Synthesis, Characterizations, and Adsorption Isotherms of CO2 on Chromium Terephthalate (MIL-101) Metal-organic Frameworks (Mofs)
Corresponding email: nasruddin@eng.ui.ac.id
Published at : 29 Nov 2019
Volume : IJtech
Vol 10, No 7 (2019)
DOI : https://doi.org/10.14716/ijtech.v10i7.3706
Yulia, F., Utami, V.J., Nasruddin, Zulys, A., 2019. Synthesis, Characterizations, and Adsorption Isotherms of CO2 on Chromium Terephthalate (MIL-101) Metal-organic Frameworks (Mofs). International Journal of Technology. Volume 10(7), pp. 1427-1436
| Fayza Yulia | Department of Mechanical Engineering, Faculty of Engineering, Universitas Indonesia, Depok, 16424, Indonesia |
| Vania Juliani Utami | Department of Mechanical Engineering, Faculty of Engineering, Universitas Indonesia, Depok, 16424, Indonesia |
| Nasruddin | Department of Mechanical Engineering, Faculty of Engineering, Universitas Indonesia, Depok, 16424, Indonesia |
| Agustino Zulys | Department of Chemistry, Faculty of Mathematics and Natural Sciences, Universitas Indonesia, Depok, 16424, Indonesia |
The concentration of CO2
in the atmosphere caused by fossil fuels, power plants, and transportation is
the most significant environmental issue in the world today. Intensive efforts have
been made to minimize CO2 levels to reduce global warming. Metal-organic
frameworks (MOFs), crystalline porous materials, exhibit great potential to
adsorb carbon dioxide. In the present study, research was conducted on the synthesis,
characterization, and adsorption isotherms of MIL-101. MIL-101, one type of
mesoporous MOF, can adsorb enormous amounts of CO2. The synthesis was
carried out using a fluorine-free hydrothermal reaction method. The porous
properties, structure, morphology, thermal stability, and chemical
functionalities of MIL-101 Cr were measured by N2
adsorption/desorption isotherms, X-ray diffraction (XRD), scanning electron microscope
(SEM), thermogravimetric analysis (TGA), and Fourier transform infrared spectroscopy
(FTIR) analysis, respectively. The volumetric uptakes of CO2 were
experimentally measured at temperatures of 298-308 K and pressure of up to 600
kPa. The experimental result was correlated with the Toth isotherm model,
showing the heterogeneity of the adsorbent. The heat of adsorption of MIL-101
was determined from the measured isotherm data, indicating the strength between
the adsorbent and adsorbate molecule.
Adsorbent characteristics; Adsorption isotherms; CO2 uptakes; MIL-101; Metal-organic frameworks
The combination of a
strong El Niño has given an impact of global temperature anomaly (GTA) temperature
increases up to 0.9oC
and carbon dioxide emissions as high as 400 ppm (Szulejko et al., 2017). It is crucial to undertake serious
efforts to reduce carbon dioxide emissions to control the rate of global
warming. The 21st annual Conference of the Parties, which was held
in Paris in 2015 resulted in a negotiated agreement among 195 countries to keep
the global temperature below 2°C above
pre-industrial levels (Szulejko et al., 2017). Various efforts have been made to reduce
the levels of carbon and gas emissions in processing and chemical industries.
