RESUMEN
CO2 possesses extraordinary thermodynamic stability, and its reduction reaction involves multiple electron-transfer processes. Thus, high-density electron occupation on a catalyst surface is an effective driving force for improving the photocatalytic activity. Here, we report on the fabrication of Fe-doped Bi2O3 catalysts (denoted as FexBi2-xO3) with different Fe contents using the solvothermal method. The self-assembled catalyst has a nanoflower-like morphology, and its performance of CO2 reduction to CO is improved largely dependent on the Fe content. In the sample with a 7.0% Fe content (Fe0.07Bi1.93O3), the CO evolution rate reaches 30.06 µmol g-1 h-1, which is about 6 times higher than the 4.95 µmol g-1 h-1 of pristine Bi2O3, and shows excellent photostability after three cycles, with each cycle lasting for 7 h. Theoretical calculation and spectral characterization reveal that such a good CO2 reduction reaction performance arises from effective surface occupation of Fe, which not only enhances sunlight absorption but also significantly increases the surface electron density on the double metal active sites. This work provides a new strategy for improving the photocatalytic performance by surface metal doping in some metal oxide photocatalysts.
RESUMEN
Single perovskite nanocrystals have emerged as a novel type of semiconductor nanostructure capable of emitting single photons with rich exciton species and fine energy-level structures. Here we focus on single excitons and biexcitons in single perovskite CsPbI_{3} nanocrystals to show, for the first time, how their optical properties are modulated by an external electric field at the cryogenic temperature. The electric field can cause a blueshift in the photoluminescence peak of single excitons, from which the existence of a permanent dipole moment can be deduced. Meanwhile, the fine energy-level structures of single excitons and biexcitons in a single CsPbI_{3} nanocrystal can be simultaneously eliminated, thus preparing a potent platform for the potential generation of polarization-entangled photon pairs.
RESUMEN
Hybrid perovskites have two properties that are absent in traditional inorganic photovoltaic materials, namely, polarization and mobile ionic defects, the interaction between which may introduce new features into the materials. By using the first-principles calculations, we find that the formation energies of the vacancy defects at a tetragonal MAPbI3(110) surface are highly related to the surface polarization. The positive total polarization and local polarization of MA facilitate the formation of surface MA vacancies, whereas the negative total polarization and local polarization of MAI are favorable for the formation of surface iodine vacancies. The phenomena can be explained quantitatively on the basis of the two kinds of Coulomb interactions between the charged defect and the polarization-induced electrostatic field. The comprehensive insights into the interaction between the polarization and the ionic defects in hybrid perovskites can provide a new avenue for defect control for high-performance perovskite solar cells via surface polarization.
RESUMEN
The chemical properties of a ferroelectric surface are polarization dependent, the underlying nature of which is, however, far from being completely understood. One of the reasons is that when the polarization direction is perpendicular to the surface, the depolarization field may induce electronic or atomic reconstruction and thus change the chemistry of the ferroelectric surface in complicated ways. Instead, the in-plane polarization results in no depolarization field. Therefore, the chemical properties of a ferroelectric surface can be more intrinsically reflected by the interplay between the in-plane polarization and the surface adsorption. By using first-principles calculations, we study the effect of the strain-induced in-plane polarization on the adsorption of a series of molecules on the reduced rutile TiO2(110) surface. We reveal that it is the surface doping caused by the charge transfer between the adsorbates and the TiO2(110) surface that dominates the polarization-induced change of the adsorption energy, as a result of screening long-range Coulomb interactions. The electrostatic interaction between the polarization of the substrate and the polar molecule is of relatively less importance. We propose that charge transfer effects generally occur for ferroelectric surfaces with no localized surface states.
RESUMEN
Two-dimensional transition metal selenides (TMSs) possess fascinating physical properties. However, many as-prepared TMSs are environmentally unstable and limited in sample size, which greatly hinder their wide applications in high-performance electrical devices. Here we develop a general two-step vapour deposition method and successfully grow different TMS films with controllable thickness, wafer size and high quality. The superconductivity of the grown NbSe2 film is comparable with sheets exfoliated from bulk materials, and can maintain stability after a variety of harsh treatments, which are ascribed to the absence of oxygen during the whole growth process. Such environmental stability can greatly simplify the fabrication procedure for device applications, and should be of both fundamental and technological significance in developing TMS-based devices.
