Thermoelectric properties of organic charge transfer salts from first-principle investigations: Role of molecular packing and triiodide anions

The potency of charge transfer (CT) salts in thermoelectric (TE) applications based on (5-CNB-EDT-TTF)4I3 is systematically explored by first-principles calculations combined with Boltzmann transport theory and deformation potential theory, focusing...

Metallic Conduction and Carrier Localization in Two-Dimensional BEDO-TTF Charge-Transfer Solid Crystals

Charge-transfer salts based on bis(ethylenedioxy)tetrathiafulvalene (BEDO-TTF or BO for short) provide a stable two-dimensional (2D) metallic state, while the electrical resistance often shows an upturn at low temperatures below ~10 K. Such 2D weak carrier localization was first recognized for BO salts in the Langmuir–Blodgett films fabricated with fatty acids; however, it has not been characterized in charge-transfer solid crystals. In this paper, we discuss the carrier localization of two crystalline BO charge-transfer salts with or without magnetic ions at low temperatures through the analysis of the weak negative magnetoresistance. The phase coherence lengths deduced with temperature dependence are largely dominated by the electron–electron scattering mechanism. These results indicate that the resistivity upturn at low temperatures is caused by the 2D weak localization. Disorders causing elastic scattering within the metallic domains, such as those of terminal ethylene groups, should be suppressed to prevent the localization.

Innovative Carbon Based Materials for Solid State Hydrogen Storage and Energy Storage

Alkali cluster-intercalated fullerides (ACIF) consist of crystalline nanostructures in which positively charged metal clusters are ionically bond to negatively charged C60 molecules, forming charge-transfer salts. These compounds have been recently investigated with renewed interest, appearing as a novel class of materials for hydrogen storage, thanks to their proven capability to uptake reversibly high amounts of hydrogen via a complex chemisorption mechanism. In this presentation, after a short summary on the hydrogen storage topic, the synthesis, the structural investigation, and the hydrogen storage properties of Li, Na, and mixed Li-Na clusters intercalated fullerides belonging to the families NaxLi12-xC60 (0 ≤ x ≤ 12) and NaxLi6-xC60 (0 ≤ x ≤ 6) will be presented. By manometric and thermal analyses, it has been proved that C60 covalently binds up to 5.5 wt% H2 at moderate temperature and pressure, thanks to the catalytic effect of the intercalated alkali clusters. Moreover, the destabilizing effect of Na in the co-intercalated NaxLi6-xC60 compounds leads to an improvement of the hydrogen-sorption kinetics by about 70%, linked to a decrease in the desorption enthalpy from 62 to 44 kJ/mol H2. The addition of Pt and Pd nanoparticles to Li fullerides increases up to 5.9 wt% H2 the absorption performances and of about 35 % the absorption rate. The ammonia storage properties of Li6C60 have also been investigated, resulting in quite appealing. Being the price of C60 quite high, cheaper C based materials are under examination. Porous biochar from agricultural waste is giving interesting results as electrode materials for high-performance supercapacitors.

Thermodynamic properties of glassy phonon states induced by strong electron correlations in 𝜃-type organic charge transfer salts

The appearance of electron correlations–induced glassy state of low-energy phonons in the non-dimeric organic charge transfer salt in [Formula: see text]-(BEDT-TTF)2CsZn(SCN)4 is considered as a strong evidence of charge lattice coupling in molecular charge transfer salts. We discuss the temperature and the magnetic field dependences of the heat capacity of this salt in terms of the soft potential model to describe the thermodynamic properties of enhanced phonons that occur in molecular glasses. The evaluated [Formula: see text] term of [Formula: see text]-(BEDT-TTF)2CsZn(SCN)4 is about 30 mJ K[Formula: see text] mol[Formula: see text], which is much larger than other charge transfer salts described by the low-temperature approximation of the Debye model. The magnetic fields dependence of the boson peak is almost negligible, but the low-energy term, for example, in the temperature-linear term of heat capacity shows a slight change, probably due to the small amount of localized spin moments. The comparison with other systems is also performed.

A new platform for development of photosystem I based thin films with superior photocurrent: TCNQ charge transfer salts derived from ZIF-8

The photosynthetic protein complex Photosystem I has been incorporated into the metal organic framework ZIF-8 and then reacted with TCNQ to form a conductive charge transfer salt, generating significant photocurrent from a biohybrid photoactive film.