i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 4 4 1 8 e1 4 4 2 8

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Density functional and microkinetic study of CO2

hydrogenation to methanol on subnanometer Pd
cluster doped by transition metal (M¼ Cu, Ni, Pt,
Rh)

Adhitya Gandaryus Saputro a,b,*, Arifin Luthfi Maulana a,

Fadjar Fathurrahman a,b, Ganes Shukri a,b,
Muhammad Haris Mahyuddin a,b, Mohammad Kemal Agusta a,b,
Triati Dewi Kencana Wungu b,c, Hermawan Kresno Dipojono a,b
a
Advanced Functional Materials Research Group, Institut Teknologi Bandung, Jl.Ganesha 10, Bandung 40132,
Indonesia
b
Research Center for Nanosciences and Nanotechnology, Institut Teknologi Bandung, Jl. Ganesha 10, Bandung
40132, Indonesia
c
Nuclear Physics and Biophysics Research Division, Institut Teknologi Bandung, Jl.Ganesha 10, Bandung 40132,
Indonesia

highlights graphical abstract

The inclusion of transition metal

dopants enhances the activity of
Pdx cluster.

Pd6M clusters are more selective
toward the formate pathway.

Pd6Ni cluster has the best activity
for CO2 hydrogenation to
methanol.

article info abstract

Article history: We study the CO2 hydrogenation to methanol on subnanometer Pd7 and transition metal
Received 19 September 2020 doped Pd6M (M ¼ Cu, Ni, Pt, and Rh) clusters using a combination of density functional
Received in revised form theory and microkinetic calculations. We find that, in general, the inclusion of transition
30 January 2021 metal dopants could decrease the activation energy of several important elementary re-
Accepted 1 February 2021 actions. This condition results in a significant improvement in the activity of the catalyst,
Available online 25 February 2021 especially for the Pd6Ni cluster. We find that the Pd6M clusters are more selective toward
the formate pathway than the RWGS þ CO hydrogenation pathway. We also compare the
turnover frequency profiles of the clusters with that of the Cu(111) surface, representing

