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Microporous and Mesoporous Materials 109 (2008) 216–222

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Adsorption of CO on LTA zeolite adsorbents: An IR investigation

Tania Montanari, Isabel Salla 1, Guido Busca *

DICheP – Università di Genova, p.le J.F. Kennedy 1, I-16129 Genova, Italy

Received 9 March 2007; received in revised form 20 April 2007; accepted 25 April 2007
Available online 3 May 2007

Abstract

The low temperature adsorption of CO on the zeolites K-LTA (3A) Na-LTA (4A) and Ca,Na-LTA (5A) has been investigated by IR
spectroscopy. For comparison, the adsorption of CO on K-MOR, Na-MOR and Ca-MOR has also been studied. CO adsorption on K-
LTA zeolite is mostly limited at the external surface. In the case of Na-LTA zeolite, terminal Na+ carbonyls are formed. In the case of
Ca,Na-LTA zeolite, Ca2+ polycarbonyls and monocarbonyls are observed. In both Na-LTA and Ca,Na-LTA zeolites strongly bonded
CO characterized by low CO stretching frequencies (2112 and 2107–2099 cm 1) are also observed. These have been identified as CO
interacting with more than one cation, through both the C atom and the O atom. Ca2+ ions in Ca,Na-LTA zeolite are also bonded
to extraframework hydroxyl and carbonate ions, which modify their coordination sphere. These results may be relevant in relation to
the use of these zeolites as adsorbents for the removal of CO from fuel gases, such as hydrogen.
 2007 Elsevier Inc. All rights reserved.

Keywords: LTA zeolites; CO adsorption; IR spectroscopy; Ca-mordenite; Ca-A zeolite; Na-A zeolite; K-A zeolite

1. Introduction Na-LTA, also denoted as 4A). In the case of Ca,Na-LTA

Zeolites denoted with the Linde Type A (LTA) code [1]
are small pore zeolites characterized by a cubic structure.
Each unit cell consists of 96 AlO4 and 96 SiO4 tetrahedra
and contains eight a cages or supercages, and eight b cages
(sodalite cages). Supercages are opened each other through
eight-membered oxygen rings (8MR). The b cages connect
to the supercages through six-membered rings (6MR), and
each other through four-membered rings (4MR). Both
6MR and 4MR are assumed to be too small for most mol-
ecules to pass through. The pore structure through which
molecular diffusion occurs is consequently limited by the
size of the 8MR that are approximately 5 Å across. The
presence of charge-balancing cations (K+, Na+ and Ca2+)
reduces the effective pore size of the opening to near 3 Å
(for K-LTA, also denoted as 3A) and near 4 Å (for
*
Corresponding author. Tel.: +39 0 10 353 6024; fax: +39 0 10 353
6028.
E-mail address: Guido.Busca@unige.it (G. Busca).
1
On leave from University Rovira i Virgili, Tarragona, Spain
(5A) only part of cationic locations is occupied, and the
pore size is near 5 Å.
Na-LTA zeolite is largely used as an ion exchanger in
the field of detergency [2]. According to their molecular
sieving properties, zeolites act as selective regenerable
adsorbants for purification of gaseous streams and separa-
tion of vapours and gases [3,4]. K-LTA, Na-LTA and
Ca,Na-LTA zeolites have in fact wide application in these
fields such as for air separation (in particular Ca,Na-LTA
[3,5]), especially by pressure swing adsorption, for drying
of technical gases and liquids and for the n/i-alkane sepa-
ration in discontinuous sorption processes [6–8]. Na-LTA
zeolite has also been considered for alkane/alkene separa-
tion [9], while Ca,Na-LTA is considered for separation of
CO2 [10,11] and NO2 [11] from gases. Several theoretical
studies also recently appeared such as the investigations
of the adsorption of NO [12] and of water, ammonia and
CO2 on Na-LTA [13].
LTA zeolites, in particular K-LTA [14], may find rele-
vant applications in bio-ethanol drying processes, for the
production of fuel grade bio-ethanol from starch or

