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The roles of CO and CO2 in high pressure methanol synthesis over Cu-based catalysts

Nielsen, Niels D.; Jensen, Anker D.; Christensen, Jakob M.

Published in:
Journal of Catalysis

Link to article, DOI:

10.1016/j.jcat.2020.11.035

Publication date:
2021

Document Version
Peer reviewed version

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Citation (APA):
Nielsen, N. D., Jensen, A. D., & Christensen, J. M. (2021). The roles of CO and CO in high pressure methanol
2
synthesis over Cu-based catalysts. Journal of Catalysis, 393, 324-334. https://doi.org/10.1016/j.jcat.2020.11.035

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 The roles of CO and CO2 in high pressure methanol synthesis over Cu-based
catalysts
Niels D. Nielsen, Anker D. Jensen and Jakob M. Christensen*
Department of Chemical and Biochemical Engineering, Technical University of Denmark,
Søltofts Plads Building 229, 2800 Kgs. Lyngby, Denmark.
*Correspondence to: jmc@kt.dtu.dk

Abstract
The roles of CO and CO2 in Cu-catalyzed methanol synthesis from syngas were evaluated in
experiments with gas switching between CO/H2 and CO2/H2 feeds and between a CO2/CO/H2 feed
and a corresponding CO-free CO2/inert/H2 feed. Switching between CO/Ar/H2 (3/29/68) and
CO2/N2/H2 (3/29/68) for Cu/Al2O3 showed that the rate of methanol synthesis on Cu is more than
an order of magnitude higher from CO2 compared to CO. Experiments switching between
CO2/CO/H2 and CO2/inert/H2 showed that at low conversion conditions with negligible product
formation, CO is purely inhibiting for Raney Cu and for a range of supported (on SiO2, TiO2,
Al2O3 and ZnO) Cu-catalysts including the industrial Cu/ZnO/Al2O3 catalyst. Given the generality
across Cu-based samples the mechanism of this inhibition is most likely competitive adsorption of
CO on the Cu surface. However, as conversion is increased by lowering the gas space velocity
there is a sharp transition from an inhibiting to a beneficial role of CO relative to a CO-free feed.
With increasing conversion more water is formed, and as water is a far stronger inhibitor to Cu-
based catalysts than CO, the beneficial effect of CO arises from the removal of water through the
water-gas shift reaction. At low conversion the methanol synthesis rate is thus highest for a CO-
free feed that minimizes CO inhibition, whereas the rate at high conversion is optimal with a CO-
rich syngas that minimizes water inhibition. The transition between these two types of behavior
occurs around the conversion range leading to 1 mol% of methanol in the effluent gas. Hence CO
has a beneficial role at commercial high conversion conditions. The ZnO support exerts a strong,
beneficial support effect at low conversion conditions, where the strong reductant CO has a purely
negative effect. This could suggest that reduced Zn-sites (oxygen vacancies in ZnO or Cu-Zn
surface alloy sites), whose concentration are expected to depend on the reductive potential of the
atmosphere, are not critical to the support effect from ZnO. At both industrial conditions (523 K,
50 bar), mild conditions (448 K, atm. pressure) and in a nominally oxidizing gas (498 K, 20 bar
with CO2 > H2) the addition of CO to the feed was detrimental to the activity of Cu/ZnO/Al2O3 at
low conversion conditions. This supports that CO plays no beneficial role by facilitating ZnO-
reduction and possibly that Zn alloyed into the Cu surface is unimportant for catalytic activity.

Introduction
Conventional methanol synthesis proceeds from syngas, a CO2/CO/H2 mixture, over a
Cu/ZnO/Al2O3 catalyst operating at 473-573 K and 50-100 bar [1–3]. Hydrogenation of CO (R1)
and CO2 (R2) constitute two potential reaction pathways for methanol synthesis on supported Cu
catalysts.

CO + 2 H2 ⇌ CH3 OH R1
CO2 + 3 H2 ⇌ CH3 OH + H2 O R2

1
For Cu itself and for the current industrial Cu/ZnO-based catalysts there is a strong preference for
the reaction pathway from CO2 (R2). Isotope labeling studies [4–7] in the 1970s/80s
unambiguously established CO2 as the primary carbon source for methanol formation with
industrial Cu/ZnO-catalysts. Experimental studies of a Cu single crystal [8] and of polycrystalline
Cu [9,10] support that for Cu itself the CO2 pathway (R2) is also intrinsically 1-2 orders of
magnitude faster than the CO pathway (R1). Although many supported systems such as
Cu/ZnO(/Al2O3) and Cu/Al2O3 qualitatively share the intrinsic properties of Cu in terms of
exhibiting a far greater rate from CO2 compared to CO [9], there is also a strong support effect,
whereby the turnover frequency (TOF) can vary by orders of magnitude depending on the support
[11–13]. For certain Cu-based catalysts, such as Cu/MgO, R1 is faster than R2. However, this is
not related to the intrinsic properties of Cu, but is instead the result of a Cu-MgO synergy that
strongly accelerates R1 [9]. This synergistic pathway is most likely relying on basic support sites
in the vicinity of the metal particle which is inhibited by the acidic gas CO2 [9]. From a CO/CO2/H2
feed this CO2-inhibition of the synergistic pathway from CO entails that even Cu/MgO primarily
produces methanol from CO2 [14], as only the CO2-pathway on the metallic Cu surface of Cu/MgO
prevails when the CO pathway is interrupted [9].
Whereas the role of CO2 as the primary reactant is relatively unambiguous in most cases, the
role of CO in the syngas feed for the industrial process is less clear. Some studies [14–18] observe
that the methanol synthesis over Cu/ZnO/Al2O3 is faster in CO2/H2 than in CO/CO2/H2, and
correspondingly kinetic studies [19] have observed a negative reaction order in CO. By contrast
other studies [16,20–22] observe a faster methanol formation from a CO-rich CO/CO2/H2 mixture.
As methanol synthesis from sustainably generated H2 and locally available CO2 point sources is
envisioned to become an important energy storage solution in a sustainable future society [23], it
is important to clarify the exact role of CO in the current industrial process from syngas.
There are several potential roles of CO that need to be unraveled. One of these roles is in
removal of water through the water-gas shift (WGS) reaction (R3), as water is observed [11,19,24]
to be a strong kinetic inhibitor of the methanol synthesis. However, this role will be limited to
higher conversions, where significant water concentrations build up.

