Malaysian Journal of Analytical Sciences Vol
24 No 3 (2020): 300 - 310
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
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