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org/Langmuir Article

The Operating Cycle of NO Adsorption and Desorption in Pd−

Chabazite for Passive NOx Adsorbers
Marvi Kaushik, Gourav Shrivastav, Tuhin S. Khan,* M. Ali Haider,* and Divesh Bhatia*
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ABSTRACT: Pd-doped chabazite (Pd/CHA) offers unique opportunities to adsorb

and desorb NOx in the target temperature range for application as a passive NOx
Downloaded via INDIAN INST OF TECH DELHI- IIT on May 3, 2023 at 05:13:29 (UTC).

adsorber (PNA). The ability of Pd/CHA to trap NOx emissions at low temperatures
(<200 °C) is facilitated by the binding of NOx species at various Pd sites available in the
CHA framework. Density functional theory (DFT) simulations are performed to
understand Pd speciation in CHA and the interaction of NO with Pd/CHA to explain
the mechanisms of NO adsorption, oxidation, and desorption processes. The
calculations are used to elucidate the important role of Pd1+ cationic species, anchored
at 6MR-3NN, in providing a strong (Eb = −272 kJ/mol) NO adsorption site in Pd/
CHA. For NO release, the redox transformation of Pd species comes into play and Pd1+
species are suggested to transform into cationic Pd2+, [PdOH]+, or [Pd−O−Pd]2+ species, all of which show significantly reduced
NO binding (−116, −153, and −117 kJ/mol, respectively) as compared to Pd1+. This enables NO desorption at the operating
temperature of a downstream catalyst for subsequent catalytic reduction.

1. INTRODUCTION (Pd(H2O)x), as small oxo-ion clusters (PdII−O−PdII)2+ or as

Aftertreatment technologies such as lean NOx traps (LNT)
and selective catalytic reduction (SCR) have been imple-
mented in various diesel-fueled vehicles to reduce the NOx
emissions. However, they are not effective at reducing NOx
emissions under cold-start conditions, which could contribute
significantly to the total emissions. Due to the progressive
lowering of engine exhaust temperatures and the implementa-
tion of stringent emission norms, it has become essential to
reduce the cold-start emissions, especially from diesel engines
with low engine-out temperatures. Passive NOx adsorbers
(PNAs) have been touted to address the cold-start NOx
emissions by trapping NOx from exhaust gas at low (<200
°C) temperatures and releasing it at a higher temperature
(>250 °C) where the downstream NOx reduction catalysts
such as LNT or SCR are active.1 While an array of materials
has been explored as potential PNAs, zeolites and especially
chabazite (CHA) containing Pd species have emerged as the
material of choice for PNAs.1−3 This is because Pd/CHA
serves the dual objectives of NO adsorption at low temper-
atures and NOx release in an appropriate temperature window
for subsequent catalytic transformation. Besides, it has been
found to exhibit good hydrothermal stability. Moreover, for a
given zeolite framework, the existence of multiple Pd species,
which are active for NO adsorption, has been proposed using a
combination of experimental findings and theoretical calcu-
lations.1−6 Clusters, nanoparticles, and metal-exchanged sites
have been identified for active NO adsorption. In addition,
infrared (IR) studies suggest ionic Pd to be responsible for NO
storage at low temperatures.2 However, the actual identity of
the site is unclear because Pd can exist in a hydrated form
monomer oxide clusters (PdIIO). Considering the significance
of PNAs in trapping NOx at low temperatures, an under-
standing of NO binding at specific Pd sites in PNAs constitutes
the state-of-the-art in materials research.
Three major streams of thought are promulgated in different
theoretical and experimental investigations that have probed
the sites and form of NO adsorption on different Pd
species.4,5,8 Foremost of all is the availability of both the PdI
and PdII species as sites for NO adsorption.2,7 However, this
view is rejected in recent density functional theory (DFT)
calculations and spectroscopic experiments by Mandal et al.
since the authors could not corroborate the existence of Pd1+
in the as-synthesized PNAs.4 Interestingly, adsorption experi-
ments conducted by Tronconi and co-workers in transient
conditions have contradicted this assertion, highlighting the
role of Pd1+ species as the most active and available site for NO
adsorption.8 During the experimental investigations, it was
observed that the majority of Pd exists in a +2 oxidation state,
but with the influx of NO or CO in the feed, there is a change
in the oxidation state of Pd (mainly from +2 to +1). Moreover,
CO was found to be a better reductant in comparison to NO
for the reduction of Pd2+ to Pd1+, and it was hypothesized that
Received: May 24, 2021
Revised: October 20, 2021
Published: November 12, 2021

© 2021 American Chemical Society https://doi.org/10.1021/acs.langmuir.1c01383

13799 Langmuir 2021, 37, 13799−13809
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Figure 1. CHA supercell with 36 T model having 8MR, 6MR, and 4MR. Colors of atoms are represented as follows: yellow - silicon; red - oxygen.
the presence of CO enhances NOx adsorption by reducing
Pd2+ to Pd1+.8 This showed that the oxidation state of Pd is
sensitive towards the environment in the vapor phase. Besides
experimental investigations, theoretical calculations carried out
by Khivantsev et al. suggest a decrease in NO binding energies
in the presence of CO.6,9 It has also been shown that the
method of synthesis of Pd/SSZ-13 plays a governing role in the
speciation of Pd sites. Khivantsev et al. devised a method for
synthesizing Pd/SSZ-13, wherein low Si/Al ratios and low Pd
loadings resulted in Pd2+ as the predominant sites.9 Bell and
co-workers pointed toward the ambiguity in spectroscopic
methods applied in studying Pd speciation.5 They highlighted
the need for electron paramagnetic resonance (EPR) spec-
troscopy experiments to confirm the presence of Pd1+ species
in the as-synthesized Pd/CHA.
