Applied Surface Science 396 (2017) 444–454

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Applied Surface Science

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

Full Length Article

Computational evaluation of sub-nanometer cluster activity of singly

exposed copper atom with various coordinative environment in
catalytic CO2 transformation
Ramasamy Shanmugam a,d , Arunachalam Thamaraichelvan b ,
Tharumeya Kuppusamy Ganesan c , Balasubramanian Viswanathan d,∗
a
Department of Chemistry, Thiagarajar College, Madurai, Tamilnadu 625 009, India
b
Faculty of Allied Health Sciences, Chettinad Hospital & Research Institute, Kelambakkam, Tamilnadu 603 103, India
c
Department of Chemistry, The American College, Madurai, Tamilnadu 625 002, India
d
National Center for Catalysis Research, Indian Institute of Technology Madras, Chennai, Tamilnadu 600 036, India

a r t i c l e i n f o a b s t r a c t

Article history: Metal cluster, at sub-nanometer level has a unique property in the activation of small molecules, in
Received 25 August 2016 contrast to that of bulk surface. In the present work, singly exposed active site of copper metal cluster
Received in revised form 19 October 2016 at sub-nanometer level was designed to arrive at the energy minimised configurations, binding energy,
Accepted 26 October 2016
electrostatic potential map, frontier molecular orbitals and partial density of states. The ab initio molecular
Available online 27 October 2016
dynamics was carried out to probe the catalytic nature of the cluster. Further, the stability of the metal
cluster and its catalytic activity in the electrochemical reduction of CO2 to CO were evaluated by means
Keywords:
of computational hydrogen electrode via calculation of the free energy profile using DFT/B3LYP level of
Cluster
Copper theory in vacuum. The activity of the cluster is ascertained from the fact that the copper atom, present in a
Carbon dioxide two coordinative environment, performs a more selective conversion of CO2 to CO at an applied potential
Carbon monoxide and DFT of −0.35 V which is comparatively lower than that of higher coordinative sites. The present study helps
to design any sub-nano level metal catalyst for electrochemical reduction of CO2 to various value added
chemicals.
© 2016 Elsevier B.V. All rights reserved.

1. Introduction
Extending the valorisation of CO2 assumes immense signifi-
cance due to its negative environmental impact. Electrochemical
reduction of CO2 on metal electrodes provides a tangible solution
for the above problem as well as depletion of fossil fuel [1], with
an advantage of product selectivity, atom economy and release of
zero hazardous substance into the environment. Among the various
metal electrodes, Cu is the most studied [2–4] due to its versa-
tile availability, low cost and exclusive production of hydrocarbon
at moderate current density and Faradaic efficiencies. Although
the electrochemical reduction of CO2 is a feasible technology, it
could be exploited commercially only by lowering the overpoten-
ital [5,6]. Nevertheless, various methods have been attempted to
lower the overpotential and increase the efficiency of reduction of
CO2 on Cu electrodes by modification of surface structure in the
bulk [7], morphologies [8] and size of the nano particle [4,9,10]. In
∗ Corresponding author.
E-mail address: bvnathan@iitm.ac.in (B. Viswanathan).
a recent review, the greater influence of the facet(s) of metal, metal
oxide and composite materials on the catalytic reactions have been
reported [11].
Recent studies have revealed that metal atom present at coor-
dinative unsaturation [12], edges and corners [13–15] performs
better than the atom in the bulk. Size-selected small clusters have
recently received greater attention due to the exceptional proper-
ties such as fluxuation, sites with coordiantive unsaturation and
better activity compared to the corresponding bulk or nano state
[16–18]. The atoms on the surface of the cluster, fully exposed to
CO2 for interaction [19], experience rise in binding energy of the
adsorbates in comparison to the atoms in the bulk. Catalysis by
single atom and single site has emerged as a stronger candidate
in the activation of small molecules [20,21]. More recently, impu-
rities of copper present in carbon have shown significant activity
during electrochemical reduction of CO2 [17]. In addition, employ-
ing operando EC-STM for elucidating the interaction between CO2
and polycrystalline Cu has shown the surface rearrangement dur-
ing the reaction process [22]. Analysis of the available literature
suggests that the activity of a catalyst mainly depends on the atom
present in singly exposed site which may be a better environment

