Microporous and Mesoporous Materials 367 (2024) 112982

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Microporous and Mesoporous Materials

journal homepage: www.elsevier.com/locate/micromeso

Effects of cage topology on ethylene adsorption mechanism in silver

exchanged CHA and RHO zeolites: An Inelastic Neutron Scattering and
Density Functional study
G. Almeida a,b , A. de Marcos-Galán b , J. Martínez-Ortigosa c , G. Sastre b , M. Jiménez-Ruiz a ,∗,
F. Rey b , T. Blasco b
a
Institut Laue-Langevin, Av. des Martyrs 71, 38042 Grenoble Cedex 9, France
b
Instituto de Tecnología Química UPV-CSIC, Universitat Politecnica de Valencia, Avenida Los Naranjos s/ n, 46022 Valencia, Spain
c
Molecular Nanotechnology Lab, Universidad de Alicante, Crtra. Alicante-S. Vicente s/n, 03690, Alicante, Spain

ARTICLE INFO ABSTRACT

Keywords: Zeolite-based adsorbents have been successfully used for many challenging separations due to their tunable
Ethylene properties. A particularly notable application involves the separation of light olefins from paraffins, wherein the
Zeolites molecular sieving properties of zeolites play a pivotal role. Additionally, the selective interaction of alkenes
Silver
with transition metal cations, positioned within the channels and cavities of microporous zeolites, further
CHA
enhances separation capabilities.
RHO
Inelastic Neutron Scattering
This study aims to comprehensively characterize the interactions between ethylene and Ag+ exchanged
DFT zeolites, employing a multidisciplinary approach, combining Inelastic Neutron Scattering (INS), Infrared (IR)
spectroscopy, Nuclear Magnetic Resonance (NMR), UV–Vis and Density Functional Theory (DFT) calculations.
CHA and RHO, zeolites largely applied in gas separation processes, were chosen due to their similar small
pore sizes and pore volume, but different cavity shapes and flexibilities.
The interpretation of derived DFT Electron Density Difference, experimentally supported by 13 C Solid
State NMR results, provide an understanding of each framework’s role during the charge transfer mechanisms
between ethylene and transition metal species. Specific deformations in the flexible framework of zeolite RHO
explain a blueshift of the band at 400 cm−1 in the librational region of INS spectra compared to CHA. This
structural change in RHO, represented by the conic shape of the cage 8-ring side pockets, increases steric
effects over the adsorbate while rendering the metallic adsorption center less exposed within the zeolite’s
cavity, finally leading to a weaker adsorption energy. The redshift of C=C stretching frequencies observed
by IR spectroscopy and DFT calculations, as well as C=C and C-H bond lengthening of ethylene confirm the
formation of 𝜋-complexes on silver in both zeolites and allowed a further evaluation of the effects of the
different frameworks cages on the aforementioned interaction.

1. Introduction for its separation and purification. Among the different alternatives,
adsorption processes based on porous solids seem to be one of the most
Ethylene (C2 H4 ) stands as a crucial commodity for the chemical promising, since these technologies are well established for very large
and petrochemical industry with a production that exceeds 200 million production volumes with a relative low energetic penalty [6,7].
tons per year. This olefin is mainly obtained by steam cracking of Zeolites have appeared as one of the first options for the separation
naphtha or ethane (C2 H6 ), providing a cracked gas in which ethane and of ethylene from ethane due to their molecular sieving properties
impurities also co-exist at significant ratios. Thus, ethylene separation that allow to control the diffusion of different components through a
and purification is required for its application in chemical processes [1–
separation column (or membrane) [8,9]. Pure silica small-pore ITQ-
4]. Currently the separation of ethylene is carried out by the traditional
55 zeolite is a successfully adsorbent for ethylene/ethane separation
cryogenic distillation, a highly energy-demanding process (responsible
due to the very different diffusional rates of such molecules inside
for more than 0.3% of annual global energy consumption) [5]. There-
fore, there is an evident need of developing alternative approaches its pore system [10]. Moreover, simulations studies have shown that

∗ Corresponding author.
E-mail address: [email protected] (M. Jiménez-Ruiz).

https://doi.org/10.1016/j.micromeso.2024.112982
Received 2 December 2023; Received in revised form 22 December 2023; Accepted 2 January 2024
Available online 4 January 2024
1387-1811/© 2024 Published by Elsevier Inc.
G. Almeida et al. Microporous and Mesoporous Materials 367 (2024) 112982

ITQ-55 zeolite that ethylene is up to almost ≈ 1 Å larger than the evidences of structural modification were found in Ag-CHA zeolite. This
nominal pore aperture, being its diffusion possible thanks to framework results lead to a less favorable energy for the formation of Ag-C2 H4
flexibility [10,11]. Ethylene molecule, slightly smaller than ethane, complexes in CsAg-RHO than in Ag-CHA, proving that the shape of
holds the pore opening during molecular diffusion being selectively the cages, i.e. the shape of the 8-ring side pockets, where the cation
adsorbed in the zeolite. However, although remarkable, the successful is located and the framework flexibility play an important role on the
case of pure silica ITQ-55 for the molecular sieving separation of ethylene-Ag interaction.
ethane and ethylene is very particular and suffers from slow adsorption
kinetics for its industrial application. 2. Materials and methods
An alternative approach for the efficient separation of ethylene
makes use of the capability of the unsaturated bonds of alkenes to 2.1. Sample preparation
donate electrons, working as Lewis bases. These electrons can interact
with compensating transition metal cations located within the zeolite Ag-CHA and CsAg-RHO zeolites were obtained by silver exchange of
pores that act as Lewis acids. Ethylene is either weakly chemisorbed Na-CHA and NaCs-RHO, which were synthesized following the proce-
or strongly physisorbed on the cationic sites while ethane is not re- dure previously reported [26,27] and described in Supporting Material.
tained. Several transition metal cations such as Co(II), Ni(II), Zn(II), The silver exchange was carried out mixing 2.3 g of zeolite a 0.3 M
Fe(III), Cu(II), Ag(I) [12–14] to mention some examples have been AgNO3 solution (0.64 g AgNO3 dissolve in 11.45 mL of distilled water)
proposed as good candidates to provide an appropriate selective bind- under stirring for 24 h at 25 ◦ C. Then, the zeolites were filtered, washed
ing with ethylene, being Ag-zeolites among the most efficient. In fact, with distilled water and dried at 100 ◦ C. The XRD patterns of Ag-
silver-exchanged zeolite A (framework code LTA) has been reported to CHA and CsAg-RHO are typical of the CHA and RHO-type structures
achieve the absolute separation of ethylene from ethane [15] being its (Fig. S1). The chemical composition of Ag-exchanged zeolites was
exceptional behavior attributed to the preferential olefin adsorption on determined by scanning electron microscopy with energy dispersive X-
silver besides the steric size exclusion of ethane. Meanwhile, the excel- ray spectroscopy (EDX-SEM) on a JEOL JSM-6300 scanning electron
lent C2 H4 /C2 H6 separation properties of silver ZK-5 (KFI) zeolite has microscope using a back-scattered electrons (BSE) detector and a beam
been explained by the stabilization of cationic Ag+ due to the proper power of 10 KV. The Ag-CHA has Si/Al = 4.9, Na/Al = 0.1 and Ag/Al
combination of framework topology and chemical composition [16]. = 0.54 molar ratios; and the CsAg-RHO was Si/Al = 4.6, Na/Al = 0.1,
In spite of the excellent results reported up to now, there is not a Cs/Al = 0.29 and Ag/Al = 0.57.
material appropriate for industrial applications. The development of The zeolites were degassed at 400 ◦ C overnight under high vacuum
a suitable adsorbent for ethylene is still an industrial challenge that conditions (∼10−5 mbar). Then, 1 and 4 molecules of ethylene per unit
requires further investigations. cell were adsorbed on CsAg-RHO (T48 O96 ) and Ag-CHA (T36 O72 ), re-
The adsorption of ethylene on Ag+ sites (and other transition metal
spectively, to carry out the INS and NMR experiments. A lower amount
cations) occurs through the 𝜋-complexation mechanism that involves
was adsorbed in the case of CsAg-RHO, because of the adsorption
the 𝜎 bonding by the electron charge transfer from the p orbitals of
problems presented by the zeolite due to a change in its structure
ethylene to the empty 5s orbital of the Ag cation. Simultaneously, there
symmetry (to be better explained in section 3.2).
is backdonation of charges from the filled 4d10 orbital of Ag+ to the an-
tibonding 𝜋* orbital of the adsorbate. The electron charge backdonation
2.2. Solid state NMR
from silver to ethylene, d(Ag+ ) ⟶ 𝜋* (C2 H4 ) dominates the adsorption
mechanism, producing a lengthening of the C=C bonds, a redshift of 13 C NMR spectra were recorded at 400 MHz on a Bruker Oxford-
the stretching vibrations and a high field shift of the 13 C NMR signal
Avance spectrometer, using a 7 mm probe and spinning the sample at
of ethylene adsorbed on Ag-zeolites or Ag-supported catalyst [17–20].
5 kHz. 13 C NMR spectra were carried out at 25 ◦ C by cross polarization
Theoretical calculations on the adsorption of ethylene on Ag+ -zeolites
sequence under angle spinning conditions (1 H-13 C CP-MAS), using 4 μ
points out to a redistribution of charges upon adsorption with a net
s 𝜋/2 pulses for 1 H with a contact time of 2 ms and a recycle delay
transfer from the 𝜋 (ethylene) to the 5s (Ag+ ) orbitals [21,22].
of 3 s. 13 C labeled ethylene (Ethylene-13 C2 99% atom 13 C, Merck)
The aim of this work is to investigate the influence of the local
was adsorbed in a vacuum line on the samples previously degassed at
geometry and the neighboring chemical composition of the Ag+ sites
400 ◦ C overnight, and adamantane (𝛿 13 C = 38.3 ppm) was used as
on the adsorption of ethylene over Ag-zeolites. For this purpose, we
have chosen two small pore silver exchanged aluminosilicate zeolites reference.
with different topologies, chabazite (CHA type) and Rho (RHO type),
which possess similar micropore volumes and pore apertures delimited 2.3. UV–visible spectroscopy
by 8 TO4 tetrahedra but differ in shapes of the cavities and the windows
that give access to them. Another relevant difference between the two A UV–Vis Cary 7000 spectrometer equipped with a diffuse re-
zeolites is the higher structural flexibility of zeolite RHO upon adsorp- flectance accessory (Praying Mantis Harrick) was employed for UV–
tion [23–25]. Therefore, comparison on the details of the adsorption of Vis experiments. The spectra were measured using BaSO4 as internal
ethylene on Ag-CHA and Ag-RHO zeolites will provide information of standard.
the influence of the geometry, the local chemical composition of the Ag
adsorption site and on the role played by the framework flexibility. The 2.4. Infrared
information on how different factors affect the adsorption of ethylene
on silver-zeolites may contribute to refine the state-of-the-art strategies Infrared spectra were recorded with a Vertex 70 Bruker FTIR spec-
to improve the selectivity in the separation of ethylene, by tuning the trometer using a deuterated triglycine sulfate (DTGS) detector and
properties of metal exchange zeolites. acquiring at 4 cm1 resolution. An IR cell allowing in situ treatments
More specifically, we have investigated the ethylene adsorption on in controlled atmospheres and temperatures from 176 to 500 ◦ C was
Ag-CHA and CsAg-RHO zeolites by applying a variety of spectroscopic connected to a vacuum system with gas dosing facility. For the in situ
techniques such as Infrared (IR), Nuclear Magnetic Resonance (NMR) studies, Ag-CHA zeolite was activated at 350 ◦ C for 4 h under dynamic
and Inelastic Neutron Scattering (INS) in combination with Density vacuum conditions. The temperature was lowered keeping the pressure
Functional Theory (DFT) calculations. The results reported here indi- at 10−4 mbar. Then, doses of ethylene were admitted to the sample cell
cate that there is a strong deformation at the 8-ring pocket zone, where until saturation point at 3.57 mbar. IR spectra were recorded after each
the Ag+ cation is placed, in CsAg-RHO zeolite. On the contrary, no dosage. After saturation, gaseous ethylene and physisorbed ethylene