One such effort is the use of carbon capture technology. Many types of
industries have applied this method, such as cement production (Cormos et al., 2017), iron and steel (Cormos, 2016), and power plants (Kanniche et al., 2010). However,
many challenges remain in
maximizing efficiency and
The adsorption method, which is part of
the carbon capture and storage (CCS) technology, is considered an efficient and
economical method for replacing conventional technology in the CO2
scrubbing process, since the technology of amine solvents is deficient in
corrosion and toxicity (Kartohardjono
et al., 2017; Kusrini et al., 2018). Moreover, large amounts of energy are required
to recycle amines, which diminishes the efficiency of energy usage, creates
high costs in power plants, and produces corrosion in the pipeline (Ye et
al., 2013; Mutyala et al., 2019). Another type of CCS technology is the membrane
separation method, but this method is expensive in design and synthesis (Brunetti
et al., 2010). Therefore, the most effective method in CCS
technology is the adsorption method, which does not require large energy inputs
in regeneration, does not cause corrosion, is inexpensive, and has a high
capacity and high selectivity of CO2 gas uptakes (Gargiulo
et al., 2014). Recently, the most-studied types of adsorbents have
been activated carbon, zeolite, and molecular carbon sieves, as conducted by
Sarker et al. (2017), who carried out a comparative study of these three
adsorbents in terms of their CO2 adsorption capacity in equilibrium
conditions. The results showed that GCA-1240 activated carbon had a large
volumetric uptake of 10 mmol/g at 293 K, followed by Zeolite 13 X, Zeolite 5 A,
and a molecular carbon sieve (MSC-3R) with the adsorption capacity reaching to
7, 4.7, and 4.2 mmol/g in sequence (Sarker
et al., 2017).
The search for the most
effective adsorbent has continued for the past five years. Metal-organic
frameworks (MOFs) have attracted attention because of their higher thermal
stability, good crystallinity, large surface area, and high pore volume (Yulia
et al., 2019). MIL-101 is the most attractive MOF for study due to
its high thermal and chemical stability, moisture resistance, rapid kinetics,
good cyclability, and high adsorption capacity (Liu et
al., 2013; Montazerolghaem
et al., 2016). MIL-101 is an expected
candidate in the future as it is eco-friendly and has better physicochemical
properties. MIL-101 has been tested with various types of gas adsorption and coupled
by molecular simulation. Llewellyn et al. (2008) conducted experiments on
the adsorption of CH4 and CO2 gas in MIL-101. Lin et al. (2014). carried out a CO2
adsorption analysis with polyethyleneimine
incorporated MIL-101, and it was found from their report that the CO2
adsorption capacity reached 4.2 mmol/g at 25°C. Many adsorption
experiments are still being conducted on the MIL-101 adsorbent, but different
methods and experiments produce various results.
The present research
explores the synthesis evaluation of the MIL-101 adsorbent, which is then
examined using various experimental techniques to observe porous, structural,
morphological, and chemical functionalities and thermal stability by N2
adsorption/desorption isotherms, X-ray diffraction (XRD) techniques, scanning
electron microscope (SEM), thermogravimetric (TGA) analysis, and Fourier transform
infrared spectroscopy (FTIR), sequentially. Next, using the volumetric method,
measurements of CO2 adsorption were carried out for MIL-101 Cr
adsorbent at temperatures of 298-308 K and pressures of up to 600 kPa. The data
obtained from the volumetric test was then regressed with the Toth isotherm
model, which represents the heterogeneity of the adsorbent capacity of MIL-101.
Analysis of the heat of adsorption was also undertaken for the
carbondioxide-MIL-101 system, which depends on the temperature and
concentration obtained from the results of the data measurements.
The synthesis of the MOF chromium terephthalate with a hydrothermal reaction without using HF solvents was performed. We evaluated the characterization of the adsorbent MOF with various experimental methods, such as XRD, SEM, TGA, FTIR, and N2 adsorption/desorption isotherms. The experiment using the volumetric apparatus was carried out with a CO2 gas adsorbate. Temperature and pressure variations were observed in isothermal adsorption tests at temperatures of 298 K to 308 K and pressures of up to 600 kPa. The maximum capacity in the isothermal adsorption test occurred at a temperature of 298 K, reaching 2.28 mmol/g at a pressure of 600 kPa. The experimental data was also regressed with the Toth isotherm adsorption model representing the heterogeneity of the adsorbent. In addition, a decreasing trend was found in the calculation of the isosteric heat of adsorption due to a strong heterogeneity in the surface structure.
Figure 7 Adsorption isotherms of CO2 on MIL-101 (?, 298 K; ?, 300 K; ?, 308 K). Solid lines represent the Toth model for CO2 adsorption
The authors are grateful for financial support from the Indonesian Ministry
of Research, Technology and Higher Education (PMDSU grant nos.
1/E1/KP.PTNBH/2019 and 234234/PKS/R/UI/2019) and the Osaka Gas Foundation.
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