Publications

Inorganic layered compounds (2D-materials), particularly transition metal dichalcogenide (TMDC), are the focus of intensive research in recent years. Shortly after the discovery of carbon nanotubes (CNTs) in 1991, it was hypothesized that nanostructures of 2D-materials can also fold and seam forming, thereby nanotubes (NTs). Indeed, nanotubes (and fullerene-like nanoparticles) of WS₂ and subsequently from MoS₂ were reported shortly after CNT. However, TMDC nanotubes received much less attention than CNT until recently, likely because they cannot be easily produced as single wall nanotubes with well-defined chiral angles. Nonetheless, NTs from inorganic layered compounds have become a fertile field of research in recent years. Much progress has been achieved in the high-temperature synthesis of TMDC nanotubes of different kinds, as well as their characterization and the study of their properties and potential applications. Their multiwall structure is found to be a blessing rather than a curse, leading to intriguing observations. This concise minireview is dedicated to the recent progress in the research of TMDC nanotubes. After reviewing the progress in their synthesis and structural characterization, their contributions to the research fields of energy conversion and storage, polymer nanocomposites, andunique optoelectronic devices are being reviewed. These studies suggest numerous potential applications for TMDC nanotubes in various technologies, which are briefly discussed.

Nanocomposite materials, integrating nanoscale additives into a polymer matrix, hold immense promise for their exceptional property amalgamation. This study delves into the fabrication and characterization of polyetherimide (PEI) nanocomposite strings fortified with multiwall WS₂ nanotubes. The manufacturing process capitalizes on the preferential alignment of WS₂ nanotubes along the string axis, corroborated by scanning electron microscopy (SEM). Mechanical measurements unveil a remarkable acceleration of strain hardening in the nanocomposite strings, chiefly attributed to the WS₂ nanotubes. Structural analyses via X-ray diffraction (XRD) and wide-angle X-ray scattering (WAXS) reveal intriguing structural alterations during tensile deformation. Notably a semi-crystalline framework ∼100 nm in diameter surrounding the WS₂ nanotubes emerges, which is stabilized by the π-π interactions between the PEI chains. The amorphous majority phase (97% by volume) undergoes also major structural changes upon strain becoming more compact and closing-up of the distance beweeetn the PEI chains. Dynamic mechanical analysis (DMA) demonstrates improved thermal stability of the evolved semi-crystalline π-π oriented PEI molecules, characterized by delayed thermal \u201cstructural melting\u201d, underscoring the pivotal role of the WS₂ nanotubes in reinforcing the nanocomposite. The insight gained in this study of WS₂ nanotube-reinforced PEI nanocomposite strings, could offer diverse applications for such tailor-made polymeric materials.

Uranium is a high-value energy element, yet also poses an appreciable environmental burden. The demand for a straightforward, low energy, and environmentally friendly method for encapsulating uranium species can be beneficial for long-term storage of spent uranium fuel and a host of other applications. Leveraging on the low melting point (60 °C) of uranyl nitrate hexahydrate and nanocapillary effect, a uranium compound is entrapped in the hollow core of WS₂ nanotubes. Followingly, the product is reduced at elevated temperatures in a hydrogen atmosphere. Nanocrystalline UO₂ nanoparticles anchor within the WS₂ nanotube lumen are obtained through this procedure. Such methodology can find utilization in the processing of spent nuclear fuel or other highly active radionuclides as well as a fuel for deep space missions. Moreover, the low melting temperatures of different heavy metal-nitrate hydrates, pave the way for their encapsulation within the hollow core of the WS₂ nanotubes, as demonstrated herein.

The inclusion of tungsten disulphide nanotubes (WS₂ NTs) in chitosan, plasticized with glycerol, facilitates the formation of a polyelectrolyte complex. The glycerol interrupts the intramolecular hydrogen bonding between chitosan chains allowing positively charged protonated amines of chitosan to form a complex with negatively charged oxygen ions chemisorbed to the tungsten atoms in defects. These interactions, with the unique mechanical and chemical properties of WS₂ NTs, result in a chitosan film with superior properties relative to unfilled chitosan. Even at low WS₂ NT loadings (≤1 wt%), the Young's modulus (E) increases by 59%, tensile strength (σ) by 40% and tensile toughness by 74%, compared to neat chitosan, without sacrificing ductility. Addition of highly dispersed WS₂ NTs significantly improves the gas barrier properties of chitosan, with a 50% reduction in oxygen permeability, while the addition of both glycerol and WS₂ NTs to chitosan effectively reduces the carbon dioxide permeability by 80% and the water vapor transmission rate by 90%. The intrinsic antimicrobial efficacy of chitosan against both Gram-positive and Gram-negative bacteria is enhanced on inclusion of WS₂ NTs. Polyelectrolyte complexation of WS₂ NTs and glycerol-plasticized chitosan provides a cost-effective, sustainable route to biodegradable films with desirable mechanical, gas barrier properties, and antimicrobial efficacy suitable for food packaging applications.

The synthesis of complex new nanostructures is challenging but also bears the potential for observing new physiochemical properties and offers unique applications in the long run. High-temperature synthesis of ternary WSe2xS2(1-x) (denoted as WSSe) nanotubes in a pure phase and in substantial quantities is particularly challenging, requiring a unique reactor design and control over several parameters, simultaneously. Here, the growth of WSSe nanotubes with the composition 0 ≤ x

The dimensional limit of ferroelectricity has been long explored. The critical contravention is that the downscaling of ferroelectricity leads to a loss of polarization. This work demonstrates a zero-dimensional ferroelectricity by the atomic sliding at the restrained van der Waals interface of crossed tungsten disufilde nanotubes. The developed zero-dimensional ferroelectric diode in this work presents not only non-volatile resistive memory, but also the programmable photovoltaic effect at the visible band. Benefiting from the intrinsic dimensional limitation, the zero-dimensional ferroelectric diode allows electrical operation at an ultra-low current. By breaking through the critical size of depolarization, this work demonstrates the ultimately downscaled interfacial ferroelectricity of zero-dimensional, and contributes to a branch of devices that integrates zero-dimensional ferroelectric memory, nano electro-mechanical system, and programmable photovoltaics in one.Down-scaled ferroelectricity normally diminishes due to the arising depolarization field. Here, the authors realize a 0D ferroelectric diode device taking advantage of the sliding at the van der Waals interface by the two crossed tungsten disulfide nanotubes.

Functionalisation of nanofillers is required for the promotion of strong interfacial interactions with polymers and is essential as a route for the preparation of (nano)composites with superior mechanical properties. Tungsten disulphide nanotubes (WS₂ NTs) were functionalized using (3-aminopropyl) triethoxysilane (APTES) for preparation of composites with poly(lactic acid) (PLA). The WS₂ NTs : APTES ratios used were 1 : 1, 1 : 2 and 1 : 4 WS₂ NTs : APTES. The APTES formed siloxane networks bound to the NTs via surface oxygen and carbon moieties adsorbed on the WS₂ NTs surface, detected by X-ray photoelectron spectroscopy (XPS) studies and chemical mapping using energy dispersive X-ray spectroscopy in the scanning transmission electron microscope (STEM-EDS). The successful silane modification of the WS2 NTs was clearly evident with both significant peak shifting by as much as 60 cm(-1) for Si-O-Si vibrations (FTIR) and peak broadening of the A(1g) band in the Raman spectra of the WS2 NTs. The evolution of new bands was also observed and are associated with Si-CH₂-CH₂ and, symmetric and assymetric -NH³⁺ deformation modes (FTIR). Further evidence for functionalization was obtained from zeta potential measurements as there was a change in surface charge from negative for pure WS₂ NTs to positive for APTES modified WS₂ NTs. Additionally, the thermal stability of APTES was shifted to much higher temperatures as it was bound to the WS₂ NTs. The APTES modified WS2 NTs were organophilic and readily dispersed in PLA, while presence of the pendant amine and hydroxyl groups resulted in strong interfacial interactions with the polymer matrix. The inclusion of as little as 0.5 wt% WS2 NTs modified with 2.0 wt% APTES resulted in an increase of 600% in both the elongation at break (a measure of ductility) and the tensile toughness relative to neat PLA, without impacting the stiffness or strength of the polymer.

Cationic photo-initiated and polymerized epoxies are characterized by good adhesion, high modulus, zero volatiles, low shrinkage and living polymerization characteristics. Radiationcured acrylate resins are characterized by rapid initial curing with increased initial strength. The combination of radiation-cured acrylates and epoxies may present advantageous attributes. Thus, the system investigated is a hybrid epoxy/methyl acrylate and three different initiators for cationic polymerization of epoxies, the radical reaction of acrylates and the thermal initiator. When incorporating additives like opaque WS₂ nanoparticles (NPs), absorption of the photo radiation takes place, which may lead to low photo activity. Curing kinetics measurements revealed that the absorbing/masking effect of WS₂ was insignificant, and surprisingly, the level of curing was enhanced when the WS₂ NPs were incorporated. FTIR results demonstrated that covalent bonds were formed between the inorganic fullerenes (IF-WS₂) and the crosslinked matrix. Viscosity measurements showed a surprising reduction of five to ten times in the low-shear viscosity upon NPs incorporation compared to neat resins. It was concluded that the decrease of viscosity by the inorganic NPs, in addition to the enhanced level of conversion, has profound advantages for structural adhesives and 3D printing resins. To the best of our knowledge, this investigation is the first to report on a radiation-induced curing system containing opaque WS₂ NPs that leads to an enhanced degree of curing and reduced shear viscosity.

Update on the synthesis and characterization of new inorganic nanotubes from 2D compounds, like W(S,Se)2 1 0≤ xS≤ 1) will be given. Fig. 1 shows scanning transmission electron microscopy (STEM) and X-ray energy dispersive spectroscopy (EDS) imaging of such nanotubes. The strong coupling between optical cavity modes confined in the nanotube and the exitonic transitions have been studied in some detail.¹² An 'artificial recording eye' combining vison, storage and writing power has been established by a 4 × 4 array of WS₂ nanotubes.³ Fruitful efforts to obtain WS₂ nanotubes of large aspect ratio (> 2000) were reported.⁴ Fig. 2 shows scanning electron microscopy (SEM) image of an assortment of such nanotubes. Recent progress in mechanically reinforcing different polymers, will be briefly discussed, mostly in relation to biomedical technologies and 3D printing.

Even though WS₂nanotubes (NTs-WS₂) have great potential as anode materials for lithium-ion batteries (LIBs) and sodium-ion batteries (SIBs) thanks to their unusual layered structure, their conductivity and cycling stability are far from satisfactory. To tackle these issues, carbon-coated WS₂(NTs-WS₂@C) nanocomposites were prepared through a facile synthesis method that involved precipitating a carbon precursor (20% sucrose) on WS₂nanotubes, followed by annealing treatment under an argon environment. Thanks to the presence of highly conductive and mechanically robust carbon on the outer surface, NTs-WS₂@C nanocomposites show improved electrochemical performance compared with bare NTs-WS₂. After 60 cycles at 80 mA g^-1current density, the cells display high capacities of 305 mAh g^-1in LIBs and 152 mAh g^-1in SIBs, respectively. As the current density increases to 600 mA g^-1, it provides specific capacities of 209 and 115 mAh g^-1, correspondingly. The enhanced electrochemical performance in LIBs and SIBs is primarily attributed to the synergistic effects of the tubular architecture of WS₂, carbon network and stable nanocomposite structure, which can effectively constrain volume variation during the metal ions intercalation/deintercalation processes.

Nanotubes of transition metal dichalcogenides such as WS2 and MoS2 offer unique quasi-1D properties and numerous potential applications. Replacing sulfur by selenium would yield ternary WS2(1x)Se2x (0 ≤ x ≤ 1; WSSe) nanotubes, which are expected to reveal strong modulation in their absorption edge as a function of selenium content, x Se. Solid WO2.72 oxide nanowhiskers were employed as a sacrificial template to gain a high yield of the nanotubes with a rather uniform size distribution. Though sulfur and selenium belong to the same period, their chemical reactivity with oxide nanowhiskers differed appreciably. Here, the closed ampoule technique was utilized to achieve the completion of the solidvapor reaction in short time scales instead of the conventional flow reactor method. The structure and chemical composition of the nanotubes were analyzed in detail. X-ray and electron diffractions indicated a systematic modulation of the WSSe lattice upon increasing the selenium content. Detailed chemical mapping showed that the sulfur and selenium atoms are distributed in random positions on the anion lattice site of the nanotubes. The optical excitonic features and absorption edges of the WSSe nanotubes do not vary linearly with the composition x Se, which was further confirmed by density functional theory calculations. The WSSe nanotubes were shown to exhibit strong lightmatter interactions forming excitonpolariton quasiparticles, which was corroborated by finite-difference time-domain simulations. Transient absorption analysis permitted following the excited state dynamics and elucidating the mechanism of the strong coupling. Thus, nanotubes of the ternary WSSe alloys offer strong band gap tunability, which would be useful for multispectral vision devices and other optoelectronic applications.

