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Exploring the catalytic activity of metal‐fullerene C 58 M (M = Mn, Fe, Co, Ni, and Cu) toward oxygen reduction and CO oxidation by density functional theory
Author(s) -
Chen Xin,
Ge Fan,
Chang Junbo,
Lai Nanjun
Publication year - 2019
Publication title -
international journal of energy research
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.808
H-Index - 95
eISSN - 1099-114X
pISSN - 0363-907X
DOI - 10.1002/er.4768
Subject(s) - catalysis , overpotential , adsorption , density functional theory , chemistry , metal , binding energy , oxygen , activation energy , inorganic chemistry , computational chemistry , electrochemistry , organic chemistry , atomic physics , physics , electrode
Summary In the present work, the catalytic activity of metal‐fullerene C 58 M (M = Mn, Fe, Co, Ni, and Cu) toward oxygen reduction reaction (ORR) and CO oxidation has been explored by detailed density functional theory calculations. Firstly, the binding energy of various ORR species (OOH, O, and OH) on C 58 M and the corresponding adsorption structures are calculated. The results show that the adsorption strength of any ORR species on C 58 M follows the order of C 58 Mn > C 58 Fe > C 58 Co > C 58 Ni > C 58 Cu and C 58 Co shows the closest binding energy compared with the Pt(111) surface. Further analysis of the free energy change of ORR indicates that C 58 Co, C 58 Ni, and C 58 Fe have different degrees of catalytic activities, with the calculated free energy change of rate‐determining step of −0.70, −0.32, and −0.04 eV, respectively. On the basis of the above results, the C 58 Co obviously has the highest ORR activity, with a relatively small overpotential of 0.53 V. In addition, the adsorption free energy of OH can be used as a good descriptor for ORR activity due to the nearly linear relationships between ∆ G *OOH , ∆ G *O , and ∆ G *OH . At last, the catalytic property of C 58 Co toward CO oxidation reaction is also explored. The calculated results show that CO oxidation on C 58 Co follows LH mechanism and the rate‐determining step is recognized as *CO + *O 2 → *OOCO, with the energy change of −0.13 eV.