http://dx.doi.org/10.1016/j.apsusc.2016.10.174
0169-4332/© 2016 Elsevier B.V. All rights reserved.
 R. Shanmugam et al. / Applied Surface Science 396 (2017) 444–454
Fig. 1. Energy minimised configurations of the single site (SS) copper cluster models
with various coordination numbers: (a) 1, (b) 2, (c) 3, (d) 4, (e) 5 & (f) 6 and 7 atom
cluster isomorph models (IS): (g) 1, (h) 2, (i) 3, (j) 4 & (k) 5.
for the catalysis. Hence, understating the electronic properties and
catalytic activity of a single site Cu with various possible coordina-
tive environments at sub-nano cluster level, may throw more light
on devising new strategies for selecting a catalyst for CO2 reduction.
In the present study, computation of possible interactions of
singly exposed copper with various adsorbates, stability and role of
the electronic property of the copper sites was undertaken. Further,
as the electrochemical reduction of CO2 to CH4 follows an 8 electron
transfer path way and formation of CO requires 2 electron reduction
[15,23], reduction of CO2 to the industrially exploited CO molecule
was taken as the model in the present study.
2. Copper cluster models
The structures of small Cu clusters have been studied exten-
sively [24,25]. Based on the literature reports, the following models
were considered for the present study. When a single atom is
considered to form a coordination number of 1–6 with required
neighbours, it is designated as single site (SS). However, when the
copper atom is present in 1–6 coordinative environment as a part
of an isomer of 7 atom cluster, it is designated as an isomorph (IS).
The energy minimised structures of both the models are presented
in Fig. 1.
3. Computational details
The geometry optimization of pure copper clusters and those
with adsorbates was performed at B3LYP level of hybrid DFT using
a basis set of LANL2DZ for Cu and 6-31G* for other elements with
default spin. The choice of functional is provided in the Supplemen-
tary information (S1). The binding energy of copper clusters was
obtained using the formula, BECu = ECun − nECu , where n, ECu and
Cun are number of copper atoms, total zero point energy (ZPE) cor-
rected electronic energy of copper and that of clusters respectively.
Counterpoise corrected (BSSE) energies were used in evaluat-
ing the properties. Binding energy of adsorbates was calculated
using the expression BEads = ECu +adsorbate − ECux − Eadsorbate , where,
X
ECu , ECux and Eadsorbate are zero point energy corrected
X +adsorbate
electronic energies of Cux + adsorbate, Cu cluster and adsorbate
respectively. AIMD simulations were performed employing an
extended lagrangian Atom Centered Density Matrix Propagation
Molecular Dynamics (ADMPMD) at B3LYP/LANL2DZ level to find
the stability of the coordination site and cluster. The optimized
geometries of the cluster was chosen as the initial geometry for
the ADMPMD run. Dynamics simulation was carried out at 500
steps with a time scale of 0.1fempto second and the fictitious elec-
tron mass of 0.1 amu. During the simulation, the temperature of
300 K was set as thermostatic temperature and marinated by using
velocity scaling method [26].
Computational hydrogen electrode method [27] was applied
to analyze the free energy of reaction pathway. For an elemen-
445
tary reaction A* + (H+ + e− ) → AH*, the free energy is defined as
GA∗ →AH ∗ (U) = GAH ∗ − GA∗ − 0.5GH2 + ne (U), where the terms G,
ne and U represent free energy, number of electrons and the
applied potential respectively for the reaction. All these quantum
mechanical calculations were carried out using Gaussian 09 soft-
ware package [28]. PDOS of the singly exposed copper with various
coordinated environments were calculated based on Generalised
Gradient Approximation coupled with Perdew–Burke–Ernzerhof
exchange-correlation functional plane wave energy cut-off of
880 eV using CASTEP code in Material Studio 5.5. [29].
4. Results and discussion
4.1. Structure and binding energies of single Cu atom sites and
seven atom copper cluster sites
In order to assess the suitability of various optimized copper
cluster models for the catalysis, structural parameters and binding
energies were calculated for the single site (SS) and 7 atom clus-
ter sites (IS) which are presented in Table 1. Binding energy is a
measure of the thermodynamic stability of the model. The bind-
ing energy data for single site reveals that clusters with increasing
coordination numbers (CN) show greater thermodynamic stability
towards the formation of cluster. The behaviour of the isomorphs
follows a similar trend except for 4 coordination which experiences
a slight decrease in binding energy.
All these values correlate well with those of earlier reports [30].
The coordinating Cu atom is connected to adjacent atoms through
different number of bonds depending upon its coordination num-
ber. The bonding was not equal in many cases with some showing
dangling nature. Hence, in order to find out the actual distance of
the coordinating atom from other atoms in the cluster, the aver-
age bond lengths were calculated and are presented in Table 1.
The analysis reveals that, the average bond length between the
cluster atoms and active site gradually increases with coordination
number in both the single site and isomorph clusters. This result
indicates that for higher coordination numbers, an increasing num-
ber of atoms, moving closer to coordinative atom, tend to repel each
other due to steric and electronic repulsions. However, a site at a
lower distance may be preferred for better electron transport.
4.2. Electrostatic potential map analysis
Electrostatic potential (ESP) of isosurface predicts, the charge
distribution on the clusters which are responsible for chemical
reactivity at sub-nanometer level. Fig. 2 depicts the ESP maps for the
SS and IS copper clusters. The positive charge on the exposed sin-
gle site decreases with increase in coordination number. However,
in isomorphs, except for CN-1 and CN-5, all others carry positive
charge on the coordination sites.
Thus, increase in the number of copper atoms causes the shift
in the charge density from positive to negative side. During the
catalytic interaction, most of the adsorbates have negative charge
on them. These adsorbates prefer sites where positive charge is
present in the active site. Hence, the lower coordination site with
greater positive charge is preferred for the reaction.
4.3. Frontier molecular orbital (FMO) analysis
An electron transfer reaction is governed by symmetry con-
servation rules. Hence, the shapes of occupied orbitals in a metal
cluster is essential to understand the catalytic activity of the metal
cluster.
The Gaussian type of FMO contours of single site and isomorph
clusters are shown in Fig. 3 which reveal that for the single site
HOMO in Cu2 , the electron density is uniformly distributed over the
446 R. Shanmugam et al. / Applied Surface Science 396 (2017) 444–454