Exploring the behavior of nanocrystals with varying shapes and sizes under high pressure is crucial to understanding the relationship between the morphology and properties of nanomaterials. In this study, we investigated the compression behaviors of WS2 nanotubes (NT−WS2) and fullerene-like nanoparticles (IF−WS2) by in situ high-pressure X-ray diffraction (XRD) and Raman spectroscopy. It was found that the bulk modulus of NT−WS2 is (81.7 GPa), which is approximately twice as large as that of IF-WS2 (46.3 GPa). This might be attributed to the fact that IF−WS2 with larger d-spacing along the c−axis and higher defect density are more compressible under isotropic pressure than NT−WS2. Thus, the slender NT−WS2 possess a more stable crystal structure than the IF-WS2. Our findings reveal that the effects of morphology and size play crucial roles in determining the high-pressure properties of WS2 nanoparticles, and provide significant insight into the relationship between structure and properties.

Several nanotubular structures from chalcogenide-based misfit layer compounds (MLC) were reported in recent years. MLCs consist of a stacking of two alternating and dissimilar (2D) atomic layers, e. g. one with rocksalt structure (MX) and the other- TX₂ with hexagonal layer structure. The layers are held together by weak van der Waals forces, i. e. they can be exfoliated with scotch-tape. Furthermore, in analogy to intercalation compounds, partial charge transfer between the layers with dissimilar work function results also in polar forces between the MX and TX₂ layers. The mismatch between the alternating (asymmetric) layers and the seaming of the dangling bonds at the edges drives them to form tubular (and also scroll-like) structures. New structural characterization whereby the nanotubes were bisected into lamella via focused ion beam and examined by TEM, are reported.

Inorganic nanotubes (NT), such as WS2NT, have unique properties making them promising candidates for op-toelectronic devices. Herein, we performed optical absorption, Raman, and time-domain terahertz spectroscopy of WS2NT in addition to the microscopy measurements to reveal their optoelectronic properties.

Asymmetric two-dimensional (2D) structures (often named Janus), like SeMoS and their nanotubes, have tremendous scope in material chemistry, nanophotonics, and nanoelectronics due to a lack of inversion symmetry and time-reversal symmetry. The synthesis of these structures is fundamentally difficult owing to the entropy-driven randomized distribution of chalcogens. Indeed, no Janus nanotubes were experimentally prepared, so far. Serendipitously, a family of asymmetric misfit layer superstructures (tubes and flakes), including LaX-TaX2 (where X = S/Se), were synthesized by high-temperature chemical vapor transport reaction in which the Se binds exclusively to the Ta atoms and La binds to S atoms rather than the anticipated random distribution.With increasing Se concentration, the LaS-TaX2 misfit structure gradually transformed into a new LaS-TaSe2-TaSe2 superstructure. No misfit structures were found for xSe = 1. These counterintuitive results shed light on the chemical selectivity and stability of misfit compounds and 2D alloys, in general. The lack of inversion symmetry in these asymmetric compounds induces very large local electrical dipoles. The loss of inversion and time-reversal symmetries in the chiral nanotubes offers intriguing physical observations and applications.

This conference contribution is focused on decoration of WS2 nanotubes (NT-WS2) with gold and silver nanoparticles via facile routes implying direct reaction of tungsten disulfide with water-soluble AuIII and AgI species at 100°C. The underlying mechanism of these interactions will be discussed in details based on extensive studies of reaction mixtures and resulting metalNT-WS2 nanocomposites, including thorough X-ray photoelectron spectroscopy (XPS) analysis. Surprising features in optical spectra of the designed nanocomposites would be reported, including suppression of plasmon resonance in tiny noble metal nanoparticles (

We present density functional theory calculations of the vibrational and electronic properties of the misfit-layer compound (MLC) LaS-CrS2 and its isolated sublayers to identify the vibrational modes of the compound. From the comparison of two model systems, (i) the fully relaxed misfit-layer compound supercell and (ii) its sublayers as isolated systems, we extract the charges, which are transferred between the two sublayers and the concomitant changes of the structural parameters upon formation of the supercell. The deformation within each sublayer indicates a strong influence of the charge transfer, confirming the important role of the interlayer interaction between the two sublayers. By comparing the vibrational properties of the two model systems, we assign several frequency regimes within the vibrations of the supercell to phonon branches of the sublayers. From polarized Raman spectra, we find that some of the Raman modes are directly inherited from the Δ-point phonons of the hypothetical isolated 1T-CrS2 layer; other Raman modes are backfolded from the A1g-associated phonon branch of the 1T-CrS2 onto the misfit-layer compound MLC Δ-point, which is a direct consequence of the supercell formation in LaS-CrS2.

Misfit layered compounds (MLCs) have been studied in the literature for the last 40 years. They are generally made of an alternating sequence of two monolayers, a distorted rocksalt structure, and a hexagonal layered compound. In a typical MLC, the c-axis is common to the two monolayers and so is one of the axes in the layer plan. However, the two compounds are non-commensurate along at least one axis, and the ratio between the two axes is an irrational number making the MLC a non-stoichiometric compound. The two main families of MLC are those based on metal dichalcogenides and CoO2 as the hexagonal layered compound. Traditionally, ternary MLCs were prepared and studied, but some quaternary and multinary MLC minerals have been known for many years. Over the last few years, interest in MLCs with four and even larger number of atoms has grown. Doping or alloying of a ternary MLC permits precise control of the charge carrier density and hence the electrical, thermoelectric, catalytic, and optical properties of such compounds. In this short review, some of these developments will be discussed with the main emphasis put on quaternary MLC nanotubes belonging to the chalcogenide series. The synthesis, structural characterization, and some of their properties are considered. Some recent developments in quaternary cobaltite MLCs and recent studies on exfoliated MLCs are discussed as well.

The non-stoichiometric misfit layered compounds (MLC) of the general formula ((MX)(1+y))(m)(TX2)(n) (abbreviated herein as MX-TX2) have been investigated quite extensively over the last 30 years. Here MX is a atomic slab of a material with distorted rocksalt structure and TX2 is a layered compound with hexagonal (octahedral) coordination between the metal T atom and the chalcogen X atom. Recognizing the mismatch between the two (MX and TX2) sublattices, nanotubes from the MLC of different compositions were described in the past. In particular, semimetallic nanotubes belonging to the family LnX-TaX2 with Ln = rare earth atom and X = S, Se, Te have been studied in the past. While some of them, like LaS-TaS2 were obtained with moderately high yields, others like YbS-TaS2 were scarce. In the present study, a new strategy for promoting the yield of such MLC nanotubes by alloying the LaS sublattice with another Ln atom is proposed. Detailed transmission electron microscopy investigation of the (mixed) Ln(x)La((1-x))S-TaS2 (Ln = Pr, Sm, Ho, Yb) nanotubes show clearly that the substituting Ln atom resides in the rocksalt LaS sublattice of the nanotubes. Raman measurements show distinct differences between mixed tubes with open-shell (Pr, Sm, Ho) and close-shell (La, Yb) rare-earth atoms. Density functional calculations show that the interplay between two important factors determine the enhanced stability of the mixed nanotubes- the size and electronic structure of the substituting rare-earth atom. The smaller is the substituting rare-earth atom (larger Z number), the more dissimilar it is to the original La atom. This dissimilarity enhances the incommensurability between the Ln(x)La((1-x))5 and the TS2 subunits, promoting thereby the stability of the mixed MLC. However, the electronic structure of the Ln atom was found to play a more significant role. The MLC lattice of the LaS-TaS2 is electron-rich and consequently the 4d(z)(2) level of Ta is full. The unoccupied 4f levels of the substituent open-shell atoms (Pr, Sm, Ho), which are positioned below the Fermi level, serve as electron acceptors. Consequently, the Ln substitution is found to enhance the stability of the mixed lattice and nanotubes thereof. This strategy can be employed for enhancing the yield of these and other misfit nanotubes using different substituents of the right size and energy profile.

Proton exchange membranes with high through-plane proton conductivity are a critical component of high-performance fuel cells, electrolyzers, and batteries. However, isotropically distributed proton-conducting channel structures of current membranes present a limitation. Herein, a proton exchange membrane with straight proton-conducting channels aligned in the thickness direction is fabricated, achieved by magnetic field-induced alignment of proton-conductive, paramagnetic, and one-dimensional (1D) tungsten disulfide nanotubes (pms-WS2) distributed in a perfluorinated sulfonic acid (Nafion) membrane. The pms-WS2 nanotubes feature straight WS2 nanotubes as a core, a polystyrenesulfonate (PSS) skin layer, and surface-decorated Fe3O4 nanoparticles. A molecular dynamics simulation suggests that straight proton-conducting channels are constructed at the interface of Nafion/pms-WS2 due to densely populated sulfonic acids. Spectroscopic investigation and magnetization measurements verify the through-plane alignment of pms-WS2 under a weak through-plane magnetic field (0.035 T) during the removal of solvent from the membrane cast. Compared with a recast Nafion membrane with the same thickness, the through-plane aligned composite membrane exhibits 69% higher proton conductivity and 51% higher power performance in a proton exchange membrane fuel cell, demonstrating its efficacy. The through-plane alignment of a proton-conductive inorganic 1D material promises improved power performance of advanced electrochemical devices.

We present the analysis of a family of nanotubes (NTs) based on the quaternary misfit layered compound (MLC) YxLa1-xS-TaS2. The NTs were successfully synthesized within the whole range of possible compositions via the chemical vapor transport technique. In-depth analysis of the NTs using electron microscopy and spectroscopy proves the in-phase (partial) substitution of La by Y in the (La,Y)S subsystem and reveals structural changes compared to the previously reported LaS-TaS2 MLC-NTs. The observed structure can be linked to the slightly different lattice parameters of LaS and YS. Raman spectroscopy and infrared transmission measurements reveal the tunability of the plasmonic and vibrational properties. Density-functional theory calculations showed that the YxLa1-xS-TaS2 MLCs are stable in all compositions. Moreover, the calculations indicated that substitution of La by Sc atoms is electronically not favorable, which explains our failed attempt to synthesize these MLC and NTs thereof.

Based on the analysis of spectral parameters, orientation angle, and the time dependency of the reaction and relaxation of the media composed of the nematic liquid crystal mesophase and WS2 nanoparticles, the correlation associated with the formation of intermolecular interaction between CN-group of the liquid crystal and WS2 nanoparticle has been established. The correlation was supported by experiments and partially by quantumchemical modeling.

Strong coupling of electric transition dipoles with optical or plasmonic resonators modifies their light-matter interaction and, therefore, their optical spectra. Semiconducting WS2 nanotubes intrinsically provide the dipoles through their excitonic resonances, and the optical cavity via their cylindrical shape. We investigate the nonequilibrium light-matter interaction in WS2 nanotubes in the time domain using femtosecond transient extinction spectroscopy. We develop a phenomenological coupled oscillator model with time-dependent parameters to describe the transient extinction spectra, allowing us to extract the underlying nonequilibrium electron dynamics. We find that the exciton and trion resonances shift due to many-body effects of the photogenerated charge carriers and their population dynamics on the femto- A nd picosecond timescale. Our results show that the time-dependent phenomenological model quantitatively reproduces the nonequilibrium optical response of strongly coupled systems.

The photovoltaic effect in traditional pn junctionswhere a p-type material (with an excess of holes) abuts an n-type material (with an excess of electrons)involves the light-induced creation of electronhole pairs and their subsequent separation, generating a current. This photovoltaic effect is particularly important for environmentally benign energy harvesting, and its efficiency has been increased dramatically, almost reaching the theoretical limit1. Further progress is anticipated by making use of the bulk photovoltaic effect (BPVE)2, which does not require a junction and occurs only in crystals with broken inversion symmetry3. However, the practical implementation of the BPVE is hampered by its low efficiency in existing materials410. Semiconductors with reduced dimensionality2 or a smaller bandgap4,5 have been suggested to be more efficient. Transition-metal dichalcogenides (TMDs) are exemplary small-bandgap, two-dimensional semiconductors11,12 in which various effects have been observed by breaking the inversion symmetry inherent in their bulk crystals1315, but the BPVE has not been investigated. Here we report the discovery of the BPVE in devices based on tungsten disulfide, a member of the TMD family. We find that systematically reducing the crystal symmetry beyond mere broken inversion symmetrymoving from a two-dimensional monolayer to a nanotube with polar propertiesgreatly enhances the BPVE. The photocurrent density thus generated is orders of magnitude larger than that of other BPVE materials. Our findings highlight not only the potential of TMD-based nanomaterials, but also more generally the importance of crystal symmetry reduction in enhancing the efficiency of converting solar to electric power.

Misfit-layered compounds (MLCs) are formed by the combination of different lattices and exhibit intriguing structural and morphological characteristics. MLC SrxLa1-xS-TaS2 nanotubes with varying Sr composition (10, 20, 40, and 60 Sr atom %, corresponding to x = 0.1, 0.2, 0.4 and 0.6, respectively) were prepared in the present study and systematically investigated using a combination of high-resolution electron microscopy and spectroscopy. These studies enable detailed insight into the structural aspects of these phases to be gained at the atomic scale. The addition of Sr had a significant impact on the formation of the nanotubes with higher Sr content, leading to a decrease in the yield of the nanotubes. This trend can be attributed to the reduced charge transfer between the rare earth/S unit (LaxSr1-xS) and the TaS2 layer in the MLC which destabilizes the MLC lattice. The influence of varying the Sr content in the nanotubes was systematically studied using Raman spectroscopy. Density functional theory calculations were carried out to support the experimental observations.

