水蒸汽浴FeS_(2)高效Fenton降解甲草胺  

Water Steam Bathed FeS_(2) for Highly Efficient Fenton Degradation of Alachlor

作　　者：江吉周 余良浪 李方轶 邓文明 潘聪 王海涛 邹菁 丁耀彬 邓凤霞 黄佳 Jizhou Jiang;Lianglang Yu;Fangyi Li;Wenming Deng;Cong Pan;Haitao Wang;Jing Zou;Yaobin Ding;Fengxia Deng;Jia Huang(School of Environmental Ecology and Biological Engineering,School of Chemistry and Environmental Engineering,School of Chemical Engineering and Pharmacy,Key Laboratory of Green Chemical Engineering Process of Ministry of Education,Engineering Research Center of Phosphorus Resources Development and Utilization of Ministry of Education,Novel Catalytic Materials of Hubei Engineering Research Center,Wuhan Institute of Technology,Wuhan 430205,China;College of Resources and Environmental Science,South-Central Minzu University,Wuhan 430074,China;State Key Laboratory of Urban Water Resources and Environment,School of Environment,Harbin Institute of Technology,Harbin 150090,China.)

机构地区：[1]武汉工程大学,环境生态与生物工程学院,化学与环境工程学院,化工与制药学院,绿色化工程教育部重点实验室,磷资源开发利用教育部工程研究中心,新型催化材料湖北省工程研究中心,武汉430205 [2]中南民族大学,资源与环境学院,武汉430074 [3]哈尔滨工业大学,环境学院,城市水资源与水环境国家重点实验室,哈尔滨150090

出　　处：《物理化学学报》2023年第3期88-97,共10页Acta Physico-Chimica Sinica

基　　金：国家自然科学基金(62004143,21876209);湖北省重点研发计划(2022BAA084);湖北省自然科学基金(2021CFB133);中央引导地方科技发展专项基金(2020ZYYD033);能量转换与存储材料化学教育部重点实验室开放基金(2021JYBKF05);磷资源开发利用教育部工程研究中心创新项目(LCX2021003);武汉工程大学绿色化工程教育部重点实验室开放基金(GCP202101)资助项目。

摘　　要：由于硫化铁在自然环境中的丰富性,其生成活性氧和降解各种有机污染物的类Fenton活性已被广泛研究。然而,由于表面含铁活性位点的暴露有限,它们的类Fenton活性通常不高。在本研究中,以黄铁矿(FeS_(2))为例,基于水蒸汽对FeS_(2)的热处理,开发了一种提高硫化铁矿物Fenton活性的新策略,研究发现经水蒸汽热处理后的FeS_(2)(Heat-FeS_(2))对甲草胺(ACL)的非均相Fenton活性比由水热反应制备的母体FeS_(2)(Fresh-FeS_(2))更高。在初始pH为6.3时,Heat-FeS_(2)-Fenton体系对ACL的降解速率为0.48 min-1,约为Fresh-FeS_(2)-Fentton体系的23倍。电子自旋共振分析和苯甲酸探针实验证实,与Fresh-FeS_(2)-Fenton体系相比,在Heat-FeS_(2)-Fenton体系中产生更多的羟基自由基(·OH)和超氧自由基(·O_(2)^(-))。HeatFeS_(2)的Fenton活性大幅增强主要可归因于含量增加的高活性表面Fe^(2+)/Fe^(3+)组份、较高的Fe^(2+)浸出量和最佳的反应p H条件。扫描电镜,透射电镜,X射线光电子能谱(XPS)和傅里叶变换红外光谱等一系列表征结果表明,热处理可显著促进晶格Fe^(2+)向表面活性Fe^(2+)的转化,同时增强表面SO42-的生成,从而形成高酸性表面。此外,热处理后Fresh-FeS_(2)表面Fe^(2+)在表面总铁中的百分比从13%提高到了Heat-FeS_(2)的29%,而且Heat-FeS_(2)的Fe^(2+)浸出量(0.23 mmol·L-1)也远高于FreshFeS_(2)的Fe^(2+)浸出量(<0.02mmol·L-1)。为了进一步阐明Heat-FeS_(2)材料ACL降解活性增强的机理,我们通过XPS技术监测类Fenton反应前后Heat-FeS_(2)表面Fe和S物种的变化关系。结果表明,H2O_(2)反应后,Fresh-FeS_(2)和Heat-Fee S_(2)中Fe^(2+)和Fe^(3+)的表面含量显著增加,而S_(2)2-物种的表面浓度则相对下降,证实了S_(2)2-物种在Fe^(3+)还原为Fe^(2+)循环中的关键作用。重要的是,本研究不仅加深了对FeS_(2)氧化转化、腐蚀及其对天然环境中有毒有机物转化与降解的认识,而且还提供了一种基于�Fenton-like activity of iron sulfides for the generation of reactive oxygen species and degradation of various organic pollutants has been extensively investigated due to its abundance in the natural environment. However, their Fenton-like activity is usually unsatisfactory due to the limited exposure of surface ferrous reactive sites. In this work, a new strategy to enhance the Fentonlike activity of iron sulfides, using pyrite(FeS_(2)) as a model, was developed based on the heat treatment of FeS_(2)by water steam. It was found that the FeS_(2)heat-treated by water steam(Heat-FeS_(2))exhibited much higher heterogeneous Fenton activity in the degradation of alachlor(ACL) than its parent FeS_(2)prepared from hydrothermal reaction(Fresh-FeS_(2)). At an initial p H of 6.3, the rate of degradation of ACL by Heat-FeS_(2)Fenton system was 0.48 min-1, which is ~23 times higher than that of Fresh-FeS_(2)Fenton system. Electron spin resonance analysis and benzoic acid probe experiments confirmed the production of more hydroxyl(·OH) and superoxide radicals(·O_(2)^(-)) in HeatFeS_(2)Fenton system than Fresh-FeS_(2)Fenton system. The increased Fenton-like activity of Heat-FeS_(2)can be attributed to the increased content of highly reactive surface bonded Fe^(2+)/Fe^(3+)species, higher amount of leached Fe^(2+), and optimal reaction p H due to stronger acidification of Heat-FeS_(2). Characterization studies by scanning electron microscopy, transmission electron microscopy, X-ray photoelectron spectroscopy(XPS), and Fourier-transform infrared spectroscopy showed that heat treatment remarkably promoted the transformation of lattice Fe^(2+)to surface reactive Fe^(2+), allowing the exposure of more surface reactive Fe^(2+)and leaching of Fe^(2+);simultaneously, heat treatment enhanced the generation of surface SO42-, creating a highly acidic surface. The surface Fe^(2+)percentage in the surface total iron was raised from 13% in Fresh-FeS_(2)to 29% in Heat-FeS_(2). Fe^(2+)leaching from Heat-FeS_(2)was 0.23 mmol·L-1, much higher

关 键 词：FeS_(2) 水蒸汽处理 FENTON 表面Fe^(2+) 甲草胺 

分 类 号：O647[理学—物理化学]