TY - JOUR
T1 - Dissociative mechanism of oxygen reduction reaction (ORR) on Pd-Cu disordered binary alloy metal surfaces
T2 - A theoretical study
AU - López-Chávez, Ernesto
AU - Garcia-Quiroz, Alberto
AU - González-García, Gerardo
AU - Peña-Castañeda, Yesica A.
AU - Díaz-Góngora, José A.I.
AU - de Landa Castillo-Alvarado, Fray
N1 - Publisher Copyright:
© 2016
PY - 2016/12/28
Y1 - 2016/12/28
N2 - Density functional theory (DFT) in conjunction with virtual crystal approximation is used to study the oxygen reduction reaction (ORR) as a function of the cooper concentration in Pd–Cu disordered binary alloy metal surfaces and as a function of applied bias. The study is realized calculating the free energy diagrams of all intermediates. Reactivity is evaluated on the basis of an oxygen reduction reaction (ORR) dissociative mechanism of four steps, it involves the splitting of the O–O bond in O2 after its adsorption, followed by hydrogenation of atomic O to OH. Then, the OH species undergoes another hydrogenation to yield H2O. For each concentration of Cu, results for low oxygen coverage are presented at zero cell potential (U = 0), at the equilibrium potential (U = 1.23 V), and at the highest potential (U = 0.80 V) where all reaction are exothermic. The results indicate that at the ORR equilibrium potential of 1.23 V, the reactivity of all surfaces is shown to be limited by the rate of OH removal from the surface, while that at a cell potential of 0.80 V, the ORR reactivity of different surfaces is dictated by the hydrogenation of O∗ and strength of oxygen adsorption. The results are compared with other non-Pt alloys.
AB - Density functional theory (DFT) in conjunction with virtual crystal approximation is used to study the oxygen reduction reaction (ORR) as a function of the cooper concentration in Pd–Cu disordered binary alloy metal surfaces and as a function of applied bias. The study is realized calculating the free energy diagrams of all intermediates. Reactivity is evaluated on the basis of an oxygen reduction reaction (ORR) dissociative mechanism of four steps, it involves the splitting of the O–O bond in O2 after its adsorption, followed by hydrogenation of atomic O to OH. Then, the OH species undergoes another hydrogenation to yield H2O. For each concentration of Cu, results for low oxygen coverage are presented at zero cell potential (U = 0), at the equilibrium potential (U = 1.23 V), and at the highest potential (U = 0.80 V) where all reaction are exothermic. The results indicate that at the ORR equilibrium potential of 1.23 V, the reactivity of all surfaces is shown to be limited by the rate of OH removal from the surface, while that at a cell potential of 0.80 V, the ORR reactivity of different surfaces is dictated by the hydrogenation of O∗ and strength of oxygen adsorption. The results are compared with other non-Pt alloys.
KW - Binary alloy
KW - Catalysis
KW - Dissociative mechanism
KW - Oxygen reduction reaction
UR - http://www.scopus.com/inward/record.url?scp=85004001424&partnerID=8YFLogxK
U2 - 10.1016/j.ijhydene.2016.09.001
DO - 10.1016/j.ijhydene.2016.09.001
M3 - Artículo
SN - 0360-3199
VL - 41
SP - 23281
EP - 23286
JO - International Journal of Hydrogen Energy
JF - International Journal of Hydrogen Energy
IS - 48
ER -