Interestingly, for a functioning PNA material, it is highly
desirable that NO should bind strongly on the adsorption sites
to trap the maximum amount of NO at low temperatures
(<200 °C). Simultaneously, it should desorb at the desired
temperature (>250 °C) for its reduction over a downstream
NOx reduction catalyst. This paradigm is analogous to the
requirement of a heterogeneous catalyst material, where the
Sabatier principle dictates that the binding on the catalyst
surface should neither be too strong nor too weak to complete
the catalytic cycle giving maximum possible turnovers. Since
Pd/CHA is now considered as the material of choice in PNAs,
we envisage a molecular-level explanation for its functioning,
which may elucidate this optimum adsorption−desorption
cycle of NOx species. Utilizing theoretical simulations, this
study reconciles some of the mechanistic understanding of the
functioning of PNAs with a spotlight on NO interaction with
Pd/CHA. This is achieved in two steps. First, DFT simulations
are invoked to unravel Pd speciation in CHA, and second, the
strength of NO interaction on different Pd sites is evaluated. In
this interaction, the oxidation of NO to NO2 is also
considered, as reported in the experiments.1,2 Transition
state calculations are performed to elucidate the mechanism
for cationic Pd reduction with simultaneous NO oxidation on
Pd sites. NO oxidation is also observed on zeolites due to
confinement effects, which are studied separately with Reactive
Forcefield (ReaxFF) molecular dynamics (MD) simulations at
a realistic operating temperature of PNAs.10,11 Experimental
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studies conducted with water as the co-feed suggest a negative
impact of water on the activity of PNAs.1−3 Moreover,
theoretical calculations carried out by Mandal et al. in the
presence of water suggest a decrease in the NO binding
energies.4 However, in a recent experimental study, it was
observed that the presence of water increases the NO
desorption temperature.8 In this work, H2O molecules are
introduced into the model system to assess their effect on the
adsorption−desorption cycle of NO. Overall, the results
provide a molecular-level insight into the functioning of
PNAs, which is likely to frame the development of effective
materials with the desired functioning.
2. METHODOLOGY
For molecular simulations, a periodic three-dimensional
siliceous CHA structure is constructed, with lattice parameters
of 13.675 Å × 13.675 Å × 14.767 Å obtained from the
database of the International Zeolite Association.12 As shown
in Figure 1, the CHA framework consists of a network of
different membered rings (MRs) such as 8MR, 6MR, and
4MR, where yMR refers to the ring in the CHA framework
having “y” number of Si atoms. For DFT simulations, a
supercell of CHA is created using 36 tetrahedral (36 T) sites
(Figure 1), in which silicon atoms at two of the T sites are
replaced by aluminum atoms to achieve the desired Si/Al ratio
(=17), which is close to the Si/Al ratio (=15) reported in
experiments for Pd/CHA PNAs.2
DFT simulations are performed using the plane-wave code
as available in the Vienna ab initio simulation package (VASP,
version 5.2). For exchange−correlation functionals, the
generalized gradient approximation (GGA) developed by
Perdew, Burke, and Ernzerhof (PBE) is invoked.13 The
interaction of NO with the Pd/BEA zeolite is studied in detail
by Wang and co-workers using the same GGA-PBE functional
to understand the trend in relative energies.14 While a higher-
order functional is expected to provide more accuracy in the
calculated energetics, computational expense remains a bottle-
neck in theoretical studies on zeolites.14 Mandal et al.
demonstrated higher accuracy in DFT calculations for Pd/
CHA using a hybrid functional (HSE06) as compared to the
GGA-PBE functional.4 However, the authors showed similar
energetic trends in comparing NO interaction with the
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Figure 2. Optimized structures of (a) 6MR-2NN, (b) 6MR-3NN, and (c) 8MR-4NN configurations with H+ as a compensating cation in the CHA
framework. All bond distances are in Å. Colors of atoms are represented as follows: yellow - silicon; red - oxygen; magenta - aluminum; white -
hydrogen. For clarity, the periodic structure of the zeolite is not shown.
different sites (e.g., Pd2+, Pd1+, and [PdIIOH]+) using the two
functionals (HSE06 and GGA-PBE). The GGA-PBE func-
tional has been consistently used in recent theoretical studies
on various zeolites including CHA, and it is considered to be
reasonably effective in estimating energy trends so as to make
informed decisions for experimental analysis.15−17
The basis set of the plane-wave is expanded to an energy cut-
off value of 396 eV, which is kept slightly higher than the
previous theoretical calculations on Pd/BEA.14,18,19 For
geometry optimization, the force on the structure is calculated
using the Hellmann and Feynmann theorem and is converged
to 0.05 eV/Å.20 The binding (adsorption) energy (Eb) of the
adsorbates on various Pd sites is calculated using eq 1.
E b = Ead − Pd/CHA − (E Pd/CHA + Ead) (1)
Here, Ead‑Pd/CHA is the absolute energy of the optimized zeolite
structure together with the adsorbate and Pd site, EPd/CHA is
the absolute energy of the zeolite, and Ead is the absolute
energy of the adsorbate in the vapor phase. All the structure
optimization calculations are carried out with neutral charge,
wherein the framework negative charges are compensated by
Pd speciation.
The reaction energy (ΔEsurface
rxn ) on the surface is calculated
using the binding energies of the products (EFS) and the
reactants (EIS) as
surface
ΔErxn = E FS − E IS (2)
The structures of the transition state (TS) on the minimum
energy path (MEP) for various reactions are located using the
nudged elastic band (NEB) method.21 A set of eight images
are linearly interpolated to connect the reactant and product
states, similar to that performed in a recent study for TS
calculations using the NEB method.22 These structures are
optimized with a force convergence criterion of 0.05 eV/Å
along the MEP. The reaction coordinate is further converged
with an improvised version of the NEB method, in which the
highest energy structure on the MEP is dictated to climb up
and satisfy the energy maxima criteria (one imaginary
frequency), as implemented in the climbing image-NEB
algorithm.23 The activation energy (Ea) of the intrinsic
reaction step is finally calculated as the difference between
the energy of the TS and initial state (IS) structures.
To get insights into the interaction of NO and O2 with
HCHA, reactive MD simulations are performed in the NVT
ensemble using the ReaxFF potential in the LAMMPS
package.24 The equations of motion are integrated using the
velocity-Verlet scheme. The cubic periodic boundary condition
is used to ensure the bulk limit. The short- and long-range
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interactions are computed as described by the ReaxFF
potential in LAMMPS. The temperature is maintained using
a Nosé−Hoover thermostat with a damping constant of 200 fs.
The initial configuration with randomly distributed six
molecules of NO and three molecules of O2 in the zeolite
framework (single unit cell) is obtained using the PACKMOL
package. This configuration corresponds to loadings of 2.77
and 1.38 mol of NO and O2, respectively, per kilogram of
zeolite. The system is equilibrated using a timestep of 0.1 fs for
5 ps at 313 K. Subsequently, a 2.5 ns long simulation with a
timestep of 0.25 fs is performed at 313 K followed by 2.5 ns
long simulations at 373 and 473 K. A similar set of simulations
is also performed without the zeolite framework using
parameters from the literature.24,25 MD simulations using
ReaxFF potentials are utilized to calculate the diffusion
coefficients of NO and H2O in the nanoporous structure of
the CHA following Einstein’s relationship. The methodology
adopted for calculation of the diffusion coefficients is similar to
the above-reported method for reactive MD simulations.