CO + H2 O ⇌ CO2 + H2 R3

It has also been proposed that the strong promoting support effect of ZnO in the industrial
Cu/ZnO/Al2O3 catalyst is due to the creation of strongly reduced Zn-sites featuring high activity,
such as oxygen vacancies in the ZnO phase [25] or Cu-Zn surface alloy sites [26,27] in the metal
surface. With CO being the most reducing component in the syngas [28–30] the CO concentration
regulates the concentration of such sites [25,27] and hence the activity, if these reduced Zn-sites
are the primary active centers. Thirdly, CO may govern the oxygen coverage on the Cu surface.
Ambient pressure X-ray Photoelectron Spectroscopy (XPS) studies [31,32] have shown that
oxygen can deposit on the Cu surface in CO2 or H2/CO2 atmospheres, but the oxygen coverage is
found to be low on the Cu surface in CO-rich syngas [24], which suggests that CO may play a role
in removing oxygen from the Cu surface.
Here we investigate the roles of CO and CO2 in Cu-catalyzed methanol synthesis using Raney
Cu and a variety of supported Cu catalysts. This work is based on methanol synthesis experiments

2
switching between CO/H2 and CO2/H2 feeds and by switching between a CO/CO2/H2 feed and a
corresponding CO-free N2/CO2/H2 feed.

2. Experimental
Gas flows are reported at normal conditions referring to a temperature of 273.15 K and a
pressure of 1 atmosphere (denoted by “N” e.g. NmL/min).

2.1 Catalysts
The catalysts were synthesized from Cu(II) nitrate hemi(pentahydrate) (98.6%, Alfa Aesar)
using co-precipitation (Cu/ZnO/Al2O3 with 56 wt% Cu, Cu/ZnO with 10 wt% Cu and Cu/Al2O3
with 67 wt% Cu), incipient wetness impregnation (Cu/SiO2 with 36 wt% Cu) or deposition
precipitation (Cu/TiO2(20) with 20 wt% Cu and Cu/TiO2(60) with 60 wt% Cu). Raney Cu (98.9
wt% Cu, 0.81 wt% Al, 0.1 wt% Fe, 0.05 wt% Ni) from Strem Chemicals was received as an
aqueous slurry and was pre-dried in air at room temperature before use. XPS and surface area
analyses of the Raney Cu presented elsewhere [24] have shown that an Al2O3 film covers ca. 60%
of the surface, whereas the metallic Cu constitutes the remaining surface. The preparation of the
co-precipitated samples is described elsewhere [33]. For the deposition-precipitation the TiO2
support material (anatase nanopowder, 21 nm particle size from Sigma Aldrich) was dispersed in
500 mL of H2O before the precipitation. The Cu was then added by dripping aqueous solutions of
Cu(II) nitrate and Na2CO3 (Sigma Aldrich, ≥99.8%) into this TiO2-containing slurry at 338 K and
a pH of 6.5 followed by 1 h ageing at 338 K with unrestricted pH (same procedure as in co-
precipitations). After precipitation the samples were washed in demineralized H2O and dried at
313 K overnight.
Cu/SiO2 was prepared by incipient wetness impregnation of crushed and sieve fractionated
(150-300 µm) silica (Saint Gobain, SS61138) with an aqueous solution of Cu(II) nitrate
hemi(pentahydrate). All catalyst precursors were calcined in 1 NL/min air flow with a 2 K/min
ramp to 573 K, which was maintained for 3 hours. Further characterization of some of these
samples using various techniques can be found elsewhere [9,24,33].

2.2 Catalyst pre-reduction/activation

All catalysts were pre-reduced in a 60 NmL/min flow of 5% H2/N2 (Air Liquide Denmark)
using a heating ramp of 1 K/min and a holding period of 1-4 hours at 448 K before further heating
with 1 K/min to 523 K for 2 hours. At both temperatures, water generation terminated as verified
by the MS within the allocated holding times. For Cu/Al2O3 the standard reduction was followed
by an additional step using 50 NmL/min of 100% H2 (Air Liquide Denmark) at 523 K for 1 h.
After reduction all samples were flushed with He at the final reduction temperature. In selected
cases the pre-reduction of the Cu/ZnO/Al2O3 sample was stopped after the holding period at 448
K and then flushed with He at 448 K in order to probe the effect of CO in the reaction gas after a
milder pre-reduction treatment.

2.3 Measurements of Cu surface area and total surface area

N2O-reactive frontal chromatography (N2O-RFC) [34,35] was used to evaluate the Cu surface
area at 333 K using a 19 NmL/min flow of 1% N2O/He on pre-reduced catalysts. This was done

3
in an Autosorb iQ2 setup according to the procedure described elsewhere [9]. The Cu surface area
was determined using a Cu:O = 2:1 stoichiometry and a Cu surface atom density of 1.47·1019
surface Cu atoms/(m2 Cu) [35,36]. Previous studies [11] using the same setup have revealed a
known uncertainty of 6% on the measurement. For ZnO-supported Cu it is known that ZnO-
reduction can distort the Cu area measured by N2O-RFC. To ensure that the surface area
measurements were not impacted by ZnO-reduction the Cu/ZnO(/Al2O3) samples were subjected
to N2O-RFC after varying pre-reduction conditions. The sample was either subjected to the
standard pre-reduction in 5% H2 with holding at 448 K and 523 K, to a milder reduction that was
terminated after the holding period at 448 K or to a harsher reduction where the standard procedure
was followed by exposure to 100% H2 at 523 K until the water evolution stopped. The results from
these 3 pre-reduction tests are shown in Fig. S1a and S1b. For the present Cu-rich Cu/Al2O3 sample
similar tests (Fig. S1c) showed that Cu reduction was completed with 5 % H2 at 523 K. However,
previous work [11] on a Cu/Al2O3 sample with lower Cu-content required the use of 100% H2 at
523 K for complete reduction. Consequently the present Cu/Al2O3 sample was also, as a precaution
to ensure complete reduction, treated with 100 % H2 at 523 K after the standard 5 % H2 pre-
reduction.
The total surface area of the samples was measured on samples that had been pre-reduced (see
section 2.2) in an Autosorb iQ2 setup. The pre-reduced samples were then rapidly transferred
through the air to a Quantachrome NOVAtouch Gas sorption analyzer and dried/degassed under
vacuum at 423 K for 16 h. After drying the total surface area was determined by a 6-point BET
surface area measurement in the NOVAtouch Gas sorption analyzer.

