Reactivity of CO on Ni4 cluster- effect of spin multiplicity and H doping-A DFT investigation

Roy, Ghanashyam; Chattopadhyay, Asoke P.

doi:10.1016/j.saa.2018.06.070

Cited by 5 publications

(3 citation statements)

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“…For example, corner atoms of Shell 405 nanoparticles can decompose hydrazine more efficiently than bulk Ir (111) surface [28]. The Kohn-Sham MOs of the Ni 4 cluster are shown in an earlier study [57], and MOs of isolated gauche hydrazine are presented in Fig. 1a From NBO analysis, it appears that for isolated N 2 H 4 molecule, the two N-H bond (BD) pairs are slightly different.…”

Section: Adsorption Of N 2 H 4 On Ni 4 Clustermentioning

confidence: 90%

“…The three-dimensional tetrahedral Ni 4 cluster is used as a model to understand the reactivity of hydrazine at molecular level on surface of Ni catalyst particle. The optimised geometrical parameters of Ni 4 cluster is presented in our earlier papers [56,57]. However, to obtain stable configuration of adsorption, different possible adsorption configurations were optimised by placing the conformers of hydrazine on the binding sites of Ni 4 cluster, as shown in Fig.…”

Section: Methodsmentioning

confidence: 99%

“…as a model of Shell 405 catalyst. However, several small Ni 4 cluster-based calculations are also reported to clarify the decomposition of small molecules on such surfaces [55][56][57]. To our knowledge, the dissociation of hydrazine on Ni 4 cluster has not been reported till date.…”

Section: Introductionmentioning

confidence: 99%

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Dissociation of hydrazine on tetrahedral Ni4 cluster by density functional theory

Roy¹,

Chattopadhyay

2019

SN Appl. Sci.

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Sequential dissociation of hydrazine has been studied on Ni 4 cluster applying density functional theory (DFT) methods. Two routes of dissociation have been discussed. The first path (A) is the consecutive dissociation of four N-H bonds to form surface N 2 via intermediate product diimide, N 2 H 2. The second path (B) is the dissociation of N-N bond to form two NH 2 species leading to formation of surface ammonia. The second elementary steps for both the routes show the highest activation energy barrier; for example in path A, N 2 H 3 + H → N 2 H 2 + 2H, E Act is 1.19 eV and in path B, 2NH 2 → NH + H+NH 2 , E Act is 1.71 eV. These are the rate-determining steps. NBO analysis shows that adsorption of hydrazine and ammonia is due to strong delocalisation of the lone pairs to the higher energy states of the cluster. Adsorption and dissociation of hydrazine and ammonia are thermodynamically feasible at standard conditions. Formation of N 2 is a slow exothermic process, whereas N-N bond dissociation to form two NH 2 species is a faster and highly exothermic process. NH species binds by two Ni-N covalent bonds. N species binds the cluster by three Ni-N bonds and three strong lone pair delocalisation at threefold site. Removal of these intermediates needs higher energy of activation. Thus, the formation and dehydrogenation of ammonia are slow and lengthy processes. New catalysts could be designed in such a way that N-N bond might not be dissociated, which is happening due to absence of lone pair of N1(LP) to Rydberg orbital of N2(RY*) delocalisation or vice versa.

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Section: Adsorption Of N 2 H 4 On Ni 4 Clustermentioning

confidence: 90%

Section: Methodsmentioning

confidence: 99%