Adding a small amount of nanocrystalline TiO2@C （TiO2 supported on nano- porous carbon） composite dramatically decreases the operating temperatures and improves the reaction kinetics for hydrogen storage in NaAlH4. ...Adding a small amount of nanocrystalline TiO2@C （TiO2 supported on nano- porous carbon） composite dramatically decreases the operating temperatures and improves the reaction kinetics for hydrogen storage in NaAlH4. The nano- crystalline TiO2@C composite synthesized at 900 ℃ （referred as TiO2@C-900） exhibits superior catalytic activity to other catalyst-containing samples. The onset dehydrogenation temperature of the TiO2@C-900-containing sample is lowered to 90 ℃; this is 65 ℃ lower than that of the pristine sample. The dehydrogenated sample is completely hydrogenated at 115 ℃ and 100 bar of hydrogen pressure with a hydrogen capacity of 4.5 wt.%. Structural analyses reveal that the Ti undergoes a reduction process of Ti^4＋→Ti^3＋→Ti^2＋→Ti during the ball milling and heating processes, and further converts to Ti hydrides or forms Ti-Al species after rehydrogenation. The catalytic activities of Ti-based catalytic species decrease in the order Al-Ti-species 〉 TiH0.71 〉 TiH2 〉 TiO2. This understanding guides further improvement in hydrogen storage properties of metal alanates using nanocrvstalline transition metal-based additives.展开更多
文摘Adding a small amount of nanocrystalline TiO2@C （TiO2 supported on nano- porous carbon） composite dramatically decreases the operating temperatures and improves the reaction kinetics for hydrogen storage in NaAlH4. The nano- crystalline TiO2@C composite synthesized at 900 ℃ （referred as TiO2@C-900） exhibits superior catalytic activity to other catalyst-containing samples. The onset dehydrogenation temperature of the TiO2@C-900-containing sample is lowered to 90 ℃; this is 65 ℃ lower than that of the pristine sample. The dehydrogenated sample is completely hydrogenated at 115 ℃ and 100 bar of hydrogen pressure with a hydrogen capacity of 4.5 wt.%. Structural analyses reveal that the Ti undergoes a reduction process of Ti^4＋→Ti^3＋→Ti^2＋→Ti during the ball milling and heating processes, and further converts to Ti hydrides or forms Ti-Al species after rehydrogenation. The catalytic activities of Ti-based catalytic species decrease in the order Al-Ti-species 〉 TiH0.71 〉 TiH2 〉 TiO2. This understanding guides further improvement in hydrogen storage properties of metal alanates using nanocrvstalline transition metal-based additives.
