Structural Features Governing the Near-Edge X-ray Absorption Spectra of Lead Halide Perovskites

X-ray absorption spectroscopy (XAS) represents the ideal complement to diffraction techniques to investigate the structure of materials. Despite its strong points and the abundance of studies devoted to lead halide perovskites for application in optoelectronics, XAS has been applied to lead halide perovskites rather infrequently to date, and with varying degrees of success. In the search of generalizable approaches to be applied to data analysis of XAS spectra of halide perovskites with different compositions, we present here an experimental and computational study on a hybrid Pb/Bi iodide solid solution as a model for halide perovskites with different compositions

HYDROCARBONS REMOVAL FROM BILGE WATER BY ADSORPTION ONTO ACTIVATED BIOCHAR FROM POSIDONIA OCEANICA

The normal operations carried out on the boats during navigation generate waste waters such as oily bilge water. The latter is the aqueous mixture of potential pollutants of different origins and types: oily fluids, lubricants and greases, cleaning fluids and other wastes that accumulate in the lower part of the vessel [1,2]. The current legislation provides that they can be discharge directly into the sea if the concentrations of some components are below the expected limits. In particular, with regard to oil / hydrocarbons contamination, the current regulatory limit is 15 mg L-1 of total hydrocarbons. The present work starts from a public/private partnership funded by a grant of the Ministry of Economic Development (MiSE). Among the aims of the project, novel methods shall be tested for the reduction of hydrocarbons concentration at values below 5 mg L-1. Moreover, instrumental techniques able to quickly measure the required low hydrocarbons concentration were tested. Among the different steps of bilge water treatment in pilot plant (coagulation, flotation, centrifugation, adsorption etc.), the latter requires the use of adsorbent materials able to reduce the oily concentration below the legal limits. Here we have hosen, optimized and tested materials obtained from bio-oil production waste, a biochar obtained by pyrolysis of Posidonia oceanica, a marine plant widespread in the Mediterranean sea. means of acid or alkali treatments. Moreover, a commercial activated carbon (Filtrasorb 400) has been used for comparison purpose. Synthetic bilge waters were prepared following the reference standards [3] for the preparation of test fluids (used to test the bilge separator plant), containing DMA (distillate marine fuel) and SLS (sodium lauryl sulfate). Batch adsorption isotherms were carried out without ionic medium and at different ionic strengths in NaCl in order to evaluate the effect of salinity on the adsorption ability of dsorbent materials. The same adsorbents were tested by column experiments. In particular, a bench pilot system was built (Figure 1.) and breakthrough curves were obtained changing amount of adsorbent material in column, flow rate, initial DMA and surfactant concentrations. Several instrumental techniques (turbidimetry, TOC, HPLC-QQQ and HPLC-FLD) have been used to measure surfactant and hydrocarbon concentrations in experimental samples. The batch experimental data were fitted with the most used isotherm models (Langmuir, Freundlich, Sips) and important considerations were made on the breakthrough curves of column experiments

Dopant-matrix interaction in solid oxide electrolytes and electrodes

Materials for solid oxide fuel cells (SOFC) are extensively investigated aiming at achieving better performances and device durability in view of the hopefully next implementation of hydrogen technology for the production of energy. This contribution deals with the structural aspects of the interaction of dopants with the solid matrix, either for electrodes or electrolytes. The report concerns materials that are likely fit for implementation, such as ceria-based electrolytes and mixed-oxide electrodes. However, in view of the importance of achieving a deeper insight in the mechanism of solid-state O2- conduction, results about Bi2O3 compounds are also reported. Finally, the host matrix-dopant interaction in proton-conducting electrolytes for intermediate temperature SOFC\u2019s is discussed

Long-Term Stability of TiS2–Alkylamine Hybrid Materials

Layered TiS2 intercalated with linear alkylamines has recently attracted significant interest as a model compound for flexible n-type thermoelectric applications, showing remarkably high power factors at room temperature. The thermal and, particularly, environmental stability of such materials is, however, a still an open challenge. In this paper, we show that amine-intercalated TiS2 prepared by a simple mechanochemical process is prone to chemical decomposition through sulfur exsolution, and that the presence of molecular oxygen is likely to mediate the decomposition reaction. Through computational analysis of the possible reaction pathways, we propose that Ti-N adducts are formed as a consequence of amine groups substituting for S vacancies on the internal surfaces of the S-Ti-S layers. These findings provide insights for possible future applications of similar hybrid compounds as devices operating in ambient conditions, and suggest isolating them from atmospheric oxygen

