1

Abstract

Single atom alloys are gaining importance as catalysts which can be extremely selective and
active towards the formation of desired products. They possess such desirable characteristics
because of the presence of a highly reactive single atom at the surface. In this work, we start
by investigating the electronic structure of these single atom alloys to look for any unusual
behavior. Then, we tested if the single atom alloys of gold, silver and copper which have
been doped with single atoms of platinum, palladium, iridium, rhodium and nickel adhere to
the d-band model of Hammer and Nrskov. Then, gold-palladium, copper-palladium, silverpalladium single atom alloys and the corresponding pure metal hosts are used in simple
dissociation of water and nitric oxide to test their catalytic behavior. We also tested the
catalytic behavior of these metals and alloys in the selective hydrogenation of acetylene to
ethylene. We observed that these alloys exhibit a sharp peak in their atom projected d-band
density of states, which we predicted could be the cause of high surface reactivity. We found
that the d-band centers and d-band widths of these systems correlated linearly, showing
adherence to the d-band model, while the energy of adsorption of a hydrogen atom on these
surfaces could not be correlated with the d-band center, or the average reactivity of the
surface. Finally, the single atom alloys, with the exception of copper-palladium showed good
catalytic behavior by activating the reactant molecules more strongly and showing favorable
reaction pathways on the free energy diagrams for the reactions investigated.

Introduction

A catalyst is a substance that can be used to increase the rate of a reaction by providing
alternate reaction pathways of lower energy. They are also known to improve the selectivity
of chemical reactions. They are used in the production of essential commodities such as fuels,
pharmaceuticals and speciality chemicals. Catalysts are also important in the reduction of
pollution in the atmosphere. They are used to convert NOx and other harmful pollutants
to less potent products, through catalytic converters. Transition metals are an important
class of catalysts known for their excellent catalytic properties in chemical processes [1].
They bind substances ideally, in a way that the binding is not too strong or too weak. Such
bonds are ideal in the process of catalyzing a reaction. Transition metals such as platinum,
palladium, ruthenium, rhodium are known to catalyze a variety of reactions, and make the
formation of products favorable [2].
However, these metals are extremely rare and precious, and efforts have been underway
for the past decade to discover new catalysts which can be substituted in place of transition
metal catalysts. Experimental and theoretical studies have investigated the use of metal
alloys in a variety of reactions, and have had a reasonable degree of success. Metal alloys
are materials whose properties can be quite different from those exhibited by its constituent
elements. In these systems the electronic interactions between the different constitutents or
supports, and the change in lattice parameters due to variations in atomic sizes could give
rise to a variety of properties, which could be of interest in the catalysis scheme of thinking
[3]. Alloys can also be tuned to exhibit desired properties and characteristics [4]. Various
groups of researchers have found that certain alloys of platinum like Pt3 Ni show manifold
increase in activity compared to the activity of a pure Pt catalyst for oxidation reduction
reactions (ORRs) [5]. Computational studies which perform large scale screening of catalysts
show the effectiveness of alloys of late transition metals and early transition metals for ORR
[6, 7, 8] hydrogen related reactions [9] and selective hydrogenation reactions [10] to name a
few.
The surface of a heterogenous catalyst consists of a variety of sites, which facilitate the
process of adsorption which is a precursor to the reaction taking place. An ideal flat (111)
surface of a metal will possess at least 3 types of sites, namely the hollow, atop and bridge
sites. A stepped surface will have even more sites like kinks, which can take part in a
reaction. A catalyst surface will never be homogenous, and will always have a huge number
of sites, which can act as active sites for a reaction [11]. A surface is said to catalyze a
particular reaction, when it makes the formation of certain products the most energetically
favorable. It simultaneously renders other side reactions unfavorable, which engenders the
concept of selectivity. Now, with so many sites available on a surface, chemists are trying