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G. Almeida et al. Microporous and Mesoporous Materials 367 (2024) 112982

were removed from the cell by means of evacuation until 100 ◦ C and
measured again.
The same procedure was used to measure the CsAg-RHO, how-
ever, ethylene adsorption did not take place. As mentioned in the
experimental part, after the sample degassing, this zeolite undergoes
a conformational change, modifying the symmetry of the catalyst. This
feature results in a decrease of gas diffusion through the channels due
to smaller pore size.

2.5. Inelastic neutron scattering experiment

INS spectra were measured at 10 K in IN1-Lagrange, an indirect neu-

tron vibrational spectrometer located at the hot source of the Institut
Laue-Langevin (ILL), in Grenoble [28,29].
Cu(220) monochromator was employed to select the incident energy
of the neutron beam towards the sample allowing to measure a range
of energy transfer from 200 to 1400 cm−1 with an energy resolution
of 𝛥𝐸∕𝐸 ≈ 2%. After interacting with the sample, the scattered neu-
trons reach a secondary spectrometer equipped with a beryllium filter
that removes higher order harmonics in the analyzer reflections. The
analyzer has a fixed final energy of 4.5 meV, which defines that only
neutrons with the same final energy are recorded by the 3He detector.
The loaded powdered samples were measured in quartz cells (Ag-CHA:
loading 4 C2 H4 /u.c. and mass 235mg/AgCs-RHO: loading 1 C2 H4 /u.c.
and mass 638mg). Side sets of measurements, such as of blank Ag-CHA
and CsAg-RHO samples and empty quartz cells were also carried out in
order to subtract background and scattering from the zeolite framework
for data reduction.
In this kind of instrument where the final wavevector k𝑓 (with
𝑘 = 2𝜋∕𝜆) is significantly smaller than the incident wavevector k𝑖 and
therefore leads to a high momentum transfer Q, the observed intensity
in INS spectra is directly proportional to the Generalized Density of
States (GDOS) [30], which by its turn is comparable to the hydrogen
partial density of states, gH (E), in the case of hydrogenated materials.

2.6. Computational methods

The theoretical Vibrational Density of States, VDOS(E), was com-

puted based on the direct method of first-principles calculations. All
models proposed in this work were conceived parting from a 1x1x1
unit cell following the same cell parameters of the crystallographic
information file provided by the International Zeolite Association [31].
The calculations were performed on the relaxed structure, at the 𝛤
point, by applying DMol3 ab-initio simulation package in Materials
Studio software [32] and the eigen modes were obtained from the
dynamical matrix, considering TS (Tkatchenko–Scheffler) as method Fig. 1. UV–Visible spectra of (A) silver exchanged (black) and degassed Ag-CHA (blue),
for DFT-D correction. Perdew–Burke–Ernzerhof parametrization of the and (B) silver exchanged (black) and degassed CsAg-RHO (red).
Generalized Gradient Approximation (PBE-GGA) [33] and double nu-
merical plus-d-function (DND) all atoms basis set were selected for
all calculations. This specific basis set applies double numeric quality 3. Results and discussion
basis set plus double numeric with polarization functions. Orbital cutoff
values were selected as ‘‘global’’, given a value based on the quality of 3.1. Identification of silver species in Ag-zeolites and their interaction with
the output. In our case these values are 6.1 and 4.8 Å, relative to fine ethylene
geometry optimization calculations for each system studied (RHO and
CHA respectively). Convergence tolerances were defined as fine quality
The UV–Vis spectra of the hydrated Ag-CHA and CsAg-RHO zeolites,
runnings, with energy, maximum force and displacement declared as
shown in Fig. 1, contain signals from 190 to 250 nm related to a
default (the corresponding values are 1.0𝑒−5 Ha, 0.002 Ha/Åand 0.005
dominant transition of Ag+ (from 4d10 state to 4d9 5s1 ) coordinated to
Å). The calculated neutron scattering spectra, that in a hydrogenated
water molecules and oxygen atoms from the lattice.
system is the partial density of states related to hydrogen gH (E), were
extracted from the eigenmodes with AbINS software [34] implemented The spectrum of the CsAg-RHO zeolite does not significantly change
by Mantid [35]. From the energy minimized structures, population after evacuation at 400◦C, indicating that silver species remain as
analysis by Mulliken atomic charges were performed to analyze the dispersed Ag+ (Fig. 1B). Meanwhile, the spectrum of the degassed Ag-
charge transfer between Ag exchanged zeolites and ethylene. DFT CHA, displayed in Fig. 1A, shows two intense new signals at 291 nm
electron density difference (EDD) calculations were also applied in and 322 nm, which are attributed to small Ag clusters. These peaks
order to investigate the binding nature in these systems, where two have been previously observed for Ag-ZSM-5 (framework code MFI)
different sets were considered (molecule and framework separately). and assigned to Ag+ 3
clusters [36] with the aid of time dependent
Norm conserving pseudopotential was selected. Both properties, popu- (TD)-DFT calculations. It must be noted that the spectra of Ag-zeolites
lation analysis and electron density difference, were obtained by using degassed at high temperature show broad bands centred at about
CASTEP package on Materials Studio. 400 nm for Ag-CHA and at 350 nm and 440 nm for CsAg-RHO,

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G. Almeida et al. Microporous and Mesoporous Materials 367 (2024) 112982

Fig. 3. INS spectra for gas phase C2 H4 (gray), C2 H4 Ag-CHA (blue) and C2 H4
CsAg-RHO (red) as measured in IN1-Lagrange.