* Corresponding author. Advanced Functional Materials Research Group, Institut Teknologi Bandung, Jl.Ganesha 10, Bandung 40132,
Indonesia.
E-mail address: ganda@tf.itb.ac.id (A.G. Saputro).
https://doi.org/10.1016/j.ijhydene.2021.02.009
0360-3199/© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 4 4 1 8 e1 4 4 2 8
the standard industrial catalyst. We find that the Pd6Ni cluster can successfully overcome
Keywords:
the TOF of Cu(111) surface, even at the low-pressure condition.
CO2 hydrogenation
© 2021 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
Methanol
Subnanometer Pd cluster
Transition metal doping
Density functional theory
Microkinetic
Introduction
Recycling CO2 into liquid methanol (CH3OH) through a series
of hydrogenation reactions is among profitable CO2 utilization
schemes in which a valuable chemical can be produced while
simultaneously decreasing the amount of this excessive
greenhouse gas from our atmosphere [1e7]. Methanol can be
exclusively exploited as liquid fuel for direct methanol fuel
cells (DMFC) and inherently used as a mean of chemical
hydrogen storage [4]. By virtue of this approach, atomic
hydrogen can be stored at a higher volumetric density in a
more readily accessible manner.
Methanol synthesis via CO2 hydrogenation reaction is
normally performed at high pressure and high temperature
using Cu-based catalysts [8,9]. The operation condition is
rather taxing because of the relatively complicated conversion
process. The necessity originates from the very stable nature
of CO2 molecules. The inert CO2 often results in a weak
interaction between CO2 and the catalyst making the ambient
operation condition is almost insurmountable [10e12]. In
addition, several elementary reactions in the catalytic cycle
present further challenges as they commonly possess high
activation energy. To surmount these problems, searching for
a new catalyst that can work at a lower pressure is urgently
required considering this will be notably beneficial for the
development of the aforementioned CO2 utilization scheme.
The desired catalyst should be able to interact well with CO2
molecules as well as capable in decreasing the activation en-
ergies for several important steps in the CO2 hydrogenation
process.
We previously studied the catalytic activity of sub-
nanometer Pdx clusters toward methanol production from
CO2 hydrogenation [13]. The clusters have distinct function-
alities than large Pd islands. The islands supported over
transition metal oxide can only act as a site for H2 dissociation.
The spill over atomic hydrogen will react with a CO2 molecule
at the transition metal oxide or at the Pd/metal oxide interface
[14e16]. Different mechanisms occur on the subnanometer
Pdx clusters. Instead of being only as an H2 dissociation center,
Pdx clusters can also facilitate CO2 hydrogenation reactions
[13]. Calculated turnover frequencies for CO2 conversion to
methanol on Pdx clusters are comparable to that of the Cu-
based catalysts. Integrating subnanometer Pdx clusters in a
Pd/metal oxide-based system is expected to enhance the
catalytic activity even further. Owing to its unique function-
alities, the possibilities to improve the performance of this
subnanometer Pdx cluster catalysts are still widely open.
14419
One commonly adopted approach in engineering the
catalyst is to add impurities deliberately. Dopant addition to
the subnanometer metal cluster often results in many inter-
esting catalytic activities [17e19]. Motivated by this phenom-
enon, we attempt to add a dopant of transition metal element
M (M ¼ Cu, Ni, Pt, or Rh) to the subnanometer Pdx cluster in
pursuit of improving the catalytic activity of the cluster. These
elements are known to show excellent activities toward hy-
drogenation and dehydrogenation reactions [11,20e28]. The
inclusion of these M dopants has been proven to be capable in
enhancing the CO2 hydrogenation on Cu and Ni surfaces
[29e34]. Our previous studies also showed that these dopants
are able to promote the interaction between a CO2 molecule
and the subnanometer Pd cluster, allowing the molecule to be
bent and adsorbed with a bidentate adsorption configuration
[35]. Such interaction is expected to be responsible in boosting
the catalytic performance of this subnanometer Pd cluster
toward CO2 hydrogenation to methanol.
In this work, we perform a combination of density func-
tional theory (DFT) calculations and microkinetic simulation
to study the mechanism of CO2 hydrogenation to methanol on
the transition metal doped subnanometer Pdx clusters. To
compare with the currently used standard catalyst, the cata-
lytic activity of this catalyst model will be benchmarked with
the activity of Cu-based catalysts.
Computational details
We use Pd7 cluster structure from our previous study as the
basic model to represent the subnanometer Pdx cluster [13].
The size of this cluster is large enough to accommodate the
co-adsorption of CO2 hydrogenation-related reactants and
products. Such small size subnanometer metal and metal-
alloy clusters have been successfully synthesized using
various techniques such as soft-landed method, mass-
selected cluster deposition and atomic layer deposition
[18,36,37]. In a more realistic catalyst model, the sub-
nanometer Pdx cluster should be placed on a support material.
However, our previous study showed that the Pd7 cluster
maintained its original structure when it was deposited on a
metal oxide surface, even though there were some insignifi-
cant geometrical reconstructions induced by the corrugated
nature of the metal oxide surface [13]. We also showed that
the property of CO2 adsorption on this supported cluster did
not change in the presence of support material, although the
presence of high H coverage might possibly affect it. There-
fore, for the sake of simplicity, we will use the unsupported
14420 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 4 4 1 8 e1 4 4 2 8
subnanometer Pd7 cluster for modelling the CO2 hydrogena-
tion reactions.
We use DFT calculations to study the CO2 hydrogenation to
methanol on subnanometer Pd7 and Pd6M clusters. The DFT
calculations are performed using the Gaussian09 package. We
use similar calculation parameters as in our previous study
about CO2 conversion to methanol on small Pdx clusters [13].
The B3LYP functional is used as the exchange-correlation
potential. We also use the 6-311þþG** basis sets for light
atoms (H, C, and O) and the LANL2DZ basis sets with effective
core potentials for the transition metal atoms (Pd, Cu, Ni, Pt,
and Rh).
We construct the transition metal doped Pd7 model by
substituting one of the Pd atoms in the cluster with a transi-
tion metal atom M (Pd6M: M ¼ Cu, Ni, Pt, and Rh). This struc-
ture is then relaxed without any geometrical constraints. This
procedure is repeated for all the possible substitution sites on
the Pd7 structure. We then compare their total energies of
these Pd6M configurations. The configuration that gives the
lowest total energy is chosen as the model for the Pd6M
cluster. The location of substitutional sites of the M atom in
the Pd7 cluster and their relative energies are given in Fig. S1
and Table S1 of Electronic Supporting Information (ESI). The
most stable structures of the Pd6M clusters are presented in
Fig. 1aee. We also check the stability of Pd7 and Pd6M clusters
by calculating their formation energy (Eform ) by using the
following formula:
Eform ¼ EPd6 X  6* EPd  EX
where EPd6 X , EPd and EM correspond to the total energy of iso-
lated Pd6X cluster (X ¼ Pd, Cu, Ni, Pt, and Rh), Pd atom, and X
atom, respectively. The result in Table 1 shows that Pd6M
clusters have relatively lower formation energy than Pd7
cluster, indicating the stability of the formation of Pd6M
clusters.
The adsorption energy (Eads ) of a molecule on Pd6M cluster
is calculated using the following relation:


