Remarkably improved hydrogen storage properties of nanocrystalline TiO2-modified NaAlH4 and evolution of Ti-containing species during dehydrogenation/hydrogenation
hydrogen storage, complex hydrides, catalyst addition, nanocrystalline TiO2@C
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 °C (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 °C; this is 65 °C lower than that of the pristine sample. The dehydrogenated sample is completely hydrogenated at 115 °C 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 Ti4+→Ti3+→Ti2+→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 nanocrystalline transition metal-based additives.
Tsinghua University Press
Xin Zhang,Yongfeng Liu,Ke Wang,Mingxia Gao,Hongge Pan, Remarkably improved hydrogen storage properties of nanocrystalline TiO2-modified NaAlH4 and evolution of Ti-containing species during dehydrogenation/hydrogenation. NanoRes.2015, 8(2): 533–545