Catalytic properties toward the Oxygen Reduction Reaction of 2D metal-organic frameworks

DIPC Seminars

Paula Abufager
Instituto de Fisica Rosario (CONICET-UNR). Argentina
Donostia International Physics Center
Nicolas Lorente
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Catalytic properties toward the Oxygen Reduction Reaction of 2D metal-organic frameworks

In general, metal porphyrins adsorb flat on metal surfaces being the SAM structure ruled by the subtle interplay between molecule-molecule and molecule-surface interactions. In the case of metal tetrapyridyl-porphyrins (M- TPyP) the lattice parameter of the SAM not only fixes the number of (metal) active sites per unit area but is also crucial to allow (or not) the pyridyl nitrogens to offer an additional coordination site for extra metal atoms which might proceed from surface environment [1] or from the surface itself. In addition, it has been experimentally shown that metal atoms M? sublimated over the M-TPyP/Au(111) SAM can also substitute the M center [2], so being able to modify its electrocatalytic activity in quite many ways [1,3]. In this work we present a Density Functional Theory (DFT) study of the structure and electrocatalytic activity for the oxygen reduction reaction (ORR) of both the FeTPyP/Au(111) SAM, and the resulting bimetal-organic framework FeTPyP+M'/Au(111) obtained by sublimation of M' (=Fe, Co) atoms. We analyse the role of intermolecular, and molecule-Au(111) interactions on the structure of the mono- and bi- metal organic SAMs [4] , and their electrocatalytic activities considering all the many possible resulting metal active sites.

[1] B. Wurster, D. Grumelli, D. Hotger, R. Gutzler, and K. Kern. J. Am. Chem. Soc. 138 3623 (2016).
[2] D. Hotger, P. Abufager, C. Morchutt, P. Alexa, D. Grumelli, J. Dreiser, S. Stepanow, P. Gambardella, H. F. Busnengo, M. Etzkorn, R. Gutzler, K. Kern, Nanoscale 10 21116 (2018).
[3] D. Hotger, M. Etzkorn, C. Morchutt, B. Wurster, J. Dreiser, S. Stepanow, D. Grumelli, R. Gutzler, K. Kern Physical Chemistry Chemical Physics 21, 2587 (2019). [4] J. M. Lombardi, D. Grumelli, R. Gultzer and H. F. Busnengo, J. Phys. Chem. C (accepted)