jp911136s_si_001.pdf (1.13 MB)
Reactivity of Aluminum Cluster Anions with Water: Origins of Reactivity and Mechanisms for H2 Release
journal contributionposted on 2010-05-27, 00:00 authored by Arthur C. Reber, Shiv N. Khanna, Patrick J. Roach, W. Hunter Woodward, A. W. Castleman
The reactivity of aluminum anion clusters with water was found to exhibit variations with size, with some clusters exhibiting negligible reactivity, others absorbing one or more water, while even others releasing H2 with addition of multiple waters. (Roach, P.J., Woodward, W.H. et al. Science, 2009, 323, 492). Herein, we provide further details on the role of complementary active sites in the breaking of the O−H bond on the cluster. We examine the reactions of Aln− + H2O where n = 7−18, and show how the complementary active sites may be best identified. The clusters with active sites are found to be reactive, and clusters with barriers to reactivity have an absence of paired active sites. The role of charge in the reactivity is considered, which could account for the observed increase in reactivity at large sizes. The H2 release in the reactivity of Al17− with multiple water molecules is also studied by comparing multiple reaction pathways, and the selective H2 production is explained by the first water inducing a new active site. A mechanism for transferring hydroxyl groups on the surface of the cluster is also discussed.