Fig. 2. 13 C MAS NMR spectra of free-ethylene gas (black) compared to ethylene

adsorbed on Ag-CHA (blue) and CsAg-RHO (red) zeolites. Spinning rotation bands are
indicated by asteriks (*). vibrations involving hydrogen atoms since they feature a much higher
incoherent cross section compared to other elements (80.3 barn for H
while for most of other elements is approximately 5 barn). Therefore,
which suggest that the samples may contain neutral silver clusters or INS is well suited for investigating adsorbed organic compounds [38–
nanoparticles. 41], as hydrogen vibrations can be observed even in regions where
Fig. 2 shows the 13 C CPMAS NMR of 13 C-ethylene free (gas phase) signals from the framework atoms would dominate the spectra if IR or
and adsorbed on Ag-CHA and CsAg-RHO zeolites. The spectrum of 13 C- Raman spectroscopies were used instead [30]. Nevertheless, both are
ethylene presents a very narrow signal at 𝛿 13 C = 123 ppm, which still complementary to INS, specially when it comes to the analysis of
broadens and shifts to high field when it is adsorbed on the Ag-zeolites. stretching modes of the adsorbed molecules.
To prove that these changes are due to the interaction with silver Fig. 3 shows the Generalized Density of States, GDOS(E), of ethylene
species, 13 C NMR of ethylene adsorbed on H-CHA containing only loaded Ag-CHA and CsAg-RHO samples in comparison with gas phase
H+ and Na-CHA zeolites with only Na+ as compensating cations were C2 H4 .
recorded (Fig. S2). The results indicate that the 13 C NMR signal of The well defined excitations at the bending region, from 700 to
the alkene adsorbed on NaCHA is practically the same than in the 1400 cm−1 , correspond to the internal modes of ethylene and are
gas phase, while it is only slightly low field shifted on the H-CHA almost not altered upon adsorption, except by those around 1050 cm−1 ,
zeolile. Meanwhile, the 13 C NMR spectrum of the 13 C-ethylene on the which are redshifted and split. The most significant difference in the
Ag-zeolites give a high field signal at 𝛿 13 C = 110 ppm, similar to spectra of adsorbed ethylene on both Ag-zeolites is the appearance of
that observed during the activation and transformation of methane a significant vibrational band at ≈ 400 cm−1 , in the librational region
on Ag/H-ZSM-5 zeolite, which was assigned to an ethylene-Ag+ com- (between 200 and 450 cm−1 ), corresponding to hindered rotations.
plex [20] and within the range of those reported for ethylene adsorbed
on Ag/SiO2 and Ag/Al2 O3 catalysts (𝛿 13 C ≈ 103-110 ppm) [17–19]. 3.2. Modeling the adsorption of ethylene on Ag zeolites
The shift to high field of the 13 C NMR resonance of ethylene adsorbed
on Ag+ (and other transition metal cations) has been claimed to be The generation of a model and its corresponding atomic positions
dominated by the d ⟶ 𝜋* from Ag+ to ethylene [37]. The observation are crucial to accurately describe some properties such as adsorption
of a unique signal at a chemical shift corresponding to CH2 =CH2 energies, fundamental frequency vibrations and electronic distribution.
adsorbed on Ag+ strongly suggests that ethylene is adsorbed on Ag+ Although the models here described were generated based on UV–Vis
sites at low recovery, although the adsorption on silver clusters cannot and NMR results, their conception holds a maximum of simplicity in
be completely ruled out. The spectrum of ethylene adsorbed on CsAg- order to facilitate the interpretation of INS results.
RHO shows the presence of a second signal at 𝛿 13 C = 115 ppm,
suggesting that ethylene is adsorbed on Ag+ sites on which the d ⟶ 3.2.1. CHA system
𝜋* backdonation from Ag+ to ethylene occurs to lesser extent. The ob- CHA unit cell can be defined as a hexagonal lattice containing
servation of two 13 C NMR signals indicates that there are two different 36 tetrahedral (T) sites and consists of double 6-rings (d6r) and cha
Ag+ sites for ethylene adsorption on CsAg-RHO. Indeed, it has been cavities (9.1 𝑥 10.8 Å2 ) interconnected by a three-dimensional pore
reported that the presence of CH2 =CH2 - Ag+ complexes and reversible system with 8-ring windows [42]. Its chemical formula is represented
adsorbed ethylene gives rise to signals at intermediate chemical shifts by M+ 𝑥 Si(36−𝑥) Al𝑥 O72 , where M+ is the compensating cation. According
due to the exchange between adsorption sites of different strength [18]. to the UV–Vis spectra depicted in Fig. 1, the thermal treatment of Ag-
Inelastic Neutron Scattering experiments were performed on ethy- CHA leads to the co-existence of two different charged silver species:
lene loaded Ag-CHA and CsAg-RHO samples. The advantage of this Ag+ and Ag+ 3
. A model that fully describes this system, with all species,
technique is that all vibrations are active and not subjected to optical would require the use of several unit cells, being too large for DFT
selection rules, allowing the observation of all vibrational bands in a calculations since it would demand excessive computing resources.
wide energy range (from 3 to 5000 cm− 1), including librational modes, Therefore, two models for CHA system were generated separately:
which are not Infrared and Raman visible. INS is mainly sensitive to one simulating the interaction of ethylene and Ag+ and another one

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G. Almeida et al. Microporous and Mesoporous Materials 367 (2024) 112982

the closest framework oxygen atoms in Ag-SAPO 34 and the calculated

adsorption energy are similar to ours. Ag-C distances reported here
agree with those obtained from the crystal structure of dehydrated
Ag-FAU and Ag-LTA upon ethylene adsorption by X-ray diffraction
techniques [47]. Meanwhile, slightly different Ag-C distances (2.23 and
2.28 Å) have been found in an Ag-SSZ-13 model (1Ag:1Al, 3Al/u.c.),
using PBE + HSE hybrid functional [45].
In fact, it is important to mention that the complex Ag-C2 H4 is
located in a specific region of the cage between two side 8-rings and
above a 6-ring. Previous studies [48,49] have addressed this zone as
8-ring side pockets, which works as a critical reactive center inside
certain zeolite cages, due to the favored energy barrier conferred by
the constrained environment. In Ag-CHA, this pocket has a rectangular
shape, as highlighted in Fig. 6.

