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四氧化三铁稳定零价铁纳米颗粒还原水溶液中的六价铬。

Chromium (VI) reduction in aqueous solutions by Fe3O4-stabilized Fe0 nanoparticles.

机构信息

Department of Environmental Engineering, Zhejiang University, Zheda Road 38#, Hangzhou 310027, People's Republic of China.

出版信息

J Hazard Mater. 2009 Dec 30;172(2-3):1640-5. doi: 10.1016/j.jhazmat.2009.08.045. Epub 2009 Aug 18.

Abstract

This paper describes the use of highly reactive magnetite (Fe(3)O(4)) nanoparticles-stabilized Fe(0) nanocomposites for the reduction and mitigation of hexavalent chromium Cr(VI) species in aqueous solutions. Higher proportions of Fe(3)O(4) in the nanocomposites could increase the rate of Cr(VI) reduction. In the absence of magnetite, the Cr(VI) mitigation rate was just 51.4% after 60 min of reaction, while with an initial Fe(3)O(4) mass loading of 3 g l(-1), the Cr(VI) mitigation rate was nearly 100% after 60 min. The optimal ratio of Fe(3)O(4):Fe(0) for the mitigation of Cr(VI) was found to be 40:1. Otherwise, solution pHs significantly affected the rate of Cr(VI) reduction, with reactions occurring more rapidly under acidic or neutral than basic conditions. It is hypothesized that the high efficiency of the Fe(3)O(4) nanoparticles-stabilized Fe(0) nanocomposites for Cr(VI) reduction was a direct result of the attachment of Fe(0) nanoparticles to the surface of magnetite, which prevents the aggregation of nano-Fe(0), moreover, the electron transfer during the reduction process most likely takes place via Fe(0) nanoparticles that are located at the magnetite octahedral sites, which are versatile redox centers as they can accommodate both Fe(III) and Fe(II), and this will promote the reduction of Cr(VI). Cr(VI) reduction is coupled with nano-Fe(0) oxidation. Nano-Fe(0) particles are located at the magnetite octahedral sites. Ions of Fe(II) and Fe(III) accommodated by magnetite octahedral sites are products of nano-Fe(0) oxidation. Therefore, Cr(VI) reduction is mediated either by nano-Fe(0) (direct reduction) or Fe(II) species (indirect reduction). Additionally, catalytic Cr(VI) reduction by molecular H(2) (or atomic H) is possible.

摘要

本文描述了使用高反应性磁铁矿(Fe(3)O(4))纳米颗粒稳定的零价铁纳米复合材料来还原和减少水溶液中的六价铬 Cr(VI)物种。纳米复合材料中较高比例的 Fe(3)O(4)可以提高 Cr(VI)还原的速率。在没有磁铁矿的情况下,60 分钟后 Cr(VI)的缓解率仅为 51.4%,而初始 Fe(3)O(4)质量负荷为 3 g l(-1)时,60 分钟后 Cr(VI)的缓解率接近 100%。发现对于 Cr(VI)的缓解,Fe(3)O(4):Fe(0)的最佳比例为 40:1。否则,溶液 pH 值对 Cr(VI)还原的速率有显著影响,在酸性或中性条件下反应比碱性条件下更快。据推测,Fe(3)O(4)纳米颗粒稳定的 Fe(0)纳米复合材料对 Cr(VI)还原的高效率是由于纳米 Fe(0)颗粒附着在磁铁矿表面上,阻止了纳米-Fe(0)的聚集,此外,还原过程中的电子转移很可能通过位于磁铁矿八面体位置的 Fe(0)纳米颗粒发生,这些位置是多功能的氧化还原中心,因为它们可以容纳 Fe(III)和 Fe(II),这将促进 Cr(VI)的还原。Cr(VI)的还原与纳米-Fe(0)的氧化偶联。纳米-Fe(0)颗粒位于磁铁矿八面体位置。磁铁矿八面体位置容纳的 Fe(II)和 Fe(III)离子是纳米-Fe(0)氧化的产物。因此,Cr(VI)的还原要么是通过纳米-Fe(0)(直接还原),要么是通过 Fe(II)物种(间接还原)介导的。此外,分子 H(2)(或原子 H)的催化 Cr(VI)还原也是可能的。

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