Hindawi

Journal of Nanomaterials
Volume 2019, Article ID 6130152, 11 pages
https://doi.org/10.1155/2019/6130152

Research Article
Adsorption of Carbon Dioxide, Methane, and Nitrogen Gases onto
ZIF Compounds with Zinc, Cobalt, and Zinc/Cobalt Metal Centers

Ahmed Awadallah-F,1 Febrian Hillman,2 Shaheen A. Al-Muhtaseb ,1

and Hae-Kwon Jeong2,3
1
Department of Chemical Engineering, Qatar University, P.O. Box 2713, Doha, Qatar
2
Artie McFerrin Department of Chemical Engineering, Texas A&M University, College Station, TX 77843-3122, USA
3
Department of Materials Science and Engineering, Texas A&M University, College Station, TX 77843-3122, USA

Correspondence should be addressed to Shaheen A. Al-Muhtaseb; s.almuhtaseb@qu.edu.qa

Received 14 May 2019; Revised 10 November 2019; Accepted 18 November 2019; Published 23 December 2019

Guest Editor: Fei Ke

Copyright © 2019 Ahmed Awadallah-F et al. This is an open access article distributed under the Creative Commons Attribution
License, which permits unrestricted use, distribution, and reproduction in any medium, provided the original work is properly
cited. The publication of this article was funded by Qatar National Library.

ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-8 are utilized in adsorbing nitrogen (N2), methane (CH4), and carbon dioxide (CO2) gases at
temperatures between 25 and 55°C and pressures up to ~1 MPa. Equilibrium adsorption isotherms and adsorption kinetics are
studied. The dual-site Langmuir equation is employed to correlate the nonisothermal adsorption equilibrium behavior. Generally,
N2 showed the lowest equilibrium adsorption quantity on the three samples, whereas CO2 showed the highest equilibrium
adsorption capacity. Amid the ZIF samples, the biggest adsorption quantities of N2 and CH4 were onto Zn/Co-ZIF-8, whereas the
highest adsorption quantity of CO2 was on ZIF-8. The isosteric heats of adsorbing these gases on ZIF-8, Co-ZIF-8, and Zn/Co-
ZIF-8 were examined. Moreover, the overall mass transfer coefficients of adsorption at different temperatures were investigated.

1. Introduction Different variables (e.g., heat, diluent vaporization, and molar

ratios) influence the product formation in the microwave-
Zeolitic imidazolate frameworks (ZIFs) are convenient sub- assisted preparation process [11].
stances for gas separation and purification applications. The The climate change phenomenon, which is driven highly
main reason is their outstanding properties such as excellent by the CO2 discharge into the atmosphere, draws the concern
chemical and thermal stabilities, surface areas, microporous of the scientific community from different fields. Therefore,
structures, and synthesis controllability [1, 2]. ZIF-8 pos- the reduction of the anthropogenic CO2 gas emissions in
sesses a large pore size of 11.6 Å and a small aperture size the atmosphere has become one of the most urgent climate
of 3.4 Å with a zinc metal center linked by an imidazole- problems to be confronted [12]. Therefore, the improvement
type of organic linkers, which looks like a neutral zeolitic of a proficient adsorbent for carbon dioxide gas is a dire need
sodalite topology [3]. and a necessary step to alleviate this problem [13]. Approxi-
Microwave technology attracted attention in the last mately 30% of CO2 gas emitted to the atmosphere emerges
decade for the chemical fabrication of nanoporous materials from fossil-fuel-based power plants and different human life
[4, 5]. The microwave-irradiation technique is featured with activities [12]. Hence, it is necessary to separate the CO2
homogenous and rapid heating with controllable rates [6], found in flue gases before being exhausted to the atmosphere.
which significantly decreases the synthesis time and increases Natural gas is known as an alternative and cleaner energy
the product yield [7]. To the authors’ knowledge, only few source to replace coal and petroleum. Nonetheless, it involves
works have tackled the subject of the microwave-assisted undesired impurities of CO2 and N2, which cause a corrosive
fabrication of ZIF-8 [8, 9]. The preparation of ZIF-8 products impact in pipelines and lower the calorific value of natural
involves several stages of crystal growth, which starts with gas [14]. Therefore, natural gas requires a pretreatment to
unstable clusters under super-saturation conditions [10]. remove these impurities before industrial applications [15].
2 Journal of Nanomaterials

Overall, worldwide research has exerted extreme efforts to cates pressure, m j refers to the quantity of monolayer satura-
develop concise and decisive methods for removing post tion on patch j, and b j indicates the tendency (affinity) for
combustion CO2 from gas mixtures [16–18]. Methods involv- adsorbing the molecules on patch j as estimated by
ing absorption, cryogenic distillation, and physical adsorp-
tion are developed to split up carbon dioxide, methane, and

