Journal of Physical Chemistry B, Vol.110, No.15, 7967-7974, 2006
Improved hydrogen release from LiB0.33N0.67H2.67 with noble metal additions
The hydrogen release behavior of the quaternary hydride LiB0.33N0.67H2.67 has been successfully improved through the incorporation of small quantities of noble metal. Adding 5 wt % Pd either as Pd metal particles or as PdCl2 reduced the temperature T-1/2 corresponding to the midpoint of the hydrogen release reaction by Delta T-1/2 = -43 degrees C and -76 degrees C, respectively. PtCl2 and Pt nanoparticles supported on a Vulcan carbon substrate proved to be even more effective, with Delta T-1/2 = -90 degrees C. The amount of NH3 released during dehydro.,enation is reduced compared to that from additive-free material, and, more importantly, at temperatures below 210 degrees C hydrogen is released with no detectable NH3. In contrast to additive-free LiB0.33N0.67H2.67 which melts completely above 190 degrees C and releases hydrogen from the liquid state only above similar to 250 degrees C. hydrogen release from LiB0.33N0.67H2.67 + 5 wt % Pt/Vulcan carbon is accompanied by partial melting Plus a cascade through a series of solid intermediate phases. Calorimetric measurements indicate that both additive-free and Pt-added LiB0.33N0.67H2.67 release hydrogen exothermically, and hence the reverse reaction is thermodynamically unfavorable. By exposing partially dehydrogenated samples to high H-2 pressures at modest temperatures, fractional hydrogen uptake (roughly 15% of the released hydrogen) has been achieved. The mechanism by which noble metals promote hydrogen release is not known, but the behavior is consistent with that expected for a catalyst, including a large effect with small additions and saturation of the effect at low concentration.