Search

© 2019 Elsevier B.V. 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 (−159 mV vs. RHE at 10 A/g), lower Tafel slope (218 mV/dec) but also delivered long-term stability (14 A/g at −250 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 Ni 3+ OOH for HER electrocatalytic activities, while the co-existence of Ni 2+ and Ni 3+ facilitates the rich redox reactions of NiS for supercapacitor.

© 2018 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim 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 µm. 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.

© 2016 American Chemical Society. This study presents a simple method that allows us to modify the composition, morphological, and surface properties of three-dimensional hierarchical Nb3O7(OH) superstructures, resulting in strongly enhanced photocatalytic H2 production. The superstructures consist of highly ordered nanowire networks and self-assemble under hydrothermal conditions. The presence of titanium affects the morphology of the superstructures, resulting in increased surface areas for higher doping levels. Up to 12 at. % titanium is incorporated into the Nb3O7(OH) crystal lattice via substitution of niobium at its octahedral lattice sites. Further titanium excess results in the formation of niobium-doped TiO2 plates, which overgrow the surface of the Nb3O7(OH) superstructures. Photoluminescence spectroscopy indicates fewer charge recombination processes near the surface of the nanostructures with an increasing titanium concentration in the crystal lattice. The combination of larger surface areas with fewer quenching sites at the crystal surface yields higher H2 evolution rates for the doped samples, with the rate being doubled by incorporation of 5.5 ± 0.7 at. % Ti.

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.

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.