1387-1811/$ - see front matter  2007 Elsevier Inc. All rights reserved.
doi:10.1016/j.micromeso.2007.04.045
 T. Montanari et al. / Microporous and Mesoporous Materials 109 (2008) 216–222
cellulosic biomasses fermentation with pressure swing
adsorption processes [15]. Mitsui Engng. & Shipbuilding
Corp., Tokyo has brought zeolite LTA membranes as the
first semi-technical zeolite membrane on the market [16].
The hydrophilic zeolite LTA membranes, in fact, are espe-
cially recommended for the separation of water by pervap-
oration or steam permeation [16].
Another possible application of LTA zeolites is in the
field of purification of hydrogen through pressure swing
adsorption (PSA) processes [17]. Ca,Na-LTA molecular
sieve has been found to allow the production of highly pure
H2 by adsorption of CH4 and CO impurities [18]. The
removal of CO is a relevant need to produce pure hydrogen
for application as a fuel of low temperature fuel cells (such
as PEMFC) and for ammonia synthesis. CO is in fact a
poison for both Pt electrodes of PEMFC and iron catalysts
for ammonia synthesis. According to literature data [7],
Na-LTA and Ca,Na-LTA zeolites may adsorb CO, so
allowing its removal, while K-LTA zeolite should not.
On the other hand, CO is also widely used as an adsorption
probe to determine the state of the cationic adsorbing sites
by IR spectroscopy in the fields of adsorbents and catalysts
[19]. However, studies on K-LTA and Ca,Na-LTA zeolites
seem to have not been published so far.
Low temperature CO adsorption has been recently used
by our group to reexamine the adsorption mechanisms on
Na-mordenite (Na-MOR) [20], and on other alkali metal
mordenites [21], as well as of Na-Y and Na-X faujasites
[22]. As usual, CO has been found to form C-bonded cat-
ion-carbonyl complexes whose stability and CO stretching
frequencies (2210–2150 cm 1) increase by increasing the
Lewis acidity of the cation, and weakly O-bonded species
whose CO stretching frequency (2130–2110 cm 1) is shifted
down with respect to the free molecule. In addition, we
found the formation of more strongly adsorbed CO species
with intermediate CO stretching frequency (2160–
2130 cm 1), which have been identified as CO molecules
interacting with two alkali ions with both the C and the
O atoms. Our interpretation has been later supported by
the theoretical and experimental work of Garrone et al.
[23] who found similar species in K-ferrierite (2148 cm 1).
With the present study we extended our investigation to
small pore zeolites of the LTA family, where the adsorp-
tion of CO has additional practical interest. The compari-
son with the results obtained with the corresponding
MOR zeolites will help the band assignment. It seems that
IR studies of CO adsorption on Ca-MOR have also not
been reported previously.
2. Experimental
K-LTA zeolite (with formula K12[(AlO2)12(SiO4)12] ·
H2O), Na-LTA zeolite (Na12[(AlO2)12(SiO4)12] · H2O)
and Ca,Na-LTA zeolite (Ca4.5Na3[(AlO2)12(SiO4)12] ·
H2O) were purchased from Fluka. Na-MOR (Si/Al = 6.5,
Na2O 6.6% wt/wt) was supplied by Zeolyst. Exchange of
217
Na-MOR with potassium and calcium has been performed
as previously reported [21].
Self-supporting pressed disks of pure zeolite powders
were activated ‘‘in situ’’ in the IR cell by outgassing at
723 K before the adsorption experiments. A conventional
gas manipulation/outgassing ramp was connected to an
IR cell which allowed cooling by liquid nitrogen in an
external jacket.
The adsorption/desorption process has been studied by
transmission FT-IR. CO adsorption was performed at
130 K (real sample temperature measured by a thermocou-
ple) by the introduction of a known dose of CO gas. The
sample was saturated with CO using sufficiently high CO
pressure (up to 20 Torr) in the cell, until the intensity of
the adsorbed species have raised a maximum. IR spectra
were later collected evacuating at increasing temperatures
between 130 and 273 K.
3. Results and discussion
In Fig. 1, the spectra relative to the low temperature
adsorption of CO on K-LTA and on K-MOR zeolites
are compared. In the case of K-MOR, at 133 K at least
four components are observed on the CO stretching region,
with the main maximum at 2162 cm 1 and shoulders
of decreasing intensities at 2150 cm 1, 2135 cm 1 and
2117 cm 1. The spectra fully agree with those reported in
the literature [21,24,25]. By progressively increasing tem-
perature upon outgassing, the two components at higher
frequencies, together with the band at 2117 cm 1, decrease
their intensities in parallel. Otherwise the band at
2135 cm 1, which also decreases its intensity under evacu-
ation at increasing temperatures, does it much slower: at
223 K this band has higher intensity than the two bands
at higher frequencies, his maximum being displaced at
2137 cm 1.
The two components at 2162 and near 2150 cm 1 are
assigned, as usual, to C-bonded CO species whose stretch-
ing frequency shift, with respect to the free gas molecule,
increases by increasing the acidity of the cation, i.e. by
decreasing its ionic radius. In the case of K-MOR the split-
ting of this band is likely associated to two different acces-
sible locations for K+ cations in the MOR structure.
According to previous studies, in fact, alkali cations
occupy three different sites of the MOR structure [26,27].
The most populated one, called (I) or A, is just in the mid-
dle of the compressed channel and is considered to be not
accessible. The others are site IV, also called D, near the
opening of the side pocket in the main channel, and site
VI, also called E, which is well exposed in the main chan-
nel. Actually, as also shown by the computer simulations
[28], the molecules adsorbed on the two accessible cations,
at sites IV and VI, lay well in the center of the main chan-
nel, no adsorbed molecules being actually located in the
side pocket. Actually, the cations in position IV (near the
center of an eight-membered oxygen ring) appear to be
more shielded by oxygens that those at position VI (off
218 T. Montanari et al. / Microporous and Mesoporous Materials 109 (2008) 216–222