εj
nitrogen gas mixtures [19–22]. b j = b0j exp , ð2Þ
The aim of this paper is to utilize ZIF compounds, in its RT
virgin shape and after fractional and complete replacement
of zinc by cobalt (to form Co-ZIF-8 and Zn/Co-ZIF-8), in where b0j refers to the adsorption affinity on patch j at infinite
order to adsorb CH4, N2, and CO2 gases at four tempera- temperature, ε j refers to the characteristic adsorption energy
tures (ranging from 25 to 55°C) and pressures up to on patch j, R refers to the universal gas constant, and T refers
~1 MPa. The influence of conformational metal content to absolute temperature.
(zinc, cobalt, or zinc/cobalt) of ZIFs on their adsorption
behaviors will be studied. The dual-site Langmuir equation 2.4.2. Isosteric Heat of Adsorption. The isosteric heat of
will be applied to correlate the adsorption equilibrium data adsorption (Qst ) can be estimated by the Clausius-
at various temperatures collectively, and the corresponding Clapeyron approximation [25] as
adsorption isosteric heats of CH4, N2, and CO2 will be esti-
 
mated. Moreover, the overall mass transfer coefficients for ∂lnP
the adsorption of these gases on ZIFs will be examined at Qst = −R : ð3Þ
∂ð1/T Þ n
various temperatures.

2. Materials and Methods The dependence of Qst on surface coverage is an implicit

indicator of energetic characteristics between the adsorbed
2.1. Materials. Zinc nitrate hexahydrate (98%, Sigma Aldrich), molecules and the adsorbent [26].
cobalt nitrate hexahydrate (≥99.99%), and 2-methylimidazole
(97%) were purchased from Sigma-Aldrich. Methanol 2.4.3. Adsorption Kinetics. The adsorption rate is determined
(99.8%) was supplied from Alfa Aesar. Gases (CH4, N2, and by the linear driving force (LDF) approximation as [27]
CO2) were of high purity (99.999%) and were supplied from
 
nt 
the National Industrial Gas Plants (NIGP, Doha, Qatar). All = 1 − e−kt , ð4Þ
chemical reagents were utilized without further purification. ne
2.2. ZIF Compound Preparation. Various ZIF compounds
(Zn-ZIF (i.e., ZIF-8), Co-ZIF-8, and Zn/Co-ZIF-8) were syn- where nt (mole/kg) refers to the adsorbed quantity at time
thesized by a microwave-assisted method as detailed else- t (sec), ne (mole/kg) refers to the adsorbed equilibrium
where [23]. quantity at the corresponding temperature and pressure,
and k denotes the overall mass transfer coefficient (sec-1).
2.3. Characterization. The characterization results of these The k-value can be estimated from experimental dynamic
ZIFs are found in a previous work [23]. Adsorption equilib- adsorption results at a specific temperature and pressure
rium isotherms of CH4, N2, and CO2 gases were measured by plotting the −ln ð1 − nt /ne Þ against t until reaching the
via a Hygra magnetic suspension microbalance (MSB, equilibrium state.
Rubotherm), with microgram sensitivity, following the same
procedures described elsewhere [24]. 2.4.4. Regression Analysis. Regression was used to obtain the
optimum fitting parameters. The least sum of squared errors
2.4. Theory (LSSE) is widely utilized for regression as [28]

2.4.1. Adsorption. The multisite Langmuir model supposes " #

N
that a heterogeneous surface of an adsorbent is composed LSSE = Minimum 〠 ðni,Calc − ni,meas Þ , 2
ð5Þ
of patches with distinctive adsorption energies. Each patch i=1
is thus considered as a homogeneous portion of the adsor-
bent surface, and the total quantity adsorbed of a gas compo- where i indicates measured data point numbers, N denotes
nent can be correlated as the total number of measured data points, and ni,Calc and
ni,meas refer, respectively, to the calculated and measured
J
mjbjP quantities adsorbed.
nads = 〠 , ð1Þ The averaged relative error (ARE, %) was utilized in
j=1
1 + bjP
order to estimate the accuracy of fitting to describe measured
data as [29]
where J is the number of homogeneous adsorption patches
 
and it depends on the extent of surface heterogeneity (usu- 100% N ni,Calc − ni,meas 
ally, J is set to 2, corresponding to the dual-site Langmuir ARE ð%Þ = 〠 : ð6Þ
(DSL) model), j refers to adsorption patch number, P indi- N i=1 ni,meas
Journal of Nanomaterials 3

0.8 1.0
25 °C
35 °C 25 °C
45 °C 35 °C
0.6 55 °C 0.8
45 °C
55 °C
(mole/kg)

0.6
nN2

0.4

(mole/kg)
0.4

nN2
0.2

0.2
0.0
0.0 0.2 0.4 0.6 0.8 1.0
0.0
P (MPa) 0.0 0.2 0.4 0.6 0.8 1.0
(a) P (MPa)
1.8 (a)
25 °C
1.6 2.0
1.4 35 °C 25 °C

1.2 45 °C 35 °C
(mole/kg)

55 °C 1.5
1.0 45 °C
nCH4

55 °C

(mole/kg)
0.8

nCH4
0.6 1.0
0.4
0.2
0.5
0.0
0.0 0.2 0.4 0.6 0.8 1.0
P (MPa) 0.0
(b) 0.0 0.2 0.4 0.6 0.8 1.0
P (MPa)
7
25 °C (b)
6
5
5 25 °C
35 °C
(mole/kg)

4 4
nCO2

45 °C
3 55 °C 35 °C
(mole/kg)

3
nCO2

2
45 °C
1 2 55 °C
0
0.0 0.2 0.4 0.6 0.8 1.0 1
P (MPa)
(c) 0
0.0 0.2 0.4 0.6 0.8 1.0
Figure 1: The adsorption equilibria of (a) nitrogen, (b) methane, P (MPa)
and (c) carbon dioxide gases on ZIF-8 at different temperatures.
(c)
The symbols indicate measured results and the lines indicate
DSL fitting. Figure 2: The adsorption equilibria of (a) nitrogen, (b) methane, and
(c) carbon dioxide on gases Co-ZIF-8 at different temperatures.
The symbols indicate measured results and the lines indicate
3. Results and Discussion DSL fitting.

