Efficient dehydrogenation of formic acid using Al 12 N 12 nanocage: A DFT study Mehdi D. Esrafili ⇑ , Roghaye Nurazar Laboratory of Theoretical Chemistry, Department of Chemistry, University of Maragheh, P.O. Box 5513864596, Maragheh, Iran article info Article history: Received 10 May 2014 Received in revised form 3 July 2014 Accepted 5 July 2014 Available online 18 July 2014 Keywords: Formic acid Decomposition Al 12 N 12 DFT Mechanism abstract We have studied the adsorption and decomposition of formic acid (HCOOH) on the surface of Al 12 N 12 fullerene-like nanocage using density functional theory. Different adsorption modes were found for HCOOH on the Al 12 N 12 , i.e. molecular and dissociative mono- dentate or bidentate adsorption. Three reaction pathways were proposed to understand gas-phase HCOOH decomposition on the Al 12 N 12 nanocage. Our results reveal that for the decomposition of HCOOH into CO 2 and H 2 , the most favorable pathway should be the CAH bond activation reaction. The reaction energies and the activation barriers obtained here suggest that for the dissocia- tive adsorption configuration on the Al 12 N 12 surface, the rate- determining step is the CAH bond breaking. Ó 2014 Elsevier Ltd. All rights reserved. 1. Introduction In recent years, hydrogen has attracted considerable attention as an efficient and important alter- native energy resource particularly when combined with fuel-cell technology [1,2]. However, the future application of hydrogen is limited by the lack of a convenient, cheap and safe storage system. Up to now, several different techniques have been proposed for hydrogen storage including liquid H 2 at cryogenic temperature, into metal hydrides compounds [3,4], carbon-based materials [5,6], adsorbed in organic polymers [7,8], or in situ produced from organic or inorganic compounds [9]. http://dx.doi.org/10.1016/j.spmi.2014.07.007 0749-6036/Ó 2014 Elsevier Ltd. All rights reserved. ⇑ Corresponding author. Tel.: +98 4212237955; fax: +98 4212276060. E-mail address: esrafili@maragheh.ac.ir (M.D. Esrafili). Superlattices and Microstructures 75 (2014) 17–26 Contents lists available at ScienceDirect Superlattices and Microstructures journal homepage: www.elsevier.com/locate/superlattices