Alkylation of nitroarenes via Vicarious Nucleophilic Substitution (VNS) was tested experimentally and modelled with DFT calculations. Mechanistic studies reveal intrinsic differences between reactions of archetypal carbanion precursor PhSO2CH2Cl, and alkyl phenyl sulfones, in which benzenesulfinate acts as a leaving group. Accordingly, for the latter precursors steric hindrance develops at the β‐elimination step, that raises energy barrier and results in the formation of byproducts.

A chronoamperometric procedure for the preparation of silver nanoparticles (AgNPs) in aqueous systems with no extra added stabilizing agents is presented. The uniqueness of the prepared nanoparticle systems was explored by theoretical considerations. The proposed theoretical model predicts the structural parameters of the obtained nanoparticle system. The parameters required for the calculations (the zeta potential, conductivity, and effective diffusion coefficient of ionic silver) are available from independently performed measurements. Chronoamperometry at a microelectrode was employed for the evaluation of the effective diffusion coefficient of ionic silver present in the AgNP solution. The values of AgNP radii predicted by the theoretical model for the selected samples were compared to those obtained by Transmission Electron Microscopy (TEM) and Dynamic Light Scattering (DLS) methods. Because of the high polydispersity of the prepared nanoparticle samples, DLS results were overestimated in comparison to both: the TEM results and some theoretical predictions. By correcting the theoretical predictions by the Debye length, the calculated nanoparticle sizes become comparable (within their expanded uncertainties) to those measured in TEM images, especially for the nanosystems at early stages of their formation via the electrosynthesis process.

Zinc orthostannate, often called zinc tin oxide (ZTO), possesses unique physical characteristics and is a promising wide band gap (3.6 eV) n-type semiconductor material for a broad range of applications. The standard solid-state fabrication of ZTO requires prolonged heat treatment of zinc oxide and stannic oxide powders at around 1000 °C. The biggest drawback of this process is the evaporation of zinc oxide during the synthesis. We report an innovative and efficient mechanochemically supported solid-state approach to Li-doped ZTO synthesis with the implementation of a low-melting lithium hydroxide sintering aid, which offers a significant lowering of the sintering temperature down to 850 °C and time to 90 min, maintaining the high quality of the resulting Lidoped ZTO materials. The effect of sintering temperatures in the range 850−900 °C on photoluminescence characteristics of the ZTO materials was studied, and the PL spectra well corroborate with the XPS data and the presence of O as well as Zn or Sn vacancies. The band gap value of the resulting ZTO materials oscillated around 3.6 eV. Moreover, a comprehensive spectroscopic and microscopic examination of the optimized Li-doped ZTO materials provided more profound insight into its vacancy-mediated formation via liquid-phase sintering and its gradual advancement in the low-temperature regime of 850−900 °C. Additionally, the surface analysis of the selected highest quality materials enabled the determination of the Zn diffusion from the Li-doped ZTO lattice to its surface, expanding the knowledge of the diffusion−evaporation process.