Eads ¼ Esystem  EPd6 M þ Emol ;
where Esystem corresponds to the total energy of an adsorption
Fig. 1 e The most stable structures of (a) Pd7, (b) Pd6Cu, (c) Pd6Ni, (d) Pd6Pt, and (e) Pd6Rh clusters and CO2 adsorption modes
on (f) Pd7, (g) Pd6Cu, (h) Pd6Ni, (i) Pd6Pt, and (j) Pd6Rh clusters.
Table 1 e The formation energy of Pd7 and Pd6M clusters.
Cluster Eform (eV)
Pd7 9.95
Pd6Cu 10.56
Pd6Ni 10.98
Pd6Pt 11.23
Pd6Rh 10.79
system, EPd6 M corresponds to the total energy of an isolated
Pd6M cluster, and Emol corresponds to the total energy of an
isolated molecule. The corresponding spin configurations for
the calculation of Esystem , EPd6M and Emol are set in their respec-
tive spin ground state configurations. Pd6M clusters are spin-
polarized systems, but spin contamination is considered to
be sufficiently small and does not affect the bond distances
because all the calculated < S2> values vary by less than 10% of
the corresponding ideal values.
The activation energy for an elementary reaction (Eact ) is
calculated by using the following formula:
Eact ¼ Ets  Eis ; (2)
where Ets and Eis correspond to the total energy of the initial
state and the transition state of the elementary reaction. The
reaction energy for an elementary reaction (DE) is defined as:
DE ¼ Efs  Eis ; (3)
where Efs corresponds to the total energy of the final state. The
structure and the energy of the transition state are calculated
using the synchronous transit-guided quasi-newton (STQN)
method. We affirm that the obtained transition state structure
only has one imaginary frequency. The geometry of the opti-
mized transition states and their respective imaginary fre-
quencies are given in Figs. S3eS5 of ESI.
The energetical data obtained from DFT calculations are
used as inputs for microkinetic simulations to obtain the turn-
over frequencies (TOFs) of CO2 hydrogenation to methanol on
Pd7 and Pd6M clusters. In treating the microkinetic model, the
(1)
ordinary differential equations (ODEs) are integrated numer-
ically. Details of the microkinetic model derivation for
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 4 4 1 8 e1 4 4 2 8 14421

