11220 Langmuir 2005, 21, 11220-11225

Adsorption of Nitrogen, Oxygen, and Argon in

Cobalt(II)-Exchanged Zeolite X
Jince Sebastian, Sunil A. Peter, and Raksh V. Jasra*
Silicates and Catalysis Discipline, Central Salt and Marine Chemicals Research Institute,
G. B. Marg, Bhavnagar-364 002, India
Received June 3, 2005. In Final Form: September 16, 2005

Adsorption of nitrogen, oxygen, and argon on cobalt(II)-exchanged zeolite X at 288.2 and 303.0 K was
studied. The nitrogen and oxygen adsorption capacities increase upon cobalt ion exchange up to 71%,
beyond which it shows a decreasing trend because of the partial degradation of the zeolite structure during
the cation exchange and high-temperature vacuum dehydration processes. The magnitude of the increase
in the adsorption capacities for nitrogen is much higher than that of oxygen. The nitrogen/oxygen as well
as nitrogen/argon selectivities in the low-pressure region increase with an increase in cobalt exchange.
Marginal oxygen selectivity over argon is observed for zeolite samples with higher cobalt exchange. The
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heats of adsorption values for nitrogen and oxygen increase and that for argon remain unaffected by cobalt
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exchange in zeolite X. The very high nitrogen adsorption capacity, selectivity, and heat of adsorption in
the low-pressure region for cobalt-exchanged zeolite X compared to the parent sodium form of the zeolite
show stronger interaction between nitrogen molecules with the extraframework cobalt cations of the
zeolite. This stronger interaction has been explained in terms of the π-complexation between nitrogen
molecules and cobalt cations of the zeolites, as confirmed by diffuse reflectance infrared Fourier transform
spectroscopy, wherein the NtN stretching frequency at 2099 cm-1 is observed for N2 molecules adsorbed
in NaCoX.

1. Introduction in terms of the electron transfer by both σ-donation from

Zeolites, crystalline inorganic solids with pore diameters
in the range of 1-10 Å, are of immense interest in gas and
chemical industries as molecular sieve adsorbents for
purification and separation.1 The extraframework cations
invariably present in zeolites play a significant role in
determining their adsorptive properties.2 Separation of
nitrogen and oxygen from air is one of the major adsorptive
separation processes used in many commercial situa-
tions.3-5 However, nitrogen and oxygen adsorption studies
in zeolites are largely confined to alkali and alkaline earth
cation exchanged zeolites,7-10 that too for zeolites A and
X, with limited studies reported for transition metal ion
exchanged zeolites.11,12 This is despite the fact that
transition metal ions, due to the presence of the d-shell,
can coordinate to adsorbate molecules and could show
different adsorption behavior compared to filled-shell
cations.11-16 For example, silver cations in zeolites are
reported to interact strongly with the adsorbed nitrogen
molecules.11-14 These strong interactions were explained
* Corresponding author. Tel.: +91 278 2471793. Fax: +91 278
2567562. E-mail: rvjasra@csmcri.org.
(1) Yang, R. T. Adsorbents: Fundamentals and Applications; Wiley-
Interscience: New York, 2003.
(2) Breck, W. Zeolites Molecular Sieves: structure, chemistry and
use; Wiley-Interscience: New York, 1974.
(3) Jasra, R. V.; Choudary, N. V.; and Bhat, S. G. T. Sep. Sci. Technol.
1991, 26, 885-930.
(4) Yang, R. T. Gas Separation by Adsorption Process; Imperial College
Press: London, 1997.
(5) Ruthven, D. M.; Farooq, S.; Knaebel, K. S. Pressure Swing
Adsorption; Wiley-VCH: New York, 1994.
(6) Jasra, R. V.; Choudary, N. V.; Bhat, S. G. T. Ind. Eng. Chem. Res.
1996, 35, 4221-4229.
(7) Chao, C. C. U.S. Patent 4859217, 1989.
(8) Chao, C. C.; Sherman, J. D.; Mullhaupt, J. T., Bolinger, C. M.
U.S. Patent 5174979, 1992.
(9) Coe, C. G.; Kirner, J. F.; Pierantozzi, R.; White, T. R. U.S. Patent
5152813, 1992.
(10) Rege S. U.; Yang, R. T. Ind. Eng. Chem. Res. 1997, 36, 5358-
5365.
