A high-pressure phase of TiO(2), which had been observed by shock-wave experiments and remained unresolved, has been studied by in situ x-ray diffraction. The single phase was formed at 20 gigapascals and 770 degrees C with the use of sintered-diamond multianvils; it has the same structure as baddeleyite, the stable phase of ZrO(2) at ambient conditions. The coordination number of Ti increases from six to seven across the rutile to baddeleyite transition, and the volume is reduced by approximately 9 percent.
A proton exchange membrane (PEM) system using a SrTiO3 gas-diffusion photoanode achieves vapor-fed photoelectrolysis of water at an applied voltage of 0.3 V.
Heteroepitaxial spinel ferrites NiFe 2 O 4 and CoFe 2 O 4 films have been prepared by pulsed laser deposition (PLD) at various temperatures (175 -690 °C) under ozone/oxygen pressure of 10 mTorr. Due to enhanced kinetic energy of ablated species at low pressure and enhanced oxidation power of ozone, epitaxy has been achieved at significantly lower temperatures than previously reported. Films grown at temperature below 550 °C show a novel growth mode, which we term "vertical step-flow" growth mode. Epitaxial spinel ferrite films with atomically flat surface over large areas and enhanced magnetic moment can be routinely obtained.Interestingly, the growth mode is independent of the nature of substrates (spinel MgAl 2 O 4 , perovskite SrTiO 3 , and rock salt MgO) and film thicknesses. The underlying growth mechanism is discussed.
On-site and on-demand photocatalytic methane conversion under ambient conditions is one of the urgent global challenges for the sustainable use of ubiquitous methane resources. However, the lack of microscopic knowledge on its reaction mechanism prevents the development of engineering strategies for methane photocatalysis. Combining real-time mass spectrometry and operando infrared absorption spectroscopy with ab initio molecular dynamics simulations, here we report key molecular-level insights into photocatalytic green utilization of methane. Activation of the robust C–H bond of methane is hardly induced by the direct interaction with photogenerated holes trapped at the surface of photocatalyst; instead, the C–H activation is significantly promoted by the photoactivated interfacial water species. The interfacial water hydrates and properly stabilizes hydrocarbon radical intermediates, thereby suppressing their overstabilization. Owing to these water-assisted effects, the photocatalytic conversion rates of methane under wet conditions are dramatically improved by typically more than 30 times at ambient temperatures (~300 K) and pressures (~1 atm) in comparison to those under dry conditions. This study sheds new light on the role of interfacial water and provides a firm basis for design strategies for non-thermal heterogeneous catalysis of methane under ambient conditions.
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