3.2.2. RHO system

RHO structure contains 48 𝑇 atoms/u.c.. Its chemical formula is
given by M𝑥 M’𝑦 Si(48−(𝑥+𝑦)) Al𝑥+𝑦 O96 , where M and M’ are compensating
cations. The 𝑇 atoms create large lta cages (11.4 x 11.4 Å2 ) linked
through double eight rings (d8r) units to six other neighboring lta
cages, forming a body-centered arrangement of interpenetrating yet
not interconnected pore systems [50]. This framework is known for
Fig. 4. Possible positions for extra-framework cations in CHA. Ag+ species preferred
exhibiting one of the highest flexibilities among zeolite structures.
position is at S2′ , which corresponds to a displacement from position S2 , protruding
into the cha cage. Upon dehydration, a structural distortion can be observed, leading the
framework to change from a high symmetry form (Im3m) ̄ to a lower
̄ m) [24,25,51]. Such distortion occurs in a way to facilitate
one (I43
the coordination of compensating cations to oxygen atoms from the
with Ag+ 3
clusters. The cell composition for each are 3Ag+ Si33 Al3 O72
+ framework. As one of the consequences of this relaxation, the originally
and Ag3 Si35 AlO72 respectively. Since Na content in the samples is
circular shape of the 8-rings becomes elliptical. Another consequence
negligible, it was disregarded in the theoretical representation. Details
is the lta cage transformation, which switches from a nearly spherical
about Ag+ 3
-CHA model is given in Supporting Material. (Fig. S3). Ad-
to conical shape. The extent of RHO’s distortion varies accordingly to
sorption energy calculations for Ag+ 3
and Ag+ models revealed that the
which extra framework cations occupy its cavities [52]. For this reason,
interaction of ethylene with silver cluster (−64 kJ/mol) is weaker than
the presence of other compensating cations have been considered in our
with Ag+ cations (−112.89 kJ/mol). Indeed, minor contributions of
calculations.
silver cluster is deduced from the comparison between experimental
As seen in Section 2.1, incomplete Ag+ cation exchange is achieved
INS spectra (Figs. S4, S5 and S6). Hence, from now on Ag-CHA model
in RHO zeolite. There are three different compensating cations: Na+ ,
will refer to ethylene interacting with Ag+ , being the one considered
Cs+ and Ag+ . Therefore, three simple theoretical models were con-
and compared to RHO system in the following discussions.
ceived: the first one containing only Ag+ as compensating cation (Ag-
For the proposed Ag-CHA model, we considered 3 Al atoms and 3
RHO), the second one with Ag+ and Na+ (NaAg-RHO) and a third
Ag+ cations (according to the sample chemical composition described considering Ag+ and Cs+ (CsAg-RHO). All models keep a very simple
in Section 2.1), with 4 C2 H4 /u.c.. Three extra-framework locations proportion of 1 Ag+ : 1 (Na+ or Cs+ ): 1 C2 H4 per unit cell, in an attempt
have been described in CHA: center of 6-rings (S2 ), center of 8-rings to understand how these cations would contribute to the structural
(S3 ) and center of d6rs (S1 ) [43,44], as can be seen on Fig. 4. We changes in RHO and, therefore, on ethylene-silver interaction.
did not consider site S1 in our calculations since silver species and Extra-framework cations on zeolite RHO can be distributed as dis-
ethylene would not fit together within this very small cage. From played in Fig. 7, where S1 1 and S1 2 correspond to sites within an
energy calculations, we observed that the most stable configuration was octagonal prism displaced from a 4-ring site. S2 is placed at the center
achieved by placing Ag cations at S2 and S3 sites, each one in a different of a six-ring while S2′ and S3 are placed within the lta cage displaced
cha cage. Therefore, Al atoms were arranged in such a way that two from the 6- and 4- rings, respectively. Site S5 lies at the center of a d8r.
are located in 6-rings and one in a 8-ring, all of them far from each According to previous studies [53], Cs+ preferably occupies site is S5
other (another configuration was also considered, revealing however within the d8r while Na+ and Ag+ are placed at site S2′ . This cationic
lower stability; energy details and the full unit cell representation for arrangement was the one considered in our models. In all cases, the
these configurations are found in fig. S7). Then, ethylene molecule ethylene molecule was placed near Ag+ , inside the lta cage in the same
was introduced inside the cha cage, close to a silver atom at the 6- direction as described for Ag-CHA model.
ring (as it presented a stronger interaction C2 H4 - Ag+ at this site, as After geometry optimization of Ag-RHO, NaAg-RHO and CsAg-RHO
shown by its Potential Energy Surface, PES, fig. S8). After geometry models, the d8r and lta cages are distorted in all of them indicating the
optimization, Ag+ cation slightly moves away from the center of 6- structural phase change from Im3m ̄ to I43̄ m. The degree of elliptical
ring, protruding into the cha cage, in the position described as S2′ , and distortion of the d8r can be quantified by a parameter 𝛥, ̄ which is the
the hydrocarbon C=C bond axis was oriented parallel to this same 6- average of the difference 𝛥 between the longest (d1) and the shortest
ring plane, in agreement with previous studies [45,46]. Fig. 5 describes (d2) O-O distances within the cross-section of the d8r windows [54]
∑
in detail the resulting system configuration, highlighting the cha cage and can be represented by the formula: 𝛥̄ = 6𝑖=1 𝛥𝑖, where i is each
containing the ethylene molecule. 8-rings in a lta cage per unit cell. The values found for the elliptical
The displacement of Ag+ towards the cha cage at position S2′ has distortion of Ag-RHO, NaAg-RHO and CsAg-RHO models are 2.10, 2.37
been previously reported when studying C2 H4 adsorption on Ag ex- and 2.17Å, respectively. These 𝛥̄ values are comparable to the ones
changed SAPO-34 (isostructural material to chabazite) by PBE reported by Grand and collaborators [52]. In their study, they investi-
exchange–correlation functional in conjunction with Grimme-type dis- gated the flexibility of RHO framework cages and the distortion of the
persion DFT calculations [46]. The distances between the Ag atom and d8r units upon water and CO2 adsorption/desorption by temperature

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G. Almeida et al. Microporous and Mesoporous Materials 367 (2024) 112982

Fig. 5. Structural details of cha cage in the energy minimized C2 H4 Ag- CHA model. The distances between Ag and the closest framework oxygen atoms, dAg−Oz , as well as Ag-C,
dC−Ag are also shown. C2 H4 molecule is represented before and after the system energy minimization with its corresponding C-H distances, dC−H . Al, Ag, C and H atoms are
highlighted and identified in the figure. O atoms are highlighted in the 6-ring where Ag cation sits, O𝑧 are the 6-ring Oxygen atoms closest to Ag. Si and O atoms of cha cage are
represented by brownish lines to facilitate Ag-C2 H4 complex visualization.

dependant in situ XRD and Rietveld refinements. For dehydrated Na-

RHO and NaCs-RHO, a 𝛥̄ of 2.10Åand 2.16 Å, respectively, were found.
Moreover, as expected, they also described the deformation of lta cages,
which adopts a conical shape in the area of the 8-ring side pockets.
Herein, Fig. 8 illustrates the differences between the two symmetries
on CsAg-RHO model (Im3m, ̄ i.e. before model geometry optimization
̄ m, after geometry optimization), indicating the deformations
and I43
of 8-rings, the d8r and the overall structure. The 8-ring side pockets
are highlighted in blue and it can also be seen in details in Fig. 9.
The same representation for Ag-RHO and NaAg-RHO models can
be found on Supporting Material, Fig. S9. The Ag-RHO, NaAg-RHO
and CsAg-RHO models present similar structural distortions. However,
there is an interesting feature differentiating them: in CsAg-RHO model,
the conical narrowing of lta cage occurs in the region where the C2 H4
- Ag+ complex lies while for the others the narrowing take place
in the opposite side of the cavity. In other words, the major axis
(d1) of the upper elliptical 8-rings in CsAg-RHO (highlighted in light
Fig. 6. Details of 8-ring side pockets in Ag-CHA model, with distance between the
center of 8 rings given in Å.
blue in Fig. 8) is in x-x’ direction while for NaAg-RHO and Ag-RHO
(Fig. S9) it is in y-y’ direction. The calculated adsorption energies
for Ag-RHO, NaAg-RHO and CsAg-RHO models are −93.46 kJ/mol,
−113.68 kJ/mol and −97.24 kJ/mol, respectively. Although NaAg-RHO
shows the highest theoretical adsorption energy, CsAg-RHO model is
the one that best describes the chemical composition of the sample
(with similar proportion of Ag and Cs and negligible presence of
Na). Moreover, the adsorption model on CsAg-RHO shows the best fit
between calculated and experimental INS data compared to Ag-RHO
and NaAg-RHO (Fig. S10), evidencing the fact that the very specific
deformation arrangement found for CsAg-RHO model, i.e. the shape
of 8-ring side pockets, is key to interpret Ag-C2 H4 interactions in Ag-
zeolites. Therefore, only CsAg-RHO model will be used to compare RHO
and CHA as ethylene adsorbents.

3.3. Comparison of INS and computational results

Fig. 10 compares the experimental and calculated INS spectra (fun-

Fig. 7. Possible positions for extra-framework cations in RHO zeolite. Cs +
preferred damental vibrations and total contribution, considering first overtones)
site is S5 and while Na+ and Ag+ prefer site S2′ . of C2 H4 adsorbed on Ag-CHA and at CsAg-RHO zeolites. Detailed INS
spectra of Ag-CHA and CsAg-RHO models are separately shown in
Figures S5 and S11. The analyses of the calculated frequencies for
each configuration enables the identification of the vibrational modes

6
G. Almeida et al. Microporous and Mesoporous Materials 367 (2024) 112982

Fig. 8. Structural details of lta cage in A. before and in B. after geometry optimized C2 H4 CsAg-RHO model. The distortion of d8r and lta cages are shown, indicating the structural
phase change from Im3m ̄ (highly symmetric) to I43 ̄ m (asymmetric). CsAg-RHO model, the conical narrowing of lta cage occurs in the region where Ag-C2 H4 complex lies. The
distances between Ag and the closest framework oxygen atoms, dAg−Oz , as well as Ag-C, dC−Ag are also displayed. C2 H4 molecule is represented before and after the system energy
minimization with its corresponding C-H distances, dC−H . Al, Ag, C and H atoms are highlighted and identified in the figure. O atoms are highlighted in 6-rings where Ag cation
sits. The other O atoms of the framework as well as Si atoms are represented by brownish (and dark blue lines in d8r details) to facilitate Ag-C2 H4 complex visualization. The
upper elliptical 8-rings in CsAg-RHO are highlighted in light blue (8-ring side pockets).

Fig. 9. Details of 8-ring side pockets in CsAg-RHO model, with distance between the
center of 8-rings given in Å.