(11) Sebastian, J.; Jasra, R. V. Chem. Commun. 2003, 268-269.
(12) Sebastian J.; Jasra, R. V. U.S. Patent No. 6572838, PCT Patent
WO 03/080236 A1, UK Patent 2 386 889 A, 2003.
the bonding π2p molecular orbital of N2 molecules to the
5s orbital of Ag+ ions and d-π2p* back-donation from the
completely occupied 4d orbital of Ag+ ions to the unoc-
cupied π2p* antibonding molecular orbital of the N2
molecule. Similarly, due to the presence of empty f orbitals,
cerium-exchanged zeolite X shows oxygen selectivity over
nitrogen and argon in the low-pressure region.15,16 How-
ever, scarce adsorption data on transition metal ion
exchanged zeolites could be due to the difficulty in
exchanging the transition metal ions into zeolites and
retaining the zeolite structure, particularly at higher
cation exchange. The present study reports on the
adsorption of nitrogen, oxygen, and argon in cobalt-
exchanged zeolite X with different exchange level. An
attempt is made to correlate the adsorption data with the
locations of the cations inside the zeolite and its coordina-
tion with the framework oxygen atoms.
2. Materials and Methods
2.1. Materials. Zeolite X (with chemical composition Na88-
Al88Si104O384‚220H2O) (Zeolites and Allied Products, Bombay,
India) and cobalt nitrate (S. D. Fine Chemicals Ltd., Bombay,
India) were used as the starting materials for the adsorbent
preparation. Oxygen (99.99%), nitrogen (99.99%), argon (99.99%),
and helium (99.99%) (Hydrogas India Pvt. Ltd., Bombay, India)
were used for the adsorption isotherm measurements.
2.2. Cation Ion Exchange. The cobalt cations were introduced
into the highly crystalline sodium form of zeolite by conventional
cation exchange from aqueous solution. Typically, the zeolite
was refluxed with a 0.05 M aqueous solution of cobalt nitrate
with a solid/liquid ratio 1:80 at 353K for 4 h. The residue was
filtered, washed with hot distilled water, until the washings were
free from ions, and dried in air at room temperature. Zeolite
(13) Chen, N.; Yang, R. T. Ind. Eng. Chem. Res. 1996, 35, 4020-4027.
(14) Hutson, N. D.; Reisner, D. A.; Yang, R. T.; Toby, B. H. Chem.
Matter 2000, 12, 3020-3031.
(15) Jasra, R. V.; Chudasama C. D. U. S. Pat. Pub. No. 2005/0090380
A1, 2005.
(16) Jayaraman, A.; Yang, R. T.; Bhat, S. G. T.; Choudary, N. V.
Adsorption 2002, 8, 271-278.

10.1021/la051460e CCC: $30.25 © 2005 American Chemical Society

Published on Web 10/22/2005
Adsorption of N, O, and Ar in NaCoX
Table 1. Chemical Composition and Structural and Textural Properties of Cobalt(II)-Exchanged Zeolites
unit cell % unit cell
formula crystal-
adsorbent (on dry basis) linity
NaX Na88Al88Si104O384 100
NaCoX 46 Co20.5Na47Al88Si104O384 84
NaCoX 71 Co31.5Na25Al88Si104O384 80
NaCoX 88 Co38.75Na10.5Al88Si104O384 79
NaCoX 93 Co41Na6Al88Si104O384 72
samples having different degrees of cation exchange were
prepared by subjecting repeated ion exchange into the zeolites.
The extent of the cobalt ion exchange on different zeolite X
samples was determined by complexometric titration with EDTA
using murexide indicator. The number in the sample name
indicates the percentage of ion exchange (e.g. NaCoX 46 means
46% of Na+ ions are replaced with Co2+ ions), as shown in Table
1. The chemical compositions of various cobalt-exchanged zeolite
X samples are also given in Table 1.
2.3. X-ray Powder Diffraction. X-ray powder diffraction
studies at ambient temperature were carried out using a PHILIPS
X’pert MPD system in the 2θ range of 5-65° using Cu KR1 (λ )
1.540 56 Å). The diffraction patterns of the zeolite samples show
the reflections in the range 5-35° typical of zeolites. Percentage
crystallinity of the cobalt ion exchanged zeolites was determined
from the X-ray diffraction pattern by summation of the intensity
of 10 major peaks at 2θ values 6.1, 10.0, 15.5, 20.1, 23.4, 26.7,
29.3, 30.5, 31.0, and 32.1. The sodium form of the zeolite was
considered as a reference sample for these calculations.
