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Single atom alloy catalyst for SO3 decomposition:

Cite this: Nanoscale, 2018, 10,
enhancement of platinum catalyst’s performance
20599 by Ag atom embedding†
Sandeep Nigam * and Chiranjib Majumder

Received 27th June 2018,
Accepted 18th September 2018
DOI: 10.1039/c8nr05179h
rsc.li/nanoscale
Recently, single atom alloy catalysts (SAA) have shown improved catalytic activity in numerous catalytic
reactions. However, to date, single atom alloy (SAA) catalyst is not available for SO3 decomposition reac-
tion, which is a key reactions in the hydrogen economy. Using state of the art density functional theory,
we report a novel single Ag atom alloy Pt catalyst in the sub-nanometer length scale (AgPt9@Al2O3)
showing superior catalytic behavior for SO3 decomposition. It was found that alloying the alumina-
supported platinum nanocluster with a single Ag atom lowers the activation barrier for S–O bond breaking
by more than 50% in comparison with the pristine platinum counterpart. Activation barrier for
AgPt9@Al2O3 catalyst is 0.52 eV, which is the lowest of any platinum based catalyst reported so far. At
variance with pure Pt10@Al2O3, which tries to detach from the support during decomposition reaction,
single atom alloy (SAA) nanocluster AgPt9@Al2O3 enhances binding with support, thus strengthening sin-
tering resistance. Notably, influence of single Ag atom is also observed at larger length scale, i.e., at Pt(111)
slab, where single Ag atom substituted surface Ag1Pt(111) shows ∼30% reduction in activation barrier in
contrast to a pristine surface. Single Ag atom works in bifunctional mode as it not only reduces the acti-
vation barrier, but also simultaneously weakly adsorbs the reaction product SO2, signifying relatively easier
desorption and better recyclability. Deeper location of silver d-electrons and lesser electronegativity of
silver is responsible for the better performance of single Ag atom alloyed Pt catalyst. We strongly believe
that these remarkable results will open new avenues for future designing and fabrication of cost-effective
catalysts for SO3 decomposition.

1. Introduction chemical cycle requires very high temperatures (between 750

Doping coinage metals with platinum group metal at very low
molar fractions or inserting isolated single atoms in a host
surface layer is referred to as single atom alloys (SAA). Such
single atom alloys (SAA) catalysts have generated significant
interest in recent years.1–22 Single atom alloy (SAA) is a perfect
approach for designing new cost-effective catalysts as they can
provide maximum metal utilization by exploiting the atomic
efficiency of noble metals. Single atom alloys (SAA) have
shown to improve catalytic activity in numerous catalytic
reactions,1–22 such as CO oxidation, C–H activation, dehydro-
genation, and hydrogenation. Even though SO3 decomposition
reaction is a key reaction for the hydrogen economy, single
atom alloy catalyst for this reaction has not been reported so
far. Decomposition of SO3 in Sulphur–Iodine (SI) thermo-
Chemistry Division, Bhabha Atomic Research Centre, Mumbai, India-400094.
E-mail: snigam.jpr@gmail.com, chimaju@barc.gov.in
† Electronic supplementary information (ESI) available. See DOI: 10.1039/
c8nr05179h
and 900 °C) and does not take place without a catalyst.23,24
Currently, the most common catalysts for SO3 decomposition
are supported iron oxide/mixed oxide particles25–31 and sup-
ported platinum group metal particles.32–39 Various materials,
e.g., TiO2, Al2O3, and BaSO4, have been used as supports for
the platinum material. Although Pt-based catalysts are con-
sidered to be the most promising candidates, the serious
issues with them are thermal sintering and loss of Pt in a cor-
rosive reaction environment. Therefore, the selection of correct
support materials for Pt catalysts is important for ensuring
their activity and stability. The drawbacks of various supports
have motivated researchers to look for an alternative support
material, which can withstand highly acidic and corrosive
environment, as well as strongly protect the platinum catalyst
against sintering. Accordingly, Ta2O5 and WO3 have emerged
as new support materials.39
Another possible way to avoid sintering can be doping the
platinum catalyst itself. It is well known that the incorporation
of an impurity atom can lead to reordering of the energy
levels, thus altering the geometry and chemical properties of a

