IJSRD - International Journal for Scientific Research & Development| Vol.

8, Issue 7, 2020 | ISSN (online): 2321-0613

An Approachable Solvothermal Synthesis of Uio-66 for Carbon Dioxide

Capture from Automobile Emissions
A. P. Pandhare1 Suyog Lokhande2 Mahesh Mengale3 Ashish Kohad4 Nikhil Jumnake5
1,2,3,4,5
Department of Mechanical Engineering
1,2,3,4,5
Savitribai Phule Pune University, Sinhgad College of Engineering Vadgaon BK, Pune, India
Abstract— Metal-organic frameworks (MOFs) are a class of In the following synthesis processes, the first two
porous material which is made by strong bonds between processes give fewer values than required. So that they are
metal ions and organic linkers. Zirconium-based MOFs are No-Go type of process but synthesis 3 process gives the
subclass of MOFs known for their high surface area, large more surface area and required pore size. Other than that,
pore volume and excellent stability especially in the this paper gives an idea about the proper selection of
presence of water. In this study, the Zr-MOF (UiO-66) was chemical grade as required in the process. Also tells the
fabricated by the solvothermalsynthesis method, with the importance of concentrated HCL (Hydrochloric acid) in the
addition of HCl to reaction mixture. A mixed-ligand Zr- synthesis process.
MOF material has been synthesized for CO2 capture at
room temperature. This Zr-MOF (UiO-66) was tested using II. EXPERIMENTAL
XRD and BET surface area test. The Study also tells about
surface area increment of defective UiO-66 and gives an A. Reagents and Chemicals
idea about the selection of the proper grade of chemical Essential information about the required chemicals given in
material required in the synthesis of UiO-66. Table 1. These given chemicals are sufficient for the
Keywords: Metal-Organic Frameworks, Zr-MOF, Uio-66, synthesis of Uio-66.
Adsorption, Carbon Dioxide, Emission Sr.
Grade/Pur Case Company
N Name
ity no. Name
I. INTRODUCTION o.
Zirconium
Carbon dioxide (CO2) and Methane (CH4) are major
(IV) 1002 Merck Life
greenhouse gases [1]. Plenty amount of greenhouse gases
1 Chloride 99.5% 6-11- Science
emitting into the atmosphere hassled to major environmental
anhydrous: 6 Pvt. Ltd.
issues, the substantial harm to the natural environment has
(ZrCl4)
caused widespread concern around the world. Among them,
CO2 is the largest contributor. So far, CO2 capture is Terephthalic LobaChemie
100-
2 (H2BDC) 98% Pvt.
important to face the challenge of climate change [2]-[3]. 21-0
Acid Ltd.
Metal-organic frameworks (MOFs) are new kinds
of porous adsorbents. MOFs have been generated that N.N- Spectrochem
exhibit the highest known surface area, high porosity, the Dimethylforma Pvt.
HPLC & 68-
lowest crystal densities, high hydrogen storage capacity and 3 mide Ltd.
AR 12-2
also CO2 capture capacity [4]-[7]. MOFs are widely used in purisss[DMF] Mumbai.
adsorption, separation, catalysis process. So far, MOF (C3H7NO) (INDIA)
materials have been synthesized and used in CO2 capture Methanol Spectrochem
[2]. Among the MOFs zirconium-based organic frameworks Anhydrous Pvt.
67-
(Zr-MOFs) Uio-66 is one who attracted more attention 4 (especially AR Ltd.
56-1
recently. For their remarkable stability, especially in the dried) Mumbai.
presence of water [8]- (CH4O) (INDIA)
Depending on final structures and properties, Research
MOFs may be prepared using several distinct synthetic Hydrochloric Lab
7647
methods such as: slow diffusion, hydrothermal, 5 Acid LR Fine
-01-0
solvothermal, electrochemical, mechanochemical, (HCL) Chem
microwave-assisted heating, and ultrasound [3], [10]-[11]. Industries
The synthesis of Uio-66 using a solvothermal process Changshu
change activation process to enhance the porous structure Hongsheng
Ethanol 64-
and its application in H2 and CO2adsorption [1], [12]. 6 LR Fine
(C2H5OH) 17-5
Post synthetic defect exchange (PSDE) reduces the Chemical
porosity of defective Uio-66 but improves both CO2 uptake Co., Ltd
and CO2 selectivity. Whereas PSE (Post Synthetic Table 1: Information about the Required Chemicals
Exchange) does not affect the porosity of non-defective Uio- B. Synthesis of Zr-MOFs (UiO-66)
66 [8]. In this paper, we are presenting the Uio-66 synthesis
1) Synthesis 1:
process for the application to capture CO2. The general
UiO-66 synthesis was performed by first dissolving
requirement of Uio-66 to capture CO2 is as follows [13]:
1) The average surface area must be ≥ 850 m2/g. equimolar amounts of ZrCl4 (3.5 mmol, 0.82 g) and
2) Pore size: 8.5Å to 11.5Å. H2BDC (3.5 mmol, 0.58 g) [14] in 50 ml DMF and stirring
for 15 minutes [1]. This clear solution was transfer into a

