ABSTRACT
The era of ever-growing worldwide energy requirements demands the development of new methods of energy conversion, where the design of novel materials and the improvement of the efficiency of existing ones are of great importance [...].
ABSTRACT
For the first time, transition metal-based chalcogenides conforming to the definition of high entropy materials, are synthesized, with the multicomponent occupation being utilized on both cationic and anionic sublattices. The pentlandite-structured (Co,Fe,Ni)9S8 and (Co,Fe,Ni)9(S,Se)8 compositions are obtained using a two-stage, solid-state reaction method. Room temperature structural analysis (XRD, SEM, Raman) in both cases indicates the presence of a homogeneous, single-phase, Fm3[combining macron]m structure, with a profound effect of Se addition on the lattice parameters. The obtained materials possess an excellent electrical conductivity of 105 S m-1, and slightly negative Seebeck coefficient values, resulting from their metallic character, combined with a low thermal conductivity of 2.5 W m-1 K-1, especially when compared with conventional analogues. The optical measurements reveal very promising behavior in the UV/vis range. The electrochemical sensitivity towards hydrazine and acetaminophen is also presented, making them potentially interesting for sensor devices. Based on the DFT analysis of various sub-systems, the origins of the observed transport and optical behavior are explained. Furthermore, it is shown that the application of the high-entropy principle to both sublattices simultaneously allows for extensive tailoring of the band structure, allowing these materials to be optimized with respect to the given application, including thermoelectric and photoelectrochemical devices and catalysis, e.g., the hydrogen evolution reaction.
ABSTRACT
For the first time, an alternative way of improving the stability of Cu-based thermoelectric materials is proposed, with the investigation of two different copper chalcogenide-copper tetrahedrite composites, rich in sulfur and selenium anions, respectively. Based on the preliminary DFT results, which indicate the instability of Sb-doped copper chalcogenide, the Cu1.97S-Cu12Sb4S13 and Cu2-xSe-Cu3SbSe3 composites are obtained using melt-solidification techniques, with the tetrahedrite phase concentration varying from 1 to 10 wt.%. Room temperature structural analysis (XRD, SEM) indicates the two-phase structure of the materials, with ternary phase precipitates embed within the copper chalcogenide matrix. The proposed solution allows for successful blocking of excessive Cu migration, with stable electrical conductivity and Seebeck coefficient values over subsequent thermal cycles. The materials exhibit a p-type, semimetallic character with high stability, represented by a near-constant power factor (PF)-temperature dependences between individual cycles. Finally, the thermoelectric figure-of-merit ZT parameter reaches about 0.26 (623 K) for the Cu1.97S-Cu12Sb4S13 system, in which case increasing content of tetrahedrite is a beneficial effect, and about 0.44 (623 K) for the Cu2-xSe-Cu3SbSe3 system, where increasing the content of Cu3SbSe3 negatively influences the thermoelectric performance.
ABSTRACT
Vibrational spectroscopy can be considered as one of the most important methods used for structural characterization of various porous aluminosilicate materials, including zeolites. On the other hand, vibrational spectra of zeolites are still difficult to interpret, particularly in the pseudolattice region, where bands related to ring oscillations can be observed. Using combination of theoretical and computational approach, a detailed analysis of these regions of spectra is possible; such analysis should be, however, carried out employing models with different level of complexity and simultaneously the same theory level. In this work, an attempt was made to identify ring oscillations in vibrational spectra of selected zeolite structures. A series of ab initio calculations focused on S4R, S6R, and as a novelty, 5-1 isolated clusters, as well as periodic siliceous frameworks built from those building units (ferrierite (FER), mordenite (MOR) and heulandite (HEU) type) have been carried out. Due to the hierarchical structure of zeolite frameworks it can be expected that the total envelope of the zeolite spectra should be with good accuracy a sum of the spectra of structural elements that build each zeolite framework. Based on the results of HF calculations, normal vibrations have been visualized and detailed analysis of pseudolattice range of resulting theoretical spectra have been carried out. Obtained results have been applied for interpretation of experimental spectra of selected zeolites.
ABSTRACT
We report a study on a hybrid mode-locked fiber laser with two saturable absorbers: slow and fast, integrated in a single device. Amorphous antimony telluride (Sb(2)Te(3)) layer was deposited on side-polished fiber to form the slow saturable absorber due to the third order nonlinear susceptibility of Sb(2)Te(3). Additionally, an unsymmetrical design of the device causes polarization-dependent losses and together with polarization controller allows to use a nonlinear polarization evolution to form the artificial fast saturable absorber. Sub-200 fs soliton pulses with 0.27 nJ of pulse energy were generated in the hybrid mode-locked Er-doped fiber laser. Differences in the dynamics of mode-locked laser are further investigated with the use of slow and fast saturable absorbers solely, and compared with the hybrid device. Joint operation of two saturable absorbers enhances the laser performance and stability. The conducted experiments allowed to define roles of each mechanism on the pulse shaping in the laser cavity.