However, in this case, the initial configuration contains 17
randomly distributed gas molecules in the 2 × 2 × 2 zeolite
framework which corresponds to a loading of 0.98 mol of gas
per kg of zeolite. In this case, the system is equilibrated using a
timestep of 0.1 fs for 2 ps at 313 K. Subsequently, a 0.25 ns
long simulation with a timestep of 0.25 fs is performed at 313
K followed by 0.25 ns long simulations at 473 K.
3. RESULTS AND DISCUSSION
3.1. Stability of Various Al Configurations in the CHA
Framework. The arrangement of Al atoms in the T site of the
framework governs the location of the active sites for NO
interaction.2 There are multiple configurations possible based
on the position of the paired Al atoms inside the ring.
Experimentally, it is observed that the majority (>50%) of Al
atoms are present in the 6MR of the CHA cage.26,27 Hence,
theoretical calculations are performed to determine the
preferential location of paired Al atoms inside the 6MR.
Similar calculations are performed for 8MR as well. The
negative charge generated due to the presence of Al atoms is
compensated by the addition of protons or metal (Pd1+ or
Pd2+) cations. The H+ ions are present on the framework
oxygen atom nearest to the aluminum atom, as shown in
Figure 2. Al configuration in the zeolite framework is defined
by the connectivity of the two Al atoms. The second nearest
neighbor is denoted as 2NN, the third nearest neighbor is
denoted as 3NN, and so on (Figure 2). For a specific Al
configuration in the CHA, multiple structures are possible.
However, we have focused only on the structures where both
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the paired Al atoms are present in the same ring. Since the
1NN Al configuration is in violation of the Löwenstein’s rule, it
is not considered for the calculations.28 The 8MR-4NN Al
configuration is found to be stable for various Cu and Fe
species and hence is considered for the calculations.29,30 The
total energies of various configurations in 6MR as well as 8MR
(2NN, 3NN, and 4NN) referenced to the lowest-energy
structure (6MR-2NN) are computed and tabulated in Table
S1 (SI). The relative energy is found to follow the trend 6MR-
2NN < 6MR-3NN < 8MR-2NN ∼ 8MR-3NN ∼ 8MR-4NN.
Schneider and co-workers performed similar calculations and
reported that, in general, the 4NN configuration is the least
stable followed by 3NN and 2NN.31 The geometries for 6MR-
2NN and 6MR-3NN are shown in Figure 2. Since the energies
of 8MR-2NN, 8MR-3NN, and 8MR-4NN are nearly the same,
the structure of only one of them (8MR-4NN) is shown in
Figure 2.
Infrared (IR) studies conducted on Pd/CHA have reported
the presence of Pd clusters and ions at temperatures as low as
298 K.3 Atomically dispersed PdOx clusters are reported in
extended X-ray absorption fine structure (EXAFS) and
transmission electron microscopy (TEM) images, mostly
located on the external surface.2,3,5,32 The ionic species are
present either as Pd1+ or Pd2+ cations or in ligands such as
[PdIIOH]+ or [PdII−O−PdII]2+.2−6 The location of these Pd
sites is correlated with the arrangement of Al atoms. Bell and
co-workers performed a thermodynamic analysis on the
stability of various Pd sites in 6MR and 8MR for different Al
distributions.5 Based on their inferences, the type and location
of Pd sites is chosen in this work for further DFT calculations.
The total energy of the CHA structure in the supercell is
calculated for each site, viz., Pd2+, Pd1+, [PdII−O−PdII]2+, and
[Pd IIOH]+ in 8MR as well as in 6MR for different
arrangements of Al atoms. For 8MR, the 4NN configuration
of Al is specifically chosen (Figure S1, SI), as suggested in the
work of Verma et al.29
For each site, the configuration (site location and arrange-
ment of Al) with the lowest absolute energy is identified.
Further, the relative energy of each site for various
configurations is calculated with reference to the lowest-energy
configuration for that particular site and is given in Table 1 for
Table 1. Relative Energies (in kJ/mol) for Different Pd Sites
Site 6MR-2NN 6MR-3NN 8MR-4NN
2+
Pd 52 0 217
Pd1+ 13 0 75
[Pd−O−Pd]2+ 107 12 0
[PdOH]+ 19 0 75
various sites and configurations. Note that for a particular site,
a comparison of the relative energy for different configurations
can be made to evaluate the stability of various configurations.
However, any inference cannot be made by a direct
comparison of the relative energy of various sites, unless they
are normalized to consider the number and type of atoms. The
geometry-optimized structures of each site in the 6MR-3NN
location are represented in Figure 3. The geometry-optimized
structures of Pd sites in other Al configurations (8MR-4NN
and 6MR-2NN) are represented in Figures S1 and S2,
respectively. For brevity, [PdIIOH]+ and [PdII−O−PdII]2+ are
referred to in the following discussion as [PdOH]+ and [Pd−
O−Pd]2+, respectively.
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For the Pd2+ ion, the 6MR-3NN configuration is calculated
to be the most stable in comparison to other configurations
and thus has a relative energy of 0. This is consistent with the
reported results for speciation of various metal cations such as
Cu2+, Co2+, Fe2+, and Ca2+ in the 6MR of CHA.30,31,33 The
positive relative energy for Pd2+ in 6MR-2NN and 8MR-4NN
configurations indicates that Pd2+ is less likely to be present in
these configurations as compared to 6MR-3NN. The
optimized structure obtained (Figure 3a) is consistent with
those reported for the Pd2+ ion anchored on the framework
oxygen atoms close to the T site of 6MR in the CHA.4,5 As
shown in Figure 3a, both the Al atoms in the 6MR-3NN Al
configuration are directly opposite to each other (in a para
position) with a distance of 5.2 Å. Pd2+ is calculated to be
symmetrically anchored on the four framework oxygen atoms
with a distance of approximately 2.1 Å.
