Lithium Titanate/Carbon Nanotubes Composites Processed by Ultrasound Irradiation as Anodes for Lithium Ion Batteries.

In this work, lithium titanate nanoparticles (nLTO)/single wall carbon nanotubes (SWCNT) composite electrodes are prepared by the combination of an ultrasound irradiation and ultrasonic spray deposition methods. It was found that a mass fraction of 15% carbon nanotubes optimizes the electrochemical performance of nLTO electrodes. These present capacities as high as 173, 130, 110 and 70 mAh.g-1 at 0.1C, 1C, 10C and 100C, respectively. Moreover, after 1000 cycles at 1C, the nLTO/SWCNT composites present a capacity loss of just 9% and a Coulombic efficiency of 99.8%. Therefore, the presented methodology might be extended to other suitable active materials in order to manufacture binder free electrodes with optimal energy storage capabilities.

Enabling Flexible Heterostructures for Li-Ion Battery Anodes Based on Nanotube and Liquid-Phase Exfoliated 2D Gallium Chalcogenide Nanosheet Colloidal Solutions.

2D metal chalcogenide (MC) nanosheets (NS) have displayed high capacities as lithium-ion battery (LiB) anodes. Nevertheless, their complicated synthesis routes coupled with low electronic conductivity greatly limit them as promising LiB electrode material. Here, this work reports a facile single-walled carbon nanotube (SWCNT) percolating strategy for efficiently maximizing the electrochemical performances of gallium chalcogenide (GaX, X = S or Se). Multiscaled flexible GaX NS/SWCNT heterostructures with abundant voids for Li+ diffusion are fabricated by embedding the liquid-exfoliated GaX NS matrix within a SWCNT-percolated network; the latter improves the electron transport and ion diffusion kinetics as well as maintains the mechanical flexibility. Consequently, high capacities (i.e., 838 mAh g-1 per gallium (II) sulfide (GaS) NS/SWCNT mass and 1107 mAh g-1 per GaS mass; the latter is close to the theoretical value) and good rate capabilities are achieved, which can be majorly attributed to the alloying processes of disordered Ga formed after the first irreversible GaX conversion reaction, as monitored by in situ X-ray diffraction. The presented approach, colloidal solution processing of SWCNT and liquid-exfoliated MC NS to produce flexible paper-based electrode, could be generalized for wearable energy storage devices with promising performances.

A New 2H-2H'/1T Cophase in Polycrystalline MoS2 and MoSe2 Thin Films.

We report on 2H-2H'/1T phase conversion of MoS2 and MoSe2 polycrystalline films grown by thermally assisted conversion. The structural conversion of the transition metal dichalcogenides was successfully carried out by organolithium treatment on chip. As a result we obtained a new 2H-2H'/1T cophase system of the TMDs thin films which was verified by Raman spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The conversion was successfully carried out on selected areas yielding a lateral heterostructure between the pristine 2H phase and the 2H'/1T cophase regions. Scanning electron microscopy and atomic force microscopy revealed changes in the surface morphology and work function of the cophase system in comparison to the pristine films, with a surprisingly sharp lateral interface region.

High-Performance Hybrid Electronic Devices from Layered PtSe2 Films Grown at Low Temperature.

Layered two-dimensional (2D) materials display great potential for a range of applications, particularly in electronics. We report the large-scale synthesis of thin films of platinum diselenide (PtSe2), a thus far scarcely investigated transition metal dichalcogenide. Importantly, the synthesis by thermally assisted conversion is performed at 400 °C, representing a breakthrough for the direct integration of this material with silicon (Si) technology. Besides the thorough characterization of this 2D material, we demonstrate its promise for applications in high-performance gas sensing with extremely short response and recovery times observed due to the 2D nature of the films. Furthermore, we realized vertically stacked heterostructures of PtSe2 on Si which act as both photodiodes and photovoltaic cells. Thus, this study establishes PtSe2 as a potential candidate for next-generation sensors and (opto-)electronic devices, using fabrication protocols compatible with established Si technologies.

Functionalization of Two-Dimensional MoS2 : On the Reaction Between MoS2 and Organic Thiols.