Fig. 1. FT-IR spectra of CO adsorbed at low temperature on K-MOR (left) and K-LTA (3A) (right). The stronger spectra are recorded at 133 K in the
presence of the gas (10 Torr). The other spectra are recorded upon warming under outgassing up to 250 K (K-MOR). In the inset, the amplification of the
spectrum of CO on K-MOR recorded after outgassing at 180 K (upper spectrum) and 223 K (lower spectrum). For K-LTA (right), the lowest spectrum is
recorded after outgassing at 150 K.

center of a six-membered ring), and this allows us to assign
the higher frequency component to CO C-bonded at posi-
tion VI cations, the lower frequency one being assigned to
CO C-bonded at position IV cations [21].
The lowest frequency component near 2115 cm 1, due
to a weakly bonded species, has been assigned, as usual,
to O-bonded CO [29]. Instead, the band centered at
2134–2137 cm 1, which appears to be the most resistant
to outgassing, has been assigned by us [21] to CO molecules
interacting with more than one K+ cation, likely through
both the C and the O atoms.
The adsorption of CO on K-LTA zeolite at 130 K gives
rise to the formation of a much weaker band, with the max-
imum at 2165–2160 cm 1, and a very weak shoulder in the
range 2145–2150 cm 1. The straightforward assignment of
the main band is to C-bonded CO species on single K+
ions. Outgassing at 120 K already causes the full disappear-
ance of the band. The weakness of this band is likely asso-
ciated to the very slow diffusion, if at all, of CO through the
small pores (near 3 Å wide) of K-LTA zeolite at so low a
temperature (130 K). It seems likely that the band is mostly
due to CO interacting with K+ ions at the external surface
of the zeolite, being its entrance in the pores forbidden in
these conditions, in agreement also with the very easy
desorption. This agrees with the lake of CO adsorption
on K-LTA zeolite reported in the literature [7]. We note
here that the very weak shoulder at 2145–2150 cm 1 resists
outgassing more than the main band. This feature could be
associated to a very small amount of CO molecules that
penetrated to zeolite pores and had be enable to bond
two K+ ions. The CO stretching frequency of this species
is near that observed by Garrone et al. [23] in the case of
CO adsorption on K-ferrierite (2148 cm 1) and assigned
to CO interacting with two K+ ions with both C and O
atoms, also on the basis of theoretical calculations.
In Fig. 2, the spectra of CO adsorbed on Na-MOR and
on Na-LTA are compared. On Na-MOR, the high-
frequency bands at 2177 and 2164 cm 1 are attributed to
C-bonded CO species over Na+ ions in the VI and IV sites,
respectively, in agreement with the assignments reported in
the literature [20,23,24,30] and the above discussion rela-
tive to K-MOR. The component at 2138 cm 1 instead,
which is the most stable upon outgassing, has been attrib-
uted by us to CO bonded to two cations [20,21].
In the case of Na-LTA, the spectrum is quite complex.
In this case the intensity of the bands is strong, about 25
times more than for K-LTA. This suggests that CO entered
the cavities of Na-LTA which have definitely larger access
(near 4 Å) than those of K-LTA. The main band at
2164 cm 1 is assigned to C-bonded CO species over Na+
ions. The band is highly symmetrical without any relevant
shift. Consequently, we cannot distinguish the existence of
the two different locations for Na+ ions in the supercage
(Na 1 and Na 2) [31], expected to be both available to inter-
act with molecules, while the third family of sites (Na 3),
located in the 4MRs, is expected to be not active in adsorp-
tion of CO. The frequency we observe here is nearly coin-
cident to that observed for CO adsorbed on Na-X and
assigned to sodium ions in the SII faujasite sites
(2165 cm 1 [22,32]). We can note here that the environment
of Na+ ions in the Na 1 sites of Na-LTA zeolite, which
should represent the 73% of the active sites, is very similar
to that of the SII faujasite sites, i.e. near the center of a
6MRs [31], with also a similar composition of the zeolite
framework (i.e. Si/Al a.r. near 1). The location of the Na
2 (that represent the other 27% of the active sites of
 T. Montanari et al. / Microporous and Mesoporous Materials 109 (2008) 216–222 219

