TY - JOUR
T1 - Electronic structure and oxygen reduction on tunable [Ti(IV)Pc]2+ and Ti(II)Pc titanyl-phthalocyanines
T2 - A quantum chemical prediction
AU - De Lile, Jeffrey Roshan
AU - Heine, Thomas
AU - Zhou, Su
N1 - Publisher Copyright:
© 2016 Elsevier B.V.
Copyright:
Copyright 2017 Elsevier B.V., All rights reserved.
PY - 2017/3/1
Y1 - 2017/3/1
N2 - The high cost of platinum-based catalysts has hampered the commercialization of polymer electrolyte membrane fuel cells (PEMFCs). Hence, the electronic structure and oxygen reduction ability of [Ti(IV)Pc]2+, Ti(II)Pc titanyl-phthalocyanines, and their tailored peripheral and axial ligand complexes were theoretically investigated to determine non-precious cathode catalysts. Our results revealed that the peripherally substituted and unsubstituted Ti(II)Pc triplet complexes can spontaneously reduce peroxide. The singlet [Ti(IV)Pc]2+ parent complex has a 6.45 eV barrier. However, fluorine substitution at peripheral positions reduced the energy barrier up to 0.45 eV. In addition, chlorine substitution has shown spontaneous peroxide reduction as in the case of triplets. The high catalytic activity of Ti(II)Pc complexes and singlet chlorine substituted complex is attributed to the optimal charge transfer between dioxygen molecule and the novel catalyst complexes. As a result, Ti(II)Pcs and chlorine substituted singlet complexes are considered as potential substitutions for the noble Pt-based catalyst for the PEMFCs.
AB - The high cost of platinum-based catalysts has hampered the commercialization of polymer electrolyte membrane fuel cells (PEMFCs). Hence, the electronic structure and oxygen reduction ability of [Ti(IV)Pc]2+, Ti(II)Pc titanyl-phthalocyanines, and their tailored peripheral and axial ligand complexes were theoretically investigated to determine non-precious cathode catalysts. Our results revealed that the peripherally substituted and unsubstituted Ti(II)Pc triplet complexes can spontaneously reduce peroxide. The singlet [Ti(IV)Pc]2+ parent complex has a 6.45 eV barrier. However, fluorine substitution at peripheral positions reduced the energy barrier up to 0.45 eV. In addition, chlorine substitution has shown spontaneous peroxide reduction as in the case of triplets. The high catalytic activity of Ti(II)Pc complexes and singlet chlorine substituted complex is attributed to the optimal charge transfer between dioxygen molecule and the novel catalyst complexes. As a result, Ti(II)Pcs and chlorine substituted singlet complexes are considered as potential substitutions for the noble Pt-based catalyst for the PEMFCs.
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U2 - 10.1016/j.commatsci.2016.12.012
DO - 10.1016/j.commatsci.2016.12.012
M3 - Article
AN - SCOPUS:85007285515
VL - 129
SP - 24
EP - 36
JO - Computational Materials Science
JF - Computational Materials Science
SN - 0927-0256
ER -