3.1. Adsorption Equilibrium Isotherms. The adsorption of

nitrogen, methane, and carbon dioxide gases onto ZIF-8, methane, and carbon dioxide as a function of both tempera-
Co-ZIF-8, and Zn/Co-ZIF-8 at different temperatures is pre- ture and pressure. The fitting parameters registered in
sented in Figures 1–3, respectively. Broadly, it is seen that the Table 1 exposed a good relation with measured results as seen
adsorption quantity decreases at higher temperatures. Over- in the solid lines in Figures 1(a)–1(c) to Figures 3(a)–3(c) and
all, N2 gas exposes the lowest adsorbed quantity, whereas by values of ARE (%) in Table 1. Figures 1(a)–1(c) exhibit the
CO2 shows the highest adsorbed quantity. The DSL equation adsorption results of nitrogen, methane, and carbon dioxide,
is applied to fit the experimentation results of nitrogen, respectively, on ZIF-8. It is observed that adsorption
4 Journal of Nanomaterials

1.0 and carbon dioxide, respectively, on Co-ZIF-8. It is

25 °C observed that the DSL model has deviated slightly from
35 °C
0.8 experimental points of nitrogen, methane, and carbon
45 °C
55 °C
dioxide adsorption isotherms. Figures 3(a)–3(c) show,
respectively, the adsorption equilibrium of nitrogen, meth-
0.6
(mole/kg)

ane, and carbon dioxide adsorptions on Zn/Co-ZIF-8.

nN2

Excellent fit of the DSL model to experimental data points

0.4 is observed in the entire range of temperatures. Further-
more, Table 1 shows that for variety of the studied
0.2 adsorption systems, one adsorption site was sufficient to
describe the corresponding isotherm data (as exhibited
0.0 by the sufficiency of J = 1), which reduces to the regular
0.0 0.2 0.4 0.6 0.8 1.0 Langmuir adsorption isotherm and refers to an energeti-
P (MPa) cally homogeneous adsorbent surface towards the corre-
(a) sponding gas. It is noted that the results of ZIF-8
reported in Awadallah-F et al. [30] are used here for the
2.0 25 °C purpose of comparison.
Figures 4(a)–4(c) illustrates the influence of various
35 °C adsorbents (i.e., ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-8) on the
1.5 45 °C adsorption equilibria of nitrogen, methane, and carbon diox-
(mole/kg)

55 °C ide, respectively, at 25°C (25°C was selected as an illustration

nCH4

1.0 for the purpose of briefness). It is observed that the quantity

adsorbed on Zn/Co-ZIF-8 is the largest in the case of N2 and
CH4 gases, whereas ZIF-8 exhibits the biggest adsorption
0.5 capacity of CO2 gas (and the lowest adsorption capacity in
the case of N2 and CH4 gases). Therefore, it can be said that
0.0 insertion of cobalt ions into ZIF-8 leads to a noticeable
0.0 0.2 0.4 0.6 0.8 1.0 change in adsorption equilibrium quantities of CH4, N2,
P (MPa) and CO2 gases.
(b)
3.2. Rate of Adsorption. Figures 5–7 illustrate the correlation
6 25 °C between the overall mass transfer coefficient (k, sec-1) of
adsorbing nitrogen, methane, and carbon dioxide on ZIF-
5 8, Co-ZIF-8, and Zn/Co-ZIF-8, correspondingly, against
35 °C
the reciprocal pressure (1/P) at different temperatures. Sym-
4 45 °C
(mole/kg)

bols and lines denote, correspondingly, measured data and

nCO2

55 °C linear regression. The regression constants were recorded

3
in Table S1 (see Supplementary File Data). As an overview,
2 it was noticed that k-values rise via rising temperature and
via diminishing pressure (or rising reciprocal pressure).
1 Furthermore, the k-values approach zero at extreme
pressures (i.e., as 1/P→0), and the influence of temperature
0
0.0 0.2 0.4 0.6 0.8 1.0 in this case is nil. Otherwise, at mild pressures, the k
P (MPa) -values were in the rough order of 10-3 s-1.
Figures 5(a)–5(c) display the k-values for adsorbing
(c)
nitrogen, methane, and carbon dioxide, respectively, on
Figure 3: The adsorption equilibria of (a) nitrogen, (b) methane, ZIF-8. It is noted that the adsorption of carbon dioxide on
and (c) carbon dioxide gases on Zn/Co-ZIF-8 at different ZIF-8 is slowest, whereas the adsorption of methane is the
temperatures. The symbols indicate measured results and the lines fastest. The sequence of gas adsorption rates on ZIF-8 is
indicate DSL fitting. CH4 > N2 > CO2 . Figures 6(a)–6(c) elucidate the k results of
adsorption on Co-ZIF-8 against 1/P. It is noted that the
adsorption of nitrogen on Co-ZIF-8 is quicker than that of
equilibria of these gases were fitted perfectly, with a minor both carbon dioxide and methane. Moreover, the adsorption
deviation, by DSL formula for the whole range of pressures of CH4 is faster than the adsorption of CO2. The sequence of
and temperatures. Further, the adsorption equilibria of var- gas adsorption rates on Co-ZIF-8 is N2 > CH4 > CO2 .
ious gases on the ZIF-8 sample exhibited a Henry’s law Figures 7(a)–7(c) expose that the adsorption of CH4 on
trend that did not seem to reach the saturation limit within Zn/Co-ZIF-8 is the most rapid amid the gases used, whereas
the examined pressure scale. Figures 2(a)–2(c) display carbon dioxide gas was the slowest. The sequence of gas
adsorption equilibrium isotherms of nitrogen, methane, adsorption rates on Zn/Co-ZIF-8 is CH4 > N2 > CO2 .
Journal of Nanomaterials 5