Transition-metal dichalcogenides (TMDs) are exemplary low-dimensional semiconductors. By breaking the inversion symmetry inherent in their bulk crystals, various exotic physical phenomena have been realized. We studied electrical responses under light illumination in such noncentrosymmetric TMDs belonging to a few different point groups, and observed a large photovoltaic effect induced by the reduction of the crystal symmetry.

Self-lubricating films are of immense importance in various tribological applications. Nanoparticles are often used as the lubricating component in such films. Inorganic fullerene-like (IF) nanoparticles of WS2 have been used in the past for variety of tribological applications including for self-lubricating polymer and metallic films. IF nanoparticles from MoS2 with superior tribological behavior were reported in the past. However, such nanoparticles, which are available in minute amounts, were not applied for self-lubricating coatings in the past. In the current work, inorganic fullerene-like nanoparticles of MoS2 (IF-MoS2) were co-evaporated with titanium (cobalt) on metal substrates. The films were characterized by different techniques and were shown to have good adhesion to the underlying substrate. Furthermore, tribological tests indicated that such coatings exhibit improved friction coefficient (roughly 0.1) and very small wear under relatively high load.

Herein, the use of highly concentrated sunlight for materials science research is reviewed. Specific research directions include: (1) the generation of inorganic nanostructures, some of which had eluded experimental realization with conventional synthetic processes, and (2) elucidating the processes governing the degradation of organic and perovskite-based photovoltaic materials and devices, along with accelerated assessment of their stability. Both approaches employ solar concentrators capable of producing flux densities exceeding those of terrestrial solar radiation by up to three orders of magnitude, and are geared toward either creating extensive ultrahot reactor conditions conducive to the rapid, safe synthesis of unusual nanomaterials or judiciously interrogating photovoltaic devices.

The synthesis and characterization of nanotubes from misfit layered compounds (MLCs) of the type (LnS)(1+y)TaS2 (denoted here as LnS-TaS2; Ln=Pr, Sm, Gd, and Yb), not reported before, are described (the bulk compound YbS-LaS2 was not previously documented). Transmission electron microscopy and selected area electron diffraction showed that the interlayer spacing along the c axis decreased with an increase in the atomic number of the lanthanide atom, which suggested tighter interaction between the LnS layer and TaS2 for the late lanthanides. The Raman spectra of the tubules were studied and compared to those of the bulk MLC compounds. Similar to the bulk MLCs, the Raman spectra could be divided into the low-frequency modes (110-150cm(-1)) of the LnS lattice and the high-frequency modes (250-400cm(-1)) of the TaS2 lattice. The Raman spectra indicated that the vibrational lattice modes of the strained layers in the tubes were stiffer than those in the bulk compounds. Furthermore, the modes of the late lanthanides were higher in energy than those of the earlier lanthanides, which suggested larger charge transfer between the LnS and TaS2 layers for the late lanthanides. Polarized Raman measurements showed the expected binodal intensity profile (antenna effect). The intensity ratio of the Raman signal showed that the E-2g mode of TaS2 was more sensitive to the light-polarization effect than its A(1g) mode. These nanotubes are expected to reveal interesting low-temperature quasi-1D transport behavior.

In this paper, we demonstrate the formation of hybrid nanostructures consisting of two distinctive components mainly in a one-to-one ratio. Thermolysis of inorganic nanotubes (INT) and closed-cage, inorganic fullerene-like (IF) nanoparticles decorated with a dense coating of metallic nanoparticles (M = Au, Ag, Pd) results in migration of relatively small NPs or surface-enhanced diffusion of atoms or clusters, generating larger particles (ripening). AuNP growth on the surface of INTs has been captured in real time using in situ electron microscopy measurements. Reaction of the AuNP-decorated INTs with an alkylthiol results in a chemically induced NP fusion process at room temperature. The NPs do not dissociate from the surfaces of the INTs and IFs, but for proximate IFs we observed fusion between AuNPs originating from different IFs.

Due to their favourable and rich electronic and optical properties, group-VI-B transition-metal dichalcogenides (TMDs) have attracted considerable interest. They have earned their position in the materials portfolio of the spintronics and valleytronics communities. The electrical performance of TMDs is enhanced by rolling up the two-dimensional (2D) sheets to form quasi-one-dimensional (1D) tubular structures. The fabrication of p-n junctions out of these tubular TMDs would boost their potential for optoelectronic devices as such junctions represent a fundamental building block. Here, we report the realization of a p-n junction out of a single, isolated WS₂-nanotube (WS₂-NT). Light-emitting diode operation and photovoltaic behaviour were observed based on such p-n junctions. The emitted light as well as the photovoltaic effect exhibit strong linear polarization characteristics due to the quasi-1D nature. The external quantum efficiency for the photovoltaic effect reaches a value as high as 4.8%, exceeding by far that of 2D TMDs and even approaching the internal quantum efficiency of the 2D TMDs. This efficiency improvement indicates that TMD nanotubes are superior candidates over 2D TMDs for optoelectronic applications.

Inorganic fullerene-like closed-cage nanoparticles of MoS2 and WS2 (IF-MoS2; IF-WS2), are synthesized in substantial amounts and their properties are widely studied. Their superior tribological properties led to large scale commercial applications as solid lubricants in numerous products and technologies. Doping of these nanoparticles can be used to tune their physical properties. In the current work, niobium (Nb) doping of the nanoparticles is accomplished to an unprecedented low level (

We report here a new methodology for the formation of freestanding nanotubes composed of individual gold nanoparticles (NPs) cross-linked by coordination complexes or porphyrin molecules using WS
₂ nanotubes (INT-WS
₂) as a template. Our method consists of three steps: (i) coverage of these robust inorganic materials with monodispersed and dense monolayers of gold NPs, (ii) formation of a molecular AuNP network by exposing these decorated tubes to solutions containing a ruthenium polypyridyl complex or meso-tetra(4-pyridyl)porphyrin, and (iii) removal of the INT-WS
₂ template with a hydrogen peroxide solution. Nanoindentation of the template-free AuNP tubes with atomic force microscopy indicates a radial elastic modulus of 4 GPa. The template-free molecular AuNP tubes are characterized using scanning and transmission electron microscopy, energy-dispersive X-ray spectroscopy, and micro-Raman spectroscopy. The methodology provides a convenient and scalable strategy for the realization of molecular AuNP tubes with a defined length and diameter, depending on the dimensions of the template.

We have synthesized quaternary chalcogenide-based misfit nanotubes LnS(Se)-TaS₂(Se) (Ln = La, Ce, Nd, and Ho). None of the compounds described here were reported in the literature as a bulk compound. The characterization of these nanotubes, at the atomic level, has been developed via different transmission electron microscopy techniques, including high-resolution scanning transmission electron microscopy, electron diffraction, and electron energy-loss spectroscopy. In particular, quantification at sub-nanometer scale was achieved by acquiring high-quality electron energy-loss spectra at high energy (∼between 1000 and 2500 eV). Remarkably, the sulfur was found to reside primarily in the distorted rocksalt LnS lattice, while the Se is associated with the hexagonal TaSe₂ site. Consequently, these quaternary misfit layered compounds in the form of nanostructures possess a double superstructure of La/Ta and S/Se with the same periodicity. In addition, the interlayer spacing between the layers and the interatomic distances within the layer vary systematically in the nanotubes, showing clear reduction when going from the lightest (La atom) to the heaviest (Ho) atom. Amorphous layers, of different nature, were observed at the surface of the nanotubes. For La-based NTs, the thin external amorphous layer (inferior to 10 nm) can be ascribed to a Se deficiency. Contrarily, for Ho-based NTs, the thick amorphous layer (between 10 and 20 nm) is clearly ascribed to oxidation. All of these findings helped us to understand the atomic structure of these new compounds and nanotubes thereof.

The nature of the interface between a reinforcement and the matrix is crucial in determining the degree of dispersion and mechanical properties. Controlling the interface is particularly important when 2D materials are used as reinforcements, as their flat nature eliminates bonding mechanisms such as mechanical lock-in. For example, we have previously shown that unfunctionalised graphene in an epoxy matrix has just a tenth of the interfacial strength of a carbon fibre. Herein, we have developed chemical functionalization of two-dimensional (2D) materials as a route to control their interface with thermosets, thermoplastics and elastomers. One well-established method for functionalizing graphene is the use of aryl diazonium chemistry. This functional step is typically applied on as-made powder, however we have found that graphene can be simultaneously functionalized and exfoliated from graphite by electroreduction. This one-step process prevents aggregation, increases thin-flake yield and leads to high quality dispersions. However, similarly structured inorganic 2D materials such as transition metal dichalcogenides (TMDs) have generally been considered to be chemically inert, with few studies into the covalent modification and functionalization of them. Previously, it was believed that only the 1T phase of TMDs could be functionalised by aryl diazonium due to the difference in electronic structure. However, in this work we demonstrate that the more stable and naturally occurring 2H-phase can be successfully functionalised via aryl diazonium chemistry. We have measured the interfacial strength of these functionalized materials within different matrices using Raman mapping of in-situ mechanical tests of single flakes and applying a simple shear lag model. Bulk composites were then produced with flakes processing different aspect ratios to prove that these micromechanics approaches can be translated to the macroscale.

Keywords: Chemistry, Multidisciplinary

The study of inorganic nanometer-scale materials with hollow closed-cage structures, such as inorganic fullerene-like (IF) nanostructures and inorganic nanotubes (INTs), is a rapidly growing field. Numerous kinds of IF nanostructures and INTs were synthesized for a variety of applications, particularly for lubrication, functional coatings, and reinforcement of polymer matrices. To date, such nanostructures have been synthesized mostly by heating a transition metal or oxide thereof in the presence of precursor gases, which are however toxic and hazardous. In this context, one frontier of research in this field is the development of new avenues for the green synthesis of IF structures and INTs, directly from the bulk of layered compounds. In the present work, we demonstrate a simple roomerature and environmentally friendly approach for the synthesis of IF nanostructures and INTs via ultrashort-pulse laser ablation of a mixture of transition-metal dichalcogenides in bulk form mixed with Pb/PbO, in ambient air. The method can be considered as a synergy of photothermally and photochemically induced chemical transformations. The ultrafast-laser-induced excitation of the material, complemented with the formation of extended hot annealing regions in the presence of the metal catalyst, facilitates the formation of different nanostructures. Being fast, easy, and material-independent, our method offers new opportunities for the synthesis of IF nanostructures and INTs from different bulk metal chalcogenide compounds. On the basis of the capabilities of laser technology as well, this method could advantageously be further developed into a versatile tool for the simultaneous growth and patterning of such nanostructures in preselected positions for a variety of applications.

The dielectric and electrical characteristics of the semiconductive WS₂ nanotubes/epoxy composites were studied as a function of the nanotubes concentration and the pressure applied during their molding. In addition, the ability of WS₂ nanotubes to serve as stress sensors in epoxy based nanocomposites, for health-monitoring applications, was studied. The nanocomposite elements were loaded in three-point bending configuration. The direct current was monitored simultaneously with stress-strain measurements. It was found that, in nanocomposites, above the percolation concentrations of the nanotubes, the electrical conductivity increases considerably with the applied load and hence WS₂ nanotubes can be potentially used as sensors for health monitoring of structural components.

Owing to their outstanding variety of properties, nanoparticles attracted considerable interest for developing a new age of novel polymer nanocomposites and adhesives. Among them, inorganic nanotubes (INTs) of tungsten disulfide (WS₂) and carbon nanotubes (CNTs) have been identified as unique candidates for many industrial applications by virtue of their superior mechanical, thermal and tribological properties. In this work, a comparative study between INT-WS₂ and multi-walled carbon nanotubes (MWCNTs) regarding the properties of structural polyurethane (PU) adhesives is presented. Specifically, we evaluate the thermomechanical properties, chemical and micro-phase structure, bonded joints performance in lap shear and peel modes, and fracture mechanisms, with aiming to highlight some of the differences between these nanotubes. The added content spanned over the range of 0.3, 0.6, 0.9 and 1.2 wt% of INT-WS₂, while CNTs are incorporated at the same volumetric fractions (e.g., 0.1, 0.2, 0.3 and 0.4 wt%). According to the results of the tests, in all measured aspects, INT-WS₂ outperformed the carbon counterparts. With regards to the thermomechanical attributes, the hard segment Tg of the PU increased by 14 °C at 0.6 wt% INTs, whereas CNTs recorded only modest improvement of 8 °C at the nanocomposite loaded with 0.4 wt%. The structural bonding performance indicates an improvement of 117% and 38% in the shear and peel strengths at 0.9 and 1.2 wt% INTs, respectively, while CNTs show moderate changes. Interestingly, the changes are also reflected by the interplay between the hard and soft segments of the PU, and different fracture mechanisms operating within the nanocomposites. At any rate, the combined attributes of >20 MPa in the shear strength and approximately 2 N/mm in (average) peel strength, targets the PU/INT nanoadhesives as promising alternative for conventional epoxy systems which has similar shear strength with inferior peel strength.