Fig. 10. Comparison between experimental and calculated INS spectra of C2 H4

of ethylene adsorbed on Ag-CHA and CsAg-RHO (Table 1). The values adsorbed in Ag-CHA and in CsAg-RHO. Full line spectra represent total contribution
(fundamental and first overtone) while the dashed line represent only fundamentals.
described in the table correspond to experimental peaks and calculated
fundamental peaks of each system.
The ethylene molecules interacting with silver centers in zeolites are
subjected to a force that induces them to adsorb in such a way that the around 400 cm−1 is blueshifted in CsAg-RHO when compared to C2 H4
angle formed between the C=C bond and the line connecting the center on Ag-CHA. This result suggests that ethylene’s librations are more
of it with the silver atom, deviates from the perpendicularity [55]. The constricted in CsAg-RHO due to the stronger steric effects imposed by
INS spectrum of ethylene adsorbed on Ag-CHA sample contains one RHO framework deformation caused by the presence of Cs+ cations
bands at 980 cm−1 , that is blue-shifted respect that of pure ethylene gas in d8r and the shape of its 8-ring side pockets. This indicates that
(Fig. 3). This band agrees with that calculated at 977 cm−1 , attributed these bands in the region from 200 to 600 cm−1 are sensitive to the
to the vibrations of CH2 wagging in an asymmetric form, which de- molecule’s surroundings, i.e. to the geometry of the zeolite cage and its
scribe the disturbance provoked by the interaction with silver species. electrostatic field.
Similar overall features are found for C2 H4 adsorbed on CsAg-RHO (see
Table 1).
3.4. Binding mechanism of ethylene on Ag-zeolites
The INS spectra of ethylene adsorbed on Ag-CHA and CsAg-RHO
present vibrational bands in the region between 200 until approxi-
mately 600 cm−1 correlated to the hampered rotations of ethylene, As the changes in the vibrational properties upon gas adsorption
in consonance with earlier publications [38–40]. In fact, the most are bound to the nature of the adsorption mechanism, electron density
significant discrepancy between CsAg-RHO and Ag-CHA configuration calculations (EDD) were carried out for both CHA and RHO systems as
in terms of INS spectra are seen in the librational region since the band an attempt to reveal such nature.

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G. Almeida et al. Microporous and Mesoporous Materials 367 (2024) 112982

Table 1
Vibrational analyses of experimental and calculated frequencies of ethylene interacting
with silver species in Ag-CHA and CsAg-RHO.

Model Experimental Calculated Vibrational modes

freq. (cm−1 ) freq. (cm−1 )

220 220
260 260 Hindered rotations
395 396
818 832 CH2 in plane
rocking (𝜈10 )
Ag-CHA 980 977 CH2 wagging (𝜈8 )
asymmetric
1044 1024, 1037 CH2 wagging (𝜈7 )
asymmetric and CH2
torsion (𝜈4 )
asymmetric
1205 1216 CH2 in plane
rocking (𝜈6 )
1309 1326 CH2 scissoring (𝜈3 )

230 221
270 275 Hindered rotations
411 419
814 825 CH2 in plane
rocking (𝜈10 )
CsAg-RHO 971 970 CH2 wagging (𝜈8 )
asymmetric
1020, 1052 CH2 wagging (𝜈7 )
1027 asymmetric and CH2
torsion (𝜈4 )
asymmetric
1205 1216 CH2 in plane
rocking (𝜈6 )
1294 1323 CH2 scissoring (𝜈3 )

The visual representation (isosurfaces) of the electron density re-

arrangement of the system’s components after their interaction are −3
Fig. 11. Isosurfaces created for −8.369eÅ , representing the electron density differ-
depicted in Fig. 11. In these EDD plots, the different colors indicate ence between ethylene and Ag-zeolites. The yellow shade represents areas of charge
zones of depletion (yellow) and accumulation (purple) of electron depletion while the blue one, of charge accumulation. This rearrangement is attributed
density. For both models, the EDD decreases nearby ethylene and to 𝜋-complexation interaction. In A. the picture illustrates the full contribution of the
increases in the region between ethylene and silver, implicating that Ag-CHA lattice atoms and the molecule, along with details and a schematic drawing,
pointing out the influence of nearest oxygen atoms in the 6-rings in the charge transfer
the 𝜋-electron cloud of the olefins overlaps with the vacant outermost
process. In B. the picture illustrates the full contribution of the CsAg-RHO lattice atoms
s -orbital forming a 𝜎 bond. Simultaneously, there is a decrease of and the molecule, also with details and schematic drawing, which, on the other hand,
the electron density at the metal and an increase along the C=C highlights the influence of nearest oxygen atoms not just from 6-rings but also from
bond, corresponding to an electron 𝜋-backdonation [46,56] from the the closest oxygen of adjacent 8-rings in the charge transfer process, as a result of RHO
phase change and shape of 8-ring side pocket.
d-orbital of the metal cation to the vacant 𝜋* anti-bonding orbitals of
the alkene. This back and forth movement of electrons responds to
the mechanism broadly referred to as 𝜋-complexation [7], which, in
terms of strength, is intermediate between a strong physisorption and a shorter and three longer bonds to the lattice oxygen atoms of this ring
weak chemisorption. The adsorption energies values we computed for (detailed in Figs. 5 and 8 for Ag-CHA and Ag-RHO systems).
Ag-CHA (−112. 89 kJ/mol) and CsAg-RHO (−97.20 kJ/mol) models The distances between Ag and 6-ring O𝑧 are longer in the Ag-CHA
are within this range. Upon complexation, the two carbon atoms of than in CsAg-RHO model. Moreover, in the CsAg-RHO model, besides
ethylene should symmetrically bond to the transition metal cations, the nearest O𝑧 of the 6-ring where the Ag+ is placed, also the nearest
giving similar bond lengths (d𝐶1−𝐴𝑔 ≈ d𝐶2−𝐴𝑔 ). oxygens of adjacent 8-rings contribute to the electron transfer to the
metal cation (as schematized in Fig. 11B.), due to lta cage narrowing
Uzunova et al. [21] adopted an interesting approach to explain the
in the region where the adsorption complex lies or, in other words, due
adsorption and activation of ethylene in transition metal exchanged
to the conic shape of 8-ring side pockets.
clinoptolite by means of DFT calculations; they correlated deformation
The coordination of Ag to oxygen atoms in CsAg-RHO increases
density maps with the role of the framework in the charge transfer from
upon its structural distortion, i.e. Ag atom is surrounded by O coming
metal species to ethylene molecule, revealing the most favorable ethy- from the 6-ring and also from ellipsoid shape 8-rings. As a consequence,
lene configurations and placement according to framework channels the total charge transfer (calculated by Mulliken Charge Analysis, Tab.
and metal cation positions. They reported that the framework oxygen S2 and S3., Figs. S12 and S13) between inorganic–organic elements in
atoms that are the nearest from the metal sites, referred to as O𝑧 , act CsAg-RHO (0.20e− ) is slightly higher than in Ag-CHA (0.17e− ). The
as an electron reservoir as they provide electrons from the negatively higher coordination of Ag+ in CsAg-RHO than in Ag-CHA is what leads
charged framework to the metallic species in 𝜋-complexation. to its weaker adsorption energy when compared with the later. This is
As mentioned previously, in CHA and RHO structures, Ag+ cations explained by the fact that, as the metal cation in RHO framework is
are placed at 6-rings, slightly displaced towards the interior of cha heavily surrounded by oxygen framework electron clouds in the 8-ring
and lta cages, respectively. In this configuration, the metal form three pocket, it is less exposed as an adsorption site for ethylene.

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G. Almeida et al. Microporous and Mesoporous Materials 367 (2024) 112982

