The surface chemistry of pristine, 6-nm silicon nanoparticles has been investigated. The particles were produced in an RF plasma and studied using a tandem differential mobility analysis apparatus, Fourier transform infrared spectroscopy (FTIR), time-of-flight secondary ion mass spectrometry (ToF-SIMS), and transmission electron microscopy. Particles were extracted from the plasma, which operates at approximately 20 Torr, into an atmospheric pressure aerosol flow tube, and then through a variable-temperature furnace that could be adjusted between room temperature and 1200 degrees C. DMA measurements show that freshly generated silicon particles shrink with heating, with particle diameters decreasing by approximately 0.25 nm between 350 and 400 degrees C. FTIR results indicate that freshly generated particles are primarily covered with SiH2 groups and smaller amounts of SiH and SiH3. Spectra recorded as a function of heating temperature indicate that the amount of surface hydrogen, as measured by the intensity of modes associated with SiH, SiH2, and SiH3, decreases with heating. ToF-SIMS measurements also suggest that hydrogen desorbs from the particles surfaces over the same temperature range that the particles shrink.

Growing concerns regarding the safety, flammability and hazards posed by Li-ion systems have led to research on alternative rechargeable metal-ion electrochemical storage technologies. Among the most notable of these are Na-ion supercapacitors and batteries, motivated, in part, by the similar electrochemistry of Li and Na ions. However, sodium ion batteries (SIBs) come with their own set of issues, especially the large size of the Na + ion, its relatively sluggish kinetics and low energy densities. This makes the development of novel materials and appropriate electrode architecture of absolute significance. Transition metal dichalcogenides (TMDs) have attracted a lot of attention in this regard due to their relative ease of exfoliation, diverse morphologies and architectures with superior electronic properties. Here, we study the electrochemical performance of Mo-based two-dimensional (2D) layered TMDs (e.g. MoS 2 , MoSe 2 and MoTe 2 ), exfoliated in a superacid, for battery and supercapacitor applications. The exfoliated TMD flakes were interfaced with reduced graphene oxide (rGO) to be used as composite electrodes. Electron microscopy, elemental mapping and Raman spectra were used to analyse the exfoliated material and confirm the formation of 2D TMD/rGO layer morphology. For supercapacitor applications in aqueous electrolyte, the sulfide-based TMD (MoS 2 ) exhibited the best performance, providing an areal capacitance of 60.25 mF cm −2 . For SIB applications, TMD electrodes exhibited significantly higher charge capacities than the neat rGO electrode. The initial desodiation capacities for the composite electrodes are 468.84 mAh g −1 (1687.82 C g −1 ), 399.10 mAh g −1 (1436.76 C g −1 ) and 387.36 mAh g −1 (1394.49 C g −1 ) for MoS 2 , MoSe 2 and MoTe 2 , respectively. Also, the MoS 2 and MoSe 2 composite electrodes provided a coulombic efficiency of near 100 % after a few initial cycles.

The earliest stages of thermal oxidation of 6 nm diameter silicon nanoparticles by molecular oxygen are examined using a tandem differential mobility analysis (TDMA) apparatus, Fourier-transform infrared (FTIR) spectroscopy, time-of-flight secondary ion mass spectroscopy (ToF-SIMS), and X-ray photoelectron spectroscopy (XPS). Particles are synthesized in and then extracted from a nonthermal RF plasma operating at approximately 20 Torr into the atmospheric pressure TDMA apparatus. The TDMA apparatus was used to measure oxidation-induced size changes over a broad range of temperature settings and N2-O2 carrier gas composition. Surface chemistry changes are evaluated in situ with an FTIR spectrometer and a hybrid flow-through cell, and ex situ with ToF-SIMS and XPS. Particle size measurements show that, at temperatures less than approximately 500 degrees C, particles shrink regardless of the carrier gas oxygen concentration, while FTIR and ToF-SIMS spectra demonstrate a loss of hydrogen from the particles and minimal oxide formation. At higher temperatures, FTIR and XPS spectra indicate that an oxide forms which tends toward, but does not fully reach, stoichiometric SiO2 with increasing temperature. Between 500 and 800 degrees C, size measurements show a small increase in particle diameter with increasing carrier gas oxygen content and temperature. Above 800 degrees C, particle growth rapidly reaches a plateau while FTIR and XPS spectra change little. ToF-SIMS signals associated with O-Si species also show an increase in intensity at 800 degrees C.

Sintering, coalescence, and compositional changes of hydrogen-terminated, crystalline silicon nanoparticles were examined as a function of temperature. Monodisperse aerosol particles ∼5 nm in diameter were synthesized by gas-to-particle conversion in a plasma reactor and then immediately heated as they flowed through a tube furnace. Particles were also collected as powders and then heated in other apparatuses. Structure and size changes were characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM), thermal behavior was characterized by differential scanning calorimetry (DSC), and silicon-hydrogen functionality changes were characterized by Fourier transform infrared spectroscopy (FTIR). At ∼500 °C, only silicon monohydride functional groups are observed in FTIR spectra. XRD results obtained after heating to that temperature indicate a small reduction in crystal size relative to the freshly generated particles, and TEM images show disorganized particle shells surrounding crystalline particle cores. Between 550 and 750 °C extensive sintering occurs and polycrystalline aggregates evolve. At temperatures greater than ∼750 °C, no silicon hydrides are observed in FTIR spectra, and extensive coalescence occurs. Temperatures of 1000 °C are required to produce single-crystalline, spherical particles. Exothermic behavior is exhibited up to 1000 °C with two conspicuous exothermic transitions centered at ∼350 and 750 °C. The transitions correlate well with desorption of higher hydrides from particle surfaces and coalescence of particle agglomerates, respectively.

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