2.4 Catalytic tests

Methanol synthesis experiments were conducted in a high pressure flow reactor setup with the
catalyst placed in a U-shaped, glass lined, stainless steel reactor. The setup and calibration
procedures are described in detail elsewhere [9]. Transient developments in product concentrations
were monitored by a Hiden HPR-20 EGA mass spectrometer (MS). Quantitative analyses of
product concentration were conducted using a Thermo Fisher Trace 1300 GC equipped with one
channel composed of a TG5 column guiding the gas to an FID detector and one channel composed
of an OV-1 column followed by a Shincarbon column guiding the gas to a TCD detector.

2.4.1 Syngas switching experiments

After catalyst pre-reduction the reactor was pressurized in He to 50 bar at 523 K before
switching to one of three syngas mixtures (CO2/CO/H2 = 3/29/68, CO/inert/H2 = 3/29/68 or
CO2/inert/H2 = 3/29/68 mol%) dosed from pure H2 (99.9999%), pure He (99.9999%), and pre-
mixed 9.50% CO/Ar, 9.00% CO2/N2 and 9.00% CO2/CO all from Air Liquide Denmark. Time
resolved monitoring of the methanol synthesis activity was based on mass spectrometry (MS)
measurements (m/z = 31), while reported activities were based on the methanol production
quantified by online gas chromatography (GC). After obtaining a steady state or quasi-steady state
in one gas mixture the feed was switched to another mixture. Catalyst loadings in the reactor were
adapted for each catalyst to yield low conversion conditions with <0.3 mol% methanol in the
effluent gas.

4
2.4.2 Impact of CO at varying conversion levels
Methanol synthesis was conducted over Cu/Al2O3 and Cu/ZnO/Al2O3 at 523 K and 50 bar at
varying conversion levels in the presence (CO2/CO/H2 = 3/29/68) and absence of CO (CO2/N2/H2
= 3/29/68). The feed flow and catalyst loading were adjusted to regulate the conversion level.
Reported effluent water concentrations for the CO-free feed were based on an oxygen balance
assuming that only methanol synthesis (R2) and WGS (R3) occur, whereby the H2O production is
equal to the sum of the produced CH3OH and CO, which are quantified by the calibrated GC.

2.4.3 Mild syngas switching experiment over Cu/ZnO/Al2O3

Cu/ZnO/Al2O3 was mildly reduced in 60 NmL/min of 5% H2/N2 by heating with 1 K/min to
448 K for 1 h to activate Cu but prevent any ZnO reduction. Next, a syngas experiment at 448 K
and atmospheric pressure was conducted by starting with CO2/N2/H2 (3/29/68) and monitoring the
catalytic activity. Once activity had stabilized the feed was switched to CO2/CO/H2 (3/29/68) at a
constant gas flow of 280 NmL/min.

2.4.4 Methanol synthesis in oxidizing atmosphere over Cu/ZnO/Al2O3

Cu/ZnO/Al2O3 was mildly reduced in 60 NmL/min of 5% H2/N2 by heating with 1 K/min to
448 K to activate Cu but prevent ZnO reduction, which according to [37] initiates above 0.05 bar
H2 at 493 K. Next, the catalyst was flushed with He and heated to 498 K, where it was pressurized
to 20 bar in He before switching to CO2/H2/He (40/30/30) and monitoring the catalytic activity.
The feed was then replaced by a feed of CO2/H2/CO (40/30/30) with the same flow rate at 498 K
and 20 bar of pressure.

2.5 Equilibrium calculations

Equilibrium constants for the WGS and methanol formation from Graaf and Winkelman [38] and
an assumption of ideality in the gas phase were used to determine the equilibrium product
composition for the present experiments.

3 Results and Discussion

3.1 Sample properties

Nielsen et al. [33] have previously reported Cu surface areas for some of the presently applied
samples. Here the Cu surface areas of all the presently applied samples are summarized in Table
1. It is well-established [37,39,40] that partial ZnO reduction can distort the Cu surface area
measured from the N2O uptake in Cu/ZnO systems. To ensure that the obtained Cu surface areas
were free of this effect, the Cu surface area of the Cu/ZnO(/Al2O3) samples was measured after
varying pre-reduction treatments to identify the onset of ZnO reduction. Here the standard pre-
reduction in 5% H2 with holding at 448 K and 523 K was compared to a milder pre-reduction
terminated after the holding period at 448 K or to a harsher pre-reduction with exposure to 100%
H2 at 523 K after the standard pre-reduction. The results from these experiments are shown in Fig.
S1 in the Supporting Information. It is concluded from the results of Kuld et al. [37] that no ZnO
reduction will take place with the pre-reduction in 5% H2 at 448 K, and Fig. S1 shows that with
5% H2 pre-reduction the Cu area is the same (within the known uncertainty) after reduction at both

5
448 K and 523 K. From this it is concluded that ZnO-reduction is negligible in the present standard
reduction program using 5% H2, and consequently the Cu areas in Table 1 should also be accurate
for the Cu/ZnO(/Al2O3) samples.

Table 1: Cu surface areas from N2O-RFC determined in this study and by Nielsen et al. [33]. The
known uncertainty on the Cu area is 6% [11].
Sample BET area Cu area
[m2/gcat.] [m2/gcat.]
Cu/SiO2 143.13 1.40
Cu/Al2O3 82.13 7.16
Cu/TiO2(60) 23.20 1.82
†
Raney Cu 13.94 5.18*
Cu/ZnO 48.18 5.00*
Cu/ZnO/Al2O3 76.92 20.25*
Cu/TiO2(20) 42.94 1.19*
†
Previously reported by Nielsen et al. [24].
*
Values reported by Nielsen et al. [33].