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 An Approachable Solvothermal Synthesis of Uio-66 for Carbon Dioxide Capture from Automobile Emissions
(IJSRD/Vol. 8/Issue 7/2020/173)

Teflon-lined stainless steel autoclave reactor. The reaction III. RESULTS AND DISCUSSION
took place at 120o C for 24 hours [14]-[15]. The resulting
A. XRD Analysis
product wash means centrifuged thrice with DMF
(commercial grade) and once with Ethanol (LR) [16]. The X-Ray Diffraction is frequently abbreviated as XRD. It is a
final product Uio-66 crystals where hot air oven-dried at non-destructive test method used to analyze the structure of
120o C for 24 hours [1]. This is how we got the final crystalline materials. It also used to identify the crystalline
product of UiO-66. But this process gives very less surface phases present in a material [19].
area because of the use of low-grade chemicals. XRD pattern was drawn by using origin software.
2) Synthesis 2: The XRD pattern in Figure 1 showed typical UiO-66 2-
For performing UiO-66 synthesis first dissolve equimolar Theta peak positions (~7.4, 8.5 and 25) as reported in
amounts of ZrCl4 (3.5 mmol, 0.82 g) and H2BDC (3.5 previous studies [1]-[2], [18], and [20]. As observed in
mmol, 0.58 g) [14] in 50 ml DMF and stirring for 15 Figure 1 there were very similarities in the XRD pattern as
minutes [1]. This clear solution was transfer into a Teflon- compared to previous observations [1]. This suggests that
lined stainless steel autoclave reactor, and to remove the addition of HCL and weight ration of ZrCl4 to H2BDC
moisture from the above surface of the solution we flush shall not harm the crystallite structure of Zr-MOF (UiO-66),
Nitrogen (N2) gas in it. The reaction took place at 120o C so it proved that weight ratio and HCL concentration is
for 24 hours [14]. The resulting product was centrifuged for correct. In Figure 2 the XRD pattern not showed the 2-Theta
10 minutes at 4000 RPM, and wash thrice with DMF (AR) peak position as reported in previous studies of UiO-66.
and one time with Methanol (LR). The final product crystal From this, we proved that quality, grade and weight ratio of
was vacuum dried at 105o C overnight. This is how we got materials effects crystalline phases present in the material.
the final product of UiO-66 having more surface area than
synthesis 1.
3) Synthesis 3:
The synthesis of UiO-66 had been carried out by dissolving
ZrCl4 and H2BDC in DMF (HPLC). The weight ratio of
ZrCl4 and H2BDC must be 1.0162 [13].
Therefore we took 1 g of ZrCl4, 0.984 g H2BDC
and 120 ml DMF (HPLC) for our synthesis process. The
solubility of ZrCl4 in DMF is enhanced by HCL, also HCL
speeds product formation [13]. Surface area measurement of
the material demonstrates that the higher HCL concentration
leads to larger surface areas [13]. Here we used 8 ml HCL
(35-38%) for the above-mentioned quantities of DMF and
ZrCl4. Stirred the above solution for 2 hours [13]. This
solution was transferred into a Teflon-lined stainless steel
autoclave reactor, to remove the moisture contain from Fig. 1: XRD pattern of synthesis 3of UiO-66
surface of the solution we flush N2 gas in it. The reaction
took place at 150o C for 12 hours in a hot air oven [13]-[18].
The resulting product then centrifuged three times with
DMF (AR) and one time with Methanol (AR). Centrifuging
done for 25minutes at 2500 RPM for every wash. The final
product crystal was vacuum dried at 120o C for 18 hours in
a vacuum dryer. By following the above-said process we got
maximum surface area (1051.827 m2/g) which is sufficient
to capture carbon dioxide. CO2 adsorption in zirconium
MOF UiO-66 almost doubles with post-synthetic exchange
of Zr by Ti (Titanium) [17].
4) Synthesis 4:
Synthesis of Uio-66 to enhancing CO2 capturing the
performance of defective Uio-66 [8]. In this process, we
increase the surface area of the material to capture CO2. The
result of synthesis 1 gives only 65.366 m2/g surface area
which was insufficient to capture CO2. To overcome this Fig. 2: XRD pattern of synthesis 2 of UiO-66.
defect we used the following method. First, we took the Figure 3 shows both the XRD pattern of UiO-66
UiO-66 in a beaker and mixed with DMF (HPLC). Then made by synthesis 3 and synthesis 2 processes. It gave a
centrifuged this solution three times with DMF (HPLC) and clear idea about the deviation of pattern and peak values of
one time with Methanol (AR). Then put it in vacuum dryer two different synthesis methods of UiO-66.
for 18 hours at 120o C. By doing this process we got new
Uio-66 having results similar to the synthesis 3.

