Aluminium clusters for molecular hydrogen storage and the corresponding alanes as fuel alternatives: A structural and energetic analysis

•Valuation of the clusters of 13th group elements for hydrogen storage.•The alanes AlnHm clusters have significant capability in producing energy.•Bare Aln clusters (n = 5, 6 and 7) are strong hydrogen acceptors.•AlnHm oxidation produce clean energy with harmless wastes.

Bare and hydrogenated aluminium clusters Aln (n = 5–7) are studied using density functional theory in order to evaluate the ability to store molecular hydrogen and to estimate the energy release upon combustion with the aim to understand these species as alternative fuel resources. Six sequential molecular hydrogenations are considered and are shown to occur without or very low activation barriers. The H2 molecule uses its occupied σ orbital to react with an appropriate electron-deficient site of the cluster; this is generally followed by H migration leading to the favoured geometry. The combustion process produces alumina (Al2O3), water and a significant quantity of energy. The exothermicity seems to be largely independent of cluster size but it depends instead on the stored hydrogen quantity.