15 research outputs found
Recommended from our members
Visualization of facet-dependent pseudo-photocatalytic behavior of TiO2 nanorods for water splitting using In situ liquid cell TEM
We report an investigation of the pseudo-photocatalytic behavior of rutile TiO2 nanorods for water splitting observed with liquid cell transmission electron microscopy (TEM). The electron beam serves as a âlightâ source to initiate the catalytic reaction and a âwater-in-saltâ aqueous solution is employed as the electrolyte. The observation reveals that bubbles are generated preferentially residing near the {110} facet of a rutile TiO2 nanorod under a low electron dose rate (9.3â18.6 e-/Ă
2·s). These bubbles are ascribed to hydrogen gas generated from the pseudo-photocatalytic water splitting. As the electron beam current density increases to 93 e-/Ă
2 ·s, bubbles are also found at the {001} and {111} facets as well as in the bulk liquid solution, demonstrating the dominant effects of water electrolysis by electron beam under higher dose rates. The facet-dependent pseudo-photocatalytic behavior of rutile TiO2 nanorods is further validated using density functional theory (DFT)calculation. Our work establishes a facile liquid cell TEM setup for the study of pseudo-photocatalytic water splitting and it may also be applied to investigation of other photo-activated phenomena occurring at the solid-liquid interfaces
On Structural Parameterizations of the Bounded-Degree Vertex Deletion Problem
We study the parameterized complexity of the Bounded-Degree Vertex Deletion problem (BDD), where the aim is to find a maximum induced subgraph whose maximum degree is below a given degree bound. Our focus lies on parameters that measure the structural properties of the input instance. We first show that the problem is W[1]-hard parameterized by a wide range of fairly restrictive structural parameters such as the feedback vertex set number, pathwidth, treedepth, and even the size of a minimum vertex deletion set into graphs of pathwidth and treedepth at most three. We thereby resolve an open question stated in Betzler, Bredereck, Niedermeier and Uhlmann (2012) concerning the complexity of BDD parameterized by the feedback vertex set number. On the positive side, we obtain fixed-parameter algorithms for the problem with respect to the decompositional parameter treecut width and a novel problem-specific parameter called the core fracture number
Recommended from our members
Atomic Resolution Observation of the Oxidation of Niobium Oxide Nanowires: Implications for Renewable Energy Applications
Niobium oxide exists in several crystal phases and valence states, yielding a variety of properties. Phase transitions between polymorphs significantly alter the properties of functional niobium oxide nanostructures, which are applied in many different renewable energy applications. This study uses environmental transmission electron microscopy to investigate the oxidation of NbO nanowires to T-Nb2O5. Small oxygen partial pressures (<1 mbar) suffice to initiate the oxidation which initially causes the destruction of the lattice ordering prior to the crystallization of the new phase. Different oxygen partial pressures and temperatures are used to manipulate the reaction kinetics. The crystallization is slow at room temperature and confined to the nanowire surface. Elevated temperatures accelerate the crystallization, resulting in the transformation of the complete nanowire. The transformation proceeds via dislocations, yielding the woven-like structure of the transformed nanowire. Despite the dramatic changes of the atomic composition of the material, an orientation relationship between the different phases is preserved. The phase transformation of NbO to T-Nb2O5 observed in situ complies with ex situ phase diagrams. This illustrates the importance of environmental transmission electron microscopy for the investigation of oxidation and reduction reactions of metal oxide nanostructures to identify the impact of shape and intrinsic defects
Recommended from our members
Nickel sulfide nanostructures prepared by laser irradiation for efficient electrocatalytic hydrogen evolution reaction and supercapacitors
Rational design and synthesis of transition metal sulfide complex nanostructures are significant for achieving desired materials properties for a variety of applications. Herein, we synthesized nickel sulfide (NiS) nanostructures using laser irradiation in an aqueous solution and under the ambient condition. Crystalline nanostructures with high phase-purity were achieved without further calcination. Other transition metal sulfides, such as CuS and ZnS, were also successfully synthesized using the laser irradiation approach, suggesting the practical application of this method. The hydrogen evolution reaction (HER) measurements show the NiS nanostructures synthesized for 4h (NiS-4h) not only exhibited competitive overpotential (â159 mV vs. RHE at 10 A/g), lower Tafel slope (218 mV/dec) but also delivered long-term stability (14 A/g at â250 mV vs. RHE for 12h). Moreover, the NiS-4h functioned as the electrode for supercapacitor with excellent specific capacitance (3761 F/g at 10 mV/s), reversibility and rate capability (1152 F/g at 100 mV/s). These superb electrochemical performances are attributed to the remarkable value of electrochemically active surface area (ECSA) and synergistic effect of Ni3+OOH for HER electrocatalytic activities, while the co-existence of Ni2+ and Ni3+ facilitates the rich redox reactions of NiS for supercapacitor
Recommended from our members
Heat-Induced Phase Transformation of Three-Dimensional Nb3O7(OH) Superstructures: Effect of Atmosphere and Electron Beam