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catalyst. Thus, by appropriate doping of the platinum catalyst,
we can possibly reduce the activation barrier and simul-
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taneously tune the nanocluster support interactions.
Reduction of the activation barrier can help in reducing the
reaction temperature, while improved platinum support inter-
action can enhance the binding and its sustainability during
the reaction. In this context, single atom alloy (SAA) catalysts
can play a huge role in optimizing the performance of Pt cata-
lysts for SO3 decomposition. Surprisingly, single atom alloy
(SAA) catalysts have not been investigated for their applications
in the decomposition of SO3. Therefore, developing single
atom alloy (SAA) Pt catalysts will be worthwhile, as they could
act as a reference for a new class of potential catalysts for SO3
decomposition. Recently, alumina-supported Ag–Pt nano-
clusters have shown high catalytic activity; also, they were
found to be stable against sintering even at higher tempera-
ture.40 Thus, the inclusion of single Ag in Pt catalyst appears
to be a good strategy for developing a single atom alloy (SAA)
catalyst for SO3 decomposition. Keeping this in mind, in the
present study we have theoretically investigated the potential
of a single Ag site embedded Pt catalyst towards SO3 decompo-
sition. Two types of substrates have been considered: (i) Pt
nanocluster supported on alumina, i.e., Pt10@Al2O3 and
(ii) Pt(111) surface. The selection of substrates was guided by
the fact that Pt nanoparticle (∼2–3 nm) on alumina support
has been successfully employed33 as a catalyst for sulfuric acid
decomposition reaction, and the (111) facet of Pt surface is
thermodynamically the most stable and therefore, any plati-
num nanoparticle is expected to predominantly have the (111)
facet. It is worth mentioning herein that size selected for Pt10
cluster on alumina support (Pt10@Al2O3) has been previously
used to catalyse other reactions41,42 and its electronic structure
resembles the Pt(111) surface.42 In order to make single atom
alloy (very low molar fraction) from these above mentioned
substrates, substitutional doping of single Ag atom into these
substrates, i.e., AgPt9@Al2O3 and Ag1Pt(111) surfaces, were per-
formed. Then, SO3 decomposition behaviours on these cata-
lysts were evaluated and compared with those of their corres-
ponding pristine counterparts. We believe that our findings
provide a new strategy for the rational design of a single atom
alloy (SAA) catalyst for SO3 decomposition and will provide a
new platform for future experimental and theoretical investi-
gations in this direction.
2. Computation details
All calculations were performed using plane wave based
pseudo-potential approach, as implemented in the Vienna
ab initio Simulation Package (VASP).43 Electron–ion interactions
were defined by the full-potential all-electron projector aug-
mented wave (PAW) method,44 as executed in VASP by Kresse
and Joubert.45 PAW pseudo-potential was generated taking
scalar relativistic corrections into account. To calculate the
exchange–correlation energy, spin polarized generalized gradi-
ent approximation46 was employed. After spin polarized calcu-
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lations, all the obtained structures were re-optimized by includ-
ing spin orbit coupling (SOC). The cut off energy for plane wave
basis set was fixed at 400 eV for all calculations performed in
this study. Geometry optimization was performed using conju-
gate gradient method. The geometries are considered to be con-
verged when forces on each ion become 0.01 eV Å−1 or less.
Total energy convergence was tested with respect to the plane-
wave basis set size and simulation cell size, and the total energy
was found to be accurate within 1 meV.
The α-Al2O3(0001) surface was modelled with 18-atomic
layer slab by truncating the bulk α-Al2O3 structure (details are
reported in our previous study).47–50 For alumina supported
Pt10 and AgPt9 platinum cluster, 3 × 3 supercell of alumina
substrate having 270 atoms with dimensions 14.30 × 14.30 ×
25.99 Å (surface area ≈ 204.4 Å2) were used. A Monkhorst–Pack
set of 5 × 5 × 1 K-points was used for all the calculations. For
structural relaxation, including the dipole correction, all 18
atomic layers were allowed to relax to avoid any error due to
interactions between two adjacent images. Other compu-
tational parameters and procedures have been kept same as
reported in our previous study.47,48
The average adsorption energy of Pt10 cluster on α-Al2O3
surface was calculated as
ΔE ¼ ½EðPt10 =Al2 O3 Þ  EðAl2 O3 Þ  EðPt10 Þgas-phase =10:
The average adsorption energy of AgPt9 cluster on α-Al2O3
surface was calculated as
ΔE ¼ ½EðAgPt9 =Al2 O3 Þ  EðAl2 O3 Þ  EðAgPt9 Þgas-phase =10:
The adsorption energy of the SO3 molecule with different
substrates has been calculated in the following manner
ΔEPt ¼ E½SO3 –ðPt10 @Al2 O3 Þ  E½Pt10 @Al2 O3   E½SO3 
ΔEAgPt ¼ E½SO3 –ðAgPt9 @Al2 O3 Þ  E½AgPt9 @Al2 O3   E½SO3 
ΔEPt-surf ¼ E½SO3 –Ptð111Þ  E½Ptð111Þ  E½SO3 
ΔEAgPt-surf ¼ E½SO3 –Ag1 Ptð111Þ  E½Ag1 Ptð111Þ  E½SO3 
The reaction enthalpy (heat of reaction) for SO3 decomposition
on different substrate was calculated in the following manner:
SO3 –ðPt10 @Al2 O3 Þ ! SO2 –ðPt10 @Al2 O3 Þ–O þ ΔH diss-Pt
ΔH diss-Pt ¼ E½SO2 –ðPt10 @Al2 O3 Þ–O  E½SO3 –ðPt10 @Al2 O3 Þ
SO3 –ðAgPt9 @Al2 O3 Þ ! SO2 –ðAgPt9 @Al2 O3 Þ–O þ ΔH diss-AgPt
ΔH diss-AgPt ¼ E½SO2 –ðAgPt9 @Al2 O3 Þ–O  E½SO3 –AgPt9 @Al2 O3 
SO3 –Ptð111Þ ! SO2 –Ptð111Þ–O þ ΔH Pt-surf
ΔH Pt-surf ¼ E½SO2 –Ptð111Þ–O  E½SO3 –Ptð111Þ
SO3 –Ag1 Ptð111Þ ! SO2 –Ag1 Ptð111Þ–O þ ΔH AgPt-surf
ΔH AgPt-surf ¼ E½SO2 –Ag1 Ptð111Þ–O  E½SO3 –Ag1 Ptð111Þ
To have qualitative understanding of the bonding nature,
electron density difference analysis for various systems has
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been carried out. Electron density difference (Δρ) at the inter-
face of AgPt9 cluster and alumina surface is calculated as:
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Δρ ¼ ρðPt10 =Al2 O3 Þ  ρðAl2 O3 Þ  ρðPt10 Þ
Δρ ¼ ρðAgPt9 =Al2 O3 Þ  ρðAl2 O3 Þ  ρðAgPt9 Þ
Δρpt ¼ ρ½SO3 –ðPt10 @Al2 O3 Þ  ρðPt10 @Al2 O3 Þ  ρðSO3 Þ
ΔρAgpt ¼ ρ½SO3 –ðAgPt9 @Al2 O3 Þ  ρðAgPt9 @Al2 O3 Þ  ρðSO3 Þ
In case of calculations for gas phase AgPt9 cluster, each
configuration was placed inside a large cubic box of 15 × 15 ×
15 Å. The Brillouin zone integrations were performed at the Γ
point only. Test calculations on SO3 molecule in the gas phase
were also performed in a similar manner. The optimized struc-
ture showed D3h symmetry with three equivalent S–O bonds of
1.44 Å.
3. Results and discussion
In a simplistic computational approach for single atom alloy
(SAA) catalyst for SO3 decomposition, calculations were per-
formed by first determining the low-lying isomer of the sup-
ported nanocluster and supported nanocluster/surface–adsor-