3.2 The carbon source in methanol synthesis over Cu

Theoretical models [14,41–43] have predicted that the rate of methanol formation on pure Cu
should be far higher from CO than from CO2. However experimental studies [8–10] unanimously
show the opposite – that the rate is far higher from CO2. A proposed [14] explanation for this
contradiction has been that stable CO2-derived intermediates may obscure the fast pathway from
CO identified by theoretical studies. To test this Cu-rich Cu/Al2O3 was used, as it possesses good
thermal stability and has previously [9] been shown to qualitatively reflect the behavior of
unsupported Cu. Cu/Al2O3 was subjected to experiments with gas switching between CO/H2 and
CO2/H2 feeds to evaluate, if the reaction rate in CO/H2 is affected by prior exposure to CO2/H2. If
very stable CO2-derived intermediates affect the pathway from CO the order of the gas mixtures
should be of great importance. Fig. 1a shows the result of this switching experiment starting from
CO2/H2, whereas Fig. 1b shows the result when starting in CO/H2. Fig. 1 illustrates that the rate of
methanol synthesis from CO2 is more than an order of magnitude faster than the rate from CO
regardless of the order of the gas mixtures. At these conditions the equilibrium methanol
concentration is 1.09 mol% from CO2/inert/H2 and 2.31 mol% from CO/inert/H2. Hence the greater
reaction rate from CO2 occurs despite a considerably closer proximity to the equilibrium. These
results show that even in the absence of CO2-derived intermediates occupying the surface, the
route from CO is still far inferior to the route from CO2. The results help to substantiate that CO2
is the primary carbon source in methanol synthesis over Cu. Our previous work [9] and additional
tests for the Cu/TiO2 catalysts (see Supporting Information Fig. S2) show that this conclusion
applies to all the Cu-based catalysts investigated here. Here we thus focus on materials that share
the intrinsic properties of Cu, where the rate from CO2 is far higher and where CO2 consequently
is the primary reactant for methanol synthesis. It may be added that the alternative synergistic
pathway for CO-hydrogenation, which is particularly strong in materials such as Cu/MgO, most
likely relies on basic support sites in the vicinity of the metal particle [9]. Consequently this

6
pathway is strongly inhibited by the acidic gas CO2 [9], but relatively uninhibited by a basic gas
such as NH3 [44].

CO2/N2/H2 CO/Ar/H2 CO2/N2/H2 CO/Ar/H2

a) 0.35

0.30
Methanol concentration [mol%]

Methanol MS signal [a.u.]

0.25

0.20

0.15

0.10

0.05

0.00
0 25 50 75 100 125 150 175 200 225 250 275 300 325 350 375
Time on stream [minutes]
CO/Ar/H2 CO2/N2/H2
b) 0.35

0.30
Methanol concentration [mol%]

Methanol MS signal [a.u.]

0.25

0.20

0.15

0.10

0.05

0.00
0 25 50 75 100 125 150
Time on stream [minutes]
Fig. 1: The effluent methanol concentration (stars) achieved over Cu/Al2O3 as function of time on
stream when switching between CO2/H2 and CO/H2 feeds (both balanced with inert gas) starting
from a) CO2/H2 or b) CO/H2. The MS signal (solid line) for methanol (m/z = 31) is also shown to
better illustrate the transient development. Flow measurement required bypass of the MS resulting
in a data gap in the MS signal in a). Reaction conditions: T = 523 K, P = 50 bar, feed flow = 275
± 3 NmL/min, COx/inert/H2 = 3/29/68, Cu/Al2O3 loading = 180.2 mg in a) 148.4 mg in b). Fig. 1b
is reproduced with permission from Nielsen et al. [9].

7
3.3 The role of CO in methanol synthesis from syngas
Since CO2 is the primary reactant for methanol synthesis on the investigated catalysts it is
relevant to elucidate the role of CO in a ternary CO/CO2/H2 atmosphere. To do this both Raney
Cu and supported Cu catalysts were allowed to stabilize in a CO2/CO/H2 feed, and the CO in the
feed was then replaced with an identical concentration of N2, while all other conditions were
maintained. In these experiments flows and catalyst loadings were adjusted to preserve low
conversion conditions (< 0.3 mol% CH3OH produced) in order to minimize the effects of the
reaction products, H2O and CH3OH. At these conditions the equilibrium methanol concentration
is 1.09 mol% for the CO-free feed and 23 mol% from CO2/CO/H2, so the present experiments are
generally also far from equilibrium. Fig. 2 shows the development in methanol productivity during
such an experiment for Cu/TiO2(20) and illustrates that the methanol production actually increases,
once CO is removed from the feed. Fig. 3 summarizes the stabilized productivity levels with and
without CO for all samples. To facilitate comparison the stabilized level in CO2/N2/H2 is assigned
as a relative productivity of 1.00 for each sample, and the final productivity in CO2/CO/H2 prior to
the shift to CO2/N2/H2 is shown relative to this level. The figure clearly illustrates that at these low
conversion conditions all samples exhibit a faster rate in CO2/N2/H2. Hence, CO is an inhibitor for
all the investigated Cu-catalysts.
This qualitative generality suggests that the inhibiting effect of CO comes from an interaction
with the metallic Cu surface, which is the only common feature of these samples. It follows from
this argument that if all the catalysts are impacted by CO interacting with the Cu surface, then the
reaction must also be located on the Cu surface for all the samples. While there have been previous
reports [19,45] of CO-inhibition for Cu/ZnO-systems the generality of this effect has not
previously been identified. These results thus clearly point to the metallic Cu surface as the location
of the active centers in methanol synthesis with supported Cu in agreement with previous studies
supporting the same conclusion. Yoshihara and Campbell [46] observed that the TOF for methanol
synthesis on an open Cu(110) single crystal surface was higher than the TOF of a supported
Cu/ZnO-system and thereby illustrated that the high rates achievable with ZnO-supported
industrial catalysts are possible on a Cu surface. Furthermore, there are numerous linear
correlations [11,47–53] between the metallic Cu surface area and the methanol synthesis rate (from
CO2) for supported catalysts. There is thus strong evidence that the reaction occurs on the metallic
surface. However, since the reaction also has a strong support effect (note the support dependent
TOF in Fig. 3), this support effect must arise from a support-induced modification to the properties
of the metallic Cu surface.
From repeated cycling between a feed with and without CO for thermally stable systems, such
as Cu/TiO2(60), it is evident that the inhibiting effect of CO is fully reversible over the time scale
of a few minutes (see Fig. S3). This suggests that the effect of CO is on the kinetics of the surface
reactions. The most likely cause for the inhibiting effect of CO is competitive adsorption. The CO
adsorbed on the Cu surface is only converted to methanol with a very low rate (Fig. 1), and
blockage of the surface with adsorbed CO will inhibit the rate by preventing the much faster
pathway from CO2. However, there could be a secondary inhibiting effect of CO. There are
indications from ambient pressure XPS studies [31] that oxygen deposits on the Cu surface in
H2/CO2 atmospheres, and it has been proposed [10] that this oxygen exerts a promotional role on

8
the methanol synthesis. In a previous study [24] we found that that the oxygen coverage on Cu
was insignificant (below our detection limit of 0.04 ML) in a CO-rich syngas. The CO may
therefore also inhibit the methanol formation by scavenging away oxygen from the metal surface.

