{"title":"Structural transformation from a 3D hydrophilic pillared-layered framework to 2D hydrophobic MOF nanosheets through ligand replacement exfoliation†","authors":"Po-Min Chuang, Pei-Rong Li and Jing-Yun Wu","doi":"10.1039/D3DT04379G","DOIUrl":null,"url":null,"abstract":"<p >A pillared-layered metal–organic framework (MOF) {[Zn<small><sub>2</sub></small>(atpt)<small><sub>2</sub></small>(bpBTD)]·<em>solv</em>}<small><sub><em>n</em></sub></small> (<strong>1</strong>), where H<small><sub>2</sub></small>atpt = 2-aminoterephthalic acid and bpBTD = bis(pyridin-4-yl)benzothiadiazole, showing a pcu net topology with double interpenetration was successfully constructed. Thermally activated <strong>1</strong> possessed free voids of 15.3% and repeatedly exhibited two-step CO<small><sub>2</sub></small> adsorption isotherms over three runs, with uptakes of 138.8 cm<small><sup>3</sup></small> g<small><sup>−1</sup></small> STP at 195 K and <em>P</em>/<em>P</em><small><sub>0</sub></small> = 1. Through a ligand replacement exfoliation approach, metal–organic framework (MOF) nanosheets {[Zn<small><sub>2</sub></small>(atpt)<small><sub>2</sub></small>(4-picoline)<small><sub>2</sub></small>]}<small><sub><em>n</em></sub></small> (<strong>1-ns</strong>) with a 2D sql net topology were obtained by immersing <strong>1</strong> in 4-picoline. Characterization of <strong>1-ns</strong> 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 <strong>1</strong> and <strong>1-ns</strong> both emitted blue-light fluorescence in H<small><sub>2</sub></small>O. In addition, measurements of water contact angles indicated that <strong>1</strong> is highly hydrophilic, while <strong>1-ns</strong> shows poor hydrophilicity compared with <strong>1</strong>. The double-sided hydrophobic surfaces of <strong>1-ns</strong> 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 <strong>1-ns</strong> modified glassy carbon electrode (<strong>1-ns</strong>/GCE) possessed much better electron transfer ability than the 3D pillared-layer framework <strong>1</strong> modified glassy carbon electrode (<strong>1</strong>/GCE), and thus improves the electrochemical performance and sensitivity.</p>","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":" 5","pages":" 1884-1895"},"PeriodicalIF":3.5000,"publicationDate":"2024-12-05","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://pubs.rsc.org/en/content/articlelanding/2025/dt/d3dt04379g","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
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.
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.