One-Pot Synthesis of Copper Iodide-Polypyrrole Nanocomposites

A novel one-pot chemical synthesis of functional copper iodide-polypyrrole composites, CuI-PPy, has been proposed. The fabrication process allows the formation of nanodimensional metal salt/polymer hybrid structures in a fully controlled time- and concentration-dependent manner. The impact of certain experimental conditions, viz., duration of synthesis, sequence of component addition and concentrations of the intact reagents on the structure, dimensionality and yield of the end-product was evaluated in detail. More specifically, the amount of marshite CuI within the hybrid composite can be ranged from 60 to 90 wt.%, depending on synthetic conditions (type and concentration of components, process duration). In addition, the conditions allowing the synthesis of nano-sized CuI distributed inside the polypyrrole matrix were found. A high morphological stability and reproducibility of the synthesized nanodimensional metal-polymer hybrid materials were approved. Finally, the electrochemical activity of the formed composites was verified by cyclic voltammetry studies. The stability of CuI-PPy composite deposited on the electrodes was strongly affected by the applied anodic limit. The proposed one-pot synthesis of the hybrid nanodimensional copper iodide-polypyrrole composites is highly innovative, meets the requirements of Green Chemistry and is potentially useful for future biosensor development. In addition, this study is expected to generally contribute to the knowledge on the hybrid nano-based composites with tailored properties

2D/3D Metallic Nano-objects Self-Organized in an Organic Molecular Thin Film

We present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF4). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner. The evolution of the morphology and electronic properties of such structures as a function of nominal metal content is studied under UHV conditions using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), and photoelectron spectroscopy (PES) techniques. Using HR-TEM, we have observed the periodicity of atomic planes of individual silver NPs. The steady formation of agglomerates from individual single nanocrystallites with intercrystallite boundaries is observed as well. PES reveals generally weak chemical interactions between silver and the organic matrix and n-doping of CuPcF4 at the initial stages of silver deposition, which is associated with charge transfer from the 2D wetting layer on the basis of core-level spectra shift analysis. Copyright © 2020 American Chemical Society

Direct electron-beam-induced formation of nanometer-scale carbon structures in STEM. - II. The growth of rods outside the substrate

Electron-beam-induced growth of self-supporting carbon-containing rods outside the substrate has been investigated. The influence of the beam current in the range of 1 to 80 pA on the shape and dimensions of the rods has been determined. Differences in rods growth at the edges of dielectric and metallic substrates have been demonstrated. Energy loss spectra have been recorded during rods formation and then analyzed. The obtained results have been ascribed to the accumulation of electrostatic charges on the formed structures

Direct electron-beam-induced formation of nanometer-scalecarbon structures in STEM. - I. Nature of "long-range" growth outside the substrate

Long-range growth of carbon-containing structures beginning from the edge of the sample has been found to occur under the action of the electron beam passing outside the sample in the column of the microscope pumped down by an oil diffusion pump. The mechanism of the phenomenon is suggested

Can the observed vibration of a cantilever of supersmall mass be explained by quantum theory?

An attempt has been made to test experimentally the consequences of the "alternative quantum theory" by electron microscopy technique. It has been found that the free end of a cantilever of 10-^15 - 10^-16 g in mass performs chaotic jumps of ≲ 100 A amplitude; the mean frequency of jumps of ~ 20 - 30 A amplitude is ~ 1 Hz. An increase in the mass of the object under observation up to (5 - 7).10^-15 g by growing the load on the free end of cantilever results in damping the vibrations for 5 - 10 days. It has been deduced that the obtained results confirm the macroscopic center-of-mass quantum fluctuations and spontaneous localization of the object, predicted by the theory

Heat-Mediated Transformation of PMMA-SiO₂ Core-Shell Particles into Hollow SiO₂ Particles

