Synthesis of metallic mixed 3R and 2H Nb1+xS2 nanoflakes by chemical vapor deposition.

In this work, we report the synthesis and characterization of mixed phase Nb1+xS2 nanoflakes prepared by chemical vapor deposition. The as-grown samples show a high density of flakes (thickness ∼50 nm) that form a continuous film. Raman and X-ray diffraction data show that the samples consist of both 2H and 3R phases, with the 2H phase containing a high concentration of Nb interstitials. These Nb interstitials sit in between the NbS2 layers to form Nb1+xS2. Cross-sectional Energy Dispersive Spectroscopy analysis with transmission electron microscopy suggests that the 2H Nb1+xS2 region is found in thinner flakes, while 3R NbS2 is observed in thicker regions of the films. The evolution of the phase from 2H Nb1+xS2 to 3R NbS2 may be attributed to the change of the growth environment from Nb-rich at the start of the growth to sulfur-rich at the latter stage. It was also found that the incorporation of Nb interstitials is highly dependent on the temperature of the NbCl5 precursor and the position of the substrate in the furnace. Samples grown at high NbCl5 temperature and with substrate located closer to the NbCl5 source show higher incorporation of Nb interstitials. Electrical measurements show linear I-V characteristics, indicating the metallic nature of the Nb1+xS2 film with relatively low resistivity of 4.1 × 10-3Ω cm.

Ultrahigh-current-density niobium disulfide catalysts for hydrogen evolution.

Metallic transition metal dichalcogenides (TMDs)1-8 are good catalysts for the hydrogen evolution reaction (HER). The overpotential and Tafel slope values of metallic phases and edges9 of two-dimensional (2D) TMDs approach those of Pt. However, the overall current density of 2D TMD catalysts remains orders of magnitude lower (~10-100 mA cm-2) than industrial Pt and Ir electrolysers (>1,000 mA cm-2)10,11. Here, we report the synthesis of the metallic 2H phase of niobium disulfide with additional niobium (2H Nb1+xS2, where x is ~0.35)12 as a HER catalyst with current densities of >5,000 mA cm-2 at ~420 mV versus a reversible hydrogen electrode. We find the exchange current density at 0 V for 2H Nb1.35S2 to be ~0.8 mA cm-2, corresponding to a turnover frequency of ~0.2 s-1. We demonstrate an electrolyser based on a 2H Nb1+xS2 cathode that can generate current densities of 1,000 mA cm-2. Our theoretical results reveal that 2H Nb1+xS2 with Nb-terminated surface has free energy for hydrogen adsorption that is close to thermoneutral, facilitating HER. Therefore, 2H Nb1+xS2 could be a viable catalyst for practical electrolysers.

Effects of Mo vapor concentration on the morphology of vertically standing MoS2 nanoflakes.

Vertically standing MoS2 nanoflakes are favourable in applications such as energy storage devices, hydrogen evolution reactions, and gas sensors due to their large surface area and high density of exposed edges. In this work, we report the effect of Mo vapor concentration on the morphology of vertical MoS2 nanoflakes prepared by chemical vapor deposition at atmospheric pressure. A series of MoS2 samples were grown under different Mo vapor concentrations by varying the separation distance (x) between the MoO3 source and the substrate. Field emission scanning electron microscopy showed the sample grown at x = 1 cm had a high density of vertical flakes (7 vertical flakes µm-2) with an average flake length of ~770 nm and thickness of ~10 nm. As x increased to 4 cm, the average flake length was reduced to ~150 nm while the flake orientation changed from vertical to lateral. That is, high Mo vapor concentration favours the formation of large and vertical MoS2 nanoflakes. However, oversupply of Mo vapor results in significantly thicker flakes. Raman spectra of all samples showed two main peaks at 380 and 407 cm-1 that correspond to the E1 2 g and A1 g vibrational peaks of MoS2. As x decreased from 4 to 1, the peak intensity ratio (E1 2g/A1 g) reduced from 0.58 to 0.42, suggesting greater dominance of vertical flakes at low x. X-ray diffraction data showed a prominent peak at 14.4°, which corresponded to the (002) diffraction peak of 2H MoS2. Transmission electron microscopy verified the flakes consist of eight layers with an interlayer spacing of 0.62 nm. Based on hydrogen evolution reaction measurements, samples with thin flakes have high catalytic activity. This work highlights the importance of optimizing Mo vapor concentration to obtain a high density of thin, large, and vertically standing MoS2 nanoflakes.

Photoluminescence Investigation of Carrier Localization in Colloidal PbS and PbS/MnS Quantum Dots.

The existence of surface organic capping ligands on quantum dots (QDs) has limited the potential in QDs emission properties and energy band gap structure alteration as well as the carrier localization. This drawback can be addressed via depositing a thin layer of a semiconductor material on the surface of QDs. Herein, we report on the comparative study for photoluminescent (PL) properties of PbS and PbS/MnS QDs. The carrier localization effect due to the alteration of energy band gap structure and carrier recombination mechanism in the QDs were investigated via PL measurements in a temperature range of 10-300 K with the variation of the excitation power from 10 to 200 mW. For PbS QDs, the gradient of integrated PL intensity (IPL) as a function of excitation power density graph was less than unity. When the MnS shell layer was deposited onto the PbS core, the PL emission exhibited a blue shift, showing dominant carrier recombination. It was also found that the full width half-maximum showed a gradual broadening with the increasing temperature, affirming the electron-phonon interaction.