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 An Approachable Solvothermal Synthesis of Uio-66 for Carbon Dioxide Capture from Automobile Emissions
(IJSRD/Vol. 8/Issue 7/2020/173)

B. BET Analysis
Brunet-Emmett-Teller (BET) theory aims to explain the
physical adsorption of gas molecules on a solid surface and
serves as a basis for an important analysis technique for the
measurement of the specific surface area of materials.
1) CO2 Adsorption-Desorption Isotherms (Synthesis 1
Results):
Carbon dioxide adsorption and desorption isotherms are
used to get the structural information about the synthesized
1 Uio-66 as shown in Figure 4 the isotherm shows linear
properties. A linear increment between the relative pressures
from 0 to 0.8 revealed that there were microspores inside.
The parameters of the porous structure calculated from these
isotherms and pore size distributions where presented in
Table 2. The calculated surface area and pore size of Uio-66
by synthesis 1 where 66.366 m2/g and 17.8 Å respectively.
Fig. 3: XRD patterns Compared to Uio- 66 reported in synthesis 3, the
sample shows a lower crystallinity. That may be due to
synthesis conditions and low grade of synthesis material.
Also, this happened due to not use of vacuum dryer.

Fig. 4: CO2 Adsorption desorption isotherms of sorbents of synthesis 1

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 An Approachable Solvothermal Synthesis of Uio-66 for Carbon Dioxide Capture from Automobile Emissions
(IJSRD/Vol. 8/Issue 7/2020/173)

2) N2 Adsorption-Desorption Isotherms (Synthesis 2 of the porous structure calculated from these isotherms and
Results): pore size distributions were presented in Table 2. The
Nitrogen adsorption and desorption isotherms are used to calculated surface area and pore size of synthesis 2 Uio-66
get the structural information about the synthesized 2 Uio- were 464.743 m2/g and 26.2 Å respectively. Compared to
66 as shown in Figure 5 that exhibited permanent micro Uio-66 reported in synthesis 3, the sample shows a lower
porosity, it gives linear nature of isotherms. The parameters crystallinity, it is because of the use of low-grade chemicals.

Fig. 5: N2 Adsorption-desorption isotherms of sorbents of synthesis 2

3) N2 Adsorption-Desorption Isotherms (Synthesis 3 porous structure calculated from these isotherms and pore
Results): size distributions were presented in Table 2. The calculated
Synthesized 3 Uio-66 is the sample which is having surface area and pore size of synthesized 3 Uio-66 where
sufficient surface area and pore size to capture carbon 1051.827 m2/g and 11.38 Å respectively. Compared to Uio-
dioxide. The isotherm in Figure 6 shows a sharp increase 66 reported in the literature [13] and [2], the sample shows a
between the relative pressures of 0.05 to 0.2 revealed that lower crystallinity. But the results are sufficient to capture
there were plenty of micropores inside. The parameter of the carbon dioxide.

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 An Approachable Solvothermal Synthesis of Uio-66 for Carbon Dioxide Capture from Automobile Emissions
(IJSRD/Vol. 8/Issue 7/2020/173)

Fig. 6: N2 Adsorption-desorption isotherms of sorbents of synthesis 3

Average
Surface Liquid
pore IV. CONCLUSION
Compound Adsorbent Area BET Density
2 radius In our study, the selection of proper weight ratio (1.0162) of
(m /g) (g/cc)
(Å) ZrCl4 to H2BDC in the synthesis process of Zr-MOF (UiO-
Uio- will produce an effect on structure and properties as shown
N2 1580 - -
66[13] in Figure 3 The addition of HCl and high HCl concentration
Uio-66[2] N2 1250 - 2.6 leads to a larger surface area. Time and temperature in the
Synthesis synthesis process plays an important role in the perfect
N2 1051.827 0.808 11.38
3 synthesis. The defective UiO-66 (less surface area) is treated
Synthesis by re-washing the material using 3 wash of HPLC grade
N2 464.743 0.808 26.2
2 DMF and last wash by AR grade methanol then uses a
Synthesis vacuum dryer for drying. This results in increment in
CO2 65.366 0.927 17.8
1 surface area.
Table 2: Structural Properties of Uio-66 by Different
Synthesis Methods

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 An Approachable Solvothermal Synthesis of Uio-66 for Carbon Dioxide Capture from Automobile Emissions
(IJSRD/Vol. 8/Issue 7/2020/173)

ACKNOWLEDGMENTS frameworks for CO2 capture, regeneration and

This work was supported by the Mechanical Department of conversion, Nature reviews materials volume 2 article
Sinhgad College of Engineering Pune, Sinhgad Dental number 17045.
College Pune, and Sinhgad Pharmacy College Pune. All the [13] Michael J. Katz, Zachary J. Brown, Yamil J. Colo, Paul
authors would like to thank all of them. W. Siu, Karl A. Scheidt, Randall Q. Snurr, Joseph T.
Hupp and Omar K. Farha, A facile synthesis of UiO-66,
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