bate (SO3) complex by exploring the potential energy surface
(PES), followed by calculating the energy barriers, and reaction
enthalpy of the decomposition reaction. Results have been pre-
sented in the following manner. Section 3.1 describes the
results obtained for SO3 decomposition on pristine Pt10 cluster
catalyst. Subsequently, the results of the single atom alloy
(SAA) catalyst AgPt9 have been reported in section 3.2. Next,
section 3.3 details the SO3 decomposition reaction on pristine
and single atom Ag substituted Pt(111) surface-Ag1Pt(111). In
section 3.4, comparisons of different catalysts and a perspec-
tive has been described.
3.1 Interaction of SO3 with Pt10 cluster supported on Al2O3
surface
In our previous study,45 we reported the equilibrium structure
of gas phase and alumina-supported Ptn (n = 1–7, 10) clusters.
It was found that Pt10 cluster undergoes significant structural
modification on an alumina substrate, transforming from
tetracapped prism structure to a bilayer configuration (Fig. 1).
Supported Pt10 cluster gets 1.15e charge (Bader charge51) from
the alumina surface. Interestingly, it is also found that
Pt10@Al2O3 and Pt(111) have similar electronic structures and
show similar oxidation behaviour.42 To obtain the most stable
geometry of SO3 adsorbed on Pt10@Al2O3, structural optimiz-
ation of several trial structures was performed. Various poss-
ible adsorption sites/faces of supported Pt10 cluster were
explored, where SO3 molecule in different configurations inter-
acted. For an exhaustive exploration, SO3 molecule was inter-
acted with two low lying isomers of Pt10 cluster. The lowest
energy structure has SO3 molecule adsorbed on the trigonal
face of the top layer platinum atoms via two platinum–oxygen
bond (2.1–2.2 Å) and three platinum–sulphur (2.3–2.9 Å) bond
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Fig. 1 Pt10@Al2O3 cluster: (a) pristine (b) with adsorbed SO3 and (c)
with dissociated SO3. Corresponding charge density difference contours
are shown in (d), (e) and (f ) respectively. Green contour shows an
increase in the charge density, and grey contour shows a decrease in
the charge density. Colour code for atoms is as follows: Red ball (S),
Blue ball (O of SO3), Orange ball (O of Al2O3), Dark green ball (Al), Pink
ball (Ag) and brown ball (Pt).
formations, as shown in Fig. 1b. Other low lying isomers are
shown in Fig. S1 of ESI.† After interactions, S–O bond length
of the SO3 molecule, connected to the trigonal face of metal
cluster, increases from 1.44 to 1.54 Å (∼7% elongation). The
adsorption energy of SO3 on Pt10@Al2O3 was estimated to be
−1.83 eV. It is worth mentioning that adsorption energies of
SO3 molecule on Pt12 on anatase TiO2 and γ-Al2O3 have been
reported34 to be in the range of 1.5–1.7 eV.
To understand the interaction between SO3 molecule and
Pt10@Al2O3, the electronic density of states (DOS) of SO3 is
analysed, as presented in Fig. 2. After interaction with the
Pt10@Al2O3, a significant change in the DOS spectrum of SO3
molecule is observed. The gas phase SO3 molecule has dis-
tinct, sharp peaks in the DOS spectrum, where HOMO levels
are distributed on oxygen atoms and LUMO has major contri-
bution from sulphur and minor contribution from oxygen
atoms (shown in ESI, Fig. S2†). After interaction with
Pt10@Al2O3, the electronic states of SO3 molecule become
wider and pushed to higher energy. The reason for such a shift
is attributed to the electronic charge injection from the
cluster–surface complex to the SO3 molecule (Bader charge
−0.79e), which leads to the elongation of S–O bond. Fig. 1e
and f depict the charge density difference contours for SO3
molecule before and after dissociation from the Pt10@Al2O3
cluster. Analysis of electronic DOS reveals that in the dissociated
product, i.e., SO2–(Pt10@Al2O3)–O, significant electron density is
localized in sulphur’s atomic states near the Fermi level.
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Fig. 2 Comparative electronic density of state (DOS) of SO3 molecule;
before adsorption on Pt10@Al2O3 (i.e. isolated), after adsorption and sub-
sequent dissociation (a) states projected on oxygen atom and (b) states
projected on sulphur atom. Vertical dotted line at zero indicates Fermi
level.
Reaction enthalpy for the decomposition reaction (ΔHdiss-Pt)
is expectedly found to be positive, i.e., SO3 decomposition on
Pt10@Al2O3 cluster requires a net energy of 0.69 eV. In order to
calculate the actual S–O bond breaking barrier (activation
barrier), nudge elastic band (NEB) method52,53 was used. A
total of four images between the reactant and product states
are considered to find the minimum energy path (MEP) in this
process. Using this method, the activation barrier for SO3
decomposition on the Pt10@Al2O3 complex was found to be
1.16 eV, as presented in Fig. 3.
3.2 Interaction of SO3 with AgPt9 cluster supported on Al2O3
surface
In order to create a single atom alloy (very low molar fraction)
catalyst from supported Pt10 cluster, substitutional doping of
single Ag atom into Pt10 was performed. Gas phase AgPt9 has a
tetracapped prism structure with Ag substituted at the bottom
layer hexacoordinated site. The bilayer structure with central
atom being Ag is 0.96 eV higher in comparison with the tetra-
capped prism structure (Fig. S3 of ESI†). To determine the
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Fig. 3 Minimum energy path (MEP) calculated by nudge elastic band
for decomposition of SO3 on Pt10@Al2O3. For clear representation,
alumina support has not been shown.
equilibrium geometry of AgPt9 cluster deposited on an
alumina support, we optimized several isomeric structures by
substituting one of the Pt atoms by an Ag atom at each poss-
ible site of the Pt10@Al2O3 cluster. It was found that the Ag
atom prefers to replace the central platinum atom of the
bilayer structure, as presented in Fig. 4. Variance in the
binding nature of Ag and Pt leads to local distortion in the
alumina-supported AgPt9 cluster. Other low lying isomers are
shown in Fig. S4 of ESI.† The next low lying isomer (ΔE =
0.46 eV) has Ag substituting a top layer Pt atom. Interestingly,
the average binding energy of the AgPt9 cluster on alumina
support is found to be 0.38 eV per atom, which is higher than
the Pt10 counterpart (0.33 eV per atom), indicating the rela-
tively stronger binding in AgPt9. For both Pt10 and AgPt9 clus-
ters, significant amount of charge is transferred from the
surface to the metal cluster as Bader charges on these clusters
are found to be −1.15e and −0.91e, respectively. Fig. 4d depicts
the charge density difference contours for AgPt9 clusters on
the Al2O3 surface. The electronic density of states of Pt10 cluster
gets slightly modified by Ag substitution as the d-band centre
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bond length of SO3 molecule that increases up to 1.71 Å,