Chirality of materials are known to affect optical, magnetic and electric properties, causing a variety of nontrivial phenomena such as circular dichiroism for chiral molecules, magnetic Skyrmions in chiral magnets and nonreciprocal carrier transport in chiral conductors. On the other hand, effect of chirality on superconducting transport has not been known. Here we report the nonreciprocity of superconductivity-unambiguous evidence of superconductivity reflecting chiral structure in which the forward and backward supercurrent flows are not equivalent because of inversion symmetry breaking. Such superconductivity is realized via ionic gating in individual chiral nanotubes of tungsten disulfide. The nonreciprocal signal is significantly enhanced in the superconducting state, being associated with unprecedented quantum Little-Parks oscillations originating from the interference of supercurrent along the circumference of the nanotube. The present results indicate that the nonreciprocity is a viable approach toward the superconductors with chiral or noncentrosymmetric structures.

We study for the first time the resonant torsional behaviors of inorganic nanotubes, specifically tungsten disulfide (WS₂) and boron nitride (BN) nanotubes, and compare them to that of carbon nanotubes. We have found WS₂ nanotubes to have the highest quality factor (Q) and torsional resonance frequency, followed by BN nanotubes and carbon nanotubes. Dynamic and static torsional spring constants of the various nanotubes were found to be different, especially in the case of WS₂, possibly due to a velocity-dependent intershell friction. These results indicate that inorganic nanotubes are promising building blocks for high-Q nanoelectromechanical systems (NEMS).

In this report, a systematic study of the effects of p- and n-type doping of the inorganic fullerene (IF) MoS₂ on the efficiency of the hydrogen evolution reaction (HER) is described. Active edge site enriched IF-MoS₂, promoted by strategically introducing Nb (p-type) and Re (n-type) dopants (below 500 ppm), enables facile HER over a range of pH values. Experimental results suggest that although Nb-doping on IF-MoS₂ leads to better electrocatalytic HER activity in an alkaline medium with an onset potential difference of 80 mV, Re-doping gives excellent activity in an acidic medium. The present work presents a systematic study of HER activity by finely tuning the activity in different electrolyte media with varied pH values through deliberate doping of the parent catalyst with p- and n- type materials. The doped IF-MoS₂ catalysts exhibit excellent catalytic activity even with sea water as an electrolyte.

The relationship between structure and properties has been followed for different nanoscale forms of tungsten disulfide (2H-WS₂) namely exfoliated monolayer and few-layer nanoplatelets, and nanotubes. The similarities and differences between these nanostructured materials have been examined using a combination of optical microscopy, scanning and high-resolution transmission electron microscopy and atomic force microscopy. Photoluminescence and Raman spectroscopy have also been used to distinguish between monolayer and few-layer material. Strain induced phonon shifts have been followed from the changes in the positions of the A_1g and E_2g¹ Raman bands during uniaxial deformation. This has been modelled for monolayer using density functional theory with excellent agreement between the measured and predicted behaviour. It has been found that as the number of WS₂ layers increases for few-layer crystals or nanotubes, the A_1g mode hardens whereas the E_2g¹ mode softens. This is believed to be due to the A_1g mode, which involves out of plane atomic movements, being constrained by the increasing number of WS₂ layers whereas easy sliding reduces stress transfer to the individual layers for the E_2g¹ mode, involving only in-plane vibrations. This finding has enabled the anomalous phonon shift behaviour in earlier pressure measurements on WS₂ to be resolved, as well as similar effects in other transition metal dichalcogenides, such as molybdenum disulfide, to be explained.

We present Raman spectra of misfit layer (PbS)(1.14)NbS2 nanotubes and lead intercalated NbS2 nanotubes. They represent interesting model systems to investigate the nature of interlayer interaction in layered materials. A direct correlation to the Raman modes of the parent 2H-NbS2 compound exists, but some modes are seen drastically upshifted in frequency in the misfit layer and intercalated compound while others remain almost unchanged. On the basis of the Raman spectroscopic investigations and with the help of supporting calculations we examine different interlayer bonding mechanisms and contribute to the discussion as to why these frequency shifts occur.

Polyvinyl alcohol (PVA) is a biocompatible, semi-crystalline and water soluble polymer with moderate tensile properties. To improve the thermal and mechanical properties of PVA, as well as to reduce water uptake, structural modification by glutaric acid (GA) and nanoparticle reinforcement by tungsten disulphide nanotubes (WSNTs) were used to prepare PVA based composites. We observed a significant drop in the water uptake of GA crosslinked PVA, an indication of the formation of a network. Fourier transform infrared spectroscopy was applied to confirm the presence of covalent bonds formed during the crosslinking. Crosslinked PVA and composites are found to have higher thermal stability and mechanical properties compared to their un-crosslinked counterparts. Tensile tests show that the presence of WSNTs increases the strength (up to 25%), modulus (up to 120%) and toughness (up to 80%) of the pristine as well as the crosslinked PVA. (C) 2016 Elsevier Ltd. All rights reserved.

The process engineering of Mg alloys is nevertheless compromised due to their relatively poor mechanical properties. To address some of these difficulties, metal-matrix composites (MMCs) of Mg-alloys have been investigated for sometime. In the present work, small amounts (up to 1 wt%) of WS2 nanotubes are mixed with Mg-alloy (AZ31) using melt-stirring process above 700 degrees C. The new MMC nano-composites exhibit much superior mechanical properties vis a vis the pristine alloy. Metallographic investigation demonstrates that the average grain size has been reduced in inverse proportion to the added amounts of nanotubes up to 1 wt%. Physical considerations suggest that the main mechanism responsible for the reinforcement effect lies in the mismatch between the thermal expansion coefficients of the metal and the nanotubes. This mismatch induced large density of dislocations in the grain boundaries in the vicinity of the nanotube-matrix interface, which obstruct the crack propagation. (C) 2015 Elsevier B.V. All rights reserved.

DC and AC electrical properties of hybrid films, consisting of carbon nanotubes and tungsten disulfide nanotubes (and fullerene like nanoparticles) were studied within the 2 - 300 K temperature range and over the 20 Hz - 1 MHz frequency range. The temperature dependences of the resistance R(T) exhibit behavior typical for the fluctuation-induced tunneling model in the intermediate temperature range. Analysis of the dependences of real and imaginary components of the impedance on the frequency (Z(f ) and Z(f )) demonstrates the rising role of the contact barriers between carbon nanotubes inside hybrid films, consisting of the carbon nanotubes and inorganic tungsten disulfide nanotubes as the temperature was decreased. The active component of the impedance was found to prevail in the AC electrical properties of the hybrid films, consisting of multiwall carbon nanotubes and WS₂ nanoparticles over the entire available temperature range.

Silica aerogels are unique solids with extremely high porosity (>99.5% air by volume), transparency and low density. With their high surface area and thermal resistivity they make excellent heat insulators. However, due to their fine structure they are fragile and therefore impractical for structural applications. To improve their mechanical properties we suggest incorporation of minute amounts of tungsten disulfide nanotubes. Nanotubes of tungsten disulfide are known for their high mechanical strength, strain and thermal stability. Adding some 0.11 wt% of tungsten disulfide nanotubes to a variety of polymers clearly lead to substantial improvement in their mechanical properties. The current study reports the preparation of silica aerogels compounded with small amounts of tungsten disulfide nanotubes. Three-point bending and uniaxial compression tests of the composite aerogel revealed 85% and 23% improvement in the composite material toughness, respectively.

The incorporation of nanostructures into nanoelectronic and nanoelectromechanical systems is a long sought-after goal. In the present article, we report the first torsional electromechanical measurements of pure inorganic nanotubes. The WS₂ nanotubes exhibited a complex and reproducible electrical response to mechanical deformation. We combined these measurements with density-functional-tight-binding calculations to understand the interplay between mechanical deformation, specifically torsion and tension, and electrical properties of WS₂ nanotubes. This yielded the understanding that the electrical response to mechanical deformation may span several orders of magnitude on one hand and detect several modes of mechanical deformation simultaneously on the other. These results demonstrate that inorganic nanotubes could thus be attractive building blocks for nanoelectromechanical systems such as highly sensitive nanometric motion sensors.

We report the synthesis and supporting density-functional-theory computations for a closed-cage, misfit layered-compound superstructure from PbS-SnS₂, generated by highly concentrated sunlight from a precursor mixture of Pb, SnS₂, and graphite. The unique reactor conditions created in our solar furnace are found to be particularly conducive to the formation of these nanomaterials. Detailed structural and chemical characterization revealed a spontaneous inside-out formation mechanism, with a broad range of nonhollow fullerene-like structures starting at a diameter of ∼20 nm and a wall thickness of ∼5 layers. The computations also reveal a counterintuitive charge transfer pathway from the SnS₂ layers to the PbS layers, which indicates that, in contrast to binary-layered compounds where it is principally van der Waals forces that hold the layers together, polar forces appear to be as important in stabilizing superstructures of misfit layered compounds. (Figure Presented).

Inorganic, fullerene-like (IF) nanoparticles of tungsten disulfide (WS2) and molybdenum disulfide (MoS2) have been synthesised in the past and their useful tribological properties have been studied quite extensively. Rhenium doping of such nanoparticles was also reported and studied to some extent. Herein, further studies of the physico-chemical properties are reported in connection to lubrication under mild loads. Due to their self-repelling character, the doped nanoparticles form tessellated monolayers on certain substrates. When mixed in small amounts, the IF nanoparticles lead to a reduction in the viscosity of water-based gels. Furthermore, the added nanoparticles lead to a precipitous reduction in traction force (friction) under mild loads. The lubrication mechanism of such nanoparticles is briefly discussed.

Impaired salivary gland (SG) function leading to oral diseases is relatively common with no adequate solution. Previously, tissue engineering of SG had been proposed to overcome this morbidity, however, not yet clinically available. Multiwall inorganic (tungsten disulfide [WS₂]) nanotubes (INT-WS₂) and fullerene-like nanoparticles (IF-WS₂) have many potential medical applications. A yet unexplored venue application is their interaction with SG, and therefore, our aim was to test the biocompatibility of INT/IF-WS₂ with the A5 and rat submandibular cells (RSC) SG cells. The cells were cultured and subjected after 1 day to different concentrations of INT-WS₂ and were compared to control groups. Growth curves, trypan blue viability test, and carboxyfluorescein succinimidyl ester (CFSE) proliferation assay were obtained. Furthermore, cells morphology and interaction with the nanoparticles were observed by light microscopy, scanning electron microscopy and transmission electron microscopy (TEM), and energy dispersive X-ray spectroscopy. The results showed no significant differences in growth curves, proliferation kinetics, and viability between the groups compared. Moreover, no alterations were observed in the cell morphology. Interestingly, TEM images indicated that the nanoparticles are uptaken by the cells and accumulate in cytoplasmic vesicles. These results suggest promising future medical applications for these nanoparticles.

Theoretical analysis of experimental data on unzipping multilayered WS ₂ nanotubes by consequent intercalation of lithium atoms and 1-octanethiol molecules [C. Nethravathi, et al., ACS Nano, 2013, 7, 7311] is presented. The radial expansion of the tube was described using continuum thin-walled cylinder approximation with parameters evaluated from ab initio calculations. Assuming that the attractive driving force of the 1-octanethiol molecule is its reaction with the intercalated Li ions ab initio calculations of a 1-octanethiol molecule bonding with Li⁺ were carried out. In addition, the non-chemical interactions of the 1-octanethiol dipole with an array of positive point charges representing Li⁺ were taken into account. Comparing between the energy gain from these interactions and the elastic strain energy of the nanotube allows us to evaluate a value for the tube wall deformation after the implantation of 1-octanethiol molecules. The ab initio molecular dynamics simulation confirmed our estimates and demonstrated that a strained WS₂ nanotube, with a decent concentration of 1-octanethiol molecules, should indeed be unzipped into the WS₂ nanoribbon.

In the present work, MoS2 nanoparticles with fullerene-like structure, and most particularly those doped with minute amounts of rhenium atoms, are used as additive to medical gels in order to facilitate their entry into constricted openings of soft material rings. This procedure is used to mimic the entry of endoscopes to constricted openings of the human body, like urethra, etc. It is shown that the Re-doped nanoparticles reduce the traction force used to retrieve the metallic lead of the endoscope from the soft ring by a factor close to three times with respect to the original gel. The mechanism of the mitigation of both friction and adhesion forces in these systems by the nanoparticles is discussed.

This minireview outlines the main scientific directions in the research of inorganic nanotubes (INT) and fullerene-like (IF) nanoparticles from layered compounds, in recent years. In particular, this review describes to some detail the progress in the synthesis of new nanotubes, including those from misfit compounds; core-shell and the successful efforts to scale-up the synthesis of WS₂ multiwall nanotubes. The high-temperature catalytic growth of nanotubes, via solar ablation is discussed as well. Furthermore, the doping of the IF-MoS₂ nanoparticles and its influence on the physiochemical properties of the nanoparticles, including their interesting tribological properties are briefly discussed. Finally, the numerous applications of these nanoparticles as superior solid lubricants and for reinforcing variety of polymers are discussed in brief.

