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Research Article

Controlled growth and composition of multivariate metal-organic frameworks-199 via a reaction-diffusion process

Razan Issa1,§, Fayrouz Abou Ibrahim1,§, Mazen Al-Ghoul1,2( ), Mohamad Hmadeh1( )
Department of Chemistry, American University of Beirut, P.O.Box 11-0236, Riad El-Solh 1107 2020, Beirut, Lebanon
Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal H2A 0B8, Canada

§ Razan Issa and Fayrouz Abou Ibrahim contributed equally to this work.

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Abstract

In this paper, we exploit our prior successful synthesis of MOF-199 single crystals using the reaction-diffusion framework (RDF), to synthesize multivariate metal-organic frameworks (MTV-MOFs) version with enhanced properties. The MTV-MOFs are synthesized by creating defects within the MOF-199 crystal structure by integrating organic linkers entailing different functional groups. Accordingly, 5-aminoisophthalic acid (NH2-BDC) and 5-hydroxyisophthalic acid (OH-BDC) are separately mixed with 1,3,5-benzenetricarboxylic acid (BTC) in three different starting ratios of X-BDC:BTC (1:3, 1:1) and 3:1). The effects of this linker on the morphology of the synthesized MTV-MOFs, their thermal stability, and their surface area are investigated. The extent of the incorporation of the linkers in the framework is elucidated via 1H-NMR spectroscopy and it is shown that the incorporation varies as a function of the location along the tubular reactor, a characteristic of RDF. The enhanced properties of the synthesized MTV-MOFs are further demonstrated by measuring its adsorptive capability for methylene blue (MB) and rhodamine B (Rh B) in aqueous solution, and compared with that of the as-synthesized MOF-199. The kinetic and thermodynamic studies reveal that MTV-MOFs with the ratio of X-BDC:BTC (1:1) exhibit the best uptakes of MB (263 mg/g) for X = OH and Rh B (156 mg/g) for X = NH2. The adsorbents are also easily regenerated for three consecutive cycles without losing their efficiency. We finally demonstrate that MTV-MOFs can be designed to tune the dye removal selectivity and enhance the removal capacity of both MB and RhB in a binary aqueous solution of these dyes.

Keywords

reaction-diffusion framework (RDF)multivariate metal-organic frameworks (MTV-MOFs)adsorptionmethylene blue (MB)rhodamine B (Rh B)

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Nano Research
Volume 14 Issue 2,
February 2021
Pages 423-431
DOI: 10.1007/s12274-020-2870-1
Cite this article:
Issa R, Ibrahim FA, Al-Ghoul M, et al. Controlled growth and composition of multivariate metal-organic frameworks-199 via a reaction-diffusion process. Nano Research, 2021, 14(2): 423-431. https://doi.org/10.1007/s12274-020-2870-1
Topics:
MetalsMorphologyNuclear magnetic resonance spectroscopyOrganic frameworks Organic polymersOrganometallics

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Received: 04 February 2020
Revised: 17 April 2020
Accepted: 09 May 2020
Published: 25 June 2020
© Tsinghua University Press and Springer-Verlag GmbH Germany, part of Springer Nature
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