Fig. 2. FT-IR spectra of CO adsorbed at low temperature on Na-MOR (left) and Na-LTA (right). The strongest spectra are recorded at 133 K in the
presence of the gas (10 Torr). The other spectra are recorded upon warming under outgassing up to 250 K. In the insets, the amplifications of the spectra
recorded after outgassing at 180 K and 223 K (lower spectrum for Na-LTA, right).

Na-LTA zeolite) could approach the location of the IV
sites of Na-MOR, both in the plane of 8 MRs [31]. In
agreement with this, mCO of CO adsorbed on the IV sites
of Na-MOR is also nearly coincident (2163 cm 1 [32]).
Thus, it seems likely that the positions of mCO of CO
adsorbed on the Na 1 and Na 2 sites of Na-LTA are too
near to be resolved.
Additional to the band assigned to the usual C-bonded
carbonyls, different weak lower frequency components
are observed, whose stabilities appear to be stronger. In
particular, a band at 2112 cm 1 seems to be due to a highly
stable species. To justify its stability and its CO stretching
frequency (lower than that of free Co), this band must be
attributed to CO interacting with more than one cation,
likely also through the oxygen atom. Other bands, at
2145 and 2128 cm 1, should also be due to species forming
different complex interactions.
We can note here that the relative intensity of the low-
frequency/strong interaction band with respect to that of
the high-frequency band due to usual C-bonded carbonyls
is much higher for Na-MOR than for Na-LTA, in spite of
the higher Na (and Al) content of LTA zeolite with respect
to MOR. However, we remark here that, while the pore
size of Na-LTA (4 Å for the 8MR) is definitely smaller
than that the main channels of Na-MOR (6.5 Å), the size
of the cavity (i.e. of the supercages) of Na-LTA (more than
10 Å) is far larger. So couples of sufficiently near Na+ ions
may be more frequent in Na-MOR than in Na-LTA. On
the other hand, the CO stretching frequency of the most
intense band that can be assigned to multiple interaction
is in the case of Na-LTA at a definitely lower frequency
(2112 cm 1) than in the case of Na-MOR (2138 cm 1) pos-
sibly due to a lower Na–Na distance in 4A.
In Fig. 3, the spectra of CO adsorbed on Ca-MOR and
on Ca,Na-LTA are compared. On Ca-MOR, the high-fre-
quency band, whose position is above the stretching of
pure CO, shows three components at 2172, 2183–2188
and 2202 cm 1, attributed to C-bonded CO species over
Ca2+ ions. However, the maxima at 2183–2188 and
2202 cm 1 seem to increase a little bit in intensity upon
outgassing. This behaviour may be justified in two ways:
either three different families of Ca2+ ions exist and CO
migrates, upon desorption, from one to another, or poly-
carbonyl species transform, upon outgassing, into di- and
mono-carbonyl species. This behaviour may be interpreted,
tentatively, by comparison with that reported by different
authors for CO adsorbed on other Ca-zeolites [19]. In
particular, in their detailed study on CO adsorption on
Ca,Na-Y, Hadjiivanov et al. [33] assigned bands observed
at low temperature and high CO pressures at 2167 cm 1 to
Na+(CO)2 dicarbonyls, at 2185 cm 1 to Ca2+(CO)3 tricar-
bonyls, and those observed upon outgassing at 2175 cm 1
to Na+CO monocarbonyls, at 2191 cm 1 to Ca2+(CO)2
dicarbonyls and at 2201 cm 1 to Ca2+CO monocarbonyls.
By outgassing polycarbonyls decompose to monocarbonyls.
The behaviour we observe in our Ca(Na)-MOR zeolite
could allow us to assign with confidence the band at
2202 cm 1 to Ca2+CO monocarbonyls. The band whose
maximum apparently shifts from 2183 to 2188 cm 1 should
