Applied Surface Science 547 (2021) 149160

Contents lists available at ScienceDirect

Applied Surface Science

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

Full Length Article

Atomically precise noble metal clusters (Ag10, Au10, Pd10 and Pt10) on
alumina support: A comprehensive DFT study for oxidative catalysis
Sandeep Nigam *, Chiranjib Majumder
Chemistry Division, Bhabha Atomic Research Centre, Mumbai 400085, India
Homi Bhabha National Institute, Mumbai 400094, India

A R T I C L E I N F O A B S T R A C T

Keywords: A comprehensive study of electronic and geometrical properties of alumina supported M10 (M = Ag, Au, Pd, Pt)
Atomically precise cluster clusters has been reported with a focus to unravel chemical reactivity towards oxidative catalysis. Au10, Ag10 and
DFT Pd10 clusters on alumina surface, adopt zigzag style hexagonal pseudo-planar structure aligning to substrate
Comparative study
template, contrary Pt10@Al2O3 does not follow surface template and forms a bilayer structure due to higher
Oxygen activation
Pt–Pt bond strength. Pd10 and Pt10 cluster bind with alumina surface stronger than Ag10 and Au10 and
accordingly receives more charge from surface. The d-band centre of finite size M10@Al2O3 cluster follows the
trends of extended M(1 1 1) surface and Pt10@Al2O3 shows close matching for d-band centre position values with
Pt(1 1 1). On interaction with O2 molecule, all four M10@Al2O3 clusters energetically prefer surface assisted
molecular adsorption (O2 bridging cluster-surface) over atop molecular adsorption demonstrating pivotal role of
substrate. In contrast, dissociative adsorption prefers atop mode configurations. During oxidation, whilst
Ag10@Al2O3, Au10@Al2O3 and Pd10@Al2O3 show increase in M–M bond-lengths and move away from substrate,
Pt10@Al2O3 displays robust behaviour by moving near to surface. Due to minimum overlap between 4d and 5s
state (large difference in energy) the O2 interaction energetics of Ag10@Al2O3 as well as Ag(1 1 1) depart from
usual d-band model.

1. Introduction coordinated arrangements [10–12]. These ultra-small metal clusters

are particularly attractive for catalysis due to high density of low co­
Noble metals like Ag, Au, Pd, Pt has been of great interest due to their ordinated sites and accessibility of nearly all metal atoms to reactants
remarkable performances in numerous catalytic reaction [1–4]. Het­ rendering relatively higher metal utilization efficiency. In the sub-
erogeneous catalytic applications rigorously utilize extended surfaces/ nanometer regime the properties of metal clusters are often non-
facet of these noble metals. There has been continuous effort to enhance scalable and do not follow the established trends extracted from larger
catalytic efficiency of noble metal catalytic particle by reducing their particle sizes or extended surfaces [13,14]. Another feature of the
dimension to nanoscale [3–9]. Larger supported particles (>1–2 nm reduced size of clusters is that their considerable fraction of atoms are
diameter) are composed of more than thousands atoms and generally located at the cluster/support interface, metal–support interaction ef­
have their atoms arranged in ordered crystalline facets. For these larger fects are likely to be more pronounced in comparison to larger nano­
nanoaparticle, electronic and structural properties are readily predicted particle catalysts, leading to drastic influence on their structural and
based on the properties of respective extended surfaces i.e. properties electronic character [15–20]. Advancements in synthesis methods haves
are predictable and scalable. For larger particles the effect of the support provided means for the production of highly dispersed ultra small sub­
is minimal and the chemistry is dictated by the exposed crystalline nanometer noble metal particles on supports [21], maximizing the
facets. However, for very small particle the structural and electronic population of active centers and enhancing beneficial metal–support
features alter drastically. interactions to get a cost-effective high performance and robust catalytic
When changing the size of metals particle from nanometer to ul­ materials.
trasmall subnanometer clusters (~2–20 atoms), their atoms gradually Size-selected or atomically precise subnanometer clusters supported
shift from being organized in crystalline facets to dominantly under- on metal oxide substrate reduces uncertainties arising due to particle

* Corresponding author.
E-mail addresses: [email protected] (S. Nigam), [email protected] (C. Majumder).

https://doi.org/10.1016/j.apsusc.2021.149160
Received 1 October 2020; Received in revised form 8 January 2021; Accepted 25 January 2021
Available online 29 January 2021
0169-4332/© 2021 Elsevier B.V. All rights reserved.
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

size distribution and facilitates controlled study of cluster support set size and simulation cell size, and the total energy was found to be
interaction and reactivity pattern of specific size [21–33]. With an accurate within 1 meV. In case of calculations of finite size cluster, each
atomically precise controlled catalyst, engineering at the atomic/mo­ configuration was placed inside a large cubic box of 15 × 15 × 15 Å. The
lecular level is likely possible, and can play a decisive role in catalyst brillouin zone integrations were carried at the Γ point only.
design strategies [34–37]. Therefore, size selected subnanometer noble The α-Al2O3(0001) surface was modeled with 18-atomic layer slab
metal clusters supported on metal oxide has meticulously served as well- by truncating the bulk α -Al2O3 structure (a = b = 4.766 Å and c =
defined model for controlled catalyst. Even though Ag, Au, Pd, and Pt 12.999 Å). To avoid the interaction between periodic slabs, we have
are known to be important in many catalytic processes and large number used a vacuum layer of 13 Å between slabs. In the present study, the 3 ×
reports are available on atomically prices cluster [25–33] of these 3 supercell (30 atoms/per unit cell) has been used to avoid interaction
metals, a comparative study on their interaction with support and between images. Overall supercell dimensions were 14.30 × 14.30 ×
reactivity pattern are rare. 25.99 Å (surface area ≈ 204.4 Å2) containing 270 atoms. Figure S1 of
Activation and dissociation of molecular oxygen is one of the pri­ supporting information displays the five different atomic layers as rep­
mary and key steps [38–41] for driving environment friendly and resented by, Al(1), O(2), Al(3), Al(4), and O(5) (viz. Figure-S1,sup­
industrially important reactions such as CO oxidation, ethylene epoxi­ porting information). To make the reading easy, we have labelled each
dation, hydrocarbon oxidation, etc. During past few decades a number adsorption site with a letter and a number indicating the type of the
of catalysts based on Ag/Au/Pd/Pt nanoclusters/particles have under­ atom and the atomic layer in the slab, respectively. A Monkhorst–Pack
gone exhaustive investigation to verify their efficacy. In particular, set of 5 × 5 × 1 K-points was used throughout all the calculations. For
subnanometer cluster of noble metals have been at the forefront of both structural relaxation, all 18 atomic layers were allowed to relax. Test
experimental and theoretical research for understanding the intrinsic calculations were also carried out on O2 molecule in the gas phase. The
mechanistic pathways of O2 activation and dissociation on these clus­ optimized structure showed O–O bond length as1.23 Å. The average
ters. Although some studies have been carried out to investigate the O2 adsorption energy of M10 cluster on α-Al2O3 surface was calculated as
adsorption and dissociation on supported subnanometer noble metal
clusters [42–62], to the best of our knowledge, no comprehensive re­ ΔE = [E(M10/Al2O3)–E(Al2O3)–E(M10)gas]/10.
ports are available on the comparison of these four noble clusters (Ag10, The binding energy of the O2 molecule with ten atoms clusters has
Au10, Pd10, Pt10) deposited onto alumina. Disintegrative leaching and been calculated in the following manner
sintering issues of the supported cluster forces researcher for deeper Binding of molecular oxygen BE = E(O2@ M10/Al2O3) – E(M10/
understanding of cluster’s inherent electronic properties in dictating Al2O3) – E(O2)
their interaction with surface and in next step, controlling the reactivity According to above equation, negative binding energies correspond
of cluster-surface complex. Thus a comprehensive and comparative to exothermic adsorption. For dissociative adsorption, the reaction
study is expected to be of utmost importance for rational design of a enthalpy (ΔH) for the reaction
cluster based catalyst with durability (against disintegration and/or sin­
tering) and higher catalytic activity for industrial applications rather M10@Al2O3 + O2 → O–(M10@Al2O3)–O + ΔH
than from a blind trial and error approach.
ΔH = E[O–(M10@Al2O3)–O]–E[M10@Al2O3]–E[O2]
In the present work we have compared the structure and chemical
reactivity of alumina supported M10 (M = Ag, Au, Pd, and Pt) clusters To understand the nature of chemical bonding between M10 cluster
toward oxidative catalysis with an aim to understand the correlation and Al2O3 substrate, the difference in charge density (Δρ) of the
between reactivity and cluster’s geometric and electronic structure (i.e. adsorbate-substrate complex has been calculated, which is expressed as
nature of adatom), support interactions. In particular it is aimed to find
out that how much the influence of alumina support differs on changing Δρ = ρ(M10/Al2O3)–ρ(Al2O3)fix–ρ(M10)fix
the adsorbed cluster. The size of ten atoms cluster was guided by the fact The first term ‘ρ(M10/Al2O3)’ is the charge density of the total sys­
that M10@Al2O3 has been found to be stable as well as catalytically tem, ρ(Al2O3)fix is the charge density of the alumina surface fixed at the
active in experiments. It is worth mentioning that ten atoms size is large adsorbed geometry, and ρ(M10) is the charge density of a metal atom/
enough to support an approximation of the bulk plasmon oscillation, but cluster isolated in the same periodic box.
small enough to ensure sufficient symmetry to retain clearly defined
excited states of the molecule-metal system [63]. In order to get deeper 3. Result and discussion
insight and understanding regarding finite size effect, the reactivity
trends of M10@Al2O3 has been compared with extended surfaces. It is 3.1. Structure of M10@Al2O3 clusters (M10 = Ag10, Au10, Pd10, Pt10)
believed that outcome of the work will act as benchmark for atomic level
designing of homo/bimetallic nano/subnano oxidative catalyst based on In order to compare the geometries of noble metal clusters in the gas
noble metals. phase with that of deposited ones, we begin our discussion by presenting
the structure of free clusters (isolated gas-phase structure) first. For
2. Computational details Ag10, Pd10 and Pt10 clusters, the lowest energy isomer of the bare clus­
ters are three dimensional in nature. This is in contrast to the Au10
All calculations were performed under the density functional theory cluster, which favours a planar structure. The atomic configurations of
formalism. The plane wave pseudo-potential based method has been these four clusters are shown in Fig. 1. For Ag10 cluster, the lowest en­
used as implemented in the Vienna ab initio Simulation Package (VASP) ergy isomer is a tricapped pentagonal bipyramid (or two interlocked
[64–66]. The electron–ion interaction was described by the full- pentagonal bi-pyramid D2d). The Pd10 cluster also forms a tricapped
potential all-electron projector augmented wave (PAW) method [67], pentagonal bipyrimid structure but the capping is different (adjacent
as implemented in VASP by Kresse and Joubert [68]. The spin polarized faces on the same side) leading to C3v symmetry. Pt10 cluster adopts
generalized gradient approximation [69] has been used to calculate the tetracapped prism isomer (~tetrahedral symmetry) as the lowest energy
exchange-correlation energy. The cut off energy for the plane wave basis structure in the gas phase. The lowest energy isomer of the Au10 cluster
set was fixed at 400 eV for all calculations performed in this study. The forms a planar hexagonal structure with the D2h point-group symmetry.
geometry optimization has been performed by ionic relaxation, using a These observations are in line with those reported in literature [70–73].
conjugate gradient method. The geometries are considered to be To get the ground state geometry of M10 clusters on alumina support,
converged when the forces on each ion becomes 0.01 eV/Å or less. The ionic relaxation was carried out for few low lying gas phase isomers
total energy convergence was tested with respect to the plane-wave basis