Two-dimensional layered transition metal dichalcogenides (TMDs) have attracted great interest owing to their unique properties and a wide array of potential applications. However, due to their inert nature, pristine TMDs are very challenging to functionalize. We demonstrate a general route to functionalize exfoliated 2H-MoS2 with cysteine. Critically, MoS2 was found to be facilitating the oxidation of the thiol cysteine to the disulfide cystine during functionalization. The resulting cystine was physisorbed on MoS2 rather than coordinated as a thiol (cysteine) filling S-vacancies in the 2H-MoS2 surface, as originally conceived. These observations were found to be true for other organic thiols and indeed other TMDs. Our findings suggest that functionalization of two-dimensional MoS2 using organic thiols may not yield covalently or datively tethered functionalities, rather, in this instance, they yield physisorbed disulfides that are easily removed.

A Commercial Conducting Polymer as Both Binder and Conductive Additive for Silicon Nanoparticle-Based Lithium-Ion Battery Negative Electrodes.

This work describes silicon nanoparticle-based lithium-ion battery negative electrodes where multiple nonactive electrode additives (usually carbon black and an inert polymer binder) are replaced with a single conductive binder, in this case, the conducting polymer PEDOT: PSS. While enabling the production of well-mixed slurry-cast electrodes with high silicon content (up to 95 wt %), this combination eliminates the well-known occurrence of capacity losses due to physical separation of the silicon and traditional inorganic conductive additives during repeated lithiation/delithiation processes. Using an in situ secondary doping treatment of the PEDOT: PSS with small quantities of formic acid, electrodes containing 80 wt % SiNPs can be prepared with electrical conductivity as high as 4.2 S/cm. Even at the relatively high areal loading of 1 mg/cm(2), this system demonstrated a first cycle lithiation capacity of 3685 mA·h/g (based on the SiNP mass) and a first cycle efficiency of ∼78%. After 100 repeated cycles at 1 A/g this electrode was still able to store an impressive 1950 mA·h/g normalized to Si mass (∼75% capacity retention), corresponding to 1542 mA·h/g when the capacity is normalized by the total electrode mass. At the maximum electrode thickness studied (∼1.5 mg/cm(2)), a high areal capacity of 3 mA·h/cm(2) was achieved. Importantly, these electrodes are based on commercially available components and are produced by the standard slurry coating methods required for large-scale electrode production. Hence, the results presented here are highly relevant for the realization of commercial LiB negative electrodes that surpass the performance of current graphite-based negative electrode systems.

Comparison of liquid exfoliated transition metal dichalcogenides reveals MoSe2 to be the most effective hydrogen evolution catalyst.

While 2D transition metal dichalcogenides are known to be promising materials for electrocatalysis of hydrogen production, it is not clear which member of this family of materials is the most effective catalyst. Here we perform a comprehensive study, comparing the catalytic performance of electrodes consisting of porous arrays of liquid exfoliated MX2 nanosheets (M = Mo, W; X = S, Se, Te). We find a clear hierarchy with selenides > sulphides > tellurides with MoSe2 clearly out-performing the other materials. In all cases the performance, as characterised by current density at a given potential, can be improved by increasing the number of active sites (via control of the electrode thickness) and/or by adding carbon nanotubes to the electrode (i.e. increasing the electrode conductivity). While all materials formed reasonably stable electrodes, addition of nanotubes tended to improve mechanical cohesion. In an attempt to maximise performance, we prepared thick (∼15 µm), free standing MoSe2/SWNT composite electrodes which displayed Tafel slopes of ∼77 mV per decade and exchange current densities of ∼0.1 mA cm(-2). These electrodes had low onset potentials, reaching -2 mA cm(-2) at -41 mV (vs. RHE) and generated high current densities of -35 mA cm(-2) at -200 mV (vs. RHE).

Liquid exfoliation of solvent-stabilized few-layer black phosphorus for applications beyond electronics.

Few-layer black phosphorus (BP) is a new two-dimensional material which is of great interest for applications, mainly in electronics. However, its lack of environmental stability severely limits its synthesis and processing. Here we demonstrate that high-quality, few-layer BP nanosheets, with controllable size and observable photoluminescence, can be produced in large quantities by liquid phase exfoliation under ambient conditions in solvents such as N-cyclohexyl-2-pyrrolidone (CHP). Nanosheets are surprisingly stable in CHP, probably due to the solvation shell protecting the nanosheets from reacting with water or oxygen. Experiments, supported by simulations, show reactions to occur only at the nanosheet edge, with the rate and extent of the reaction dependent on the water/oxygen content. We demonstrate that liquid-exfoliated BP nanosheets are potentially useful in a range of applications from ultrafast saturable absorbers to gas sensors to fillers for composite reinforcement.

