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具有混合节点的水稳定锌有机框架及其用于水溶液中高效发光检测铁、铬酸盐和重铬酸盐的便捷混合基质膜。

Water-Robust Zinc-Organic Framework with Mixed Nodes and Its Handy Mixed-Matrix Membrane for Highly Effective Luminescent Detection of Fe, CrO, and CrO in Aqueous Solution.

作者信息

Qin Bowen, Zhang Xiaoying, Qiu Jingjing, Gahungu Godefroid, Yuan Haiyan, Zhang Jingping

机构信息

Advanced Energy Materials Research Center, Faculty of Chemistry, Northeast Normal University, Changchun 130024, P. R. China.

Department of Chemistry, University of Burundi, BP 2700, Bujumbura, Burundi.

出版信息

Inorg Chem. 2021 Feb 1;60(3):1716-1725. doi: 10.1021/acs.inorgchem.0c03214. Epub 2021 Jan 20.

Abstract

Metal-organic frameworks (MOFs) and MOF-based composites as luminescent sensors with excellent economic practicability and handy operability have attracted much attention. Herein, we designed and fabricated a porous Zn-based MOF, [Zn(OBA)(L)·2DMA] [; HOBA = 4,4'-oxybis(benzoic acid), L = 2,4,6-tris(4-pyridyl)pyridine, and DMA = ,-dimethylacetamide], with mixed nodes under solvothermal conditions, and the pore size of 5.9 Å was calculated from N adsorption isotherms by using a density functional theory model. The as-synthesized compound is stable in different boiling organic solvents and water solutions with a wide pH range of 2-12 and exhibits intense luminescence emission at 360 nm under excitation of 290 nm. Significantly, compound shows high selective detection of Fe, CrO, and CrO in aqueous solution even under the interference of other ions. Compound can quickly sense these ions in a short time and has a striking sensitivity toward Fe with an ultralow limit of detection (LOD) of 1.06 μM. The relatively low LODs for CrO and CrO are 3.87 and 2.37 μM, respectively, compared to the reported works. Meanwhile, compound can be reused to detect Fe, CrO, and CrO six times by simple regeneration. Considering the practicability, a mixed-matrix membrane (MMM) incorporated compound and poly(methyl methacrylate) has been constructed. This MMM displays quick detection of Fe, CrO, and CrO and prompt regeneration by lifting from the analyte. This useful MMM shows a comparable LOD below 4.35 μM for these ions. This work presents a cost-effective Zn-based MOF as a functional platform for simple but useful sensing of Fe, CrO, and CrO in aqueous solution.

摘要

金属有机框架材料(MOFs)以及基于MOF的复合材料作为具有出色经济实用性和便捷操作性的发光传感器,已备受关注。在此,我们在溶剂热条件下设计并制备了一种具有混合节点的多孔锌基金属有机框架材料[Zn(OBA)(L)·2DMA] [;HOBA = 4,4'-氧联二苯甲酸,L = 2,4,6-三(4-吡啶基)吡啶,DMA = N,N-二甲基乙酰胺],通过密度泛函理论模型根据氮气吸附等温线计算出其孔径为5.9 Å。所合成的化合物在不同沸点的有机溶剂以及pH值范围为2 - 12的水溶液中均稳定,在290 nm激发下于360 nm处呈现出强烈的发光发射。值得注意的是,即使在其他离子存在干扰的情况下,化合物对水溶液中的Fe³⁺、CrO₄²⁻和Cr₂O₇²⁻仍表现出高选择性检测能力。化合物能够在短时间内快速检测这些离子,并且对Fe³⁺具有显著的灵敏度,其超低检测限(LOD)为1.06 μM。与已报道的工作相比,CrO₄²⁻和Cr₂O₇²⁻的相对较低检测限分别为3.87 μM和2.37 μM。同时,化合物通过简单再生可重复用于检测Fe³⁺、CrO₄²⁻和Cr₂O₇²⁻六次。考虑到实用性,构建了一种包含化合物和聚甲基丙烯酸甲酯的混合基质膜(MMM)。该MMM能够快速检测Fe³⁺、CrO₄²⁻和Cr₂O₇²⁻,并且通过从分析物中取出即可迅速再生。这种实用的MMM对这些离子的检测限低于4.35 μM,具有可比性。这项工作展示了一种具有成本效益的锌基金属有机框架材料作为在水溶液中简单而有效地传感Fe³⁺、CrO₄²⁻和Cr₂O₇²⁻的功能平台。

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