Changes in the morphology and structure of the core-shell particles of polymethyl methacrylate-silicon dioxide and hollow SiO2 particles during their heat treatment were studied by electron microscopy, infrared spectroscopy, and X-ray diffraction. The polymeric core of the PMMA-SiO2 hybrid particle was found to undergo an unusual transformation when exposed to the electron microscope beam: its shrinkage occurs through the formation of a spherical cavity. It was shown that the process of silica-shell formation occurs in the temperature range of 200–600 °C and is accompanied by the loss of vinyl- and OH-groups. It was determined by the method of X-ray diffraction, that in the place of the interaction of PMMA and the shell, the degree of ordering of the polymer is higher than that in the volume of the polymer core. It was shown that the frequency of the TO3-vibrational mode (asymmetric stretching vibrations of the Si–O–Si bonds) increases with an increase in the annealing temperature, which is associated with the densification of the silicon dioxide shell

Heat-Mediated Transformation of PMMA-SiO2 Core-Shell Particles into Hollow SiO2 Particles

Changes in the morphology and structure of the core-shell particles of polymethyl methacrylate-silicon dioxide and hollow SiO2 particles during their heat treatment were studied by electron microscopy, infrared spectroscopy, and X-ray diffraction. The polymeric core of the PMMA-SiO2 hybrid particle was found to undergo an unusual transformation when exposed to the electron microscope beam: its shrinkage occurs through the formation of a spherical cavity. It was shown that the process of silica-shell formation occurs in the temperature range of 200–600 °C and is accompanied by the loss of vinyl- and OH-groups. It was determined by the method of X-ray diffraction, that in the place of the interaction of PMMA and the shell, the degree of ordering of the polymer is higher than that in the volume of the polymer core. It was shown that the frequency of the TO3-vibrational mode (asymmetric stretching vibrations of the Si–O–Si bonds) increases with an increase in the annealing temperature, which is associated with the densification of the silicon dioxide shell

2D/3D Metallic Nano-objects Self-Organized in an Organic Molecular Thin Film

We present the fabrication and investigation of the properties of nanocomposite structures consisting of two-dimensional (2D) and three-dimensional (3D) metallic nano-objects self-organized on the surface and inside of organic molecular thin-film copper tetrafluorophthalocyanine (CuPcF$_4$). Metallic atoms, deposited under ultrahigh vacuum (UHV) conditions onto the organic ultrathin film, diffuse along the surface and self-assemble into a system of 2D metallic overlayers. At the same time, the majority of the metal atoms diffuse into the organic matrix and self-organize into 3D nanoparticles (NPs) in a well-defined manner. The evolution of the morphology and electronic properties of such structures as a function of nominal metal content is studied under UHV conditions using transmission electron microscopy (TEM), high-resolution transmission electron microscopy (HR-TEM), and photoelectron spectroscopy (PES) techniques. Using HR-TEM, we have observed the periodicity of atomic planes of individual silver NPs. The steady formation of agglomerates from individual single nanocrystallites with intercrystallite boundaries is observed as well. PES reveals generally weak chemical interactions between silver and the organic matrix and n-doping of CuPcF$_4$ at the initial stages of silver deposition, which is associated with charge transfer from the 2D wetting layer on the basis of core-level spectra shift analysis

Synthesis and structure of high-quality films of copper polyphthalocyanine-2D conductive polymer

Sedlovets DM, Shuvalov MV, Vishnevskiy Y, et al. Synthesis and structure of high-quality films of copper polyphthalocyanine-2D conductive polymer. Materials Research Bulletin. 2013;48(10):3955-3960.Copper polyphthalocyanine (CuPPC), a 2D conjugated polymer, is a promising material for electronics and photovoltaics, but its applications were hindered by a poor processability. We propose an experimental approach, by which thin films of CuPPC, can be directly synthesized in a chemical vapor deposition (CVD) set-up at mild temperature (420 degrees C). High polymerization degree and high crystallinity of the films were confirmed by TEM, FTIR and UV-vis studies. From XRD and TEM electron diffraction, we conclude that the polymer has AA layer stacking with the inter-layer distance of 0.32 nm. The assignment of X-ray and TEM diffraction patterns was based on quantum-chemical calculations. Based on the latter, we also discuss electronic structure and conclude that CuPPC is rather a semi-metal than semi-conductor. (c) 2013 Elsevier Ltd. All rights reserved