Fig. 2. Electrostatic potential map for copper clusters with single site various coordination numbers (a) 1, (b) 2, (c) 3, (d) 4, (e), 5 & (f) 6 and isomorph sites (g) 1, (h) 2, (i) 3,
(j) 4 & (k) 5 in a.u.

two atoms without any node. As the cluster size increases (b–f), the
orbitals are separated by a symmetric node up to (d) with (e) and (f)
exhibiting multiple nodes. As for the LUMO, the node is observed
right from (a) to (f). Although, symmetry was present in (a), (c), (e)
and (f), due to the availability of adjacent atoms for additional over-
lap, it is not so with (b) and (d). In isomorph, since it contains seven
atoms, (g) and (h) have ␴ character while all other models have
␲ character in HOMO. In case of LUMO, (i)-(k) experience overlap-
ping with adjacent atoms which is absent in (g) and (h). The FMOs of
single site Cun show ␴ and ␲ like character in Cu1 and Cu2-5 respec-
tively. Though d orbital contribution in HOMO nature is highlighted
for Cu6 cluster, no exclusive d like character was observed in LUMO.
In CO2 , FMO of HOMO is on O and that of LUMO is on C exhibiting ␲
orbital like shape. A comparison of the shapes of metal orbitals with
those of free CO2 (shown in Supplement information S2) reveals
that lower clusters with less than 6 Cu atoms have ␲ like shape.
This implies that direct electron transfer is possible in lower atom
clusters compared to higher atom copper clusters.
4.4. Partial density of states (PDOS) of coordinative sites
The local environment of the site determines the nature of inter-
action between the adsorbate and surface. It helps to predict the
electron transfer. Partial density of states of 3d orbital of single site
 R. Shanmugam et al. / Applied Surface Science 396 (2017) 444–454 447

Fig. 3. Frontier molecular orbital contours of single site Cu cluster with coordination numbers (a) 1, (b) 2, (c) 3, (d) 4, (e), 5 & (f) 6 and isomorph sites with coordination
numbers (g) 1, (h) 2, (i) 3, (j) 4 & (k) 5 in a.u.