to engineer active sites so that reactivity and selectivity can be controlled. One school of
thought that has resulted out of this active site engineering process, are single atom alloy
catalysts. The rationale behind this idea was to design catalysts that contain only the sites
requried to perform or assist a target reaction [12].
Single atom alloys are alloys in which one metal constitutes the majority of the alloy, and
the other metal is doped with extremely low concentrations on the surface of the alloy. They
are known to show enhanced reactivity and selectivity in hydrogenation reactions [13]. It
was recently shown that alloying one percent of Pd atoms into a Cu(111) surface significantly
promotes the dissociation of H2 , while not overbinding the H atoms formed [14]. Such alloys
also promote spillover the H atoms across the surface of the catalyst, as shown in the work of
Sykes and coworkers [3]. A lot of research has gone into the use of alloys consisting of coinage
metals liks Au, Ag and Cu and late transition metals such as Pd, Pt etc [15]. Sykes and
coworkers have published substantial work in the sphere of single atom alloys [16], especially
on H2 activation [17] and selective hydrogenation [13, 18].
In this work, we develop a bottom up approach to investigating the use of single atom
alloy catalysts in simple reactions. To begin with, we undertook a screening process where a
variety of bimetallic alloys were screened for unusual electronic structure and behavior. The
alloys were those of Cu, Au and Ag, in which one surface atom was replaced by at atom of
Pt, Pd, Ir, Rh or Ni. Using the d-band density of states and other d-band characteristics,
we identified 3 potential candidates for the single atom alloys, which were AuPd, AgPd and
CuPd. Next, we investigated the limit of dilution from a computational standpoint, and
were able to choose a 3 3 surface unit cell which best represented a compromise between
computational expense and single atom alloy behavior. Having chosen a representative
candidate set, and their surface configuration, we set about testing their catalytic behavior
in simple dissociation reactions such as dissociation of water and nitric oxide. Owing to
the positive results from the use of single atom alloys in selective hydrogenation reactions,
we also studied the selective hydrogenation of acetylene to ethylene. The results of our
investigations provided insight into how the unusual electronic structure of the single atom
alloy surface plays a role in the reactions. We found that the adsorbates bond to the Pd atom
exceptionally well when compared to bonding on pure metals, while adsorbing in a different
geometry to that on pure surfaces of Au, Cu and Ag. We plotted reaction pathways through
potential energy diagrams, and found that for the selective hydrogenation of acetylene, the
formation of reaction intermediates is stable, and facilitates a forward reaction towards the
formation of ethylene.

3
3.1

Methods
Computational Details

In this work, alloys chosen for investigation are those of copper, silver and gold. One atom
was replaced with a palladium atom, such that it was completely isolated from other palladium atoms, thus exhibiting single atom alloy behavior. All calculations were done using the
Vienna ab initio simulation package code (VASP) [19, 20, 21]. VASP solves the Kohn-Sham
equations in an iterative manner within a planewave basis set, while employing periodic
boundary conditions. The interaction between the core and valence electrons was described
by the application of the projector augmented wave (PAW) method [22]. A plane wave
cutoff of 350 eV and a Gaussian smearing width of 0.1 eV was chosen as parameters for
these calculations. The exchange correlation functional used was the Perdew Burke Ernzerhof (GGA-PBE) functional [23]. The parameters and exchange correlation functional were
chosen to represent the best compromise between computational expense and depiction of
the actual system. To begin with, bulk calculations were performed for each system in the
configuration XY3 , where X is the single atom, and Y is the host metal. Lattice constants
used were of the host metal. Lattice constants optimized for the calculation parameters used
were obtained by fitting an equation of state and obtaining the lattice constant corresponding to the minimum energy. The calculated lattice constants for the metals considered are
Pt: 3.9671 , Pd: 3.9397 , Ir: 3.8729 , Rh: 3.8234 , Ni: 3.5099 , Cu: 3.6358 ,
Au: 4.1560 and Ag: 4.1441 . These values are in excellent agreement with experimental
lattice constants [24]. Finally, a Monkhorst-Pack k-point grid of 12 12 12 was used for a
simple unit cell consisting of one atom of the metal. The k-point grid was accordingly scaled
up or down based on the dimensions of the system considered [25].
Next, calculations were performed to determine if the behavior of these single atom alloy
systems can be described by the d-band model developed by Hammer and Nrskov [26]. The
electronic structure for each system has been calculated from the atom projected density
of states (DOS). For this, a single atom of hydrogen was adsorbed at the hollow site of
three facets fcc(111), fcc(100) and fcc(211) and relaxed to the ground state. The d-band
DOS of the single atom, which takes part in the adsorption of hydrogen was obtained. A
Wigner Seitz radius of 1.5 was used to truncate the orbitals and prevent double counting
of electrons from neighboring atoms. The d-band center was calculated as
R the square root of
EdE
the first moment of the d-band with respect to the Fermi level as d = R dE . The d-band
width was calculated as the
s square root of the second moment of the d band with respect to
R

the Fermi level as Wd =

2
RE dE .

dE

These values are desciptors used in the d-band model.