CO2/CO/H2 CO2/N2/H2
0.075

Methanol concentration [mol%]

Methanol MS signal [a.u.]

0.050

0.025

0.000
0 50 100 150

Time on stream [minutes]

Fig. 2: The methanol concentration (stars) as a function time on stream for Cu/TiO2(20), when
switching from a CO2/CO/H2 feed to a CO2/N2/H2 feed. The MS signal (solid line) for methanol
(m/z = 31) is also included. Reaction Conditions: T = 523 K, P = 50 bar, feed flow = 280 ± 5
NmL/min, CO2/X/H2 = 3/29/68 with X = CO or N2, Cu/TiO2(20) loading = 261.5 mg. Here the
final measurement in each gas is used to construct Fig. 3.

9
Fig. 3: The normalized methanol productivity (left vertical axis) in CO/CO2/H2 (red bars) and
CO2/N2/H2 (blue bars) for Raney Cu and various supported Cu-samples. Each catalyst is allowed
to stabilize in CO/CO2/H2 before replacing CO with an identical concentration of N2 as illustrated
in Fig. 2. The black data points (triangle and diamond) show the effluent methanol concentration
in each experiment on the right vertical axis. The TOF for methanol formation (per Cu surface
atom) in the CO-free feed is also shown above each set of bars. Cu/ZnO was allowed to stabilize
for a prolonged period prior to the gas switch, and as sintering may have occurred no TOF is
reported for this sample. Reaction conditions: T = 523 K, P = 50 bar, CO2/X/H2 = 3/29/68 with X
= CO or N2). Space velocity was varied (between 3.1·104 and 145·104 NmL/gcat/h) to ensure low
conversion conditions.

Fig. 3 shows that stronger CO inhibition generally occurs in the experiments with the lowest
conversions and hence the lowest product concentration in the effluent. This indicates that the
impact of CO is dependent on the conversion level. It is well known that the water produced in the
methanol synthesis reaction (R1) is strongly inhibiting to Cu-catalyzed methanol synthesis. Thrane
et al. [11] found that adding 1500 ppmv H2O to the syngas feed caused the methanol synthesis rate
over Cu/ZnO/Al2O3 to drop by 60-70% when operating in the 493-523 K range at 41 bar.
Sahibzada et al. [18] also found that such a catalyst lost 90% of its methanol synthesis activity,
when 2 vol% H2O was added to the feed at 523 K and 50 bar of pressure. The occurrence of water
inhibition for Cu-catalysts is not support specific, as Yang et al. [54] found that adding 0.2 mol%
H2O to the feed caused Cu/SiO2 to lose approximately 40% of its methanol synthesis activity at
413 K and 6 bar. Hence, the water inhibition is general for Cu catalysts, although the available
data do not rule out that the strength of the effect could be support dependent. Saito et al. [45] also
conducted direct comparisons of inhibition from CO and H2O for Cu/ZnO/ZrO2 and found that
H2O is a far stronger inhibitor than CO. Hence, at higher conversion CO can exert a relative
positive effect by removing a worse inhibitor, water, through the WGS reaction (R3).
To investigate the water scavenging effect at higher conversion, switching experiments between
CO2/CO/H2 and CO2/N2/H2 were conducted for Cu/Al2O3 and Cu/ZnO/Al2O3 at varying
conversion levels. The conversion was varied by adjusting the catalyst loading and feed flow to
change the space velocity/residence time. Fig. 4 shows the results from such experiments with
Cu/Al2O3, where the gas switch is conducted at different space velocities. Fig. 4a shows that at the

10
highest space velocity (lowest conversion and water concentration) there is a slight negative effect
of CO. Fig. 4b shows that for lower space velocities, where conversion and water concentration
are higher, there is oppositely a significant positive effect of CO relative to a CO-free gas. Here it
is important to emphasize that both CO and H2O are inhibitors, and the highest productivity occurs
with high space velocity and no CO in the feed (Fig. 4a), whereby the total presence of the
inhibitors is minimized. The benefit of CO is a relative benefit due to the exchange of a stronger
inhibitor (H2O) with a weaker one (CO).

11
 9.4 x 104 NmL/gcat/h
CO2/CO/H2 CO2/N2/H2
a) 0.4

Methanol productivity [gMeOH/gcat/h]

0.3

0.2

0.1

0.0
0 50 100 150 200 250
Time on stream [minutes]

3.8 x 104 NmL/gcat/h 1.38 x 104 NmL/gcat/h

CO2/CO/H2 CO2/N2/H2 CO2/CO/H2 CO2/N2/H2
b) 0.4
Methanol productivity [gMeOH/gcat/h]

Methanol MS signal [a.u.]

0.3

0.2

0.1

0.0
0 50 100 150 200 250 300 350 400
Time on stream [minutes]
Fig. 4: The methanol production rate as a function of time on stream with Cu/Al2O3 and a gas
space velocity of a) (9.42 ± 0.07)·104 NmL/gcat/h and b) both (3.80 ± 0.06)·104 NmL/gcat/h and
(1.38 ± 0.04)·104 Nml/gcat/h. In b) the methanol MS signal (m/z = 31) is also shown to illustrate
that the product concentration as expected is higher for the lower space velocity. Gaps in the
methanol MS signal are due to bypass for flow measurements. Reaction conditions: T = 523 K, P
= 50 bar, CO2/X/H2 = 3/29/68 with X = CO or N2, Cu/Al2O3 loading = 178.6 mg in a) and 433.7
mg in b).