While most of the studies on PNAs have corroborated the
presence of Pd2+ species in Pd/CHA, recent works by Bell and
co-workers, Harold and co-workers, and Tronconi and co-
workers, alluded toward the existence of Pd1+ cationic species,
anchored on the zeolite framework.5,7,8 In fact, Bell and co-
workers pointed toward the ambiguity in the assignment of
oxidation states (Pd2+ or Pd1+) in EXAFS, X-ray absorption
near-edge structure (XANES), and UV−vis experiments.5 The
authors highlighted the need for additional electron para-
magnetic resonance (EPR) spectroscopy measurements to
establish the correct oxidation state for Pd cationic species,
which will be helpful in clearly establishing the presence of
Pd1+, preferentially occupying the 6MR sites. These observa-
tions stand in contrast to the measurements of Mandal et al.,
wherein the authors used EXAFS and diffused reflectance
infrared transmission spectroscopy (DRIFTS) measurements
to conclude the presence of Pd2+ cationic species and ignored
the presence of Pd1+ species as NO storage sites.4 Interestingly,
transient adsorption and desorption experiments by Tronconi
and co-workers established that Pd1+ is indeed the preferred
NO adsorption site in CHA.8 Following these results, DFT
calculations are performed in this study to calculate the
energetics of Pd1+ species on different Al configurations at the
6MR (2NN and 3NN) and 8MR (4NN) sites, as shown in
Table 1. As listed in Table 1, the trend in the energetics of Pd1+
anchoring on different Al sites is the same as that calculated for
Pd2+, wherein the 6MR-3NN site is the most stable location for
Pd1+. Figure 3b shows the Pd1+-6MR-3NN configuration,
wherein Pd1+ is observed equidistant (at 2.2 Å) from three
framework oxygen atoms.
Based on CO-DRIFTS spectra, Zheng et al. suggested the
presence of [Pd−O−Pd]2+ species in the CHA framework.2
However, Khivantsev et al. did not observe Pd−O−Pd
coordination in their EXAFS studies.9 Interestingly, in a
separate study on Fourier transform infrared (FTIR) character-
ization of Pd/CHA, Khivantsev et al. reported a peak at 2110
cm−1, which can be assigned to both Pd2+ (2114 cm−1) and
[Pd−O−Pd]2+ (2116 cm−1), as indicated in their DFT
calculations.6 Table 1 lists the relative energies for the [Pd−
O−Pd]2+ species anchored at different locations (8MR-4NN,
6MR-3NN, and 6MR-2NN) in Pd/CHA. The stability of
[Pd−O−Pd]2+ species in 6MR-3NN and 8MR-4NN is nearly
the same (with a slight energy difference of 12 kJ/mol), while
6MR-2NN is highly unstable (107 kJ/mol). The slightly higher
stability of [Pd−O−Pd]2+ in 8MR-4NN as compared to 6MR-
3NN is possibly due to the bigger size of 8MR (8 Å) as
compared to that of 6MR (3.9 Å) in Pd/CHA, which stabilizes
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Figure 3. Optimized structures of Pd sites in 6MR-3NN: (a) Pd2+, (b) Pd1+, (c) [Pd−O−Pd]2+, and (d) [PdOH]+. All bond distances are in Å.
Colors of atoms are represented as follows: green - palladium; yellow - silicon; red - oxygen; magenta - aluminum; white - hydrogen. For clarity, the
periodic structure of the zeolite is not shown.

Figure 4. NO adsorption on various Pd sites in 6MR-3NN: (a) Pd2+, (b) Pd1+, (c) [Pd−O−Pd]2+, and (d) [PdOH]+. All bond distances are in Å.
Colors of atoms are represented as follows: blue - nitrogen; green - palladium; yellow - silicon; red - oxygen; magenta - aluminum; white -
hydrogen. For clarity, the periodic structure of the zeolite is not shown.

the anchoring of the bigger Pd-oxo-ion. However, the energy
difference of 12 kJ/mol is relatively less significant, and [Pd−
O−Pd]2+ may exist in 6MR-3NN as well as in 8MR-4NN.
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Similarly, the Cu−Ox−Cu species in CHA are considered
stable (by 42 kJ/mol) in the 8MR site as compared to those in
the 6MR site.29 The structure of [Pd−O−Pd]2+ in 6MR-3NN
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is included in Figure 3c for comparison with other Pd species
in the same location, while the configuration of [Pd−O−Pd]2+
in 8MR-4NN is included in the Supporting Information (SI),
Figure S1(c). As shown in Figure 3c, the Pd atoms are
symmetrically located in 6MR-3NN with a Pd−Oz distance of
2.2 Å. The bridging oxygen located between the two Pd atoms
is at a Pd−O distance of 1.8 Å. Bell and co-workers and
Khivantsev et al. also performed similar calculations to
understand the speciation of [Pd−O−Pd]2+ in 6MR-3NN
and reported Pd−O z distances of 2.14 and 2.19 Å,
respectively.5,6
The hydroxylation of the [Pd−O−Pd]2+ site is suggested to
produce [PdOH]+ in Pd/CHA, which is also identified in the
CO-DRIFTS spectra.2 The transition state calculation for this
conversion indicates an intrinsic barrier of 32 kJ/mol, as
discussed later in Section 3.3. This transformation of [Pd−O−
Pd]2+ sites to [PdOH]+ is similar to the one reported for Pd/
BEA (Ea = 39 kJ/mol).14 The presence of the [PdOH]+ site is
fortified in the experiments by Tronconi and co-workers, who
proposed the conversion of [PdOH]+ to Pd1+ upon exposure
to CO.8 Table 1 lists the energetics of [PdOH]+ at 6MR-3NN,
6MR-2NN, and 8MR-4NN locations, and it is observed that
the 6MR-3NN configuration is the most stable. Figure 3d
represents the [PdOH]+ site in the 6MR-3NN configuration
with Pd symmetrically anchored to two framework oxygen
atoms with a bond distance of 2.1 Å. To summarize, the 6MR-
3NN configuration is the most stable for the various Pd sites,
except for [Pd−O−Pd]2+ for which 8MR-4NN is slightly more
stable than 6MR-3NN. All the aforementioned sites listed in
Table 1 are further studied for NO interaction.
3.2. NO Adsorption on Pd Sites. The binding strength of
NO on various Pd sites in the CHA zeolite is calculated using
eq 1 for different Al configurations. The geometries for
adsorbed NO on various Pd sites at the 6MR-3NN location are
shown in Figure 4, since the 6MR-3NN configuration is found
to be the most stable for nearly all of the Pd sites (Table 1).
Even though [Pd−O−Pd]2+-6MR-3NN is found to be slightly
less stable (by 12 kJ/mol) than [Pd−O−Pd]2+-8MR-4NN,
Figure 4c shows the NO binding on 6MR-3NN for a better
comparison. The NO binding geometries for various Pd sites
in 8MR-4NN and 6MR-2NN configurations are respectively
included in Figures S3 and S4 (SI).
