We report in situ spectroscopic measurements in nonaqueous media designed to trap an exceptionally strong oxidant generated electrochemically from an iron-containing nickel layered double hydroxide ([NiFe]-LDH) material. Anodic polarization of this material in acetonitrile produces metal-oxo vibrational spectroscopic signatures along with an extremely narrow near-infrared luminescence peak that strongly indicate that the reactive intermediate is cis-dioxo-iron(VI). Chemical trapping experiments reveal that addition of H₂O to the polarized electrochemical cell produces hydrogen peroxide; and, most importantly, addition of HO^– generates oxygen. Repolarization of the electrode restores the iron(VI) spectroscopic features, confirming that the high-valent oxo complex is active in the electrocatalytic water oxidation cycle.

我们报告了在非水介质中的原位光谱测量结果，该介质旨在捕获由含铁的镍层状双氢氧化物（[NiFe] -LDH）材料电化学生成的异常强的氧化剂。这种材料在乙腈中的阳极极化会产生金属-氧代振动光谱信号，以及一个非常窄的近红外发光峰，这强烈表明该反应性中间体是 顺式-二氧代-铁（VI）。化学捕集实验表明，向极化电化学电池中添加H ₂ O会产生过氧化氢。最重要的是，添加HO ^–产生氧气。电极的重新极化可恢复铁（VI）的光谱特征，从而证实高价氧合络合物在电催化水氧化循环中具有活性。