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Article history:
Received 7 March 2014
Received in revised form 8 April 2014
Accepted 10 April 2014
Available online 24 April 2014
Keywords:
Adsorptive denitrogenation
Cuprous ion
Metalorganic framework
p-Complexation
a b s t r a c t
CuCl impregnated MIL-100(Cr) was prepared with a facile method and then utilized for the adsorptive
denitrogenation of model fossil fuels. CuCl was produced from CuCl2 solution at ambient temperature
and pressure by reduction of CuCl2 using sodium sulte as a mild reducing agent. Although the porosity of the adsorbent was reduced after impregnation, the adsorption of nitrogen-containing compounds (NCCs) increased. However, the adsorption of NCCs over CuCl2/MIL-100(Cr), which was
produced in a similar manner but in the absence of Na2SO3, was decreased as a result of the reduced
porosity. The maximum adsorption capacities of CuCl/MIL-100(Cr) as compared to pristine MIL100(Cr) for quinoline (QUI) and indole (IND) were improved by 9% and 15%, respectively, which
may be attributed to the p-complexation effect of the Cu+ sites of CuCl.
2014 Elsevier B.V. All rights reserved.
1. Introduction
With the continuous increase in the worldwide population and
consumption of energy, the optimized utilization of energy and
stable environmental parameters are the primary concerns of the
human race in this century. Because of the scarcity of regular
sources, new and unusual sources of fossil fuels need to be
exploited in the upcoming decades for the high amount of energy
required by society. Therefore, fossil fuels containing high amounts
of contaminants, particularly sulfur- and nitrogen-containing
compounds (SCCs and NCCs), need to be utilized [14]. Acid rain
Corresponding author. Fax: +82 53 950 6330.
E-mail address: sung@knu.ac.kr (S.H. Jhung).
http://dx.doi.org/10.1016/j.cej.2014.04.044
1385-8947/ 2014 Elsevier B.V. All rights reserved.
36
2. Experimental
2.1. Chemicals and synthesis of adsorbents
p-Xylene and n-octane were purchased from Junsei chemical
company. Hydrochloric acid (HCl, 35%) and hydrouoric acid (HF,
48.0%) were obtained from OCI Company Ltd. Benzothiophene
(BT), quinoline (QUI), indole (IND), trimesic acid (H3BTC) and
metallic chromium (Cr) were obtained from SigmaAldrich Co.
All the chemicals in this study were used without further
purication. The syntheses were carried out solvothermally under
microwave irradiation [67]. Detailed synthetic procedures for
MIL-100(Cr) are listed below. Metallic chromium, HF, H3BTC and
H2O were mixed at a molar ratio of 1:2:0.67:265. The mixture
was then transferred to a Teon-lined autoclave and heated in a
microwave oven (Mars-5, CEM) for 2 h at 220 C. After synthesis,
the MOF was ltered, washed, and puried by stirring at rst with
water then with ethanol and nally dried in a drying oven at
100 C.
An exact amount (0.1 g) of MIL-100(Cr) was transferred to glass
vials containing 0.5, 1.0 or 2.0 mL of a 0.2 M CuCl2 aqueous solution
and stirred magnetically for 30 min at room temperature. An equal
amount (0.5, 1.0, or 2.0 mL) of a 0.1 M Na2SO3 aqueous solution
was then added dropwise while stirring to the CuCl2 solution containing MIL-100(Cr). The resulting mixture was allowed to stir for
30 min and then 1 mL of a sulfurous acid (H2SO3) solution was
added. The sulfurous acid solution was prepared by mixing
25.0 mL of 0.25 mM Na2SO3 and 3.0 mL of 0.2 M HCl. The mixture
was then ltered and washed with sulfurous acid solution. Finally,
the wet solids were transferred to a vacuum oven (to avoid air contact) and dried overnight at 100 C. The adsorbents were named
CuCl (x)/MIL-100(Cr) where x corresponds to the volume of the
CuCl2 (or Na2SO3) solution used in the preparation.
2.2. Characterization
The X-ray powder diffraction patterns were obtained using a
diffractometer D2 Phaser (Bruker, with Cu Ka radiation). The nitrogen adsorption experiments of the adsorbents were carried out at
196 C with a surface area and porosity analyzer (Micromeritics,
Tristar II 3020) after evacuation at 150 C for 12 h. XPS analyses
were carried out using a Quantera SXM X-ray photoelectron
spectrometer (ULVAC-PHI) equipped with a dual beam charge
neutralizer.