The NO adsorption energies on different Pd sites for various
locations and Al arrangements are given in Table 2. In contrast
Table 2. Binding Energy of NO (in kJ/mol) on Various Pd
Sites and Al Configurations
Site 6MR-2NN 6MR-3NN 8MR-4NN
Pd2+
−102 −116 −121
Pd1+ −249 −272 −307
[Pd−O−Pd]2+ −105 −117 −130
[PdOH]+ −139 −153 −148
to Table 1, all the values reported in Table 2 can be compared
against each other. It is generally observed from Table 2 that
both the location of the active sites (6MR or 8MR) and the Al
configuration (2NN, 3NN, 4NN) impact the binding strength.
On the Pd2+-6MR-3NN site, NO is linearly adsorbed with the
nitrogen atom attached to the Pd atom at a bond distance of
1.9 Å (Figure 4a). This binding geometry is similar to the one
reported for Pd2+ in theoretical studies.4,14 Interestingly, the
binding for NO adsorption on the Pd2+ sites in CHA (−116
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kJ/mol, Table 2) is significantly weaker as compared to that on
the same site in Pd/HBEA (Eb = −256 kJ/mol).14 The
reduced binding strength can be ascribed to the geometric
(confinement) effect of small pores of CHA as compared to
those of HBEA. While several authors have reported the
abundance of Pd2+ sites in Pd/CHA from experiments and
theoretical calculations, it has also been reported that the
reduced Pd1+ sites are more active for NO adsorption.8 Hence,
NO binding on Pd1+ is explored as the next step.
As shown in Figure 4b, NO binds to the Pd1+-6MR-3NN
site via the N atom at a distance of 1.8 Å with an adsorption
energy of −272 kJ/mol (Table 2). NO adsorption energies on
Pd1+ for all other Al configurations are reported in Table 2.
Among the different Al configurations considered for NO
interaction with Pd1+, NO binds strongly when Pd1+ is present
in the 8MR-4NN configuration, with a binding energy of −307
kJ/mol (Table 2). However, the Pd1+-8MR-4NN itself is
unstable (Table 1), leading to the detachment of the Pd atom
from the framework and resulting in the formation of a mobile
Pd−nitrosyl complex, as represented in Figure S3(b). In
comparison, the binding of NO on Pd1+-6MR-3NN is slightly
weaker (Eb = −272 kJ/mol, Table 2) than that on Pd1+-8MR-
4NN but is significantly stronger than that on Pd2+-6MR-3NN
(−116 kJ/mol, Table 2). Since the availability of Pd1+ sites is
evidenced in several experiments, we consider it as the main
site for NO adsorption in Pd/CHA for application in
PNAs.2,3,8 However, NO adsorption can also take place on
the Pd2+ sites as well but with a relatively lower contribution
because of weaker binding. The strong binding on Pd1+ is likely
to enable NO adsorption at low temperatures (<200 °C) for its
potential application in PNAs. Interestingly, NO binding on
cationic Pd1+ sites in Pd/HBEA calculated by Wang and co-
workers using the same GGA-PBE functional is of the same
order (250−255 kJ/mol).14
The NO adsorption energy is also calculated on [Pd−O−
Pd]2+ and [PdOH]+ sites. NO binds to one of the Pd atoms
bent inward in [Pd−O−Pd]2+, with the N atom at a distance of
1.8 Å, as represented in Figure 4c. NO binds slightly stronger
on [Pd−O−Pd]2+-8MR-4NN (−130 kJ/mol) in comparison
to that on [Pd−O−Pd]2+-6MR-3NN (−117 kJ/mol), which is
attributed to the anchoring of NO to both Pd atoms in [Pd−
O−Pd]2+-8MR-4NN. Figure S3(c) shows the NO adsorption
on [Pd−O−Pd]2+-8MR-4NN, wherein NO is equidistant from
both the Pd atoms. NO in 6MR-3NN binds to [PdOH]+
through the N atom with a Pd−N bond distance of 1.9 Å, as
shown in Figure 4d. The adsorption energy of NO on
[PdOH]+ (−153 kJ/mol, Table 2) is consistent with earlier
reports (Eb = −177 kJ/mol).6 The binding strength of NO on
both [Pd−O−Pd]2+ and [PdOH]+ sites is found to be
significantly weaker as compared to that on Pd1+. In fact, as
compared to NO binding on the same Pd sites in Pd/HBEA
(Eb = −164 kJ/mol on [PdOH]+, −172 kJ/mol on [Pd−O−
Pd]2+), the NO binding on these sites in Pd/CHA is observed
to be considerably weaker.14 We hypothesize that these sites
are more suited for NO desorption (within the target range of
temperature), which is a desired function of PNAs. The link
between the separate adsorption and desorption sites in Pd/
CHA is provided by their rapid redox transformation, which
was evidenced in adsorption−desorption experiments.8
3.3. Interconversion of Pd Sites and NO Oxidation.
Tronconi and co-workers in transient state NOx adsorption/
desorption experiments suggested that the adsorption of NO
on Pd sites ([PdOH]+ and [Pd−O−Pd]2+) leads to the
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Figure 5. Optimized structures of the reactant, product, intermediate, and transition state for NO oxidation on [PdOH]+-6MR-3NN to produce
Pd1+ sites via reaction mechanism R1. For clarity, the periodic structure of the zeolite is not shown.

Figure 6. Optimized structures of the reactant, product, and transition state for NO oxidation on [Pd−O−Pd]2+-6MR-3NN site to produce Pd1+
site via reaction R2.