2
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Fig. 1. Ground state structure of gas phase and Al2O3 supported M10 cluster. Top five atomic layers are shown in different colour for clear presentation and rep­
resented by, Al(1), O(2), Al(3), Al(4), and O(5).

placed at well-defined adsorption sites on the Al2O3 surface in different alumina support (as shown in Fig. 1) it is seen that the all these clusters
orientations (parallel, perpendicular and tilted to the surface). From the adopt zigzag patterned hexagonal pseudo-planar structure aligning in
comparison of total energy of different isomers of each M10 clusters on Al2O3 template, irrespective of the configurations they adopt as the
alumina support (Figure S2 of the supporting information), it is clear lowest energy isomer in the gas phase. This clearly underlines the effect
that the geometry of the ground state isomer modifies upon interaction of surface morphology or the template of the alumina surface top layer.
with alumina support. This feature corroborates the influence of support In general, out of ten metal atoms, four atoms bind atop site (Al-1) site,
on the geometry and electronic structure of sub-nano clusters. From the three atoms occupy the ‘Al-4’ hollow site and the remaining three atoms
structure of the lowest energy isomers of Au10, Ag10 and Pd10 clusters on (central atoms) reside over the ‘Al-3’ site. The Pt10 cluster shows

3
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

transition from three layer pyramid structure to a bilayer structure as the Table 2
ground state on the alumina surface. Template based planar zig-zag Comparison of structural parameter, bader charge and adsorption energy of
isomer is 0.30 eV higher in energy. The other low lying isomers for M10@Al2O3 cluster. For charge calculation, we have employed the Bader
M10@Al2O3 are presented in Fig. S2 of the supporting information. Thus, method [76] numerical implemented by Henkelman et al [77].
it is clear that the geometry of M10 clusters on alumina support differ M–M M–M Deposited- M10 bader Adsorption
significantly from the respective gas phase geometry. In this context we distance in distance in Average charge Energy (M10)
the gas the distance (gained With respect
may recollect [75] that preference of Au clusters to have planar upto
phase (no. deposited from surface from to gas phase
Au10-14. In contrast, palladium cluster prefer non-planar 3D growth of bonds) (no. of surface)
motif starting from tetramer onwards [72]. Gas phase Ag clusters, bonds)
despite their preference to be planar upto n = 6, for n = 10 favors tri- Ag 2.81 (23) 2.82 (19) 2.75 − 0.43e − 0.21 eV/
capped pentagonal pyramid. Thus the formation of a pseudo planar atom
configuration for Pd10@Al2O3 is worth to notice. In fact according to the Au 2.71 (19) 2.75 (19) 2.78 − 0.76e − 0.23 eV/
literature, the growth of Pd clusters on TiO2 (1 1 0) surface has already atom
Pd 2.70 (26) 2.67 (19) 2.54 − 1.30e − 0.35 eV/
been reported to be pseudo-planar instead of non-planar 3D structures
atom
[57]. Gas phase Ptn cluster in 2–7 size range prefer planar cluster, Pt10 Pt 2.64 (24) 2.66 (21) 2.36#
− 1.16e − 0.33 eV/
cluster have 3D ground state structure [18]. However this 3D structure atom
of Pt10 unlike Pd10, does not prefer to rearrange itself in Al2O3 template. #
From connecting pseudo-planar layer (omitting top layer).
The reason behind going away of Pt10@Al2O3 from the surface template
is the large cohesion between Pt-Pt atoms. To underscore the metal
for Pd10@Al2O3 and Pt10@Al2O3 clusters, the major contribution in the
cohesion, we have calculated the cohesive energy of bulk metals and are
Fermi energy level is from surface oxygen 2p state along with contri­
presented in Table 1. The experimental value of cohesive energy has
bution of d-states of metal cluster, for Ag10@Al2O3 and Au10@Al2O3 the
been taken from Ref. [74]. In fact the bulk cohesive energy of Pt is 5.28
Fermi energy level comprises of sd-mixed states from metal atoms. Bader
eV/atom, which is significantly larger than Pd i.e. 3.74 eV/atom. As a
charge analysis (shown in Table 2) also suggests higher amount of
consequence, Pt atoms prefer to bind with Pt atoms over Pt-surface after
charge transfer from alumina surface to the M10 cluster in the case of
a certain size where it is possible to make more coordination.
Pd10 and Pt10 in comparison to Ag10 and Au10 cluster. It is worth
After considering the cohesive strength of metals we have focused on
mentioning here that cluster-surface distance for Pd10 and Pt10 clusters
metal substrate interaction because, the ground state geometry of a
is less in comparison to Ag10 and Au10 clusters.
cluster on a substrate is governed by energy balance between the (1)
For deeper understanding of chemical bonding at the interface of M10
Metal-Metal interactions (cohesive strength) and (2) Metal-substrate
cluster and Al2O3 substrate, the difference in charge density (Δρ) of the
interaction. The strength of metal-metal interaction within a cluster is
adsorbate-substrate complex has been estimated and presented in Fig. 3.
proportional to the average inter-atomic separation and number of bond
It is observed that when metal atoms are occupying a hollow site around
formation. This is corroborated by the relative stability of different
Al(4) or nearby bridge position, charge is transferred to the nearby oxygen
isomers, which closely matches with the average bond length and the
atoms. In contrast, when the metal atom is directly connected to the top
number of bonds within the cluster. Upon adsorption, the deposited
layer Al(1), a finite amount of charge transfer takes place from the
clusters reorient in such a way that it can maximize the metal-surface
surface to the adsorbate atom. When metal atoms are occupying a hol­
interaction with minimum sacrifice in the metal-metal bonds. In table
low site around Al(3), negligible charge transfer is observed. Moreover
2 we have compared the structural parameter, charge transfer and
for metal-Al(1) connection, the electron density is localized along the
adsorption energy for Mn@Al2O3 cluster. On the basis of these results it
M–Al bond. Overall, in all four cases a significant charge is transferred
is seen that the adsorption energy for group 10 metal clusters is higher
from surface to the cluster leading to polarization of the alumina surface.
(Pt10 and Pd10 cluster ~0.33–35 eV/atom) than group 11 metal clusters
To show the effect of charge transfer on the top layer of alumina surface,
(Ag10 and Au10 cluster ~0.20 eV/atom). This is in line with the fact that
2D contour plot is also shown in the Fig. 3. For 2D plot, the red colour
average M–M bond distance and cluster-surface separation for Pd10 and
represents the maximum electron density and it systematically decreases
Pt10 clusters are less in comparison to Ag10 and Au10 clusters. It should
as the colour changes from red to blue in the rainbow. From the varia­
be noted that the valence electronic configuration of Ag and Au is d10s1
tion in the colour of the charge density difference plot it is clear that
and for Pd and Pt is d8s2. Consequently the number of unpaired elec­
significant redistribution of charge in top layer of Al2O3 slab. The
trons, which are primarily responsible for bonding, is more for Pd and Pt
observed polarization in surface is proportional to the amount of charge
atoms in addition to the vacant d-orbitals. Thus, the higher adsorption
transfer (bader charge) which is summarized in Table 2. For
energy of Pd and Pt clusters than Ag and Au clusters on the alumina
Pd10@Al2O3 and Pt10@Al2O3, where more electronic charge has been
surface is due to the larger d-orbital contribution in the bonding.
transferred from surface to cluster, more polarization is observed in the
To underscore the electronic structure effect, projected density of
surface plane. Contrary to this trend, for Ag10@Al2O3 and Au10@Al2O3
states (PDOS) for M10 clusters before and after deposition on the
lesser amount of charge is transferred and consequently lesser polari­
alumina is presented in Fig. 2. As expected, based on atomic electronic
zation happens in the top layer of surface plane as shown in Fig. 3.
configuration, for all M10 cluster d-orbital contribution is significantly
Further we analyse the charge distribution by estimating the charge
higher than s-orbital contributions. Moreover, upon adsorption the
density difference (Δρ) of M10@Al2O3 cluster as shown in Fig. 3. The
sharper electronic states of the M10 clusters become broader. Whereas
blue colour represents decrease of charge while orange indicates accu­
mulation of charge. Δρ has been represented with an iso-surface value of
Table 1
0.002e/bohr3. For the 2D plot of the different atomic layers of slab,
Calculated lattice constant and cohesive energy of bulk metals. The experi­
charge increased from blue to red in the rainbow from − 0.002e to
mental values are taken from Ref. [74].
+0.002e. Blue indicated depletion of charge, red indicates increase of
Calculated Exp. Lattice Calculated Exp. Cohesive
charge.
Lattice constant constant(Å) Cohesive energy energy (eV/
(Å) (eV/atom) atom)