The d-band width was plotted against the d-band center to ascertain if these systems adhere
to the model. We also plotted the peak energy in the DOS against the d-band center to
4

determine if the behavior of these systems can be determined by the shape of the d-band
[27].
Finally, we proceeded to investigate the catalytic activity of single atom alloys in certain reactions namely, 1) Dissociation of water, 2) Selective hydrogenation of acetylene to
ethylene and 3) Dissociation of nitric oxide. As a precursor to these calculations, we had
to determine the size of the surface unit cell on which adsorption would take place. Two
main considerations were kept in mind. One, multiple adsorption sites must be available for
adsorption of species i.e at least four hollow sites must be available. Two, the size of the
slab should ensure moderate computational expense, while describing physics of the system
in the most accurate manner possible. A larger surface unit cell would be most representative of adsorbate coverages observed in these systems. These considerations ensured that
we could carry out preliminary calculations where we determined the most favorable adsorption sites for all the species involved in the reactions. Surface formation energies were
calulated by subtracting the energy of a bulk system from the energy of a surface, both having identical configuration. This method calculates the energy of incorporating a vacuum in
the z-direction, hence forming a surface. The final surface energy is calculated using a per
atom basis for comparison. Based on the results obtained, and the considerations mentioned
above, we chose a surface having configuration 3 3 3, which is a 3 3 surface unit cell
having 3 layers in the z-direction. The bottom two layers of the slabs were fixed, while the
top layer and the adsorbates were allowed to relax.
3.2

Conventions

The binding energy for the species is calculated as the difference in the energy between an
adsorbed system and the energies of the relaxed surface and the gas phase adsorbate. This
is shown in equation 1.
Eadsorption = Eadsorbed system (Esurface + Egas phase adsorbate )

(1)

The reaction energy for each step in the mechanism is calculated as the difference in the
energies of the products and the reactants. Based on these energies a Born-Haber cycle is
constructed. In this cycle, the energies of every individual step in the mechanism is a sum
of the energies of all preceding reactions. The reaction energies are plotted, along with the
activation barriers where applicable. The calculated energies refer only to a change in the
electronic energy of the system, and an estimate of the overall heat of the reaction. The
energies are relative to the initial state energy, and calculation of the actual reaction energy
will require calculation of zero point energies and incorporation of thermochemistry into the
calculations.

3.3

Dissociation of Water

For this reaction, the surfaces chosen were the fcc(111) facets of Au, AuPd, Ag, AgPd,
Cu, CuPd and Pd. Calculations were performed to determine the most favorable sites for
adsorption of the dissociated species and the water molecule. The species were adsorbed on
the hollow and atop sites and were allowed to relax, without any constraints. Additionally,
we calculated the energies of co-adsorption of the species H and OH on adjacent hollow
sites, in order to determine if the interaction energies were significant in the system. The
mechanism of dissociation was that put forward by Schneider and coworkers [28]. The
stepwise dissociation mechanism is given as

3.4

H2 O(g) + H2 O

(1)

H2 O H + OH co-adsorbed

(2)

H + OH co-adsorbed H + OH infinite separation

(3)

OH O + H co-adsorbed

(4)

O + H co-adsorbed O + H infinite separation

(5)

Determination of Activation Barriers

Activation barriers for step 2 and step 4 in the prescribed mechanism were calculated using
a multistep procedure. In the first step of this procedure, the dissociating H and OH groups
were separated by a specific bond length. This bond length was increased over multiple
images such that the dissociating species move towards their preferred adsorption sites. The
bond length between O and the dissociating H atom is fixed, and the groups are allowed all
other degrees of freedom in the process of attaining the ground state. The images are allowed
to relax using ASEs inbuilt optimizer BFGS, to determine the geometry of the adsorbates,
while constraining the bond length between O and the dissociating H. VASP was used to
calculate the energy and forces for each ionic step, which was then fed back to the BFGS
optimizer, which provided the geometry for the next iteration. This iterative process is
driven by the optimizer till a preset force convergence criteria of 0.05 eV was attained. The
image with the highest energy provides a good initial state guess for the actual transition
state, and its corresponding bond length. This image is then used as the initial state for
obtaining the transition state using the Improved Dimer Method [29]. This method consists
of two steps. The first step involves a vibrational analysis of the system under consideration.
From the step, the eigenvalues which will drive the energy of the system in an upward
6

trajectory are obtained. The second step makes use of these eigenvalues, with the dimer
method algorithm (ibrion=44), to converge at a transition state. The difference in energy
between the initial state and the transition state is the activation barrier for the step. These
activation barriers are incorporated in the Born-Haber cycle, providing a complete picture
of the reaction energetics.
3.5

