Journal of Catalysis 360 (2018) 168–174

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Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat

Ab initio study of CO2 hydrogenation mechanisms on inverse ZnO/Cu

catalysts q
Thomas Reichenbach a, Krishnakanta Mondal a, Marc Jäger a,c, Thomas Vent-Schmidt a,c, Daniel Himmel a,c,
Valentin Dybbert a,c, Albert Bruix d, Ingo Krossing a,c, Michael Walter a,b,⇑, Michael Moseler a,b
a
Freiburger Materialforschungszentrum, Stefan-Meier-Str. 21, 79104 Freiburg, Germany
b
Physikalisches Institut, Universität Freiburg, Herrmann-Herder-Str. 3, 79104 Freiburg, Germany
c
Institut für Anorganische und Analytische Chemie, Universität Freiburg, Albertstr. 21, 79104 Freiburg, Germany
d
Interdisciplinary Nanoscience Center (iNANO), Department of Physics and Astronomy, Aarhus University, DK-8000 Aarhus C, Denmark

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

Article history: Methanol formation from CO2 and molecular hydrogen on ZnO/Cu catalysts is studied by gradient cor-
Received 6 November 2017 rected density functional theory. The catalytically active region is modeled as a minimum size inverse
Revised 19 January 2018 catalyst represented by ZnXOY(H) clusters of different size and a ZnO nano-ribbon on an extended Cu
Accepted 30 January 2018
(1 1 1) surface. These systems are chosen as a representative of thermodynamically stable catalyst struc-
tures under typical reaction conditions. Comparison to a high level wave function method reveals that
density functional theory systematically underestimates reaction barriers, but nevertheless conserves
Keywords:
their energetic ordering. In contrast to other metal-supported oxides like ceria and zirconia, the reaction
Inverse catalyst
methanol
proceeds through the formation of formate on ZnOX/Cu, thus avoiding the CO intermediate. The differ-
CO2 ence between the oxides is attributed to variance in the initial activation of CO2. The energetics of the
Renewable energy formate reaction pathway is insensitive to the exact environment of undercoordinated Zn active sites,
hydrogenation which points to a general mechanism for Cu-Zn based catalysts.
DFT Ó 2018 Elsevier Inc. All rights reserved.
Coupled cluster

1. Introduction
Mankind is facing considerable challenges in their quest to
secure sufficient energy supply for the future and to solve the glo-
bal warming problem [1]. Future energy sources have to be renew-
ables. Most of all wind and solar energy already cover an
unexpectedly large part of our energy production and are likely
to dominate the energy market in near future. However, renewable
energies are often produced when they are not needed while their
production is low at times of large demand. Therefore, large scale
effective energy storage is needed. Electric energy can be used to
split water resulting in H2 as energy carrier. Since molecular hydro-
gen is delicate to handle, it should be processed further. The syn-
thesis of the base chemical methanol (currently produced from
q
Supplementary Material (SM) available: [Details of the computational method-
ology, the global minima search and comparison to (DLPNO-)CCSD(T) calculations.
Methodology for the inclusion of thermodynamics. Evaluation of the crucial steps
using different models. Structure of the nano-ribbons. Wannier orbitals analysis of
CO2. Energetics and structures of the full reaction network.]
⇑ Corresponding author at: Freiburger Materialforschungszentrum, Stefan-Meier-
Str. 21, 79104 Freiburg, Germany.
E-mail address: Michael.Walter@fmf.uni-freiburg.de (M. Walter).
fossil resources) from the greenhouse gas CO2 and H2 is a promis-
ing strategy to store renewable energy and produce a chemical
feedstock (CO2 + 3H2 ! CH3OH + H2O) [2,3]. Contrary to H2,
methanol is liquid at room temperature and thus it can easily be
stored, transported and further processed e.g. to oxymethylenedi-
methylethers (a novel class of fuels that promises rich applications
[4]). Furthermore, conversion of CO2 to methanol is of great envi-
ronmental relevance as a strategy for reducing the concentration
of this anthropogenic green house gas in the atmosphere [5,6].
The catalyst used for synthesizing methanol from synthesis gas
(syngas) containing CO and CO2 on industrial scale corresponds to
composites of Cu/ZnO/Al2O3 [7–9] and the role and interplay of the
different components under reaction conditions are under active
debate. Some studies claim that the active phase corresponds to
the CuZn alloy formed under reaction conditions upon the partial
reduction of the ZnO phase [10,9,11]. In contrast, industrial cata-
lysts were reported to contain a ZnOX-overlayer on metallic Cu-
nanoparticles [7] and recent experimental results show evidence
of an improved catalytic activity [12,13] of ZnOX particles on Cu
(1 1 1) as compared to the conventional metal-on-oxide configura-
tion [14–16]. These results strongly suggest that the active sites in
methanol synthesis catalysts correspond to the ZnO phase or to the
ZnO-Cu interface [8,12,7,17,18,13]. In addition to their often supe-

