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Strategic Design and Functionalization of an Amine-Decorated Luminescent Metal Organic Framework for Selective Gas/Vapor Sorption and Nanomolar Sensing of 2,4,6-Trinitrophenol in Water
ACS Applied Materials & Interfaces ( IF 9.5 ) Pub Date : 2018-06-29 00:00:00 , DOI: 10.1021/acsami.8b06339
Prasenjit Das 1 , Sanjay K. Mandal 1
Affiliation  

On the basis of the strategic design of a triazine-based dicarboxylate ligand with two primary amino groups and one secondary amino group, an amine-functionalized autofluorescent and polar three-dimensional metal organic framework (MOF) {[Cd(ATAIA)]·4H2O}n (1), where H2ATAIA = 5-((4,6-diamino-1,3,5-triazin-2-yl)amino)isophthalic acid, has been synthesized under two different solvothermal conditions and structurally characterized. Single-crystal X-ray analysis reveals that 1 crystallizes in the orthorhombic polar space group Fdd2, where each ATAIA ligand acts as a linear linker to connect four Cd(II) centers, resulting in the formation of a three-dimensional framework with a repeat of a double helical metal chain. It has been further characterized by elemental analysis, UV–vis and Fourier transform infrared spectroscopy, and thermogravimetric analysis. Its bulk phase purity and stability in aqueous acid and base solutions are confirmed by powder X-ray diffraction. Both field emission scanning electron microscopy and high resolution transmission electron microscopy images of 1 reflect the formation of microflowers by self-assembly of nanopetals. With the dehydrated framework of 1, sorption studies of different gases (N2, H2, and CO2) as well as polar and nonpolar solvents, such as water, benzene (Bz), and cyclohexane (Cy), have been performed. The CO2 sorption isotherm depicts type I isotherm at 298 and 273 K and type IV isotherm at 195 K. Furthermore, with an uptake of 129.2 cm3 g–1 (25.62 wt %) at 195 K, sorption of CO2 is selective over N2 (77 K) and H2 (77 K) because of the strong adsorbate–adsorbent interaction as clearly evident from an isosteric heat of adsorption (Qst) at zero coverage of 37.5 kJ mol–1, which is exceptionally higher than that of other functionalized MOFs. Using the ideal adsorption solution theory calculation for a CO2/N2 (15:85) mixture, selectivity values are found to be 54.08 (298 K) and 46.96 (273 K) at 100 kPa. For a major application, activated 1 has been utilized for selective and ultrafast detection of 2,4,6-trinitrophenol (TNP) in water with a limit of 0.94 nM (0.2 ppb), which supersedes any previous reported value. Excellent recyclability and stability of 1 for sensing experiments have been established. Time-resolved fluorescence studies and density functional theory calculations have been used to establish its mechanism of action. Furthermore, a prototype experiment for the real-time sensing of TNP in the vapor phase by fluorescence microscopy provides an easy colorimetric monitoring.

中文翻译:

胺装饰的发光金属有机框架的选择性气体/蒸汽吸附和水中2,4,6-三硝基苯酚的纳摩尔感测的战略设计和功能化。

基于具有两个伯氨基和一个仲氨基的三嗪基二羧酸酯配体的策略设计,胺官能化的自发荧光和极性三维金属有机骨架(MOF){[Cd(ATAIA)]·4H 2 O} n1),其中H 2 ATAIA = 5-((4,6-二氨基-1,3,5-三嗪-2-基)氨基)间苯二甲酸,已在两种不同的溶剂热条件下合成,并且在结构上表征。单晶X射线分析表明,在正交的极性空间群Fdd中1个结晶2,其中每个ATAIA配体均充当连接四个Cd(II)中心的线性接头,从而形成带有重复的双螺旋金属链的三维骨架。它通过元素分析,UV-vis和傅立叶变换红外光谱以及热重分析进一步表征。通过粉末X射线衍射证实了其本体相的纯度和在酸水溶液和碱溶液中的稳定性。两个场发射扫描电子显微镜和的高分辨率透射电子显微镜图像1反映通过自组装nanopetals的microflowers的形成。随着脱水的框架1,(不同气体的吸附研究Ñ 2,H 2和CO 2)以及极性和非极性溶剂,例如水,苯(Bz)和环己烷(Cy)。CO 2吸附等温线表示298 K和273 K时的I型等温线和195 K时的IV型等温线。此外,在195 K下的吸收量为129.2 cm 3 g –1(25.62 wt%)时,CO 2的吸附比N 2(77 K)和H 2(77 K)是由于强烈的吸附物-吸附剂相互作用所致,这在零覆盖率37.5 kJ mol –1处的等距吸附热(Q st)上可以清楚地看出,这要比后者高得多。其他功能化的MOF。使用理想吸附溶液理论计算一氧化碳2 / N 2(15:85)混合物,在100 kPa时的选择性值为54.08(298 K)和46.96(273 K)。对于主要应用,活化的1已被用于选择性和超快速检测水中的2,4,6-三硝基苯酚(TNP),其极限值为0.94 nM(0.2 ppb),可替代任何先前报道的值。已建立了用于传感实验的出色的可回收性和稳定性1。时间分辨荧光研究和密度泛函理论计算已用于建立其作用机理。此外,通过荧光显微镜实时检测气相中TNP的原型实验提供了简便的比色监控。
更新日期:2018-06-29
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