12
Fig. 5 shows the ratio between the rates with and without CO as a function of the water
concentration in the effluent for the CO-free feed. The water concentration is estimated from an
oxygen balance as the sum of the production of methanol and CO assuming that only reactions R1
and R3 occur. Since negligible formation of DME or other products were detected by the GC, this
is expected to be a good assumption. Fig. 8 shows that at low conversion the H2O formation is
low, and CO only impacts the activity negatively for both Cu/ZnO/Al2O3 and Cu/Al2O3. By
increasing the conversion level the H2O concentrations rises, and for both Cu/ZnO/Al2O3 and
Cu/Al2O3 there is a sharp transition, where CO becomes beneficial compared to a CO-free gas. As
described above this benefit can be attributed to the role of CO as a scavenger of water by the
WGS reaction. The transition to a positive effect of CO occurs at a lower water concentration for
Cu/ZnO/Al2O3. This can be rationalized from the known support effect of ZnO upon the heat of
adsorption of water on the catalyst. In the limit of zero water coverage the heat of adsorption of
water on Cu/ZnO/Al2O3 is 65 kJ/mol [55], whereas the heat of adsorption on pure Cu is around 45
kJ/mol [56–58]. It would be consistent with the stronger bonding of water on Cu/ZnO/Al2O3 that
the inhibiting effect of water, and hence the need for water removal by reaction with CO, becomes
important at a lower water concentration for Cu/ZnO/Al2O3. However, the beneficial effect of CO
also emerges for Cu/Al2O3 although at a higher water concentration. This is in agreement with the
results of Yang et al. [54] showing that water inhibition is also important for ZnO-free supports.
For the experiments in Fig. 5 with a CO-free feed, where the water content can be accurately
estimated through the oxygen balance, the approach to equilibrium for WGS and methanol
synthesis were evaluated, and the results are summarized in Table S1 in the supporting
information. The highest approach to equilibrium among these tests were 59.1% for the WGS and
20.8% for methanol synthesis. Hence, both reactions are in the kinetically controlled regime
although with the faster (reverse) WGS generally closer to an equilibration.

13
 3.0

2.5
Cu/ZnO/Al2O3 Cu/Al2O3
Rate incl. CO / Rate excl. CO 2.0

1.5

1.0

0.5
Increasing conversion

0.0
0.0 0.2 0.4 0.6 0.8 1.0 1.2 1.4 1.6 1.8 2.0
Effluent H2O concentration in CO2/H2 [mol%]

Fig. 5: The ratio between the methanol formation rates in CO2/CO/H2 and CO2/N2/H2 as a function
of the estimated effluent concentration of water in the CO2/N2/H2 atmosphere for Cu/Al2O3 and
Cu/ZnO/Al2O3. Reaction conditions: T = 523 K, P = 50 bar, GHSV = (2.4-14.5)·105 NmL/gcat/h
for Cu/ZnO/Al2O3 and (1.4-94.1)·104 NmL/gcat/h for Cu/Al2O3.

3.4 Optimal CO/CO2 ratio for methanol synthesis over Cu/ZnO-based catalysts
As the hydrogenation of CO2 provides a faster pathway (Fig. 1) the concentration of CO2 in the
syngas feed is obviously important. Fig 6 summarizes the literature [59–61] on the effect of the
CO2 partial pressure in the feed, when only the CO2 concentration is varied. Fig. 6 shows that the
methanol synthesis is approximately 1st order in CO2 to around 1 bar of pressure and then becomes
0th order in CO2 for higher partial pressures. IR studies [59,61] suggest that the stagnation occurs
because the concentration of formate intermediates on the Cu surface saturates.

14
 120

Relative CH3OH formation rate [%]

100

80

60

40

20

0
0 1 2 3 4 5 6 7
CO2 partial pressure [bar]

Fig. 6: The relative methanol production rate of Cu/ZnO-based catalysts as a function of the CO2
partial pressure in the feed. Data (in the 496-523 K range) from: Amenomiya and Tagawa [61]
(), Le Peltier et al. [59] (), and Nomura et al. [60] (). The data are normalized by setting the
highest productivity in each study to 100%.

Studies that instead vary the CO/CO2 ratio in the COx part of the syngas have yielded seemingly
contradictory observations, as optimal activity has been reported for both CO-free and CO-rich
atmospheres. The observation of a transition from a detrimental to a beneficial effect of CO on the
activity, when varying the conversion level (Figs. 4 and 5), can help to rationalize these
observations. At low conversion the inhibiting effect of CO means that the CO concentration
should be as low as possible, but at high conversion a high concentration of CO is needed to
remove water. Fig. 7 summarizes literature results for Cu/ZnO(/Al2O3) catalysts by showing the
normalized methanol productivity as a function of the fraction of CO2 in the COx part of syngas
feed with a fixed COx/H2 ratio. These results are obtained at industrially relevant high pressure
conditions. The literature results are separated into low conversion conditions with negligible
product formation (Fig. 7a) and high conversion conditions with non-negligible product formation
(Fig. 7b). An analysis (see Table S4) of the product concentrations in the experiments in Fig. 7
shows that this low conversion behavior in Fig. 7a occurs for methanol effluent concentrations
below ca. 1 mol%, whereas the high conversion behavior in Fig. 7b occurs above ca. 1 mol%
methanol in the effluent. Hence, the transition between the two types of behavior occurs around
the conversion region leading to 1 mol% methanol in the effluent gas.