leading to ∼19% elongation.
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Detailed electronic structure analysis was performed to

Fig. 4 AgPt9@Al2O3 cluster: (a) pristine (b) with adsorbed SO3 (c) with
dissociated SO3. Corresponding charge density difference contours are
shown in (d), (e) and (f ) respectively. Green contour shows an increase
in the charge density, and grey contour shows a decrease in the charge
density.
understand this elongation. Electronic density of state shows
that a significant amount of electronic charge is inserted into
sulphur’s atomic state by the cluster–surface complex (−1.01e),
which results in a shift in energy level of SO3 and an additional
electronic state of sulphur atom prior to the Fermi level
(Fig. 5). Reaction enthalpy for the decomposition reaction
(ΔHdiss-AgPt) is found to be +0.37 eV, which is much lower than
that of the Pt10@Al2O3 counterpart (ΔHdiss-Pt = +0.69 eV).
Moreover, the S–O bond breaking reaction barrier (activation
barrier) for SO3–(AgPt9@Al2O3) was obtained to be only 0.52 eV
(Fig. 6) using NEB method, which is almost half of barrier
obtained for the SO3–(Pt10@Al2O3) complex.
In order to understand the effect of single atom alloying
towards SO3 decomposition, various features of Pt10@Al2O3
and AgPt9@Al2O3 complexes has been vis-à-vis compared in
Table 1. From the table, it is clear that adsorption of SO3 on
alumina supported AgPt9 cluster is energetically weaker, but at
the same time, it leads to elongation of the S–O bond to a

