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Preparation and Characterization of Bi-metallic and Tri-metallic Metal Organic Frameworks Based on Trimesic Acid and Co(II), Ni(II), and Cu(II) Ions

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Abstract

Trimesic acid-M1(II):M2(II) (M1,2(II)=M(II)=Co(II), Ni(II) and Cu(II)) bi-metallic or tri-metallic organic frameworks (MOFs) were synthesized by the reaction of trimesic acid (H3BTC) ligand with the corresponding MCl2nH2O aqueous solutions. Here, bi- and tri-metallic MOF preparations were demonstrated by using H3BTC as an organic linker, with dual metal ion mixtures at different mole ratios such as Co(II):Ni(II), Ni(II):Cu(II), and Cu(II):Co(II) as metal ion sources in the synthesis of bi-metallic MOFs, and the triple metal ion mixture of Co(II):Ni(II):Cu(II) as the metal ion source in the synthesis of tri-metallic MOFs. The bi- or tri-metallic MOFs were characterized via the Brunauer–Emmett–Teller method, thermogravimetric analyzer (TGA), and magnetic susceptibility measurements with the Gouy method, FT-IR spectroscopy, and electronic spectral studies. The results revealed that the H3BTC MOFs have octahedral and distorted octahedral arrangement around the metal ions, and the d–d transition was not observed in the complex. It was further found that all the prepared MOFs contain water molecules confirmed by Fourier transform infrared (FT-IR) and TGA analyses. The FT-IR spectra of the MOF complexes were characterized by the appearance of a broad band in the region of 3454–3300 cm−1 due to the ν(-OH) of the coordinated water; therefore, the location of the two water molecules was assumed to be inside the complex structure. Remarkably, the synthesized bi-metallic MOFs had unique and distinct colors depending on the amounts of metal ions used in the feed, implying that these bi-metallic MOFs with tunable M1(II) and M2(II) ratios offer great potential in the design of color-coded materials for use as sensors.

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Acknowledgement

Support from the Turkish Academy of Science (TUBA) is greatly appreciated under the 2008 TUBA-GEBIP (TUBA-Young incentive award) program.

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Authors and Affiliations

  1. Chemistry Department, Faculty of Science and Arts, Canakkale Onsekiz Mart University, Terzioglu Campus, 17100, Canakkale, Turkey

    Nurettin Sahiner, Sahin Demirci & Mustafa Yildiz

  2. Nanoscience and Technology Research and Application Center (NANORAC), Faculty of Science and Arts, Canakkale Onsekiz Mart University, Terzioglu Campus, 17100, Canakkale, Turkey

    Nurettin Sahiner & Mustafa Yildiz

Authors
  1. Nurettin Sahiner
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  2. Sahin Demirci
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Correspondence to Nurettin Sahiner.

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Supp. Figure 1

The FT-IR spectra of H3BTC-based (a) Ni(II):Cu(II), and (b) Cu(II):Co(II) bi-metallic MOFs with different mole ratios of metal ions. (JPEG 98 kb)

Supp. Figure 2

The FT-IR spectra of H3BTC-based (a) Co(II):Ni(II):Cu(II) tri-metallic, and (b) Cu(II):Co(II) bi-metallic MOFs prepared with different mole ratios of metal ions. (JPEG 99 kb)

Supp. Figure 3

The PXRD spectra of H3BTC-based (a) Co(II) (b) Ni(II), (c) Cu(II), (d) Co(II):Ni(II) (50:50), (e) Ni(II):Cu(II) (50:50), (f) Co(II):Cu(II) (50:50) bi-metallic, and (g) Co(II):Ni(II):Cu(II) tri-metallic MOFs. (JPEG 81 kb)

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Sahiner, N., Demirci, S. & Yildiz, M. Preparation and Characterization of Bi-metallic and Tri-metallic Metal Organic Frameworks Based on Trimesic Acid and Co(II), Ni(II), and Cu(II) Ions. J. Electron. Mater. 46, 790–801 (2017). https://doi.org/10.1007/s11664-016-4969-4

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  • DOI: https://doi.org/10.1007/s11664-016-4969-4

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