| Autor: |
Nguyen, AI, Wang, J, Levine, DS, Ziegler, MS, Tilley, TD |
| Jazyk: |
angličtina |
| Rok vydání: |
2017 |
| Zdroj: |
Nguyen, AI; Wang, J; Levine, DS; Ziegler, MS; & Tilley, TD. (2017). Synthetic control and empirical prediction of redox potentials for Co4O4cubanes over a 1.4 v range: Implications for catalyst design and evaluation of high-valent intermediates in water oxidation. Chemical Science, 8(6), 4274-4284. doi: 10.1039/c7sc00627f. Lawrence Berkeley National Laboratory: Retrieved from: http://www.escholarship.org/uc/item/7ch8q021 |
| Popis: |
© 2017 The Royal Society of Chemistry. The oxo-cobalt cubane unit [Co4O4] is of interest as a homogeneous oxygen-evolution reaction (OER) catalyst, and as a functional mimic of heterogeneous cobalt oxide OER catalysts. The synthesis of several new cubanes allows evaluation of redox potentials for the [Co4O4] cluster, which are highly sensitive to the ligand environment and span a remarkable range of 1.42 V. The [CoIII4O4]4+/[CoIII3CoIVO4]5+and [CoIII3CoIVO4]5+/[CoIII2CoIV2O4]6+redox potentials are reliably predicted by the pKas of the ligands. Hydrogen bonding is also shown to significantly raise the redox potentials, by ∼500 mV. The potential-pKacorrelation is used to evaluate the feasibility of various proposed OER catalytic intermediates, including high-valent Co-oxo species. The synthetic methods and structure-reactivity relationships developed by these studies should better guide the design of new cubane-based OER catalysts. |
| Databáze: |
OpenAIRE |
| Externí odkaz: |
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