Fig. 4. Partial density of states of d-orbital for ␣,␤ spin density of singly exposed copper atom in a) single site (1) Cu-1, (2) Cu-2, (3) Cu-3, (4) Cu-4, (5) Cu-5 & (6) Cu-6 and
b) isomorph (1) Cu-1, (2) Cu-2, (3) Cu-3, (4) Cu-4 & (5) Cu-5.(For interpretation of the references to color in text, the reader is referred to the web version of this article.)

Cu in Cun for the six model nano cluster models, (1) Cu1 , (2) Cu2 , (3) lines in Fig. 4a and magenta and dark yellow lines in Fig. 4a denote
Cu3 , (4) Cu4 , (5) Cu5 , and (6) Cu6 are provided in Fig. 4a and those the spin density of ␣ and ␤ electrons respectively. The line EF refers
for the isomorph are depicted in Fig. 4b. The solid green and red to the Fermi energy level in vacuum. Fig. 4a and b reveal the effect
448 R. Shanmugam et al. / Applied Surface Science 396 (2017) 444–454

of increase in coordination environment of a copper site from 1 to

Cu-OH
6. All the occupied energy states are present below the Fermi level

1.81
1.79
1.78
1.83
1.85
1.8
SS
and unoccupied acceptor states are absent. ␤ spin is nearer to EF
than ␣ spin which shows that electron transfer mainly depends on
␤ spin states. PDOS plot indicates that the occupied level is not over-
lapping with Fermi level with a gap energy of 2.5, 2.6, 2.5, 2.9, 3.1
Cu-H

1.54
1.55
1.69
1.55
1.55
1.54
and 3.2 eV for coordination numbers 1–6 respectively. This reveals

SS
that the site in the low coordination environment has a lower
energy barrier than that of higher coordination number. Further,
it explains why small clusters perform better than bulk and pre-
dicts that direct electron transfer is possible. However, 3d orbital
1.96
1.91

1.88
1.92
1.99
1.9
CO

energy level moves towards more negative region with respective

SS

to the Fermi level revealing the stabilisation of the site. The peak
broadening may be due to overlap of adjacent p and d orbitals in the
clusters [31]. The orbital energy level makes the electron transfer
less feasible. The PDOS profile of isomorphs show that the arrange-
COOH
Adsorption distance

1.95
1.95
1.95
1.94
1.95
1.95

ment of atoms plays an important role in altering the shape and

SS

position of the energy level of the coordination sites in spite of hav-

ing same number of copper atoms. Here too, the shift in the peaks
(Å) Cu-C

was observed towards negative direction suggesting that atoms

Cu-C

with low coordination number have lower energy barrier for the
2.23
2.18

2.16
2.37
2.65
CO2

2.2
SS

transport of electrons.

4.5. Ab initio molecular dynamics stimulation

0.093
0.099

0.102
0.07

Under reaction conditions, the surface atoms undergo relax-

IS

ation and rearrangement leading sometimes to deactivation of the

charge(q) on CO2
Total Mullikan

catalyst. Hence, during the reaction process, the coordination site

must retain its structure to be stable till the end of the reaction.
The stability of the cluster was evaluated with the help of ab initio
0.114
0.122
0.113
0.088
0.106

0.089

molecular dynamics method. The potential energy profile versus

SS

time trajectory of 50fs of the single site copper cluster, calculated

using Atom-centered density matrix propagation (ADMP), is shown
in Fig. 5. The table, given as inset in the plot, presents the structural
features of the corresponding cluster in a dynamic environment
0.19
0.17

0.19

at different time scales. A close scrutiny of potential energy pro-

IS
CO2 binding energy

–
Binding enrgy, Mullikan charge and structural parameters of single site and Isomorph copper clusters.

file of single site suggests that all the atoms in the cluster undergo
motion, thus leading to change in the potential energy. The bond
length between the coordination site and the neigboring atom is
increased by about 0.25 Å for single site with coordination num-
−0.17

