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首页> 外文期刊>RSC Advances >Generation of reactive cobalt oxo oxamate radical species for biomimetic oxidation of contaminants
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Generation of reactive cobalt oxo oxamate radical species for biomimetic oxidation of contaminants

机译：生成活性钴氧杂草酸自由基基团，用于污染物的仿生氧化

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The non-heme oxamate anionic cobalt(III) complexes [CoIII(opbaX)]? (opbaX = 4-X-o-phenylenebis(oxamate), X = H, NO2, CH3) with different substituents were synthesized and applied to targeted micropollutant degradation. Typical radical scavengers (isopropanol and chlorine anions) have no negative effect on the catalytic oxidation of substrates, and no DMPO–˙OH or DMPO–˙OOH (DMPO = 5,5-dimethyl-pyrroline-oxide) signal was detected by electron paramagnetic resonance spin-trap technique in [CoIII(opbaX)]?/H2O2 system, suggesting that the non-hydroxyl radical biomimetic catalytic mechanism was dominant in the oxidation process. The results of high-definition ESI-MS pronounced the presence of cobalt-oxo intermediates which played a key role in the catalytic oxidation of substrates. Furthermore, density functional theory calculations were used to evaluate the viability of such cobalt-oxo species and it demonstrated an optimizing electromer with a formulation of [CoIVO˙]? or [CoIII–OH]˙. The calculations explained that the catalytic activity of [CoIII(opbaX)]? was significantly enhanced by introducing an electron-withdrawing substituent which could change the coordination environment of cobalt to generate more electron-deficient cobalt-oxo species with stronger oxidizing power. This paper made a progress in verifying bio-mimic high oxidation state species and applied it to water purification, which provided deep insight into the properties of transition-metal centers in aqueous catalysis.
机译：非血红素草酸酯阴离子钴（ III ）配合物[Co III （opbaX）] ？ （opbaX = 4-X- o -亚苯基双（草酸酯），X = H，NO 2 ，CH 合成了具有不同取代基的 3 ）并将其用于目标微污染物的降解。典型的自由基清除剂（异丙醇和氯阴离子）对底物的催化氧化没有负面影响，并且顺磁电子也未检测到DMPO-˙OH或DMPO-˙OOH（DMPO = 5,5-二甲基-吡咯啉氧化物）信号[Co III （opbaX）] ？ / H 中的共振自旋陷阱技术2 O 2 体系，表明非羟基自由基仿生催化机理在氧化过程中占主导地位。高清晰度ESI-MS的结果表明存在钴-羰基中间体，该中间体在底物的催化氧化中起关键作用。此外，使用密度泛函理论计算来评估此类钴-氧代物种的生存能力，并证明了以[Co IV O˙] ？ 或[Co III –OH]˙。计算结果表明，引入[Co III （opbaX）] ？ 的催化活性显着增强。吸电子取代基可以改变钴的配位环境，生成更多的电子不足的钴-氧代物种，具有更强的氧化能力。本文在验证仿生物高氧化态物种方面取得了进展，并将其应用于水净化中，为深入了解过渡金属中心在水性催化中的性质提供了深刻的见识。

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