Table 2 e Energetical data for elementary reactions involved in the CO2 hydrogenation to methanol through formate and
RWGS pathways. All energy are in eV. * and X* indicate a free adsorption site and an adsorbed X species on the cluster
surface.
No Elementary Reaction Pd7 Pd6Cu Pd6Ni Pd6Pt Pd6Rh
Eact DE Eact DE Eact DE Eact DE Eact DE
R0 H2(g) þ 2* / 2H* e 0.73 e 0.64 e 0.58 e 0.48 e 0.73
R1 CO2(g) þ * / CO2* e 0.21 e 0.45 e 0.40 e 0.10 e 0.24
R2a CO2* þ H* / HCOO* þ * 0.93 0.21 1.06 0.31 0.87 0.22 1.29 0.17 0.94 0.19
R3a HCOO* þ H* / HCOOH* þ * 1.16 0.94 1.05 1.05 1.05 0.72 1.15 0.87 1.19 1.02
R4a HCOOH* þ H* / H2COOH* þ * 1.39 0.33 0.99 0.11 0.41 0.19 1.42 0.99 1.12 0.60
R5a H2COOH* þ * / H2CO* þ OH* 1.00 0.92 0.79 0.72 0.57 0.49 0.69 0.16 0.17 0.17
R6a H2CO* þ OH* þ H*/ H2CO* þ H2O* þ * 0.00 1.23 0.43 0.98 0.14 1.15 0.24 0.12 0.56 0.67
R7a H2CO* þ H2O* / H2CO* þ H2O(g) þ * e 0.34 e 0.37 e 0.35 e 0.35 e 0.32
R2b CO2* þ H* / HOCO* þ * 1.90 0.39 1.92 0.48 0.80 0.27 1.19 0.61 1.71 0.22
R3b HOCO* þ * / CO* þ OH* 0.44 1.05 0.83 0.88 1.04 0.85 0.00 0.23 0.63 0.51
R4b CO* þ OH* þ H* / CO* þ H2O* þ * 1.26 0.17 1.12 0.22 0.71 0.47 1.13 0.03 0.84 0.28
R5b CO* þ H2O* / CO* þ H2O(g) þ * e 0.51 e 1.16 e 0.44 e 0.93 e 0.35
R6b CO* þ H* / HCO* þ * 1.44 1.26 1.55 1.49 1.58 1.13 1.32 1.31 1.39 1.05
R7b HCO* þ H* / H2CO* þ * 0.85 0.21 0.62 0.40 0.61 0.06 0.76 0.23 0.35 0.01
R8 H2CO* þ H* / H3CO* þ * 1.10 0.61 0.84 0.44 0.97 0.57 1.23 0.85 0.74 0.34
R9 H3CO* þ H* / CH3COH* þ * 1.06 0.67 0.46 0.77 0.43 0.78 0.67 0.71 0.93 0.70
R10 CH3OH * / CH3OH(g) þ * e 0.55 e 0.63 e 0.49 e 0.40 e 0.34
R11 HCOOH* / HCOOH(g) þ * e 0.50 e 0.55 e 0.43 e 0.26 e 0.31
R12 CO* / CO(g) þ * e 1.88 e 1.24 e 1.86 e 1.70 e 1.28

hydrogenation reaction can be found in Section 2 of ESI and
our recent works [13,32,38,39].
Results and discussions
The first step of CO2 hydrogenation process on the Pd cluster
is the reaction between the adsorbed CO2 molecule and H
atom. Therefore, the properties of CO2 adsorption on the
surface will play an important role in determining the nature
of CO2 hydrogenation reaction. The most stable CO2
adsorption configurations and adsorption energies on the
Pd7 and Pd6M clusters (ECO
ads ) are given in Fig. 1fej and Table 2
2 and their energy profiles are shown in Figs. 2 and 3, respec-
(ECO
ads is equivalent to DE in reaction R1), respectively. In
2
The process of CO2 hydrogenation to methanol is
composed of several complex elementary reactions. The
product of the first hydrogenation reaction (CO2* þ H*) will
dictate the type of hydrogenation pathways. The products of
this reaction are formate (HCOO*) and hydrocarboxyl
(HOCO*). CO2 hydrogenation to methanol through the for-
mation of formate is known as formate pathway while the
hydrogenation through the formation of hydrocarboxyl is
known as reversible water gas shift (RWGS) þ CO hydroge-
nation pathway. The elementary reactions and energetical
data involved in these two reaction pathways are presented in
Table 2. The schematic for these two hydrogenation pathways
tively. The formate pathway proceeds through the following

elementary reactions:
general, the inclusion of transition metal doping could in-
crease the CO2 adsorption energy and allow the CO2 to be

R0/R1/R2a/R3a/R4a/R5a/R6a/R7a/R8/
adsorbed with a bidentate configuration, except for the Pd6Pt
R9/R10,
case where the molecule adsorbed with a weak adsorption
energy while maintaining its initial linear structure. This
while the RWGS þ CO hydrogenation pathway proceed
result is consistent with our previous calculation which used
through the following elementary reactions:
smaller basis sets [35]. The formation of bidentate adsorp-
tion configuration on the Pd7 and Pd6M clusters is originated