also be due to Ca2+ poly- and/or mono-carbonyls, the
shift being possibly associated to the decomposition of
Ca2+(CO)3 tricarbonyls (2183 cm 1) to Ca2+(CO)2 dicarbo-
nyls (2188 cm 1). The quite labile band at 2172 cm 1 could
be due to CO adsorbed on residual Na+ ions.
The band at 2139 cm 1 appears to correspond to the
most labile species, and can consequently be confidently
assigned to liquid CO, as usually done [19]. Weakly bonded
species responsible for low-frequency bands are likely
O-bonded CO species. We have not for Ca-MOR a
clear evidence for low-frequency, high-stability species, in
220 T. Montanari et al. / Microporous and Mesoporous Materials 109 (2008) 216–222
Fig. 3. FT-IR spectra of CO adsorbed at low temperature on Ca-MOR (left) and Ca,Na-LTA (right). The strongst spectra are recorded at 133 K in the
presence of the gas (10 Torr). The other spectra are recorded upon warming under outgassing up to 250 K. In the insets, the amplifications of the spectra
recorded after outgassing at 180 K.
contrast with what we observe for Na-, K- and Cs-MOR
[21]. However, we can note that the cation density of Ca-
MOR is obviously half than that of alkali-MOR and, for
this reason, the probability of formation of doubly bonded
species is certainly much lowered.
The spectra of CO adsorbed on Ca,Na-LTA zeolite show
a main strong band centered at 2168 cm 1, that compares
well with what has been reported in a previous paper [34].
Upon outgassing this band shifts a little bit towards higher
frequencies. At the lowest coverages, however, a new band
grows at 2187 cm 1. The last band is certainly due to CO
interacting with Ca2+, while it seems likely that the main
component may be at least in part due to Na+ carbonyls,
the stretching frequency being only a little higher than that
found on Na-LTA. The behaviour observed, however,
seems to be quite unlikely. It should in fact be concluded
that CO adsorbs at higher pressure on Na+ ions, but part
of it should desorb from Na+ ions and readsorb on Ca2+
ions upon outgassing. An alternative and more likely
assignment of the band at 2168 cm 1 is to Ca2+(CO)2 dicar-
bonyls, that upon outgassing should decompose to give
Ca2+CO monocarbonyls, absorbing at 2187 cm 1. The fre-
quencies attributed to calcium di- and mono-carbonyls on
Ca,Na-LTA should be definitely shifted downwards with
respect those observed on Ca-Y and Ca-MOR. We can also
note here that, according to the crystal structure analysis,
Ca2+ ions are all located near the center of 6MRs in Ca-A
zeolite [35]. However, four fifths of them project in the
superacage, so they are expected to be active in adsorption.
One fifth of Ca2+ ions, instead, project into the soldalite
unit and are expected to be not active in adsorption. Thus,
we do not expect any splitting of the bands of adsorbed CO
due to the multiplicity of the adsorbing sites.
The expansion of the spectra recorded for Ca,Na-LTA
zeolite, at lower frequencies, shows components which
are more stable than those assigned to C-bonded CO spe-
cies. In particular, a band centered near 2100 cm 1, possi-
bly with two components at 2107 and 2099 cm 1 is very
likely due to small amounts of species bonded to two cat-
ions. The frequency is a little lower than that of the corre-
sponding species observed on Na-LTA zeolite, likely
because of the participation of species where Ca2+ ions
bond the oxygen atom of carbon monoxide (Ca–CO–Ca
or Na–CO–Ca). The intensity of these low-frequency bands
is indeed very weak here, much weaker than for Na-LTA.