The UV–Vis spectra of degassed samples show the occurrence of

different silver species depending on the zeolite structure. Highly dis-
persed Ag+ are the only species in CsAg-RHO, while Ag+ coexists
with Ag3 + in the Ag-CHA zeolite, indicating that silver has partially
agglomerated in this sample. 13 C NMR spectrum indicates a single
resonance at a chemical shift characteristic of the C2 H4 -Ag+ complex
(𝛿 13 C = 110 ppm). These results suggest that at low loadings, ethylene
must be selectively adsorbed on Ag+ , leading us to focus our attention
on the adsorption on Ag+ in the CHA zeolite. The model of the proposed
ethylene-Ag+ complex is confirmed by comparing the calculated and
experimental INS data. The 8-ring side pocket, a region within the cage
that accommodates the complex, works as a critical reactive center due
to the favored energy barrier conferred by the constrained environment
and adopts a rectangular shape in Ag-CHA. On the other hand, DFT
calculations confirms the widely known ellipsoid deformation of RHO’s
8-rings and consequently of 𝑙𝑡𝑎 cages due to the presence of Cs+ cations.
Specifically, 𝑙𝑡𝑎 cages undergo a narrowing in the 8-rings side pocket,
which in this topology assumes a conic shape.
Fig. 12. IR spectrum for ethylene adsorbed on Ag-CHA. It shows a redshift of C=C Comparison of the INS spectra of ethylene adsorbed on the CsAg-
stretching if compared to gas phase ethylene (1623 cm−1 ), suggesting an effective RHO and Ag-CHA zeolites shows that the characteristic band at
interaction between Ag species and the molecule.
400 cm−1 , related to the molecule’s librational mode, is blue-shifted
for the RHO type structure, due to the higher steric hindrance within
its 𝑙𝑡𝑎 cage, confirming that this mode is highly sensitive to ethylene’s
The charge transfer dynamic between ethylene and silver weakens surroundings. It must be noted that the 13 C NMR spectrum of ethylene
and lengthens the molecule’s C=C double bond, causing the redshift adsorbed on CsAg-RHO features, besides the signal at 𝛿 13 C = 110 ppm
of C=C frequency. Upon adsorption, also the C-H bonds of ethylene of the ethylene-Ag+ complex on zeolite Ag-CHA, a second resonance
are affected by 𝜋-complexation and by the electrostatic field within at 𝛿 13 13C = 115 ppm between. Since only Ag+ sites are present in
zeolite’s cavity [21], which is in agreement with our DFT calculations the CsAg-RHO zeolite, the presence of two resonances in the spectrum
(Figs. 5 and 8). Since INS spectroscopy is mainly sensitive to vibrations must be associated to ethylene adsorbed on Ag+ cations in a different
involving hydrogen atoms, C=C stretching is measured as a riding mode environment. It is interesting to note that the ethylene adsorbed on the
with a low intensity at 1500 cm−1 , and could probably be overlapped two sites do not experience chemical exchange, indicating that they
by the overtones of the fundamental vibrations. In this case, IR spec- correspond to two separated sites, i.e. there is site heterogeneity.
troscopy is a complementary technique that allows the observation Electron Density Difference calculations, supported by 13 C NMR,
of the C=C stretching band within the interval 1600–1650 cm−1 . In suggests that the adsorption mechanism of ethylene on Ag+ relies
fact, Carter and collaborators [55] reported a correlation between the on the 𝜋-complexation scheme. The ethylene donates electrons from
shift of the ethylene C=C stretching and the heat of adsorption of its 𝜋-orbital to the outermost empty orbital of the cation, forming a
ethylene on silver-zeolite. In their study, C=C stretching vibrational 𝜎 bond. At the same time, there is a transfer of electrons from the
modes of adsorbed ethylene were featured at lower frequencies than network oxygen atoms to Ag+ and then to the 𝜋* orbital of the adsorbed
in the gas phase, showing redshifts from 30–70 cm−1 . Fig. 12 shows ethylene. Mulliken Charge Analysis indicates a higher charge transfer
the IR spectrum obtained for Ag-CHA. In our work, the experimental in CsAg-RHO model than in Ag-CHA. This higher charge transfer is due
C=C stretching frequencies of ethylene adsorbed in Ag-CHA is red to the increase coordination of silver to O atoms from the framework
shifted 48 cm−1 respect the gas phase (pure gas C=C stretching fre- created by the conical shape of 8-ring side pocket in CsAg-RHO. This
quency reference is 1623 cm−1 ), in excellent agreement with the ≈ way, more framework oxygen atoms contribute to charge transfer by
46 cm−1 found by DFT predictions (details about this calculation are in donating electrons to Ag+ . As a result, the Ag+ adsorption center is
Supporting Material, Fig. S16). DFT also indicates a C=C bond length- partially ’’blocked’’ by the extra electron cloud and the stronger elec-
ening of 0.03Åand shows that C-H bonds in this model undergo some trostatic field of the zeolite framework, which weakens the adsorption
changes upon adsorption passing from equally distanced 1.094Åto energy of C2 H4 -Ag+ complex in CsAg-RHO comparing to Ag-CHA. The
varied lengths between 1.095 and 1.096Å(Fig. 5). We could not obtain redshift of C=C stretching frequencies of infrared spectra of adsorbed
a satisfying spectrum of ethylene adsorbed on CsAg-RHO under the ethylene, besides the C=C and C-H bond lengthening provided by DFT
experimental conditions of in-situ IR. Nevertheless, DFT calculations calculations, further confirms this adsorption model.
predict a redshift of 56 cm−1 , a C=C bond lengthening of 0.03Åand From the industrial point of view, where the aim is to employ less
C-H bonds going from 1.092Åto uneven lengths ranging from 1.094 energy as possible to recover the ethylene, the weaker interaction of
to 1.096Å. Although they are correlated, the redshift experienced by ethylene-silver in the flexible CsAg-RHO zeolite turns this adsorbent
C=C stretching frequency is not directly proportional to the C=C bond more promising than Ag-CHA. However, the mandatory presence of
lengthening once the C-H bonds also suffer the effects of backdonation cesium in RHO framework may limit the accessibility to its pores and
during 𝜋-complexation and of the electrostatic framework [21]. Table 2 cages, becoming less efficient than Ag- CHA. Therefore, an optimized
summarizes all parameters analyzed to evaluate the extent of such adsorbent must reach a compromise between separation efficiency and
adsorption models (experimental isotherms for these systems can be energy demand.
found in Supp. Material, Figs. S14 and S15). In this regard, the combination of theoretical and experimental
approaches for ethylene 𝜋-complexation studies in silver zeolites may
4. Conclusions be extended to investigations in many alike materials (whether other
zeolites or different microporous systems, e.g. Metal-Organic Frame-
Herein, the interaction between ethylene and silver exchanged alu- works) providing satisfactory qualitative and quantitative information.
minosilicate zeolites CHA and RHO has been investigated by applying This would allow the fine tuning of the synthesis conditions, facilitating
INS, NMR, UV- vis and Infrared spectroscopies in combination with the process of obtaining zeolites with target properties for separation
periodic DFT calculations. processes.

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G. Almeida et al. Microporous and Mesoporous Materials 367 (2024) 112982

Table 2
Summarizing table addressing structural details such as cage diameter (D𝑐𝑎𝑔𝑒 ), distances between Ag-O𝑧 , Ag-C and C–H, charge transfer (𝛥e− ), C=C stretching redshift, C=C bond
lengthening (𝛥 𝐶=𝐶 ) and adsorption energies for C2 H4 Ag-CHA and CsAg-RHO.
Model D𝑐𝑎𝑔𝑒 (Å) d𝐴𝑔−𝑂𝑧 (Å) d𝐶1,2−𝐴𝑔 (Å) d𝐶−𝐻 (Å) 𝛥e− C=C stretc. 𝛥C=C (Å) Ads. Energy
(kJ/mol)
C2 H4 Ag-CHA 10.7 2.46, 2.64, 3.02 2.43, 2.45 1.095-1.096 0.17 48 (exp), 46 (calc) 0.03 −112.89
(1.094 before ads)
C2 H4 CsAg-RHO 10 2.49, 2.51, 2.84 2.44, 2.45 1.094-1.096 0.20 56 (calc) 0.03 −97.20
(1.091 before ads)