Table 1: The fitting constants of the DSL equation for CH4, N2, and CO2 on ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-8.

Specimens
ZIF-8 Co-ZIF-8 Zn/Co-ZIF-8
Constants Gas
Carbon Carbon Carbon
Nitrogen Methane Nitrogen Methane Nitrogen Methane
dioxide dioxide dioxide
m1 (mole/kg) 38359 9.58 97.28 12139 7.37 21.83 13139 8.45 42.85
b0 (MPa-1) 1:84 × 10−6 9:98 × 10−4 2:14 × 10−9 3:91 × 10−6 1:90 × 10−3 1:38 × 10−5 40:10 × 10−6 1:17 × 10−3 2:45 × 10−4
ε/R (K) 693.55 1582 5038 881.97 1535.11 2917.13 861.97 1649.61 1904.60
m2 (mole/kg) 0 0 27.89 0 0 0 0 0 0
b0 (MPa-1) 0 0 7:61 × 10−2 0 0 0 0 0 0
ε/R (K) 0 0 0 0 0 0 0 0 0
SSE 0.020 0.0082 1.07 2.04 0.13 0.22 1.52 0.11 0.22
ARE (%) 8.82 3.54 7.46 34.61 12.15 27.98 45.30 9.32 18.26

Figure 8 shows the influence of the ZIF sample type (i.e., Figure 9(b) displays that the Qst of nitrogen adsorbed
ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-8) on the k results of nitro- on Co-ZIF-8 settled at ~10 kJ/mole for loadings up to
gen, methane, and carbon dioxide gases at the temperatures ~0.75 mole/kg. The Qst of carbon dioxide gas rises from
of 25 and 55°C (note that these temperatures were selected ~24 kJ/mole to ~31 kJ/mole when augmenting its loading
as examples for the purpose of briefness). It was observed from 0.25 to 2.56 kg/mole. Furthermore, it is seen that the
from Figures 8(a) and 8(b) that, at both temperatures, Qst of CH4 rises from ~32 kJ/mole at ~0.23 mole/kg to
adsorbing N2 is fastest onto the Co-ZIF-8 sample, followed ~41 kJ/mole at 1.40 mole/kg.
by Zn/Co-ZIF-8 and then ZIF-8. Figures 8(c) and 8(d) indi- Figure 9(c) exposes that the Qst of the adsorption of
cate that the adsorption rate of the CH4 gas at both tempera- nitrogen on Zn/Co-ZIF-8 augments from ~8 kJ/mole up
tures followed the trend of ZIF‐8 > Co‐ZIF‐8 > Zn/Co‐ZIF‐8. to ~11 kJ/mole when increasing the corresponding loading
Additionally, it is noted from Figures 8(e) and 8(f) that the from 0.05 mole/kg to 0.76 mole/kg. The Qst of carbon dioxide
rate of CO2 adsorption follows the order of Zn/Co‐ZIF‐8 > gas remains at around ~20-21 kJ/mole for the entire range of its
ZIF‐8 > ZIF‐8. It is noted that the results of ZIF-8 reported loading. In contrast, the Qst of methane rises from ~20 kJ/mole
in Awadallah-F et al. [30] were used here for the purpose at an adsorbed amount of 0.14 mole/kg up to ~27 kJ/mole at
of comparison. 1.51 mole/kg.
Figures 10(a)–10(c) elucidate a disparity between the
3.3. Isosteric Heat of Adsorption. Isosteric heats of adsorption isosteric heat values of nitrogen, methane, and carbon
(Qst ) were determined from the numerical differentiation of dioxide, respectively, on various ZIFs. Overall, it was
the experimental adsorption data at various temperatures in noticed from Figure 10(a) that the Qst values of N2 obeys
accordance to Clausius-Clapeyron’s equation (Equation the trend ZIF‐8 > Zn/Co‐ZIF‐8 > Co‐ZIF‐8. Additionally,
(3)). Figures 9(a)–9(c) expose the isosteric heats (Qst ) of the Qst of the adsorption of nitrogen augments with the
nitrogen, methane, and carbon dioxide adsorbed on ZIF-8, adsorbed amount of gas on Zn/Co-ZIF-8, ZIF-8, and to a
Co-ZIF-8, and Zn/Co-ZIF-8, respectively. In general, it was lesser extent on Co-ZIF-8. Figure 10(b) displays that the
observed that the Qst of different components rises to various order of Qst for CH4 is Co‐ZIF‐8 > Zn/Co‐ZIF‐8 > ZIF‐8
levels when the loading of each gas on the ZIF surface rises. in the range from 0.15 to 0.97 mole/kg. After 0.97 mole/kg,
This is a sign of auspicious interactions amid the molecules the order of Qst for CH4 turns out to be Co‐ZIF‐8 > ZIF‐
adsorbed to the ZIF surface [26]. The consequent trend of 8 > Zn/Co‐ZIF‐8. It is seen from Figure 10(c) that the Qst
adsorption isosteric heats of different components (at similar value of CO2 was always highest for Co-ZIF-8. The Qst
gas loadings) is methane > carbon dioxide > nitrogen, which for CO2 on Zn/Co-ZIF-8 was nearly constant at values
reflects their affinity for adsorption. higher than that on ZIF-8 up to a loading of 1.57 mole/kg,
Nevertheless, it is noticed from Figure 9(a) that the Qst of after which the isosteric heat on ZIF-8 becomes greater
nitrogen on ZIF-8 augments from ~9 kJ/mole at a loading of than that on Zn/Co-ZIF-8. It is noted that the results of
0.048 mole/kg up to ~11 kJ/mole at 0.3 mole/kg. Then, it set- ZIF-8 reported in Awadallah-F et al. [30] were used for
tles at about this amount, which reveals either adsorption on the purpose of comparison.
a nearly nonheterogeneous surface of ZIF [26] or an equiva-
lence between positive and negative interactions. The Qst of 4. Conclusions
carbon dioxide augments from ~14 kJ/mole at 0.36 mole/kg
to ~33 kJ/mole at 2.81 mole/kg. Further, the Qst of methane ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-8 were produced by a
rose from ~16 kJ/mole at a loading of 0.10 mole/kg up to microwave-irradiation technique. The adsorption of CH4,
~31 kJ/mole at 1.2 mole/kg. N2, and CO2 on ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-8 was
6 Journal of Nanomaterials

