Biomimicking vitamin B12. A Co phthalocyanine pyridine axial ligand coordinated catalyst for the oxygen reduction reaction. (1st March 2018)

• Record Type: Journal Article
• Authors: Riquelme, Jorge; Neira, Karinna; Marco, José F.; Hermosilla-Ibáñez, Patricio; Orellana, Walter; Zagal, José H.; Tasca, Federico
• Is Part Of: Electrochimica acta. Volume 265(2018)
• Page Start: 547
• Page End: 555
• Publication Date: 2018-03-01
• Subjects: Co phthalocyanine -- Vitamin B12 -- Oxygen reduction reaction -- Electrocatalysis -- Fuel cell cathode; Electrochemistry -- Periodicals; Electrochemistry, Industrial -- Periodicals; 541.37
• DOI: 10.1016/j.electacta.2018.01.177
• Languages: English
• ISSNs: 0013-4686

Abstract

Abstract: CoN4 complexes like Co phthalocyanines (CoPc) have been extensively studied as electrocatalysts for the oxygen reduction reaction (ORR) but they only promote the 2-electron reduction of O2 to give peroxide. In contrast, vitamin B12 a Co macrocyclic naturally occurring molecule has attracted the attention of the scientific community because instead of catalysing the 2-electron reduction of O2 to H2 O2 like the other Co macrocycles it promotes the 4-electron reduction to H2 O. Vitamin B12 possesses an axial back ligand and this seems to be the reason for its higher activity and selectivity for the 4-electron reduction of O2 . To test this hypothesis, we synthetized a CoPc axially coordinated to pyridine anchored to carbon nano-tubes (CoPc-Py-CNT). The Co centre is therefore coordinated to 5 N as in vitamin B12 . The modified CoPc containing catalytic material was characterized by EPR and XPS spectroscopy. Ab initio calculations, Koutecky– Levich extrapolation and Tafel plots well describe the similarities between the 2 complexes and reveal insights into the mechanism of action of Co penta-coordinated complexes. According to our results the pyridine back ligand increases the Co-O2 binding energy and making it more similar to that of Vitamin B12, favouring the splitting of the O-O bond. The back ligand then plays a crucial role in modifying Co-O2 binding energy which is a well know reactivity descriptor. Graphical abstract: Image 1