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Improving the Cd2+ detection capability of a new anionic rare earth metal–organic framework based on a [RE6(μ3-OH)8]10+ secondary building unit: an ion-exchange approach towards more efficient sensors
Molecular Systems Design & Engineering ( IF 3.2 ) Pub Date : 2020-04-23 , DOI: 10.1039/c9me00176j
Nikos Panagiotou 1, 2, 3, 4 , Kasiani Evangelou 1, 2, 3, 4 , Athanasia Psalti 1, 5, 6, 7 , Nektaria Varnava 1, 2, 3, 4 , Giasemi K. Angeli 1, 7, 8, 9 , Pantelis N. Trikalitis 1, 7, 8, 9 , John C. Plakatouras 1, 2, 3, 4, 10 , Theodore Lazarides 1, 5, 6, 7 , Anastasios J. Tasiopoulos 1, 2, 3, 4
Affiliation  

The synthesis and characterization of a new family of rare earth (RE) MOFs based on a hexanuclear (RE3+)6 secondary building unit (SBU) and the angular dicarboxylic ligand 4,4′-oxybisbenzoic acid (H2OBA) with the formula {((CH3)2NH2)2[RE63-OH)8(OBA)6]} (((CH3)2NH2)2(1)(RE); RE: Y, Tb, Dy, Ho) is reported. Gas sorption studies indicated a moderate Langmuir area of 377 m2 g−1. Photoluminescence studies in the visible region of the ((CH3)2NH2)2(1)(Y) doped with 5% Eu3+ or 5% Tb3+ revealed the presence of the characteristic emission bands for these RE3+ ions. Cd2+ sensing studies of ((CH3)2NH2)2(1)(Y) doped with Eu3+ however, indicated slow exchange kinetics prohibiting the use of this material for sensing applications. Successful counter ion exchange of the as synthesized compound with Na+ and Mg2+ led to the isolation of Na2(1)(Y) and Mg(1)(Y). Interestingly, the exchanged analogue Na2(1)(Y) doped with 5% Eu3+ exhibited fast Cd2+ sorption kinetics and was proven to be a greatly improved sensor for this metal ion both in terms of kinetics and sensitivity. Batch Cd2+ sorption experiments at room temperature of Na2(1)(Y) revealed a maximum sorption capacity of 63 ± 2 mg g−1 corresponding to the insertion of ∼1.25 equivalents Cd2+ per (Y3+)6 SBU. Overall this work demonstrates the post-synthetic ion exchange of the bulky ((CH3)2NH2)+ counter-ions by inorganic cations as an excellent method for the improvement of the sensing capability of RE-based anionic MOFs.

中文翻译:

基于[RE6(μ3-OH)8] 10+二级构建单元,提高新型阴离子稀土金属-有机框架对Cd2 +的检测能力:采用离子交换方法实现更高效的传感器

基于六核(RE 3+6二级结构单元(SBU)和有角二羧酸配体4,4'-氧双苯甲酸(H 2 OBA)的新型稀土(MO)家族的合成和表征式{((CH 32 NH 22 [RE 6(μ 3 -OH)8(OBA)6 ]} (((CH 32 NH 221)(RE); RE:Y ,Tb,Dy,Ho)。气体吸附研究表明,中等的Langmuir面积为377 m 2 g-1。在掺有5%Eu 3+或5%Tb 3+的((CH 3 2 NH 2 2 1)(Y)的可见区中的光致发光研究表明,这些RE 3+具有特征发射带。离子。Cd 2+对Eu( 3+)掺杂的((CH 3 2 NH 2 2 1)(Y)的传感研究表明,缓慢的交换动力学阻碍了该材料在传感领域的应用。合成的化合物与Na +成功进行抗衡离子交换Mg 2+导致Na 21)(Y)和Mg(1)(Y)分离。有趣的是,掺杂有5%Eu 3+的交换后的类似物Na 21)(Y)表现出快速的Cd 2+吸附动力学,并且在动力学和灵敏度方面均被证明是对该金属离子的大大改进的传感器。Na 21)(Y)在室温下的分批Cd 2+吸附实验表明,最大吸附容量为63±2 mg g -1,相当于每(Y 3+6插入约1.25当量Cd 2+。SBU。总体而言,这项工作证明了大体积((CH 32 NH 2+抗衡离子通过无机阳离子的合成后离子交换,是改善基于RE的阴离子MOF传感能力的出色方法。
更新日期:2020-04-23
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