2.4. Activation and Isotherm Measurements. Prior to
adsorption measurements, the samples were initially dried at
353 K for 24 h. The samples were further activated in situ by
increasing the temperature (at a heating rate <1 K min-1) to 673
K under vacuum (5 × 10-3 mmHg), and the temperature and
vacuum were maintained for 8 h before the sorption measure-
ments. Nitrogen, oxygen, and argon adsorption isotherms were
measured at 288.2 and 303.0 K using a static volumetric system
(Micromeritics ASAP 2010). Adsorption temperature was main-
tained ((0.1 K) by circulating water from a constant-temperature
bath (Julabo F25). The requisite amount of the adsorbate gas
was injected into the volumetric set up at volumes required to
achieve a targeted set of pressures ranging from 0.1 to 850 mmHg.
Three pressure transducers of capacities 1 mmHg (accuracy
within 0.12% of the reading), 10 mmHg (accuracy within 0.15%
of the reading), and 1000 mmHg (accuracy within 0.073% of the
full scale) were used for the pressure measurements. A minimum
equilibrium interval of 5 s with a relative target tolerance of
5.0% of the targeted pressure and an absolute target tolerance
of 5.000 mmHg were used to determine the equilibrium for each
measurement point. The adsorption and desorption were com-
pletely reversible, and it is possible to remove the adsorbed gases
by simple evacuation.
The isotherms were fitted in various adsorption isotherm
models such as the Langmuir equation, Virial equation, and
Dubinin-Astakhov equation.
Langmuir equation: P/qP0 ) 1/bqm + P/qmP0 (1)
Virial equation: ln(p/q) ) A + Bq + Cq2 + ... (2)
Henry’s constant, K, was determined from the Virial coefficient
using the equation
K ) exp(-A) (3)
Dubinin-Astakhov equation:
log(V) ) log(V0) - (RT/βE0)N[log(P0/P)]N (4)
where q is the amount of gas adsorbed per unit weight of the
adsorbent; qm is the monolayer capacity of the adsorbent; b is the
Langmuir constant; P is the equilibrium pressure; P0 is the
saturation vapor pressure; A, B, and C are the first, second, and
third Virial coefficients, respectively; V is the volume adsorbed
at equilibrium pressure; V0 is the micropore capacity; T is the
analysis bath temperature; R is universal gas constant; E0 is the
Langmuir, Vol. 21, No. 24, 2005 11221
t-plot
BET micropore external
dimension, surface surface surface
Å area, m2g-1 area, m2g-1 area, m2g-1
24.94 542 518 24
24.91 676 623 53
24.91 696 616 80
24.91 662 541 121
24.90 669 508 161
characteristic energy; N is the Astakhov exponent; and β is the
affinity coefficient of the analysis gas.
Adsorption capacity, selectivity, and isosteric heat of adsorption
were determined from the adsorption isotherms measured at
288.2 and 303.0 K.
The pure component selectivity of two gases, A and B, was
calculated by using the equation
RA/B ) [VA/VB]P,T (5)
where VA and VB are the volumes of gas A and B respectively
adsorbed at any given pressure P and temperature T.
Isosteric heats of adsorption were calculated from the adsorp-
tion data collected at 288.2 and 303.0 K using the Clausius-
Clapeyron equation.
∆adH° ) R{[∂(ln p)]/[∂(1/T)]}θ (6)
where R is the universal gas constant, θ is the fraction of the
adsorbed sites at a pressure p and temperature T. The errors in
the Henry constant, adsorption selectivity, and heat of adsorption
estimated from the propagation of errors method were 0.5%,
0.4%, and 0.4%, respectively.
Surface areas of the cation-exchanged zeolites were determined
from N2 adsorption data at 77.35 K. The nitrogen adsorption at
77.35 K was also measured using a Micromeritics ASAP 2010
after activating the sample at 673 K under vacuum. Micropore
surface areas of the various samples were determined from a
t-plot. In this method, the amount of nitrogen adsorbed is replotted
against t, the corresponding multilayer thickness for the adsorp-
tion of nitrogen on the nonporous reference solid.17 The slope of
the t-plot is directly proportional to the surface area of the sample.
