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

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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.

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Acknowledgments

We gratefully thank Manal Ammar and Dr. Ali Youssef for their substantial contribution and support. We thank the funding provided by the American University of Beirut Research Board and the K. Shair Central Research Science Laboratory. M. G. acknowledges the support of the Arab Fund Fellowship Program. We also acknowledge the funding provided by the Lebanese National Council for Scientific Research (Nos. 103496 and 103487) and the Masri Institute (No. 103214).

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

Authors and Affiliations

  1. Department of Chemistry, American University of Beirut, P.O.Box 11-0236, Riad El-Solh 1107, 2020, Beirut, Lebanon

    Razan Issa, Fayrouz Abou Ibrahim, Mazen Al-Ghoul & Mohamad Hmadeh

  2. Department of Chemistry, McGill University, 801 Sherbrooke Street West, Montreal, H2A 0B8, Canada

    Mazen Al-Ghoul

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  1. Razan Issa
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Issa, R., Ibrahim, F.A., Al-Ghoul, M. et al. Controlled growth and composition of multivariate metal-organic frameworks-199 via a reaction-diffusion process. Nano Res. 14, 423–431 (2021). https://doi.org/10.1007/s12274-020-2870-1

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