Analysis of Porphyrines as Catalysts for Electrochemical Reduction of O-2 and Oxidation of H2O
Artikel i vetenskaplig tidskrift, 2014

Bioinspired structures are promising as improved catalysts for various redox reactions. One example is metal hangman-porphyrines (MHP), which recently have been suggested for oxygen reduction/evolution reaction (ORR/OER). The unique properties of the MHPs are attributed to both the hangman scaffold and the C6F5 side groups. Herein, the OER/ORR over various transition metal MHPs is investigated by density functional theory calculations within an electrochemical framework. A comparison of the reaction landscape for MHP, metal porphyrine (MP) and metaltetrafluorophenyloporphyrines (MTFPP), allow for a disentanglement of the different roles of the hangman motif and the side groups. In agreement with experimental studies, it is found that Fe and Co are the best MHP Metal centers to catalyze these reactions. We find that the addition of the three-dimensional moiety in the form of hangman scaffold does not break the apparently universal energy relation between *OH and *OOH intermediates. However, the hangman motif is found to stabilize the oxygen intermediate, whereas addition of C6F5 groups reduces the binding energy of all reaction intermediates. Our results indicate that the combination of these two effects allow new design possibilities for macromolecular systems with enhanced catalytic OER/ORR activity.

HANGMAN PORPHYRINS

OXIDE SURFACES

TRANSITION-METAL

EVOLUTION

FUNCTIONALIZED GRAPHITIC MATERIALS

FUEL-CELL CATHODE

HYDROGEN

DENSITY

OXYGEN REDUCTION

WATER OXIDATION

Författare

Jakub Baran

Kompetenscentrum katalys (KCK)

Chalmers, Teknisk fysik, Kemisk fysik

Henrik Grönbeck

Chalmers, Teknisk fysik, Kemisk fysik

Kompetenscentrum katalys (KCK)

Anders Hellman

Chalmers, Teknisk fysik, Kemisk fysik

Kompetenscentrum katalys (KCK)

Journal of the American Chemical Society

0002-7863 (ISSN) 1520-5126 (eISSN)

Vol. 136 4 1320-1326

Styrkeområden

Nanovetenskap och nanoteknik

Transport

Energi

Materialvetenskap

Infrastruktur

C3SE (Chalmers Centre for Computational Science and Engineering)

Ämneskategorier

Kemi

DOI

10.1021/ja4060299

Mer information

Skapat

2017-10-08