Any upward deviations from linearity are due to the capillary
condensation inside the pores, and the initial slope is proportional
to the micropore surface area.
2.5. DRIFT IR Spectroscopy. Diffuse reflectance infrared
Fourier transform (DRIFT) spectroscopic studies of the adsorbed
N2 molecules were carried out at 303 K using a Perkin-Elmer
Spectrum GX equipped with The Selector DRIFT accessory
(Graseby Specac, P/N 199900 series) incorporating an environ-
mental chamber (EC) assembly (Graseby Specac, P/N 19930
series) after the in situ activation at 673 K under nitrogen flow
(30 cm3 min-1). The spectra were recorded using a self-supported
zeolite wafer sample in the range of 400-4000 cm-1. The spectra
were recorded at 303 K under dry nitrogen flow (30 cm3 min-1)
and after in situ activation at 673 K using an automatic
temperature controller (Graseby Specac, P/N 19930 series)
connected with the EC at a heating rate of 10 K min-1. Typically,
30 scans were coadded at a resolution of 4 cm-1.
3. Results and Discussion
The structure of the zeolite X is retained during the
cation exchange process, as observed from the retention
of all the characteristic peaks in XRD patterns after the
cation exchange process (Figure 1).
The percentage crystallinity and unit cell dimensions
were determined from the X-ray powder patterns, and
the values of which are also given in Table 1.
Complete ion exchange of Na+ with Co2+ in zeolite X
was attempted from aqueous solution at 353 K, but the
(17) Sing, K. S. W. In Characterization of Powder Surfaces; Parfitt,
G. D., Sing, K. S. W., Eds.; Academic Press: London, 1976.
11222 Langmuir, Vol. 21, No. 24, 2005
Figure 1. X-ray powder diffraction patterns of NaX and NaCoX
zeolite samples.
complete Co2+exchange was not achieved. For example,
hydronium ions may have attacked the zeolite framework
Figure 2. Adsorption isotherms of N2, O2, and Ar on NaCoX samples measured at 303.0 K.
Sebastian et al.
to a minor degree, leading to a loss of Al3+ ions and crystal-
linity, and this is increased with the temperature of cation
exchange. Co2+ in fully dehydrated zeolites A and X is
reported to cause strong six-ring deformations, as seen
from the UV-Vis-NIR spectra.18 The theoretical study,
which used cluster models for Co(II) in an isolated six-
ring without coordinating H2O or OH-, showed that the
effective coordination number of Co(II) depends on the
local Si and Al arrangement, and the aluminum-deficient
six-rings behave differently from Si3Al3O6 six-rings.18
The surface areas of the various cobalt-exchanged zeolite
X samples were determined from the N2 gas adsorption
data at 77.35 K. The surface areas of the cobalt exchanged
zeolite X increases with an increase in the percentage of
cobalt ion exchange. This is due to the decrease in the
number of extraframework cations, while two monovalent
sodium ions are replaced with one divalent cobalt ion.
Co2+ (0.74 Å) cations also occupy less space in the zeolite
cavity compared to Na+ (0.94 Å) cations. The external
surface area determined from the t-plot also increases
Adsorption of N, O, and Ar in NaCoX Langmuir, Vol. 21, No. 24, 2005 11223

Table 2. Equilibrium Adsorption Capacities for N2, O2, and Ar on Various Cobalt(II)-Exchanged Zeolites
equilibrium adsorption capacity (molecules/unit cell) at 101.3 kPa
288.2 K 303.0 K
adsorbent nitrogen oxygen argon nitrogen oxygen argon
NaX 7.7 2.4 2.2 5.5 1.8 1.7
NaCoX 46 8.5 2.5 2.1 7.0 2.0 1.7
NaCoX 71 10.0 2.6 2.1 8.4 2.1 1.6
NaCoX 88 9.2 2.7 2.1 7.9 2.1 1.6
NaCoX 93 7.8 2.7 2.0 6.7 2.1 1.5

Table 3. Langmuir Fittings Data at 303.0 K on
Cobalt(II)-Exchanged Zeolites
slope Langmuir constant, b
adsorbent nitrogen oxygen argon nitrogen oxygen argon
NaX 0.014 0.0099 0.014 0.160 0.034 0.044
NaCoX 46 0.055 0.022 0.019 0.746 0.104 0.048
NaCoX 71 0.057 0.033 0.022 2.465 0.111 0.057
NaCoX 88 0.080 0.057 0.100 2.703 0.148 0.245
NaCoX 93 0.082 0.063 0.127 4.103 0.187 0.271
with the percentage of cobalt exchange. This can be
explained in terms of the structural deformation leading
into the formation of an amorphous phase during the
vacuum dehydration of the cobalt ion exchanged zeolite
X at higher temperatures. This is also supported by the
decrease in percentage crystallinity with an increase in
cobalt exchange (Table 1).