Dissociation of Nitric Oxide

The surfaces chosen to study the dissociation of the simple diatomic molecule NO were Au,
AuPd, Ag, AgPd, Cu, CuPd and Pd. For all these reactions, dissociative adsorption data has
been comprehensively reported in sources like in the work of Nilsson, Pettersson and Nrskov
[30]. Preliminary calculations involved finding the most favorable site for adsorption of all
the species involved in the reaction. This included adsorbing the species at the hollow,
atop and bridge sites and relaxing the systems to ground state. NO dissociated through a
simple multistep mechanism. We referenced the work of Gajdo, Hafner and Eichler [31, 32].
The mechanism for dissociation consists of various cleavage and recombination steps. The
mechanism is given below.
N O(g) + N O

(1)

N O N + Oco-adsorbed

(2)

N + Oco-adsorbed
+ N + Oinfinite
separation

(3)

N + Ninfinite
separation N + Nco-adsorbed +

(4)

O + Oinfinite
separation O + Oco-adsorbed +

(5)

N + N + O + Oco-adsorbed
N2(g) + O2(g) + 2

(6)

Reaction energies for each step in the mechanism were calculated and plotted as part of a
potential energy diagram.
3.6

Selective Hydrogenation of Acetylene to Ethylene

This reaction was studied on the fcc(111) facets of Au, AuPd, Ag, AgPd and Pd. The
rationale behind choosing these metals is that Pd is most widely used as a selective hydrogenation catalyst in the industry. Catalysts in which Pd is alloyed with Ag are also
used extensively in the industry. It has also been reported in literature that Au is extremely selective towards the formation of ethylene [33, 34, 35]. Calculations were per7

formed to determine the most favorable sites for adsorption of acetylene, co-adsorbed acetylene and hydrogen and ethylene. The species were adsorbed on the hollow, atop and
bridge sites and were allowed to relax into their most favorable sites, without any constraints. The geometries of adsorption were constructed based on the work of Bos and
Westerterp [36]. The mechanism of hydrogenation was that provided by the work of Neurock et al. [37]. The mechanism is of a Langmuir-Hinshelwood type and is given below.
C2 H2(g) + C2 H2

(1)

H2(g) + 2 2H

(2)

C2 H2 + H C2 H3 +

(3)

C2 H3 + H C2 H4 +

(4)

C2 H4 C2 H4(g) +

(5)

C2 H2(g) + H2(g) C2 H4(g)

(overall)

The reaction energy for each step was calculated from the convention mentioned previously,
and the reaction pathway diagram was plotted.

4
4.1

Results and Discussion

Density of States

The single atom alloys of Au, Ag and Cu, in which one atom was substituted by Pt, Pd, Ni,
Rh, or Ir were investigated for their surface electronic structure. The d-band atom projected
DOS of the single atom for the alloys is shown in Figure 1. The grid plot is such that the
rows indicate the host metals Au, Ag and Cu, and the columns indicate the single atoms
Pt, Pd, Ni, Rh and Ir. A general observation from these plots is a sharp feature close to
the Fermi level. There appears to be a sharp increase in the number of occupied states at
energies close to the Fermi level. This peak could be a result of an ineffective mixing of
the electron densities of the host metal and the single atom. It is also known that the host
metals may not form homogenous alloys with the single atom metals, as they are immiscible
[38]. Another observation made from the plot was the lack of sharp features in the DOS
of Cu based alloys. Electron densities of the constituent metals do intermix, and result in
a broadened d-band DOS. Within the space of Ag and Au alloys, the single atom is said
to possess gas phase characteristics, and may show an enhanced reactivity. The gas phase

characteristics can be seen in Figure 2. This could result in an enhanced catalytic behavior.
There may also be an enhanced reactivity shown by the Cu alloys, but we predict that this
enhancement may be lower than that exhibited by the Au and Ag alloys.