Ag 4.17 4.08 2.48 2.95 3.2. Oxidation behavior of M10@Al2O3 clusters

Au 4.18 4.07 3.08 3.81
Pd 3.95 3.86 3.74 3.89 Understanding oxidation process is not only required for funda­
Pt 3.98 3.92 5.28 5.84
mental insight but also forms an important class of reaction in terms of

4
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Fig. 2. Projected density of states (PDOS) of gas phase and Al2O3 supported M10 cluster.

industrial chemical synthesis. In oxidative catalysis, the catalyst mate­ relaxations of all atoms. Two important modes of chemisorption in low
rial assists in activating the O–O bond of the oxygen molecule and lying minima are: (i) atop mode, where both oxygen atoms of the O2
subsequently oxidizes the reactant molecule. Therefore, adsorption of molecule are bonded with atoms of the deposited cluster (ii) bridge-
molecular oxygen and its activation is the first and key step. Once the mode, where one oxygenatom of the O2 binds with cluster and the
activation of molecular oxygen is done, further oxidation reactions can other oxygen atom binds with one of the nearest Al atoms of the sur­
occur either via O–O bond dissociation to atomic oxygen followed by faces. Fig. 4 represents the equilibrium geometries of the O2 adsorbed
oxidation of reactant or direct oxidation of the reactant by activated O2 complexes in these two modes. The comparison of total energies of these
molecule itself. The ground state of the molecular oxygen is spin triplet structures reveals that adsorption in bridge mode is energetically
with two unpaired electrons occupying the degenerate anti-bonding favourable as the lowest energy isomer. In general, both bridge and atop
2πu* orbitals. Activation of oxygen molecule requires significant inter­ mode adsorption of oxygen molecule are stable and stretch the O–O
action with the catalytic surface i.e. chemisorption and subsequent bond. Interestingly, we find very weak binding of O2 molecule with
electron transfer to these 2πu* orbitals. In this section, we describe the Au10@Al2O3 in atop mode. The binding energy is 0.03 eV approx.,
adsorption behaviour of the molecular oxygen on M10@Al2O3 cluster. which suggest as van der Waals complex formation. This is comparable
The interaction of molecular oxygen with M10@Al2O3 was carried out in to what is reported [49–51] for molecule O2 interaction with Au10‾
two modes; (i) placing the molecule oxygen at different locations on the cluster in the gas phase. For all other cases the interaction of molecular
deposited cluster (molecular adsorption) and (ii) two oxygen atoms are oxygen with deposited M10@Al2O3 induces bond length stretching of
placed separately on the M10 cluster (dissociative chemisorption). O–O from 1.23 to 1.33–1.40 Å. The O2 binding energy for both atop
Different low lying isomers of oxygen interaction are presented in modes follow trends i.e. Au10@Al2O3 < Ag10@Al2O3 < Pd10@Al2O3 <
Figures S3-S6 of the Supporting Information. A significant energy bar­ Pt10@Al2O3, while for bridge mode the trend is Au10@Al2O3 <
rier exists between these two configurations (molecular and dissociative Ag10@Al2O3 < Pt10@Al2O3 < Pd10@Al2O3. Weaker Pd-Pd interaction
adsorption). However, since oxidative catalysis depends on either acti­ during atop mode oxygen interaction reduces the binding energy. In
vated oxygen molecule or atomic oxygen attached to the substrate, we general the binding of O2 with M10@Al2O3 complexes in bridge mode is
focus mainly on resultant configurations of molecular and dissociative higher than atop mode. Moreover, the adsorption of O2 with M10@Al2O3
adsorption. In the present work the primary objective is to compare complexes involves charge transfer from the metal cluster to the mo­
between the molecular and dissociative adsorption pattern of four noble lecular oxygen. The extent of charge transfer is higher in the bridge
metal cluster i.e. M10@Al2O3 cluster. mode than atop mode, which is in line with observed higher binding
In order to search the energetically most favourable atomic config­ energy in the bridge mode.
uration for O2 molecule adsorption, starting configurations considered Strong chemisorption of oxygen with metal- clusters is expected to
by placing the O2 molecule at various possible sites in different orien­ perturb the electronic structure of oxygen molecule and host cluster
tations with respect to the deposited cluster followed by ionic significantly. Gas phase oxygen molecule has distinct and sharp peaks

5
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Fig. 3. Charge density difference (Δρ) contours for M10@Al2O3 cluster. The blue represent decrease of charge while orange indicates accumulation of charge. Δρ has
been represented with an iso surface value of 0.002e/bohr3. For the 2D plot of the different atomic layers of slab, charge increased from blue to red in the rainbow
from − 0.002e to +0.002e. Blue indicated depletion of charge, red indicates increase of charge.