moves from −2.36 eV to −2.27 eV, i.e., a 0.08 eV shift towards

Fermi level (Fig. S5 of ESI†). These observations clearly reveal
that substitutional doping of single Ag atom has greatly
modified the physicochemical properties of the Pt10@Al2O3
cluster.
After finding the equilibrium geometry of the alloy cluster
on alumina support, we investigated its interaction with the
SO3 molecule. To locate the most optimum geometrical con-
figuration, SO3 molecule was interacted with two low lying
isomers of the AgPt9 cluster (ground state isomer with Ag in
the central position and another isomer with Ag in the top
layer). Various coordination sites and faces of each AgPt9
isomer were considered for SO3 interaction. The ground state
AgPt9 isomer adsorbs SO3 on one of its edges, resulting in the
formation of one metal–oxygen and two metal–sulphur bonds,
as presented in Fig. S6 of ESI.† S–O bond length of SO3 mole-
cule, interacting with AgPt9@Al2O3, increases up to 1.56 Å.
Moreover, another isomer of SO3–(AgPt9@Al2O3) system, which
is energetically favourable by 0.07 eV, is achieved when SO3
interacts with the high energy isomer of AgPt9 having silver
atom in the top layer. In this case, SO3–(AgPt9@Al2O3) inter-
action results in the formation of three metal–oxygen and one
silver–sulphur bonds with the top layer of metal cluster, result-
ing in an adsorption energy of −1.61 eV (viz. Fig. 4b). Thus,
based on the energetics, it can be inferred that SO3 molecule
Fig. 5 Comparative electronic density of state (DOS) of SO3 molecule
prefer to bind with the higher energy AgPt9 isomer in compari-
for before adsorption on AgPt9@Al2O3 (i.e. isolated), after adsorption
son with the ground state AgPt9 isomer. Other low lying and subsequent dissociation (a) states projected on oxygen atom and (b)
isomers are shown in Fig. S6 of the ESI.† Furthermore, the states projected on sulphur atom. Vertical dotted line at zero indicates
lowest energy structure of SO3–(AgPt9@Al2O3) has one S–O Fermi level.

