Synthetic control and empirical prediction of redox potentials for Co(4)O(4) cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation.
Synthetic control and empirical prediction of redox potentials for Co(4)O(4) cubanes over a 1.4 V range: implications for catalyst design and evaluation of high-valent intermediates in water oxidation.
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DOI：
10.1039/c7sc00627f
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发表时间：
2017-06-01
期刊：
影响因子：
8.4
通讯作者：
Tilley TD
中科院分区：
文献类型：
--
作者：
Nguyen AI;Wang J;Levine DS;Ziegler MS;Tilley TD
氧代钴立方烷单元 [Co4O4] 作为均相析氧反应 (OER) 催化剂以及作为非均相氧化钴 OER 催化剂的功能模拟物而受到关注。氧代钴立方烷单元 [Co4O4] 作为均相析氧反应 (OER) 催化剂以及作为非均相氧化钴 OER 催化剂的功能模拟物而受到关注。几种新古巴烷的合成可以评估 [Co4O4] 簇的氧化还原电位，这些簇对配体环境高度敏感，并且跨越 1.42 V 的显着范围。[CoIII4O4]4+/[CoIII3CoIVO4]5+ 和 [CoIII3CoIVO4]5+/[CoIII2CoIV2O4]6+ 氧化还原电位可以通过配体的 pK 可靠预测。氢键也被证明可以显着提高氧化还原电位，约 500 mV。电势-pKa 相关性用于评估各种拟议的 OER 催化中间体（包括高价 Co-oxo 物质）的可行性。这些研究开发的合成方法和结构-反应性关系应该更好地指导新型立方烷基 OER 催化剂的设计。
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 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 pK as of the ligands. Hydrogen bonding is also shown to significantly raise the redox potentials, by ∼500 mV. The potential-pK a correlation 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.
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