Yudan Dong, Si Sun, Yunzhe Zheng, Jiamei Liu, Peng Zhou, Zhaokun Xiong, Jing Zhang, Zhi-Cheng Pan, Chuan-Shu He, Bo Lai
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引用次数: 0
摘要
人们对锰前体的阴离子配体如何影响无定形锰氧化物(MnOx)在类似芬顿过程中的催化活性知之甚少。在此,研究人员对由含不同配体的锰(II)前体合成的五种无定形氧化锰进行了表征,并将其用于活化过乙酸(PAA)以降解双酚 A(BPA)。尽管在五种 MnOx/PAA 工艺中,通过吸附和氧化两种方式,双酚 A 的去除率均大于 90%,但氧化作用因配体类型的不同而有很大差异,顺序为 MnOx-N > MnOx-S > MnOx-Cl > MnOx-AA > MnOx-OA。配体类型会影响氧化锰的比表面积及其吸附双酚 A 的能力,但这并不是决定污染物氧化效率的决定性因素。多项实验结果表明,配体诱导产生的氧空位会改变锰(III)/锰(IV)的比例,最终导致直接电子转移机制驱动的双酚 A 氧化效率不同。此外,无定形氧化锰具有良好的稳定性,有望实际应用于各种微污染物的催化 PAA。本研究加深了人们对配体调控非晶态氧化锰催化 PAA 过程的基本认识。
Revealing the essence of anion ligands in regulating amorphous MnOx to activate peracetic acid for micropollutant removal.
How the anion ligands of manganese precursors affect the catalytic activity of amorphous manganese oxides (MnOx) in Fenton-like process is poorly understood. Here, five amorphous MnOx synthesized by Mn(II) precursors with different ligands were characterized and adopted to activate peracetic acid (PAA) for bisphenol A (BPA) degradation. Although > 90 % BPA removal was achieved in the five MnOx/PAA processes via both adsorption and oxidation, the oxidation kobs greatly differentiates by the ligands types with the order of MnOx-N > MnOx-S > MnOx-Cl > MnOx-AA > MnOx-OA. Ligands types would affect the specific surface area of MnOx and their ability to adsorb BPA, however which is not the decisive factor in determining the contaminant oxidation efficiency. Multiple experimental results indicate that the generation of oxygen vacancies induced by the ligands alters the Mn(III)/Mn(IV) ratio, ultimately contributing to the different efficiency of BPA oxidation driven by the direct electron transfer mechanism. Moreover, amorphous MnOx holds the promise of practical applications in catalytic PAA of various micropollutants with good stability. This study advances the fundamental understanding of ligand-regulated amorphous MnOx-catalyzed PAA process.