College of Environmental Science and Engineering, Biomedical Multidisciplinary Innovation Research Institute, Shanghai East Hospital, State Key Laboratory of Pollution Control and Resource Reuse, Tongji University, 1239 Siping Road, Shanghai, 200092, China; Shanghai Institute of Pollution Control and Ecological Security, Shanghai, 200092, China.
SCNU Environmental Research Institute, Guangdong Provincial Key Laboratory of Chemical Pollution and Environmental Safety & MOE Key Laboratory Theoretical Chemistry of Environment, South China Normal University, Guangzhou, 510006, China.
J Hazard Mater. 2021 Feb 5;403:123691. doi: 10.1016/j.jhazmat.2020.123691. Epub 2020 Aug 15.
The contribution of Cu(III) produced during heterogeneous peroxydisulfate (PDS) activation to pollutant removal is largely unknown. Herein, a composite catalyst is prepared with Cu-based metal organic framework (Cu-MOF) derived Cu nanoparticles decorated in a three-dimensional reduced graphene oxide (3D RGO) network. The 3D RGO network overcomes the aggregation of nanosized zero-valent copper and reduces the copper consumption during the PDS activation reaction. The Cu/RGO catalyst exhibits high catalytic activity for 2,4-dichlorophenol (2,4-DCP) degradation in a wide pH range of 3-9, with a low Cu dosage that is only 0.075 times that of previous reports with zero-valent copper. Moreover, a high mineralization ratio (69.2 %) of 2,4-DCP is achieved within 30 min, and the Cu/RGO catalyst shows high reactivity toward aromatic compounds with hydroxyl and chlorinated groups. Unlike normal sulfate radical-based advanced oxidation, alcohols show negligible impacts on the reaction, suggesting that Cu(III), rather than SO and OH, dominates the degradation process. We believe that PDS activation by 3D Cu/RGO, with Cu(III) as the main active species, provides new insights in selective organic pollutant removal in wastewater treatment.
在多相过一硫酸盐（PDS）活化过程中产生的 Cu(III) 对污染物去除的贡献在很大程度上是未知的。本文制备了一种复合催化剂，该催化剂由负载在三维还原氧化石墨烯（3D RGO）网络中的 Cu 基金属有机骨架（Cu-MOF）衍生的 Cu 纳米粒子组成。3D RGO 网络克服了纳米零价铜的聚集，并减少了 PDS 活化反应过程中的铜消耗。Cu/RGO 催化剂在 pH 值为 3-9 的较宽范围内对 2,4-二氯苯酚（2,4-DCP）的降解表现出高催化活性，Cu 用量仅为以前报道的零价铜的 0.075 倍。此外，在 30 分钟内实现了 2,4-DCP 的高矿化率（69.2%），并且 Cu/RGO 催化剂对具有羟基和氯化基团的芳香族化合物表现出高反应性。与正常的硫酸盐基高级氧化不同，醇对反应的影响可以忽略不计，这表明 Cu(III)，而不是 SO 和 OH，主导着降解过程。我们相信，3D Cu/RGO 对 PDS 的活化作用，以 Cu(III) 作为主要的活性物质，为废水处理中选择性去除有机污染物提供了新的思路。
