Application of Si-doped graphene as a metal-free catalyst for decomposition of formic acid: A theoretical study

Using density functional theory calculations, the adsorption and catalytic decomposition of formic acid (HCOOH) over Si-doped graphene are investigated. For the stable adsorption geometries of HCOOH over Si-doped graphene, the electronic structure properties are analyzed by adsorption energy, density of states, and charge density difference. A comparison of the reaction pathways reveals that both dehydration and dehydrogenation of HCOOH can occur over Si-doped graphene. The estimated reaction energies and the activation barriers suggest that for the dehydration of HCOOH on the Si-doped graphene, the rate-controlling step is H+OH H2O reaction. For the dehydrogenation of HCOOH, the rate-determining step is the breaking of the CH bond of the HCOO group to form the CO2 molecule and the atomic H. Our results reveal that the low cost Si-doped graphene can be used as an efficient nonmetal catalyst for OH bond cleavage of HCOOH. (c) 2015 Wiley Periodicals, Inc.