Malaysian Journal of Analytical Sciences Vol 24 No 2 (2020): 159 - 164

 

 

 

 

IONOTHERMAL SYNTHESIS OF Zn-BASED METAL ORGANIC FRAMEWORKS IN PYRIDINIUM IONIC LIQUID

 

(Sintesis Ionotermal Kerangka Logam-Organik Berasaskan Logam Zink Menggunakan Cecair Ionik Piridinium)

 

Haslina Ahmad1,2*, Nur Aininie Yusoh1, Khairulazhar Jumbri3,  Mohd Basyaruddin Abdul Rahman1,2

 

1Chemistry Department, Faculty of Science
2Integrated Chemical Biophysics Research, Faculty of Science

Universiti Putra Malaysia, 43400 UPM Serdang, Selangor, Malaysia

3Department of Fundamental and Applied Sciences,

Universiti Teknologi Petronas, Bandar Seri Iskandar, 32610, Perak, Malaysia

 

*Corresponding author:  haslina_ahmad@upm.edu.my

 

 

Received: 20 November 2019; Accepted: 24 February 2020

 

 

Abstract

Metal organic frameworks (MOFs) are crystalline porous frameworks which have been investigated as absorbent for removing dye, metal ion, drug contaminant, and organic solvent from water. However, the traditional synthesis of MOF involves the use of organic solvents and also requires high temperature; termed solvothermal reaction. This study aimed to synthesis MOF in a rather mild condition (room temperature) using ionic liquids (ILs) instead of organic solvents. Theoretically, high ionic conductivity of cetyl pyridinium bromide (C16PyBr) ionic liquid can develop novel MOF compounds thus, this study also aimed to investigate the possible effects of using ionic liquid in MOF synthesis. Zinc nitrate hexahydrate (Zn(NO3)2.6H2O) was used as the metal precursor and was reacted with the organic ligands, which is either benzene-1,3,5-tricarboxylic acid (H3BTC) or benzene-1,4-dicarboxylate (H2BDC), at 6:1 ratio in C16PyBr ionic liquid at room temperature. We hope to fabricate Zn-BDC and Zn-BTC MOFs with the same compositions, and thus recognize the effects of ILs. The powder X-ray diffraction (PXRD) and Fourier Transform Infrared Spectroscopy (FTIR) spectra of both newly synthesized MOFs showed that both Zn-BDC and Zn-BTC MOFs can be reproduced with these conditions. ILs have also been found to significantly accelerate the formation of MOFs at room temperature as the reaction time is shortened to 6 hours in IL, meanwhile the organic solvent DMF needs at least 120 hours.

 

Keywords:  metal organic frameworks, ionic liquids, zinc, pyridinium

 

Abstrak

Kerangka logam-organik (MOF) adalah kerangka kristal berliang yang telah disiasat sebagai penyerap untuk mengeluarkan perwarna, logam ion, bahan pencemar daripada ubat-ubatan, dan pelarut organik daripada air. Walau bagaimanapun, sintesis tradisional MOF melibatkan penggunaan pelarut organik dan juga memerlukan suhu yang tinggi; dipanggil tindak balas solvotermal. Kajian ini bertujuan untuk mensintesiskan MOF dalam keadaan yang agak ringan (suhu bilik) menggunakan cecair ionik (ILs) dan bukan pelarut organik.  Secara teori, kekonduksian ionik yang tinggi di dalam cecair ionik piridinium bromida (C16PyBr) boleh membangunkan perkembangan sebatian MOF yang baharu, oleh itu, kajian ini juga bertujuan untuk mengkaji kemungkinan pengaruh menggunakan cecair ionik dalam sintesis MOF. Zink nitrat heksahidrat (Zn(NO3)2.6H2O) digunakan sebagai pelopor logam dan di campur dengan ligan organik, sama ada asid benzena-1,3,5-trikarbosilik (H3BTC) atau benzena-1,4-dikarbosilat (H2BDC), pada nisbah 6:1 menggunakan pelarut cecair ionik C16PyBr pada suhu bilik. Kami berharap dapat menghasilkan MOF Zn-BDC dan Zn-BTC dengan komposisi yang sama, dan dengan itu dapat mengiktiraf pengaruh ILs. Pembelauan serbuk sinar-X (PXRD) dan spektroskopi inframerah transformasi Fourier (FTIR) daripada kedua-dua MOF yang di sintesis menunjukkan bahawa kedua-dua MOF Zn-BDC dan Zn-BTC boleh dihasilkan semula dengan keadaan ini. IL juga didapati dengan ketara dapat mempercepat pembentukan MOF pada suhu bilik apabila masa tindak balas dipendekkan kepada 6 jam apabila menggunakan IL, di mana pelarut organik, DMF memerlukan sekurang-kurangnya 120 jam.