CRediT authorship contribution statement References

[1] D. Saha, M.-B. Kim, A.J. Robinson, R. Babarao, P.K. Thallapally, Elucidating
G. Almeida: Writing – original draft, Formal analysis. A. de Marcos- the mechanisms of paraffin-olefin separations using nanoporous adsorbents: An
Galán: Writing – original draft, Formal analysis. J. Martínez-Ortigosa: overview, iScience 24 (9) (2021) 103042, http://dx.doi.org/10.1016/j.isci.2021.
Data curation. G. Sastre: Investigation. M. Jiménez-Ruiz: Writing 103042.
– review & editing, Supervision, Investigation, Funding acquisition, [2] Y. Wu, B.M. Weckhuysen, Separation and purification of hydrocarbons with
porous materials, Angew. Chem. 63 (35) (2021) 18930–18949, http://dx.doi.
Conceptualization. F. Rey: Writing – review & editing, Supervision, org/10.1002/anie.202104318.
Methodology, Investigation, Funding acquisition, Conceptualization. T. [3] T. Ren, M. Patel, K. Blok, Steam cracking and methane to olefins: Energy
Blasco: Writing – review & editing, Supervision, Project administration, use, CO2 emissions and production costs, Energy 33 (5) (2008) 817–833, http:
//dx.doi.org/10.1016/j.energy.2008.01.002.
Investigation, Funding acquisition, Conceptualization.
[4] J. Hou, P. Liu, M. Jiang, L. Yu, L. Li, Z. Tang, Olefin/paraffin separation through
membranes: From mechanisms to critical materials, J. Mater. Chem. A (7) (2019)
23489–23511, http://dx.doi.org/10.1039/c9ta06329c.
Declaration of competing interest [5] N. Lu, Q. Gao, Y.M. Zhang, Y. Gao, L.Y. Wu, Y.A. Zhao, L.Z. Chen,
Ethane/ethylene separation in a metal-organic framework with shape-matching
ethane traps, J. Solid State Chem. 304 (2021) 122594, http://dx.doi.org/10.
The authors declare the following financial interests/personal rela- 1016/j.jssc.2021.122594.
tionships which may be considered as potential competing interests: [6] Y. Wang, S.B. Peh, D. Zhao, Alternatives to cryogenic distillation: Advanced
Teresa Blasco reports financial support was provided by Spanish Sci- porous materials in adsorptive light olefin/paraffin separations, Small 15 (25)
entific Research Council. Gabrielli Almeida reports financial support (2019) 1900058, http://dx.doi.org/10.1002/smll.201900058.
[7] M. Sun, Q. Gu, A. Hanif, T. Wang, J. Shang, Transition metal cation-exchanged
was provided by European Research Executive Agency. Alessandra de
SSZ-13 zeolites for CO2 capture and separation from N2, Chem. Eng. J. 370
Marcos Galan reports financial support was provided by Severo Ochoa (2019) 1450–1458, http://dx.doi.org/10.1016/j.cej.2019.03.234.
Foundation. If there are other authors, they declare that they have [8] E.M. Flanigen, Molecular sieve zeolite technology - The first twenty-five years,
no known competing financial interests or personal relationships that Pure Appl. Chem. 52 (9) (2009) http://dx.doi.org/10.1351/pac198052092191.
[9] E. Pérez-Botella, S. Valencia, F. Rey, Zeolites in adsorption processes: State
could have appeared to influence the work reported in this paper.
of art and future prospects, Chem. Rev. 122 (24) (2022) 17647–17695, http:
//dx.doi.org/10.1021/acs.chemrev.2c00140.
[10] P.J. Bereciatuga, Á. Cantín, A. Corma, J.L. Jordá, M. Palomino, F. Rey, S.
Data availability Valencia, E.W.C. Jr., P. Kortunov, P.I. Ravikovitch, A. Burton, C.Y.Y. Wang, C.
Paur, Javier, A.R. Bishop, G.L. Casty, Control of zeolite framework flexibility and
pore topology for separation of ethane and ethylene, Science 358 (6366) (2017)
Data will be made available on request. 1068–1071, http://dx.doi.org/10.1126/science.aao0092.
[11] R. Bai, X. Song, W. Yan, J. Yu, Low energy adsorptive separation by zeolites,
Natl. Sci. Rev. 9 (9) (2022) 2–15, http://dx.doi.org/10.1093/nsr/nwac064.
Acknowledgments [12] Q.H. Trinh, S.B. Lee, Y.S. Mok, Removal of ethylene from air stream by
adsorption and plasma-catalytic oxidation using silver-based bimetallic catalysts
supported on zeolite, J. Hazard. Mater. 285 (2015) 525–534, http://dx.doi.org/
Financial support by the Spanish Ministry of Science and Innovation 10.1016/j.jhazmat.2014.12.019.
by MCIN/AEI/10.13039/501100011033 and ‘‘ERDF A way of mak- [13] N.J. Abreu, H. Valdesa, C.A. Zaror, F. Azzolina-Jury, M.F. Melendrez, Ethy-
lene adsorption onto natural and transition metal modified Chilean zeolite:
ing Europe’’ (Projects: CEX2021–001230-S, PID2022-136934OB-I00) is
An operando DRIFTS approach, Microporous Mesoporous Mater. 274 (2019)
deeply acknowledged. The authors also thank the Spanish Ministry 138–148, http://dx.doi.org/10.1016/j.micromeso.2018.07.043.
of Science and Innovation by MCIN /AEI /10.13039/501100011033 [14] H. Xiang, A. Ameen, P. Gorgojo, F.R. Siperstein, S.M. Holmes, X. Fan, Selective
and ‘‘European Union Next Generation EU/PRTR’’ (Projects: TED2021– adsorption of ethane over ethylene on m(bdc)(ted)0.5 (M=Co, Cu, Ni, Zn)
metal-organic frameworks (MOFs), Microporous Mesoporous Mater. 292 (2020)
130191B-C41), Generalitat Valenciana, Spain (Project: Prometeo 2021/
109724, http://dx.doi.org/10.1016/j.micromeso.2019.109724.
077) and ‘‘Advanced Materials Programme’’ of Generalitat Valenciana [15] S. Aguado, G. Bergeret, C. Daniel, D. Farrusseng, Absolute molecular sieve
‘‘European Union Next Generation EU/PRTR’’ (project: MFA/2022/047). separation of ethylene/ethane mixtures with silver zeolite A, J. Am. Chem. Soc.
All authors thank ILL for neutron beam-time allocation (experiments 134 (36) (2012) 14635–14637, http://dx.doi.org/10.1021/ja305663k.
7-05-488 and 7 05-522) and ILL C-Lab for computational support. [16] J. Min, K. Kemp, S. Hong, Silver ZK-5 zeolites for selective ethylene/ ethane
separation, Separ. Purif. Technol. 250 (2020) 117146, http://dx.doi.org/10.
G.A. thanks funding from the European Union’s Horizon 2020 research 1016/j.seppur.2020.117146.
and innovation programme under the Marie Sklodowska-Curie grant [17] I.L. Mudrakovskii, V.M. Mastikhin, N.E. Bogdanchikova, A.V. Khasin, Nature
agreement No 847439. A.M.G. thanks funding of the grant No SEV of ethylene complexes on the surface of Ag/SiO2 as evidenced by 13C NMR
data, React. Kinetics Catal. Lett. 34 (1987) 185–190, http://dx.doi.org/10.1007/
2016-0683-19-2 from Severo Ochoa programme.
BF02069222.
[18] J.K. Plischke, A.J. Benesi, M.A. Vannice, A 13C NMR study of ethylene adsorbed
on reduced and oxygen-covered Ag surfaces, J. Catalysis 138 (1) (1992) 223–239,
Appendix A. Supplementary data http://dx.doi.org/10.1016/0021-9517(92)90019-E.
[19] Y.H. Chin, P.D. Ellis, Chemisorption of ethylene onto supported platinum gamma
alumina and silver gamma alumina as followed by solid-state static and CP/MAS
Supplementary material related to this article can be found online carbon-13 and static proton NMR spectroscopy, J. Am. Chem. Soc. 115 (1) (1993)
at https://doi.org/10.1016/j.micromeso.2024.112982. 204–211, http://dx.doi.org/10.1021/ja00054a029.