(viz. Fig. S7 of supporting information). When oxygen molecule in­ attached on Au10 cluster is bi-coordinated. On the basis of the total
teracts with the cluster, the molecular energy states is expected to energy consideration between molecular and dissociated oxygen
become wider and diffused based on the strength of interaction. Fig. 5 adsorption, it is found that the atomic (dissociative) adsorption is
shows a comparative pattern of the density of states of metal cluster energetically more favourable than molecular adsorption. More metal-
projected on the p-orbital of the oxygen atom after adsorption in atop oxygen bonds are formed in case of dissociative adsorption than mo­
and bridge modes. From Fig. 5 it is clear that the effect of chemisorption lecular adsorption. This is ascribed to higher binding of oxygen atom in
on the electronic structure of oxygen molecule is more in the bridge dissociated fashion. Also the extent of charge transfer to two oxygen
mode. This is due to the higher interaction energy and charge transfer in atoms is more (~1.7 to 1.8e) than molecular adsorption.
the bridge mode. It is also observed that for Pd10@Al2O3 and The reaction enthalpy (ΔH) trend for atomic adsorption follow the
Pt10@Al2O3, higher interaction energy and charge transfer leads to order as Au10@Al2O3 < Ag10@Al2O3 < Pt10@Al2O3 < Pd10@Al2O3.
greater broadening of oxygen p-states near Fermi level in comparison to Because of the strong binding of oxygen molecule in dissociative
Ag10@Al2O3 and Au10@Al2O3 cluster. In order to get deeper insight of manner, significant structural changes are induced in the host cluster
the bonding aspects comparative analysis of density of states projected (change in average metal-metal bond distance). The maximum change
on the metal atoms of M10@Al2O3 cluster before and after interaction in the internal moiety of the M10 clusters has been observed for
with oxygen molecule was carried out and results are presented in Ag10@Al2O3 and minimum for Pt10@Al2O3 cluster. The details of these
Fig. S8-S9 of supporting information. It is observed that the d-states of changes in geometrical parameters are presented in Table 3. In addition,
metal clusters have lesser effect (almost negligible) of O2 interaction. In the oxidation of supported metal clusters alters the interface between
contrast, the s-states of M10@Al2O3 cluster (s-states) are significantly the cluster and surface which is evident from the cluster-surface dis­
influenced and extent is maximised for the Ag10@Al2O3. tance. For Ag10@Al2O3, Au10@Al2O3, Pd10@Al2O3 cases the cluster-
After molecular adsorption, we have looked in the dissociative surface separation increases during oxidation. In contrast the Pt10
adsorption of O2 on the M10@Al2O3 cluster. Different configurations of moves closer to the Al2O3 surface during oxidation process. On the basis
M10@Al2O3 with dissociated oxygen atoms (atomic oxygen) were of this result it can be inferred that the Pt10 cluster on alumina support is
examined. The optimized lowest energy structures of these complexes robust enough to strongly bind the surface even during oxidation.
(in atop and bridge mode) are displayed in Fig. 6. Contrary to molecular Moreover, the strong binding of Pt clusters with alumina substrate can
adsorption, where bridge site adsorption has been the most favourable, help in avoiding sintering during oxidation reaction.
for dissociative adsorption atop mode of adsorption is more stable than The activation barriers of the O2 dissociation are determined by two
the bridge mode. These results are corroborated by the higher reaction factors: (i) the activation of O2 molecularly adsorbed and (ii) by the
enthalpy value in the atop mode. For Ag10@Al2O3, Pt10@Al2O3 and deformation of the supported metal clusters along the reaction pathway
Pd10@Al2O3 the oxygen atom favours to cap one of the trigonal faces of [54]. Considering these two facts it is expected that Pt10@Al2O3 should
the metal cluster, leading to three coordination of oxygen atom. For have least barrier for O2 dissociation among the four clusters, because it
Au10@Al2O3 the lowest energy structure showed oxygen atoms bind at provides close to maximum molecular oxygen activation and least
the Au–Au bond edge leading to formation of Au-O-Au linkages with bi- deformation during oxidation process.
coordinated oxygen atoms. Even in case of bridge mode the oxygen atom Fig. 7 shows a comparative density of states pattern of metal cluster

6
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Fig. 4. Structure showing molecular oxygen interaction with M10@Al2O3 cluster in atop and bridge mode. Binding energy (BE) released and electronic bader charge
transferred to oxygen molecule during interaction is also presented.

projected on the p-orbital of the oxygen atom after oxidation of cluster. 3.3. Comparison of oxidation behaviour of M10@Al2O3 clusters with M-
From this figure it is clear that p-states of the oxide product [O- (1 1 1) surface
M10@Al2O3-O] for silver and gold are similar and have greater intensity
around Fermi level. Contrary to this, for Pd10@Al2O3 and Pt10@Al2O3, p- In order to underscore the finite size effects of the of the M10 clusters
states have larger intensity in deeper states (away from Fermi level). For on Al2O3 surface we have investigated the adsorption behaviour of ox­
further insight into the bonding a comparative analysis of PDOS of ygen molecule on the periodic slab of M(1 1 1) surface. In this regard we
M10@Al2O3 and oxide product [O-M10@Al2O3-O] are presented in show a comparison between the electronic structure of M10@Al2O3 and
Figures-S10- S11 of supporting information. It is observed that elec­ M(1 1 1) surface as shown in Fig. 8. The results show that the d-band
tronic states of metal cluster are red shifted which is in line with the fact centre for M10@Al2O3 is red shifted (towards Fermi level) with respect
that M10 cluster have positive value of bader charge indicating shift of to M(1 1 1) counterpart and indeed this is in line with the fundamental
electronic states. The extent of shift in d and s-states is maximum for understanding of quantum size effects in finite size systems. In partic­
silver cluster which shows standout maximum positive value. Among all ular, while the d-band centre of Pt10@Al2O3 and Pt(1 1 1) surface is
four metals, Ag has minimum electronegativity (1.9) in comparison to almost aligned the d-band centre position of Au10@Al2O3 cluster are
remaining three metals (Au = 2.4, Pd = 2.2, Pt = 2.2). Therefore, it is 0.55 eV red shifted with respected to Au(1 1 1) surface. The d-band
expected that silver can transfer maximum charge to oxygen atom. It is center of Ag10@Al2O3 and Pd10@Al2O3 system shows in between shift
worth to mention here that for M10@Al2O3 clusters, the change in inter values (~0.2 eV) with respect to their respective extended surfaces.
M–M bond distance as well as cluster –surface distance is also quite Moreover the extent of resemblance between the DOS of M10@Al2O3
significant. For other metal clusters, features of d-states of metal clusters and M(1 1 1) is more for d-states rather than s-states. Specially around
have lesser effect on oxidation. Contrary to this, s-states of all four metal the Fermi level the s-states of M10@Al2O3 and M(1 1 1) are quite
clusters are significantly influenced during oxidation as presented in different in terms of their intensity and splitting in the energy states.
Fig. S10 of the supporting information. The interaction of oxygen with M(1 1 1) was optimized in two modes;
(i) molecular adsorption and (ii) dissociative adsorption. The lowest
energy structures are shown in Fig. 9 and the top view of these

7
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Fig. 5. Density of states(DOS) projected on oxygen atoms of adsorbed oxygen molecule on M10@Al2O3.

configurations is presented in Fig. S12 in the supporting information. (1 1 1) surface with finite size M10@Al2O3 counterpart has been pre­
The molecular adsorption leads to elongation of the O–O bond upto sented in Table 4. Energetically, O2 can bind with M10@Al2O3 stronger
1.34–1.4 Å. The O–O bond length and binding energy values obtained than M(1 1 1) because of higher degrees of freedom, which leads to more
in the present work are in line with those reported in literature (viz. local reconstruction.
Table-S1 of supporting information). The adsorbed oxygen molecule In the next step we have attempted to study the dissociative
receives ~0.6–0.7e charge from the metal surface. A comparison of adsorption of O2 molecule by placing two O atoms separately on the M
O–O bond-length, bader charge and binding energy of O2 on the M (1 1 1) surface. The results showed higher stability and reaction enthalpy

8
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Fig. 6. Structure showing dissociated oxygen adsorbed on M10@Al2O3 cluster in atop and bridge mode. Reaction enthalpy (eV) for the oxidation reaction is
also presented.