reduction of Pd2+ to Pd1+ accompanied by NO2 formation.8
Zheng et al. observed NO2 release at low temperatures (100
°C), which was attributed to the reduction of [PdOH]+ and
[Pd−O−Pd]2+ by NO to Pd1+.2 This indicates the presence of
a redox cycle, wherein NO oxidizes to NO2 and PdII species
are reduced to Pd1+. Also, IR studies by Harold and co-workers
have suggested that Pd2+ undergoes reduction to form Pd1+
with the evolution of NO2.7 More specifically, IR spectroscopic
studies conducted for NO adsorption in the absence of O2
suggested a transfer of an electron from NO to cationic Pd
species, which led to the reduction of ionic Pd species and
simultaneous formation of NO2.3 From these observations, it
can be hypothesized that there are some sites present in the
zeolite with oxygen coordinated to the Pd atom that can
facilitate this NO2 formation. Theoretical calculations are
therefore performed on [PdOH]+ and [Pd−O−Pd]2+ sites to
calculate the energetics of their transformation into Pd1+ along
with NO oxidation.2,14 It is proposed that NO2 formation on
[PdOH]+ and [Pd−O−Pd]2+ sites takes place by reactions R1
(a,b) and R2, respectively.2,14 It is also observed that the
reduction of Pd2+ to Pd1+ is a one-electron transfer process,
while the formation of one molecule of NO2 involves two
electrons. Hence, two [PdOH]+ sites are required for the
conversion of NO to NO2. Further, transition state calculations
are performed, and the activation energy barrier is obtained on
the two sites. Moreover, as discussed later, calculations are also
performed for the hydroxylation of [Pd−O−Pd]2+ as well as
Pd2+ to form [PdOH]+, which is involved in the formation of
NO2 from NO.
Z−[PdOH]+ [PdOH]+ Z− + NO
→ Z−[Pd−ONOH]+ [PdOH]+ Z− (R1a)
Z−[Pd−ONOH]+ [PdOH]+ Z−
→ Z−[Pd1 +−Pd1 +]Z− + NO2 + H 2O (R1b)

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Z−[Pd−O−Pd]2 + Z− + NO → Z−[Pd1 +−Pd1 +]Z− + NO2
(R2)
The structures of transition states and optimized structures of
the reactant and product for NO oxidation on [PdOH]+ are
represented in Figure 5. NO anchored on one of the Pd atoms
(Figure 5A) readily interacts with the OH ligand attached to
the other Pd atom to form Pd−ONOH (Figure 5B) with a
negligible activation barrier of 9 kJ/mol. The ONOH species is
symmetrically bound to both the Pd atoms with a bond
distance of 2.1 Å, as shown in the TS geometry of Figure 5.
The Pd-ONOH species transfers its proton to the OH ligand
of the other Pd atom anchored on the zeolite framework,
resulting in the formation of Pd1+−NO2 and Pd1+−H2O
(Figure 5C). NO2 and H2O can desorb from the Pd1+ sites,
and the desorption energy is calculated to be 181 kJ/mol and
58 kJ/mol, respectively. The high NO2 desorption energy is
consistent with the experimental observation of NO2 at high
temperatures.2,3 The intrinsic reaction step resulting in the
transformation of [PdOH]+ to Pd1+ requires an activation
energy of 29 kJ/mol and has a reaction energy of −64 kJ/mol.
Thus, with such a low activation barrier, [PdOH]+ sites are
likely to reduce in the presence of NO to produce more Pd1+
sites accompanied by NO2 formation at higher temperatures. A
similar activation barrier (Ea = 8 and 42 kJ/mol) for this two-
step reduction of [PdOH]+ sites to Pd1+ is reported for Pd/
HBEA as well.14
For conversion of [Pd−O−Pd]2+ to Pd1+, the optimized
structures of the reactant, product, and transition state are
shown in Figure 6. NO is anchored on one of the Pd atoms of
the dimer site at a bond distance of 1.9 Å. It interacts further
with the oxygen atom of the dimer site, which is at a distance
of 1.5 Å from the N atom to form NO2. The dimeric [Pd−O−
Pd]2+ site reduces to Pd1+−Pd1+ on NO2 formation. This
intrinsic reaction step leading to the transformation of [Pd−
O−Pd]2+ to Pd1+ (and oxidation of NO) is endothermic with a
reaction energy of 32 kJ/mol and an activation energy of 74
kJ/mol (Figure 6). Further, the NO2 desorption energy is
found to be 123 kJ/mol from the reduced Pd1+−Pd1+ site, due
to which NO2 is observed at high temperatures.2,3 The reaction
energetics of the transformation of [Pd−O−Pd]2+ to Pd1+-Pd1+
is comparable to the one calculated for [Pd−O−Pd]2+
reduction to cationic Pd sites (Pd1+) in Pd/HBEA in the
presence of NO (Ea = 74 kJ/mol, ΔHrxn = +37 kJ/mol).14 As
compared to the conversion of [PdOH]+ to Pd1+, this
transformation of [Pd−O−Pd]2+ to Pd1+ may not be that
facile. Nevertheless, this may be considered as one feasible
route for the generation of Pd1+ sites in Pd/CHA.
Interestingly, [Pd−O−Pd]2+ could also be transformed to
[PdOH]+ via hydroxylation, as per reaction R3. The optimized
structures of the reactant, product, and transition state for the
hydroxylation of [Pd−O−Pd]2+ are shown in Figure S5. The
activation barrier for this transformation is calculated to be 32
kJ/mol and the reaction energy is -51 kJ/mol, suggesting a
facile transformation. In addition to [Pd−O−Pd]2+, Pd2+ can
also undergo hydroxylation to form [PdOH]+ (Figure S6) and
is represented by reaction R4. [PdOH]+ thus formed
transforms to Pd1+ via reactions R1a and R1b with
simultaneous NO oxidation. This transformation is endother-
mic with a reaction energy of +75 kJ/mol and an activation
barrier of 40 kJ/mol.
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Z−[Pd−O−Pd]2 + Z− + H 2O
→ Z−[PdOH]+ − [PdOH]+ Z− (R3)
Z−[Pd]2 + Z− + H 2O → Z−[PdOH]+ H+Z− (R4)
+
[PdOH] sites are also readily produced in Pd/CHA from the
PdO sites. Experimental studies report that the PdO monomer
is the most abundant site in the CHA framework at low Pd
loadings.1−3 Bell and co-workers suggested a mechanism for
PdO conversion to [PdOH]+ on interaction with the BAS
(Brønsted acid sites) of the zeolite and is given by reaction
R5.5 The protonolysis of the PdO site to form [PdOH]+ has an
activation barrier of 23 kJ/mol and a reaction energy of -242
kJ/mol. This suggests facile protonolysis of the PdO sites to
form [PdOH]+. Figure S7 represents the optimized reactant,
product, and transition state structures for protonolysis of the
PdO site.
