Zn Redistribution and Volatility in ZnZrOx Catalysts for CO2 Hydrogenation.

ZnO-ZrO2 mixed oxide (ZnZrOx) catalysts are widely studied as selective catalysts for CO2 hydrogenation into methanol at high-temperature conditions (300-350 °C) that are preferred for the subsequent in situ zeolite-catalyzed conversion of methanol into hydrocarbons in a tandem process. Zn, a key ingredient of these mixed oxide catalysts, is known to volatilize from ZnO under high-temperature conditions, but little is known about Zn mobility and volatility in mixed oxides. Here, an array of ex situ and in situ characterization techniques (scanning electron microscopy/energy dispersive X-ray spectroscopy (SEM/EDX), transmission electron microscopy (TEM), powder X-ray diffraction (PXRD), X-ray absorption spectroscopy (XAS), X-ray photoelectron spectroscopy (XPS), Infrared (IR)) was used to reveal that Zn2+ species are mobile between the solid solution phase with ZrO2 and segregated and/or embedded ZnO clusters. Upon reductive heat treatments, partially reversible ZnO cluster growth was observed above 250 °C and eventual Zn evaporation above 550 °C. Extensive Zn evaporation leads to catalyst deactivation and methanol selectivity decline in CO2 hydrogenation. These findings extend the fundamental knowledge of Zn-containing mixed oxide catalysts and are highly relevant for the CO2-to-hydrocarbon process optimization.

Tailoring the Vertical and Planar Growth of 2D WS2 Thin Films Using Pulsed Laser Deposition for Enhanced Gas Sensing Properties.

In this study, pulsed laser deposition has been utilized for the controllable synthesis of WS2 thin films with growth orientation ranging from vertically to horizontally aligned layers, and the effect of growth parameters has been investigated. The growth of thin films on SiO2 substrates at three different pressures (30, 50, and 70 mTorr) and three different temperatures (400, 500, and 600 °C) has been studied. Detailed characterizations carried out on the as-grown layers clearly show the formation of the 2H-WS2 phase and its morphological evolution with deposition conditions. Atomic force microscopy and cross-sectional transmission electron microscopy have been used to deduce the growth mechanism of the vertical and planar films with different deposition parameters. The samples grown with a combination of lower temperatures and higher pressures exhibit a vertical flake-like growth with a flake thickness of ∼2-5 nm. However, at higher temperatures and lower pressures, the film growth is observed to be rather planar. The gas sensing parameters and the underlying mechanism have been observed to be quite different for vertically and horizontally grown layers. The vertical layers showed a selective response toward NO2 gas at room temperature (RT) with a limit of detection less than 50 ppb. In comparison, a very subdued and poor gas sensing response was recorded for the planar film at RT. A large specific area and abundance of active edge sites along with the flat basal plane present in the vertically grown layers seem to be responsible for efficient gas sensing toward NO2.