高等学校化学学报

高等学校化学学报

• 研究论文 • 上一篇    下一篇

黄铁矿-Fe(Ⅲ)表面Lewis酸位点增强微囊藻毒素水解

兰星1,贺玉婷1,张清1,方艳芬1,邓安平2,赵海霞3,张兆年4   

  1. 1. 三峡大学材料与化工学院，  2.  宜昌东阳光生化制药有限公司， 3.  三峡大学基础医学院， 4.  湖北省生态环境厅宜昌生态环境监测中心，宜昌 443002
  • 收稿日期:2024-02-21 修回日期:2024-04-24 网络首发:2024-04-25 发布日期:2024-04-25
  • 通讯作者: 方艳芬 E-mail:fangyf@ctgu.edu.cn
  • 基金资助:
    国家自然科学基金面上项目(No. 22076098, 21577078, 22376118)、湖北省自然科学基金杰出青年项目(2023AFA054)和地方高校能源和环境材料化学学科创新引智基地(No. D20015).

Lewis Acid Sites on the Surface of Pyrite-Fe (Ⅲ) Enhance Hydrolysis of Microcystins

LAN Xing1, HE Yuiting1, ZHANG Qing1, FANG Yanfen1, DENG Anping2, ZHAO Haixia3, ZHANG Zhaonian4   

  1. 1. China Three Gorges University, School of Materials and Chemical Engineering;  2. Yichang East Sunshine Biochemical Pharmaceutical Co., Ltd.;  3.  China Three Gorges University, College of Basic Medical Sciences;  4.  Yichang Ecological Environment Monitoring Center of Hubei Provincial Department of Ecological Environment, Yichang 443002, China
  • Received:2024-02-21 Revised:2024-04-24 Online First:2024-04-25 Published:2024-04-25
  • Contact: FANG Yanfen E-mail:fangyf@ctgu.edu.cn
  • Supported by:
    Supported by the National Natural Science Foundation of China (Nos. 22076098, 22376118, 21577078), the Outstanding Youth Project of the Natural Science Foundation of Hubei Province，China(No.2023AFA054) and the 111 Project of China (No. D20015).

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摘要： 天然黄铁矿(Pyrite)在高温 (60℃)下能有效降解(k=0.072 min-1)水中微囊藻毒素(Microcystins，MCs)，但如何突破高温瓶颈，实现常温条件(25±5℃)下MCs的高效降解仍是目前水处理技术难点。本文发现外加铁离子(Fe3+，FeCl3)能加速Pyrite常温体系对微囊藻毒素-RR(Microcystin-RR，MC-RR)的水解效率(水解贡献率77.94%)，其降解速率常数(0.36 h-1)是单独Pyrite体系(0.12 h-1)的3倍。通过X射线光电子能谱仪(XPS)、循环伏安法(CV)、原位表面衰减全反射红外光谱(in situ ATR-FTIR)和密度泛函理论(DFT)等研究发现，外加Fe3+通过形成Fe(III)-O键增加了Pyrite表面Lewis酸铁位点数，再通过其与C=O配位实现了对MC-RR酰胺键的水解。此外，外加的Fe3+还能将Pyrite表面多价态硫物种(Sn2?、S22?)氧化为单质硫(S0)，通过形成氢键-NH???S进一步促进MC-RR的水解。本研究不仅为蓝藻水华治理提供了一种常温矿物处理技术，还为自然水体中酰胺类有机污染物的自净机制提供了理论依据。

关键词: 微囊藻毒素, Lewis酸位点, 水解, 黄铁矿, 催化机制

Abstract: Natural mineral (Pyrite) can effectively degrade microcystins (Microcystins, MCs) in water at warm temperature (60 ℃) (k=0.072 min-1) , but how to break through the heat bottleneck and attain efficient degradation of MCs at room temperature (25±5 ℃) is still a technical issue in water treatment nowadays. In this study, the addition of iron ions (Fe3+, FeCl3) can accelerate the hydrolysis efficiency of microcystins-RR (Microcystin-RR, MC-RR) in pyrite system at room temperature (hydrolysis contribution rate 77.94%), and the degradation rate constant (0.36 h-l) was three times higher than that of pyrite alone (0.12 h-l). X-ray photoelectron spectroscopy (XPS), Cyclic voltammetry (CV), In situ attenuated total reflection-Fourier transform infrared spectroscopy (in situ ATR-FTIR) and Density functional theory (DFT) suggesting that the addition of Fe3+ enhanced the amount of iron sites of Lewis acid on pyrite surface by forming Fe(III)-O bond, and then hydrolyzed MC-RR amide bond through its coordination with C=O. Additionally, the addition of Fe3+ can oxidize the multivalent sulfur species on the surface of pyrite (Sn2-,S22-) to elemental sulfur (S0), further promoting the hydrolysis of MC-RR by forming hydrogen bond (-NH???S). This study not only provides a normal temperature mineral treatment technology for cyanobacteria bloom treatment, but also provides a theoretical basis for the self-purification mechanism of amide organic pollutants in natural water.

Key words: Microcystins, Lewis acid sites; , Hydrolysis, Pyrite, Catalytic mechanism

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