近日,華中農業大學植物科學技術學院李建洪教授團隊研究成果以“A novel magnetic double MOF composite is synthesized for removing azole fungicides economically and efficiently”為題在Applied Surface Science上發表。該研究合成了一種新型磁性雙MOF吸附材料并圍繞該材料建立了稻田生態系統中5種唑類殺菌劑多殘留的快速去除方法。
研究人員通過金屬有機框架ZIF-90 和 MIL-68(Al) 合成了一種新型的磁性雙MOF復合材料---Fe3O4@ZIF-90@MIL-68(Al),并將其用于稻田生態系統中唑類殺菌劑的殘留去除。經FT-IR,TEM,SEM,XRD,VSM,Zeta,BET,TG等一系列表征分析證實,與傳統單MOF材料相比,該材料化學性質更穩定,可以快速分散在水環境中,更適合田間實際應用,且對環境中殘留的農藥具有優良的吸附性能。此外,采用HPLC及FT-IR分析技術考察了其重復利用性,發現在連續十次吸附-解吸循環后,對目標農藥的去除效率仍保持較高水平。與其他吸附材料相比,Fe3O4@ZIF-90@MIL-68(Al)在吸附能力和再生能力方面表現出雙金屬有機框架材料的特有優勢。最后,作者應用該吸附材料建立了稻田生態系統中5種唑類殺菌劑多殘留的快速去除方法。在實際樣本加標實驗中,目標農藥去除效率均達80 %以上。該研究對稻田生態系統中農藥殘留凈化去除具有重要意義。
研究團隊在MOF修飾的生物質復合材料研發中,將小麥秸稈制成生物炭與磁性MOF材料結合,制備了可同時去除唑類殺菌劑殘留又兼具較高殺菌活性的新型吸附材料,也為材料的多功能化研究提供了新的思路;在MOF材料與唑類農藥吸附機理研究方面,運用molclus等軟件結合吸附動力學、吸附熱力學及XPS等表征分析技術,從分子模擬、理論計算、表征推斷、實際驗證等多個層面揭示MOF材料特異性吸附唑類農藥的機理,為進一步從分子結構出發,合成特異性吸附劑打下良好基礎;在磁性MOF材料基于的MSPE農藥殘留快檢技術研究中,合成了多種唑類農藥特異性吸附劑,將MSPE技術與QuEChERS方法聯用,擴大MSPE技術的應用范圍,簡化QuEChERS方法凈化過程,對快速檢測食品中農藥殘留具有重要意義。
植物科學技術學院碩士研究生周冬冬為該論文第一作者,楊中華副教授為通訊作者。該研究得到國家重點研發計劃項目(2019YFD1002103)湖北省自然科學基金(2020CFB528)和國家自然科學基金資助(21507032)。
【英文摘要】
In this study, Fe3O4@ZIF-90@MIL-68(Al) composite was synthesized by a facile method and used as a reusable adsorbent to effectively remove azole fungicides from paddy field water. Notably, the introduction of ZIF-90 made the magnetic adsorbent more stable and significantly improved the adsorption performance. Specifically, a series of characterization analysis were carried out and this composite displayed a high specific surface area, excellent magnetic strength, and good thermal stability, which meet the expectations. Additionally, the adsorption behaviors and mechanisms of Fe3O4@ZIF-90@MIL-68(Al) toward azole fungicides were studied systematically. The pseudo-second-order kinetic model and Langmuir isotherm model was confirmed to be more suitable for describing this adsorption process. Besides, the adsorption process of azole fungicides onto Fe3O4@ZIF-90@MIL-68(Al) was mainly based on pore filling, surface complexation, covalent bonding, π-π stacking effect and hydrogen bonding. Interestingly, the maximum adsorption capacity of Fe3O4@ZIF-90@MIL-68(Al) toward prochloraz was 352.32 mg g?1, which was probably one of the highest adsorption capacities reported. Meanwhile, the magnetic adsorbent can be regenerated by methanol treatment and maintain a high adsorption capacity after the 10th cycle. Hence, this work provides an economical and feasible method for removing azole fungicides from field water samples.
論文鏈接:https://doi.org/10.1016/j.apsusc.2022.153441