−0.12
−0.66
−0.07
−0.06

0.06
(eV)

ber 1(CN-1)when the system moves from the initial to final state.
SS

Also, the potential energy increases with time. This indicates that
the atoms are dynamic in nature. For the corresponding SS with
coordination numbers of 2,3 &5 (CN-2, CN-3 and CN-5), there is
no significant change in the structural features revealing that the
2.36
2.43
2.48
2.49
2.51
2.54
IS

structures are stable. In case of coordination numbers of 4 and 6

length of Cu(Å)
Average Bond

(CN-4 and CN-6), the bond lengths of Cu1-Cu4 and Cu6-Cu7 are
increased. The resultant distances between the atoms indicate that
the there is no bonding at 10fs. ADMP molecular dynamics poten-
Cu − Cu/n n-Number of bond in coordination site.
2.25
2.32
2.41
2.42
2.43
2.54

tial energy versus the time trajectory of isomorph clusters along

SS
b

with their structural features are depicted in Fig. 6. The changes in

potential energy in all the clusters can be attributed to the stable
nature of bonds showing negligible changes.
−11.22

−11.23
−11.37
−10.18
−10.82

−10.79

4.6. Structural features of adsorbates

IS
d
Cu binding energy

During the transformation of CO2 , the species such as CO2 and

CN - Coordination number.

*COOH have considerable interaction with the active sites. Hence,

the structural features of these species on the active site were
−11.34
−5.22
−6.52
−8.62
−2.01
−3.01

examined initially to get new insights into the interaction between

Isomorph Site (IS).
(eV)

SS

Single Site (SS).

the adsorbate and adsorbent.

c

4.6.1. Adsorption of CO2

The first step in CO2 transformation is the interaction of CO2
n
Table 1


CN

on active sties. In order to understand how the coordination num-

1
2
3
4
5
6
a

d
a

bers in different environments play a role on CO2 activation, CO2

 R. Shanmugam et al. / Applied Surface Science 396 (2017) 444–454 449

Fig. 5. ADMP molecular dynamics potential energy profile for the single site clusters with different coordination numbers: (a) 1, (b) 2, (c) 3, (d) 4, (e) 5 and (f) 6.

was adsorbed on each of the active site with a bent configuration
to verify if the interaction is through physisorption or chemisorp-
tion and relaxed. The energy minimised structures are presented
in Fig. 7 The corresponding structural parameters are presented in
Table 1.
The structural parameters and binding energy of CO2 on coordi-
nation site in the final state suggest a weak interaction, as evidenced
by regeneration of the linear geometry of CO2 . Similar results have
been observed in bulk surfaces [32] with a distance of 1.17 Å for
C O when it is nearer to the metal site. The distance of 1.16 Å
for the other C O bond and the angle of 179.57◦ for O C O bond
remain the same in all the cases. Mullikan charge on CO2 indicates
that there is no effective transfer of charge from the coordination
sites and hence predicted the CO2 to be in a physisorbed state. It
450 R. Shanmugam et al. / Applied Surface Science 396 (2017) 444–454

Fig. 6. ADMP molecular dynamics potential energy profile for the isomorph clusters with different coordination numbers: (a) 1, (b) 2, (c) 3, (d) 4 and (e) 5.