15
 Fig. 7a shows that at low conversion conditions the methanol formation rate rises strongly until
CO2 constitutes 10-20% of the COx whereafter the increase continues albeit less profoundly until
CO2 is the only COx component. The sharper initial rise in Fig. 7a until 10-20% CO2 in the COx
can be attributed to the regime, where the reaction has a positive dependence on CO2 (see Fig. 6)
and where CO2 thus brings an advantage of its own. Above this level additional CO2 may not bring
strong beneficial effects of its own, since the reaction becomes 0th order in CO2. However, as CO
is inhibiting it is nevertheless still beneficial to replace CO with CO2, and maximal activity occurs
in a completely CO–free gas.
Fig. 7b shows that at high conversion conditions with higher product concentrations the
methanol production is optimal for a syngas w ith a COx fraction of ca. 10% CO2 and 90% CO. At
high conversion it is beneficial to include sufficient CO2 to reach the 1-2 bar CO2 partial pressure
that saturates the beneficial effect of CO2 (see Fig. 6). However, once this CO2-concentration is
reached, the CO2 offers no additional benefit, and it is instead preferable that the remaining part of
the COx is CO in order to optimize the removal of water by the WGS reaction. The optimal COx
composition is thus a CO-rich mixture at higher conversions. The composition dependencies in
Fig. 7 can thus be described in terms of the beneficial effect of CO2 (Nielsen et al. [9] and Figs. 1
and 6), the inhibiting effect of CO (Fig. 3), and the inhibiting effect of water (e.g. Thrane et al.
[11] and Yang et al. [54]) that all are general among Cu catalysts regardless of the support. This
implies that it is the kinetics of the surface reactions on Cu and not support-dependent effects that
cause the dependencies on the COx composition. However, Fig. 5 clearly shows that the transition
between the two regimes in Fig. 7 will depend upon the support, and any support-dependencies in
the formate coverage could also cause factors such as the location of the optimum in Fig. 7b to
vary with the support.
It should be added that at high conversion with significant methanol concentrations, the water
scavenging effect of CO operates in parallel to a methanol-assisted autocatalytic mechanism,
whereby methanol facilities the generation of additional methanol [11]. For catalysts such as
Cu/ZnO/Al2O3 the combined effect of the autocatalytic acceleration and the water scavenging
means that the absolute rate increases with increasing conversion for CO-rich feeds [11]. The
alcohol-assisted mechanism that causes the autocatalytic effect does not seem to require CO [62–
64]. The increase in absolute activity of Cu/ZnO/Al2O3 with increasing conversion in the presence
of CO is therefore not likely to be the result of CO participating directly in the autocatalytic
pathway, but rather the result of CO removing water and thus providing optimal conditions for the
autocatalytic pathway.

16
 a) 100

Relative CH3OH formation rate [%]

80

60
Low conversion conditions
(< ca. 1 mol% CH3OH in effluent)
40

20

0
0 20 40 60 80 100
Percentage of CO2 in CO+CO2 [%]
b) 100
Relative CH3OH formation rate [%]

High conversion conditions

80 ( > ca. 1 mol% CH3OH in effluent)

60

40

20

0
0 20 40 60 80 100
Percentage of CO2 in CO+CO2 [%]
Fig. 7: The relative methanol synthesis activity for Cu/ZnO(/Al2O3) catalysts as a function of the
CO2 fraction in the COx part of the syngas for: a) low conversion conditions with negligible product
concentrations and b) high conversion conditions with non-negligible product concentrations.
Here the COx composition is varied at a fixed COx/H2 ratio and all studies are normalized to the
highest activity achieved in the study. Data in a) from: Studt et al. [14] (), Chanchlani et al. [15]
() and Lee et al. [16] (). Data in b) from: Martin and Perez-Ramirez [20] (), Barbier et al.
[21] (), Sahibzada et al. [18] (), Lee et al. [16] () and Klier et al. [22] (×). The exact data
used from the literature studies are specified in Tables S2-S4 in the Supporting Information.

17
3.5 Role of CO-induced rise in reductive potential for Cu/ZnO-catalysts
It is well established that ZnO exerts a strong support effect on the Cu-catalyzed methanol
synthesis (see Fig. 3 and refs. [11–13,65,66]), although the exact mechanism by which this support
effect operates remains imperfectly understood. One proposal is that reduced Zn-sites, such as
oxygen vacancies in the ZnO [25] or Zn alloyed into the metallic surface [27,37,67–70], are sites
of particularly high activity. The reductive potential of the syngas, which is governed by especially
the CO/CO2 ratio, will have a major impact on the concentration of such reduced Zn-sites [25,27],
which should be reflected in a major impact on the catalytic activity.
Fig. 8 shows the turnover frequency (TOF) in methanol synthesis per Cu surface atom for
Raney Cu and Cu/ZnO/Al2O3 at the low conversion conditions of Fig. 3 both with and without CO
in the feed.
Methanol TOF [CH3OH molec./Cu surface atom/s]

0.1

0.01
CO2/CO/H2

CO2/CO/H2
CO2/N2/H2

CO2/N2/H2

0.001
Raney Cu Cu/ZnO/Al2O3
Fig. 8: The turnover frequency for methanol synthesis (per Cu surface atom) for Raney Cu and
Cu/ZnO/Al2O3 in both CO2/N2/H2 (red) and CO2/CO/H2 (blue). These results are at low conversion
conditions (see effluent concentrations in Fig. 3). Reaction conditions: T = 523 K, P = 50 bar,
CO2/X/H2 = 3/29/68 with X being CO or N2, GHSV = (8.3-8.4)·104 NmL/gcat/h (Raney Cu) and
(1.4-1.5)·106 NmL/gcat/h (Cu/ZnO/Al2O3).

We have previously [24] confirmed that the Raney Cu sample is a good quantitative approximation
to the intrinsic properties of Cu, and Fig. 8 shows that at these low conversion conditions the TOF
for Cu/ZnO/Al2O3 is 7-8 times higher than the TOF for Raney Cu. Fig. 8 also illustrates that at
these conditions a strong support effect is present, but the most reducing component in the gas,
CO, nevertheless has a negative effect on the performance of the Cu/ZnO/Al2O3 system. This could
suggest that reduced Zn-sites, whose concentration rises with increasing CO/CO2 ratio [25,27], are

18
not important for the catalytic activity. However, it cannot be fully excluded that the high hydrogen
pressure at the conditions of Fig. 8 is sufficient to saturate the concentration of such reduced Zn-
sites. Switching experiments were therefore conducted at two sets of model conditions, where the
presence of CO should be essential for the creation of reduced Zn-sites, such as Cu-Zn surface
alloy sites.
Cu/ZnO/Al2O3 was subjected to mild (5% H2 at 448 K and atm. pressure) pre-reduction to
ensure minimal reduction of the ZnO component. The methanol synthesis activity was then
investigated at 448 K and atmospheric pressure starting from a less reducing CO2/N2/H2 mixture
and then switched to a more reducing CO2/CO/H2 gas mixture. The N2 and CO concentrations
were identical to ensure that all other parameters remained constant. Fig. 9 shows the methanol
formation during the switching experiment and illustrates that also at these conditions CO exerts
an exclusively negative effect and causes a 34% drop in the methanol formation rate. Equilibrium
methanol concentrations at these conditions are 9136 ppm for CO2/CO/H2 and 201 ppm for
CO2/N2/H2. Hence, the rate in the absence of CO is higher despite a considerably closer proximity
to the equilibrium, which emphasizes the role of CO as a kinetic inhibitor. The negative role of
CO at these conditions is in good agreement with the results of Cherifi et al. [19], who studied the
reaction kinetics with a similar catalyst and conditions and also observed an exclusively negative
effect of CO.