https://doi.org/10.1016/j.jcat.2018.01.035
0021-9517/Ó 2018 Elsevier Inc. All rights reserved.
 T. Reichenbach et al. / Journal of Catalysis 360 (2018) 168–174
rior activity, inverse catalysts have become a valuable tool for
investigating reaction mechanisms and the role of the oxide and
the metal-oxide interface [19–22]. Similarly, recent density func-
tional theory studies of supported oxide-clusters-models brought
new insights to the catalytic activity of PtCo/TiO2 and PtCo/ZrO2-
catalysts regarding CO2-hydrogenation [23]. The CeOX/Cu(1 1 1)-
system was reported to show an even superior performance as
compared to ZnOX/Cu(1 11 ), with the reaction mechanism consist-
ing of a reverse water–gas shift (RWGS, CO2+H2 ! CO + H2O) fol-
lowed by the CO hydrogenation (CO + 2H2 ! CH3OH) [19]. A
similar reaction path was recently proposed on Cu supported
ZrO2 and on TiO2 [24]. In contrast, the majority of theoretical and
experimental investigations indicate that the hydrogenation of
CO2 does not proceed through a CO-intermediate using Cu/ZnO
catalysts [8,25,18,26,27,13]. Although the ZnOX/Cu(1 1 1) was
already suggested and explored in early experiments [12,28], only
very recently a copper supported Zn6(OH)7 structure was consid-
ered as possible catalyst [13]. Our work further rationalizes the
importance of such structures, explores their global minima struc-
ture, and shows the broad independence of the results from the
explicit size and composition of the reduced ZnO/Cu inverse
catalyst.
2. Computational setup
We have explored the complex reaction network for methanol
synthesis catalyzed by Cu-supported zinc oxide by means of ab ini-
tio modeling. Because of the heavy computational burden of the
high level quantum chemistry, we use the smallest possible sup-
ported zinc oxide unit that still describes the relevant reactions.
Methods based on density functional theory (DFT) are used for
large scale electronic structure calculations of nanostructures sup-
ported by extended surfaces. The accuracy of these calculations is
verified by comparing the DFT energetics of gas-phase reactions
and a subset of catalytic processes with the Coupled Cluster
method (CCSD(T)), the gold standard of quantum chemistry, that
is considered to give accurate agreement with experiment [29–
32] if numerical settings are converged [33,34].
The main part of the calculations use the projector augmented
wave method as implemented in GPAW [35,36] where the wave
functions are represented on real space grids with grid spacing
h  0:18 Å. The exchange correlation energy is modeled in the gen-
eralized gradient approximation as proposed by Perdew, Burke and
Ernzerhof (PBE) [37]. We contrast these results using the BEEF-
vdW-functional [38], which is better suited for van der Waals con-
tributions. A detailed description of the methods applied and
parameters chosen can be found in Supplemantary Material (SM).
3. Discussion
As the first step, we have searched for global minima of the ZnX-
OY/Cu(111)-system using a recently implemented genetic algo-
rithm [39,40] in the size range X ¼ 3  9 and selected Y. The
ZnXOY units were modeled on a continuous Cu(111) slab to take
into account the metallic nature of the copper support. This study
revealed that the typical ZnO/Cu-interface can be conveniently
approximated by a Zn3O-unit, i.e. a reduced form of ZnO, c.f.
Fig. 1. Interestingly, the Zn3O-unit is part of the bulk ZnO wurtzite
structure and this structural motif can also be found in ZnO over-
layers in industrial Cu/ZnO catalysts under certain conditions [7].
Larger ZnXOY units show similar motifs and additional oxygen
atoms do not improve stability (see Supplementary Material for
details). According to our ab initio thermodynamics analysis,
zinc-oxide is strongly reduced at typical reaction conditions [8],
such that Zn3O and Zn7O3 from Fig. 1 are thermodynamically stable
169
Zn3O Zn7O3 Zn9O7 W3
Fig. 1. Global minima structures of Zn3O, Zn7O3, Zn9O7 and a zigzag edge ZnO nano-
ribbon (W3) supported on Cu(111). Zn: light blue, O: red, Cu: brown. (For
interpretation of the references to colour in this figure legend, the reader is
referred to the web version of this article.)
forms. This results in a stabilized Zn3O unit on the extended Cu
(111) surface as a minimal model for ZnO/Cu catalysts. A more
detailed description of the full thermodynamic analysis performed
is in preparation and will be published elsewhere.
In the next step, reaction pathways and transition barriers for
methanol formation catalyzed by Zn3O/Cu(111) are determined.
However, before studying the entire reaction network the applica-
bility of DFT was verified.
The PBE functional is able to predict the relevant gas-phase
energetics in good agreement to CCSD(T), DLPNO-CCSD(T) [42–
49] (see SM for the details) and experiment as is shown in Table 1,
where BEEF-vdW performs much worse [50,51]. The only excep-
tion is RWGS with a deviation of 0:45eV with respect to experi-
ment. This error can be attributed to a destabilization of gas-
phase CO by the PBE functional [52]. Accordingly, CO adsorption
on Cu(111) is known to be overestimated within the generalised
gradient approximation (GGA) by 0.32–0.41 eV [53]. The erroneous
gas-phase CO energetics in GGAs is therefore not to be expected to
affect the energetic ordering of supported species discussed below
and a correction [51] is not needed.
DFT within the generalized gradient approximation is also
known to underestimate reaction barriers [54,55] (database tests
for catalysis showed mean signed errors of PBE up to 0:59 eV
[56]), however. In order to approve the accuracy and applicability
of our DFT approach in the present systems we have performed
single point high level DLPNO-CCSD(T) quantum chemistry calcu-
lations for selected key reactions. DLPNO-CCSD(T) is computation-
ally very demanding such that the reactions have to be described
on a copper cluster model of finite size.
We have chosen the Cu4Zn3O cluster as structural model (see
lower panels of Fig. 2 a). The four Cu-atoms were fixed using the
experimental lattice constant 3:61 Å of bulk Cu to imitate the Cu
(111)-surface [57], while the supported Zn3O and the adsorbates
were relaxed using PBE. The values reported for BEEF-vdW and
for DLPNO-CCSD(T) were obtained from subsequent single-point
calculations.
Four key reaction steps have been chosen as benchmark. A: ini-
tial transition of CO2 from a linear to a bent configuration, B:
hydrogenation of oxygen in a carboxyl intermediate, C: second
hydrogenation of an HCO intermediate and D: hydrogenation of
the carbon atom in the carboxyl group. The energetics was deter-
mined for the Zn3OCu4 cluster model as well as for the Zn3O/Cu
(111) extended surface model for all four test reactions. The differ-
ences between the energies of the initial state EIS and the final state
EFS compare reasonably well between all computational
approaches on the cluster model, i.e. these energy differences are
fairly well described by DFT.
The most important quantities are the barriers determined by
their corresponding transition state energy ETS . These were deter-
mined by the nudged elastic band method [58] combined with a
climbing image condition [59]. Fig. 2 shows both forward
(ETS  EIS ) and backward barriers (ETS  EFS ) for the chosen reac-
tions. The predicted barrier heights from PBE and BEEF-vdW are
170 T. Reichenbach et al. / Journal of Catalysis 360 (2018) 168–174

