Influence of Mesityl and Thiophene Peripheral Substituents on Surface Attachment, Redox Chemistry, and ORR Activity of Molecular Iron Porphyrin Catalysts on Electrodes

Inorganic Chemistry
R GötzInez M Weidinger

Abstract

Two iron porphyrin complexes with either mesityl (FeTMP) or thiophene (FeT3ThP) peripheral substituents were attached to basal pyrolytic graphite and Ag electrodes via different immobilization methods. By combining cyclic voltammetry and in-operando surface-enhanced Raman spectroscopy along with MD simulations and DFT calculations, their respective surface attachment, redox chemistry and activity toward electrocatalytic oxygen reduction was investigated. For both porphyrin complexes, it could be shown that catalytic activity is restricted to the first (few) molecular layer(s), although electrodes covered with thiophene-substituted complexes showed a better capability to consume the oxygen at a given overpotential even in thicker films. The spectroscopic data and simulations suggest that both porphyrin complexes attach to a Ag electrode surface in a way that maximum planarity and minimum distance between the catalytic iron site and the electrode is achieved. However, due to the distinctive design of the FeT3ThP complex, the thiophene rings are capable of occupying a conformation, via rotation around the bonding axis to the porphyrin, in which all four sulfur atoms can coordinate to the Ag surface. This effect creates a dense and...Continue Reading

References

Sep 15, 1997·Journal of Colloid and Interface Science·K MukherjeeT N Misra
Jul 15, 1996·Physical Review. B, Condensed Matter·S GoedeckerJ Hutter
Oct 28, 1996·Physical Review Letters·J P PerdewM Ernzerhof
Dec 23, 2004·Accounts of Chemical Research·Daniel H Murgida, Peter Hildebrandt
Sep 7, 2006·Journal of Computational Chemistry·Stefan Grimme
Dec 21, 2006·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Florian BuchnerHubertus Marbach
Jul 3, 2008·Journal of the American Chemical Society·Anja KranichDaniel H Murgida
Oct 29, 2008·Chemical Communications : Chem Comm·James P Collman, Richard A Decréau
Apr 6, 2011·Journal of the American Chemical Society·Wolfgang HieringerJ Michael Gottfried
May 8, 2013·Proceedings of the National Academy of Sciences of the United States of America·Kushal SenguptaAbhishek Dey
Feb 5, 2015·Journal of the American Chemical Society·Nicholas C BoazJohn T Groves
Apr 25, 2015·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Patrycja KielbInez M Weidinger
Oct 7, 2016·Chemical Communications : Chem Comm·Nathan CoutardVincent Artero
Feb 9, 2017·Chemistry : a European Journal·R Morris BullockAaron M Appel
Apr 7, 2017·The Journal of Physical Chemistry. B·Patrycja KielbInez Weidinger
Aug 11, 2017·Analytical Sciences : the International Journal of the Japan Society for Analytical Chemistry·Ryo MatsuokaMakoto Yuasa
Feb 7, 2018·Chemical Reviews·Michael L PegisJames M Mayer
Mar 25, 2018·Angewandte Chemie·Ibrahim Halil ÖnerInez M Weidinger

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