From Chain- to Graphene-like Hydroxyl-terminated (ZnO)n Clusters with n≤6 Obtained via Zinc Dimethoxide Hydrolysis and Condensation: Ab initio Structural, Electronic, Vibrational and Optical Properties Calculations.

Recent reports are focusing on the structural evolution from the atomic-scale and also at the expenses of alkyl zinc alkoxide precursors towards (ZnO)n clusters and nanostructures with different interesting motifs, but still not much is known about their electronic properties. In this manuscript, we present a theoretical study using DFT and TD-DFT methodologies on the hydrolysis and condensation of zinc dimethoxide precursor in its monomeric, dimeric and trimeric forms towards thermodynamically stable hydroxyl-terminated (ZnO)n clusters with novel chain- and graphene-like fashions. For all cases, distinct vibrational and optical spectra features were assigned evidencing a global monotonic decrease in the opto-electronic gap with increasing oligomerization and cyclization stages. In addition, the electron-affinity of all clusters was also observed to be enhanced with increasing oligomerization and cyclization stages and the electronic charge localization in -e charged clusters was observed to be strongly related to the presence of zinc-oxo subunits and other particular structural features. Our calculations also indicate that the stabilization through hydroxyl termination of both chain- and graphene-like ZnO clusters not only could be a promising driving force to obtain larger atomic-scale 1D and 2D nanostructures but also envisage interesting properties, particularly as electronic acceptor materials for energy applications.

Hybrid Organic-Inorganic Materials and Interfaces With Mixed Ionic-Electronic Transport Properties: Advances in Experimental and Theoretical Approaches.

The main goal of this mini-review is to provide an updated state-of-the-art of the hybrid organic-inorganic materials focusing mainly on interface phenomena involving ionic and electronic transport properties. First, we review the most relevant preparation techniques and the structural features of hybrid organic-inorganic materials prepared by solution-phase reaction of inorganic/organic precursor into organic/inorganic hosts and vapor-phase infiltration of the inorganic precursor into organic hosts and molecular layer deposition of organic precursor onto the inorganic surface. Particular emphasis is given to the advances in joint experimental and theoretical studies discussing diverse types of computational simulations for hybrid-organic materials and interfaces. We make a specific revision on the separately ionic, and electronic transport properties of these hybrid organic-inorganic materials focusing mostly on interface phenomena. Finally, we deepen into mixed ionic-electronic transport properties and provide our concluding remarks and give some perspectives about this growing field of research.

Mini-Review: Mixed Ionic-Electronic Charge Carrier Localization and Transport in Hybrid Organic-Inorganic Nanomaterials.

In this mini-review, a comprehensive discussion on the state of the art of hybrid organic-inorganic mixed ionic-electronic conductors (hOI-MIECs) is given, focusing on conducting polymer nanocomposites comprising inorganic nanoparticles ranging from ceramic-in-polymer to polymer-in-ceramic concentration regimes. First, a brief discussion on fundamental aspects of mixed ionic-electronic transport phenomena considering the charge carrier transport at bulk regions together with the effect of the organic-inorganic interphase of hybrid nanocomposites is presented. We also make a recount of updated instrumentation techniques to characterize structure, microstructure, chemical composition, and mixed ionic-electronic transport with special focus on those relevant for hOI-MIECs. Raman imaging and impedance spectroscopy instrumentation techniques are particularly discussed as relatively simple and versatile tools to study the charge carrier localization and transport at different regions of hOI-MIECs including both bulk and interphase regions to shed some light on the mixed ionic-electronic transport mechanism. In addition, we will also refer to different device assembly configurations and in situ/operando measurements experiments to analyze mixed ionic-electronic conduction phenomena for different specific applications. Finally, we will also review the broad range of promising applications of hOI-MIECs, mainly in the field of energy storage and conversion, but also in the emerging field of electronics and bioelectronics.

Experimental and Theoretical Study of Ionic Pair Dissociation in a Lithium Ion-Linear Polyethylenimine-Polyacrylonitrile Blend for Solid Polymer Electrolytes.

Herein, we report the preparation and characterization of a novel polymeric blend between linear polyethylene imine (PEI) and polyacrylonitrile (PAN), with the purpose of facilitating the dissociation of lithium perchlorate salt (LiClO4) and thus to enhance Li ion transport. It is a joint theoretical and experimental procedure for evaluating and thus demonstrating the lithium salt dissociation. The procedure implies the correlation between the theoretical pair distribution function (PDF) and conventional X-ray diffraction (XRD) by means of a molecular dynamics (MD) approach. Additionally, we correlated the experimental and theoretical Raman and infrared spectroscopy for vibrational characterization of the lithium salt after dissociation in the polymeric blend. We also performed confocal Raman microscopy analysis to evidence the homogeneity on the distribution of all components and the LiClO4 dissociation in the polymer blend. The electrochemical impedance analysis confirmed that the Li-PAN-PEI blend presents a slightly better lithium conductivity of ∼8 × 10-7 S cm-1. These results suggest that this polymer blend material is promising for the development of novel fluorine-free solid polymer lithium ion electrolytes, and the methodology is suitable for characterizing similar polymeric systems.