Fig. 2. Selected reactions and barrier heights computed by different ab initio methods. a) The structures for initial (IS), transition (TS) and final states (FS) for the surface and
corresponding cluster models. (b) Energetic differences between final and initial state, (c) forward barriers (from initial to transition state) and (d) backward barriers (from
final to transition state). Energies are in eV (1 eV = 96.49 kJ/mol). Zn: light blue, O: red, Cu: brown, C:grey, H: white. (For interpretation of the references to colour in this figure
legend, the reader is referred to the web version of this article.)

Table 1
Electronic energy differences of gas phase reactions compared to experimental data [41] corrected for thermodynamic and zero point energy contributions (uncorrected values
are given in brackets). Ensemble estimate errors [38] are given for BEEF-vdW. See Supplementary Material for the computational procedure.

Reaction corr. Exp. (Exp.) CCSD(T) DLPNO-CCSD(T) PBE BEEF-vdW

H2+CO2 ! H2O + CO 0.31 (0.43) 0.24 0.21 0.76 0.740.13
H2+CO2 ! HCOOH 0.08 (0.15) 0.12 0.12 0.10 0.110.12
2H2+CO2 ! H2O + H2CO 0.10 (0.45) 0.03 0.01 0.18 0.410.13
3H2+CO2 ! H2O + CH3OH 1.16 (0.51) 1.24 1.27 1.10 0.610.20