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greater extent. S–O interatomic separation increases with an
increase in charge injected into SO3 molecule by the cluster–
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surface complex. These results are in line with the obser-
vations from our previous study on SO3 decomposition on Ag/
Pd mix cluster supported on alumina substrate.50 While the
presence on only Ag–Pd bond in Ag2Pd2@Al2O3 elongates the
S–O bond to 1.64 Å, the presence of heterogeneous bonds,
namely, Ag–Pt and Pt–Pt, in silver diluted AgPt9@Al2O3 cluster
Fig. 6 Minimum energy path (MEP) calculated by nudge elastic band
for decomposition of SO3 on AgPt9@Al2O3. For clear representation,
alumina support has not been shown.
Table 1 Comparison of different properties for adsorption and decomposition of SO3 on supported Pt10 and AgPt9 metal clusters
Property/cluster
SO3 adsorption energy (ΔE) released
Bader charge present on adsorbed SO3
S–O bond elongation (±Δx) in comparison to pristine SO3
Activation barrier for S–O bond breaking
Decomposition reaction enthalpy (ΔH)
Vertical movement of cluster during SO3 adsorption/decomposition (±Δz)
Decomposition product’s (i.e. SO2) distance from adsorbate cluster
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elongates the S–O bond up to 1.71 Å. Table 1 also indicates
that for Pt10@Al2O3 complex, during the SO3 adsorption and
decomposition, the cluster–substrate separation increases,
leading to weakening of adhesion. These results are in line
with the experimental observations,33 where it was found that
Pt nanoparticle (∼2–3 nm) supported by alumina suffers from
thermal sintering. However, on the contrary, interaction of SO3
with AgPt9@Al2O3 leads to a reduction in the metal cluster–
alumina surface separation. Thus, it can be inferred that AgPt9
remains immobilized on alumina support during its reaction
with SO3 molecule. This strong grip of AgPt9 clusters on
alumina substrate can help avoid the possible sintering during
SO3 decomposition. It is worth mentioning that alumina sup-
ported Ag–Pt nanoclusters were found to stable against sinter-
ing during CO oxidation reaction.40
For any catalytic reaction, it is important that products
formed should be easily desorbed for better performance and
recyclability. The desorption of reaction products is dictated by
the strength of binding between reaction products and sub-
strate. In the present case, binding of decomposition product
SO2 is relatively weaker for the alloy catalyst AgPt9@Al2O3 in
comparison with the pristine catalyst Pt10@Al2O3, as reflected
by bond lengths presented in Table 1. Therefore, desorption of
SO2 from the alloy catalyst appears easier in comparison with
the pristine counterpart. Overall, it can be inferred that substi-
tutional inclusion of single Ag atom in the Pt10 cluster facili-
tates the SO3 decomposition reaction in the following ways. (i)
It reduces the activation barrier for S–O bond breaking by
more than 50% and hence, can reduce the reaction tempera-
ture significantly. (ii) It strengthens the binding of metal
cluster with the alumina substrate, which survives during SO3
decomposition reaction, and therefore helps avoiding sinter-
ing of the nanocluster. (iii) It weakens the binding of reaction
product SO2 with the cluster, which aids easy desorption.
Thus, the reordering of properties upon single atom alloying
of platinum nanocluster has improved the potential of the
pristine catalyst.
3.3 Interaction of SO3 with Pt(111) and Ag1Pt(111) slab
In the previous sections, it was established that at sub-nano-
metre length scale, the presence of a single Ag atom in the Pt
nanocluster significantly improves its potential as a catalyst for
SO3 decomposition. In order to further ascertain the role of
Pt10@Al2O3 AgPt9@Al2O3
1.83 eV 1.61 eV
−0.79e −1.01e
0.10 Å (6.94%) 0.27 Å (18.75%)
1.16 eV 0.52 eV
0.69 eV 0.37 eV
0.19 Å away from surface 0.10 Å towards the surface
Pt–S: 2.21 Å Ag–S: 2.49 Å
Pt–S: 2.83 Å Pt–S: 2.93 Å
Pt–O: 2.13 Å Pt–O: 2.15 Å
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Fig. 7 SO3 adsorbed on (a) Pt(111) and (b) Ag1Pt(111) surface.
Corresponding charge density difference contours are shown in (c) and
(d) respectively. Green contour shows an increase in the charge density,
and grey contour shows a decrease in the charge density.
Fig. 8 Comparative electronic density of state (DOS) of SO3 molecule
on (a) Pt(111) and (b) Ag1Pt(111) surface. States projected on oxygen and
sulphur atom are shown separately. Vertical dotted line at zero indicates
Fermi level.
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single Ag site at larger length scale, interaction of SO3 was
investigated with Pt(111) surface before and after single atom
alloying (substitutional doping with Ag). Since (111) facet is
thermodynamically the most stable facet of Pt surface, large
sized platinum nanoparticle is expected to predominantly have
the (111) facets.
It is well known that although Pt and Ag are not bulk-misci-
ble, surface alloying of these two metals is quite possible.54,55
Ag atoms/clusters embedded in Pt(111) have been located by
spot profile analysis low energy electron diffraction.56
Substitution of Pt atom of Pt(111) surface by Ag atom at lower
concentration of silver has been observed.57,58 Therefore,
doping of Pt(111) by Ag atom is practically feasible.
In the present study, to model the Pt(111) slab, we con-
structed a (5 × 5) surface unit cell in a plane with four vertical
atomic layers. Each atomic layer contains 25 platinum atoms,
leading to a total of 100 atoms in the slab. For single atom
alloy (SAA) catalyst, one platinum atom from the uppermost
layer was replaced with a silver atom, leading to 1% silver con-
centration in the total slab. Embedding of single Ag atom in Pt
(111) surface induces localized distortion, and the silver atom
remains 0.35 Å above the plane to minimize the strain. In
Fig. 9 Minimum energy path (MEP) calculated by nudge elastic band
for decomposition of SO3 on Pt(111) surface.
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Fig. 10 Minimum energy path (MEP) calculated by nudge elastic band
for decomposition of SO3 on Ag1Pt(111) alloy surface.
single Ag atom substituted Pt(111) surface, i.e., Ag1Pt(111), the
Ag–Pt bond distance is 2.90 Å, which is 0.1 Å larger than the
Pt–Pt bond lengths (Fig. S7 of ESI†). These observations are in
line with the fact that Ag and Pt have around 4.2% lattice mis-