PdIIO + H+Z− → [PdOH]+ Z− (R5)
Besides the various mechanisms for NO2 formation involving
the reduction of Pd sites discussed earlier in this section, NO2
formation is also observed in the absence of Pd sites. This NO
oxidation is catalyzed by the zeolite cages as observed by
Iglesia and co-workers.10 In a separate set of calculations, MD
simulations are performed with NO+O2 mixtures in two
different setups at 313 and 473 K, representing the range of
operating temperature of PNAs. In the first setup, simulations
are performed in the absence of any zeolite environment, and
in the second setup, the zeolite cage is included in the
simulations to understand the confinement effect. Calculations
done in the absence of the zeolite using the parameters from
Bai et al.24 showed that NO exhibited a higher affinity for
dimerization or trimerization but exhibited a low affinity for
combination with O2 molecules. Further, using the parameters
from Goddard and co-workers,25 NO exhibited a relatively
higher affinity for O2 molecules. This resulted in the formation
of species like NO−OO−NO, which is also one of the key
intermediates in the formation of NO2. However, in both
cases, the formation of NO2 is not observed during the
simulation time at both the temperatures, viz., 313 and 473 K.
Similar to the simulations performed without the zeolite
framework, the NO molecule is found to form dimeric and
trimeric units in the zeolite framework. However, in the zeolite
framework, the NO molecules abstracted the protons from the
BAS on oxygen atoms close to the aluminum sites to form
NOH species at 313 K (Figure S8(b)). The resulting NOH
species then lead to the formation of a water molecule with the
subsequent chemisorption of N on an undercoordinated
oxygen atom on the aluminum site (Figure S8(c)). The
temperature is then increased to 473 K, and the simulation is
performed for 2.5 ns. At 473 K, the hydroxyl group from water
combined with another NO molecule present in the framework
to form HONO, which then lead to the formation of NO2.
3.4. The Cycle of NO Adsorption and Desorption. It is
observed from Table 2 that the binding of NO on Pd1+ is
considerably stronger as compared to the sites with the +2
oxidation state of Pd. Even though a Pd1+ site would result in
strong binding of NO, it may not be the desired site for NOx
desorption during the post-cold-start period. Hence, a change
of the oxidation state of Pd from +1 to +2 in the desired
temperature range could be beneficial for releasing the stored
NOx because of the relatively weaker binding on these sites.
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Figure 7. The operating cycle of NO adsorption and desorption on Pd sites in Pd/CHA enabling the functioning of PNAs.
Through various microreactor and adsorption−desorption
experiments, Tronconi and co-workers concluded that Pd1+
species are reoxidized to PdII species in an oxidizing
atmosphere.8 They hypothesized that the NOx binding
becomes weaker with an increase in the oxidizing nature of
the species. Moreover, Khivantsev et al. proposed that Pd1+
sites are transformed to Pd2+ sites in the presence of O2.3
Herein, we propose that O2 would dissociate on a vacant Pd1+
site and would interact with the BAS in the vicinity of Pd1+−
NO. The migrating protons react with the OH− ion to form
H2O, while simultaneously resulting in the transformation of
Pd1+ sites to Pd2+ sites, and is represented by reaction R6.
Thus, even if NO is adsorbed on the Pd1+ site, the presence of
favorable conditions (high temperature and oxidant concen-
tration) can convert the Pd1+ site to a Pd2+ site. Since the NO
binding on the newly formed Pd2+ site is relatively weaker
(Table 2), it can desorb from the Pd2+ site at a relatively lower
temperature as compared to the case where NO desorption
needs to occur from the Pd1+ sites. Thus, the reoxidation of Pd
sites is likely to facilitate the release of stored NOx in an
optimum temperature range.
2Z−[Pd1 +−NO]H+Z− + 2Z−[Pd1 +]H+Z− + O2
→ 2Z−[Pd2 +−NO]Z− + 2Z−[Pd2 +]Z− + 2H 2O (R6)
It is further hypothesized that the oxidation of Pd1+ to [Pd−
O−Pd]2+ could also take place in the presence of oxygen with
simultaneous oxidation of NO to produce NO2, as represented
in Figure S9 (SI). However, since the amount of NO2
produced is relatively lower,8 this transformation may not be
the dominant route.
Overall, from the aforementioned calculations, a unique
adsorption−desorption cycle of NO appears to be functioning
in Pd/CHA. This cycle is constructed in Figure 7. NO is
strongly adsorbed on Pd1+ sites at the 6MR-3NN location of
the zeolite (Eb= −272 kJ/mol). The NO binding energy on
Pd1+ sites is equivalent to its binding at similar Pd sites in Pd/
HBEA. While Pd1+ sites are available in the as-synthesized Pd/
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CHA, there are at least two more distinct routes for the
generation of Pd1+ sites in the presence of NO or CO, which
are from the reduction of [PdOH]+ and/or [Pd−O−Pd]2+, as
discussed earlier in Section 3.3.2,8,14 In the redox environment,
Pd1+ species are oxidized to PdII species ([PdOH]+, [Pd−O−
Pd]2+, and Pd2+), where NO binding is relatively weaker as
compared to Pd1+ (Edes < 155 kJ/mol, Figure 7). Hence, these
sites may function as the desorption sites for NO. The redox
transformation of Pd1+ to PdII sites followed by NO desorption
regenerates the sites thus completing the cycle. As discussed in
Section 3.3, adsorbed NO could also be oxidized on various Pd
sites and is released in the form of NO2 at higher temperatures.
As shown in Figure 7, NO adsorption could also take place on
the PdII sites, however, with a weaker binding as compared to
Pd1+.
The redox transformation of Pd species, highlighting the
central role of Pd1+ in NO adsorption, is demonstrated in the
experiments of Tronconi and co-workers.8 Interestingly here,
in contrast to Pd-HBEA, NO adsorption is considered to occur
predominantly on the Pd1+ sites, while NO binding on other
PdII sites ([PdOH]+, [Pd−O−Pd]2+, and Pd2+) is significantly
weaker.14 On the contrary, the PdII sites provide the desired
desorption platform for NO. This observation stands in
contrast to the assertion of Mandal et al., wherein Pd2+ sites are
considered central to both NO adsorption and desorption.4
Since Pd speciation in CHA leads to the formation of a diverse
array of sites ([PdOH]+, [Pd−O−Pd]2+, Pd1+, and Pd2+),
ambiguity in the correct assignment and identification of NO
adsorption and desorption is likely to prevail in both
experiments and theory. Nevertheless, DFT calculations
presented here affirm some of the thoughtful theoretical and
experimental studies conducted by Bell and co-workers and
Tronconi and co-workers, which are consistent with the cycle
depicted in Figure 7.5,8
Final calculations in this series are performed to understand
the effect of water coadsorption on NO binding during the
adsorption−desorption cycle. From the mean square displace-
ment versus time plots, MD simulations estimated a higher
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diffusivity of water (DH2O = 2.6 × 10−10 m2/s, Figure S10 (SI))
in CHA as compared to that of NO (DNO = 4.9 × 10−11 m2/s,
Figure S10). The concentration of water (5−15%) is
considerably high in the diesel exhaust as compared to that
of NO (∼102 ppm) and has been reported to have an adverse
effect on NOx adsorption in PNAs.1−3 To elucidate the effect
of water, NO binding calculations are performed in the
presence of a co-adsorbed water molecule on Pd2+, Pd1+, [Pd−
O−Pd]2+, and [PdOH]+ sites in the 6MR-3NN configuration.
