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通过一种基于新型C@ZVAl-PS的顺序还原-氧化过程增强硝基酚的矿化作用。

Enhanced mineralization of nitrophenols by a novel C@ZVAl-PS based sequential reduction-oxidation process.

作者信息

Li Xin, Li Yang, Yang Shiying

机构信息

Key Laboratory of Marine Environment and Ecology, Ministry of Education, Qingdao 266100, China; College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100, China.

College of Environmental Science and Engineering, Ocean University of China, Qingdao 266100, China.

出版信息

Sci Total Environ. 2024 Nov 10;950:175288. doi: 10.1016/j.scitotenv.2024.175288. Epub 2024 Aug 5.

Abstract

Widely employed nitrophenols (NPs) are refractory and antioxidant due to their strong electron-withdrawing group (-NO). Actually, NPs are readily reduced to aminophenols (APs). However, APs remain toxic and necessitate further treatment. Herein, we utilized a novel sequential reduction-oxidation system of carbon-modified zero-valent aluminum (C@ZVAl) combined with persulfate (PS) for the thorough removal of both NPs and APs. The results demonstrated that p-nitrophenol (PNP, up to 1000 mg/L) exhibited complete reduction to p-aminophenol (PAP), and then over 98.0 % of PAP could be effectively oxidized, in the meantime the removal rate of chemical oxygen demand (COD) was as high as 95.9 %. Based on the SEM and XPS characterizations, we found that C@ZVAl has exceptionally high reactivity that generates massive electrons and reduces PNP to PAP through accelerated electron transfer. In the subsequent oxidation step, PS can be rapidly activated by C@ZVAl to generate SO radicals for PAP oxidization. Meanwhile, the mineralization of COD proceeds. The temporal binding of reduction and oxidation can be regulated by varying the PS dosing time. Namely, the appropriate delay in PS dosing facilitates sufficient reduction to provide enough reactants for oxidation, favoring the mineralization of PNP and COD. More crucially, dinitrodiazophenol (DDNP) in an actual explosive wastewater without any pretreatment can be effectively mineralized by this sequential reduction-oxidation system, affirming the excellent performance of this process in practical applications. In conclusion, the C@ZVAl-PS based sequential reduction-oxidation looks very promising for enhanced mineralization of nitro-substituted organic contaminants.

摘要

广泛使用的硝基酚(NPs)由于其强吸电子基团(-NO)而具有难降解性和抗氧化性。实际上,NPs很容易被还原为氨基酚(APs)。然而,APs仍然有毒,需要进一步处理。在此,我们利用一种新型的碳改性零价铝(C@ZVAl)与过硫酸盐(PS)相结合的顺序还原-氧化系统,以彻底去除NPs和APs。结果表明,对硝基酚(PNP,高达1000 mg/L)完全还原为对氨基酚(PAP),然后超过98.0%的PAP可以被有效氧化,同时化学需氧量(COD)的去除率高达95.9%。基于扫描电子显微镜(SEM)和X射线光电子能谱(XPS)表征,我们发现C@ZVAl具有极高的反应活性,能够产生大量电子,并通过加速电子转移将PNP还原为PAP。在随后的氧化步骤中,PS可以被C@ZVAl快速激活,产生SO自由基用于氧化PAP。同时,COD的矿化过程得以进行。还原和氧化的时间结合可以通过改变PS投加时间来调节。也就是说,适当延迟PS投加有利于充分还原,为氧化提供足够的反应物,有利于PNP和COD的矿化。更关键的是,该顺序还原-氧化系统可以有效矿化实际爆炸废水中未经任何预处理的二硝基重氮酚(DDNP),证实了该工艺在实际应用中的优异性能。总之,基于C@ZVAl-PS的顺序还原-氧化在增强硝基取代有机污染物的矿化方面看起来非常有前景。

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