1.0 50
-8
ZIF F- 8
o- -ZI
55 °C
/C Co 40
0.8 Zn 45 °C
-8 35 °C
ZIF
30

kN2 × 104
(sec–1)
(mole/kg)

0.6 25 °C
nN2

20
0.4
10
0.2
0
0 1 2 3 4 5 6
0.0
0.0 0.2 0.4 0.6 0.8 1.0 1/P (MPa–1)
P (MPa) (a)
(a) 100
°C
55
F-8 80
2.0 o-ZI
F-8
Zn
/C -ZI 45 °
C
Co

kCH4 × 104
60 C
35 °

(sec–1)
1.5 -8
ZIF
(mole/kg)

40
nCH4

25 °C
1.0
20

0.5
0
1 2 3 4 5 6
0.0 1/P (MPa–1)
0.0 0.2 0.4 0.6 0.8 1.0 (b)
P (MPa)
12
(b)
°C
10 55
7
F-8
6 ZI 8
8
IF-
kCO2 × 104
(sec–1)

-Z
/ Co 6
5 Zn C 35 °C
45 °
-8
ZIF
(mole/kg)

4 4
Co- 25 °C
nCO2

3 2

2 0
0 2 4 6 8 10 12
1 1/P (MPa–1)

0 (c)
0.0 0.2 0.4 0.6 0.8 1.0
P (MPa)
Figure 5: k-values for adsorbing (a) nitrogen, (b) methane, and (c)
carbon dioxide gases on ZIF-8 samples at diverse temperatures.
(c) Symbols and lines indicate, respectively, estimated data and linear
regression.
Figure 4: Influence of ZIF types (ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-
8) on their adsorption of (a) nitrogen, (b) methane, and (c) carbon
dioxide at the temperature of 25°C. The symbols indicate
measured data and the lines indicate DSL fitting.
adsorb carbon dioxide. The order of adsorption quantities
of nitrogen and methane gases on different ZIFs is Zn/Co‐
ZIF‐8 > Co‐ZIF‐8 > ZIF‐8. Moreover, the order of adsorp-
studied at a range of temperatures (25 to 55°C) and pressures tion capacities of carbon dioxide gas onto different ZIFs is
(~0 to ~1 MPa). The dual-site Langmuir (DSL) model was ZIF‐8 > Zn/Co‐ZIF‐8 > Co‐ZIF‐8. The overall mass transfer
used to describe experimental adsorption equilibria at differ- coefficients have been evaluated to indicate the rates of
ent pressures and temperatures. Zn/Co-ZIF-8 displays the adsorbing CH4, N2, and CO2 gases on various ZIFs. Overall,
largest capacity to adsorb nitrogen and methane at various the mass transfer coefficients were augmented when raising
temperatures, while ZIF-8 shows the largest capacity to the temperature or reducing the pressure. Furthermore, the
Journal of Nanomaterials 7

210 40
55 °C 35
200
30 °C
190 55
45 °C 25

kN2 × 104
180

(sec–1)
kN2 × 104

°C
(sec–1)