Nitrogen, oxygen, and argon adsorption isotherms on
cobalt(II)-exchanged zeolites X were measured at 288.2
and 303.0 K, and the adsorption isotherms on various
NaCoX samples at 303.0K are given in Figure 2. The
nitrogen adsorption sharply increases with pressure in
the low-pressure region and the nitrogen adsorption
isotherm becomes nonlinear. Oxygen adsorption capacity
also increases; however, argon adsorption capacity re-
mains almost unaffected. The oxygen adsorption increases
linearly with pressure. The magnitude of the increase in
the adsorption capacity of oxygen is much lower than that
of nitrogen in the low-pressure region. The sharp increase
in the nitrogen adsorption in the low-pressure region
shows strong interaction of the nitrogen molecules with
some of the extraframework cobalt ions.
The equilibrium adsorption capacities for nitrogen, oxy-
gen, and argon on zeolite X containing different amounts
of cobalt ions were determined from the adsorption iso-
therms, and the numbers of molecules adsorbed per unit
cell at 101.3 kPa are given in Table 2. The nitrogen and oxy-
gen adsorption capacities increase on cobalt ion exchange
up to 71%, beyond which it shows a decreasing trend.
Adsorption capacities of oxygen increase marginally, while
those of argon do not show significant change with cobalt
exchange. The magnitude of the increase in the adsorption
capacities for nitrogen is much higher than that of oxygen.
The adsorption data obtained at 288.2 and 303.0 K were
fitted in the Langmuir equation, and the slope, intercept,
and Langmuir constant were determined. The values for
the Langmuir constant (b) increase for nitrogen, oxygen,
and argon upon cobalt exchange and increases linearly
with an increase in the percentage of cobalt exchange on
zeolite X. The Langmuir fitting data of zeolite X samples
with different amounts of cobalt ion exchanged at 303.0
K are given in Table 3.
The nitrogen, oxygen, and argon adsorption data
obtained at 288.2 and 303.0 K were also fitted in the Virial
equation. The Virial coefficients (A, B, and C) were
determined from the Virial plots. The values for the
(18) Pierloot, K.; Delabie, A.; Ribbing, C.; Verberckmoes, A. A.;
Schoonheydt, R. A. J. Phys. Chem. B, 1998, 102, 10789-10798.
Henry’s constant (K) were calculated from the Virial
coefficient. The values of the Virial coefficients A and
Henry’s constant K at 303.0 K are given in Table 4. The
Henry’s constant value for nitrogen increases with an
increase in the cobalt content in the zeolite. Henry’s
constant for oxygen decreases initially and then increases
with an increases in the amount of cobalt in the zeolite,
while that of argon decreases gradually with an increase
in the amount of cobalt in the zeolite.
The nitrogen, oxygen, and argon adsorption at 288.2
and 303.0 K were also fitted in the Dubinin-Astakhov
equation. The values of the slope, intercept, energy, and
volume were determined, and values of slope and energy
at 303.0 K are given in Table 5. The slope of the Dubinin-
Astakhov-transformed isotherm for nitrogen adsorption
on cobalt(II)-exchanged zeolite X increases with an
increase in the cobalt content in the zeolite. The slope of
the Dubinin-Astakhov-transformed oxygen adsorption
isotherm decreases initially and then increases with an
increase in the amount of cobalt in the zeolite, while that
of argon remains almost unaffected. The Dubinin-
Astakhov energy for nitrogen, oxygen, and argon adsorp-
tion increases with an increase in the amount of cobalt in
zeolite X. The magnitude of the increase in the Dubinin-
Astakhov energy follows the order N2 . Ar > O2.