very similar. The latter gives slightly higher values in particular for
the backward barriers of steps C and D, where both H2CO and
HCOOH are van der Waals bonded to Zn3O. The DFT results system-
atically underestimate the barriers predicted by DLPNO-CCSD(T),
in particular the PBE values lie approximately 0:5 eV below
DLPNO-CCSD(T). Despite its good description of transition state
energies for dissociation on transition metal surfaces [60,61]
BEEF-vdW generally has the same tendency, but improves in cases
where van der Waals contributions are important [62]. The under-
estimation is rather independent of the reaction itself such that the
relative heights of the DFT barriers generally show good qualitative
agreement to DLPNO-CCSD(T). Most importantly, the ordering of
the barriers is not changed. We therefore conclude that the DFT
description of the underlying processes is qualitatively correct
and can indeed be used to determine the most probable reaction
path.
Some larger variations can be observed when the cluster model
is compared to the surface model. The deviation between the mod-
els is largest for steps C and D, in particular for the ETS  EIS term.
The energy difference in these configurations is caused by the
hydrogen atom that is attached solely to copper, a situation that
obviously is poorly represented by the Cu4 cluster in comparison
to the extended Cu(111) surface. The Cu4 cluster cannot account
for the metallic nature of the copper surface due to its molecule
like orbitals that do not resemble a band structure. Otherwise,
the cluster model captures the main features of the reactions on
the surface model, particularly those related to the ZnO-part,
where the reaction steps take place.
We proceed to investigate various possible reaction pathways
[63,64] on the Zn3O/Cu(111) surface model (depicted schemati-
cally in Fig. 3) employing PBE gradient corrections. Since H2 is pre-
sent in large quantities during the reaction, the adsorption of
hydrogen atoms on various sites is considered. We find that hydro-
gen adsorption is energetically favored only on the O-atom of the
Zn3O-unit. Therefore, one hydrogen atom on top of the oxygen is
included resulting in an additional Zn3OH/Cu(111) surface model
(see SM for details). All reaction steps are also explored on the
Zn3O/Cu(111) models where only marginal deviations to Zn3OH/
Cu(111) are found as detailed below. The reactions need many dis-
sociated hydrogen atoms that are considered to be available on the
Cu(111) surface under reaction conditions [8] (despite a small pos-
itive Gibbs free energy difference DG ¼ 0:15 V). Gibbs free energies
are calculated using ab initio thermodynamics at T = 500 K, 40 bars
of H2, 10 bars CO2 and 1 bar of methanol, CO and H2O, correspond-
ing to the operating conditions for ZnO/Cu catalysts. While changes
in these parameters might strongly influence reaction rates [3],
their influence on the calculated energetics is rather small.
All reaction routes, except the lowest energy pathway, start
with an initial activation of CO2 by transforming it to a bent config-
uration with the carbon atom attached to the Cu support and one
of the oxygen atoms to Zn. This bent configuration is typical for
reductive CO2 activation by hetero-bimetallic systems and was
observed in manifold for molecular systems in organometallic cat-
alysts. This may lead to either activation [65] or even a complete
disruption of the C = O bond in CO2 and subsequent formation of
a M-O-M0 -CO system [66]. In contrast to these coordination com-
plexes and other oxides [19,24] this configuration is energetically
unfavorable on reduced zinc-oxide and leads to relatively large
barriers. Combined with the loss of entropy upon adsorption,
1.07 eV is required to activate CO2 in this way. The corresponding
backward reaction CO2⁄⁄!CO2⁄ is barrier-less (0:01 eV) such that
a further forward barrier of 0.58 eV has to be overcome in order to
bind H⁄ to oxygen, resulting in a total barrier of 1.64 eV (see Fig. 3).
Splitting off CO in the RWGS reaction needs up to 2:08 eV. The
alternative trans-COOH pathway is strongly hindered energeti-
cally, having to overcome an effective barrier of 2.96 eV due to
insufficient stabilization of reaction intermediates (see SM for the
energetics of the whole reaction network). These reaction paths
are thus rather improbable on the Cu/ZnO system.
We have further investigated the initial activation of CO2 by
analyzing the corresponding Wannier orbitals, shown in Fig. 4.
Wannier orbitals are formed from the occupied Kohn-Sham orbi-
 T. Reichenbach et al. / Journal of Catalysis 360 (2018) 168–174
Fig. 3. Schematic view of the reaction pathways investigated in this article. The
most important barriers are indicated and their height on Zn3OH/Cu(111) and Zn3O/
Cu(111) [in square brackets] is given. The favored path connected through blue
arrows is highlighted, the highest barriers of the excluded paths are marked red,
