The Study On The Structural,Electronic Properties Of Ru₁₃@Pt_42-nMo_n?n=0?18?and O₂ Dissociation And CO Oxidition Reaction On The Surface Of Ru₁₃@Pt_42-nMo_n?N=0?18? Nanoclusters

The structural,electronic properties of Ru13@Pt42-nMon(n=0?18)nanoclusters and the adsorption of oxygen molecule,oxygen atom,and CO molecule,the oxygen molecule dissociation reaction,and the CO oxidation reaction on the surface of Ru13@Pt42-nMon(n=0?18)nanoclusters were studied by Density Function Theory.The results are listed as follows:1)The Mo atoms occupy vertex sites when n?4,while occupy edge sites when n?5 in the Ru13@Pt42-nMon(n=0?18)nanoclusters.Anlysis of excess energy,dissolution potential,and core-shell interaction energy show addition of Mo atoms contributes the stability of Ru13@Pt42-nMon(n=0?18)nanoclusters.The Bader charge shows that Pt atoms get electrons from the Mo and Ru atoms,even the Ru atoms can obtain electrons from Mo atoms,which is consistent with electronegativity.The transferred electron number is relational with the coordination number.Besides,the d-band center exhibits a negtive relationship with the coordination number.Moreover,the d-band center of Pt can be affected by the site Mo occupying,and d-band centre of Mo is relational with the excess energy.2)There are five different kinds of(111)face in the Ru13@Pt42-nMon(n=0?18)nanoclusters,on which the adsorptions of oxygen molecule and oxygen atom and the dissociation reaction are studied.The oxygen molecule is adsorbed on the Bridge1 site of(111)face without Mo atom which is called first kind(111)face preferentially.Moreover,the oxygen molecule is adsorbed on the Mo site of(111)face.It is need to be mentioned that oxygen molecule is dissociated when adsorbed on the third kind,fourth kind,and fifth kind(111)faces.Moreover,the adsorption energy exhibits a negtive liner relationship with the d-band center of Mo.The Bader charge shows the oxygen atoms get electrons from nanoclusters,and get more electrons when the oxygen molecule is dissociated.Furthermore,the energy barrier is caused by activation of O-O bond,and gets lower when the(111)face has Mo atom.3)The adsorption of carbon monoxide molecule and oxidation reaction are studied on the five different kinds of(111)face in the Ru13@Pt42-nMon(n=0?18)nanoclusters.The CO is adsorbed verically on the Pt atom in the(111)face.Moreover,the adsorption energy exhibits a negtive relationship with d-band center of Pt,which is the higher d-band center,the lower the adsorption energy.Bader charge shows the oxygen atom gets electrons and the carbon atom loses electrons in the carbon monoxide.In totally,the carbon monoxide gets electrons from nanocluster.Furthermore,the Bader charge of oxygen atoms is relational with adsorption energy,namely the higher adsorption energy,the less electrons oxygen atom gets.The reaction process in the oxidation reaction of carbon monoxide is consisted of migration of oxygen atom and carbon monoxide,the formation of O-C-O bond,adsorption of carbon dioxide,and desorption of carbon dioxide.The energy barrier in the oxidation reaction is the migration of oxygen atom for first kind(111)face,while the main energy barrier is the formation of O-C-O bond for other kinds(111)faces.Besides,the energy barrier is increased for the five kinds(111)face when Mo added.