10
G. Almeida et al. Microporous and Mesoporous Materials 367 (2024) 112982

[20] A.A. Gabrienko, S.S. Arzumanov, I.B. Moroz, A.V. Toktarev, W. Wang, A.G. [39] J. Howard, Z.A. Kadir, K. Robson, Infrared spectroscopic studies of ethylene
Stepanov, Methane activation and transformation on Ag/H-ZSM-5 zeolite studied adsorbed on silver A zeolite, Zeolites 3 (1982) http://dx.doi.org/10.1016/0144-
with solid-state NMR, J. Phys. Chem. C 117 (15) (2013) 7690–7702, http: 2449(83)90198-7.
//dx.doi.org/10.1021/jp4006795. [40] J. Howard, T.C. Wassingt, C.J. Wright, Ethylene adsorbed by silver exchanged
[21] E.L. Uzunova, H. Mikosch, Adsorption and activation of ethene in transition 13X zeolite; an inelastic neutron scattering study, J. Chem. Soc. Chem. Commun.
metal exchanged zeolite clinoptilolite: A density functional study, ACS Catalysis (1975) 775–776, http://dx.doi.org/10.1039/C39750000775.
3 (2013) 2759–2767, http://dx.doi.org/10.1021/cs4005997. [41] Y. Chai, X. Han, W. Li, S. Liu, S. Yao, C. Wang, W. Shi, I. da Silva, P. Manuel,
[22] E. Kassab, K. Seiti, M. Allavena, Determination of structure and acidity scales in Y. Cheng, L.D. Daemen, A. J., Ramirez-Cuesta, C.C. Tang, L. Jiang, S. Yang,
zeolite systems by ab initio and pseudopotential calculations, J. Phys. Chem. 92 N. Guan, L. Li, Control of zeolite pore interior for chemoselective alkyne/olefin
(23) (1988) 6705–6709, http://dx.doi.org/10.1021/j100334a043. separations, Science 368 (2020) 1002–1006, http://dx.doi.org/10.1126/science.
[23] J.B. Parise, X. Liu, D.R. Corbin, G.A. Jones, Flexibility of the zeolite Rho aay8447.
framework: The redistribution of extra framework cations as a function of [42] L. Dent, J.V. Smith, Crystal structure of chabazite, a molecular sieve, Nature 181
temperature, MRS Online Proc. Library 233 (1991) 267–272, http://dx.doi.org/ (1958) 1794–1796.
10.1557/PROC-233-267. [43] M. Calligaris, A. Mezzetti, G. Nardin, L. Randaccio, Cation sites and framework
[24] M.M. Lozinska, J.P.S. Mowat, P.A. Wright, S.P. Thompson, J.L. Jorda, M. deformations in dehydrated chabazites. crystal structure of a fully silver-
Palomino, S. Valencia, F. Rey, Cation gating and relocation during the highly exchanged chabazite, Zeolites 4 (1984) 323–328, http://dx.doi.org/10.1016/
selective trapdoor adsorption of CO2 on univalent cation forms of zeolite Rho, 0144-2449(84)90007-1.
Chem. Mater. 26 (2014) 2052–2061, http://dx.doi.org/10.1021/cm404028f. [44] L. Smith, A. Davidson, A. Cheetham, A neutron diffraction and infrared
[25] M. Palomino, A. Corma, J.L. Jordá, F. Rey, S. Valencia, Zeolite Rho: A highly spectroscopy study of the acid form of the aluminosilicate zeolite, chabazite
selective adsorbent for CO2/CH4 separation induces by a structural phase (H- SSZ-13), Catalysis Lett. 49 (1997) 143–146, http://dx.doi.org/10.1023/A:
modification, Chem. Commun. 48 (2) (2011) 231–238, http://dx.doi.org/10. 1019097019846.
1039/c1cc16320e. [45] C. Horvatits, D. Li, M. Dupuis, E.A. Kyriakidou, E.A. Walker, Ethylene and water
[26] D.E. Akporiaye, I.M. Dahl, H.B. Mostad, R. Wendelbo, Aluminum distribution in Co-adsorption on Ag/SSZ-13 zeolites: A theoretical study, J. Phys. Chem. C 124
chabazite: An experimental and computational study, J. Phys. Chem. 100 (10) (2020) 7295–7306.
(1996) 4148–4153, http://dx.doi.org/10.1021/jp952189k. [46] M. Fischer, R. Bell, Cation-exchanged SAPO-34 for adsorption-based hydrocarbon
[27] T. Chatelain, J. Patarin, E. Fousson, M. Soulard, J. Guth, P. Schulz, Synthesis separations: predictions from dispersion-corrected DFT calculations, Phys. Chem.
and characterization of high-silica zeolite RHO prepared in the presence of 18- Chem. Phys. 16 (2014) 21062–21072, http://dx.doi.org/10.1039/C4CP01049C.
crown-6 ether as organic template, Microporous Mater. 4 (2) (1995) 231–238, [47] Y.M. Lee, S.J. Choi, Y. Kim, Crystal structure of an ethylene sorption complex of
http://dx.doi.org/10.1016/0927-6513(95)00009-X. fully vacuum-dehydrated fully Ag+-exchanged zeolite X (FAU). Silver atoms have
[28] A. Ivanov, M. Jiménez-Ruiz, J. Kulda, IN1-LAGRANGE – The new ILL instrument reduced ethylene to give CH2 2- carbanions at framework oxide vacancies, J.
to explore vibration dynamics of complex materials, J. Phys.: Conf. Ser. 554 Phys. Chem. B 109 (2005) 20137–20144, http://dx.doi.org/10.1021/jp058185p.
(2014) 012001–012007, http://dx.doi.org/10.1088/1742-6596/554/1/012001. [48] Z. Liu, X. Yi, G. Wang, X. Tang, G. Li, L. Huang, A. Zheng, Roles of 8-
[29] G. Almeida, A. de Marcos-Galan, T. Blasco, A.V. Moya, F. Rey, M. Palomino, M. ring and 12-ring channels in mordenite for carbonylation reaction: From the
Jiménez-Ruiz, INS study of ethylene on Ag+ exchanged zeolites, 2021. . ILL perspective of molecular adsorption and diffusion, AIChE J. (66) (2020) 16269,
Data Portal. http://dx.doi.org/10.1016/j.jcat.2018.11.024.
[30] P. Mitchell, S.F. Parker, A.J. Ramirez-Cuesta, J. Tomkinson, Vibrational spec- [49] Z. Liu, J. Zhou, X. Tang, F. Liu, J. Yuan, G. Li, L. Huang, R. Krishna, K. Huang,
troscopy with Neutrons with Applications in Chemistry, Biology, Materials A. Zheng, Dependence of zeolite topology on alkane diffusion inside diverse
Science and Catalysis, third ed., World Scientific, United Kingdom, 2005. channels, AIChE J. (66) (2020) 16269, http://dx.doi.org/10.1002/aic.16269.
[31] Ch. Baerlocher and l.b. McCusker, 2022, Database of Zeolite Structures: http: [50] L. Abrams, D.R. Corbin, Sorption properties of zeolite Rho, J. Catalysis 127 (1)
//www.iza-structure.org/databases/. (Accessed: 06 June 2022). (1991) 9–21, http://dx.doi.org/10.1016/0021-9517(91)90204-H.
[32] BIOVIA materials studio, 2023, http://accelrys.com/products/materials-studio. [51] L. Xu, A. Okrut, G.L. Tate, R. Ohnishi, K.-L. Wu, D. Xie, A. Kulkarni, T.
[33] J. Perdew, K. Burke, M. Ernzerhof, Generalized gradient approximation made Takewaki, J.R. Monnier, A. Katz, Cs-RHO goes from worst to best as water
simple, Phys. Rev. Lett. 77 (1996) 3865–3868, http://dx.doi.org/10.1103/ enhances equilibrium CO2 adsorption via phase change, Langmuir 37 (2021)
PhysRevLett.77.3865. 13903–13908, http://dx.doi.org/10.1021/acs.langmuir.1c02430.
[34] K. Dymkowski, S.F. Parker, F. Fernandez-Alonso, S. Mukhopadhyay, AbINS: [52] J. Grand, N. Barrier, M. Debost, E.B. Clatworthy, F. Laine, P. Boullay, N.
The modern software for INS interpretation, Physica B (443–448) (2018) http: Nesterenko, J.-P. Dath, J.-P. Gilson, S. Mintova, Flexible template-free RHO nano-
//dx.doi.org/10.1016/j.physb.2018.02.034. sized zeolite for selective CO2 adsorption, Chem. Mater. 32 (2020) 5985–5993,
[35] O. Arnold, Mantid—Data analysis and visualization package for neutron scatter- http://dx.doi.org/10.1021/acs.chemmater.0c01016.
ing and microSR experiments, nuclear instruments and methods, Phys. Res. A [53] J. Sadlo, M. Danilczukb, J. Michalik, Interaction of tetrameric silver with
764 (2014) 156–166, http://dx.doi.org/10.1016/j.nima.2014.07.029. ammonia in AgCs-Rho zeolite, Phys. Chem. Chem. Phys. 3 (2001) 1717–1720,
[36] T. Yumura, A. Oda, H. Torigoe, A. Itadani, Y. Kuroda, T. Wakasugi, H. Kobayashi, http://dx.doi.org/10.1039/b008246p.
Combined experimental and computational approaches to elucidate the structures [54] S.R.G. Balestra, J.J. Gutiérrez-Sevillano, P.J. Merkling, D. Dubbeldam, S. Calero,
of silver clusters inside the ZSM 5 cavity, J. Phys. Chem. C 118 (2014) Simulation study of structural changes in zeolite RHO, J. Phys. Chem. C 117
23874–23887, http://dx.doi.org/10.1021/jp508150w. (2013) 11592–11599, http://dx.doi.org/10.1021/jp4026283.
[37] J. Mehara, A.K. Surendran, T. van Wieringen, D. Setia, C. Foroutan-Nejad, M. [55] J.L. Carter, V. Kevorkian, The adsorption of ethylene on a series of near-faujasite
Straka, L. Rulíšek, J. Roithová, Cationic gold(II) complexes: Experimental and zeolites studied by infrared spectroscopy and calorimetry, J. Phys. Chem. 70 (4)
theoretical study, Chemistry A Eur. J. 28 (60) (2022) http://dx.doi.org/10.1002/ (1966) 1126–1136, http://dx.doi.org/10.1021/j100876a026.
chem.202201794. [56] M.S. Nechaev, V.M. Rayón, G. Frenking, Energy partitioning analysis of the
[38] J. Howard, K. Robson, T.C. Waddington, Z.A. Kadir, Inelastic neutron scattering bonding in ethylene and acetylene complexes of group 6, 8, and 11 met-
study of ethylene adsorbed on silver - A zeolite, Zeolites 2 (1982) 2–12, http: als, J. Phys. Chem. A 108 (2004) 3134–3142, http://dx.doi.org/10.1021/acs.
//dx.doi.org/10.1016/S0144-2449(82)80033-X. chemmater.0c01016.

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