Abstract: Unique and distinctive properties could be obtained on such two-dimensional (2D) semiconductor as tungsten trioxide (WO3) when the reduction from multi-layer to one fundamental layer thickness takes place. This transition without damaging single-layer on a large spatial resolution remained elusive until the atomic layer deposition (ALD) technique was utilized. Here we report the ALD-enabled atomic-layer-precision development of a single layer WO3 with thickness of 0.77±0.07 nm on a large spatial resolution by using (tBuN)2W(NMe2)2 as tungsten precursor and H2O as oxygen precursor, without affecting the underlying SiO2/Si substrate. Versatility of ALD is in tuning recipe in order to achieve the complete WO3 with desired number of WO3 layers including monolayer. Governed by self-limiting surface reactions, the ALD-enabled approach is versatile, scalable and applicable for a broader range of 2D semiconductors and various device applications.
Abstract: WO3/SiO2 catalysts were modified by an ion exchange
method with sodium hydroxide or potassium hydroxide solution. The
performance of the modified catalysts was tested in the metathesis of
ethylene and trans-2-butene to propylene. During ion exchange,
sodium and potassium ions played different roles. Sodium modified
catalysts revealed constant trans-2-butene conversion and propylene
selectivity when the concentrations of sodium in the solution were
varied. In contrast, potassium modified catalysts showed reduction of
the conversion and increase of the selectivity. From these results,
potassium hydroxide may affect the transformation of tungsten oxide
active species, resulting in the decrease in conversion whereas
sodium hydroxide did not. Moreover, the modification of catalysts by
this method improved the catalyst stability by lowering the amount of
coke deposited on the catalyst surface.
Abstract: The effect of additional magnesium oxide (MgO) was
investigated by using the tungsten oxide supported on silica catalyst
(WOx/SiO2) physically mixed with MgO in a weight ratio 1:1. The
both fresh and spent catalysts were characterized by FT-Raman
spectrometer, UV-Vis spectrometer, X-Ray diffraction (XRD) and
temperature programmed oxidation (TPO). The results indicated that
the additional MgO could enhance the conversion of trans-2-butene
due to isomerization reaction. However, adding MgO would increase
the amount of coke deposit on the WOx/SiO2 catalyst. The TPO
profile presented two peaks when the WOx/SiO2 catalyst was
physically mixed with MgO. The further peak was suggested that
came from coke precursor could be produced by isomerization
reaction of undesired product. Then, the occurred coke precursor
could deposit and form coke on the acid catalyst.
Abstract: Propylene self-metathesis to ethylene and butene was
studied over WOx/SiO2 catalysts at 450oC and atmospheric pressure.
The WOx/SiO2 catalysts were prepared by incipient wetness
impregnation of ammonium metatungstate aqueous solution. It was
found that, adding nano-sized extra supports (SiO2 and TiO2) by
physical mixing with the WOx/SiO2 enhanced propylene conversion.
The UV-Vis and FT-Raman results revealed that WOx could migrate
from the original silica support to the extra support, leading to a
better dispersion of WOx. The ICP-OES results also indicate that
WOx existed on the extra support. Coke formation was investigated
on the catalysts after 10 h time-on-stream by TPO. However, adding
nano-sized extra supports led to higher coke formation which may be
related to acidity as characterized by NH3-TPD.