while the highest barriers of the most probable path are depicted in green. Only the
metal atoms participating in bonds with the reactants are indicated. (For interpre-
tation of the references to colour in this figure legend, the reader is referred to the
web version of this article.)
tals and are required to be maximally spatially localized [67,36,68].
This lets the orbitals to appear like bonds as can be seen in the
molecular examples in Fig. 4. While there is a single bond between
the carbon and one of the oxygen atoms in formic acid, there are
only double bonds between C and O in the formate ion and CO 2.
A similar Wannier analysis of the surface species shows that the
initial activation of CO2 between Zn and Ce or Zr is indeed differ-
ent: The bonding Wannier orbitals of CO2 on Zn are similar to
the formate ion on the Zn3OH cluster both in the straight and the
bent configuration. A comparison of the bond lengths given in
Table 2 supports the assignment of CO double bonds in particular
for the straight configuration. While a Bader charge analysis
[69,70] given in Table 2 reveals straight CO2 to be neutral, the bent
configuration is charged by 0.7 electrons which is partly received
from the neighboring Zn. Replacing the binding zinc atom by a cer-
ium atom, largely stabilizes the bent configuration [19] (Table 2).
The activation on Ce has much more covalent character as indi-
cated by the corresponding Wannier orbitals, which resemble for-
mic acid more closely. Again, the bond lengths agree with a
primarily single CO bond for the oxygen attached to Ce. An even
further enhanced energetic preference of the bent configuration
171
Fig. 4. (a) Definition of bond lengths du ; dM and CO2 angle h for the values listed in
Table 2. (b) Wannier orbitals of [CO2], [HCOO] (formate) and HCOOH (formic
acid), and CO2 bound straight to Zn, bent to Zn, Ce and Zr in the surface model. Only
the binding metal atoms of the surface model are colored. Wannier orbitals
corresponding to triple bonds are depicted in green, double bonds are depicted in
yellow and Wannier orbitals corresponding to single bonds in blue. Representative
formal Lewis structures are depicted below. O:red, C:gray, Cu: brown, Zn: light blue,
Ce: light yellow, Zr: cyan. (For interpretation of the references to colour in this
figure legend, the reader is referred to the web version of this article.)
accompanied by similar Wannier orbitals is found for a replace-
ment of the binding Zn with zirconium, which relates to the ability
of this element to directly split CO2 in organometallic complexes
[66]. ZrO2 is used as support to enhance activity in methanol for-
mation [3], but is also considered as active material for methanol
synthesis itself [24]. Otherwise, Ce and Zr are very similar, both
in their effect on bent CO2 as well as in their Bader charge, indicat-
ing that these are in a similar oxidation state in this reduced envi-
ronment modeled here. The strength of the CO2-metal bond
correlates with the main oxidation state of the metal atom that
is Zn(II), Ce(III), and Zr(IV), respectively. These results thus eluci-
date the electronic structure origin of the different bonding mech-
anisms for CO2 on supported oxides (see SM for further details).
The initial bonding preference of CO2 results in a situation
where the mechanism with the lowest maximum barrier is the for-
mate pathway, that is initiated via a direct hydrogenation of a van
der Waals bonded CO2 molecule on a Zn atom. The energetics of
the full reaction path on Zn3OH/Cu(111) is given in part a) of
Fig. 5. While intermediates of this pathway are exclusively bonded
to zinc, copper acts mainly as a hydrogen reservoir and helps to
reduce zinc-oxide in the Cu-Zn interface region. We consider
hydrogen to be already pre-dissociated in sufficient amount [8]
and immediately available for the reaction due to its low diffusion
barrier of 0.14 eV on the copper surface [71]. This initial hydro-
genation leads to formation of the formate intermediate in agree-
ment to what is proposed in the literature for Zn atoms in Cu
steps [8,18] or on copper clusters [26,72]. Formate attached to
the Zn3OH cluster is very stable such that the subsequent hydro-
genation step represents the highest barrier in the full reaction
path in agreement with recent experimental results [25]. The
hydrogenation might happen either at the carbon or at one of
the oxygen atoms with very comparable barriers of 1.28 eV and
1.20 eV, respectively (both barriers are lower than the initial barri-
ers of the other pathways discussed above). The latter process is
thus slightly preferred, but leads to formic acid (HCOOH) that
can desorb to the gas-phase. Further hydrogenation leads to H2-
COOH in both cases which is split into water (H2O) and formalde-
hyde (H2CO) after another hydrogenation step. H2CO might then
desorb to the gas-phase. Hydrogenation of the C atom in formalde-
172 T. Reichenbach et al. / Journal of Catalysis 360 (2018) 168–174