Figure 1: d-band density of states for the single atom alloys investigated in this work. The d-band plotted
in red is that of the host metal atom, while the d-band in green is that of the single atom in the alloy. The
rows of the grid are the host metals, and the columns are the single atoms. For reference, the third plot in
the 2nd row is that of Au-Ir.

Figure 2: d-band density of states of gas phase single atoms.

4.2

Adherence to d-band model

Having predicted an enhanced reactivity due to the presence of a sharp feature in the DOS,
the next step in the investigation was to see if these alloys adhered to the d-band model
developed by Hammer and Nrskov. We constructed a simple 3 layer 2 2 surface unit
cell. A hydrogen molecule was adsorbed at a hollow site. The d-band model postulates that
if the energy of the d-band increases, then there will be in upshift in the d-band center of
the system and the d-band narrows. If there is a decrease in the energy of the d-band then
there is a broadening of the d-band and a corresponding downshift in the d-band center. On
observing the d-band characteristics, it can be seen that the d-band center or the average
energy of the d-band may increase due to the gas phase characteristics of the single atom.
However, on plotting the d-band center () vs the d-band width (Wd ) of these systems, as
well as that of pure metals in Figure 3, we see there is a general adherence to the d-band
model. The scatter of the data points around the linear fit is low in magnitude (~ 0.2 eV).

Figure 3: The plot of d-band width (Wd ) vs the d-band center (). The general linear dependence is shown
by the solid black line.

This result can be rationalized by the similarity in offset of the d-band center and the
d-band width due to the single atom. Also, the shift in the d-band center is quite low, in
terms of eVs (~ 0.1 eV). Hence, these systems are well within the purview of the d-band
model, and their reactivity can be predicted by the same. This is because the d-band center
10

in most cases, determines the reactivity of the surfaces due to the variations in the way the
d-band electrons contribute to the bonding capability of the surface [39].
The next course of action was to see if the reactivity of the alloy agrees with that predicted
by the d-band model. The dissociative energy of adsorption of a hydrogen molecule Eads was
plotted against the d-band center (). This plot is shown in Figure 4. There is a significant
amount of scatter in the plot, which tells us that the reactivity of these alloys does not
correspond directly to the d-band characteristics observed in the previous section. This
observation also lends credence to the idea that the gas phase behavior of the Pd atom
is significant in determining the reactivity of the alloy. On observing the geometry of the
adsorbed system, we observed that in case of the alloy, the hydrogen atom is adsorbed closer
to the Pd atom, when compared to adsorption at the hollow site of the host metal surface.
The lack of concurrency between figures 3 and 4 is a result of these observations. The dband model is more inclusive of the overall surface electron density, and its corresponding
d-band characteristics, while in the single atom alloy, the behavior of the single atom tends
to dominate.

Figure 4: Plot of dissociative energy of adsorption (Eads ) of hydrogen on the single atom alloys and the host
metals. The linear fit is shown by the solid line, and is for reference.

11

4.3

Choice of Surface Configuration

Having seen the unusual electronic characteristics and reactivity of single atom alloys, we
moved on to testing their applicability and effectiveness in simple dissociation reactions.
The reactions studied in this work are 1) Dissociation of Water, 2) Dissociation of Nitric
Oxide and 3) Selective Hydrogenation of Acetylene to Ethylene. It was important to choose
a surface configuration which could accomodate and adsorb all species involved in the study,
as well as maintain the characteristics of a single atom alloy. The surface formation energies
calculated for a number of surface unit cell configurations are shown in Table 1.
Configuration
of Unit Cell
22
32
33
43
44

Surface Formation Energy

(eV)
0.1709
0.1549
0.1471
0.1427
0.1457

Table 1: Surface formation energies in eV for various surface unit cell configurations

We see that increasing the size of the surface unit cell increases the dilution of the Pd
atom, while marginally decreasing the energy required to form the surface. These results
are on expected lines because smaller unit cells will possess more strain on the surface due
to the mismatch in the lattice constants of Pd and host metal. These strain effects will
affect the reactivity of the surface [40]. Hence, larger surface unit cells were required for
the calculations. Next, we looked at the number of available sites for adsorption on each of
these configurations, mainly hollow and atop sites. We find that the 3 3 surface unit cell
has sufficient number of sites to accomodate all the adsorbate species we encounter in our
investigations. It is also large enough to ensure a separation between larger adsorbates like
ethylene and vinyl. This is important because it ensures that inter-adsorbate interactions
are negligibly small and do not affect the energetics of the reaction in any way. It was also
important to minimize any steric hindrance that may be present in the system. The 3
3 unit cell also ensures that the computational expense is not too much. Hence, for all
subsequent calculations we chose the 3 3 surface unit cell with 3 layers in the z-direction.
This configuration is shown in Figure 5.

