The possibility of using ammonia as a hydrogen carrier is discussed. Compared to other hydrogen storage materials, ammonia has the advantages of a high hydrogen density, a well-developed technology for synthesis and distribution, and easy catalytic decomposition. Compared to hydrocarbons and alcohols, it has the advantage that there is no CO 2 emission at the end user. The drawbacks are mainly the toxicity of liquid ammonia and the problems related to trace amounts of ammonia in the hydrogen after decomposition. Storage of ammonia in metal ammine salts is discussed, and it is shown that this maintains the high volumetric hydrogen density while alleviating the problems of handling the ammonia. Some of the remaining challenges for research in ammonia as a hydrogen carrier are outlined.
The indirect hydrogen storage capabilities of Mg(NH 3) 6Cl 2, Ca(NH 3) 8Cl 2, Mn(NH 3) 6Cl 2, and Ni(NH 3) 6Cl 2 are investigated. All four metal ammine chlorides can be compacted to solid tablets with densities of at least 95% of the crystal density. This gives very high indirect hydrogen densities both gravimetrically and volumetrically. Upon heating, NH 3 is released from the salts, and by employing an appropriate catalyst, H 2 can be released corresponding to up to 9.78 wt % H and 0.116 kg H/L for the Ca(NH 3) 8Cl 2 salt. The NH 3 release from all four salts is investigated using temperature-programmed desorption employing different heating rates. The desorption is found mainly to be limited by heat transfer, indicating that the desorption kinetics are extremely fast for all steps. During desorption from solid tablets of Mg(NH 3) 6Cl 2, Mn(NH 3) 6Cl 2, and Ni(NH 3) 6Cl 2, nanoporous structures develop, which facilitates desorption from the interior of large, compact tablets. Density functional theory calculations reproduce trends in desorption enthalpies for the systems studied, and a mechanism in which individual chains of the ammines are released from the surface of the crystal is proposed to explain the fast absorption/desorption processes.
Promoted Ru/C catalysts for decomposition of ammonia are incorporated into micro-fabricated reactors for the first time. With the reported preparation technique, the performance is increased more than two orders of magnitude compared to previously known micro-fabricated reactors for ammonia decomposition. The catalytic activities for production of hydrogen from ammonia are determined for different promoters and promoter levels on graphite supported ruthenium catalysts. The reactivity trends of the Ru/C catalysts promoted with Cs and Ba are in excellent agreement with those known from earlier studies of both ammonia synthesis and decomposition, and it is shown how proper promotion can facilitate ammonia decomposition at temperatures below 500 K.
Nanosized Na 2 Ti 3 O 7 , K 2 Ti 6 O 13 and Cs 2 Ti 6 O 13 materials were prepared and used as supports of ruthenium nanoparticles for catalytic ammonia decomposition. It is shown that these catalysts exhibit higher catalytic activity than ruthenium supported on TiO 2 nanoparticles promoted with cesium. The difference is attributed to the use of nanostructured materials with incorporated alkali metals in the crystal lattice, which apparently gives a higher effect of the promoter. All samples were characterized by X-ray powder diffraction, transmission electron microscopy and N 2 physisorption measurements. Furthermore, the effect of ruthenium loading on the catalytic decomposition of ammonia was investigated.
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