Search results for: ionicity

Authors: Hamad R. Jappor, Zeyad Adnan Saleh, Mudar A. Abdulsattar

Abstract:

The ab initio restricted Hartree-Fock method is used to simulate the electronic structure of indium phosphide (InP) nanocrystals (NCs) (216-738 atoms) with sizes ranging up to about 2.5 nm in diameter. The calculations are divided into two parts, surface, and core. The oxygenated (001)-(1×1) facet that expands with larger sizes of nanocrystals is investigated to determine the rule of the surface in nanocrystals electronic structure. Results show that lattice constant and ionicity of the core part show decreasing order as nanocrystals grow up in size. The smallest investigated nanocrystal is 1.6% larger in lattice constant and 131.05% larger in ionicity than the converged value of largest investigated nanocrystal. Increasing nanocrystals size also resulted in an increase of core cohesive energy (absolute value), increase of core energy gap, and increase of core valence. The surface states are found mostly non-degenerated because of the effect of surface discontinuity and oxygen atoms. Valence bandwidth is wider on the surface due to splitting and oxygen atoms. The method also shows fluctuations in the converged energy gap, valence bandwidth and cohesive energy of core part of nanocrystals duo to shape variation. The present work suggests the addition of ionicity and lattice constant to the quantities that are affected by quantum confinement phenomenon. The method of the present model has threefold results; it can be used to approach the electronic structure of crystals bulk, surface, and nanocrystals.

Keywords: InP, nanocrystals core, ionicity, Hartree-Fock method, large unit cell

Procedia PDF Downloads 362

Authors: Julian Mehler, Marcus Fischer, Martin Hartmann, Peter S. Schulz

Abstract:

During the last two decades, the synthesis of metal-organic frameworks (MOFs) has gained ever increasing attention. Based on their pore size and shape as well as host-guest interactions, they are of interest for numerous fields related to porous materials, like catalysis and gas separation. Usually, MOF-synthesis takes place in an organic solvent between room temperature and approximately 220 °C, with mixtures of polyfunctional organic linker molecules and metal precursors as substrates. Reaction temperatures above the boiling point of the solvent, i.e. solvothermal reactions, are run in autoclaves or sealed glass vessels under autogenous pressures. A relatively new approach for the synthesis of MOFs is the so-called ionothermal synthesis route. It applies an ionic liquid as a solvent, which can serve as a structure-directing template and/or a charge-compensating agent in the final coordination polymer structure. Furthermore, this method often allows for less harsh reaction conditions than the solvothermal route. Here a variation of the ionothermal approach is reported, where the ionic liquid also serves as an organic linker source. By using 1-ethyl-3-methylimidazolium terephthalates ([EMIM][Hbdc] and [EMIM]₂[bdc]), the one-step synthesis of MIL-53(Al)/Boehemite composites with interesting features is possible. The resulting material is already formed at moderate temperatures (90-130 °C) and is stabilized in the usually unfavored ht-phase. Additionally, in contrast to already published procedures for MIL-53(Al) synthesis, no further activation at high temperatures is mandatory. A full characterization of this novel composite material is provided, including XRD, SS-NMR, El-Al., SEM as well as sorption measurements and its interesting features are compared to MIL-53(Al) samples produced by the classical solvothermal route. Furthermore, the syntheses of the applied ionic liquids and salts is discussed. The influence of the degree of ionicity of the linker source [EMIM]x[H(2-x)bdc] on the crystal structure and the achievable synthesis temperature are investigated and give insight into the role of the IL during synthesis. Aside from the synthesis of MIL-53 from EMIM terephthalates, the use of the phosphonium cation in this approach is discussed as well. Additionally, the employment of ILs in the preparation of other MOFs is presented briefly. This includes the ZIF-4 framework from the respective imidazolate ILs and chiral camphorate based frameworks from their imidazolium precursors.

Keywords: ionic liquids, ionothermal synthesis, material synthesis, MIL-53, MOFs

Procedia PDF Downloads 167