The adsorption selectivities of the pure components were
calculated at different pressures, and the values are given
in Table 6. The nitrogen/oxygen as well as nitrogen/argon
selectivities in the low-pressure region increase from 3.4
to 21.8 and 3.7 to 28.6, respectively, with an increase in
cobalt exchange. Marginal oxygen selectivity over argon
is observed for zeolite samples with higher cobalt exchange.
NaCoX 71 shows the maximum oxygen/argon selectivity
value of 1.57 at 101.99 kPa.
The isosteric heats of adsorption for nitrogen, oxygen,
and argon adsorption on cobalt-exchanged zeolite X were
calculated using the Clausius-Clapeyron equation and
are given in Table 7. The heats of adsorption values for
nitrogen and oxygen increase and that for argon remains
unaffected upon cobalt exchange in zeolite X.
The variation in the nitrogen heats of adsorption with
the amount of N2 adsorbed on NaX and various cobalt-
exchanged zeolite X is shown in Figure 3. The nitrogen
heat of adsorption decreases with an increase in adsorption
coverage and finally became similar to that of the NaX.
The decrease in the heat of adsorption of nitrogen with
adsorption coverage shows that the number of Co2+ sites
that can strongly interact with nitrogen molecules is
limited only. It was also observed that the number of
strongly nitrogen interacting centers increases with an
increase in the cobalt exchange, while oxygen and argon
molecules have feeble interaction with these sites, due to
lower quadrupole moment values, and do not show
significant variation with adsorption coverage.
Zeolites are a class of materials that have crystallo-
graphically well-defined channels and cavities.2 The
framework structure of zeolites is composed of a three-
dimensional network of basic structural units consisting
11224 Langmuir, Vol. 21, No. 24, 2005 Sebastian et al.

Table 4. Virial Coefficient and Henry’s Constant at 303.0 K on Cobalt(II)-Exchanged Zeolites

virial coefficient, A Henry’s constant, K (10-5 cm3 g-1 Pa-1)
adsorbent nitrogen oxygen argon nitrogen oxygen argon
NaX 4.296 5.528 5.568 10.22 2.98 2.86
NaCoX 46 3.971 6.230 5.927 14.15 1.48 2.00
NaCoX 71 2.571 5.608 5.908 37.37 1.75 1.84
NaCoX 88 2.784 5.862 6.260 46.33 2.14 1.73
NaCoX 93 2.652 5.830 6.104 52.90 2.20 1.68

Table 5. Dubinin-Astakhov Fittings Data at 303.0 K on Adsorbate molecules can interact with the zeolite surface
Cobalt(II)-Exchanged Zeolites through lattice oxygen atoms, accessible extraframework
slope energy, kJ mol-1 cations, and Al and Si atoms. The Al and Si atoms present
adsorbent nitrogen oxygen argon nitrogen oxygen argon
at the center of tetrahedra are not directly exposed to the
sorbate molecules. Consequently, their interactions with
NaX -0.940 -0.988 -0.985 12.19 10.38 10.63 the sorbate molecules are negligible. Therefore, the
NaCoX 46 -0.788 -1.091 -0.985 14.59 10.46 10.74 principal interactions of these sorbate molecules with the
NaCoX 71 -0.545 -0.961 -0.986 21.19 10.82 10.80
NaCoX 88 -0.523 -0.950 -0.987 21.89 11.08 12.56 zeolite surface are with lattice oxygen atoms and ex-
NaCoX 93 -0.484 -0.936 -0.990 23.39 11.36 12.64 traframework cations.19
Zeolite X is a synthetic, aluminum-rich analogue of the
Table 6. Adsorption Selectivities on naturally occurring mineral faujasite (Figure 4). The 14-
Cobalt(II)-Exchanged Zeolites hedron with 24 vertexes, known as the sodalite cavity or
adsorption selectivity β-cage, may be viewed as its principal building block. These
RN2/O2 RN2/Ar RO2/Ar β-cages are connected tetrahedrally at six-rings by bridg-
ing oxygen to give double six-rings (D6Rs, hexagonal
3.33 101.99 3.33 101.99 3.33 101.99 prisms) and, concomitantly, an interconnected set of even
adsorbent kPa kPa kPa kPa kPa kPa
larger cavities (supercage) accessible in three dimensions
NaX 3.4 3.1 3.7 3.3 1.08 1.07 through 12-ring (24-membered) windows.20 The extra
NaCoX 46 7.7 3.3 8.3 3.7 1.08 1.12 framework cations are usually found at the sites shown
NaCoX 71 20.7 4.1 30.3 6.4 1.46 1.57
in Figure 4.