match. The large lattice mismatch was manifested in ener-
getics, where it was found that substitution of Ag atom in the
top most layer is favoured over substitution in sublayers
(Fig. S7 of ESI†).
Interaction of SO3 with Pt(111) and Ag1Pt(111) was per-
formed by considering different possible adsorption sites (tri-
Table 2 Comparison of different properties for adsorption and decomposition of SO3 on Pt(111) and Ag1Pt(111) surface
Property/cluster
SO3 adsorption energy (ΔE) released
Bader charge present on adsorbed SO3
S–O bond elongation (±Δx) in comparison to pristine SO3
Activation barrier for S–O bond breaking
Decomposition reaction enthalpy (ΔH)
Decomposition product’s (i.e. SO2) distance from adsorbate surface
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gonal face, Pt–Pt bond edge, atop mode) and different orien-
tations of SO3 molecule. SO3 molecules primarily adsorbed
above a threefold hollow site of the Pt(111) surface in a tilted
fashion, forming two Pt–O and two Pt–S bonds, as presented
in the Fig. 7. Another low lying isomer has been presented in
Fig. S8 of ESI.† S–O bond length of SO3 molecule interacting
with the catalyst surface increases up to 1.54 Å. Alloying a
single Ag atom in the Pt(111) surface increases the S–O intera-
tomic separation to 1.59 Å. The electronic density of states
(DOS) of SO3 molecule adsorbed on the Pt(111) surface/Ag1Pt(111)
surface are shown in Fig. 8, where the influence of low concen-
tration Ag on the states of SO3 is clearly visualized.
Reaction enthalpy for the decomposition reaction on the Pt
surface is found to be 1.01 eV. The S–O bond breaking reaction
barrier (activation barrier) was calculated under NEB method
using four images between the reactant and product states.
Results reveal that the activation barrier for SO3 decompo-
sition on the Pt(111) surface is 1.73 eV, as presented in Fig. 9.
In case of Ag-substituted Pt(111) surfaces, adsorption of SO3
on the single Ag site leads to elongation of the bond up to
1.59 Å. Furthermore, the reaction enthalpy of decomposition
and activation barrier for such surfaces were found to be 0.52
and 1.2 eV, respectively, as presented in Fig. 10. Interestingly,
for both AgPt9@Al2O3 and Ag1Pt(111), the minimum energy
paths for SO3 decomposition show double hump character,
while those of their respective platinum counterparts show
single hump barriers.
Table 2 compares the various parameters for SO3 decompo-
sition reaction on Pt(111) and Ag1Pt(111) surfaces. Analogous
to the results of sub-nanometre scale, at larger scale, the
Ag-embedded catalyst, i.e., the Ag1Pt(111) surface, exhibits
better performance in catalysing the decomposition of SO3.
Single Ag substitution leads to reduction of activation barrier
by ∼30% to facilitate the S–O bond breaking and simul-
taneously, its presence leads to weaker binding of reaction
product.
3.4 Comparative discussion and perspective
In previous sections, it was established that the presence of
single Ag atom inside the Pt cluster or surface can substan-
tially improve the overall catalytic performance. It is known
that Ag atom’s valence electrons primarily show s-character,
while Pt atom’s valence electrons, participating in the
bonding, mainly show d-character. Ag atom contributes only a
Pt(111) Ag1Pt(111)
1.18 eV 0.39 eV
−0.69e −0.86e
0.10 Å (6.94%) 0.15 Å (10.42%)
1.73 eV 1.22 eV
1.01 eV 0.52 eV
Pt–S: 2.32 Å Ag–S: 2.72 Å
Pt–S: 3.11 Å Pt–S: 3.20 Å
Pt–O: 2.16 Å Pt–O: 2.30 Å
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few valence level electrons to bonding, leading to weaker positions, as the d-band centre of Ag(111) is located at much
bonding interactions in comparison with Pt. This feature is lower energy compared with that of Pt(111).60 When a mole-
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seen in the second and third ionization potentials of silver
atom and Platinum atom. These values for silver (II → 21.49
eV, III → 34.83 eV) are much higher in comparison with those
for platinum (II → 18.56 eV, III → 28 eV).59 The deeper location
of silver d-electrons is further manifested in the d-band centre
Fig. 11 Electronic density of states of SO3 molecule projected on
sulphur atom near the Fermi level in different cases. Vertical dotted line
at zero indicates Fermi level.
cule such as SO3/SO2 approaches silver atoms, higher binding
energy of d-electrons prevents the effective interaction of Ag
with LUMO of the incoming molecule, leading to weaker
bonding between silver and the molecule. Poor binding of
silver substrate to various molecules has been previously
observed by many researchers.61–64 Furthermore, it is impor-
tant to note that Pauling electronegativity values59 of S, Pt and
Ag are 2.58, 2.28, and 1.93, respectively. Electronegativity is a
measure of the tendency to attract bonding electrons.
Therefore, a large difference in electronegativity of S and Ag
indicates that electron density involved in the Ag–S bond will
remain shifted towards sulphur. Thus, S atom will receive
more amount of charge in Ag–S bond in comparison with a
Pt–S bond.
Therefore, inclusion of single Ag site in the Pt nanocluster
or surface leads to weaker bonding with the SO3 molecule
(longer Ag–S separation). In addition, the higher electro-
negativity difference between Ag and S leads to injection of
more charge into sulphur atom. Since LUMO of SO3 molecule
has anti-bonding character and it is mainly focused on the
p-orbital of sulphur atoms, insertion of charge into sulphur
results in populating an antibonding molecular orbital of SO3,
leading to elongation of the S–O bond. As more amount of
charge is injected into the antibonding LUMO centred on the
sulphur atom, S–O bond further weakens. This feature has
been explained in the comparative DOS for sulphur electronic
states near the Fermi level, as presented in Fig. 11. As more
number of sulphur states appear below the Fermi level, the
S–O bond breaking reaction barrier (activation barrier) reduces
systematically. For the AgPt9@Al2O3 system, huge amount of
charge is injected into sulphur, which results in the formation
of two new peaks at around −3.2 eV and −1.1 eV. This in turn
leads to a decrease in the activation barrier to 0.52 eV.
As shown in Table 3, we have compared the activation bar-
riers of different reported catalysts with our proposed catalyst
in our present study. For the sake of comparison, previous
theoretical prediction on Pt12 cluster-based catalytic system34