[lower] d-band center value exhibits stronger [weaker] affinity to

Table 3
adsorbate molecule due to reduced [enhanced] filling of adsorbate-metal
Summary of change in M10@Al2O3 cluster properties during oxidation reaction.
antibonding states. Bonding of oxygen atom to transition metal results in
M Reaction Movement of Inter cluster Bader Bader the formation of bonding and anti-bonding states below and above the
enthalpy cluster during M–M bond charge on charge on
(eV) oxidation extension Å M10 cluster M10 cluster
metal d bands. Variations in M–O bond strength for oxygen adsorption
process during before after on transition metals depend on the filling of the antibonding oxygen 2p-
oxidation oxidation oxidation states. To achieve stronger M–O bonding, lower population of electrons
Ag − 2.31 1.1 Å away 2.80 to 2.91 − 0.43e +1.36e in the antibonding state is required. In other words strong M–O bonding
from surface occurs if antibonding states of oxygen atom are shifted upwards from the
Au − 1.46 0.7 Å away 2.74 to 2.88 − 0.76e +0.62e Fermi level and remains unoccupied/empty. Otherwise the bonding
from surface states should shift down from the Fermi level (and become filled). Thus
Pd − 3.53 0.06 Å away 2.67 to 2.79 − 1.30e
the electronic population of bonding and antibonding states is depen­
+0.67e
from surface
Pt − 2.46 0.06 Å 2.69 to 2.70 − 1.16e +0.33e dent on the distribution of metal d-states relative to the Fermi level (i.e.
towards d-band centre).
surface The projected density of states (PDOS) for oxygen atoms (molecular
and atomic) adsorbed on M(1 1 1) surface are presented in Fig. 10. From
the figure it is clear that the energy states of oxygen are significantly
of dissociative adsorption of oxygen atoms than molecular adsorption.
modified after interaction with metal surface and extent of modification
In addition, we find that the reaction enthalpy of the oxygen adsorption
is more for dissociative adsorption. A direct comparison of these energy
is more for M10@Al2O3 than M(1 1 1) surface. The higher reaction
states of oxygen during interaction with M10@Al2O3 and M(1 1 1) sur­
enthalpy of oxidation for M10@Al2O3 than that for M(1 1 1) surface is a
face is presented in Figures S13-S14. From these figures it is clear that
result of higher flexibility and reconstruction of finite size cluster, which
both Pd and Pt systems (both finite size M10@Al2O3-cluster and
in other words lower the geometrical strain during oxidation of the
extended M(1 1 1) surface) have d-band centre closer to Fermi level, and
M10@Al2O3 than extended M(1 1 1) surface.
in the PDOS of adsorbed oxygen atom, the peak intensity in the lower
In order to get further insight, we have used the d-band model
energy range (i.e. bonding state of oxygen atom) is higher than intensity
[79–81] to understand the chemical reactivity of the M10@Al2O3-cluster
of peaks close to Fermi level (antibonding states of oxygen atoms). Ac­
vis-a-vis M(1 1 1) surface (viz. Table 5). Previously, Hammer and Nor­
cording to d-band model, this leads to higher reaction enthalpy of
skov had shown that d-band center derived from the DOS, (which is
oxidation. Indeed, for Pd10@Al2O3/Pd(1 1 1) and Pt10@Al2O3/Pt(1 1 1),
defined as the average energy of the d-band density of states) can be used
the reaction enthalpy of oxidation follow the d-band model and show
as index for determining the reactivity of substrate and reaction energy
linear dependence on the d-band centre values. Contrary to this trend,
of the oxidation process [79]. In general, any metal site with a higher

9
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Fig. 7. Density of states(DOS) projected on oxygen atoms of dissociated oxygen molecule on M10@Al2O3.

for Ag10@Al2O3/Ag(1 1 1) and Au10@Al2O3/Au(1 1 1), the peaks near d-band model is not applicable for the reactivity index of noble metals
the Fermi level are more intense than peaks at the lower energy range. with filled d-orbital [82]. The trend reversal in the physico-chemical
This difference is explained due to the shift in the d-band center position, properties between Ag and Au can be ascribed to the stronger relativ­
which is away from the Fermi energy than the case of Pd and Pt. These istic effect [83], which leads to larger contraction of 5d orbital of Au.
results in weaker binding and lower reaction enthalpy values for Ag and This can be easily realised by smaller/comparable atomic radii of Au
Au systems than Pd and Pt systems. In this context we further note that (1.44 Å) than Ag (1.45 Å). In terms of the electronic structure, Ag shows
even though the d-band center of Ag10@Al2O3/Ag(1 1 1) is much deeper deeper and relatively narrower d-band which is not pinned to the Fermi
(away from Fermi energy level) than Au10@Al2O3/Au(1 1 1), it shows level. The Fermi level for Ag10@Al2O3/Ag(1 1 1)/Ag bulk has sharp s-
higher values of reaction enthalpy over gold, which is contrary to the states (viz. Fig. S15 of supporting information). While for gold, signifi­
prediction of d-band model reactivity index. Thus we may infer that the cant hybridization between 6s and 5d states occurs, for silver

10
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Fig. 8. Comparison of electronic structure of M10@Al2O3 clusters with M-(1 1 1) surface. The vertical dotted pink and red lines represent the d-band centre of M-
(1 1 1) surface and M10@Al2O3 clusters respectively.

hybridization between 5s and 4d states are minimal due to larger energy the charge.
separation. Hence for Ag the 4d-states are widely separated from 5s,
which mostly comprises the Fermi energy level and thus govers its 4. Conclusion
chemical reactivity. (viz. Fig. S16 of supporting information). Indeed the
DOS spectrum of Ag supports this conjecture and shows sharp 5s states Size selected subnanometer noble metal clusters supported on metal
(near Fermi level) of primarily participate in bonding (viz. Figures S17- oxide serves as well-defined model for controlled catalyst and provide
S20 of supporting information) with oxygen and significantly transfer opportunity to understand the correlation between reactivity and

11
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Fig. 9. Oxygen adsorption (molecular and dissociative) on M(1 1 1) surface.

Table 4
Comparison of molecular adsorption of O2 on finite size M10@Al2O3 (atop mode) with extended slab.
M O2 Binding Energy (BE) eV Activated O2 Bond length(Å) Bader charge on activated O2 molecule

M10@Al2O3 M(1 1 1) M10@Al2O3 M(1 1 1) M10@Al2O3 M(1 1 1)

Ag − 0.47 − 0.13 1.33 1.38 − 0.56e − 0.77e

Au − 0.03 +0.004* 1.24 1.343* 0.00e − 0.59e*
Pd − 1.51 − 0.87 1.41 1.37 − 0.76e − 0.65e
Pt − 1.68 − 0.62 1.39 1.404 − 0.67e − 0.69e

* In line with literature [78], present calculation also finds that Au(1 1 1) bond does not favour binding with molecular oxygen. The given values are for configuration
where O2 is bonded with surface.