NaCoX 88 20.6 3.7 28.7 5.3 1.39 1.45
NaCoX 93 21.8 3.6 28.6 4.9 1.31 1.42 The crystal structures of cobalt-exchanged zeolite X are
reported in the literature.21 Co2+ ions occupy sites I′, II,
Table 7. Isosteric Heats of Adsorption of N2, O2, and Ar and III′ in zeolite X. In the sample with 46 Co2+ ions per
on Cobalt(II)-Exchanged Zeolites unit cell, cobalt ions are found at five different crystal-
heat of adsorption, kJ mol-1 a lographic sites and sodium ions at a single site, as shown
adsorbent nitrogen oxygen argon
in Table 8. The spectroscopic studies of the cobalt-
exchanged zeolites22 show that the cobalt ion migrates
NaX 19.4 15.1 13.4 toward smaller cavities and occupy well-defined cation
NaCoX 46 34.5 17.2 13.3 sites. In zeolite X, the extraframework cations in sites I
NaCoX 71 36.4 17.9 13.9
NaCoX 88 38.2 18.1 14.1 and I′ are not accessible to the oxygen, nitrogen, and argon
NaCoX 93 40.7 18.5 14.1 molecules. The cation sitting in site II and II′ can interact
with the adsorbate molecules through the six-member-
a At 1.0 cm3 g-1 coverage. ring windows, and the cations in site III and III′ can
of SiO4 and AlO4 tetrahedrons linked to each other by interact directly with these adsorbate molecules.
sharing apical oxygen atoms. The resulting aluminosilicate The Co-O distances in NaCoX (Table 8) are longer
structures, which are generally highly porous, possess compared to the sum of the ionic radii of Co2+ and O2-
three-dimensional pores, the access to which is through (0.74 + 1.32 ) 2.06 Å, and 2.130 Å in Co-O). The
molecular-sized windows. Most zeolites contain exchange- coordinately unsaturated Co2+ ions located at sites II′ and
able extraframework cations in their channels and cavi- III′ can interact strongly with the nitrogen molecules by
ties, as needed to balance the anionic charges of their both σ-donation (electron transfer from bonding π2p
frameworks. They may also contain easily replaceable orbitals of N2 molecules to 4s orbital of Co2+ ions) and
guest molecules such as water or organic molecules.2,19 d-π2p* back-donation (electron transfer from the 3d orbital

Figure 3. Variation of heats of adsorption of (a) nitrogen and (b) oxygen and argon with adsorption coverage in NaX and various
cobalt(II)-exchanged zeolite X samples.
Adsorption of N, O, and Ar in NaCoX
Figure 4. The framework structure of zeolite X; near the center
of the each line segment is an oxygen atom. The numbers 1-4
indicate the different oxygen atoms. Extraframework cation
positions are labeled with Roman numerals. site I is at the
center of the D6R, I′ in the sodalite cavity on the opposite side
of one of the D6Rs six-rings from site I, II′ inside the sodalite
cavity near a S6R, II at the center of the S6R or displaced from
this point into a supercage, III in the supercage on a 2-fold axis
opposite a four-ring between two 12-rings, and III′ somewhat
or substantially off III (off the 2-fold axis) on the inner surface
of the supercage.
Table 8. Cation Site Occupancies and M-O Distances in
NaCoX17
no. of M-O
cation location cations distance, Å
site I 8 (Na+) 2.623
site I′ (2 different) 16 (Co2+) 2.149 and 2.32
site II 19 (Co2+) 2.129
site II′ 1 (Co2+) 2.33
site III 10 (Co2+) 2.30 and 2.27
of Co2+ ions to the unoccupied π2p* of the N2 molecule).
This π-complexation of nitrogen molecules with Co2+ ions
in the zeolite results in a high value for heat of adsorption,
Henry’s constant, adsorption selectivity, and adsorption
capacity for nitrogen in the low-pressure region.