Table 3 Comparison of activation barrier of SO3 decomposition obtained in the present study with respect to previously reported barriers obtained
for other reported catalysts

Catalyst Barrier Ref. Remarks

Fe2O3 pallet fragment 1.72 eV Ref. 29 Experimental

Fe2O3-coated Si/SiC honeycomb fragments 2.32 eV Ref. 29 Experimental
Fe2O3 particle supported on Al2O3 1.44 eV Ref. 28 Experimental
Pt particle on antase TiO2 0.97 eV Ref. 38 Experimental
Pt particle on rutile TiO2 1.66 eV Ref. 38 Experimental
Pt particle on Nb2O5 0.96 eV Ref. 39 Experimental
Pt particle on Ta2O5 0.81 eV Ref. 39 Experimental
Pt particle on WO3 0.86 eV Ref. 39 Experimental
Pt12 cluster on rutile TiO2 0.90 eV Ref. 34 Theoretical
Pt12 cluster on γ-Al2O3 0.70 eV Ref. 34 Theoretical
Pt(111) surface 1.73 eV Present work Theoretical
Ag1Pt(111) surface (single atom alloy (SAA)) 1.22 eV Present work Theoretical
Pt10 cluster on α-Al2O3 1.16 eV Present work Theoretical
AgPt9 cluster on α-Al2O3 (single atom alloy (SAA)) 0.52 eV Present work Theoretical

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has also been included in the list. It is clear from this table
that the present single atom alloy (SAA) catalyst, i.e., AgPt9
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cluster on α-Al2O3 support, shows the least activation barrier
value. Additionally, embedding of single Ag atom in the cata-
lyst not only reduced the activation barrier, but also rendered
weaker adsorption of the SO2 on catalyst due to the deep level
d-orbital, thus enabling easy desorption of the reaction
product. For the nanocluster catalyst, the presence of single Ag
atom has improved the alumina substrate binding efficiency of
the Pt cluster. The binding of the cluster with support strongly
depends on the intrinsic/inherent thermodynamic stability of
the cluster. A very stable cluster leads to weaker binding with
the substrate. Substitution of Ag in the Pt cluster leads to re-
placement of few strong Pt–Pt bonds with weaker Ag–Pt bonds.
This slightly hampers the overall thermodynamic stability of
the cluster, but in turn prompts the Pt cluster catalyst to
strongly bind with the surface to minimize stability loss.
Improved binding efficiency of Pt cluster on the alumina
support can prevent subsequent sintering-induced decay in
the catalytic performance.
4. Conclusions
With an aim to design single atom alloy (SAA)-based catalysts
for SO3 decomposition reaction, which is the most endother-
mic step of the SI thermochemical cycle, we performed a sys-
tematic theoretical investigation on single atom alloy Pt nano-
cluster (AgPt9@Al2O3) and single atom alloy Pt (111) surface,
i.e., Ag1Pt(111). The calculated results indicate the following
points.
(i) Implanting single Ag atom in alumina supported plati-
num cluster Pt10@Al2O3 and in the Pt(111) surface leads to sig-
nificant reduction in activation barrier for S–O bond cleavage.
(ii) Interaction of SO3 molecule with the AgPt9@Al2O3
cluster leads to ∼19% elongation in the bond length of one of
the S–O bonds, leading to lowering of decomposition barrier
up to 0.52 eV. This is the lowest barrier value for any platinum-
based catalyst reported so far.
(iii) The product of decomposition reaction, i.e., SO2 mole-
cule, weakly adsorbed on single Ag atom alloy Pt catalyst in
contrast to the pristine Pt catalyst, which indicates easier de-
sorption of reaction product from the former for better
recyclability.
(iv) For alumina-supported platinum nanocluster, single Ag
atom alloying enhances its binding with the alumina sub-
strate, which remains stable during SO3 decomposition reac-
tion, suggesting better stability against sintering for single
atom alloy catalyst.
(v) Deeper position of silver d-electrons and smaller electro-
negativity value of silver have been attributed as key reasons
for better performance by the single Ag atom alloy catalyst.
We hope that the proposed single Ag atom alloy platinum
catalyst will provide a new pathway for designing a catalyst for
SO3 decomposition and a novel platform for future experi-
mental and theoretical investigations in this direction.
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Conflicts of interest
There are no conflicts to declare.
Acknowledgements
We are thankful to the members of the Computer Division,
BARC, for their kind cooperation during this study.
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