Table 2
Atomic distances du ; dM in Å, CO2 angle h in degrees, CO2 adsorption energy (negative energies are exothermic) Eads in eV and the Bader charge on the CO2-part qCO2 and on the
metal atom qM in unit charges for the molecules in different configurations (see Fig. 4 for the labelling). The values are given for the MZn2OH and the MZn2O model [in square
brackets].

du dM h Eads qCO2 qM

CO2 1.18 1.18 180 0

[CO2] 1.23 1.23 141 1
[HCOO] 1.26 1.26 131 0.9
cis-HCOOH 1.21 1.36 122 0.7
M = Zn straight 1.17 [1.17] 1.18 [1.18] 179 [180] 0.12 [0.11] 0 [0] 0.4 [0.6]
M = Zn bent 1.23 [1.23] 1.28 [1.27] 131 [131] 0.35 [0.47] 0.7 [-0.7] 0.7 [0.8]
M = Ce bent 1.27 [1.23] 1.31 [1.33] 118 [122] 0.61 [0.65] 1.0 [0.9] 1.9 [1.8]
M = Zr bent 1.25 [1.24] 1.33 [1.32] 121 [123] 0.72 [0.93] 1.0 [0.9] 1.9 [1.9]

Fig. 5. a) Reaction pathway of CO2 hydrogenation to methanol on the Zn3OH/Cu(111)-system and the Gibbs free energy diagram calculated at T = 500 K and partial pressures
of 40; 10; 1; 1, and 1 bars of H2, CO2, methanol, CO, and H2O, respectively. All energies are relative to CO2 in the gas phase, 6H⁄/Cu(111) far from ZnO and the bare cluster
Zn3OH/Cu(111). Gas-phase species are marked by (g), while molecules marked with ⁄ are adsorbed. In addition, energy levels of transition states are denoted with the
corresponding forward barrier. Only the metal atoms participating in bonds with the reactants are indicated. (b) Electronic energies of the rate limiting barriers enclosed in
the orange rectangle in (a) for different model structures. (c) Structure of H2CO2 intermediates on Zn7O3H and Zn7O3.