37
C i C f V
qt
m
(a)
Intensity (a.u.)
MIL-100 (Cr)
CuCl (1.0)/MIl-100 (Cr)
CuCl
CuCl2
15
30
Ce Ce
1
qe Q o Q o b
where Ce is the equilibrium concentration of the adsorbate (mg/L),
qe the amount adsorbed at equilibrium (measured similarly as qt,
mg/g), Qo the Langmuir constant (maximum adsorption capacity,
mg/g) and b is the Langmuir constant (L/mg).
Therefore, the maximum adsorption capacity Qo can be obtained
from the reciprocal of the slope of a plot of Ce/qe against Ce.
3. Results and discussion
3.1. Textural properties and characteristics of CuCl/MIL-100(Cr)
Fig. 1(a) displays the XRD patterns of MIL-100(Cr) and CuCl
(1.0)/MIL-100(Cr), along with the XRD patterns of CuCl and CuCl2,
which exhibited a similar structure of the virgin and impregnated
(b)
Cu
Cu
Intensity (a.u)
45
960
2 theta (deg)
940
BE (eV)
Fig. 1. (a) XRD patterns and (b) nitrogen XPS spectra of MIL-100(Cr) and CuCl/MIL-100(Cr). Pure CuCl and CuCl2 are also included in both gures for reference.
600
(b)
6
450
300
MIL-100 (Cr)
CuCl (1.0)/MIl-100 (Cr)
dV/dlog (D)
(a)
MIL-100 (Cr)
CuCl (1.0)/MIl-100 (Cr)
4
150
0
0.0
0.2
0.4
0.6
0.8
1.0
15
30
45
Pore Diameter ()
Fig. 2. (a) N2 adsorption isotherms and (b) pore size distributions of MIL-100(Cr) and CuCl (1.0)/MIL-100(Cr).
60
38
Table 1
Textural properties of MIL-100(Cr) and CuCl (1.0)/MIL-100(Cr) and Langmuir parameters of QUI and IND adsorption over the two adsorbents.
Adsorbent
Adsorbate
Qo (mg/g)
b-Value (L/mg)
MIL-100(Cr)
1510
0.985
0.402
CuCl (1.0)/MIL-100(Cr)
1310
0.635
0.399
QUI
IND
QUI
IND
420
149
457
171
7.06 103
3.14 103
1.03 102
3.22 103
30
250
(a)
(b)
MIL-100 (Cr)
CuCl (0.5)/MIl-100 (Cr)
CuCl (1.0)/MIl-100 (Cr)
CuCl (2.0)/MIl-100 (Cr)
qt (mg/g)
qt (mg/g)
20
200
150
100
10
50
0
0
Time (hr)
Time (hr)
60
(c)
qt (mg/g)
45
30
15
0
0
Time (hr)
Fig. 3. Adsorption of (a) BT, (b) QUI and (c) IND with time over MIL-100(Cr) and CuCl/MIL-100(Cr)s.
materials. CuCl shows peaks at angles 24.3 and 43.1 while CuCl2
shows peaks mainly at 16, 26.3, 31.2, 38.5 and 49.2. No
diffraction patterns for CuCl2 were observed because of the reduction of CuCl2 into CuCl or well-dispersed CuCl2. The absence of CuCl
diffraction patterns (the presence of CuCl was conrmed by XPS,
see below) indicated that a uniform, well-dispersed, and small
amount of CuCl was present within the pores of MIL-100(Cr). The
nitrogen adsorption analyses also supported the XRD data because
there was small effect of impregnation procedure on the surface
area or pore volume of the MOF, as shown in Fig. 2. Table 1 and
Fig. 2 show that the surface area and the pore volume of CuCl
(1.0)/MIL-100(Cr) were slightly smaller than those of the virgin
MIL-100(Cr). Moreover, the loading procedure affected the pore
structure of the MOF a bit because the pore volume (particularly
the large pore) decreased for the loaded MIL-100(Cr). The impregnated salt was in the Cu+ state which was conrmed by the XPS
analysis (Fig. 1(b)). The XPS patterns of impregnated adsorbent
was compared to those of standard CuCl and CuCl2 [70] and only
the peaks corresponding to CuCl were found in the impregnated
adsorbent.