12

Figure 5: Alloy with 3 3 3 surface unit cell, with the central Au atom replaced by Pd.

4.4

Dissociation of Water

Preliminary calculations were done to identify the site preferences for all the species present
in the dissociation process. The water molecule prefers to adsorb at the atop site for all
metals. However, the difference in adsorption energy for a hollow site and the atop site is
approximately 0.05 eV. Hence, the atop position was chosen as the preferred site for adsorption of the water molecule because in the eventual transition state calculation, we found
that there were lowest site diffusion barriers associated with an atop site, when compared
to adsorption at the hollow site. We also found that OH and H preferentially adsorb at
adjacent hollow sites. Grabow et al. reported that OH preferentially adsorbs in a tilted
geometry at the atop site [41]. However co-adsorbing OH with H appears to stabilize the
OH group at the hollow site. For the alloys, adsorption of the water molecule at the atop
site (on the Pd atom) was significantly more favorable than adsorption at the hollow site.
OH and H relaxed at the hollow sites, and their geometry varied with alloy used. The H
atom adsorbed at the hollow site, slightly offset towards the Pd atom, while the OH group
aligned itself at a slight angle to the perpendicular. It adsorbed at the hollow site for AuPd
and AgPd, and at the bridge site for CuPd. These geometries are shown in Figure 6.

13

Figure 6: Geometries indicating preferred sites for adsorption of the water molecule. Clockwise from top
left, water adsorbed atop the Pd molecule. This geometry is seen in all alloys. The next three panel images
show OH and H adsorbed with differing geometries.

Figure 7: Images showing geometries where the OH-H bond length was fixed, and subjected to relaxation.
Images number row-wise from left to right. Plot shows the energy of each image relative to the inital state.

The next step in the dissociation process is the bond cleavage of the OH group. Preliminary
calculations determined the preferred adsorption sites for O and H to be adjacent hollow
sites, on either side of the Pd atom. Again, both atoms adsorbed close to the Pd atom.
For the metals, adsorption was stable at the center of the hollow sites. For the pure metal
surfaces, the preferred sites for adsorption were adjacent hollow sites.
To determine the reaction energy barriers, we relaxed the a series of adsorbate-surface
geometries in which the OH-H bond length was steadily increased and fixed, in the process
of relaxation. In every geometry, the OH and H species were positioned along a path which
would lead them to their preferred sites, post dissociation. This increase in bond length,
and subsequent relaxation is seen as a chain of images in Figure 7. The system shown is
that of AuPd. From the plot, we see that the geometry with the highest energy is the 4th
image. Using this geometry, the transition state was obtained, and consequently the barrier
14

for dissociation. The same procedure was repeated for the second dissociation step, i.e the
O-H bond cleavage. The potential energy diagram for the stepwise dissociation was plotted,
and is shown in Figure 8.

Figure 8: Potential energy diagram for the dissociation of water on single atom alloys. Lighter shades
represent dissociation on pure metal surfaces, while darker shades represent the dissociation pathway on
corresponding single atom alloys.

A quick look at Figure 8 tells us that the single atom alloys of AuPd and AgPd favor
dissociation by being around 0.5 eV more favorable than pure Au and Ag, for every step
of the dissociation process. CuPd performs worse than Cu, energetically, in this reaction.
Transition state energies for the two dissociation steps in the reaction are also less than
those on the pure metals. This suggests that the Brnsted-Evans-Polanyi relations do hold
for this reaction, and this has been reported in the work of Nrskov and coworkers [42].
CuPd performing worse than Cu is an intriguing result. This suggests that the Pd atom is
not enhacing the reactivity of the surface. This deduction is also supported by the DOS plot
for CuPd in Figure 1, which does not show a sharp and pronounced peak. Electron density
seems to have delocalized well across the surface of the alloy. Hence, we see that adding an
atom of Pd to Au and Ag surfaces does enhance the reactivity of the suface, while the same
cannot be said for Cu.