Ureteral stents and urethral catheters are commonly used medical devices for maintaining urinary flow. However, long-term placement (>30 days) of these devices in the urinary tracts is limited by the development of encrustation, a phenomenon that holds a prevalence of 50% within this patient population, resulting in a great deal of morbidity to the patients. Here we report the influence of surface coating of an all-silicone catheter with rhenium-doped fullerene-like molybdenum disulfide (Re:IF-MoS₂) nanoparticles on the growth and attachment of in vitro encrustation stones. Scanning electron microscopy (SEM), energy dispersive X-ray spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS) and X-ray powder diffraction (XRD) analyses indicated a remarkable attenuation in encrustation occupation on the Re:IF-MoS₂-coated catheter surfaces compared to neat catheters. The doped nanoparticles displayed a unique tendency to self-assemble into mosaic-like arrangements, modifying the surface to be encrustation-repellent. The mechanism of encrustation retardation on the surface coated catheters is discussed in some detail. The ramification of these results for the clogging of other body indwelling devices is briefly discussed. This journal is

The synthesis of inorganic nanotubes (INT) from layered compounds of a small size (

Carbon fullerenes and nanotubes revolutionized understandingof the reactivity of nanoscale compounds. Subsequently, our group and others discovered analogous inorganic compounds with hollow, closed nanostructures. Such inorganic nanostructures offer many applications, particularly in the energy and electronics industries.One way to create inorganic nanostructures is via misfit layer-ed compounds (MLC), which are stacks of alternating two-dimensional molecular slabs, typically held together via weak van der Waals forces. They contain "misfits" in their a-b plane structures that can make them unstable, leading to collapse of the slabs into tubular nanostructures. For example, metal chalcogenide MLCs of the general formula (MX)_1+y/ TX₂ (M = Sn, Pb, Bi, Sb, and other rare earths; T = Sn, Ti, V, Cr, Nb, Ta, etc.; X = S or Se) consist of a superstructure of alternating layers where the MX unit belongs to a (distorted NaCl) orthorhombic symmetry group (O), the TX₂ layer possesses trigonal (T) or octahedral symmetry, and the two layers are held together via both van der Waals and polar forces. A misfit in the a axis or both a and b axes of the two sublattices may lead to the formation of nanostructures as the lattices relax via scrolling. Previous research has also shown that the abundance of atoms with dangling bonds in the rims makes nanoparticles of compounds with layered structure unstable in the planar form, and they tend to fold into hollow closed structures such as nanotubes.This Account shows that combining these two triggers, misfits and dangling bond annihilation in the slab rims, leads to new kinds of nanotubes from MLCs. In particular, we report the structure of two new types of nanotubes from misfits, namely, the SnS/SnS₂ and PbS/NbS₂ series. To decipher the complex structures of these nanotubes, we use a range of methods: high-resolution transmission electron microscopy (HRTEM), energy-dispersive X-ray spectroscopy (EDS), selected area electron diffraction (SAED) analyses, scanning electron microscopy (SEM), and Cs-corrected scanning transmission electron microscopy (STEM) in the high-angle annular dark-field mode (HAADF). In both new types, the lattice mismatch between the two alternating sublayers dictates the relative layer-stacking order and leads to a variety of chiral tubular structures. In particular, the incommensuration (a type of misfit) of the SnS₂/SnS system in both the (in plane) a and b directions leads to a variety of relative in-plane orientation and stacking orders along the common c-axis. Thus the SnS/SnS₂ nanotubes form superstructures with the sequence O-T and O-T-T, and mixtures thereof. We also report nanotubes of the misfit layered compound (PbS)_1.14NbS₂, and of NbS ₂ intercalated with Pb atoms, with the chemical formula PbNbS ₂. Thus, the possibility to use two kinds of folding mechanisms jointly offers a new apparatus for the synthesis of unique 1-D nanostructures of great complexity and a potentially large diversity of physicochemical properties.

Next-generation catalysts for water splitting are crucial towards a renewable hydrogen economy. MoS₂ and WS₂ represent earth-abundant, noble metal cathode alternatives with high catalytic activity at edge sites. One challenge in their development is to nanostructure these materials in order to achieve increased performance through the creation of additional edge sites. In this work, we demonstrate a simple route to form nanostructured-WS₂ using sonochemical exfoliation to break interlayer and intralayer bonds in WS₂ nanotubes. The resulting few-layer nanoflakes are ∼100 nm wide with a high density of edge sites. WS₂ nanoflakes are utilized as cathodes for the hydrogen evolution reaction (HER) and exhibit superior performance to WS₂ nanotubes and bulk particles, with a lower onset potential, shallower Tafel slope and increased current density. Future work may employ ultra-small nanoflakes, dopant atoms, or graphene hybrids to further improve electrocatalytic activity. [Figure not available: see fulltext.]

Al₂O₃/IF-WS₂ nanocomposite coating was prepared in a two-step process. The Al₂O₃ nano-fibers are the matrix of the composite and the nanoparticles of WS₂ with fullerene-like structure (IF-WS₂) are the dispersed phase material, which can improve the mechanical and tribological properties of the nanocomposite. Detailed structural analysis of the nanocomposites was performed using scanning electron microscopy (SEM) and X-ray diffraction. These analyses show that the IF nanoparticles are entrapped in the microporous surface-film of the alumina matrix. The structure and mechanical properties of the nanosized Al₂O₃/IF-WS₂ nanocomposite film was analyzed. This analysis demonstrates that the hardness and composition of the film exhibits graded functional material characteristics, suggesting possible tribological applications.

Insertion of endoscopes and other medical devices into the human body are ubiquitous, especially among aged males. The applied force for the insertion/extraction of the device from the urethra must overcome endoscope-surface-human-tissue interactions. In daily practice a gel is applied on the endoscope surface, in order to facilitate its entry into the urethra, providing also for local anesthesia. In the present work, a new solid-state lubricant has been added to the gel, in order to reduce the metal-urethra interaction and alleviate the potential damage to the epithelial tissue. For that purpose, a urethra model was designed and fabricated, which allowed a quantitative assessment of the applied force for extraction of the endoscope from a soft polymer-based ring. It is shown that the addition of MoS₂ nanoparticles with fullerene-like structure (IF-MoS₂) and in particular rhenium-doped nanoparticles (Re:IF-MoS₂) to Esracain gel applied on the metal-lead reduced the friction substantially. The Re:IF-MoS ₂ showed better results than the undoped fullerene-like nanoparticles and both performed better than the gel alone. The mechanism of friction reduction is attributed to fullerenes' ability to roll and act as a separator between the active parts of the model.

We report a reasonably high yield (∼50%) synthesis of silicon carbide (SiC) nanowires from silicon oxides and carbon in vacuum, by novel solar and lamp photothermal ablation methods that obviate the need for catalysis, and allow relatively short reaction times (∼10 min) in a nominally one-step process that does not involve toxic reagents. The one-dimensional core/shell β-SiC/SiO_x nanostructures - characterized by SEM, TEM, HRTEM, SAED, XRD and EDS - are typically several microns long, with core and outer diameters of about 10 and 30 nm, respectively. HRTEM revealed additional distinctive nanoscale structures that also shed light on the formation pathways.

WS₂ nanoribbons have been synthesized by chemical unzipping of WS₂ nanotubes. Lithium atoms are intercalated in WS₂ nanotubes by a solvothermal reaction with n-butyllithium in hexane. The lithiated WS₂ nanotubes are then reacted with various solvents - water, ethanol, and long chain thiols. While the tubes break into pieces when treated with water and ethanol, they unzip through longitudinal cutting along the axes to yield nanoribbons when treated with long chain thiols, 1-octanethiol and 1-dodecanethiol. The slow diffusion of the long chain thiols reduces the aggression of the reaction, leading to controlled opening of the tubes.

We investigated the infrared vibrational properties of pristine and Re-substituted MoS₂ nanoparticles and analyzed the extracted phonon lifetimes in terms of multiple scattering events. Our measurements reveal both size- and doping-dependent changes that we attribute to grain boundary scattering and charge and mass effects, respectively. By contrast, Born charge is affected only by size. These findings illustrate the utility of reaching beyond traditional bulk semiconductors and quantum dots to explore how doping and confinement impact carrier-phonon interactions in low-dimensional semiconducting nanomaterials.

We investigated the optical properties of rhenium-doped MoS₂ nanoparticles and compared our findings with the pristine and bulk analogues. Our measurements reveal that confinement softens the exciton positions and reduces spin-orbit coupling, whereas doping has the opposite effect. We model the carrier-induced exciton blue shift in terms of the Burstein-Moss effect. These findings are important for understanding doping and finite length scale effects in low-dimensional nanoscale materials.

Mo₂C nanoparticles encapsulated within MoS₂ inorganic fullerene-like nanoparticles and nanotubes were produced by carbothermal reaction at 1200-1300 °C inside a vertical induction furnace. The particles were analyzed using various electron microscopy techniques and complementary methods.

Inorganic fullerene-like (IF) nanoparticles (NP) and inorganic nanotubes (INT) of layered compounds, such as WS₂, have been of particular interest due to their unique structural characteristics. Recently, the catalytic decomposition of thiophene using INT of WS₂ decorated with Co NP was demonstrated. This finding also suggests that these materials could be also suitable for the photocatalytic treatment of pollutants in wastewaters. In the present work, the photocatalytic decomposition of methyl orange (MO) in aqueous solution using Co-coated INT-WS₂ as well as other NP was investigated. The photocatalytic reactivity under visible light illumination of this photocatalyst was measured and compared with that of various IF and INT and TiO₂ (P25). The Co NP-coated INT-WS₂ exhibited the highest photodegradation of MO among the studied NP. The significant enhancement in the photoactivity of the hybrid nanostructure can be attributed to the combination of the metallic Co NP and the semiconducting WS₂ nanotubes. The hybrid nanostructure enables the efficient light absorption by the INT and the subsequent charge separation of the hybrid semiconductormetal NP under visible light illumination. In addition, Raman spectroscopy technique was used to verify that the MO was decomposed by Co-coated nanotubes and not adsorbed in large amounts on the hybrid NP surface.

A reactivity screening of new nano-hydrodesulfurization (HDS) catalysts was conducted using an ambient pressure flow reactor as well as ultra-high vacuum kinetics techniques. Thiophene was used as a probe molecule. Clean multiwall WS₂ nanotubes (INT-WS₂ ) as well as Ni- and Cocoated INT-WS₂ were considered. In addition, undoped MoS₂ and Re-doped nanoparticles with fullerene-like structures were studied. Commercial Ni and Co HDS catalysts from Haldor Topsoe (Denmark) as well as "nano MoS₂" from Impex Corp. (USA) were considered as reference materials. The lab-synthesized and commercial systems broke down thiophene into quite similar non-sulfur containing products, as identified by a gas chromatograph. The Ni and Co promoted catalysts showed similar thiophene conversion rates. Although the commercial catalysts had larger thiophene conversion rates than the laboratory-synthesized systems, the Re-doped nano-HDS catalyst showed quite low rates of formation of H₂S, an undesirable by-product.

A new procedure for the synthesis of MoS ₂ nanotubes is reported, and additionally demonstrated for MoSe ₂, WS ₂, and WSe ₂. Highly concentrated sunlight creates continuous high temperatures, strong temperature gradients, and extended hot annealing regions, which, together with a metallic (Pb) catalyst, are conducive to the formation of different inorganic nanotubes. Structural characterization (including atomic resolution images) reveals a three-step reaction mechanism. In the first step, MoS ₂ platelets react with water-air residues, decompose by intense solar irradiation, and are converted to molybdenum oxide. Subsequently, the hot annealing environment leads to the growth of Pb-stabilized MoO _3-x nanowhiskers. Shortly afterward, the surface of the MoO _3-x starts to react with the sulfur vapor supplied by the decomposition of nearby MoS ₂ platelets and becomes enveloped by MoS ₂ layers. Finally, the molybdenum oxide core is gradually transformed into MoS ₂ nanotubes. These findings augur well for similar syntheses of as yet unattained nanotubes from other metal chalcogenides.

Tubular structures of the SnS ₂/SnS misfit compound, which are currently prepared in large amounts, are reported. The lattice mismatch between the two alternating sublayers of SnS ₂ and SnS leads to a variety of chiral tubular structures. Such tubular structures are studied via high resolution transmission electron microscopy (HRTEM) and selected area electron diffraction (SAED). The diversity of the structures manifests itself through different stacking orders of SnS ₂ and SnS layers along their common c-axis and their relative in-plane orientation. Folding vectors and chiral angles of both subsystems can be determined.

We propose that a photodetector based on nanotubes formed from layered structure may have a faster response than nanowires or nanobelts. The layered compound tungsten disulfide (WS ₂) can absorb visible and near-infrared lights. We fabricated photodetectors based on individual WS ₂ nanotubes. The photodetectors exhibited a remarkable response to excitation with 633 and 785 nm light. The nanotube-based photodetectors exhibited short rise and decay times of a few hundred μs, high on/off ratio, and high spectral responsivity and external quantum efficiency. Our results imply that WS ₂ nanotubes are prospective candidates for high-performance nanoscale optoelectronic devices.

The electrostatic effects in tribological systems have been studied in the past, especially with regards to data storage media. Nanoparticles (NP) of WS2 and MoS2 with fullerene-like structure (IF) have been studied in the past and showed very good tribological behavior. Being semiconductors, their electrical properties can be controlled by, e.g., substituting the lattice Mo (W) atoms with Re (n-type conductivity) and Nb (p-type conductivity) atoms. In this study doping of IF-MoS2, and to a lesser degree IF-WS ₂, NP with small amounts (

Metallic films impregnated with fullerene-like-WS2 (MoS2) nanoparticles were fabricated on stainless steel and Ti-Ni substrates using galvanic and electroless deposition. The coatings were obtained from aqueous suspensions containing the metallic salts as well as the dispersed nanoparticles. Tribological tests showed that the films have low friction and wear. Such coatings could be useful for numerous civilian and defense-related applications.

