Structural transformation from a 3D hydrophilic pillared-layered framework to 2D hydrophobic MOF nanosheets through ligand replacement exfoliation†

IF 3.5 3区 化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR
Po-Min Chuang, Pei-Rong Li and Jing-Yun Wu
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Abstract

A pillared-layered metal–organic framework (MOF) {[Zn2(atpt)2(bpBTD)]·solv}n (1), where H2atpt = 2-aminoterephthalic acid and bpBTD = bis(pyridin-4-yl)benzothiadiazole, showing a pcu net topology with double interpenetration was successfully constructed. Thermally activated 1 possessed free voids of 15.3% and repeatedly exhibited two-step CO2 adsorption isotherms over three runs, with uptakes of 138.8 cm3 g−1 STP at 195 K and P/P0 = 1. Through a ligand replacement exfoliation approach, metal–organic framework (MOF) nanosheets {[Zn2(atpt)2(4-picoline)2]}n (1-ns) with a 2D sql net topology were obtained by immersing 1 in 4-picoline. Characterization of 1-ns was achieved using energy-dispersive X-ray spectroscopy (EDS), infrared (IR) spectroscopy, X-ray powder diffraction (XRPD) patterns, and elemental analyses (EA) as well as scanning electron microscopy (SEM), atomic force microscopy (AFM), and X-ray photoelectron spectroscopy (XPS). Photoluminescence spectra showed that 1 and 1-ns both emitted blue-light fluorescence in H2O. In addition, measurements of water contact angles indicated that 1 is highly hydrophilic, while 1-ns shows poor hydrophilicity compared with 1. The double-sided hydrophobic surfaces of 1-ns allowed oil (dichloromethane) but not water to pass through, making it a good candidate for oil/water separation. Electrochemical measurement revealed that the 2D metal–organic nanosheet 1-ns modified glassy carbon electrode (1-ns/GCE) possessed much better electron transfer ability than the 3D pillared-layer framework 1 modified glassy carbon electrode (1/GCE), and thus improves the electrochemical performance and sensitivity.

Abstract Image

通过配体置换剥离,从三维亲水柱状层状框架到二维疏水MOF纳米片的结构转变
在H2atpt = 2-氨基对苯二甲酸,bpBTD =双(吡啶-4-基)苯并噻唑的情况下,成功构建了具有双互穿结构的柱状层状金属-有机骨架(MOF) {[Zn2(atpt)2(bpBTD)]∙solv}n(1)。热活化的1具有15.3%的自由空隙,并且在三次运行中反复表现出两步CO2吸附等温线,在195 K和P/P0 = 1时吸收量为138.8 cm3 g−1 STP。通过配体置换剥离法,将1浸入4-吡啶中,得到了具有二维sql网拓扑结构的金属-有机骨架(MOF)纳米片{[Zn2(atpt)2(4-吡啶)2]}n (1-ns)。利用能量色散x射线能谱(EDS)、红外(IR)光谱、x射线粉末衍射(XRPD)图谱、元素分析(EA)、扫描电子显微镜(SEM)、原子力显微镜(AFM)和x射线光电子能谱(XPS)对1-ns进行了表征。光致发光光谱显示,1和1-ns在水中均发出蓝光荧光。此外,对接触角的测定表明,1具有较强的亲水性,而1-ns的亲水性较1差。1-ns的双面疏水表面允许油(二氯甲烷)通过,但保护水通过,是油水分离的理想选择。电化学测量结果表明,与三维柱状层框架1修饰玻碳电极(1/GCE)相比,二维金属有机纳米片1-ns修饰玻碳电极(1-ns/GCE)具有更好的电子传递能力,从而提高了电化学性能和灵敏度。
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来源期刊
Dalton Transactions
Dalton Transactions 化学-无机化学与核化学
CiteScore
6.60
自引率
7.50%
发文量
1832
审稿时长
1.5 months
期刊介绍: Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.
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