20
170 25
35 °C 15 °C
160 35
10
25 °C
150 5
140 0
0 2 4 6 8
130
0.5 1.0 1.5 2.0 2.5 3.0 3.5 4.0 1/P (MPa–1)
1/P (MPa–1) (a)
(a) 60
60 °C
50 55
55 °C °C
45 35 °C
50 40
45 °C

kCH4 × 104
(sec–1)
35 °C
40 30 C
25 °
kCH4 × 104
(sec–1)

25 °C 20
30

10
20
0
10 0 2 4 6 8 10 12
1/P (MPa–1)
0
0 1 2 3 4 5 6 (b)
1/P (MPa–1) 25
(b)
20
10 °C
55
kCO2 × 104

15 °C
(sec–1)

8 55 °C 25
45 °C
35 °C 10 °C
6 35
kCO2 × 104

25 °C °C
(sec–1)

5 45
4
0
0 2 4 6 8
2
1/P (MPa–1)
(c)
0
0 2 4 6 8 10 12 Figure 7: k-values for adsorbing (a) nitrogen, (b) methane, and (c)
1/P (MPa–1) carbon dioxide gases on Zn/Co-ZIF-8 samples at diverse
temperatures. Symbols and lines denote, respectively, estimated
(c)
data and linear regression.
Figure 6: k-values for adsorbing (a) nitrogen, (b) methane, and (c)
carbon dioxide gases on Co-ZIF-8 samples at diverse temperatures.
Symbols and lines denote, respectively, estimated data and linear ally, the isosteric heats of adsorbing CH4, N2, and CO2 gases
regression. on ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-8 were estimated.
Across study findings, it has been noticed that the isosteric
heats vary in accordance with the ZIF type utilized, but they
adsorption of CO2 gas was slowest on all ZIFs. On the other were mostly highest for CH4 and lowest for N2.
hand, the adsorption of CH4 gas was the fastest on ZIF-8 and
Co/Zn-ZIF-8, while nitrogen adsorption was fastest on Co- Data Availability
ZIF-8. These disparities, which are due to the existence of
cobalt into the matrix of ZIFs, can be utilized to boost the The data used to support the findings of this study are
kinetic separations of CH4, N2, and CO2 mixtures. Addition- included within the article.
8 Journal of Nanomaterials

180 250
-8
Co-ZIF
160 IF-8
200 Co-Z
140
120
150

kN2 × 104
kN2 × 104

100

(sec–1)
(sec–1)

80
100
60 -8
Zn/Co-ZIF IF-8
40 50 Zn/Co-Z
20 ZIF-8
ZIF-8
0 0
0 1 2 3 4 5 6 0 1 2 3 4 5 6
1/P (MPa–1) 1/P (MPa–1)
(a) (b)
40 70

-8
35 60

ZIF
8

8
IF-
8
-8

IF-
IF-

30 -Z 50
ZIF

-Z
Co
-Z

/ F-8

Co
Zn
Co

-ZI
kCH4 × 104

25 kCH4 × 104 40 o
(sec–1)

(sec–1) Z n/C
20 30

15 20

10 10

5 0
0 2 4 6 8 10 12 0 2 4 6 8 10 12
1/P (MPa–1) 1/P (MPa–1)
(c) (d)
20 25
18 8
F-
8

20
F-

ZI

16
ZI

o-
/C
o-

14
/C

Zn

15
Zn

12
kCO2 × 104

kCO2 × 104
(sec–1)

(sec–1)

10 -8
ZIF 10 ZIF-8
8
6
-8 5
4 Co-ZIF
Co-ZIF-8
2 0
0

0 2 4 6 8 10 12 0 2 4 6 8 10 12
1/P (MPa–1) 1/P (MPa–1)
(e) (f)

Figure 8: Impact of ZIF types (i.e., ZIF-8, Co-ZIF-8, and Zn/Co-ZIF-8) on k for (a, b) nitrogen, (c, d) methane, and (e, f) carbon dioxide at
25°C (a, c, e) and 55°C (b, d, f). Symbols and lines denote to estimated data and linear regression, correspondingly.

Disclosure role in the design, execution, interpretation, or writing

of the study.
Ahmed Awadallah-F is on leave from the Radiation Research
of Polymer Department, National Centre for Radiation Conflicts of Interest
Research and Technology, Atomic Energy Authority, P.O.
Box 29, Nasr City, Cairo, Egypt. The sponsors had no The authors declare no conflict of interest.
Journal of Nanomaterials 9

35 12.0
N2 -8
30 CH4 ZIF
11.5

25 CO2 11.0
(kJ/mole)

(kJ/mole)
8
Qst

20 IF-
-Z

Qst
10.5
/Co

8
15 Zn

IF-
-Z
10.0
N2

Co
10 ZIF-8
9.5
5
0.0 0.5 1.0 1.5 2.0 2.5 3.0
9.0
Loading (mole/kg)
0.0 0.2 0.4 0.6 0.8
(a) Loading (mole/kg)
45 (a)
40 CH4
45
35 CH4 -8
40 Co-ZIF
CO2
30
(kJ/mole)

35
Qst

25 -8
ZIF

(kJ/mole)
20 30
15 Qst 8
25
-Z IF-
10 N2 Co-ZIF-8 /Co
20 Zn
5
0.0 0.5 1.0 1.5 2.0 2.5 3.0
15
Loading (mole/kg)
(b) 10
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6
30 Loading (mole/kg)
CH4
(b)
25
35