Figure S11 (SI) represents the adsorption of NO on Pd2+,
Pd1+, [Pd−O−Pd]2+, and [PdOH]+ sites with preadsorbed
H2O. The corresponding binding energies with and without
preadsorbed H2O are given in Table S2 (SI). Water has a
negligible effect on NO desorption energetics over the Pd2+,
Pd1+, and [Pd−O−Pd]2+ sites. Spectroscopic and experimental
studies have also indicated that the NO binding capability on
some Pd sites remains nearly unaffected in the presence of
water.1,4 Moreover, Tronconi and co-workers specifically
pointed toward the adverse effect of water on the redox
conversion of Pd species (rather than on NO adsorption and
desorption processes).8 It is also observed from Table S2 that
NO binding on the [PdOH]+ site becomes significantly weaker
in the presence of H2O. This could explain the measured
negative impact of water on the activity of PNAs.1−3
Nevertheless, as depicted in Figure 7, the adsorption of NO
on Pd1+ sites and its desorption from PdII species is likely to
stay operational in PNAs, even in the presence of water.
4. CONCLUSIONS
Pd speciation in CHA and its redox transformation in the
presence of oxidizing (O2) and reducing (CO/NO) agents
provide a Sabatier-type optimum adsorption−desorption cycle
for the binding and release of NO. In this cycle, the central role
of Pd1+ species is to facilitate strong NO binding, with a
relatively lower contribution of PdII sites in NOx adsorption.
While Pd1+ species are available in the as-synthesized Pd/CHA
and are also obtained on the reduction of [PdOH]+ by NO (or
CO), this study shows another route for Pd1+ generation by
NO oxidation on [Pd−O−Pd]2+ sites. Under an oxidizing
environment, Pd1+ species are expected to transform into Pd2+,
[PdOH]+, and [Pd−O−Pd]2+, where NO desorption is
facilitated with significantly reduced energetics, thus complet-
ing the NOx adsorption−desorption cycle. The interconversion
of various Pd species such as the hydroxylation of Pd2+ and
[Pd−O−Pd]2+ to [PdOH]+ and the protonolysis of PdO to
Pd2+ can take place as well. While water is calculated to
introduce negligible changes in NO binding on a majority of
the Pd sites (Pd1+, Pd2+, and [Pd−O−Pd]2+), it has a slightly
greater impact on NO desorption from [PdOH]+. Overall,
water is expected to inhibit the redox conversion of Pd species,
as suggested in previous reports.8 In summary, the availability
of Pd1+ as an excellent binding site for NO and its
transformation into optimum NO desorption sites with
reduced binding strength elucidate the growing relevance of
Pd/CHA as the state-of-the-art material for PNAs.
■
ASSOCIATED CONTENT
*
sı Supporting Information
The Supporting Information is available free of charge at
https://pubs.acs.org/doi/10.1021/acs.langmuir.1c01383.
Relative energy of the supercell and Al−Al distances for
different Al configurations in H-CHA; optimized
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structures of Pd sites (Pd2+, Pd1+, [Pd−O−Pd]2+, and
[PdOH] + ) in 8MR-4NN and 6MR-2NN CHA;
optimized structures of NO adsorbed on various Pd
sites (Pd2+, Pd1+, [Pd−O−Pd]2+, and [PdOH]+) in
8MR-4NN and 6MR-2NN CHA; optimized structures
of the reactant, product, and transition state for
hydroxylation on [Pd−O−Pd]2+-6MR-3NN and Pd2+-
6MR-3NN; optimized structures of reactant, product,
and transition state for protonolysis of [PdIIO]-6MR-
3NN; structures obtained using ReaxFF simulations
during interaction of NO and O2 in CHA; optimized
structures of the reactant, product, and transition state
for reoxidation of [Pd1+−Pd1+]-NO-6MR-3NN; mean
square displacement plot of NO and H2O inside CHA;
optimized structures for NO adsorption on water-
occupied Pd sites (Pd2+, Pd1+, [Pd−O−Pd]2+, and
[PdOH]+) in 6MR-3NN CHA; and binding energy of
NO adsorption on Pd sites (Pd2+, Pd1+, [Pd−O−Pd]2+,
and [PdOH]+) with and without preadsorbed water
(PDF)
■
AUTHOR INFORMATION
Corresponding Authors
Tuhin S. Khan − Light Stock Processing Division, CSIR
Indian Institute of Petroleum, Dehradun 248005, India;
Email: tuhins.khan@iip.res.in
M. Ali Haider − Department of Chemical Engineering, Indian
Institute of Technology Delhi, New Delhi 110016, India;
orcid.org/0000-0002-8885-5454; Email: haider@
iitd.ac.in
Divesh Bhatia − Department of Chemical Engineering, Indian
Institute of Technology Delhi, New Delhi 110016, India;
orcid.org/0000-0002-7777-3824; Email: dbhatia@
chemical.iitd.ac.in
Authors
Marvi Kaushik − Department of Chemical Engineering, Indian
Institute of Technology Delhi, New Delhi 110016, India
Gourav Shrivastav − Department of Chemical and Biological
Engineering, Drexel University, Philadelphia, Pennsylvania
19104, United States
Complete contact information is available at:
https://pubs.acs.org/10.1021/acs.langmuir.1c01383
Funding
This research did not receive any specific grant from funding
agencies in the public, commercial, or not-for-profit sectors.
Notes
The authors declare no competing financial interest.
■
ACKNOWLEDGMENTS
The authors thank the IIT Delhi high performance computing
(HPC) facility for providing computational resources. Authors
would like to acknowledge and appreciate the design for cover
illustration by Mohammad Asjad Maswood. T.S.K. would like
to acknowledge the Director, CSIR-IIP, for his continuous help
and encouragement.
■
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https://doi.org/10.1021/acs.langmuir.1c01383
Langmuir 2021, 37, 13799−13809