Density Functional Theory Modeling of Reactions of Addition of H₂ Molecules to Magnesium Clusters Mg₁₇M Doped with Atoms M of Transition 3d Elements

Abstract

Density functional theory calculations of potential energy surface (PES) have been performed for elementary hydrogenation reactions Mg 17 M + H 2 → Mg 17 MH 2 of magnesium clusters Mg 17 M doped by transition 3d metals (M = Ti−Ni), and for consecutive reactions Mg 17 Ni + nH 2 → Mg 17 NiH 2n of addition of n hydrogen molecules to Ni-doped clusters Mg 17 Ni and Mg 17 NiH 2 . Energetic, geometric, and spectroscopic features of intermediates and transition states along the minimum energy pathway have been found, and their trends were analyzed with dopants changing along the 3d series and with increasing number of atoms H attached to the surface positions of the magnesium backbone.

Density Functional Study of Size-Dependent Hydrogen Adsorption on AgnCr (n = 1–12) Clusters

“…Following the pioneering work of Nonose and co-workers on the chemisorption of small clusters of aluminum with hydrogen, the reaction mechanism of charged and neutral aluminum clusters and their doped species with H 2 has been later explored in terms of both theoretical and experimental approaches. − The geometric and electronic structures of hydrogenated scandium, titanium, and zirconium clusters have been examined by Kumar et al and Sheng et al , Swart and co-workers investigated the H 2 adsorption on 3d transition metal clusters in combined infrared spectroscopy and density functional study . Density functional theory (DFT) calculations have been performed to understand the adsorption and dissociation pathway of H 2 molecule on magnesium doped with transition metal atoms. − The bonding characters and adsorption energies of H 2 molecules on pure and decorated boron fullerenes/spheres have been extensively studied due to their potential for hydrogen storage media. − …”

“… 17 Density functional theory (DFT) calculations have been performed to understand the adsorption and dissociation pathway of H 2 molecule on magnesium doped with transition metal atoms. 18 − 20 The bonding characters and adsorption energies of H 2 molecules on pure and decorated boron fullerenes/spheres have been extensively studied due to their potential for hydrogen storage media. 21 − 29…”

Alloying Ratio Versus Cluster Size for Reversible Hydrogen Storage in Ni Doped Small Mg Clusters: Dispersion Corrected DFT Study

“…Ma et al have reported that adding Ti and Nb into M g 55 cluster enhances the stability and also improve the hydrogenation kinetics [38].Very recently, Samantaray et al have been able to synthesize NiMg alloy nanocomposites with up to 5.4 wt% hydrogenation capacity [40]. The issue of hydrogenation kinetics in M g 17 M clusters doped with different 3d transition metal atoms (M) have recently appeared in a series of DFT studies by Charkin and Maltsev [41,42,43,44]. They have confirmed Mg17Ni cluster to have the most favourable reaction kinetics in forming M g 17 M H 2 systems [41].…”

Accentuating the Competency of $3d$ Transition Metal Doped $Mg_4$ Clusters towards Molecular Hydrogen Adsorption: A DFT Study

“…In another study Cui et al have explored the hydrogen storage properties of a series of Mg-TM (TM=Ti, Nb, V, Co, Mo, Ni) nanocomposites and ranked the dehydro-genation performance as [42]. Charkin and Maltsev have recently studied the reaction kinetics for the hydrogenation of different 3d transition metal (M) doped M g 17 M clusters [43,44,45]. They have reported that Ni shows the most favourable reaction kinetics in the formation of M g 17 M H 2 systems [45].…”

“…Charkin and Maltsev have recently studied the reaction kinetics for the hydrogenation of different 3d transition metal (M) doped M g 17 M clusters [43,44,45]. They have reported that Ni shows the most favourable reaction kinetics in the formation of M g 17 M H 2 systems [45]. Trivedi and Bandopadhyay studied the hydrogen adsorption on Rh and Co doped Mg clusters in two different DFT studies and reported M g 5 Co and M g 9 Rh as the most effective hydrogen storage clusters [29,31].…”