RESUMEN
The influence of externally applied strain on water adsorption and dissociation on a defect-free rutile TiO2(110) surface is studied by using first-principles calculations. We found that while compressive strain makes water adsorption and dissociation less favorable, tensile strain increases the energy gain of water adsorption, and decreases the energy cost of water dissociation. Specifically, dissociative water becomes more stable than molecular water when an 8% tensile in-plane strain is applied. Moreover, the dissociation barrier decreases with increasing strain more rapidly for more isolated water. The rate of decrease of this barrier for nearly isolated water is 0.017 eV per 1% biaxial strain. This demonstrates that applying strain is a possible way to engineer the surface adsorption and dissociation of water on a TiO2(110) surface, and therefore engineer the relevant surface reactivity.
RESUMEN
Carbon alloy catalysts (CACs) are promising oxygen reduction reaction (ORR) catalysts to substitute platinum. However, despite extensive studies on CACs, the reaction sites and mechanisms for ORR are still in controversy. Herein, we present rather general consideration on possible ORR mechanisms for various structures in nitrogen doped CACs based on the first-principles calculations. Our study indicates that only a particular structure of a nitrogen pair doped Stone-Wales defect provides a good active site. The ORR activity of this structure can be tuned by the curvature around the active site, which makes its limiting potential approaching the maximum limiting potential (0.80 V) in the volcano plot for the ORR activity of CACs. The calculated results can be compared with the recent experimental ones of the half-wave potential for CAC systems that range from 0.60 to 0.80 V in the reversible-hydrogen-electrode (RHE) scale.
RESUMEN
Surfaces with high reactivity usually have a low area percentage, which greatly limits the efficiency of surface reactivity. In this Letter we demonstrate a generic way of increasing the percentage of the highly reactive surface by using external strain. Bulk and surface elastic properties of TiO2 are studied via density functional theory calculations. The equilibrium shape of anatase TiO2 under applied strain is discussed based on the elastic properties. We find that when 5% compressive strain is applied biaxially along [100] and [010]; directions, the area percentage of the anatase (001) surface can be increased by ~5 times in comparison with the case when no strain is applied. Since the moderate strain does not introduce extrinsic defects into the material, we propose that it is an ideal way to increase the reactivity of titanium dioxide crystallites by applying biaxial compressive external strain along the a axis.
RESUMEN
We report here a unique in-plane self-templating electrochemical growth of arrays of copper nanopearl chains from an ultrathin layer of CuSO4 electrolyte. Scanning electron microscopy indicates that the electrodeposit filaments form equally spaced bundles, which consist of long, straight, pearl-chain-like copper filaments with corrugated periodic structure. The bundle separation can be tuned by changing the applied electric current in electrodeposition. Experiments show that the periodic morphology on the nanopearl chain corresponds to the periodic distribution of copper and cuprous oxide. The mechanism for the bundle formation is discussed.
RESUMEN
Comprehensive first-principle calculations on strained rutile TiO2(110) indicate that the formation energy of different types of oxygen vacancies depends on the external strain. For the unstrained state, the energetically favorable oxygen vacancy (EFOV) appears on the bridging site of the first layer; when 3% tensile strain along [11[over ]0] is applied, EFOV moves to the in-plane site, while 2% compressive strain along either [001] or [11[over ]0] shifts EFOV to the subbridging site. We therefore suggest that the distribution of oxygen vacancies can be engineered by external strain, which may help to improve the applications of a TiO2 surface where oxygen vacancy plays an important role.
RESUMEN
We report in this Letter that when radiation is incident on a metal surface perforated with an array of ring-shaped subwavelength apertures, the phase difference between the propagating surface Bloch wave and the localized surface wave can be tailored by the geometrical parameters of the array so as to affect the shape of the transmission spectrum. Above the resonant frequency of the aperture, interference between the two kinds of surface waves leads to a minimum in the transmission spectrum, whereas below it, the interference leads to a maximum. We suggest that this feature provides flexibility in engineering surface-wave-based all-optical devices.
RESUMEN
A consecutive rotation of crystallographic orientation has been observed in lateral crystallization of NH4Cl on a glass substrate, which induces a periodic distribution of faceted and roughened regions on the surface of a crystallite aggregate. Experimental observation indicates that this phenomenon derives from the asymmetric surface energies at the growth front, which deform the nascent nucleus and tilt the crystallographic orientation in the nucleation-mediated layered growth. We suggest that this effect is significant for a class of lateral growth where nucleation plays a dominate role.
RESUMEN
The self-assembly of iron dots on the insulating surface of NaCl(001) is investigated experimentally and theoretically. Under proper growth conditions, nanometer-scale magnetic iron dots with remarkably narrow size distributions can be achieved in the absence of a wetting layer. Furthermore, both the vertical and lateral sizes of the dots can be tuned with the iron dosage without introducing apparent size broadening, even though the clustering is clearly in the strong coarsening regime. These observations are interpreted using a phenomenological mean-field theory, in which a coverage-dependent optimal dot size is selected by strain-mediated dot-dot interactions.
