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.

Nanostructure-assisted charge transfer in α-Fe2O3/g-C3N4 heterojunctions for efficient and highly stable photoelectrochemical water splitting.

The development of semiconductor heterojunctions is a promising and yet challenging strategy to boost the performance in photoelectrochemical (PEC) water splitting. This paper describes the fabrication of a heterojunction photoanode by coupling α-Fe2O3 and g-C3N4via aerosol-assisted chemical vapour deposition (AACVD) followed by spin coating and air annealing. Enhanced PEC performance and stability are observed for the α-Fe2O3/g-C3N4 heterojunction photoanode in comparison to pristine α-Fe2O3 and the reason is systematically discussed in this paper. Most importantly, the fabricated α-Fe2O3/g-C3N4 film shows impressive stability, retaining more than 90% of the initial current over 12 h operating time. The excellent stability of the heterojunction photoanode is achieved due to the unique nanoflake structure of α-Fe2O3 induced by AACVD. This nanostructure promotes good adhesion with the g-C3N4 particles, as the particles tend to be trapped within the α-Fe2O3 valleys and eventually create strong and large interfacial contacts. This leads to improved separation of charge carriers at the α-Fe2O3/g-C3N4 interface and suppression of charge recombination in the photoanode, which are confirmed by the transient decay time, charge transfer efficiency and electrochemical impedance analysis. Our findings demonstrate the importance of nanostructure engineering for developing heterojunction structures with efficient charge transfer dynamics.

Rapid fabrication of oxygen defective α-Fe2O3(110) for enhanced photoelectrochemical activities.

Defect engineering is increasingly recognized as a viable strategy for boosting the performance of photoelectrochemical (PEC) water splitting using metal oxide-based photoelectrodes. However, previously developed methods for generating point defects associated with oxygen vacancies are rather time-consuming. Herein, high density oxygen deficient α-Fe2O3 with the dominant (110) crystal plane is developed in a very short timescale of 10 minutes by employing aerosol-assisted chemical vapor deposition and pure nitrogen as a gas carrier. The oxygen-defective film exhibits almost 8 times higher photocurrent density compared to a hematite photoanode with a low concentration of oxygen vacancies which is prepared in purified air. The existence of oxygen vacancies improves light absorption ability, accelerates charge transport in the bulk of films, and promotes charge separation at the electrolyte/semiconductor interface. DFT simulations verify that oxygen-defective hematite has a narrow bandgap, electron-hole trapped centre, and strong adsorption energy of water molecules compared to pristine hematite. This strategy might bring PEC technology another step further towards large-scale fabrication for future commercialization.