However, we have to note again that the bivalent cation
density of Ca,Na-LTA is obviously half than that of the
monovalent alkali-LTA and, for this reason, the probabil-
ity of formation of doubly bonded species is certainly much
lowered.
To try to explain the lower mCO frequencies of
C-bonded CO on Ca,Na-LTA with respect to Ca-MOR
(and Ca-Y), we may analyze the overall spectra of the zeo-
lite disks. In Fig. 4 the spectra of the disks of Ca-MOR,
Ca,Na-LTA, Na-LTA and K-LTA are reported, as
recorded just after activation, before cooling and CO
adsorption. These spectra may be compared with those of
Na-LTA and Ca,Na-LTA zeolites as recently discussed
by Beta et al. [36]. While the sample K-LTA does not show
any band in the region of the hydroxyl groups and of the
carbonate species, Na-LTA shows residual hydroxyls
(OH stretching band, broad, with broad components at
3608 and 3425 cm 1), in agreement with Beta et al. [36].
A very weak sharp feature at 1667 cm 1 should be due to
the scissoring mode of residual molecular water, whose
OH stretching should correspond to the band near
3425 cm 1. The component at 3608 cm 1 could correspond
to that observed by Beta [36] at 3611 cm 1 on Ca,Na-LTA
zeolite, and assigned to few residual Si(OH)Al bridging OH
groups in 8MRs perturbed by extraframework species,
 T. Montanari et al. / Microporous and Mesoporous Materials 109 (2008) 216–222
Fig. 4. FT-IR spectra Ca-MOR, Ca,Na-LTA (5A), Na-LTA (4A) and K-LTA (3A) after activation, recorded at room temperature.
although a possible assignment to molecular water (OH
asymmetric stretching) is more likely. In fact the bridging
OH groups in the case of H,Na-LTA zeolite have been
found at slightly higher frequencies (3620 cm 1) and much
sharper [37], while in the Al-containing ITQ-29 zeolite,
which is H-LTA, two hydroxyl bands are reported at
3620 and 3550 cm 1 [38]. Nevertheless, in our case there
is no evidence for interaction of these OHs with carbon
monoxide.
The spectrum of the Ca,Na-LTA zeolite, clearly shows
quite strong bands of hydroxyl groups, with strong compo-
nents at 3555 and 3514 cm 1, in agreement with the litera-
ture [36,39]. The component at 3514 cm 1 has been
assigned to Si(OH)Al bridging OH groups in 6MRs while
the component at 3555 cm 1 has been assigned to residual
[Ca(OH)]+ groups [36,39]. The analysis of the OH stretch-
ing region during CO adsorption does not show a definite
perturbation of the OH stretching bands upon CO adsorp-
tion. This could suggest that either the Si(OH)Al bridging
OH groups in 6MRs are not available, for steric hindrance,
to interact with CO, or the entire OH stretching massive is
actually associated to [Ca(OH)]+ groups, which are strongly
basic and do not interact with CO. On the other hand, the
interaction of CO with Si(OH)Al bridging OH groups of
protonic zeolites gives rise to species whose CO stretching
is observed near 2170 cm 1 [40]. In this case the band,
expected to be weak, could be superimposed to that
observed at 2168 cm 1, assigned to Ca2+(CO)2 dicarbonyls.
A sharp split band at 1450, 1435 cm 1 is also evident in
the spectrum of Ca,Na-LTA, certainly due to ‘‘symmetri-
cal’’ carbonate ions (CO3 asymmetric stretching [41]). This
observation, reported also by other authors for activated
Ca,Na-LTA zeolite [42] is in agreement with the presence
of [Ca(OH)]+ groups, i.e. with the evidence of the presence
of strongly basic extraframework oxygen species part of
which may have reacted with CO2 from the environment.
221
The existence of extraframework material in Ca,Na-LTA