On-surface derivatisation of aromatic molecules on graphene: the importance of packing density.

An efficient, high-throughput method for the formation of densely packed molecular films on graphene is reported. The films exhibit high stability and remain intact during a subsequent derivatisation reaction, offering a versatile route for the non-covalent functionalisation of graphene.

Atomic layer deposition on 2D transition metal chalcogenides: layer dependent reactivity and seeding with organic ad-layers.

This commmunication presents a study of atomic layer deposition of Al2O3 on transition metal dichalcogenide (TMD) two-dimensional films which is crucial for use of these promising materials for electronic applications. Deposition of Al2O3 on pristine chemical vapour deposited MoS2 and WS2 crystals is demonstrated. This deposition is dependent on the number of TMD layers as there is no deposition on pristine monolayers. In addition, we show that it is possible to reliably seed the deposition, even on the monolayer, using non-covalent functionalisation with perylene derivatives as anchor unit.

Understanding and optimising the packing density of perylene bisimide layers on CVD-grown graphene.

The non-covalent functionalisation of graphene is an attractive strategy to alter the surface chemistry of graphene without damaging its superior electrical and mechanical properties. Using the facile method of aqueous-phase functionalisation on large-scale CVD-grown graphene, we investigated the formation of different packing densities in self-assembled monolayers (SAMs) of perylene bisimide derivatives and related this to the amount of substrate contamination. We were able to directly observe wet-chemically deposited SAMs in scanning tunnelling microscopy (STM) on transferred CVD graphene and revealed that the densely packed perylene ad-layers adsorb with the conjugated π-system of the core perpendicular to the graphene substrate. This elucidation of the non-covalent functionalisation of graphene has major implications on controlling its surface chemistry and opens new pathways for adaptable functionalisation in ambient conditions and on the large scale.

Direct Observation of Degenerate Two-Photon Absorption and Its Saturation in WS2 and MoS2 Monolayer and Few-Layer Films.

The optical nonlinearity of WS2 and MoS2 monolayer and few-layer films was investigated using the Z-scan technique with femtosecond pulses from the visible to the near-infrared range. The nonlinear absorption of few- and multilayer WS2 and MoS2 films and their dependences on excitation wavelength were studied. WS2 films with 1-3 layers exhibited a giant two-photon absorption (TPA) coefficient as high as (1.0 ± 0.8) × 10(4) cm/GW. TPA saturation was observed for the WS2 film with 1-3 layers and for the MoS2 film with 25-27 layers. The giant nonlinearity of WS2 and MoS2 films is attributed to a two-dimensional confinement, a giant exciton effect, and the band edge resonance of TPA.

Basal-Plane Functionalization of Chemically Exfoliated Molybdenum Disulfide by Diazonium Salts.

Although transition metal dichalcogenides such as MoS2 have been recognized as highly potent two-dimensional nanomaterials, general methods to chemically functionalize them are scarce. Herein, we demonstrate a functionalization route that results in organic groups bonded to the MoS2 surface via covalent C-S bonds. This is based on lithium intercalation, chemical exfoliation and subsequent quenching of the negative charges residing on the MoS2 by electrophiles such as diazonium salts. Typical degrees of functionalization are 10-20 atom % and are potentially tunable by the choice of intercalation conditions. Significantly, no further defects are introduced, and annealing at 350 °C restores the pristine 2H-MoS2. We show that, unlike both chemically exfoliated and pristine MoS2, the functionalized MoS2 is very well dispersible in anisole, confirming a significant modification of the surface properties by functionalization. DFT calculations show that the grafting of the functional group to the sulfur atoms of (charged) MoS2 is energetically favorable and that S-C bonds are formed.

Noncovalently functionalized monolayer graphene for sensitivity enhancement of surface plasmon resonance immunosensors.

A highly efficient surface plasmon resonance (SPR) immunosensor is described using a functionalized single graphene layer on a thin gold film. The aim of this approach was two-fold: first, to amplify the SPR signal by growing graphene through chemical vapor deposition and, second, to control the immobilization of biotinylated cholera toxin antigen on copper coordinated nitrilotriacetic acid (NTA) using graphene as an ultrathin layer. The NTA groups were attached to graphene via pyrene derivatives implying π-π interactions. With this setup, an immunosensor for the specific antibody anticholera toxin with a detection limit of 4 pg mL(-1) was obtained. In parallel, NTA polypyrrole films of different thicknesses were electrogenerated on the gold sensing platform where the optimal electropolymerization conditions were determined. For this optimized polypyrrole-NTA setup, the simple presence of a graphene layer between the gold and polymer film led to a significant increase of the SPR signal.