15

4.5

Dissociation of Nitric Oxide

The surfaces chosen to study the dissociation of nitric oxide were pure metals of Au, Ag, Cu
and Pd, and the single atom alloys of AuPd, AgPd and CuPd. Previous work by Gajdo
[32, 31] suggested that the NO molecule could adsorb on the surface in two geometries. One
geometry is where the axis of the N=O bond is parallel to the surface, and the other is where
the axis is perpendicular to the surface. Prelminiary calculations for the pure metal surfaces
of Cu and Ag showed that NO adsorbs with a stable geometry in which the molecular axis of
NO is perpendicular to the surface, with the nitrogen atom embedded at a hollow site. We
also found that in a co-adsorbed state oxygen and nitrogen atoms relaxed at adjacent hollow
sites. This was also true for isolated nitrogen and oxygen atoms adsorbed on the surfaces.
For Au, the results obtained conform perfectly with the geometry predicted by the reference
work, i.e the NO molecule adsorbs with a strong tilt at the bridge sites. Geometries for the
adsorption of NO on Cu and CuPd are shown in the Figure 9. For the adsorption of nitric
oxide on the single atom alloys, the molecules adsorbed in a similar manner to that on pure
metal surfaces, with the exception of that on CuPd, on which it adsorbs at a slight angle to
the perpendicular to the surface.

Figure 9: Nitric oxide adsorbs perpendicular to the surface on a pure Cu surface, but adsorbs with a slight
tilt on the CuPd surface, at the hollow sites.

16

Figure 10: Potential energy diagram showing the dissociation pathway of NO on pure metal surfaces and
single atom alloy surfaces.

The potential energy diagram for this reaction was constructed from the the stepwise
mechanism described earlier in this work. This is shown in Figure 10. From a quick glance
we deduce that the single atom alloys AuPd and AgPd show good catalytic behavior towards
the dissociation of NO. CuPd appears to be less active towards the dissociation of NO. This
observation is line with those from the dissociation of water. CuPd does not possess an
enhanced reactivity at the surface, and this may be attributed to the lack of sharp feature
in the DOS of of the d-band of CuPd. Another point to consider is that Pd is a larger atom
embedded in a surface having smaller lattice parameters. It is possible that there are strain
effects on the surface, which may lead to an apparent decrease in surface reactivity due to
the redistribution of electron density around the Pd atom [43].
4.6

Selective Hydrogenation of Acetylene to Ethylene

The final reaction studied in this work was the selective hydrogenation of acetylene to ethylene. This reaction was studied on Au, Ag, AuPd, AgPd and Pd surfaces. We chose these
alloys because they are all employed in the industry as hydrogenation catalysts, as pure
metals and alloys. Studies have reported that alloying of Pd with noble metals enhances
selectivity towards ethylene [44]. Single atom alloys have not been reported to be used for
17

this reaction in literature. The first step was to find the preferred adsorption sites for all the
species involved in the reaction. Bos and Westerterp [36] report that ethylene and acetylene
adsorb as -bonded complexes or as di--adsorbed complexes on catalyst surfaces. Based
on these reports, and experimental observations, acetylene was adsorbed in the fcc site on
the surface. On relaxation, we found that for Au, AuPd, Ag and AgPd, acetylene adsorbs
most favorably at the fcc site. Ethylene preferentially adsorbs atop the Pd atom for the alloy surfaces, and also prefers to adsorb atop a pure metal molecule. Comparison of binding
energies of acetylene at the fcc site, with that at atop sites reveals that for all surfaces except
Pd, the difference in binding energies is 0.015 eV for Au, 0.111 eV for AuPd, 0.105 eV for
Ag and 0.008 eV for AgPd. Adsorption on AuPd is an order of magnitude more exothermic
than adsorption over Au. Similarly, for ethylene, binding energies differ by 0.07 for Au, 0.23
eV for AuPd, 0.018 eV for Ag and 0.019 eV for AgPd, all favoring the atop site. The most
significant takeaway from these observations is that both acetylene and ethylene prefer to
bond to the metal surface through -bonded complexes. The lack of stability at bridge sites,
for both species rules out the possibility of a di--adsorbed complex. The adsorbed acetylene
geometries over Au and AuPd are shown in Figure 11

Figure 11: Geometries in the first column are acetylene and ethylene adsorbed over Au. Adsorption is weak,
adsorbate height is large, and both species are linear in geometry. Geometries in the second column ar
acetylene and ethylene adsorbed over AuPd. Adsorption is stronger, adsorbate height is smaller, and C-H
bond loses triple bond and double bond character, adsorbing with a bent geometry.