zeolite was also reported in a paper by Pluth and Smith
[35]. The bands of carbonate species are not found at all
for Ca-MOR where very small features at 3745 and
3610 cm 1 are due to residual terminal silanols and
Si(OH)Al bridging OH groups typical of H-MOR [43],
showing that the exchange with Ca2+ ions is actually near
to complete. However, we may note that the concentration
of Ca2+ in zeolite Ca,Na-LTA is likely much higher than
that in Ca-MOR, because of the much higher Al content.
According to these data, we may propose that Ca2+ ions
in Ca,Na-LTA may have, after our pre-treatment, a differ-
ent coordination sphere than in Ca-MOR (and possibly
Ca-Y) being also bonded to hydroxyl groups and to car-
bonate ions, besides to the framework oxygen atoms. The
higher coordination sphere for Ca2+ causes a lower elec-
tron withdrawing character which is reflected in the lower
CO stretching frequency of adsorbed CO.
4. Conclusions
The data above reported and described allow us to pro-
pose the following conclusions:
1. Low temperature CO adsorption on K-LTA (3A) zeolite
is extremely weak. It essentially occurs at the external
surface in the form of C-bonded potassium carbonyls
(mCO 2161–2164 cm 1), although a very small number
of CO molecules may penetrate the channels.
2. Low temperature CO adsorption on Na-LTA (4A) zeo-
lite occurs in the cavities mostly in the form of C-bonded
sodium carbonyls (mCO 2164 cm 1). The interaction of
CO with Na 1 and Na 2 sites probably gives rise to
bands too near to be resolved. Additionally, a small
number of CO molecules bond to more than one cation,
probably with both C and O atoms, giving rise to
222 T. Montanari et al. / Microporous and Mesoporous Materials 109 (2008) 216–222
strongly adsorbed species characterized by a low CO
stretching frequency (mCO 2112 cm 1). This kind of
interaction might be the most important in CO separa-
tion by adsorption as well as in the adsorbent regenera-
tion step.
3. Low CO stretching frequency high-stability species are
relatively less abundant in Na-LTA than in Na-MOR.
This is attributed to the larger size of the supercages
of LTA, that make less likely the formation of CO com-
plexes with two cations, with respect to the main chan-
nels of MOR.
4. Low temperature CO adsorption on Ca,Na-LTA (5A)
zeolite occurs in the cavities in the form of Ca2+(CO)2
gem-dicarbonyls (mCO 2168 cm 1), that convert at very
low CO pressure to Ca2+CO monocarbonyls (mCO
2187 cm 1). However, a small number of CO molecules
bond to more than one cation giving rise to strongly
adsorbed species characterized by a low CO stretching
frequency (mCO 2107–2099 cm 1).
5. Ca2+ ions in Ca,Na-LTA zeolite are, at least in part,
bonded to extraframework hydroxyl groups and car-
bonate ions after conventional activation procedure.
This decreases their acidity and, consequently, the CO
stretching frequency of adsorbed carbon monoxide, with
respect to other Ca-zeolites (Ca-Y and Ca-MOR).
6. low temperature CO adsorption on Ca-MOR zeolite,
which also has not been described previously in the liter-
ature, occurs in the form of Ca2+(CO)2 gem-dicarbonyls
or tricarbonyls (mCO 2183–2187 cm 1), that convert at
very low CO pressure to Ca2+CO monocarbonyls
(mCO 2202 cm 1). Another component, more labile
(mCO 2172 cm 1) may be due to Na+ monocarbonyls.
In this case the formation of low-frequency strongly
adsorbed species is not observed, probably because of
the low cation concentration that makes unlikely the
formation of multiply-bonded species.
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