Roll 'em up, move 'em out: The growth of SnS ₂ and SnS ₂/SnS nanotubes and nanoscrolls with ordered superstructures is promoted by the relaxation of stress between adjacent SnS ₂ and SnS layers. Partial decomposition of the SnS ₂ precursor to more sulfur-deficient SnS was manifested in the exfoliation of layers and scrolling. The presence of the two main structures (see picture) was confirmed by HRTEM and Raman spectroscopy.

It is now possible to synthesize inorganic nanotubes (INT) of WS2 in a pure phase and substantial amounts. Due to their crystalline perfection, they are characterized by excellent mechanical behavior. This study is dedicated to the investigation of the effect of INT-WS2 on the mechanical, thermal, adhesion and tribological properties of epoxy based nanocomposites. Various concentrations up to 1.0 wt% of the INT were added to the epoxy matrix. First a method was developed to mix the nanotubes in the epoxy resin matrix. A combination of both magnetic stirring and ultrasonic mixing was used. The adhesion, fracture toughness and strain energy release rate were studied. The INT-WS2 were found to significantly improve all these properties. The wear of the nanotubes-reinforced epoxy was eight-times lower than that of pure epoxy. These results suggest numerous applications.

In this work chromium-rich coatings impregnated with fullerene-like (IF)-WS₂ nanoparticles were deposited on stainless steel substrates. The coatings were obtained from a trivalent chromium bath at pH 2 by galvanostatic electrodeposition. Zinc and cobalt salts were added to the aqueous solution in small amounts serving as cationic growth promoters. Photodeposition of tin-palladium nanoparticles was used as seeding enhancer for the co-deposition of the fullerene-like nanoparticles. The coatings were characterized by a number of techniques and were found to show a decreasing gradient of the IF nanoparticles towards the film-substrate interface. Tribological tests showed that in contrast to the substrate and the pure metal coating, the IF-containing films exhibit low friction and wear.

We report on the synthesis of inorganic fullerene-like molybdenum disulfide (MoS₂) nanoparticles by pulsed laser ablation (PLA) in water. The final products were characterized by scanning electron microscopy, X-ray diffraction, transmission electron microscopy, and resonance Raman spectroscopy, etc. Cell viability studies show that the as-prepared MoS₂ nanoparticles have good solubility and biocompatibility, which may show a great potential in various biomedical applications. It is shown that the technique of PLA in water also provides a green and convenient method to synthesize novel nanomaterials, especially for biocompatible nanomaterials.

The ability to form blends of polymers offers the opportunity of creating a new class of materials with enhanced properties. In addition to the polymer components, recent advances in nanoengineering have resulted in the development of nanosized inorganic particles that can be used to improve the properties of the blend, such as the flammability and the mechanical properties. While traditional methods using copolymer compatibilizers have been used to strengthen polymer blends, here, we show that the inorganic nanosized filler additive can also serve as a compatibilizer as it can localize to the interface between the polymers. We use experimental and theoretical studies to show the fundamental mechanisms by which inorganic fillers with large aspect ratio and at least one-dimension in the nanometer range, can act as non-specific compatibilizers for polymer blends. We examine a series of nanosized fillers, ranging from nanotubes to nanoclays (with varying aspect ratios) in a model polystyrene (PS)/poly(methylmethacyralate) (PMMA) blend. Using a number of experimental techniques such as transmission electron microscopy (TEM), scanning tunneling X-ray microscopy (STXM), and atomic force microscopy (AFM) we postulate that the mechanism of compatibilization occurs as a result of the fillers forming in situ grafts with the immiscible polymers. We also use theoretical studies to show that the aspect ratio and the bending energy of the fillers play a key role in the compatibilization process. Our results indicate that the compatibilization is a general phenomenon, which should occur with all large aspect ratio nanofiller additives to polymer blends.

Various inorganic salts can be encapsulated inside the comparatively narrow (0.8-2 nm) hollow core of single-walled carbon nanotubes (SWNTs) by molten phase capillary wetting. A new synthetic strategy is presented allowing the formation of one dimensional (1D) inorganic crystals or core- shell nanotubular structures by using multiwall WS₂ nanotubes as host templates. Molten phase wetting with CsI results in the formation of 1D crystal structures inside WS₂ nanocapillaries with a Moiré pattern. The relatively large diameter of the WS₂ nanotube (with inner and outer diameters of ca. 10 and 20 nm, respectively), allows a conformal folding of the guest PbI₂ layers (PbI₂@WS₂ core-shell nanotubes) on the interior wall of the WS₂ nanotube-template, thusleading to relatively efect-free core-shell inorganic nanotubular structures, which have not been previously observed within carbon nanotubes (CNTs). Core-shell WS ₂@MoS₂ nanotubes can be obtained by the gas-phase reaction of MoCl₅ with sulfur in the presence of WS₂ nanotubes. The mechanism of imbibition/solidification of the molten salt into the hollow cores of MoS₂ nanotubes has been studied by molecular dynamics simulations, showing major differences between layered compounds and those with quasi-isotropic structure. Theoretical considerations also show the conditions for the stability of such core-shell 1D nanostructures. These new strategies can open up many possibilities for the synthesis of new nanotubular structures.

A nanostructure, being either an Inorganic Fullerene-like (IF) nanostructure or an Inorganic Nanotube (INT), A1-x-Bx-chalcogenide are described. A being a metal or transition metal or an alloy of metals and/or transition metals, B being a metal or transition metal B different from that of A and x being ≤0.3. A process for their manufacture and their use for modifying the electronic character of A-chalcogenide are described.

Nanoparticles of materials with layered structure are able to spontaneously form closed-cage nanostructures such as nested fullerene-like nanoparticles and nanotubes. This propensity has been demonstrated in a large number of compounds such as WS₂, NiCl₂, and others. Layered metal oxides possess a higher ionic character and consequently are stiffer and cannot be evenly folded. Vanadium pentoxide (V₂O₅), a layered metal oxide, has received much attention due to its attractive qualities in numerous applications such as catalysis and electronic and optical devices and as an electrode material for lithium rechargeable batteries. The synthesis by pulsed laser ablation (PLA) of V₂O₅ hollow nanoparticles, which are closely (nearly) associated with inorganic fullerene-like (NIF-V ₂O₅) nanoparticles, but not quite as perfect, is reported in the present work. The relation between the PLA conditions and the NIF-V ₂O₅ morphology is elucidated. A new mechanism leading to hollow nanostructure via crystallization of lower density amorphous nanoparticles is proposed. Transmission electron microscopy (TEM) is used extensively in conjunction with structural modeling of the NIF-V ₂O₅ in order to study the complex 3-D structure of the NIF-V₂O₅ nanoparticles. This structure was shown to be composed of facets with their low-energy surfaces pointing outward and seamed by defective domains. These understandings are used to formulate a formation mechanism and may improve the function of V₂O₅ in its many uses through additional morphological control. Furthermore, this study outlines which properties are required from layered compounds to fold into perfectly closed-cage IF nanoparticles.

Nanoparticles of inorganic compounds with layered (2D) structures, like graphite and MoS₂, were shown to be unstable in the planar from and fold on themselves forming seamless hollow structures like multiwall nanotubes and fullerene-like nanoparticles. The present concise tutorial review reports on the salient developments in this field over the last several years. Numerous applications for such nanophases have been proposed, like solid lubricants, ultra-strong nanocomposites, catalysts, etc.

WS₂ belongs to a family of layered metal dichalcogenide compounds that are known to form cylindrical (inorganic nanotubes-INT) and polyhedral nanostructures - onion or nested fullerene-like (IF) particles. The outermost layers of these IF nanoparticles can be peeled under shear stress, thus IF nanoparticles have been studied for their use as solid lubricants. However, the IF nanoparticles tend to agglomerate, presumably because of surface structural defects induced by elastic strain and curvature, a fact that has a deleterious effect on their tribological properties. In the present work, chemical modification of the IF-WS₂ surface with alkyl-silane molecules is reported. The surface-modified IF nanoparticles display improved dispersion in oil-based suspensions. The alkyl-silane coating reduces the IF-WS₂ nanoparticles' tendency to agglomerate and consequently improves the long-term tribological behavior of oil formulated with the IF additive.

Using a new quartz-made reactor, large amounts of fullerene-like (IF) MoS ₂ nanoparticles were synthesized by reacting MoO ₃ vapor with H ₂S in a reducing atmosphere. The nanoparticles were found to be of high crystalline order; with an average size of 70 nm and consist of more than 30 closed shells. Extensive tribological testing of the nanoparticles in two types of synthetic oils- poly-alpha olefins (PAO)- was carried out and compared to that of bulk (2H platelets) MoS ₂ and IF-WS ₂. These tests indicated that under high pressure and relatively low humidity, the IF-MoS ₂ exhibited a friction coefficient as low as 0.03 and the smallest wear rate of the measured systems. However, its performance was found to be lower in comparison to IF-WS ₂ after 2500 cycles, due probably to its inferior chemical stability. This study indicates that the tribological performance of the IF nanoparticles depends strongly on their crystalline order and size.

Inorganic fullerene-like WS₂ and MoS₂ nanoparticles have been synthesized using exclusively solid precursors, by reaction of the corresponding metal oxide nanopowder, sulfur and a hydrogen-releasing agent (NaBH₄ or LiAlH₄), achieved either by conventional furnace heating up to a 900 °C or by photothermal ablation at far higher temperatures driven by highly concentrated white light. In contrast to the established syntheses that require toxic and hazardous gases, working solely with solid precursors permits relatively safer reactor conditions conducive to industrial scale-up.

With the emergence and commercialization of nanoparticles, new opportunities have emerged for toughening of epoxy adhesives using nanoparticles without sacrificing strength, rigidity and glass transition temperature, as is the case with conventional elastomeric tougheners. Inorganic Fullerene-like tungsten disulfide (IF-WS₂) nanoparticles and functionalized nano-POSS (Polyhedral-Oligomeric-Sil-Sesquioxane) were used to study the effects of nanoparticles on the toughening and mechanical properties of low and high temperature curing epoxy systems. Experimental results indicated that IF-WS ₂ increased the fracture toughness by more than 10 fold in both epoxy systems at very low concentrations (0.3-0.5 wt%) while increasing its storage modulus and preserving its glass transition temperature. Epoxy functionalized POSS demonstrated an increase in toughness in addition to preserving rigidity and thermal properties at higher concentrations (3 wt%). It was postulated that chemical interaction of the sulfide and the epoxy matrix and the inherent properties of WS₂ were the decisive factors with respect to the outstanding nano-effect in the case IF-WS₂.

The synthesis of a pure phase of WS₂ nanotubes in the large-scale fluidized-bed reactor is discussed in some detail. Characterization of the nanotubes, which grow catalyst-free, by a number of analytical techniques is reported. The majority of the nanotubes range from 10 to 50 micron in length and 20-180 nm in diameter. The nanotubes reveal highly crystalline order suggesting very good mechanical behavior and numerous applications, especially in the field of nanocomposites.

Further understanding of the growth mechanism and the detailed structure of fullerene-like MoS₂ (IF-MoS₂) nanoparticles was achieved by using a new kind of reactor. The annealed nanoparticles consist of >30 closed layers and their average diameter is 50-80 nm although a small (

The synthesis of WS2 inorganic nanotubes (INT) and inorganic fullerene-like (IF) structures in 1992 signified the opening of a fertile and challenging field of scientific endeavor. These structures were the first of a long and ever-expanding series of INT and IF structures. Although initially much of the effort concentrated on the synthesis of INT and IF from compounds with layered structures, recently there his been a surge of efforts to synthesize crystalline and polycrystalline nanotubular structures from compounds with quasi-isotropic structures, like spinels, BaTiO3, SiO2, TiO2, and many others. The present review summarizes some of the progress in this field in recent years. Much of the progress in this field was achieved through strong interaction between theoretical and experimental work. This article has four themes: (a) new synthetic approaches leading to new kinds of Wand INT; (b) study of the molecular structure Of Such nanoparticles with new tools, such as aberration-corrected transmission electron microscopy (TEM) and high-angle annular dark field (HAADF); (c) recent progress in the investigation of the properties of such nanostructures; and (d) examples of applications for which clear progress has been accomplished, in particular in solid lubrication and high-strength nanocomposites.

We experimentally observed atomic-scale torsional stick-slip behavior in individual nanotubes of tungsten disulfide (WS₂). When an external torque is applied to a WS₂ nanotube, all its walls initially stick and twist together, until a critical torsion angle, at which the outer wall slips and twists around the inner walls, further undergoing a series of stick-slip torque oscillations. We present a theoretical model based on density-functional-based tight-binding calculations, which explains the torsional stick-slip behavior in terms of a competition between the effects of the in-plane shear stiffness of the WS₂ walls and the interwall friction arising from the atomic corrugation of the interaction between adjacent WS₂ walls.

