Metal inhibition on the reactivity of manganese dioxide toward organic contaminant oxidation in relation to metal adsorption and ionic potential
Metal inhibition on the reactivity of manganese dioxide toward organic contaminant oxidation in relation to metal adsorption and ionic potential
复制标题
金属对二氧化锰对有机污染物氧化反应活性的抑制与金属吸附和离子势有关
DOI：
10.1016/j.chemosphere.2016.12.015
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发表时间：
2017-03-01
期刊：
影响因子：
8.8
通讯作者：
Sheng, G. Daniel
中科院分区：
文献类型：
--
作者：
Jiang, Jing;Wang, Zhuopu;Sheng, G. Daniel
在金属-有机复合污染物水体中，共存金属离子可显著抑制锰氧化物对有机污染物的氧化反应。虽然金属对锰氧化物氧化有机污染物的抑制作用已有报道，但与金属性质有关的抑制程度尚未确定。对六种碱金属、碱性金属和过渡金属以及两种测试金属的抑制水钠铝石反应活性的能力进行了评估。不管苯酚和敌草隆的氧化途径(聚合和破裂)如何，金属的抑制程度主要取决于金属本身及其浓度。金属缓蚀率的大小顺序为：Mn2+和GT；Co2+和Gt；Cu2+和Gt；Al3+和Gt；Mg2+和Gt；K+，与金属在水钠石上的吸附情况一致。一阶有机氧化速率常数k(Obs)与水钠石对金属的吸附(q(E))呈线性负相关。这些观察结果表明，金属缓蚀剂的缓蚀效率取决于水钠铝石对金属的吸附。K(OBS-QE)的斜率因金属不同而不同，大小顺序为：K+和GT；钙和GT；镁和GT；Mn2+和GT；Cd 2+和GT；Co2+和GT；Cu2+和GT；Al3+。这些斜率定义了金属的内在抑制能力。当金属被水合水合金属吸附时，其本征缓蚀能力与金属的离子势呈显著的线性关系，呈一条直线。在最外层轨道上有多个d电子的金属，其极化能量促进了水解，它们位于这条线的略下方，反之亦然。(C)2016爱思唯尔有限公司。保留所有权利。
Coexisting metal ions may significantly inhibit the oxidative reactivity of manganese oxides toward organic contaminants in metal-organic multi-pollutant waters. While the metal inhibition on the oxidation of organic contaminants by manganese oxides has previously been reported, the extent of the inhibition in relation to metal properties has not been established. Six alkali, alkaline, and transition metals, as well as two testing metals were evaluated for their abilities to inhibit the reactivity of birnessite. Regardless of the pathways of phenol and diuron oxidation (polymerization vs. breakdown), the extent of metal inhibition depended mainly on the metal itself and its concentration. The observed metal inhibition efficiency followed the order of Mn2+ > Co2+ > Cu2+ > Al3+ > Mg2+ > K+, consistent with metal adsorption on birnessite. The first-order organic oxidation rate constant (k(obs)) was linearly negatively correlated with metal adsorption (q(e)) on birnessite. These observations demonstrated that the metal inhibition efficiency was determined by metal adsorption on birnessite. The slopes of the k(obs-qe) varied among metals and followed the order of K+ > Ca2+ > Mg2+ > Mn2+ > Cd2+ > Co2+ > Cu2+ > Al3+. These slopes defined intrinsic inhibitory abilities of metals. As metals were adsorbed hydrated on birnessite, the intrinsic inhibitory ability was significantly linearly correlated with ionic potentials of metals, leading to a single straight line. Metals with multiple d electrons in the outermost orbit with polarizing energy that promotes hydrolysis sat slightly below the line, and vice versa. (C) 2016 Elsevier Ltd. All rights reserved.