39
250
60
(a)
(b)
200
qt (mg/g)
qt (mg/g)
40
150
100
0.5 h
2h
4h
6h
50
20
0
0.0
0.5
1.0
1.5
2.0
0.0
0.5
1.0
1.5
2.0
Fig. 4. Adsorbed amounts of (a) QUI and (b) IND over CuCl/MIL-100(Cr)s having different amount of CuCl in various adsorption times.
450
150
(a)
(b)
300
qe (mg/g)
qe (mg/g)
100
MIL-100 (Cr)
CuCl (1.0)/MIl-100 (Cr)
150
50
0
0
300
600
900
1200
300
600
Ce (ppm)
900
1200
Ce (ppm)
Fig. 5. Adsorption isotherms for (a) QUI and (b) IND over MIL-100(Cr) and CuCl (1.0)/MIL-100(Cr).
3.0
(b)
(a)
9
2.5
R = 0.984
R = 0.995
1.5
ce/qe
ce/qe
2.0
R = 0.997
6
2
R = 0.995
1.0
3
0.5
MIL-100 (Cr)
CuCl (1.0)/MIl-100 (Cr)
0.0
0
0
400
800
1200
Ce (ppm)
400
800
1200
Ce (ppm)
Fig. 6. Langmuir plots obtained from adsorption isotherms for (a) QUI and (b) IND over MIL-100(Cr) and CuCl (1.0)/MIL-100(Cr). Correlation factors (R2) are shown alongside
the respective plots.
pore sizes (1.5 nm, as shown in Fig. 2) of the adsorbents. However, the overall kinetics of the adsorption was remarkably fast
which conrms the favorable adsorption of NCCs over the adsorbents. Fig. 4 displays the relationship between the adsorbed
amount of NCCs and the CuCl2 content (used in impregnation),
which was adopted from Fig. 3. The adsorbed amounts of both
40
300
75
(a)
(b)
1 hr
6 hr
225
qt (mg/g)
qt (mg/g)
50
150
25
75
0
MIL-100 (Cr)
MIL-100 (Cr)
Adsorbent
Adsorbent
Fig. 7. Comparison of adsorptions of (a) QUI and (b) IND over MIL-100(Cr), CuCl (1.0)/MIL-100(Cr) and CuCl2 (1.0)/MIL-100(Cr).
2
or 2Cu2 SO2
3 H2 O ! 2Cu SO4 2H
The +1 oxidation state of the loaded copper species was the active
component for ADN which was demonstrated for the favorable
interaction between Cu+ and SCCs [33] or NCCs [43] through
p-complex formation.
In order to conrm the effects of p-complexation in the adsorption procedure, an adsorption experiment was also carried out
using the CuCl2 loaded onto MIL-100(Cr) without reducing the
CuCl2 with Na2SO3. In this case a combined solution of BT, QUI,
and IND was used under the same conditions as the previous
experiments. Fig. 7 shows the adsorption results of QUI and IND
over the virgin MIL-100(Cr), CuCl (1.0)/MIL-100(Cr), and CuCl2
(1.0)/MIL-100(Cr). It was found that the adsorbed amounts of
QUI and IND followed the trend of CuCl (1.0)/MIL-100(Cr) > virgin
MIL-100(Cr) > and CuCl2 (1.0)/MIL-100(Cr). The minimal adsorption of QUI and IND over CuCl2 (1.0)/MIL-100(Cr) was likely a result
of the reduced porosity and the lack of interactions between CuCl2
and the adsorbates. CuCl2 is known to not exhibit p-complexion
which makes CuCl2 loaded MIL-100(Cr) less capable of adsorption
compared to CuCl loaded MIL-100(Cr) or the virgin MIL-100(Cr).
4. Conclusion
The impregnation of the Cu+ sites onto a MOF (MIL-100(Cr))
was carried out for the rst time by reducing CuCl2 salt with
sodium sulte, which is a very mild, facile and energy efcient procedure. The impregnated material showed an improved adsorption
capacity of QUI and IND relative to the virgin MIL-100(Cr) as a
result of p-complexation. The adsorption of QUI and IND in this
41
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