The characterization of nanostructures down to the atomic scale is essential to understand some physical properties. Such a characterization is possible today using direct imaging methods such as aberration-corrected high-resolution transmission electron microscopy (HRTEM), when iteratively backed by advanced modeling produced by theoretical structure calculations and image calculations. Aberration-corrected HRTEM is therefore extremely useful for investigating low-dimensional structures, such as inorganic fullerene-like particles and inorganic nanotubes. The atomic arrangement in these nanostructures can lead to new insights into the growth mechanism or physical properties, where imminent commercial applications are unfolding. This article will focus on two structures that are symmetric and reproducible. The first structure that will be dealt with is the smallest stable symmetric closed-cage structure in the inorganic system, a MoS₂ nanooctahedron. It is investigated by means of aberration-corrected microscopy which allowed validating the suggested DFTB-MD model. It will be shown that structures diverging from the energetically most stable structures are present in the laser ablated soot and that the alignment of the different shells is parallel, unlike the bulk material where the alignment is antiparallel. These findings correspond well with the high-energy synthetic route and they provide more insight into the growth mechanism. The second structure studied is WS ₂ nanotubes, which have already been shown to have a unique structure with very desirable mechanical properties. The joint HRTEM study combined with modeling reveals new information regarding the chirality of the different shells and provides a better understanding of their growth mechanism.

The time dependent chemical changes occurring at the surface of inorganic fullerene-like (IF) nanoparticles of WS₂ were investigated using X-ray photoelectron spectroscopy (XPS) and compared to those of bulk powder, 2H-WS₂. It was possible to follow the long term surface oxidation and carbonization occurring at defects on the outermost surface (0001) molecular layers of the inorganic fullerene-like nanoparticles. Vacuum annealing was shown to remove most of these contaminants and bring the surface close to its pristine stoichiometric composition. In accordance with previous measurements, further evidence was obtained for the existence of water molecules, which were entrapped in the hollow core and interstitial defects of the fullerene-like nanoparticles during the synthesis. These water molecules were also shown to be removable by the vacuum annealing process. Chemically resolved electrical measurements (CREM) in the XPS showed that the IF samples had become less p-type after the vacuum annealing. Finally, tribological measurements showed that the vacuum annealed IF samples performed better as an oil additive than the non-annealed IF samples and the 2H-WS₂ powder.

Inorganic fullerene-like (IF) Mo_1-xRe_xS₂ and W_1-xRe_xS₂ nanoparticles have been synthesized by a gasphase reaction involving the respective metal halides with H₂S. The IF-Mo(W)_1-xRe_xS₂ nanoparticles, contain - ing up to 5% Re, were characterized by a variety of experimental techniques. Analyses of the X-ray powder diffraction and different electron microscopy techniques show that the Re is doped in the MoS₂ host lattice. Interestingly, Re-dop ed MoS₂ nanotubes are present as well, although in small quantities (∼5%). XPS results confirm the nanoparticles to be more n-type arising from the effect of Re doping. Additionally, density-functional tight-binding (DFTB) calculations support the observed n-type behavior.

The mechanical properties of individual WS2 nanotubes were investigated and directly related to their atomic structure details by in situ transmission electron microscope measurements. A brittle mode deformation was observed in bending tests of short (ca. 1 mu m in length) multilayer nanotubes. This mode can be related to the atomic structure of their shells. In addition, longer nanotubes (6-7 mu m in length) were deformed in situ scanning electron microscope, but no plastic deformation was detected. A "sword-in-sheath" fracture mechanism was revealed in tensile loading of a nanotube, and the sliding of inner shells inside the outermost shell was imaged "on-line". Furthermore, bending modulus of 217 GPa was obtained from measurements of the electric-field-induced resonance of these nanotubes.

We present the advancement of electron tomography for three-dimensional structure reconstruction of fullerene-like particles toward atomic-scale resolution. The three-dimensional reconstruction of nested molybdenum disulfide nanooctahedra is achieved by the combination of low voltage operation of the electron microscope with aberration-corrected phase contrast imaging. The method enables the study of defects and irregularities in the three-dimensional structure of individual fullerene-like particles on the scale of 2-3 Å. Control over shape, size, and atomic architecture is a key issue in synthesis and design of functional nanoparticles. Transmission electron microscopy (TEM) is the primary technique to characterize materials down to the atomic level, albeit the images are two-dimensional projections of the studied objects. Recent advancements in aberration-corrected TEM have demonstrated single atom sensitivity for light elements at subångström resolution. Yet, the resolution of tomographic schemes for three-dimensional structure reconstruction has not surpassed 1 nm³, preventing it from becoming a powerful tool for characterization in the physical sciences on the atomic scale. Here we demonstrate that negative spherical aberration imaging at low acceleration voltage enables tomography down to the atomic scale at reduced radiation damage. First experimental data on the three-dimensional reconstruction of nested molybdenum disulfide nanooctahedra is presented. The method is applicable to the analysis of the atomic architecture of a wide range of nanostructures where strong electron channeling is absent, in particular to carbon fullerenes and inorganic fullerenes.

Inorganic fullerene-like (IF) nanoparticles of WS2 and MoS2 with extremely useful tribological characteristics have been realized. One of the disadvantages in application of IF is their aggregation. Two aspects of the problem will be considered: the effect of the aggregates on friction and wear and the effect of the loading scheme on the efficacy of IF.It was found out that the reproducibility of the friction results for the pairs lubricated with oil +IF is determined by the size and the size- distribution of the aggregates. Decreasing the size of the ggregates increases the probability for the IF penetration into the interface and decrease remarkably the friction coefficient. It was reveiled that wedge clearance in the inlet of contact affect considerably on penetration of IF into interface. The application of friction device with wedge clearance in the inlet of the contact limits the efficacy of the IF. The analysis of results allows to conclude that one of the ways to improve the efficacy of IF nanoparticles is decreasing their size down to a value lesser than 50 nm. Another important way allowing to limit the agglomeration of the IF nanoparticles and thus to improve their efficacy is by the application of surfactants.

This review summarizes recent work on the polymer-assisted fabrication of well-defined inorganic and organic nanoparticles with controlled shape, size, and functional properties. The discussion concentrates on the physical-chemical aspects of the problem. Special attention is paid to the preparation of nanocomposites with individual (non-aggregated) nanoparticles with narrow size distribution and versatile morphologies, including the design of nanoparticles and nanocomposites that can serve multifunctional purposes. We have focused also on the problem of the spatial arrangement of nanoparticles and elucidation of the role of polymers in this process because it is a key problem in nanotechnology industrialization. The potential applications of nanoparticles encapsulated in polymers and in nanocomposites are briefly discussed. We try also to emphasize the synergistic role of the ingredients on the performance of nanocomposites.

Back in 1992 it was proposed that nanoparticles of layered compounds will be unstable against folding and will close up into fullerene-like structures (IF) and nanotubes. In the years that followed nanotubes and fullerene-like structures were synthesized from numerous compounds with layered structure. More recently, crystalline and noncrystalline nanotubes of compounds with a 3D, i.e., quasi-isotropic lattice have been intensively investigated. In view of their eminent applications potential, much effort and substantial progress has been achieved in the scaling-up of the synthesis of inorganic nanotubes and fullerene-like nanoparticles of WS(2) and MoS(2) and also other compounds. Early on it was suggested that hollow nano-octahedra consisting of a few hundred MoS(2) moieties make the true analogs of C(60), etc. This notion has been advanced considerably in recent years through a combined experimental-theoretical effort. Substantial progress has been accomplished in the use of such nanoparticles for tribological applications and lately for impact resilient nanocomposites. These tests indicated that IF-MoS(2) and IF-WS(2) are heading for large-scale applications in the automotive, machining, aerospace, electronics, defense, medical and numerous other kinds of industries. A few products based on these nanoparticles have been recently commercialized by "ApNano Materials, Inc" ("NanoMaterials, Ltd.", see also www.apnano.com). Most recently, a manufacturing facility for the commercialization of these nanomaterials has been erected and sales of the product started. Novel applications of inorganic nanotubes and fullerene-like nanoparticles in the fields of catalysis; microelectronics; Li rechargeable batteries; medical and optoelectronics will be discussed.

Solar ablation creates the sharp radiative and temperature gradients, as well as the high-temperature annealing environment, that favor nanomaterial syntheses. Using highly concentrated sunlight, we generated fullerene-like MoS₂, ranging from single-walled nanotubes and closed-cage structures to their larger multi-walled counterparts. TEM, HRTEM and EDS unambiguously established the nanostructures, some achieving fundamentally minimum sizes predicted by molecular structural theory. Irradiation of MoS₂ and powdered mixtures of MoS₂ + SiO₂ in evacuated quartz ampoules also generated nanofibers and nanospheres of amorphous SiO₂: the first production of SiO₂ nanostructures purely from quartz. Also, solar ablation of MoS₂ + SiO mixtures produced nanowires and nanospheres of crystalline Si.

It is already well established today that numerous materials form closed-cage structures, of which carbon fullerenes and nanotubes are a special case [1]. Inorganic fullerene-like nanoparticles (designated IF) and inorganic nanotubes (INT) have been produced by different routes and experimental techniques, achieving persistent growth of a variety of materials and structural wealth within them. The research in this area has focused on synthesizing new IF and INT materials and understanding their different properties as well as scaling up the synthetic process in order to make it suitable for industrial applications. In this review, the main synthetic procedures to obtain inorganic fullerene-like nanoparticles and nanotubes will be discussed alongside with the different mechanisms that affect the morphology of the final product. The main differences between the morphologies will be presented. Some general considerations relating the properties of the parent compound with the morphology of the product will be mentioned.

Fullerene-like WS ₂ (MoS ₂) nanoparticles (IF) have been studied in the past as solid lubricants. Using the tribological ball-on-flat experiments, it was shown that the size of the aggregates and their distribution determine the penetration and entrapping of the IF nanoparticles at the interface. It is expected that the wedge clearance at the inlet of the contact, i.e., the oblique-angle entrance to the contact zone between the two mating tribological surfaces, as well as the average surface roughness, can limit the supply of the lubricant into the interface in, e.g., the block-on-ring experiment. In the present series of experiments, the Stribeck curve was designed first using a linear loading scheme and pure oil. It was concluded that a wedge clearance (oblique-angle) in the inlet of the contact zone leads to entrapment of the IF nanoparticles and their compaction, which hamper the supply of the fluid lubricant into the interface. A ball-on-flat and flat block-on-ring friction devices with wedge clearance in the inlet of the contact can distort the efficacy of IF. Procedures for improving the supply of the IF nanoparticles to the contact zone and improving thereby their efficacy are considered.

To investigate phonon confinement in nanoscale metal dichalcogenides, we measured the low-temperature specific heat of layered and nanoparticle WS ₂. Below 9 K, the specific heat of the nanoparticles deviates from that of the bulk counterpart. Further, it deviates from the usual T³ dependence below 4 K due to finite size effects that eliminate long wavelength acoustic phonons and interparticle-motion entropy. This separation of nanoscale effects from T³ dependence can be modeled by assuming that the phonon density of states is flexible, changing with size and shape. We invoke relationships between the low-temperature T³ phonon term, Young's modulus, and friction coefficient to assess the difference in the tribological properties. On the basis of this analysis, we conclude that the improved lubrication properties of the nanoparticles are extrinsic.

Composite coatings of Co + fullerene-like WS₂ nanoparticles on stainless steel substrate were obtained through electroless deposition, using DMAB (dimethyl borane complex, 97%) as the reducing agent, and by electroplating in acidic solution. Phase analysis results show that the coatings consist of Co and the fullerene-like WS₂ nanoparticles alone. Tribological measurements show reduced wear and friction of the composite coatings as compared with the pure cobalt film or the stainless steel substrate.

MoS₂ nanooctahedra are believed to be the smallest stable closed-cage structures of MoS₂, i.e., the genuine inorganic fullerenes. Here a combination of experiments and density functional tight binding calculations with molecular dynamics annealing are used to elucidate the structures and electronic properties of octahedral MoS₂ fullerenes. Through the use of these calculations MoS₂ octahedra were found to be stable beyond n_MO > 100 but with the loss of 12 sulfur atoms in the six corners. In contrast to bulk and nanotubular MoS₂, which are semiconductors, the Fermi level of the nanooctahedra is situated within the band, thus making them metallic-like. A model is used for extending the calculations to much larger sizes. These model calculations show that, in agreement with experiment, the multiwall nanooctahedra are stable over a limited size range of 10⁴-10⁵ atoms, whereupon they are converted into multiwall MoS₂ nanoparticles with a quasi-spherical shape. On the experimental side, targets of MoS₂ and MoSe₂ were laser-ablated and analyzed mostly through transmission electron microscopy. This analysis shows that, in qualitative agreement with the theoretical analysis, multilayer nanooctahedra of MoS₂ with 1000-25 000 atoms (Mo + S) are stable. Furthermore, this and previous work show that beyond ∼10⁵ atoms fullerene-like structures with quasi-spherical forms and 30-100 layers become stable. Laser-ablated WS₂ samples yielded much less faceted and sometimes spherically symmetric nanocages.

A simple, inexpensive, and reproducible photothermal procedure for synthesizing IF-Cs₂O nanoparticles with immensely concentrated sunlight was demonstrated. The solar-driven synthesis of IF-Cs₂O was performed in evacuated quartz ampoules that contained 3R-Cs₂-O crystallites under continuous irradiation with a concentrated solar power of 2.0-7.7 W, and periods ranging from 30 to 840 s. Samples were collected from the deposit that gathered on the quartz ampoule during the solar irradiation for TEM analysis. The interaction of the beam with the materials led to thermal motion, charging, desorption of trace quantities, or possible chemical changes. The results of the electron energy loss spectroscopy and imaging with a Gatan imaging filters proved that only cesium and oxygen were present in the nanoparticles.