R0/R1/R2b/R3b/R4b/R5b/R6b/R7b/R8/
from the interaction of d-orbitals of the cluster and lowest
R9/R10.
unoccupied antibonding molecular orbital (LUMO) of CO2
molecule. The occupancy of the antibonding orbital en-
A special care is needed for reaction R3a. Several studies
hances the repulsion between C and O atoms of CO2 mole-
suggest that reaction (3a) on Cu surface-based catalyst prefers
cule and disturbs the linearity of OeCeO angle. In the case of
dioxymethylene (H2COO) production instead of formic acid
the Pd6Pt cluster, the charge transferred to the CO2 molecule
(HCOOH) [40e42]. However, a recent theoretical study shows
is significantly smaller than that on the other Pd6M clusters,
that the formation of HCOOH* is more reasonable since it is
and this prevents the formation of CO2 bidentate adsorption
more stable than H2COO* [11]. Similar case also occurs on the
configuration on the Pd6Pt cluster [35]. The formation of
Pd6M clusters. Our calculation results suggest that HCOOH*
bidentate CO2 adsorption configuration is known to be able
adsorption is more stable than H2COO* adsorption (differs by
to facilitate the CO2 hydrogenation process on the sub-
1e2 eV). Therefore, we will only consider HCOOH* as the
nanometer Pdx cluster [13]. We expect that similar effect also
product of reaction R3a on Pd6M clusters.
occurs on the Pd6M cluster systems.
14422 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 4 4 1 8 e1 4 4 2 8
Fig. 2 e Schematic of reaction networks for CO2
hydrogenation to methanol on Pd7 and Pd6M clusters.
From Table 2, we can see that in general the inclusion of
transition metal doping could reduce the activation energies
of some elementary reactions of formate pathway with
respect to the undoped Pd7 cluster. Obviously, there will be
some exceptions such as in the case of reaction R2a (formate
formation) where the inclusion Cu and Pt doping increases the
activation energy of the reaction with respect to the Pd7
Fig. 3 e Potential energy profiles for CO2 hydrogenation to methanol through (a) formate and (b) RWGS þ CO hydrogenation
pathways.
cluster system. The highest activation energy for formate
pathway on the undoped Pd7 cluster (1.39 eV) originates from
reaction R4a, the formation of hydroxy methoxy intermediate
(H2COOH*) from the hydrogenation of formic acid (HCOOH).
We can see that the inclusion of transition metal doping
significantly reduces the activation energy of reaction R4a,
especially for the Pd6Ni cluster (0.41 eV). This shifts the
highest activation energy for Pd6Cu, Pd6Ni, and Pd6Rh clusters
to reaction R3a (formic acid formation), and to reaction R2a
(formate formation) for Pd6Pt cluster case. Interestingly, the
highest activation energies for formate pathway on the Pd6Cu
and Pd6Ni clusters (reaction R3a, both 1.05 eV) are still smaller
than that for the undoped Pd7 case (1.16 eV).
Similar trend also can be observed in the RWGS þ CO hy-
drogenation pathway. The highest activation energy for this
pathway on the undoped Pd7 cluster (1.90 eV) originates from
reaction R2b, the hydrogenation of CO2 into HOCO interme-
diate. The inclusion of transition metal doped decreases the
activation energy for R2b quite significantly, except for the
Pd6Cu case where the activation energy slightly increases of
about 0.02 eV. Similar as in the formate hydrogenation
pathway, the greatest reduction is again achieved in the Pd6Ni
cluster.
The Pd6Ni cluster system is very interesting because it can
greatly reduce the activation energies for important elemen-
tary reactions on both hydrogenation pathways as compared
to the other clusters, especially for reaction R4a and R2b. The
trend of activation energy for these reactions can be partially
explained by inspecting the structure of their transition states
(TS). All the TS structures of reactions R4a and R2b include the
desorption of the H atom from the cluster toward the adsor-
bed HCOOH and CO2, as shown in Figs. S3 and S4 of ESI. The
Pd6Ni cluster system has the lowest activation energies for
these reactions because this system has low H adsorption
energy (H adsorption energy is approximately half of the DE in
ad  0:5DE ), allowing the H atom to desorb
reaction R0, EH R0
easily from the cluster to facilitate the reaction as compared to
the other clusters. Interestingly, this mechanism does not
apply to the Pd6Pt cluster. While this cluster has the lowest H
adsorption energy among the other clusters, the activation
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 4 4 1 8 e1 4 4 2 8 14423

