Symmetric domain segmentation in WS2flakes: correlating spatially resolved photoluminescence, conductance with valley polarization.

The incidence of intra-flake heterogeneity of spectroscopic and electrical properties in chemical vapour deposited (CVD) WS2flakes is explored in a multi-physics investigation via spatially resolved spectroscopic maps correlated with electrical, electronic and mechanical properties. The investigation demonstrates that the three-fold symmetric segregation of spectroscopic response, in topographically uniform WS2flakes are accompanied by commensurate segmentation of electronic properties e.g. local carrier density and the differences in the mechanics of tip-sample interactions, evidenced via scanning probe microscopy phase maps. Overall, the differences are understood to originate from point defects, namely sulfur vacancies within the flake along with a dominant role played by the substrate. While evolution of the multi-physics maps upon sulfur annealing elucidates the role played by sulfur vacancy, substrate-induced effects are investigated by contrasting data from WS2flake on Si and Au surfaces. Local charge depletion induced by the nature of the sample-substrate junction in case of WS2on Au is seen to invert the electrical response with comprehensible effects on their spectroscopic properties. Finally, the role of these optoelectronic properties in preserving valley polarization that affects valleytronic applications in WS2flakes, is investigated via circular polarization discriminated photoluminescence experiments. The study provides a thorough understanding of spatial heterogeneity in optoelectronic properties of WS2and other transition metal chalcogenides, which are critical for device fabrication and potential applications.

Phosphorene-quantum-dot-interspersed few-layered MoS2 hybrids as efficient bifunctional electrocatalysts for hydrogen and oxygen evolution.

0-D/2-D hybrids made up of phosphorene quantum dot (PQD)-interspersed few-layered MoS2 nanosheets were demonstrated to be efficient electrocatalysts with remarkable bifunctional electrocatalytic activity for oxygen and hydrogen evolution in an alkaline medium. The excellent performance of the PQD/MoS2 hybrids was attributed to their unique morphology, which facilitated charge transfer, leading to improved HER and OER kinetics.

Lithium-Ion-Based Electrochemical Energy Storage in a Layered Vanadium Formate Coordination Polymer.

A vanadium formate (VF) coordination polymer and its composite with partially reduced graphene oxide (prGO), namely VF-prGO, can be applied as anode materials for Li-ion based electrochemical energy storage (EcES) systems in the potential range of 0-3 V (vs Li+ /Li). This study shows that a reversible capacity of 329 mAh g-1 at a current density of 50 mA g-1 after 50 cycles can be realized for VF along with a high rate capability. The composite exhibits even a higher capacity of 504 mAh g-1 at 50 mA g-1 . A good capacity retention is observed even after 140 cycles for both VF and the composite. An ex-situ X-ray photoelectron spectroscopy study indicates the involvement of V3+ /V4+ redox couple in the charge storage mechanism. A significant contribution of this reversible capacity is attributed to the pseudocapacitive behavior of the system.

Electrocatalysis on Edge-Rich Spiral WS2 for Hydrogen Evolution.

Transition metal dichalcogenides (TMDs) exhibit promising catalytic properties for hydrogen generation, and several approaches including defect engineering have been shown to increase the active catalytic sites. Despite preliminary understandings in defect engineering, insights on the role of various types of defects in TMDs for hydrogen evolution catalysis are limited. Screw dislocation-driven (SDD) growth is a line defect and yields fascinating spiral and pyramidal morphologies for TMDs with a large number of edge sites, resulting in very interesting electronic and catalytic properties. The role of dislocation lines and edge sites of these spiral structures on their hydrogen evolution catalytic properties is unexplored. Here we show that the large number of active edge sites connected together by dislocation lines in the vertical direction for a spiral WS2 domain results in exceptional catalytic properties toward hydrogen evolution reaction. A micro-electrochemical cell fabricated by photo- and electron beam-lithography processes is used to study the electrocatalytic activity of a single spiral WS2 domain, controllably grown by chemical vapor deposition. Conductive atomic force microscopy studies show improved vertical conduction for the spiral domain, which is compared with monolayer and mechanically exfoliated thick WS2 flakes. The obtained results are interesting and shed light on the role of SDD line defects, which contribute to large number of edge sites without compromising the vertical electrical conduction, on the electrocatalytic properties of TMDs for hydrogen evolution.

High degree of circular polarization in WS2 spiral nanostructures induced by broken symmetry.

We present helicity resolved photoluminescence (PL) measurements of WS2 spiral (SPI) nanostructures. We show that very high degree of circular polarization (DCP) (~94 ± 4%) is obtained from multilayer SPI samples at room temperature upon excitation with a circularly polarized laser at a wavelength near-resonant with the A-exciton (633 nm). TEM analysis showed that these SPI nanostructures have AB stacking in which the inversion symmetry is broken, and hence this leads to very high DCP. Comparison with PL from monolayer and bi-layer WS2 samples, along with polarization resolved PL studies provide evidence for suppression of interlayer/intravalley scattering in the multilayer SPI samples.

Nanostructured Na2Ti9O19 for Hybrid Sodium-Ion Capacitors with Excellent Rate Capability.

