Insights into Ru-Based Molecular Water Oxidation Catalysts: Electronic and Noncovalent-Interaction Effects on Their Catalytic Activities

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• 作者：Lele Duan ; Lei Wang ; A. Ken Inge ; Andreas Fischer ; Xiaodong Zou ; Licheng Sun
• 刊名：Inorganic Chemistry
• 出版年：2013
• 出版时间：July 15, 2013
• 年：2013
• 卷：52
• 期：14
• 页码：7844-7852
• 全文大小：499K
• 年卷期：v.52,no.14(July 15, 2013)
• ISSN：1520-510X

文摘

A series of Ru-bda water oxidation catalysts [Ru(bda)L₂] (H₂bda = 2,2鈥?bipyridine-6,6鈥?dicarboxylic acid; L = [HNEt₃][3-SO₃-pyridine], 1; 4-(EtOOC)-pyridine, 2; 4-bromopyridine, 3; pyridine, 4; 4-methoxypyridine, 5; 4-(Me₂N)-pyridine, 6; 4-[Ph(CH₂)₃]-pyridine, 7) were synthesized with electron-donating/-withdrawing groups and hydrophilic/hydrophobic groups in the axial ligands. These complexes were characterized by ¹H NMR spectroscopy, high-resolution mass spectrometry, elemental analysis, and electrochemistry. In addition, complexes 1 and 6 were further identified by single crystal X-ray crystallography, revealing a highly distorted octahedral configuration of the Ru coordination sphere. All of these complexes are highly active toward Ce^IV-driven (Ce^IV = Ce(NH₄)₂(NO₃)₆) water oxidation with oxygen evolution rates up to 119 mols of O₂ per mole of catalyst per second. Their structure鈥揳ctivity relationship was investigated. Electron-withdrawing and noncovalent interactions (attraction) exhibit positive effect on the catalytic activity of Ru-bda catalysts.