RESUMO
We report on a nonoxidative topochemical route for the synthesis of a novel indate-based oxyfluoride, LaBaInO3F2, using a low-temperature reaction of Ruddlesden-Popper-type LaBaInO4 with polyvinylidene difluoride as a fluorinating agent. The reaction involves the replacement of oxide ions with fluoride ions as well as the insertion of fluoride ions into the interstitial sites. From the characterization via powder X-ray diffraction (PXRD) and Rietveld analysis as well as automated electron diffraction tomography (ADT), it is deduced that the fluorination results in a symmetry lowering from I4/mmm (139) to monoclinic C2/c (15) with an expansion perpendicular to the perovskite layers and a strong tilting of the octahedra in the ab plane. Disorder of the anions on the apical and interstitial sites seems to be favored. The most stable configuration for the anion ordering is estimated based on an evaluation of bond distances from the ADT measurements via bond valence sums (BVSs). The observed disordering of the anions in the oxyfluoride results in changes in the optical properties and thus shows that the topochemical anion modification can present a viable route to alter the optical properties. Partial densities of states (PDOSs) obtained from ab initio density functional theory (DFT) calculations reveal a bandgap modification upon fluoride-ion introduction which originates from the presence of the oxide anions on the interstitial sites. The photocatalytic performance of the oxide and oxyfluoride shows that both materials are photocatalytically active for hydrogen (H2) evolution.
RESUMO
All-inorganic perovskites have emerged as promising photovoltaic materials due to their superior thermal stability compared to their heat-sensitive hybrid organic-inorganic counterparts. In particular, CsPbI2 Br shows the highest potential for developing thermally-stable perovskite solar cells (PSCs) among all-inorganic compositions. However, controlling the crystallinity and morphology of all-inorganic compositions is a significant challenge. Here, a simple, thermal gradient- and antisolvent-free method is reported to control the crystallization of CsPbI2 Br films. Optical in situ characterization is used to investigate the dynamic film formation during spin-coating and annealing to understand and optimize the evolving film properties. This leads to high-quality perovskite films with micrometer-scale grain sizes with a noteworthy performance of 17% (≈16% stabilized), fill factor (FF) of 80.5%, and open-circuit voltage (VOC ) of 1.27 V. Moreover, excellent phase and thermal stability are demonstrated even after extreme thermal stressing at 300 °C.
RESUMO
In this work, we report a facile way to fabricate composite nanofibrous mats of polyvinyl alcohol (PVA), polydimethylsiloxane (PDMS), and stearic acid (SA) by employing the electrospinning-technique, with PDMS fraction ranging from 40w% to nearly 80w%. The results show that for a predetermined fraction of PVA and SA, incorporation of an optimal amount of PDMS is necessary for which the mats exhibit the best mechanical behavior. Beyond this optimal PDMS fraction, the mechanical properties of the composite mats deteriorate. This result has been attributed to the ability of the SA molecules to mediate binding between the PVA and PDMS long-chain molecules via van-der-Waals bonding. The morphological, structural, mechanical, and thermal characterizations respectively using SEM, XRD, DMA/tensile test, and DSC lend support to this explanation. By this method, it is possible to control the hydrophilicity/oleophilicity of the mats, and the mats show an excellent selective permeability to oil as compared to water and successfully filter water from a water-in-oil emulsion. Incorporation of SA not only serves to aid in electrospinning of a PDMS-rich nanofibrous mat with good mechanical strength and control over hydrophilicity/oleophilicity, but also has a potential use in fabricating sheets impregnated with phase change materials for thermal energy storage.
