RESUMEN
Rechargeable aqueous zinc-ion batteries (ZIBs) are considered as one of the most promising large-scale energy storage system due to their high energy density, low cost and inherent safety. However, the notorious dendrite growth and severe side reactions, impede their practical application. Herein, we constructed a multifunctional gradient composite fluorinated coating with insulating ZnF2 outside and Zn/Sn alloy inside. ZnF2 outside and Zn/Sn alloy inside perform their own functions and solve the dendrites and side reactions jointly. Density functional theory (DFT) calculations and Molecular dynamics (MD) simulations demonstrate that the electronically insulating ZnF2 layer on the surface can regulate the transport of Zn2+ cations, limit the free H2O molecules and improve the dissolution of Zn2+, at the same time, the zincophilicity Zn/Sn alloy inside work as the favorable nucleation sites for Zn atoms and lowers the Zn2+ diffusion energy barrier. As a result, the ZnF2-Sn@Zn electrode in a symmetrical cell exhibits a long cycle life of about 1400 h, as well as 91 % capacity retention after 1400 cycles at 1 A/g in the ZnF2-Sn@Zn//MnO2@CNT full batteries. This work provides a practically promising strategy and new insights for the electrolyte and anode interface design.
RESUMEN
Recently, hybrid perovskites have gained attention as sensitizers for molecular triplet generation. Layered, two-dimensional (2D) perovskites are especially well-suited for this purpose because the triplet donor (inorganic framework) and triplet acceptor (organic layer) are self-assembled into adjacent sheets, so that with the appropriate energetics, triplets can be driven across the interface. Here we examine interlayer energy transfer in a series of mixed-halide Dion-Jacobson 2D perovskites containing divalent naphthalene cations. We find that the sensitized phosphorescence in these compounds is dominated by naphthalene triplet excimer emission, but when the inorganic exciton is tuned near resonance with the naphthalene triplet, naphthalene monomer phosphorescence competes with triplet excimer formation. The interlayer energy-transfer process is further revealed by ultrafast transient absorption spectroscopy through kinetic variations in triplet excimer formation times. Ultimately, gaining control over interlayer interactions in 2D perovskites through cation design will help uncover new functions and applications for these materials.
RESUMEN
Singlet fission is a spin-allowed process of exciton multiplication that has the potential to enhance the efficiency of photovoltaic devices. The majority of studies to date have emphasized understanding the first step of singlet fission, where the correlated triplet pair is produced. Here, we examine separation of correlated triplet pairs. We conducted temperature-dependent transient absorption on 6,3-bis(tri isopropylsilylethynyl)pentacene (TIPS-Pn) films, where singlet fission is exothermic. We evaluated time constants to show that their temperature dependence is inconsistent with an exclusively thermally activated process. Instead, we found that the trends can be modeled by a triplet-triplet energy transfer. The fitted reorganization energy and electronic coupling agree closely with values calculated using density matrix renormalization group quantum-chemical theory. We conclude that dissociation of the correlated triplet pair to separated (but spin-entangled) triplet excitons in TIPS-Pn occurs by triplet-triplet energy transfer with a hopping time constant of approximately 3.5 ps at room temperature.
RESUMEN
Self-assembly of 3D reduced graphene oxide (rGO) sponges has received increasing attention in recent years. By far, chemical reduction, hydrothermal treatment, template-directed chemical vapor deposition, and electrodeposition are the typical methods. Herein, the utilization of zinc nanoparticles as a reducing agent to fabricate 3D rGO sponges is reported. The relative negative standard electrode potential of zinc to graphene oxide (GO) allowed the spontaneous formation of the rGO-Zn hydrogel. Zinc-free 3D rGO sponges were recovered by acid leaching of the zinc species and freeze-drying. This room-temperature electroless gelation is dependent on pH. The structure and electrochemical performance of the as-synthesized rGO sponges were determined by the mass ratio of Zn to GO. Comprehensive physical and chemical characterizations were utilized to understand the 3D structure evolution of the rGO sponges. The rGO sponge, with an optimized texture, showed high capacitance and good stability in 1 m H2 SO4 electrolyte.
RESUMEN
Contrast-enhanced ultrasound (CEUS) has been used to diagnose gallbladder (GB) diseases for recent years because it is sensitive to visualize vascularity. Herein, we report a case who had a 1.7 cm × 1.2 cm polypoid lesion located in the gallbladder fundus with a feeding artery located in the stalk. On CEUS, the lesion showed early arterial phase enhancement (time to peak enhancement 18 s), persisting throughout the venous and delay phases. This enhancing pattern suggested that the lesion was a GB adenoma rather than a GB carcinoma. Cholecystectomy was performed, and pathology of the tissue revealed tubular adenoma of the GB.