Nanostructured niobium oxides and hydroxides are potential candidates for photochemical applications due to their excellent optical and electronic properties. In the present work the thermal stability of Nb3O7(OH) superstructures prepared by a simple hydrothermal approach is investigated at the atomic scale. Transmission electron microscopy and electron energy-loss spectroscopy provide insights into the phase transformation occurring at elevated temperatures and probe the effect of the atmospheric conditions. In the presence of oxygen, H2O is released from the crystal at temperatures above 500 °C, and the crystallographic structure changes to H-Nb2O5. In addition to the high thermal stability of Nb3O7(OH), the morphology was found to be stable, and first changes in the form of a merging of nanowires are not observed until 850 °C. Under reducing conditions in a transmission electron microscope and during electron beam bombardment, an oxygen-deficient phase is formed at temperatures above 750 °C. This transformation starts with the formation of defects in the crystal lattice at 450 °C and goes along with the formation of pores in the nanowires which accommodate the volume differences of the two crystal phases
Recommended from our members
Heat-Induced Phase Transformation of Three-Dimensional Nb3O7(OH) Superstructures: Effect of Atmosphere and Electron Beam
Nanostructured niobium oxides and hydroxides are potential candidates for photochemical applications due to their excellent optical and electronic properties. In the present work the thermal stability of Nb3O7(OH) superstructures prepared by a simple hydrothermal approach is investigated at the atomic scale. Transmission electron microscopy and electron energy-loss spectroscopy provide insights into the phase transformation occurring at elevated temperatures and probe the effect of the atmospheric conditions. In the presence of oxygen, H2O is released from the crystal at temperatures above 500 °C, and the crystallographic structure changes to H-Nb2O5. In addition to the high thermal stability of Nb3O7(OH), the morphology was found to be stable, and first changes in the form of a merging of nanowires are not observed until 850 °C. Under reducing conditions in a transmission electron microscope and during electron beam bombardment, an oxygen-deficient phase is formed at temperatures above 750 °C. This transformation starts with the formation of defects in the crystal lattice at 450 °C and goes along with the formation of pores in the nanowires which accommodate the volume differences of the two crystal phases
Recommended from our members
Theoretical and Experimental Study on the Optoelectronic Properties of Nb3O7(OH) and Nb2O5 Photoelectrodes
Nb3O7(OH) and Nb2O5 nanostructures are promising alternative materials to conventionally used oxides, e.g. TiO2, in the field of photoelectrodes in dye-sensitized solar cells and photoelectrochemical cells. Despite this important future application, some of their central electronic properties such as the density of states, band gap, and dielectric function are not well understood. In this work, we present combined theoretical and experimental studies on Nb3O7(OH) and H-Nb2O5 to elucidate their spectroscopic, electronic, and transport properties. The theoretical results were obtained within the framework of density functional theory based on the full potential linearized augmented plane wave method. In particular, we show that the position of the H atom in Nb3O7(OH) has an important effect on its electronic properties. To verify theoretical predictions, we measured electron energy-loss spectra (EELS) in the low loss region, as well as, the O-K and Nb-M3 element-specific edges. These results are compared with corresponding theoretical EELS calculations and are discussed in detail. In addition, our calculations of thermoelectric conductivity show that Nb3O7(OH) has more suitable optoelectronic and transport properties for photochemical application than the calcined H-Nb2O5 phase
Recommended from our members
Lithium Tin Sulfideâa High-Refractive-Index 2D Material for Humidity-Responsive Photonic Crystals
Extending the portfolio of novel stimuli-responsive, high-refractive-index (RI) materials besides titania is key to improve the optical quality and sensing performance of existing photonic devices. Herein, lithium tin sulfide (LTS) nanosheets are introduced as a novel solution processable ultrahigh RI material (n = 2.50), which can be casted into homogeneous thin films using wet-chemical deposition methods. Owing to its 2D morphology, thin films of LTS nanosheets are able to swell in response to changes of relative humidity. Integration of LTS nanosheets into Bragg stacks (BSs) based on TiO2, SiO2, nanoparticles or H3Sb3P2O14 nanosheets affords multilayer systems with high optical quality at an extremely low device thickness of below 1 ”m. Owing to the ultrahigh RI of LTS nanosheets and the high transparency of the thin films, BSs based on porous titania as the low-RI material are realized for the first time, showing potential application in light-managing devices. Moreover, the highest RI contrast ever realized in BSs based on SiO2 and LTS nanosheets is reported. Finally, exceptional swelling capability of an all-nanosheet BS based on LTS and H3Sb3P2O14 nanosheets is demonstrated, which bodes well for a new generation of humidity sensors with extremely high sensitivity
Recommended from our members
Visualization of facet-dependent pseudo-photocatalytic behavior of TiO2 nanorods for water splitting using In situ liquid cell TEM
We report an investigation of the pseudo-photocatalytic behavior of rutile TiO2 nanorods for water splitting observed with liquid cell transmission electron microscopy (TEM). The electron beam serves as a âlightâ source to initiate the catalytic reaction and a âwater-in-saltâ aqueous solution is employed as the electrolyte. The observation reveals that bubbles are generated preferentially residing near the {110} facet of a rutile TiO2 nanorod under a low electron dose rate (9.3â18.6 e-/Ă
2·s). These bubbles are ascribed to hydrogen gas generated from the pseudo-photocatalytic water splitting. As the electron beam current density increases to 93 e-/Ă
2 ·s, bubbles are also found at the {001} and {111} facets as well as in the bulk liquid solution, demonstrating the dominant effects of water electrolysis by electron beam under higher dose rates. The facet-dependent pseudo-photocatalytic behavior of rutile TiO2 nanorods is further validated using density functional theory (DFT)calculation. Our work establishes a facile liquid cell TEM setup for the study of pseudo-photocatalytic water splitting and it may also be applied to investigation of other photo-activated phenomena occurring at the solid-liquid interfaces