Functionalization of liquid-exfoliated two-dimensional 2H-MoS2.

Layered two-dimensional (2D) inorganic transition-metal dichalchogenides (TMDs) have attracted great interest as a result of their potential application in optoelectronics, catalysis, and medicine. However, methods to functionalize and process such 2D TMDs remain scarce. We have established a facile route towards functionalized layered MoS2 . We found that the reaction of liquid-exfoliated 2D MoS2 , with M(OAc)2 salts (M=Ni, Cu, Zn; OAc=acetate) yielded functionalized MoS2 -M(OAc)2 materials. Importantly, this method furnished the 2H-polytype of MoS2 which is a semiconductor. X-ray photoelectron spectroscopy (XPS), diffuse reflectance infrared Fourier transform spectroscopy (DRIFT-IR), and thermogravimetric analysis (TGA) provide strong evidence for the coordination of MoS2 surface sulfur atoms to the M(OAc)2 salt. Interestingly, functionalization of 2H-MoS2 allows for its dispersion/processing in more conventional laboratory solvents.

Transition metal dichalcogenide growth via close proximity precursor supply.

Reliable chemical vapour deposition (CVD) of transition metal dichalcogenides (TMDs) is currently a highly pressing research field, as numerous potential applications rely on the production of high quality films on a macroscopic scale. Here, we show the use of liquid phase exfoliated nanosheets and patterned sputter deposited layers as solid precursors for chemical vapour deposition. TMD monolayers were realized using a close proximity precursor supply in a CVD microreactor setup. A model describing the growth mechanism, which is capable of producing TMD monolayers on arbitrary substrates, is presented. Raman spectroscopy, photoluminescence, X-ray photoelectron spectroscopy, atomic force microscopy, transmission electron microscopy, scanning electron microscopy and electrical transport measurements reveal the high quality of the TMD samples produced. Furthermore, through patterning of the precursor supply, we achieve patterned growth of monolayer TMDs in defined locations, which could be adapted for the facile production of electronic device components.

Edge and confinement effects allow in situ measurement of size and thickness of liquid-exfoliated nanosheets.

Two-dimensional nanomaterials such as MoS2 are of great interest both because of their novel physical properties and their applications potential. Liquid exfoliation, an important production method, is limited by our inability to quickly and easily measure nanosheet size, thickness or concentration. Here we demonstrate a method to simultaneously determine mean values of these properties from an optical extinction spectrum measured on a liquid dispersion of MoS2 nanosheets. The concentration measurement is based on the size-independence of the low-wavelength extinction coefficient, while the size and thickness measurements rely on the effect of edges and quantum confinement on the optical spectra. The resultant controllability of concentration, size and thickness facilitates the preparation of dispersions with pre-determined properties such as high monolayer-content, leading to first measurement of A-exciton MoS2 luminescence in liquid suspensions. These techniques are general and can be applied to a range of two-dimensional materials including WS2, MoSe2 and WSe2.

Molybdenum disulfide/pyrolytic carbon hybrid electrodes for scalable hydrogen evolution.

The electrochemical generation of hydrogen fuel via the proton reduction in the Hydrogen Evolution Reaction (HER) in aqueous media is currently dependent on the use expensive noble metal catalysts for which alternatives must be sought. Molybdenum disulfide (MoS2) has shown great promise as a suitable electrocatalyst in this regard. While many lab-scale experiments on the HER activity of this material have demonstrated its viability and explored some fundamental mechanistic features of HER at MoS2, these experimental techniques are often ill-suited to large scale production of such electrodes. In this study we present work on the fabrication of MoS2/pyrolytic carbon (PyC) electrodes via vapour phase sulfurization of Mo thin films. These hybrid electrodes combine the catalytic activity of MoS2 with the conductivity and stability of PyC, whilst using industrially compatible processing techniques. Structural defects in the sulfur lattice were found to be key catalytically active sites for HER and thinner MoS2 films displayed a higher quantity of these defects and, hence, an improved HER activity. The observed Tafel slope of 95 mV decade(-1) is comparable to previous literature works on MoS2 HER performance.