For the catalyst to be selective towards ethylene, over ethylene, the energy required to
desorb ethylene from the surface should be lesser than the energy required to hydrogenate it
further to ethane. Neurock and coworkers [37] suggested that the more strongly bound acetylene molecule displaces the weakly bound ethylene from the surface, the instant it is formed.
With adsorption on AuPd being significantly more than that on Au, the rate of adsorption,
and consequently, hydrogenation is bound to be more. Ethylene prefers to adsorb atop surface atoms, and the smaller acetylene preferring hollow sites, It is possible for a surface to
18

be covered to a larger extent by the smaller acetylene molecule. The heat of adsorption of
ethylene is more than that of ethylene. These occurrences are also bound to increase the rate
of reaction, while maintaining a high degree of selectivity. Vinyl intermediates are formed in
the hydrogenation step. These intermediates are adsorbed quite strongly at the surface of
the single atom alloys, compared the the strength of adsorption of acetylene and ethylene on
the same. The geometry of the intermediates suggest that vinyl again prefers to bond atop
the Pd atom, and exhibits a C-C bond length which is almost that of a C=C. The relaxed
geometries of vinyl, and vinyl co-adsorbed with a hydrogen atom is shown in Figure 12.

Figure 12: Geometries in the first column are vinyl adsorbed over Au. Adsorption is favorable but weak, and
vinyl favors a linear geometry. Geometries in the second column ar vinyl adsorbed over AuPd. Adsorption
is stronger, adsorbate height is smaller, and favors a skewed linear geometry.

A Haber cycle was constructed to plot the potential energy diagram for this hydrogenation
reaction. The energy diagram is shown in Figure 13. We see that the energetics of the
hydrogenation reaction are more favorable for the single atom alloys, than their respective
pure metals.

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Figure 13: Potential energy diagram for the hydrogenation of acetlyene to ethylene. As mentioned in the
legend accompanying the plot, darker shades represent single atom alloys, while the corresponding lighter
shades represent the pure metal surfaces. The pathway for Pd is represented in red.

A key point to be noted is that the single atom alloys are very favorable to the formation
of the vinyl intermediate, and their reaction pathway from here on starts to mimic that
of Pd. This can be attributed to the intermediates adsorbing strongly on the Pd atom,
and showing excellent selectivity towards the formation of ethylene. The co-adsorption step
after the formation of the vinyl intermediate is indicative of the pathways being very close
in energy. This suggests that the Pd atom in the alloys is singularly resposible for driving
the reaction forward. These Pd doped alloys show excellent catalytic behavior towards the
formation of ethylene.

Conclusion

Alloys of gold and silver which are with doped one atom of palladium on the surface show
enhanced reactivity in the reactions investigated in this work. The single palladium atom
shows gas phase characteristics and a correspondingly high reactivity. This is due to the
ineffective mixing of the electron densities of palladium and that of gold or silver. This
manifests itself into a sharp peak near the Fermi level, in the d-band density of states for the
alloys, projected on the palladium atom. The high reactivity showcased by palladium alters
20

the geometries of adsorbates by making them adsorb closer to the palladium atom, or atop
the palladium atom. This results in adsorption being a more favorable process, which in turn
makes the energetics of dissociation more favorable, in the case of water and nitric oxide. In
the selective hydrogenation of acetlyene to ethylene, we predict an enhancement of rate of
hydrogenation, with an increased degree of selectivity, due to the more favorable energetics of
adsorption. The copper-palladium single atom alloy does not enhance reactivity, and shows
less favorable energetics for the reactions studied in this work. This can be attributed to a
better mixing of surface electron densities of palladium and copper. This is seen through the
absence of the sharp peak in the d-band density of states for the alloy. We also postulate that
because Pd is a larger atom in a smaller copper lattice, these strain effects have an impact
on the reactivity of the alloy. Finally, we can conclude by saying that these alloys exhibit
unusual d-band characteristics, and this behavior manifests itself in enhanced reactivity, thus
enhancing the catalytic behavior of single atom alloys.

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