during oxidation. On the contrary, group-11 metal cluster Ag10 and Au10
Table 5
have relatively poor binding with surface, interact weakly with molec­
Comparison of reaction enthalpy of oxidation for finite size M10@Al2O3 with
ular oxygen. In particular Au10@Al2O3 shows weakest affinity for O2 in
extended slab M(1 1 1) along with respective d-band centre. The d-band centre
atop mode leading to physisorbed Van der Waal complex only. Poor
values of M(1 1 1) surface in brackets, are the values reported in Ref. [80].
reactivity of Au10@Al2O3 towards oxygen in atop fashion is alike to poor
M10@Al2O3 M(1 1 1) surface M10@Al2O3 d- M(1 1 1)
reactivity of gas phase anionic Au10‾ cluster reported in literature
Reaction enthalpy Reaction band centre(eV) surface d-
(eV) enthalpy (eV) band centre before. The binding of O2 with M10@Al2O3 complexes in bridge mode is
(eV) higher than atop mode. On bridging the cluster and surface, the con­
Ag − 2.31 − 0.82 − 3.97 − 4.21
necting oxygen molecule receive greater amount of charge than what it
(− 4.30) receives in atop mode. Contrary to molecular adsorption, dissociative
Au − 1.46 − 0.65 − 3.04 − 3.59 adsorption favours atop mode rather than bridge mode which is re­
(− 3.56) flected in higher reaction enthalpy value in the atop mode. Even though
Pd − 3.53 − 2.41 − 1.61 − 1.84
for all four cases of M10@Al2O3, dissociative adsorption of oxygen
(− 1.83)
Pt − 2.46 − 2.15 − 2.34 − 2.40 molecule is energetically preferred but structural modification in
(− 2.25) cluster-substrate complex during the oxidation process differs case to
case. Whilst for Ag10@Al2O3, Pd10@Al2O3 and Au10@Al2O3 oxidation
leads to increase in inter-metallic bond lengths as well as pushes the
cluster’s geometric and electronic structure, support interactions. In the deposited cluster away from surface, contrary and Pt10@Al2O3 show
present work we have compared the structure and chemical reactivity of robust behaviour during oxidation and infact come closer to the surface.
M10 (M = Ag, Au, Pd, and Pt) clusters. In order to get further insight A direct comparison between oxygen interaction with M10@Al2O3 and
about the finite size effect we have compared the results of deposited those obtained for O2 adsorption on the respective M(1 1 1) surfaces
clusters with corresponding extended M (1 1 1) surfaces. On alumina reveals that structural and energetic trends of M10@Al2O3 follow the
support, Ag10, Au10 and Pd10 clusters adopt zigzag patterned hexagonal same pattern as that of extended surfaces. The reaction enthalpy of
pseudo-planar structure aligning to Al2O3 template, irrespective of the oxidation for both finite size clusters as well as for extended surface
configurations they adopt as the lowest energy isomer in the gas phase. varies linearly with d-band centre position. However despite
Unlike this, Pt10 cluster does not prefer to rearrange itself in Al2O3 Ag10@Al2O3/Ag(1 1 1) has wider separation between d-band centre and
template. Higher cohesion between metal atom results in preference for Fermi level than Au10@Al2O3/Au(1 1 1), silver shows higher values of
bilayer structure of Pt10. Stronger binding of Pd10 and Pt10 clusters reaction enthalpy over gold. Unlike Au, where the energy difference
(group-10 metal clusters) with the alumina surface proceed via large between 6s and 5d states are smaller, Ag has larger separation between
electron transfer leading to polarization of surface charge density. This 5s and 4d energy state. As a consequence, gold have significant hy­
feature has been corroborated by larger contribution of d-states along bridization between 6s and 5d states, silver lack the sufficient hybridi­
the Fermi energy level which in turn offers higher binding with oxygen zation between 5s and 4d states, leading to higher weightage of 5s-states

12
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Molecular Dissociated
6 Ag(111)-molecular-O2 s 6 Ag(111)-diss-O2 s
p p

DOS(1/eV)
DOS(1/eV)
4 4

2 2

0 0
-8 -6 -4 -2 0 2 -8 -6 -4 -2 0 2
Energy(eV) Energy(eV)

6 Au(111)-molecular-O2 s 6 Au(111)-diss-O2 s
p p
DOS(1/eV)

DOS(1/eV)
4 4

2 2

0 0
-8 -6 -4 -2 0 2 -8 -6 -4 -2 0 2
Energy(eV) Energy(eV)
Pd(111)-molecular-O2 s Pd(111)-diss-O2 s
6
p p
6
DOS(1/eV)
DOS(1/eV)

4
4

2
2

0 0
-8 -6 -4 -2 0 2 -8 -6 -4 -2 0 2
Energy(eV) Energy(eV)

Pt(111)-molecular-O2 s 6 Pt(111)-diss-O2 s
6
p p

4
DOS(1/eV)
DOS(1/eV)

2 2

0 0
-8 -6 -4 -2 0 2 -8 -6 -4 -2 0 2
Energy(eV) Energy(eV)

Fig. 10. Density of states(DOS) projected on oxygen atoms of molecular and dissociatively adsorb oxygen molecule on M(1 1 1) surface.

to the Fermi level dictating the bonding. Moreover, because of this strategies to engineer metal/oxide interfaces for optimized heteroge­
feature, Ag10@Al2O3/Ag(1 1 1) also has sharp 5s states around Fermi neous catalysis.
level which explains higher reaction enthalpy of Ag; not following the
usual trend of d-electron derived d-band centre positions values. We CRediT authorship contribution statement
believe that present study contributes to atomic-level understanding and
correlating of the noble metal cluster’s inherent nature and resultant Sandeep Nigam: Conceptualization, Data curation, Investigation,
catalytic activity. This understanding will be helpful in planning Validation, Writing - original draft, Writing - review & editing. C.

