain (FDTD) simulations based on the structural model derived from SAXS. The predictions of high and homogenous field enhancement are evidenced by scanning TEM electron energy loss spectroscopy (STEM-EELS) measurement on single-particle level. Thus, comprehensive understanding of structural and optical properties is achieved for this class of nanoparticles, paving the way for photonic applications where a defined and robust unit cell is crucial.
Polyacrylonitrile-containing amphiphilic block copolymers: self-assembly and porous membrane formation
The development of hierarchically porous block copolymer (BCP) membranes via the application of the self-assembly and non-solvent induced phase separation (SNIPS) process is one important achievement in BCP science in the last decades. In this work, we present the synthesis of polyacrylonitrile-containing amphiphilic BCPs and their unique microphase separation capability, as well as their applicability for the SNIPS process leading to isoporous integral asymmetric membranes. Poly(styrene-co-acrylonitrile)-b-poly(2-hydroxyethyl methacrylate)s (PSAN-b-PHEMA) are synthesized via a two-step atom transfer radical polymerization (ATRP) procedure rendering PSAN copolymers and BCPs with overall molar masses of up to 82 kDa while maintaining low dispersity index values in the range of Đ = 1.13-1.25. The polymers are characterized using size-exclusion chromatography (SEC) and NMR spectroscopy. Self-assembly capabilities in the bulk state are examined using transmission electron microscopy (TEM) and small-angle X-ray scattering (SAXS) measurements. The fabrication of isoporous integral asymmetric membranes is investigated, and membranes are examined by scanning electron microscopy (SEM). The introduction of acrylonitrile moieties within the membrane matrix could improve the membranes’ mechanical properties, which was confirmed by nanomechanical analysis using atomic force microscopy (AFM).