Modelling the structural disorder in trigonal-prismatic coordinated transition metal dichalcogenides

Trigonal-prismatic coordinated transition metal dichalcogenides (TMDCs) are formed from stacked (chalcogen)-(transition metal)-(chalcogen) triple layers, where the chemical bond is covalent within the triple layers and van der Waals (vdW) forces are effective between the layers. Bonding is at the origin of the great interest in these compounds, which are used as 2D materials in applications such as catalysis, electronics, photoelectronics, sensors, batteries and thermoelectricity. This paper addresses the issue of modelling the structural disorder in multilayer TMDCs. The structural model takes into account stacking faults, correlated displacement of atoms and average crystallite size/shape, and is assessed by simulation of the X-ray diffraction pattern and fitting to the experimental data relative to a powdered sample of MoS2 exfoliated and restacked via lithiation. From fitting, an average crystallite size of about 50 angstrom, nearly spherical crystallites and a definite probability of deviation from the fully eclipsed atomic arrangement present in the ordered structure are determined. The increased interlayer distance and correlated intralayer and interlayer atomic displacement are attributed to the presence of lithium intercalated in the vdW gap between triple layers (Li/Mo molar ratio of about 0.06). The model holds for the whole class of trigonal-prismatic coordinated TMDCs, and is suitably flexible to take into account different preparation routes

Solid-state compatibility of Ca:LaNbO4 with perovskite cathodes: Evidences from X-ray microspectroscopy

The solid-state compatibility between calcium-doped lanthanum niobate and three perovskite cathode materials was investigated using two X-ray microbeam techniques, micro X-ray fluorescence and micro X-ray absorption spectroscopy. The cathode powders (lanthanum strontium ferrite, either cobalt or copper-doped, and lanthanum strontium cobaltite) in contact with the dense electrolyte pellet were annealed at 1150°C for 12–144 h to simulate the effect of thermal stresses due to fabrication and long-term operation. As a result, several interdiffusion phenomena were then observed on the bilayer cross-sections: in particular, the chemical state and coordination environment of calcium, iron, niobium and lanthanum were probed with space-resolved X-ray absorption spectroscopy. The ab initio modeling of the near-edge X-ray absorption spectra reveal that the cation interdiffusion is facilitated by the structural flexibility of the perovskite structure, which is able to accommodate a variety of foreign cations in different oxidation states. Limited stability at high-temperatures was found for all candidate perovskite compositions in contact with lanthanum niobate

Toward a new hybrid proton conductor: lanthanum niobate layered perovskites as a source of tailorable surfaces

The modification of metal oxide surfaces with organic moieties has been widely studied as a method of preparing organic-inorganic hybrid materials for various applications. Among inorganic oxides, the ion-exchangeable layered perovskites [1], materials composed by perovskite-like slabs and intercalated cations, stimulated authors\u2019 interest in reason of some encouraging electronic and reactive properties. In particular it is well known that the interlayer surface of such materials in their protonated form can be easily functionalized with organic groups (such as alcohols [2-3] or organophosphonic acids [4]) thus allowing the production of stable hybrid materials with new electronic and reactive features. As a first step to design a new inorganic-organic hybrid proton conductor, a comprehensive theoretical investigation of the MLaNb2O7 (M=H, Li, Na, K, Rb and Cs) series of ion-exchangeable layered perovskite is presented. In particular, their structural and electronic properties have been investigated by periodic calculations in the framework of DFT. A general very good agreement with the available experimental data has been found. The protonated compound (HLaNb2O7) has been then functionalized with imidazole trying two different settings: in the first arrangement the molecule is adsorbed on the layered oxide exposing the interlayer surface, in the second the organic moiety is just put between two perovskites slabs. This latter model, including the effect of the confinement, allowed to better reproduce the experimental structural XRD data and 13C-NMR measurements of the hybrid system. [1] Schaak, R. E. and Mallouk T. E., Chem. Mat. 2002, 14, 1455-1471. [2] Takahashi S. et al., Inorg. Chem. 1995, 34, 5065-5069. [3] Suzuki H. et al., Chem. Mater. 2003, 15, 636-641. [4] Shimada, A. et al., Chem. Mat. 2009, 21, 4155-4162