8
CO2 CO2

ZIF-
(kJ/mole)

20
F-8
Qst

30 -ZI
15 Co

25
(kJ/mole)

10 N2 Zn/Co-ZIF-8
Qst

Zn/Co-ZIF-8
20
5
0 1 2 3 4 5
Loading (mole/kg) 15
(c)
10
Figure 9: Qst of adsorption of nitrogen, methane, and carbon 0 1 2 3 4 5
dioxide gases upon (a) ZIF-8, (b) Co-ZIF-8, and (c) Zn/Co-ZIF-8. Loading (mole/kg)
(c)
Acknowledgments
Figure 10: The Qst of adsorption for (a) N2, (b) CH4, and (c) CO2
This publication was made possible by the NPRP awards on various ZIFs.
(NPRP 08-014-2-003 and NPRP-8-001-2-001) from the
Qatar National Research Fund (a member of The Qatar
Foundation). H.-K.J. acknowledges support from the Supplementary Materials
National Science Foundation (CMMI-1561897). The state-
ments made herein are solely the responsibility of the S1: regression of mass transfer coefficients. Table S1 sum-
authors. Technical support from the Department of Chemi- marizes the regression of mass transfer coefficients for the
cal Engineering, the Central Laboratory Unit (CLU), and adsorption of nitrogen, methane, and carbon dioxide gases
the Gas Processing Centre (GPC) at Qatar University is also onto different adsorbents of ZIFs: ZIF, Co-ZIF-8, and
acknowledged. The publication of this article was funded by Zn/Co-ZIF-8. Table S1: regression and the coefficients of
the Qatar National Library. determination (R2 ) for the overall mass transfer coefficient
10 Journal of Nanomaterials

