{"title":"Pore-Specific Anisotropic Etching of Zeolitic Imidazolate Frameworks by Carboxylic Acid Vapors","authors":"Xianchun Chen, Wenjun Cai, Lu Wang, Bo Wang","doi":"10.1021/jacs.4c05044","DOIUrl":null,"url":null,"abstract":"Anisotropic etching is a powerful way to customize metal–organic frameworks with advanced nanostructures, but it is still in its infancy. Herein, we proposed an unprecedented etching strategy that created anisotropic hollow structures in various zeolitic imidazolate framework (ZIF) nano/single crystals via pore-specific carving. The etching occurred through a newly discovered gas–solid reaction where carboxylic acid vapors bind with ligands in ZIFs at room temperature to form ionic liquid (IL). A series of experiments were conducted to decode the origin of anisotropy and the “hollowing out” effect. We found that large pore openings on {111} facets provide access for the entry of carboxylic acid vapors and the outflow of the IL, resulting in pore-dependent anisotropy features. The unique “etching after adsorption” mechanism and the adsorption capacity of the IL enable acid vapors to hollow out nanocrystals and even single crystals. By altering carboxylic acids and ligands in ZIFs, the etching process can be precisely tuned from the inside out or the outside in. This new method demonstrates broad universality and brings unprecedented morphologies and complexities. It may offer great opportunities for achieving purposeful modification of ZIFs and the rational construction of intricate architectures.","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-07-17","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1021/jacs.4c05044","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Anisotropic etching is a powerful way to customize metal–organic frameworks with advanced nanostructures, but it is still in its infancy. Herein, we proposed an unprecedented etching strategy that created anisotropic hollow structures in various zeolitic imidazolate framework (ZIF) nano/single crystals via pore-specific carving. The etching occurred through a newly discovered gas–solid reaction where carboxylic acid vapors bind with ligands in ZIFs at room temperature to form ionic liquid (IL). A series of experiments were conducted to decode the origin of anisotropy and the “hollowing out” effect. We found that large pore openings on {111} facets provide access for the entry of carboxylic acid vapors and the outflow of the IL, resulting in pore-dependent anisotropy features. The unique “etching after adsorption” mechanism and the adsorption capacity of the IL enable acid vapors to hollow out nanocrystals and even single crystals. By altering carboxylic acids and ligands in ZIFs, the etching process can be precisely tuned from the inside out or the outside in. This new method demonstrates broad universality and brings unprecedented morphologies and complexities. It may offer great opportunities for achieving purposeful modification of ZIFs and the rational construction of intricate architectures.
各向异性蚀刻是定制具有先进纳米结构的金属有机框架的有力方法,但目前仍处于起步阶段。在此,我们提出了一种前所未有的蚀刻策略,通过特定孔隙雕刻在各种沸石咪唑盐酸盐框架(ZIF)纳米/单晶体中创建各向异性中空结构。蚀刻是通过一种新发现的气固反应进行的,在这种反应中,羧酸蒸汽与 ZIF 中的配体在室温下结合形成离子液体(IL)。为了破解各向异性和 "掏空 "效应的起源,我们进行了一系列实验。我们发现,{111}面上的大孔开口为羧酸蒸汽的进入和离子液体的流出提供了通道,从而产生了依赖于孔的各向异性特征。IL独特的 "吸附后蚀刻 "机制和吸附能力使酸蒸汽能够掏空纳米晶体甚至单晶体。通过改变 ZIF 中的羧酸和配体,可以从内到外或从外到内精确调整蚀刻过程。这种新方法具有广泛的通用性,带来了前所未有的形态和复杂性。它可能为实现对 ZIF 的有目的改性和合理构建复杂的体系结构提供巨大的机遇。
期刊介绍:
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