Interplay of Chemical, Electronic, and Structural Effects in the Triple-Conducting BaFeO3-Ba(Zr,Y)O3 Solid Solution

Triple-conducting oxides with mobile protons, oxygen vacancies, and holes are key functional materials for protonic ceramic fuel/electrolysis cells. We comprehensively investigate the Ba(Zr,Y,Fe)O3-delta perovskite solid solution series ranging from electrolyte to electrode-type materials depending on iron content. From thermogravimetry and impedance spectroscopy, the proton and oxygen vacancy concentrations as well as electronic and ionic conductivities are determined. X-ray spectroscopy (Fe K-edge XANES, O K-edge Raman scattering, Fe, Zr, Y K-edge EXAFS) elucidates the finer features of the electronic structure and local distortions. A low Fe content of <= 10% strongly decreases the degree of hydration, while comparably high Fe concentrations of >= 70% are required to obtain an electronic conductivity sufficient for an electrode material. The transport of ionic and electronic carriers is interrelated in a complex way and is closely linked to details of the electronic structure (strength of Fe-O hybridization) and geometrical distortions (Fe-O-Fe and Fe-O-(Zr,Y) buckling). As a result, an optimum combination of proton concentration and electronic conductivity is not obtained in the middle of the solid solution series but rather found for Fe-rich materials with 20-30% doping with oversized, redox-inactive cations. A similar behavior is also expected for related solid solutions between a large-band gap electrolyte and small-band gap redox-active perovskites

Solid-Solid Interfaces in Protonic Ceramic Devices: A Critical Review

The literature concerning protonic ceramic devices is critically reviewed focusing the reader's attention on the structure, composition, and phenomena taking place at solid-solid interfaces. These interfaces play a crucial role in the overall device performance, and the relevance of understanding the phenomena taking place at the interfaces for the further improvement of electrochemical protonic ceramic devices is therefore stressed. The grain boundaries and heterostructures in electrolytic membranes, the electrode-electrolyte contacts, and the interfaces within composite anode and cathode materials are all considered, with specific concern to advanced techniques of characterization and to computational modeling by ab initio approaches. An outlook about future developments and improvements highlights the necessity of a deeper insight into the advanced analysis of what happens at the solid-solid interfaces and of in situ/operando investigations that are presently sporadic in the literature on protonic ceramic devices

Interface Diffusion and Compatibility of (Ba,La)FeO3−δ Perovskite Electrodes in Contact with Barium Zirconate and Ceria

Ba1-x La (x) FeO3-delta perovskites (BLF) capable of conducting electrons, protons, and oxygen ions are promising oxygen electrodes for efficient solid oxide cells (fuel cells or electrolyzers), an integral part of prospected large-scale power-to-gas energy storage systems. We investigated the compatibility of BLF with lanthanum content between 5 and 50%, in contact with oxide-ion-conducting Ce0.8Gd0.2O2-delta and proton-conducting Ba-Zr0.825Y0.175O3-delta electrolytes, annealing the electrode-electrolyte bilayers at high temperature to simulate thermal stresses of fabrication and prolonged operation. By employing both bulk X-ray diffraction and synchrotron X-ray microspectroscopy, we present a space-resolved picture of the interaction between electrode and electrolyte as what concerns cation interdiffusion, exsolution, and phase stability. We found that the phase stability of BLF in contact with other phases is correlated with the Goldschmidt tolerance factor, in turn determined by the La/Ba ratio, and appropriate doping strategies with oversized cations (Zn2+, Y3+) could improve structural stability. While extensive reactivity and/or interdiffusion was often observed, we put forward that most products of interfacial reactions, including proton-conducting Ba-(Ce,Gd)-O3-delta and mixed-conducting (Ba,La)-(Fe,Zr,Y)-O3-delta, may not be very detrimental for practical cell operation