104 × k (s-1) against 1/P (MPa-1) for adsorption of methane, ammonium bromide)),” Energy, vol. 106, pp. 546–553,
nitrogen, and carbon dioxide gases on ZIF-8, Co-ZIF-8, 2016.
and Zn/Co-ZIF-8 adsorbents at different temperatures. [14] A. Dugstad, M. Halseid, and B. Morland, “Testing of
(Supplementary Materials) CO2 specifications with respect to corrosion and bulk
phase reactions,” Energy Procedia, vol. 63, pp. 2547–
References 2556, 2014.
[15] K. Dalane, H. F. Svendsen, M. Hillestad, and L. Deng, “Mem-
[1] J. Duan, Y. Pan, G. Liu, and W. Jin, “Metal-organic framework brane contactor for subsea natural gas dehydration: model
adsorbents and membranes for separation applications,” Cur- development and sensitivity study,” Journal of Membrane Sci-
rent Opinion in Chemical Engineering, vol. 20, pp. 122–131, ence, vol. 556, pp. 263–276, 2018.
2018. [16] A. Kumar and K. A. Subramanian, “Control of greenhouse
[2] A. Awadallah-F, F. Hillman, S. A. Al-Muhtaseb, and H. K. gas emissions (CO2, CH4 and N2O) of a biodiesel (B100)
Jeong, “Influence of doped metal center on morphology and fueled automotive diesel engine using increased compres-
pore structure of ZIF-8,” Material Research Society Communi- sion ratio,” Applied Thermal Engineering, vol. 127, pp. 95–
cations, vol. 9, no. 01, pp. 288–291, 2019. 105, 2017.
[3] W. Li, Y. Zhang, Q. Li, and G. Zhang, “Metal−organic frame- [17] S. Rani, B. K. Prusty, and S. K. Pal, “Adsorption kinetics and
work composite membranes: synthesis and separation applica- diffusion modeling of CH4 and CO2 in Indian shales,” Fuel,
tions,” Chemical Engineering Science, vol. 135, pp. 232–257, vol. 216, pp. 61–70, 2018.
2015. [18] X. He, T. J. Kim, and M. B. Hägg, “Hybrid fixed-site-carrier
[4] L. S. Lai, Y. F. Yeong, K. K. Lau, and A. M. Shariff, “Effect membranes for CO2 removal from high pressure natural
of synthesis parameters on the formation of ZIF-8 under gas: membrane optimization and process condition investi-
microwave-assisted solvothermal,” Procedia engineering, gation,” Journal of Membrane Science, vol. 470, pp. 266–
vol. 148, pp. 35–42, 2016. 274, 2014.
[5] V. V. Butova, A. P. Budnik, E. A. Bulanova, and A. V. Soldatov, [19] S. K. Das, X. Wang, M. M. Ostwal, and Z. Lai, “A highly
“New microwave-assisted synthesis of ZIF-8,” Mendeleev stable microporous covalent imine network adsorbent for
Communications, vol. 26, no. 1, pp. 43-44, 2016. natural gas upgrading and flue gas CO2 capture,” Separa-
[6] A. A. Oladipo, “Microwave-assisted synthesis of high- tion and Purification Technology, vol. 170, pp. 68–77,
performance polymer-based nanoadsorbents for pollution 2016.
control,” in New polymer nanocomposites for environmental [20] B. Wu, X. Zhang, Y. Xu, D. Bao, and S. Zhang, “Assess-
remediation, C. M. Hussain and A. K. Mishra, Eds., pp. 337– ment of the energy consumption of the biogas upgrading
359, Elsevier Inc, Amsterdam, 2018. process with pressure swing adsorption using novel adsor-
[7] A. Mirzaei and G. Neri, “Microwave-assisted synthesis bents,” Journal of Cleaner Production, vol. 101, pp. 251–
of metal oxide nanostructures for gas sensing application: a 261, 2015.
review,” Sensors and Actuators B: Chemical, vol. 237, [21] S. Yu, J. Bo, and L. Fengjuan, “Competitive adsorption of
pp. 749–775, 2016. CO2/N2/CH4 onto coal vitrinite macromolecular: effects of
[8] H. Zhang, C. Duan, F. Li, X. Yan, and H. Xi, “Green and rapid electrostatic interactions and oxygen functionalities,” Fuel,
synthesis of hierarchical porous zeolitic imidazolate frame- vol. 235, pp. 23–38, 2019.
works for enhanced CO2 capture,” Inorganica Chimica Acta, [22] L. Chong and E. M. Myshakin, “Molecular simulations of
vol. 482, pp. 358–363, 2018. competitive adsorption of carbon dioxide - methane mixture
[9] A. Awadallah-F, F. Hillman, S. A. Al-Muhtaseb, and on illitic clay surfaces,” Fluid Phase Equilibria, vol. 472,
H.-K. Jeong, “On the nanogate-opening pressures of copper- pp. 185–195, 2018.
doped zeolitic imidazolate framework ZIF-8 for the adsorp- [23] F. Hillman, J. M. Zimmerman, S. M. Paek, M. R. A. Hamid,
tion of propane, propylene, isobutane, and N-butane,” Jour- W. T. Lim, and H. K. Jeong, “Rapid microwave-assisted syn-
nal of Materials Science, vol. 54, no. 7, pp. 5513–5527, thesis of hybrid zeolitic–imidazolate frameworks with mixed
2019. metals and mixed linkers,” Journal of Materials Chemistry A,
[10] J. Peng, X. Sun, Y. Li et al., “Controllable growth of ZIF-8 vol. 5, no. 13, pp. 6090–6099, 2017.
layers with nanometer-level precision on SiO2 nano- [24] A. Awadallah-F, S. A. al-Muhtaseb, and H. K. Jeong, “Selective
powders via liquid phase epitaxy stepwise growth approach,” adsorption of carbon dioxide, methane and nitrogen using
Microporous and Mesoporous Materials, vol. 268, pp. 268– resorcinol-formaldehyde-xerogel activated carbon,” Adsorp-
275, 2018. tion, vol. 23, no. 7-8, pp. 933–944, 2017.
[11] J. H. ter Horst, C. Schmidt, and J. Ulrich, “Fundamentals of [25] A. Awadallah-F and S. A. Al-Muhtaseb, “Carbon dioxide
industrial crystallization,” in Handbook of Crystal Growth, sequestration and methane removal from exhaust gases using
pp. 1317–1349, Bulk Crystal Growth Handbook of Crystal resorcinol–formaldehyde activated carbon xerogel,” Adsorp-
Growth, 2015. tion, vol. 19, no. 5, pp. 967–977, 2013.
[12] X. Wang, B. Yuan, X. Zhou et al., “Novel glucose-based [26] H. Li, J. Kang, F. Zhou, Z. Qiang, and G. Li, “Adsorption heat
adsorbents (Glc-Cs) with high CO2 capacity and excellent features of coalbed methane based on microcalorimeter,” Jour-
CO2/CH4/N2 adsorption selectivity,” Chemical Engineering nal of Loss Prevention in the Process Industries, vol. 55,
Journal, vol. 327, pp. 51–59, 2017. pp. 437–449, 2018.
[13] M. Yang, W. Jing, J. Zhao, Z. Ling, and Y. Song, “Promotion [27] D. Leinekugel-le-Cocq, M. Tayakout-Fayolle, Y. Le Gorrec,
of hydrate-based CO2 capture from flue gas by additive and C. Jallut, “A double linear driving force approximation
mixtures (THF (tetrahydrofuran) + TBAB (tetra-n-butyl for non-isothermal mass transfer modeling through bi-
Journal of Nanomaterials 11

disperse adsorbents,” Chemical Engineering Science, vol. 62,

no. 15, pp. 4040–4053, 2007.
[28] M. Li and X. Liu, “The least squares based iterative algorithms
for parameter estimation of a bilinear system with autoregres-
sive noise using the data filtering technique,” Signal Process,
vol. 147, pp. 23–34, 2018.
[29] V. S. Mane and P. V. V. Babu, “Studies on the adsorption of
brilliant green dye from aqueous solution onto low-cost NaOH
treated saw dust,” Desalination, vol. 273, no. 2-3, pp. 321–329,
2011.
[30] A. Awadallah-F, F. Hillman, S. A. al-Muhtaseb, and H. K.
Jeong, “Adsorption equilibrium and kinetics of nitrogen,
methane and carbon dioxide gases onto ZIF-8, Cu10%/ZIF-8,
and Cu30%/ZIF-8,” Industrial & Engineering Chemistry
Research, vol. 58, no. 16, pp. 6653–6661, 2019.
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