13
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

Majumder: Supervision, Writing - review & editing. [25] A. Beniya, N. Isomura, H. Hiratab, Y. Watanabe, Morphology and chemical states
of size-selected Ptn clusters on an aluminium oxide film on NiAl(110), Phys. Chem.
Chem. Phys. 16 (2014) 26485–26492.
Declaration of Competing Interest [26] F. R. Negreiros, A. Halder, C. Yin, A. Singh, G. Barcaro, L. Sementa, Eric C. Tyo, M.
J. Pellin, S. Bartling, K. Meiwes-Broer, S. Seifert, P. Sen, S. Nigam, C. Majumder, N.
Fukui, H. Yasumatsu, S. Vajda, A. Fortunelli, Bimetallic Ag-Pt Sub-nanometer
Authors declare no conflict of interest.
Supported Clusters as Highly Efficient and Robust Oxidation Catalysts, Angew.
Chem. Int. Ed. 57 (2018) 1209–1213.
Acknowledgment [27] C. Yin, F. R. Negreiros, G. Barcaro, A. Beniya, L. Sementa, Eric C. Tyo, S. Bartling,
Karl-Heinz Meiwes-Broer, S. Seifert, H. Hirata, N. Isomura, S. Nigam, C. Majumder,
Y. Watanabe, A. Fortunelli, S. Vajda, Alumina-supported sub-nanometer Pt10
We are thankful to the members of the Computer Division, BARC, for clusters: amorphization and role of the support material in a highly active CO
their kind cooperation during this work. oxidation catalyst, J. Mater. Chem. A 5 (2017) 4923-4931.
[28] I. Chakraborty, T. Pradeep, Atomically Precise Clusters of Noble Metals: Emerging
Link between Atoms and Nanoparticles, Chem. Rev. 117 (2017) 8208–8271.
Appendix A. Supplementary material [29] S. Vajda, M.G. White, Catalysis Applications of Size-Selected Cluster Deposition,
ACS Catal. 5 (2015) 7152–7176.
Supplementary data to this article can be found online at https://doi. [30] J.A. Van Bokhoven, S. Vajda, Size selected clusters and particles: from physical
chemistry and chemical physics to catalysis, Phys. Chem.Chem. Phys. 16 (2014)
org/10.1016/j.apsusc.2021.149160. 26418–26420.
[31] G. Kwon, G. A. Ferguson, C. J. Heard, E. C. Tyo, C. Yin, J. DeBartolo, S. Seifert, R. E.
References Winans, A. J. Kropf, J. Greeley, R. L. Johnston, L. A. Curtiss, M. J. Pellin, S. Vajda,
Size-Dependent Subnanometer Pd Cluster (Pd4, Pd6, and Pd17) Water Oxidation
Electrocatalysis, ACS Nano 7 (2013) 5808–5817.
[1] M.M. Montemore, M.A. Van Spronsen, R.J. Madix, C.M. Friend, O2 Activation by
[32] X. Du. R. Jin, Atomically Precise Metal Nanoclusters for Catalysis, ACS Nano 13
Metal Surfaces: Implications for Bonding and Reactivity on Heterogeneous
(2019) 7383− 7387.
Catalysts, Chem. Rev. 118 (2018) 2816–2862.
[33] S. Nigam, C. Majumder, A first principle study of SO3 decomposition on silver
[2] Y. Du, H. Sheng, D. Astruc, M. Zhu, Atomically Precise Noble Metal Nanoclusters as
nano-clusters: Implications toward hydrogen production, Int. J.Hyd. Energy 37
Efficient Catalysts: A Bridge between Structure and Properties, Chem. Rev. 120
(2012) 3645–3651.
(2020) 526–562.
[34] S. Nigam, C. Majumder, Single atom alloy catalyst for SO3 decomposition:
[3] R. Jin, The impacts of nanotechnology on catalysis by precious metal
enhancement of platinum catalyst’s performance by Ag atom embedding,
nanoparticles, Nanotechnol. Rev. 1 (2012) 31–56.
Nanoscale 10 (2018) 20599–20610.
[4] Y. Xu, L. Chen, X. Wang, W. Yao, Q. Zhang, Recent advances in noble metal based
[35] S. Nigam, C. Majumder, Are Deposited Bimetallic Clusters More Effective for SO3
composite nanocatalysts: colloidal synthesis, properties, and catalytic applications,
Decomposition? A Systematic Study Using First Principles Theory, J. Phys. Chem. C
Nanoscale 7 (2015) 10559–10583.
116 (2012) 25594–25601.
[5] C. Xi, C. Zou, M. Wang, D. Wu, H. Liu, C. Dong, X.-W. Du, A Bond-Energy-
[36] W. Li, C. Liu, H. Abroshan, Q. Ge, X. Yang, H. Xu, G. Li, Catalytic CO Oxidation
Integrated-Based Descriptor for High-Throughput Screening of Transition Metal
Using Bimetallic MxAu25− x Clusters: A Combined Experimental and Computational
Catalysts, J. Phys. Chem. C 124 (2020) 5241–5247.
Study on Doping Effects, J. Phys. Chem. C 120 (2016) 10261–10267.
[6] P.S. Rice, P. Hu, Understanding supported noble metal catalysts using first-
[37] G. Zhanga, R. Wang, G. Li, Non-metallic gold nanoclusters for oxygen activation
principles calculations, J. Chem. Phys. 151 (2019), 180902.
and aerobic Oxidation, Chin. Chem. Lett. 29 (2018) 687–693.
[7] C.T. Campbell, N. López, S. Vajda, Catalytic properties of model supported
[38] X. Deng, C.M. Friend, Selective Oxidation of Styrene on an Oxygen-Covered Au
nanoparticles, J. Chem. Phys. 152 (2020), 140401.
(111), J. Am. Chem. Soc. 127 (2005) 17178–17179.
[8] R. Ferrando, G. Rossi, A. C. Levi, Z. Kuntová, F. Nita, A. Jelea, C. Mottet, G.
[39] D. Eisenberg, T.K. Slot, G. Rothenberg, Understanding Oxygen Activation on Metal-
Barcaro, A. Fortunelli, J. Goniakowski, Structures of metal nanoparticles adsorbed
and Nitrogen-Codoped Carbon Catalysts, ACS Catal. 8 (2018) 8618–8629.
on MgO(001). I. Ag and Au, J. Chem. Phys. 130 (2009) 174702.
[40] X. Liu, Y. Ryabenkova, M. Conte, Catalytic oxygen activation versus autoxidation
[9] J. Goniakowski, A. Jelea, C. Mottet, G. Barcaro, A. Fortunelli, Z. Kuntová, F. Nita,
for industrial applications: a physicochemical approach, Phys. Chem. Chem. Phys.
A. C. Levi, G. Rossi, R. Ferrando, Structures of metal nanoparticles adsorbed on
17 (2015) 715–731.
MgO(001). II. Pt and Pd, J. Chem. Phys. 130 (2009) 174703.
[41] C.F. Dickens, J.H. Montoya, A.R. Kulkarni, M. Bajdich, J.K. Nørskov, An electronic
[10] A.S. Crampton, M.D. Rötzer, C.J. Ridge, B. Yoon, F.F. Schweinberger, U. Landman,
structure descriptor for oxygen reactivity at metal and metal oxide surfaces, Surf.
U. Heiz, Assessing the concept of structure sensitivity or insensitivity for sub-
Sci. 681 (2019) 122–129.
nanometer catalyst materials, Surf. Sci. 652 (2016) 7–19.
[42] A. Corma, H. Garcia, Supported Gold Nanoparticles as Catalysts for Organic
[11] X.-Q. Gong, A. Selloni, O. Dulub, P. Jacobson, U. Diebold, Small Au and Pt clusters
Reactions, Chem. Soc. Rev. 37 (2008) 2096–2126.
at the anatase TiO2(101) surface: Behavior at terraces, steps, and surface oxygen
[43] J.-X. Liu, I.A.W. Filot, Y. Su, B.E.J.M. Zijlstra, Hensen, Optimum Particle Size for
vacancies, J. Am. Chem. Soc. 130 (2008) 370–381.
Gold-Catalyzed CO Oxidation, J. Phys. Chem. C 122 (2018) 8327–8340.
[12] Y. Lei, F. Mehmood, S. Lee, J. Greeley, B. Lee, S. Seifert, R.E. Winans, J.W. Elam, R.
[44] Y. Gao, N. Shao, Y. Pei, Z. Chen, X.C. Zeng, Catalytic Activities of Subnanometer
J. Meyer, P.C. Redfern, D. Teschner, R. Schlogl, M.J. Pellin, L.A. Curtiss, S. Vajda,
Gold Clusters (Au16-Au18, Au20 and Au27-Au35) for CO Oxidation, ACS Nano 5
Increased silver activity for direct propylene epoxidation via subnanometer size
(2011) 7818–7829.
effects, Science 328 (2010) 224–228.
[45] L.D. Socaciu, J. Hagen, J. Le Roux, D. Popolan, T.M. Bernhardt, L. Wöste, Š. Vajda,
[13] Z.A. Luo, W. Castleman, S.N. Khanna, Reactivity of Metal Clusters, Chem. Rev. 116
Strongly cluster size dependent reaction behavior of CO with O2 on free silver
(2016) 14456–14492.
cluster anions, J. Chem. Phys. 120 (2004) 2078.
[14] P. Ferrari, J. Vanbuel, E. Janssens, P. Lievens, Tuning the Reactivity of Small Metal
[46] J. Hagen, L. D. Socaciu, J. Le Roux, D. Popolan, T. M. Bernhardt, L. Wöste, R.
Clusters by Heteroatom Doping, Acc. Chem. Res. 51 (2018) 3174–3182.
Mitrić, H. Noack, V. Bonačić-Koutecký, Cooperative Effects in the Activation of
[15] S. Nigam, C. Majumder, Growth pattern of Agn (n = 1-8) clusters on the α-Al2O3
Molecular Oxygen by Anionic Silver Clusters, J. Am. Chem. Soc. 126 (2004)
(0001) surface: A first principles study, Langmuir 26 (2010) 18776-12787.
3442− 3443.
[16] S. Nigam, C. Majumder, Adsorption of small palladium clusters on the α-Al2O3
[47] J. Xu, T. White, P. Li, C. He, J. Yu, W. Yuan, Y.-F. Han, Biphasic Pd− Au Alloy
(0001) surface: A first principles study, J. Phys. Chem. C 116 (2012) 2863–2871.
Catalyst for Low-Temperature CO Oxidation, J. Am. Chem. Soc. 132 (2010)
[17] C. Rajesh, S. Nigam, C. Majumder, The structural and electronic properties of Aun
10398–10406.
clusters on the α-Al2O3 (0001) surface: A first principles study, Phys. Chem. Chem.
[48] R. Pal, L.-M. Wang, Y. Pei, L.-S. Wang, X.-C. Zeng, Unraveling the Mechanisms of
Phys. 16 (2014) 26561–26569.
O2 Activation by Size-Selected Gold Clusters: Transition from Superoxo to Peroxo
[18] S. Nigam, C. Majumder, Substrate induced reconstruction and activation of
Chemisorption, J. Am. Chem. Soc. 134 (2012) 9438–9445.
platinum clusters: A systematic DFT study, Appl. Surf. Sci. 422 (2017) 1075–1081.
[49] W. Huang, L.-S. Wang, Au10‾: isomerism and structure-dependent O2 reactivity,
[19] G. Pacchioni, Electronic interactions and charge transfers of metal atoms and
Phys. Chem. Chem. Phys. 11 (2009) 2663–2667.
clusters on oxide surfaces, Phys. Chem. Chem. Phys. 15 (2013) 1737–1757.
[50] M. Okumura, M. Haruta, Y. Kitagawa, K. Yamaguchi, Theoretical Study of H2O and
[20] B. Yoon, H. Hakkinen, U. Landman, A.S. Wörz, J.-M. Antonietti, S. Abbet, K. Judai,
O2 adsorption on Au small cluster, Gold Bull. 1 (2007) 40-44.
U. Heiz, Charging effects on bonding and catalyzed oxidation of CO on Au8 clusters
[51] T. Wang, J. Ma, B. Yin, X. Xing, Adsorption of O2 on Anionic Gold Clusters in the
on MgO, Science 307 (2005) 403–407.
0− 1 nm Size Range: An Insight into the Electron Transfer Dynamics from Kinetic
[21] C. Yin, E. Tyo, K. Kuchta, B. von Issendorff, S. Vajda, Atomically precise (catalytic)
Measurements, J. Phys. Chem. A 122 (2018) 13, 3346–3352.
particles synthesized by a novel cluster deposition instrument, J. Chem. Phys. 140
[52] A.P. Woodham, G. Meijer, A. Fielicke, Charge Separation Promoted Activation of
(2014), 174201.
Molecular Oxygen by Neutral Gold Clusters, J. Am. Chem. Soc. 135 (2013)
[22] A. Halder, M.-A. Ha, H. Zhai, B. Yang, M.J. Pellin, S. Seifert, A.N. Alexandrova,
1727–1730.
S. Vajda, Oxidative Dehydrogenation of Cyclohexane by Cu vs Pd Clusters:
[53] J. Ma, X. Cao, X. Xing, X. Wang, J.H. Parks, Adsorption of O2 on anionic silver
Selectivity Control by Specific Cluster Dynamics Chem, Cat. Chem. 12 (2020)
clusters: spins and electron binding energies dominate in the range up to nano
1307–1315.
sizes, Phys. Chem. Chem. Phys. 18 (2016) 743–748.
[23] E.C. Tyo, S. Vajda, Catalysis by clusters with precise numbers of atoms, Nat.
[54] A. M. Shor, S. S. Laletina, E. A. Ivanova-Shor, V. A. Nasluzov, Theoretical study of
Nanotechnol. 10 (2015) 577–588.
O2 interaction with subnanometer-sized Ag clusters supported on defective SiO2
[24] A. Halder, L.A. Curtiss, A. Fortunelli, S. Vajda, Perspective: Size selected clusters
surface, Comput. Theoret. Chem. 1144 (2018) 56–65.
for catalysis and electrochemistry, J. Chem. Phys. 148 (2018), 110901.