energies for reactions R4a and R2b on this cluster are quite
high, especially for reaction R4a. This is because, unlike the
other clusters, the Pd6Pt cluster in general also has the
weakest interactions with CO2 and HCOOH molecules, as
suggested by the value of their adsorption energy. This situ-
ation will greatly affect the TOF value for methanol formation
on Pd6Pt, as will be discussed in the next subsection.
TOF for CO2 hydrogenation to methanol
The profile of TOF as a function of temperature for CO2 hy-
drogenation to methanol on Pd7 and Pd6M clusters are shown
in Fig. 4a and b. The TOF is calculated at p ¼ 75 bar with CO2:H2
pressure ratio of 1:3. These are the typical reaction conditions
for methanol production on the standard Cu-based catalyst.
We also calculate the apparent activation energy (EApp ) from
the TOF profile to probe the dependence of the overall rate on
temperature using the following equation:
2 3
6vðln rÞ7 vln r
EApp
¼  R4   5 ¼ RT2
vT
v T
1
where R is the universal gas constant and T is temperature. r is
the lowest rate among all the elementary reactions, and it
defines the TOF (see Section 2 of ESI). Positive apparent acti-
vation energy implies that temperature increase would lead to
an increase in overall reaction rate. The profile of EApp for
formate and RWGSþCO hydrogenation pathways are shown
in Fig. 4c and d. The dynamics of the TOFs as a function of
temperature can be explained by the apparent activation en-
ergy plot. For example, we find that the TOF for RWGSþCO
hydrogenation pathway on Pd6Cu decreases at temperature
range of 550e690 K. At this range, we observe negative values
for the corresponding EApp , thus explaining why the TOF is
decreasing as the temperature is increased. The trend for the
remaining clusters and pathways can be interpreted similarly.
The inclusion of transition metal doping is indeed can
improve the TOF profile of the Pd7 cluster. The order of the TOF
trend for the formate pathway is Pd6Ni > Pd6Rh > Pd6Cu > Pd7 >-
Pd6Pt while the order for the RWGS þ CO hydrogenation
pathway is Pd6Rh > Pd6Pt > Pd6Ni > Pd7 > Pd6Cu. In general, the
TOFs for the formate pathway are always higher than those
for the RWGS þ CO hydrogenation pathway. This means that
the CO2 hydrogenation to methanol on Pd6M clusters is more
(4) selective toward the formate pathway. The best TOF profile for
the formate pathway is achieved in the Pd6Ni cluster, while for
the RWGS þ CO hydrogenation pathway is achieved in the
Pd6Rh cluster. The inclusion of Ni and Rh dopants could

Fig. 4 e TOF profile as a function temperature for CO2 hydrogenation to methanol through (a) formate and (b) RWGSþCO
hydrogenation pathways on Pd7 and Pd6M clusters. The TOF is calculated at p ¼ 75 bar with a CO2:H2 pressure ratio of a1:3.
The apparent activation energies for formate and RWGS þ CO hydrogenation pathways are shown in (c) and (d),
respectively.
14424 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 4 4 1 8 e1 4 4 2 8
significantly improve the TOF of the Pd7 cluster. This is
because the Pd6Ni and Pd6Rh clusters could decrease the
majority of the activation energies that are involved in both
reaction pathways.
The surface coverage of species involved in CO2 hydroge-
nation through formate and RWGS þ CO hydrogenation
pathways are presented in Fig. 5 and Fig. 6, respectively. The
surface coverage profiles for the formate pathway on Pd7 and
Pd6M clusters have a similar pattern, except for the Pd6Pt
cluster. The HCOO* coverage is high at the lower temperature
region, and the H* coverage and free site start to increase at
higher temperature region. The high HCOO* coverage at the
lower temperature region is caused by the high activation
energy for the HCOO hydrogenation reaction to HCOOH (R3a).
At higher temperatures, the clusters can overcome the barrier
for this reaction, and this results in the decrease of HCOO*
coverage and the increase in the free site, indicating the
continuation of hydrogenation reactions to methanol. For the
case of the RWGS þ CO hydrogenation pathway, the surface
coverage profiles on Pd7, Pd6Cu, and Pd6Ni clusters show an
interesting behaviour. The CO coverage on these surfaces is
very high even at lower temperature region. This situation
indicates the possibility of CO poisoning, which is supported
by the value of CO adsorption energies on these clusters (R12).
It explains why these clusters have quite low TOF for
RWGS þ CO hydrogenation pathway.
Now we discuss the profile for the Pd6Pt system which,
has low TOF for both CO2 hydrogenation pathways. The
surface coverage of species on the Pd6Pt cluster for both
reaction pathways has a similar profile (Figs. 5d and 6d):
Fig. 5 e The surface coverage for species involved in CO2 hydrogenation through the formate pathway on (a) Pd7, (b) Pd6Cu,
(c) Pd6Ni, (d) Pd6Pt, and (e) Pd6Rh clusters.
high H* coverage at lower temperature region and high free
site at higher temperature region. The high coverage of H*
at lower temperature region indicates only a small amount
of H* are consumed by CO2 to form HCOO (R2a) or HOCO
(R2b) since these steps require quite high activation en-
ergies (Eact > 1.2 eV). Moreover, since CO2 is only weakly
adsorbed on the Pd6Pt cluster, it might be desorbed from the
surface, and this process produces a free site. This explains
why Pd6Pt has a larger free site portion at lower tempera-
tures than the other clusters. At higher temperatures, the
Pd6Pt system could overcome the activation energies for
hydrogenation reactions, and hence more of the H* are
consumed, resulting in the decrease of H* coverage and the
increase of free site.
Comparison with Cu
In this subsection we compare the potential energy profile
of Pd6M clusters with that of Cu system, the standard in-
dustrial catalyst for CO2 hydrogenation to methanol. For
benchmarking purposes, we compare the activity of Pd7
and Pd6M clusters with Cu(111) surface. For the Cu(111)
surface case, the energetical data from Refs. [11,31] are
used as the input for our microkinetic simulation to obtain
the TOF. The TOFs are calculated per active site of each
catalyst, which makes it rational to compare the TOF be-
tween cluster and non-cluster catalysts in a more
straightforward manner. We also perform additional cal-
culations for Cu7 cluster to compare the activity of Cu
system with a similar size as the Pd7 and Pd6M clusters.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 4 4 1 8 e1 4 4 2 8 14425

