Zeng Liang, Chen Quan, Liang Ni, Ji Pixia, Lu Meng, Wu Min, Oleszczuk Patryk, Pan Bo, Xing Baoshan
Yunnan Provincial Key Laboratory of Soil Carbon Sequestration and Pollution Control, Faculty of Environmental Science & Engineering, Kunming University of Science & Technology, Kunming 650500, China.
Department of Environmental Chemistry, Faculty of Chemistry, Maria Curie-Skłodowska University, 20-031 Lublin, Poland.
J Hazard Mater. 2023 Sep 15;458:131774. doi: 10.1016/j.jhazmat.2023.131774. Epub 2023 Jun 3.
Organic pollutant degradation by biochar could be promoted by Fe because of the Fenton-like reaction. However, studies have also confirmed that reactive oxygen species (ROS) play only a limited role in organic pollutant degradation by biochar. Herein, we quantitatively identified 2,4-dichlorophenol (2,4-DCP) adsorption and degradation in Fe-biochar systems and obtained degradation (k) and adsorption rate constants (k) by two-compartment first-order kinetics modeling. The k was approximately 7-10 times lower than the corresponding k and the positive correlation between k and k illustrated that adsorption and degradation were kinetically associated. ROS quenching only slightly inhibited 2,4-DCP degradation. Chemicals with similar structures to ROS quenchers (without quenching ability) also inhibited 2,4-DCP degradation, probably because of the competition of the active degradation sites on biochars. Electrochemical analysis and pH-impact experiments further elucidated that 2,4-DCP underwent oxidation-dominated degradation in the adsorbed phase via direct electron transfer. Fe(III) obviously increased 2,4-DCP adsorption through cation bridging and enhanced electron density by Fe-O conjugations on the biochar surface, which facilitated subsequent degradation. This study emphasized the importance of degradation on the biochar solid phase and that a breakthrough of the mass transfer bottleneck of adsorption will greatly promote degradation.
由于类芬顿反应,铁可以促进生物炭对有机污染物的降解。然而,研究也证实,活性氧物种(ROS)在生物炭降解有机污染物过程中仅起有限作用。在此,我们定量确定了铁-生物炭体系中2,4-二氯苯酚(2,4-DCP)的吸附和降解情况,并通过两室一级动力学模型获得了降解速率常数(k)和吸附速率常数(k)。降解速率常数k比相应的吸附速率常数k低约7至10倍,且k与k之间的正相关表明吸附和降解在动力学上相关联。ROS猝灭仅轻微抑制2,4-DCP的降解。与ROS猝灭剂结构相似(无猝灭能力)的化学物质也抑制2,4-DCP的降解,这可能是由于生物炭上活性降解位点的竞争。电化学分析和pH影响实验进一步阐明,2,4-DCP在吸附相通过直接电子转移进行以氧化为主的降解。Fe(III)通过阳离子桥连明显增加了2,4-DCP的吸附,并通过生物炭表面的Fe-O共轭增强了电子密度,从而促进了后续降解。本研究强调了生物炭固相降解的重要性,以及突破吸附传质瓶颈将极大地促进降解。