is quite interesting to see that when CO2 is interacting with the
active site in the isomorph sites with coordination numbers 1 and
4. (CN-1 and CN-4) the configurations of the sites were rearranged
to those of the active sites observed for coordination number 2
and 6 (CN-2 and CN-6) respectively as shown in Fig. 7. CN-1 and
CN-4 hold CO2 in horizontal and linear fashions respectively sug-
gesting a decrease in the stability of active site after interaction.
These sites are not available for further interaction and thus, the
number of active sites in the reaction medium gradually decreases.
Further, interactions of CO2 on isomorph sites with coordination
 R. Shanmugam et al. / Applied Surface Science 396 (2017) 444–454
Fig. 7. Interaction of CO2 with single sites with different coordination numbers: (a)
1, (b) 2, (c) 3, (d) 4, (e) 5 & (f) 6 and isomorph active sites with various coordination
numbers: (g) 1, (h) 2, (i) 3, (j) 4 & (k) 5.
number 2,3 and 5 (CN-2, CN-3 and CN-5) revealed physisorption
from binding energy. The structural parameters resemble those of
single site clusters and Mullikan charge predicts that transferred
charge is insufficient to alter the structural features of CO2 . Due to
the unstable nature of CN-1 and CN-4 isomorph clusters, they were
not considered for further study.
4.6.2. Adsorption of COOH
On the active site, *COOH interacts through C via mono den-
tate bent mode of adsorption. Energy minimised configurations
of *COOH for single site and isomorph clusters are presented in
Fig. 8. For single site, the *COOH has a Cu-C distance of ∼1.95 Å in
the entire coordination environment without affecting the struc-
ture of the cluster. The results prove that structural transformation
occurs in CN-2 and CN-3 for the bridge bidentate and monodentate
modes of adsorption respectively. The cluster CN-5 retained the
configuration, though *COOH is held as bridge bidenate. This result
suggests that on the active site, unsaturated atoms are present in
adjacent positions. On the isomorph clusters, CO2 undergoes defor-
mation easily and leaves the active site instantly. However, this is
not occurring in single site coordination environment. It is thus
deduced that single site environment with low atoms is essen-
tial for the catalytic reaction. Hence, single site environment was
chosen for further analysis.
451
Fig. 8. Energy minimised configurations of single site with different coordination
numbers: (a) 1, (b) 2, (c) 3, (d) 4, (e) 5 & (f) 6 and isomorph active sites with various
coordination numbers: (h) 2, (i) 3 & (j) 5 with *COOH.
Fig. 9. Binding energy of various adsorbates on single site copper cluster at various
coordination numbers.
Fig. 10. Schematic representation of CO2 to CO transformation on Copper active
site.
4.7. Binding energy of adsorbates formed during electroreduction
of CO2 to CO
In the medium for CO2 reduction, intermediates such as CO,
COOH, OH and H species were found to be competitively adsorbed
on the active site of a catalyst [33]. Hence, these species play an
important role in controlling the catalytic activity of a catalyst. To
assess the adsorption strength of the above species on various coor-
dinative environments, the binding energies were calculated and
are plotted in Fig. 9. The values of distance between the active site
and intermediate species are given in Table 1.
The first step in the CO2 electro reduction of CO2 is capture
of an electron and a proton by CO2 to form COOH*. This COOH*,
after chemisorption on Cu site through C, should participate spon-
452 R. Shanmugam et al. / Applied Surface Science 396 (2017) 444–454

Fig. 11. Free-energy profile for the reduction of CO2 to CO at 0 V and the required applied potential (UL ) for formation of CO from CO2 at various Cu sites with different
coordination numbers (CN-1 to CN-6 = Coordination numbers, 1–6).