Fig. 6 e The surface coverage for species involved in CO2 hydrogenation through the RWGSþCO hydrogenation pathway on
(a) Pd7, (b) Pd6Cu, (c) Pd6Ni, (d) Pd6Pt, and (e) Pd6Rh clusters.

The energetical data for the Cu7 cluster case are presented
in Table S3 of ESI. The comparison for these systems is
presented in Fig. 7. From the calculated TOF, we can
observe that Cu(111) surface prefers the formate pathway
over the RWGSþCO hydrogenation pathway. This trend is
in agreement with experimental and theoretical results
[11,31,43e45]. In contrast with the Cu(111) surface, the Cu7
cluster prefers the RWGSþCO hydrogenation pathway over
the formate pathway. Moreover, the TOF of the Cu7 cluster
for the formate pathway is significantly lower than the Pd7,
Pd6M, and Cu(111) surface. This is because some of the
important elementary steps on the Cu7 cluster have quite

Fig. 7 e TOF profile as a function temperature for CO2 hydrogenation to methanol through formate and RWGSþCO
hydrogenation pathways on Pd7, Pd6M, and Cu7 clusters and Cu(111) surface. The TOF is calculated at p ¼ 75 bar with a
CO2:H2 pressure ratio of 1:3.
14426 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 4 4 1 8 e1 4 4 2 8

