二维 MOFs 的不饱和铁中心介导了高效的 Fenton-like 反应以消除有机污染物

IF 6.9 2区环境科学与生态学 Q1 ENGINEERING, CHEMICAL

Process Safety and Environmental Protection Pub Date : 2024-11-06 DOI:10.1016/j.psep.2024.11.023

Siqi Wu , Xiaoyun He , Guanlong Wang, Xiaoli Dong, Xiufang Zhang

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引用次数: 0

摘要

铁基金属有机框架（Fe-MOFs）目前被认为是一种很有前景的异质芬顿类反应候选物质，可用于消除废水中的有机污染物。然而，如何提高 Fe(II)/Fe(III) 的循环速率以创建一个高效的异质 Fenton-like 系统仍然是一个挑战。在此，我们采用简便的方法制备了二维 MIL-88B(Fe)-NO2。与三维 MIL-88B(Fe)-NO2相比，二维 MIL-88B(Fe)-NO2具有更高的降解污染物的能力，尤其是二维-M30的Fenton-like性能最好，6分钟内苯酚的去除率约为97.2%，动力学降解常数为0.57 min-1。磷酸盐添加实验证实，二维 MIL-88B(Fe)-NO2 上的不饱和配位 Fe 是 H2O2 活化的主要活性位点。此外，通过 CO 吸附原位红外光谱和比表面积测量可以得出结论，二维 MIL-88B(Fe)-NO2 比 MIL-88B(Fe)-NO2 具有更多的不饱和配位 Fe。二维 MOFs 卓越的 Fenton 类催化效率归因于金属节点配位位点的缺陷。此外，由于配位铁的不饱和，Fe(III)的电子云密度降低，从而促进了Fe(II)/Fe(III)的转变。这种方法为合理设计和创建高效的异质 Fenton 类催化剂提供了创新思路。

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Unsaturated Fe centers of 2D MOFs mediated the efficient Fenton-like reaction for organic pollutant elimination

Fe-based metal-organic frameworks (Fe-MOFs) are currently regarded as a promising candidate for heterogeneous Fenton-like reactions to eliminate organic contaminants in wastewater. However, improving the cycling rate of Fe(II)/Fe(III) to create a highly efficient heterogeneous Fenton-like system continues to be a challenge. Here, we prepared 2D MIL-88B(Fe)-NO₂ by a facile approach. 2D MIL-88B(Fe)-NO₂ has a higher capacity to degrade pollutants than 3D MIL-88B(Fe)-NO₂, 2D-M30 showed the best Fenton-like performance in particular, with a phenol removal rate of approximately 97.2 % within 6 min and a kinetic degradation constant of 0.57 min⁻¹. The phosphate addition experiment confirmed that the unsaturated coordination Fe on 2D MIL-88B(Fe)-NO₂ was the main active site for H₂O₂ activation. Additionally, it can be concluded by CO adsorption in-situ infrared spectra and specific surface area measurement that 2D MIL-88B(Fe)-NO₂ has more unsaturated coordinated Fe than MIL-88B(Fe)-NO₂. The outstanding Fenton-like catalytic efficiency was attributed to the defects of metal node coordination sites at the 2D MOFs. Furthermore, the electron cloud density of Fe(III) decreased due to the unsaturation of the coordinated Fe, which encourages the transition of Fe(II)/Fe(III). This approach provides innovative ideas for the logical design and creation of efficient heterogeneous Fenton-like catalysts.

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来源期刊

Process Safety and Environmental Protection 环境科学-工程：化工

CiteScore

11.40

自引率

15.40%

发文量

929

审稿时长

8.0 months

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