The DRIFT spectroscopic study of the adsorbed N2
molecules also supports the stronger interaction of
nitrogen molecules with extraframework cobalt ions
present in the zeolite. N2 molecules being totally symmetric
do not absorb IR radiation. However, N2 molecules
adsorbed in zeolites experience an induced dipole moment,
which varies during vibration, and an induced band is
observed.23,24 The magnitude of the induced dipole moment
depends on the strength of the interaction of the nitrogen
molecules with the extraframework cations. At 303 K, N2
molecules adsorbed on NaCoX 88 give the adsorption band
at 2099 cm-1, as shown in Figure 5. The adsorption bands
observed at 3400 and 1643 cm-1 show the presence of a
small amount of moisture in the zeolite, despite in situ
activation of the zeolite sample and a dry nitrogen purge.
(19) De Lara, E. C.; Delaval, Y. J. Chem. Soc. Faraday Trans. 2
1978, 74, 790-797.
(20) Barrer, R. M. Zeolites and Clay Minerals as Sorbents and
Molecular Sieves: Academic Press: London, 1973.
(21) Olson, D. H. Zeolites 1995, 15, 439-443.
(22) Base, D.; Seff, K. Microporous Mesoporous Mater. 1999, 33, 265-
280.
(23) Verberckmoes, A. A.; Weckhuysen, B. M.; Schoonheydt, R. A.
Microporous Mesoporous Mater. 1998, 22, 165-178.
(24) Geobaldo, F.; Lamberti, C.; Ricchiardi, G.; Bordiga, S.; Zecchina,
A.; Palomino, G. T.; Aren, C. O. J. Phys. Chem. 1995, 99, 11167-11177.
Langmuir, Vol. 21, No. 24, 2005 11225
Figure 5. Diffuse reflectance infrared Fourier transform
spectra of NaCoX 88 with and without adsorbed N2 molecules
measured at 303 K.
Transition metal complexes are reported25 to interact
with N2 through end-on coordination (M-NtN). This
M-N2 bonding is interpreted in terms of the σ-donation
and π-back-donation. It is further reported25 that ν(NtN)
shifts in the range 2220-1850 cm-1 on π-complexation
with transition metals from 2331 cm-1 expected for free
N2 molecule. For example, NtN stretching frequency in
dinitrogen complexes [Ru(N2)(NH3)5]Br2, Co(N2)(PPh3)3,
[Os(N2)(NH3)5]Cl2, and Ir(N2)Cl(PPh3)2 are observed at
2105, 2093, 2022, and 2105 cm-1, respectively. The NtN
stretching frequency at 2099 cm-1 observed for the N2
molecule adsorbed in zeolite NaCoX 88 is closer to these
values, confirming the π-complexation between the ni-
trogen molecule and the cobalt cations of the zeolite. The
IR spectrum of N2 molecules adsorbed in LiLSX zeolite
showed adsorption bands at 2320-2340 cm-1.26 These
results also support the proposal that a shift of the
adsorption band toward lower frequencies in NaCoX is
caused by the stronger interaction of the N2 molecules
with the extraframework cobalt cations via π-complexation
4. Conclusions
In this work, the adsorption of nitrogen, oxygen, and
argon on the cobalt-exchanged zeolite X with different co-
balt content was investigated. It was observed that adsorp-
tion capacity, Henry’s constant, Langmuir constant,
Dubinin-Astakhov energy, heat of adsorption for nitrogen
adsorption, and adsorption selectivities over oxygen and
argon in the low-pressure region increase with an increase
in cobalt exchange. Marginal oxygen selectivity over argon
was also observed for zeolite samples with higher cobalt ex-
change level. The stronger interactions of the nitrogen mol-
ecules were explained in terms of the π-complexation be-
tween nitrogen molecules and cobalt cations of the zeolites.
Acknowledgment. We acknowledge the financial
assistance and support from Department of Science and
Technology, Council of Scientific and Industrial Research,
and Dr. P. K. Ghosh, Director, CSMCRI.
LA051460E
(25) Nakamoto, K. Infrared and Raman Spectra of Inorganic and
Coordination Compounds-sPart B: Applications in Coordination,
Organometallic and Bioinorganic Chemistry, 5th ed.; Wiley-Inter-
science: New York, 1997; pp 173-177.
(26) Coe, C. G., Structural Effects of the Adsorptive Properties of
Molecular Sieves for Air Separation, in Access in Nanoporous Materials;
Pinnavaia, T. J., Thorpe, M. F., Eds.; Plenum Press: New York, 1995;
pp 213-229.