high activation energies, especially for HCOOH formation

(R3a; Eact ¼ 1.59 eV) and CH3OH formation (R9; Eact-
¼ 1.80 eV) steps.
From the TOF comparison for formate pathway, we can see
that Pd6Ni cluster can overcame the TOF of Cu(111) surface for
formate pathway at temperature larger than 500 K. However,
the other clusters could not approach the TOF of the Cu(111)
surface, except for the Pd6Cu cluster which able to reach the
TOF of Cu(111) system at a quite high temperature (T ~ 800 K).
The Pd6Ni cluster could overcome the TOF of Cu(111) system
because it has smaller activation energies for some of
elementary reactions in the formate pathway, especially for
the rate-limiting reactions of Cu(111) surface: the H2COOH
dissociation (R5a) and H3CO hydrogenation (R9). The first re-
action, H2COOH dissociation, has an interesting feature on the
Cu(111) surface. This dissociation step has quite low activa- Fig. 8 e TOF profile as a function pressure for CO2
tion energy (0.74 eV) but the backward reaction has zero hydrogenation to methanol through formate pathway on
activation energy. This suggests that the dissociated state Pd6Ni cluster, Cu7 cluster, and Cu(111) surface. The TOF is
(H2CO þ OH) is energetically unstable and it prefers to go back calculated at T ¼ 523 K with a CO2:H2 pressure ratio of 1:3.
to its pre-dissociated state on the Cu(111) surface. Moreover,
the removal of the adsorbed OH through water formation on
Cu(111) also required a quite high activation energy (1.18 eV).
This suggests that the dissociation of H2COOH might be one of
the most important rate limiting reaction on Cu(111) surface. inclusion of transition metal doping could improve the cata-
If the adsorbed OH is not removed quick enough from the lytic activity of subnanometer Pd7 cluster. The activity of this
surface, the subsequent reaction, H2CO hydrogenation to subnanometer catalyst still can be further improved by opti-
H3CO (R8), cannot be proceed and this dissociated state most mizing several parameters such as cluster size, support ma-
likely will be reverted back to H2COOH. On the Pd6Ni cluster, terials (metal-oxide based surface), and doping composition
this reaction has lower activation energy (0.57 eV). However, [13,15,16,33,46e52].
the activation energy for the backward reaction is relatively
larger than that on the Cu(111) surface (0.08 eV). Depending on
the reaction conditions, this will hinder the spontaneous Summary
backward reaction to reform the H2COOH. Moreover, water
formation from OH hydrogenation on these clusters is much We report on a theoretical study of CO2 hydrogenation to
easier (0.14 eV) than that on the Cu(111) surface. Therefore, methanol on Pd7 and transition metal doped subnanometer
the subsequent hydrogenation of H2CO could proceed rela- Pd6M clusters using the combination of DFT and microkinetic
tively easier on this cluster than that on the Cu(111) surface. calculations. We find that in general, the inclusion of transi-
The second reaction, H3CO hydrogenation into CH3OH (R9), is tion metal doping could decrease the activation energies of
known as the main rate-limiting reaction on Cu(111) surface elementary reactions on Pd7, and this results in a significant
(Eact ¼ 1.17e1.25 eV) [11,31], and similar behaviour also occurs improvement in its catalytic activity, especially in the case of
in the Cu7 cluster. However, the activation barriers for this the Pd6Ni cluster. We also find that the Pd6M clusters are in
reaction on Pd6Ni clusters is much lower low (0.43 eV). This is general, more selective toward the formate pathway than the
because the profiles of H3CO hydrogenation on Pd6M clusters RWGS þ CO hydrogenation pathway.
are more exothermic due to the stabilization of CH3OH We also find that only the Pd6Ni cluster system can suc-
adsorption which is caused by the strong cluster-adsorbate cessfully overcome the TOF of Cu(111) surface, which repre-
interaction [13]. sents the standard industrial catalyst. The Pd6Ni cluster has
One of the goal in the development of new CO2 hydroge- better TOF profiles than the Cu(111) surface for the formate
nation to methanol catalyst is to find a catalyst that can work pathway, even at lower pressure conditions. This suggests
at lower pressure than the standard Cu-based catalyst. We that the subnanometer Pd6Ni cluster is a potential catalyst for
plot the TOF of Pd6Ni as a function of pressure in Fig. 8. The CO2 hydrogenation to methanol. The activity of this sub-
TOFs of Cu(111) surface and Cu7 cluster are calculated at 523 K, nanometer catalyst can be further improved by optimizing
a typical temperature for methanol production on the stan- several parameters such as cluster size, support materials,
dard Cu-based catalyst. We can see from the figure that the and doping composition.
TOF for the Pd6Ni system is still better than the Cu(111) surface
even at lower pressure region. This suggests that the Pd6Ni
also has a potential to be used as a low-pressure catalyst for Declaration of competing interest
CO2 hydrogenation to methanol.
All of the above comparisons indicate that the sub- The authors declare that they have no known competing
nanometer Pd6Ni cluster is indeed a potential catalyst for CO2 financial interests or personal relationships that could have
hydrogenation to methanol. This result also proves that the appeared to influence the work reported in this paper.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 6 ( 2 0 2 1 ) 1 4 4 1 8 e1 4 4 2 8
Acknowledgement
This work is partially supported by Institut Teknologi Ban-
dung through the “Riset KK B” program, the Ministry of Edu-
cation and Culture, and the Ministry of Research and
Technology of Republic of Indonesia, under the grant scheme
“Penelitian Dasar Unggulan Perguruan Tinggi (PDUPT) 2020”,
“Insentif Riset Nasional, INSINAS”, and the WCU Program
managed by ITB.
Appendix A. Supplementary data
Supplementary data to this article can be found online at
https://doi.org/10.1016/j.ijhydene.2021.02.009.
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