Publication date: 15th May 2025
Ternary spinel oxide nanocrystals of general formula AB2O4 are attractive materials for photo- and electrocatalytic applications due to their chemical stability and ability to accommodate multiple oxidation states and cation geometries within the same material. The presence of both tetrahedral and octahedral crystal sites offers unique opportunities for structural tunability while the mixed-valent composition combined with the incorporation of redox-active transition metal cations provides redox flexibility. However, little is known about how the composition of ternary spinel oxide nanocrystals impacts their surface chemistry. Recently, our group has become interested in the role that redox-active transition metal cations play in mediating charge transfer processes at ternary spinel oxide surfaces. This poster presents recent results from two different projects in our group focused on this topic. The first project involves preliminary electrochemical characterizations of proton-coupled electron transfer (PCET) processes at the surfaces of a series of nanostructured metal ferrite materials of formula MFe2O4, where M = Fe, Co, Ni, Zn. Changing the identity of M does not significantly impact the observed PCET reactions, suggesting that these processes occur primarily at iron sites. The second project investigates the origin of intense optical features that appear upon addition of thiol ligands to colloidal cobalt-containing spinel oxide nanocrystals. We propose that these features arise from localized ligand-to-metal charge transfer transitions between thiolate ligands and surface cobalt ions
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