Herein, we report a new Na-insertion electrode material, Na2Ti9O19, as a potential candidate for Na-ion hybrid capacitors. We study the structural properties of nanostructured Na2Ti9O19, synthesized by a hydrothermal technique, upon electrochemical cycling vs Na. Average and local structures of Na2Ti9O19 are elucidated from neutron Rietveld refinement and pair distribution function (PDF), respectively, to investigate the initial discharge and charge events. Rietveld refinement reveals electrochemical cycling of Na2Ti9O19 is driven by single-phase solid solution reaction during (de)sodiation without any major structural deterioration, keeping the average structure intact. Unit cell volume and lattice evolution on discharge process is inherently related to TiO6 distortion and Na ion perturbations, while the PDF reveals the deviation in the local structure after sodiation. Raman spectroscopy and X-ray photoelectron spectroscopy studies further corroborate the average and local structural behavior derived from neutron diffraction measurements. Also, Na2Ti9O19 shows excellent Na-ion kinetics with a capacitve nature of 86% at 1.0 mV s-1, indicating that the material is a good anode candidate for a sodium-ion hybrid capacitor. A full cell hybrid Na-ion capacitor is fabricated by using Na2Ti9O19 as anode and activated porous carbon as cathode, which exhibits excellent electrochemical properties, with a maximum energy density of 54 Wh kg-1 and a maximum power density of 5 kW kg-1. Both structural insights and electrochemical investigation suggest that Na2Ti9O19 is a promising negative electrode for sodium-ion batteries and hybrid capacitors.

CaO nanocrystals grown over SiO2 microtubes for efficient CO2 capture: organogel sets the platform.

Materials that can capture and store CO2 are important. Though CaO is a cheap sorbent, it is inefficient for practical purposes due to sintering and poor diffusion of CO2 through the surface-CaCO3 layer. We have developed a high performance, sintering-resistant CaO-based sorbent by uniformly nanofabricating the CaO nanocrystals on SiO2 microtubes made by organogel templated polymerization.

The synthesis of high coercivity cobalt-in-carbon nanotube hybrid structures and their optical limiting properties.

Magnetic heterostructures with carbon nanotubes having multiple functionalities are fascinating materials which can be manipulated by means of an external magnetic field. In this paper we report our investigations on the synthesis and optical limiting properties of pristine cobalt nanotubes and high coercivity cobalt-in-carbon nanotubes (a new nanosystem where carbon nanotubes are filled with cobalt nanotubes). A general mobility assisted growth mechanism for the formation of one-dimensional nanostructures inside nanopores is verified in the case of carbon nanotubes. The open-aperture z-scan technique is employed for the optical limiting measurements in which nanosecond laser pulses at 532 nm have been used for optical excitation. Compared to the benchmark pristine carbon nanotubes these materials show an enhanced nonlinear optical absorption, and the nonlinear optical parameters calculated from the data show that these materials are efficient optical limiters. To the best of our knowledge this is the first report where the optical limiting properties of metal nanotubes are compared to those of carbon nanotubes.

On the synthesis and magnetic properties of multiwall carbon nanotube-superparamagnetic iron oxide nanoparticle nanocomposites.

Multiwall carbon nanotubes (MWCNTs) possessing an average inner diameter of 150 nm were synthesized by template assisted chemical vapor deposition over an alumina template. Aqueous ferrofluid based on superparamagnetic iron oxide nanoparticles (SPIONs) was prepared by a controlled co-precipitation technique, and this ferrofluid was used to fill the MWCNTs by nanocapillarity. The filling of nanotubes with iron oxide nanoparticles was confirmed by electron microscopy. Selected area electron diffraction indicated the presence of iron oxide and graphitic carbon from MWCNTs. The magnetic phase transition during cooling of the MWCNT-SPION composite was investigated by low temperature magnetization studies and zero field cooled (ZFC) and field cooled experiments. The ZFC curve exhibited a blocking at approximately 110 K. A peculiar ferromagnetic ordering exhibited by the MWCNT-SPION composite above room temperature is because of the ferromagnetic interaction emanating from the clustering of superparamagnetic particles in the constrained volume of an MWCNT. This kind of MWCNT-SPION composite can be envisaged as a good agent for various biomedical applications.

Direct growth of aligned carbon nanotubes on bulk metals.

There are several advantages of growing carbon nanotubes (CNTs) directly on bulk metals, for example in the formation of robust CNT-metal contacts during growth. Usually, aligned CNTs are grown either by using thin catalyst layers predeposited on substrates or through vapour-phase catalyst delivery. The latter method, although flexible, is unsuitable for growing CNTs directly on metallic substrates. Here we report on the growth of aligned multiwalled CNTs on a metallic alloy, Inconel 600 (Inconel), using vapour-phase catalyst delivery. The CNTs are well anchored to the substrate and show excellent electrical contact with it. These CNT-metal structures were then used to fabricate double-layer capacitors and field-emitter devices, which demonstrated improved performance over previously designed CNT structures. Inconel coatings can also be used to grow CNTs on other metallic substrates. This finding overcomes the substrate limitation for nanotube growth which should assist the development of future CNT-related technologies.