Graphite conjugation of a macrocyclic cobalt complex enhances nitrite electroreduction to ammonia

SE Braley, J Xie, Y Losovyj… - Journal of the American …, 2021 - ACS Publications
SE Braley, J Xie, Y Losovyj, JM Smith
Journal of the American Chemical Society, 2021ACS Publications
This work reports on the generation of a graphite-conjugated diimine macrocyclic Co
catalyst (GCC-CoDIM) that is assembled at o-quinone edge defects on graphitic carbon
electrodes. X-ray photoelectron spectroscopy and X-ray absorption spectroscopy confirm the
existence of a new Co surface species with a coordination environment that is the same as
that of the molecular analogue,[Co (DIM) Br2]+. GCC-CoDIM selectively reduces nitrite to
ammonium with quantitative Faradaic efficiency and at a rate that approaches enzymatic …
This work reports on the generation of a graphite-conjugated diimine macrocyclic Co catalyst (GCC-CoDIM) that is assembled at o-quinone edge defects on graphitic carbon electrodes. X-ray photoelectron spectroscopy and X-ray absorption spectroscopy confirm the existence of a new Co surface species with a coordination environment that is the same as that of the molecular analogue, [Co(DIM)Br2]+. GCC-CoDIM selectively reduces nitrite to ammonium with quantitative Faradaic efficiency and at a rate that approaches enzymatic catalysis. Preliminary mechanistic investigations suggest that the increased rate is accompanied by a change in mechanism from the molecular analogue. These results provide a template for creating macrocycle-based electrocatalysts based on first-row transition metals conjugated to an extreme redox-active ligand.
ACS Publications
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