 

Kata kunci:  kerangka logam-organik, cecair ionik, zink, piridinium

 

References

1.       Sang, X., Zhang, J., Xiang, J., Cui, J., Zheng, L. and Zhang, J. (2017). Ionic liquid accelerates the crystallization of Zr-based metal-organic framework. Nature Communications, 8(175): 1-7.

2.       Zhang, Z. H., Liu, B., Xu, L. and Jiao, H. (2015). Combination effect of ionic liquid components on the structure and properties in 1,4-benzene-dicarboxylate based zinc metal-organic frameworks. The Royal Society of Chemistry. Dalton Transactions, 44: 17980-17989.

3.       Xu, L., Choi, E. Y. and Kwon, Y. U. (2007). Ionothermal synthesis of six three-dimensional zinc metal-organic frameworks with 1-alkyl-3-methylimidazolium bromide ionic liquids as solvents. Inorganic Chemistry, 46(25): 10670-10680.

4.       Tranchemontagne, D. J., Hunt, J. R. and Yaghi, O. M. (2008). Room temperature synthesis of metal-organic frameworks: MOF-5, MOF-74, MOF-177, MOF-199 and IRMOF-0. Elsevier, Tetrahedron, 64: 8553-8557.

5.       Gao, J., Ye, K., Tang, L., Xiong, W. W., Ye, L., Wang, Y. and Zhang, Q. (2014). Growing crystalline zinc-1,3,5-benzenetricarboxylate metal-organic frameworks in different surfactants. American Chemical Society. Inorganic Chemistry, 53: 691-693.

6.       Mohamed Isa, E. D., Abdul Rahman, M. B. and Ahmad, H. (2018). Monodispersed mesoporous silica nanoparticles based on pyridinium ionic liquids. Journal of Porous Materials, 25(5): 1439-1446.

7.       Vaid, T. P., Kelley, S. P. and Rogers, R. D. (2017). Structure-directing effects of ionic liquids in the ionothermal synthesis of metal-organic frameworks. Topical Reviews, IUCrJ, 4: 380-392.

8.       Sang, X., Zhang, J., Peng, L., Liu, C., Ma, X., Han, B. and Yang, G. (2015). Assembly of mesoporous metal-organic framework templated by an ionic liquid/ethylene glycol interface. Wiley, ChemPhysChem Communications, 16: 2317-2321.

9.       Eddaoudi, M., Moler, D. B., Li, H., Chen, B., O’Keeffe, M. and Yaghi, O. M. (2000). Modular chemistry: Secondary building units as a basis for the design of highly porous and robust metal-organic carboxylate frameworks. American Chemical Society, Accounts of Chemical Research, 34(4): 319-330.

10.    Chen, R., Zhang, J., Chelora, J., Xiong, Y., Kershaw, S. V., Li, K. F., Lo, P., Cheah, K. W., Rogach, A. L. Zapien, J. A. and Lee, C. (2017). Ruthenium(II) complex incorporated UiO-67 metal-organic framework nanoparticles for enhanced two-photon fluorescence imaging and photodynamic cancer therapy. American Chemical Society, Applied Material and Interfaces, 9: 5699-5708.

11.    Iswarya, N., Kumar, M. G., Rajan, K. S. and Balaguru, R. J. B. (2012). Synthesis, characterization and adsorption capability of MOF-5. Science Alert, Asian Journal of Scientific Research, 5(4): 247-254.

 

 

 

 

 

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