14
S. Nigam and C. Majumder Applied Surface Science 547 (2021) 149160

[55] B. Huber, P. Koskinen, H. Hakkinen, M. Moseler, Oxidation of magnesia-supported [69] J.P. Perdew, J.A. Chevary, S.K. Vosko, K.A. Jackson, M.R. Pederson, D.J. Singh,
Pd-clusters leads to the ultimate limit of epitaxy with a catalytic function, Nat. C. Fiolhias, Atoms, molecules, solids, and surfaces: Applications of the generalized
Mater. 5 (2006) 44–47. gradient approximation for exchange and correlation, Phys. Rev. B. 46 (1992)
[56] S.M. Lang, I. Fleischer, T.M. Bernhardt, R.N. Barnett, U. Landman, Low- 6671–6687.
Temperature CO Oxidation Catalyzed by Free Palladium Clusters: Similarities and [70] D. A. Gotz, R. Schafer, P. Schwerdtfeger, The Performance of Density Functional
Differences to Pd Surfaces and Supported Particles, ACS Catal. 5 (2015) and Wavefunction-Based Methods for 2D and 3D Structures of Au10, J. Comput.
2275–2289. Chem. 34 (2013) 1975-1981.
[57] Y. Li, C. Liu, Z. Pu, L. Bao, Y. Zhu, J. Ma, Planar versus Nonplanar Pd Clusters: [71] P. V. Nhat, N. T. Si, M. T. Nguyen, Comment on “Theoretical Investigations on
Stability and CO Oxidation Activity of Pd Clusters with and without TiO2(110) Geometrical and Electronic Structures of Silver Clusters”, J. Comput. Chem. 40
Substrate, J. Phys. Chem. C 123 (2019) 13739–13747. (2019) 1990-1993.
[58] R. Robles, S. N. Khanna, Oxidation of Pdn (n=1–7, 10) clusters supported on [72] D. Chattaraj, S.C. Parida, S. Dash, C. Majumder, Influence of U doping on the
alumina/NiAl(110), Phys. Rev. B 82 (2010) 085428. growth behavior, electronic structure and magnetic properties of Pdn (n = 1–12)
[59] F. Von Gynz-Rekowski, G. Gantefor, Y.D. Kim, Interaction of Pd cluster anions clusters: a first principles study, Eur. Phys. J.D 68 (2014) 302.
(Pd− n, n < 11) with oxygen, Eur. Phys. J. D 43 (2007) 81–84. [73] V. Kumar, Y. Kawazoe, Evolution of atomic and electronic structure of Pt clusters:
[60] S. Nigam, C. Majumder, ORR viability of alumina-supported platinum nanocluster: Planar, layered, pyramidal, cage, cubic, and octahedral growth, Phys. Rev. B 77
exploring oxidation behaviour by DFT, Phys. Chem. Chem.Phys. 19 (2017) (2008), 205418.
19308–19315. [74] C. Kittel, Introduction to Solid State Physics, Wiley, 2004.
[61] S. Oh, H. Ha, H. Choi, C. Jo, J. Cho, H. Choi, R. Ryoo, H.Y. Kim, J.Y. Park, Oxygen [75] B.R. Goldsmith, J. Florian, J.-M. Liu, P. Gruene, J.T. Lyon, D.M. Rayner, A. Fielicke,
activation on the interface between Pt nanoparticles and mesoporous defective M. Scheffler, L.M. Ghiringhelli, Two-to-three dimensional transition in neutral gold
TiO2 during CO oxidation, J. Chem. Phys. 151 (2019), 234716. clusters: The crucial role of van der Waals interactions and temperature, Phys. Rev.
[62] F. Sloan Roberts, M. D. Kane, E. T. Baxtera, S. L. Anderson Oxygen activation and Mat. 3 (2019), 016002.
CO oxidation over size-selected Ptn/alumina/Re(0001) model catalysts: [76] R. Bader, Atoms in Molecules: A Quantum Theory, Oxford University Press, New
correlations with valence electronic structure, physical structure, and binding sites, York, 1990.
Phys. Chem. Chem. Phys. 16 (2014) 26443-26457. [77] G. Henkelman, A. Arnaldsson, H. Jόnsson, A fast and robust algorithm for Bader
[63] R.L. Birke, V. Znamenskiy, J.R. Lombardi, A charge-transfer surface enhanced decomposition of charge density, Comput. Mater. Sci. 36 (2006) 254− 360.
Raman scattering model from time-dependent density functional theory [78] Y. Xu, M. Mavrikakis, Adsorption and Dissociation of O2 on Gold Surfaces: Effect of
calculations on a Ag10‾ pyridine complex, J. Chem. Phys. 132 (2010), 214707. Steps and Strain, J. Phys. Chem. B 107 (2003) 9298–9307.
[64] G. Kresse, J. Furthmuller, Efficient iterative schemes for ab initio total-energy [79] B. Hammer. J. K. Nørskov, Theoretical Surface Science and Catalysis: Calculations
calculations using a plane-wave basis set, Phys. Rev. B 54 (1996) 11169–11186. and Concepts, Adv. Catal. 45 (2000) 71-129.
[65] G. Kresse, J. Furthmuller, Efficiency of ab-initio total energy calculations for metals [80] J. K. Nørskov, F. Studt, F. Abild-Pedersen, T. Bligaard (Ed.), Fundamental Concepts
and semiconductors using a plane-wave basis set, Comp. Mater. Sci. 6 (1996) in Heterogeneous Catalysis, first ed. John Wiley & Sons, Inc. (2014)Chapter-8,
15–50. pp114-137.
[66] D. Vanderbilt, Soft self-consistent pseudopotentials in a generalized eigenvalue [81] H. Xin, A. Vojvodic, J. Voss, J.K. Nørskov, F. Abild-Pedersen, Effects of d-band
formalism, Phys. Rev. B 41 (1990) 7892–7895. shape on the surface reactivity of transition-metal alloys, Phys. Rev. B 89 (2014),
[67] P. E. Blochl, Projector augmented-wave method, Phys. Rev. B 50 (1994) 17953- 115114.
17979. [82] T. Bligaard, J. K. Nørskov, Chemical Bonding at Surfaces and Interfaces Nilsson, A.
[68] G. Kresse, D. Joubert, From ultrasoft pseudopotentials to the projector augmented- Pettersson, L. G. M. Nørskov J. K. (Editors) (2008) chapter-4, pp. 255-351.
wave method, Phys. Rev. B 59 (1999) 1758–1775. [83] H. Häkkinen, M. Moseler, U. Landman, Bonding in Cu, Ag, and Au Clusters:
Relativistic Effects, Trends, and Surprises, Phys. Rev. Lett, 89 (2002) 033401.

15