taneously in the forward reaction with a more negative free energy
of adsorption. Simultaneously, a proton in the medium also accepts
an electron to form a chemisorbed H* on the active site. In a similar
way, surface oxygen combines with a proton to form a OH* species.
The above two reactions are competitive. If chemisorption of H* is
more favourable, it leads to competitive hydrogen evolution. If OH*
is formed easily, then H* will combine with OH* to form H2 O. The
plot (Fig. 9) reveals that binding energy of OH* and H* follow the
same trend with coordination number, although, *OH has higher
(∼ −0.2–−0.6 eV) binding energy than *H. This reveals that the *OH
was an ineluctable candidate in the medium [34]. All the patterns
being similar, it is essential to select the most preferred CN site with
a suitable coordination number. Among the various sites, CN-2 hav-
ing more binding energy than the rest can rapidly capture *COOH
species in the medium. However, rapid conversion of *COOH to CO
needs weaker adsorption of *COOH compared to *CO which ensures
spontaneity of this step. The energy profile of *CO reveals that CN-5
has greater binding energy than other CNs. This result contradicts
 R. Shanmugam et al. / Applied Surface Science 396 (2017) 444–454
the observation that CN-2 prefers CO to COOH for adsorption. This
conclusion answers why conversion of CO2 was not an effective
process, since the steps involved in the reaction were independent
from one another. Hence, multiple reaction sites are required for
the simultaneous adjacent reactions.
4.8. Activity of single site in electrochemical reduction of CO2
The activity of the copper site was evaluated by using
computational electro-chemical reduction method. In general,
electrochemical reduction of CO2 yields a variety of products.
The main intermediate is CO the formation of all products which
requires only four electrons while other products need more elec-
trons and protons. For this reason, the transformation of CO2 to CO
was taken as a model reaction for the present study. The schematic
representation of CO2 to CO conversion is illustrated in Fig. 10.
Initially the CO2 is physically held on the active site. In CO2 elec-
troreduction, the first step involves adding of H+ + e− to the CO2 to
form *COOH species which can readily be chemisorbed on the active
site. Normally this step requires energy to propagate towards for-
ward direction. COOH* should be more spontaneously formed from
gaseous CO2 , less stable on the active site and dissociation *COOH
must be faster to produce CO* + H2 O.
The calculated free energy profile of CO2 to CO transformation on
various coordinative active sites based on computational hydrogen
electrode model is depicted in Fig. 11. The plot reveals that electro-
chemical reduction of CO2 reduction by proton coupled electron
transfer step has a thermodynamic barrier. The corresponding bar-
rier energy was supplied in the form of an applied potential. At
0 V, none of the coordination sites was able to effect the reaction
thermodynamically, as all of them are constrained by a limiting
potential(UL ). Hence, the minimum potential required to go down-
hill along the free-energy barrier for CO evolution in the absence of
an applied potential and the limiting potential that corresponds to
the reaction in presence of a catalyst are also presented in Fig. 11.
For the different coordination sites, the limiting potential is of the
order, 1 > 5 > 3 > 4 > 6 > 2. From this, CN-2 exhibits the lowest lim-
iting potential among all sites. This value is smaller, compared to
that for the selective transformation of CO2 to CO on Au(211) [2]
surface indicating higher activity towards CO on Cu. Further, sites
with atoms, having even number of coordination appear to have
less overpotential than the one with odd coordination numbers.
5. Conclusion
To achieve a better CO2 transformation on copper catalytic site,
it is necessary to keep copper atoms in various coordinative sites
stable under the experimental condition. A study on comparison of
the catalysis of the reaction by singly exposed copper atom with
that by 7 Cu atom isomorphs under different coordinative envi-
ronments was undertaken with respect to their general stability
and stability under catalytic reaction. In general, each and every
step was found to be unique and independent of one another.
However, in heterogeneous environment, keeping this individu-
ality is a challenging one which opens up a new window to the
development of synthetic strategies for keeping the sites under
stable environment. The present computational study reveals that
among the singly exposed Cu atom (SS) and Cu atom in a 7 atom
cluster isomorphs(IS), IS was found to be relatively more stable.
Further, compared to higher coordinations, the lower coordination
sites (singly exposed) have greater stability under experimental
conditions. Further, for the singly exposed Cu atoms, two coordina-
tion is preferred to others. These at an applied potential of −0.35 V
which is comparatively lower than that of higher coordinative sites
results are obtained on the basis of binding energy, total Mulliken
453
charge on CO2 , adsorption distance from metal atom, electrostatic
potential map analysis, FMO calculations, PDOS, ADMP molecular
dynamics potential energy profile, energy minimisation of pure cat-
alyst and catalyst-CO2 configurations and free energy profile for
reduction. Based on the above results, the SS model of copper was
chosen to study the electrocatalytic reduction of CO2 to CO. The
present study helps to design any sub-nano level metal catalyst for
electrochemical reduction of CO2 to various value added chemicals.
Acknowledgements
We acknowledge Department of Science and Technology (DST),
India, for setting up the National Centre for Catalysis Research
(NCCR). The authors also acknowledge the High Performance Com-
puting Environment (HPCE), Indian Institute of Technology Madras
(IITM) for furnishing computational facilities. The author R. S. is
thankful to Council of Scientific and Industrial Research (CSIR)
for providing financial support vide., Ref. No. 08/117(0001)-2013-
EMR-I.
Appendix A. Supplementary data
Supplementary data associated with this article can be found, in
the online version, at http://dx.doi.org/10.1016/j.apsusc.2016.10.
174.
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