RESUMEN
One merit of organic-inorganic hybrid perovskites is their tunable bandgap by adjusting the halide stoichiometry, an aspect critical to their application in tandem solar cells, wavelength-tunable light emitting diodes (LEDs), and lasers. However, the phase separation of mixed-halide perovskites caused by light or applied bias results in undesirable recombination at iodide-rich domains, meaning open-circuit voltage (VOC) pinning in solar cells and infrared emission in LEDs. Here, we report an approach to suppress halide redistribution by self-assembled long-chain organic ammonium capping layers at nanometer-sized grain surfaces. Using the stable mixed-halide perovskite films, we are able to fabricate efficient and wavelength-tunable perovskite LEDs from infrared to green with high external quantum efficiencies of up to 5%, as well as linearly tuned VOC from 1.05 to 1.45 V in solar cells.
RESUMEN
Organic-inorganic hybrid perovskite materials are emerging as semiconductors with potential application in optoelectronic devices. In particular, perovskites are very promising for light-emitting devices (LEDs) due to their high color purity, low nonradiative recombination rates, and tunable bandgap. Here, using pure CH3 NH3 PbI3 perovskite LEDs with an external quantum efficiency (EQE) of 5.9% as a platform, it is shown that electrical stress can influence device performance significantly, increasing the EQE from an initial 5.9% to as high as 7.4%. Consistent with the enhanced device performance, both the steady-state photoluminescence (PL) intensity and the time-resolved PL decay lifetime increase after electrical stress, indicating a reduction in nonradiative recombination in the perovskite film. By investigating the temperature-dependent characteristics of the perovskite LEDs and the cross-sectional elemental depth profile, it is proposed that trap reduction and resulting device-performance enhancement is due to local ionic motion of excess ions, likely excess mobile iodide, in the perovskite film that fills vacancies and reduces interstitial defects. On the other hand, it is found that overstressed LEDs show irreversibly degraded device performance, possibly because ions initially on the perovskite lattice are displaced during extended electrical stress and create defects such as vacancies.
RESUMEN
Hybrid organic-inorganic halide perovskite semiconductors are attractive candidates for optoelectronic applications, such as photovoltaics, light-emitting diodes, and lasers. Perovskite nanocrystals are of particular interest, where electrons and holes can be confined spatially, promoting radiative recombination. However, nanocrystalline films based on traditional colloidal nanocrystal synthesis strategies suffer from the use of long insulating ligands, low colloidal nanocrystal concentration, and significant aggregation during film formation. Here, we demonstrate a facile method for preparing perovskite nanocrystal films in situ and that the electroluminescence of light-emitting devices can be enhanced up to 40-fold through this nanocrystal film formation strategy. Briefly, the method involves the use of bulky organoammonium halides as additives to confine crystal growth of perovskites during film formation, achieving CH3NH3PbI3 and CH3NH3PbBr3 perovskite nanocrystals with an average crystal size of 5.4 ± 0.8 nm and 6.4 ± 1.3 nm, respectively, as confirmed through transmission electron microscopy measurements. Additive-confined perovskite nanocrystals show significantly improved photoluminescence quantum yield and decay lifetime. Finally, we demonstrate highly efficient CH3NH3PbI3 red/near-infrared LEDs and CH3NH3PbBr3 green LEDs based on this strategy, achieving an external quantum efficiency of 7.9% and 7.0%, respectively, which represent a 40-fold and 23-fold improvement over control devices fabricated without the additives.
RESUMEN
The respiratory chain of Vibrio cholerae contains three bd-type quinol oxygen reductases as well as one cbb(3) oxygen reductase. The cbb(3) oxygen reductase has been previously isolated and characterized; however, the natural mobile electron donor(s) that shuttles electrons between the bc(1) complex and the cbb(3) oxygen reductase is not known. The most likely candidates are the diheme cytochrome c(4) and monoheme cytochrome c(5), which have been previously shown to be present in the periplasm of aerobically grown cultures of V. cholerae. Both cytochromes c(4) and c(5) from V. cholerae have been cloned and expressed heterologously in Escherichia coli. It is shown that reduced cytochrome c(4) is a substrate for the purified cbb(3) oxygen reductase and can support steady state oxygen reductase activity of at least 300 e(-1)/s. In contrast, reduced cytochrome c(5) is not a good substrate for the cbb(3) oxygen reductase. Surprisingly, the dependence of the oxygen reductase activity on the concentration of cytochrome c(4) does not exhibit saturation. Global spectroscopic analysis of the time course of the oxidation of cytochrome c(4) indicates that the apparent lack of saturation is due to the strong dependence of K(M) and V(max) on the concentration of oxidized cytochrome c(4). Whether this is an artifact of the in vitro assay or has physiological significance remains unknown. Cyclic voltammetry was used to determine that the midpoint potentials of the two hemes in cytochrome c(4) are 240 and 340 mV (vs standard hydrogen electrode), similar to the electrochemical properties of other c(4)-type cytochromes. Genomic analysis shows a strong correlation between the presence of a c(4)-type cytochrome and a cbb(3) oxygen reductase within the beta- and gamma-proteobacterial clades, suggesting that cytochrome c(4) is the likely natural electron donor to the cbb(3) oxygen reductases within these organisms. These would include the beta-proteobacteria Neisseria meningitidis and Neisseria gonnorhoeae, in which the cbb(3) oxygen reductases are the only terminal oxidases in their respiratory chains, and the gamma-proteobacterium Pseudomonas stutzeri.