hyde proceeds via a surprisingly low barrier (0.14 eV) leading to
the strongly bound CH3O radical that reacts to the methanol pro-
duct with an activation energy of 0.70 eV.
The rate limiting step for methanol synthesis on the ZnOH/Cu
(111) is the hydrogenation of formate towards H2COOH in agree-
ment to the literature [8,63,13]. To validate the universality of this
minimal model, we have investigated this main step in the reaction
path as well as the energetics of the CO2 activation also on Zn7O3(-
H)/Cu(111)) and on a nano-ribbon supported on Cu(111) generated
by cutting a planar ZnO sheet [73–76] along the zigzag edge. The
ribbon is three ZnO units wide and the reactions are considered
on the Zn terminated edge that resembles the Zn3O motif (see
Fig. 1). The reaction barriers compared in Fig. 5 b) are very similar
on all systems with the overall barrier ranging from 1.30 eV (Zn7-
O3H) to 1.67 eV (Zn3O). The lowest barrier for formate hydrogena-
tion is found on Zn7O3H where the reaction product H2CO2 finds a
low energy binding configuration thus lowering the barrier accord-
ing to the Bell-Evans-Polanyi principle [77,78] [see Fig. 5 c) for the
‘‘usual” binding motif on Zn7O3 vs. the special case of Zn7O3H]. This
exceptionally strong bonding in turn increases the barrier for the
next hydrogenation step and thus leads to a similar overall barrier
of 1.30 eV as in the other models. Similarly, none of the models sta-
bilizes activated CO2 significantly (see Table S2 in SM) underlining
the generality and the importance of the initial activation for selec-
tion of the formate path.
4. Conclusions
In conclusion, our ZnXOYH/Cu(111) and ZnO-nanoribbon/Cu
(111) models for the industrial ZnOX/Cu catalyst show that the
reaction proceeds via the formate pathway, thus avoiding CO inter-
mediates. This finding is in agreement with studies using isotopi-
cally labeled CO2 species [79], showing that methanol is formed
solely from CO2, and is in contrast to theoretical results for ceria
based catalysts that favor the reverse water gas shift reaction path.
This indicates that the preferred reaction mechanism of methanol
formation can be changed by varying the oxide (e.g. from ZnOX to
CeOX) - a result that was already suspected in literature [2]. The
difference between the oxides can be traced back to the altered
ability of the more positively charged metal to stabilize a delocal-
ized formiate (Zn) or localized Cu-C(=O)-O-M structure (M = Zr,
Ce). Thus, the higher charged metals in higher oxidation states
 T. Reichenbach et al. / Journal of Catalysis 360 (2018) 168–174
(III, IV) naturally seek for a localized structure as for example found
in Zr(IV)-carboxylates [80], while the less charged Zn(II) seeks a
delocalized environment as found frequently in the paddle wheel
structures [M2(O2CR)4] of the 3d-series (M = Cr-Zn) [81].
It is relevant to highlight that the reaction mechanisms on other
systems involving under-coordinated Zn sites such as the Zn-
terminated ZnO(0001) surface [82] and CuZn alloy stepped sur-
faces [8] were also found to proceed through the formate path;
we have checked that the initial CO2 binding energy as well as
the rate determinating barriers in Fig. 5 (HCOO !H2CO2) are very
similar for various reduced ZnO structures supported on Cu(111)
(see SM). Our results are robust against changes in the form and
size of the reduced zinc-oxide. These similarities suggest that the
reaction path found is generally the same on any under-
coordinated Zn sites in ZnO/Cu catalysts, i.e. in the border region
of a real ZnO catalyst in contact with metallic copper.
The gain in entropy in the gas-phase causes all stable species
(CO2, CO, HCOOH, H2CO, H3COH, and H2O) to desorb. While this
effect helps preventing water poisoning, desorption simultane-
ously drops the methanol formation rate as it competes with the
reactions HCOOH!H2COOH and H2CO!H3CO. Decreasing the
reaction temperature helps in this respect, but also hinders over-
coming the reaction barriers.
A promising strategy to improve the catalyst could involve
reducing the highest barrier in the main reaction pathway, i.e.
the hydrogenation of formate. Therefore, substrate modifications
that either bind formate more weakly or H2CO2 more strongly
could improve catalytic performance. Such modifications consist
of e.g. alloying Cu with other metals or modifying the oxide via
the introduction of nitrides [83] or other metal oxides. A related
suggestion to tune activity by using different oxides was recently
given for oxide-supported PtCo catalysts [23]. However, as we have
just shown for Zn, Ce, and Zr, modifications of the metal oxide
influences the bonding mechanism of CO2, which leads to varia-
tions in the preferred reaction pathways. It is thus clear that the
synergies between different oxides in contact with a metal offer
rich possibilities, and that these can be explored by means of com-
putational models of inverse oxide-on-metal catalysts.
Acknowledgements
Funding from sustainability center Freiburg within the HyCO2
project and through the project BioMethanol funded by the Federal
Ministry of Education and Research Germany is acknowledged. The
authors are thankful for the computing time granted by the John
von Neumann Institute for Computing (NIC) and provided on the
supercomputer JURECA at Jülich Supercomputing Centre (JSC) as
well as the computational resource bwUni-Cluster funded by the
Ministry of Science, Research and the Arts Baden-Württemberg
and the Universities of the State of Baden-Württemberg, Germany,
within the framework program bwHPC.
Appendix A. Supplementary material
Supplementary data associated with this article can be found, in
the online version, at https://doi.org/10.1016/j.jcat.2018.01.035.
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