We have proposed in 1992 that nanoparticles of layered compounds will be unstable against folding and close into fullerene-like structures and nanotubes (IF). Nanotubes and fullerene-like structures were prepared from numerous compounds with layered and recently also non-layered structure by various groups. Much progress has been achieved in the synthesis of inorganic nanotubes and fullerene-like nanoparticles of WS₂ and MoS₂ and many other metal dichalcogenides over the last few years. Substantial progress has been accomplished in the use of such nanoparticles for tribological applications and lately for impact resilient nanocomposites. These tests indicated that IF-MoS₂ and IF-WS₂ are heading for large scale applications in the automotive, machining, aerospace, electronics, defense, medical and numerous other kinds of industries. A few products based on these nanoparticles have been recently commercialized by "ApNano Materials, Inc". Novel applications of inorganic nanotubes and fullerene-like nanoparticles in the fields of catalysis; microelectronics; Li rechargeable batteries; medical and opto-electronics will be discussed.

Inorganic fullerene-like ( IF) nanoparticles of MoS2 were synthesized using gas-phase reaction starting from MoCl5 and H2S. The IF-MoS2 nanoparticles are spherical and in some cases faceted with diameters in general ranging between 20 and 80 nm. The IF-MoS2 nanoparticles have large hollow cores, filled in some cases with amorphous material. Various parameters have been investigated to understand the growth and formation of the IF-MoS2 nanoparticles. The parameters that have been studied include flow rates of the various carrier gases, temperature at which the reaction was carried out, time of the reaction and heating of the precursor material. The best set of conditions wherein maximum yields of the IF-MoS2 nanoparticles are obtained have been identified. Additionally, annealing the as-obtained samples or heating them in a mixture of H-2 along with H2S improves the crystallinity and reduces the amorphous material filling in the core. Apart from the fullerene-like nanoparticles under certain experimental conditions nanotubes of MoS2 have also been obtained nonetheless in small yields.

Current-voltage characteristics measured using STM on fullerene-like WS₂ nanoparticles show zero-bias current and contain segments in which the tunneling current flows opposite to the applied bias voltage. In addition, negative differential conductance peaks emerge in these reversed current segments, and the characteristics are hysteretic with respect to the change in the voltage sweep direction. Such unusual features resemble those appearing in cyclic voltammograms, but are uniquely observed here in tunneling spectra measured in vacuum, as well as in ambient and dry atmosphere conditions. This behavior is attributed to tunneling-driven electrochemical processes.

Fullerene-like WS₂ (MoS₂) nanoparticles (IF) have been studied in the past. Their efficacy as additives for lubrication fluids has been demonstrated. It was shown that the IF nanoparticles are usually delaminated in the inlet of the smooth contact. Thin sheets of broken IF nanoparticles can be entrapped between the rubbed surfaces and thus favorably affect the friction and the wear. Friction pairs at real mechanical macrosystems are often subjected to friction-induced vibrations. It was shown that the mechanical excitations can improve the supplying and preservation of fluid lubricant film in the interface. It can be hypothesized that under vibrations in a definite range of frequencies and amplitudes, the probability for small IF aggregates to be entrapped into the interface is increased. The main goal of this work was to study the effect of artificial mechanical excitations on the friction and wear of contact pairs rubbed with nanoparticles. In order to avoid friction-induced excitations, a new ball-on-flat friction device was developed. The frequency and the amplitude of the ball were varied using a motion of miniature micromotor attached to the ball holder. The behavior of IF nanoparticles in friction tests with and without external mechanical excitations was compared with the tribological behavior of the contact pair lubricated with pure paraffin oil. It was found that the external mechanical excitation of the mechanical parts rubbed with nanoparticles allows a penetration of these nanoparticles into interface. This effect leads to a remarkable shortening of the run-in period and improves the tribological properties of contact pairs. From the present results it may be anticipated that the accidental friction-induced vibrations, which are determined by the stiffness and damping force of the device, lead to preferential penetration of the IF nanoparticles into the contact area, affecting thereby the tribological behavior of the interface.

We report the rapid high-yield generation of inorganic fullerene-like cesium oxide (IF-CS2O) nanoparticles, activated by highly concentrated sunlight. The solar process represents an alternative to the only reported method for synthesizing IF-CS2O nanostructures: laser ablation. IF-CS2O formed at solar irradiation >= 6W, confirmed by high resolution transmission electron microscopy. These closed-cage Cs2O nanostructures are stable under electron microscope conditions, and also when exposed temporarily to air - of significance for their use in a variety of photonic devices.

We measured the infrared vibrational properties of bulk and nanoparticle W S2 in order to investigate the structure-property relations in these materials. In addition to the symmetry-breaking effects of local strain, nanoparticle curvature modifies the local charging environment of the bulk material. Performing a charge analysis on the xy -polarized E1u vibrational mode, we find an approximate 1.5:1 intralayer charge difference between the layered 2H material and inorganic fullerene-like (IF) nanoparticles. This effective charge difference may impact the solid-state lubrication properties of nanoscale metal dichalcogenides.

TiS2 nanoparticles with nested fullerene-like structure (IF) 60-120 nm in size consisting of up to 100 concentric molecular layers and having quite a perfectly spherical shape were obtained by reacting TiCl4 and H2S using first a horizontal and subsequently a vertical reactor. The proposed growth mechanism of these nanoparticles, i.e. nucleation and growth, is radically different from the one proposed for the growth of the fullerene-like WS2 from the respective oxide nanoparticles. It was found that adding 1-2% IF-TiS2 improves the behavior of lubricating oil substantially. The improved performance of the additive was attributed to the nearly spherical shape of the nanoparticles which promotes rolling friction.

We obtained a Raman signal from an individual WS2 nanotube mounted on an atomic force microscopy cantilever tip. We discuss the implications for simultaneous investigations of the mechanical properties of WS2 nanotubes by combining different experimental methods. From the orientation dependence of this nanotube's resonant Raman intensity, we estimate the ratio of the perpendicular to parallel polarizabilities αXXαZZ0.16. We compare the WS2 nanotube with single-walled carbon nanotubes and expect a similarly strong depolarization effect for multiwalled carbon nanotubes.

We present the results from an experimental study of the magnetotransport of superconducting wires of amorphous indium-oxide having widths in the range 40-120 nm. We find that, below the superconducting transition temperature, the wires exhibit clear, reproducible, oscillations in their resistance as a function of magnetic field. The oscillations are reminiscent of those that underlie the operation of a superconducting quantum interference device.

(Figure Presented) Fullerene-like Cs₂O nanoparticles were prepared by laser ablation of 3R-Cs₂O powder in evacuated quartz ampoules. The Cs₂O closed cages, such as the faceted nanoparticle shown in the picture, are remarkably stable as compared with the corresponding extremely unstable but technically important bulk compound, which makes them potentially useful in applications involving cesium oxide coatings, for example, photoemissive devices and catalytic converters.

The dynamic pressure-resitance capacity of inorganic fullerene (IF) cages in uniaxial shockwave pressures up to 30 GPa, was studied. It was observed that to a limit of 25 GPa, except those IFs mixed with nanotubes, others suffered light damages. It was also observed that a perfectly hollow and small IF cage consists an ability to withstand much higher shock wave pressure. These inorganic fullerenes can be used as lubricant at severe loading conditions, or as a coating or composite phase in cases of anti-shock or high-pressure environment.

Nanoparticles of WS₂ and MoS₂ with a closed cage structure (fullerene-like) that are termed IF phases are synthesized in large amounts in a pure form. These nanoparticles were shown to play a favorable role as solid lubricants under severe conditions where fluids are unable to support the heavy load and are squeezed away from the contact area. Various tribological scenarios are presented for these superior solid lubricants, demonstrating the large scale potential for applications of these materials. The mechanism of action of these solid lubricants is briefly discussed. Various other potential applications of IF phases for nanocomposites with high impact resistance; in rechargeable batteries and in optical devices are discussed in short.

Fullerene-like WS₂ (MoS₂) nanoparticles (IF) have been studied in the past. Their efficacy as additives for lubrication fluids has been demonstrated. Recently, IF-WS₂ nanoparticles were confined inside a porous and densified bronze-graphite matrix, prepared by powder metallurgy (PM) technique. Substantial reduction in both friction and wear, and an increase in the critical load were observed. Novel applications of IF nanoparticles as development of polymer nanocomposites, burnishing, and friction of ceramic materials under severe contact conditions were presented. Polymer nanococomposites with embedded IF nanoparticles exhibited excellent tribological properties. The main friction mechanism was the transfer of the IF nanoparticles from the surface of the polymer composite to the surface of the mating steel disk leading to a reduction in both the friction coefficient and wear rate of the contact surfaces. This is an abstract presented at the World Tribology Congress III (Washington, DC 9/12-16/2005).

When dispersed in a synthetic polyalphaolefin (PAO) base oil, inorganic fullerene-like (IF-MS₂) nanoparticles of metal dichalcogenides (IF-MoS₂, IF-WS₂, IF-NbS₂) lead to a significant reduction of both friction and wear under boundary lubrication. The effect of the contact pressure on the tribological properties of IF nanoparticles is particularly interesting. Results show that the higher is the pressure, the lower is the friction coefficient. The effect of the concentration shows that, even used at a low concentration (0.1%wt), IF-MS₂ is able to decrease friction (0.05) compared to base oil only (0.08). A steady state friction coefficient of 0.04 was reached with IF-WS₂ at 1%wt in PAO. Friction-induced transformation of the IF-MS₂ nanoparticles into H-MS₂ single sheets was evidenced by High Resolution Transmission Electron Microscopy (HRTEM). Some of these superimposed sheets are found in incommensurate positions, thus possibly explaining the very low friction coefficient of 0.04 obtained with IF-WS₂. In-situ Raman spectroscopy was performed during a friction test to follow this structural modification. The lubrication mechanism of IF-MS₂ is very similar to a "drug delivery system". A very low concentration of additives is sufficient and the activation is obtained by the opening of the nested structure, like in certain micellar structures. Furthermore, no chemical reaction is required to obtain interesting properties. Thus, fullerene-like nanoparticles are active at the very beginning of the test and even at ambient and low temperature.

Individual WS2 multiwalled nanotubes, 2-3 micron in length, and with 15 - 25 nm diameter were mounted on AFM cantilevers tips. The nanotube orientation along the cantilever cone axis was confirmed by scanning electron microscopy (SEM). Micro-Raman spectra of these individual nanotubes showed similar vibrational frequencies as in the bulk material. The highly anisotropic shape of the nanotubes, however, leads to a strong antenna effect as it is known from single-walled carbon nanotubes. A qualitative assessment of the radiation field screening for polarization perpendicular to the nanombe axis is given.

Adding guest atoms to inorganic nanotubes, known as 'doping', influences their room-temperature magnetic properties - properties that could be exploited in 'spintronic' devices and computer memory.

Cesium oxides are materials of great interest to the photodetection industry because of their relatively low work function (∼1 eV). Used mainly as coating films for photoemissive devices, they provide high wavelength thresholds and high photocurrents. However, they are unstable, air-sensitive, and hygroscopic, rendering them short-lived and limiting their applications. Although the technology of these devices is highly developed, their characterization on the micro- and nanoscale suffers from their poor chemical stability and poor crystallinity. In the present study, cesium oxides were synthesized from the elements and were characterized using a combination of chemical and structural analysis techniques. Because the reaction products were extremely sensitive to humidity, sample analysis without atmospheric exposure was essential, and techniques were developed for the transfer of the samples to the measurements systems. Extensive data obtained from X-ray energy-dispersive spectroscopy (EDS), X-ray photoelectron spectroscopy (XPS), transmission electron microscopy (TEM), selected-area electron diffraction (SAED), X-ray diffraction (XRD), and Raman microscopy were obtained. Raman spectra with bands at 103, 742, and 1134 cm^-1 strongly confirmed the presence of the oxide, peroxide, and Superoxide ions, respectively, as well as the absence of carbonate as an impurity. The A_1g mode of Cs₂O was detected as an anti-Stokes band at 103 cm^-1. This study provides further insight into the reactivity of the various cesium oxides.

Inorganic fullerene-like materials have been identified as being of potentially utmost importance for many industrial applications. MoS₂ and WS₂ hollow nanoparticles have been identified as strong candidates for tribological applications such as solid lubricants. The main goal of this work was to evaluate the mechanical properties of solid lubricant particles in ensemble under hydrostatic pressure. The behavior of nanopowders under compression has been described on the basis of constitutive models of continuum mechanics. The model will be applied to an isotropic compaction of copper (well-studied medium), fullerene-like (IF-WS₂) nanoparticles and a natural powder of 2H-WS₂ platelets. The morphology of individual nanoparticles and nanoparticle ensembles will be examined and discussed. Another aspect of this work was to study the applicability and limitations of the proposed constitutive model for the understanding of the tribological behavior of solid lubricant nanoparticles. Compression with the maximal pressure (500 MPa) showed that the shape of the IF nanoparticles is preserved. The dominant mechanism of damage was found to be the delamination or peeling-off of the external sheets of hollow nanoparticles. Strong destruction of 2H-WS₂ platelets was observed under compression.