CO2/N2/H2 CO2/CO/H2
50

45
Methanol concentration [ppmv]

40

35

30

25

20

15

10

0
0 20 40 60 80 100 120 140
Time on stream [minutes]

Fig. 9: The methanol production as a function of time on stream when mildly pre-reduced (5%
H2/N2 at 448 K) Cu/ZnO/Al2O3 is exposed to first CO2/N2/H2 followed by replacement of the N2
with CO. Reaction conditions: T = 448 K, atmospheric pressure feed flow = 281 ± 4 NmL/min,
CO2/X/H2 = 3/29/68 with X = N2 or CO, Cu/ZnO/Al2O3 loading = 25.3 mg.

In a second model study Cu/ZnO/Al2O3 was mildly (5% H2 at 448 K) pre-reduced before being
heated in He to 498 K and pressurized to 20 bar. The sample was then subjected to a CO2/He/H2
(40/30/30) feed i.e. a nominally oxidizing gas (CO2 > H2). The methanol formation was allowed
to stabilize before the He was replaced with CO, which changed the atmosphere to a nominally

19
reducing gas (CO+H2 > CO2). Fig. 10 shows the methanol formation during the stabilization and
gas switch and illustrates that CO is also inhibiting at these conditions, as the activity drops by 40-
50% upon introduction of CO.
These results clearly illustrate that CO plays no beneficial role in facilitating the reduction of
Cu/ZnO/Al2O3. Additionally, the fact that CO has a negative effect at these model conditions,
where the reductive power of CO should be critical to the formation of reduced Zn-sites, suggests
that e.g. Cu-Zn surface alloy sites are not the source of the beneficial support effect from ZnO.
The present results showing that a CO-induced rise in the reductive potential to be detrimental for
the catalytic activity are in conceptual agreement with the results of Frei et al. [71], who observed
that raising the reductive potential during pre-reduction through increasing temperature was
detrimental for a Cu/ZnO/Al2O3 catalyst in terms of TOF and activation energy.
In conclusion the present results have two primary implications for the support effect in Cu-
catalyzed methanol synthesis. The generality in how reaction conditions, such as the CO
concentration, impacts a wide variety of Cu-based catalysts (Figs. 3 and 5) implies that the active
sites are located on the metallic Cu surface, which is the only common feature of these samples.
This suggests that support effects, such as the beneficial effect of ZnO, arise from a modification
of the metallic Cu surface. However, the detrimental effect of CO even under model conditions
(Figs. 9 and 10), where an increased reductive potential should influence the alloying of Zn into
the metallic surface makes it unlikely that such CuZn surface alloying is the source of the support
induced modifications to the properties of the metallic Cu surface.

CO2/He/H2 CO2/CO/H2
1000

900
Methanol concentration [ppmv]

800

700

600

500

400

300

200

100

0
0 50 100 150 200 250 300 350 400
Time on stream [minutes]

Fig. 10: The methanol concentration as a function of time on stream when mildly pre-reduced (5%
H2/N2 at 448 K) Cu/ZnO/Al2O3 is exposed to first a formally oxidizing CO2/He/H2 atmosphere
followed by replacement of He with CO to create a formally reducing atmosphere. Reaction
conditions: T = 498 K, P = 20 bar, feed flow = 280 ± 3 NmL/min, X/H2/CO2 = 30/30/40, GHSV
= 1.23·106 NmL/gcat/h. The equilibrium methanol concentrations at these conditions are 3.62 mol%
with CO in the feed and 0.37 mol% without CO in the feed. Hence, the results are in the kinetically
controlled regime.

20
4. Conclusion
Catalytic methanol synthesis is currently a major industrial process operating from CO/CO2/H2
with a Cu-based catalyst. However, future uses of the process could involve the conversion of
CO2/H2 feeds from sustainably derived hydrogen and CO2 captured at locally available point
sources. It is therefore relevant to evaluate the roles of CO and CO2 for the Cu-catalyzed reaction.
Here we have conducted switching experiments between feeds with and without CO over Cu based
catalysts to elucidate the roles of CO and CO2 at varying conversion levels. Switching between
CO/H2 and CO2/H2 feeds for Cu/Al2O3 clearly showed that the methanol synthesis rate from CO2
is more than an order of magnitude faster than the rate from CO, which helps to substantiate that
CO2 is the immediate carbon source for methanol on Cu. Low conversion experiments switching
between CO/CO2/H2 and N2/CO2/H2 feeds, where the presence or absence of CO is the only
change, showed that CO is inhibiting to Raney Cu and to Cu supported on Al2O3, SiO2, TiO2, ZnO
and ZnO/Al2O3. Competitive adsorption on the Cu surface may explain the observations, although
the removal of promotional oxygen species from the Cu surface by CO cannot be fully excluded
as a reason for the inhibiting effect of CO. At higher conversion the presence of CO was found to
be beneficial compared to conditions without CO in the feed. This can be explained by the ability
of CO to remove a worse inhibitor, water, through the WGS reaction. As a result the optimal feed
is a CO-free gas at low conversion, but at higher conversion a CO-rich syngas that efficiently
removes produced water is preferable. The transition between these two types of behavior occurs
around the conversion range leading to 1 mol% of methanol in the effluent gas.
Comparisons of Cu/ZnO/Al2O3 and Raney Cu showed that a strong, beneficial support effect
from ZnO was present at low conversion conditions, where the effect of CO is observed to be
purely detrimental for both samples. One proposed mechanism for the ZnO-support effect has been
that reduced Zn species are alloyed into the metal surface, and the CO concentration has previously
been found to be important for the creation of the reduced Zn-species. The fact that the support
effect is strong at conditions where the carbon monoxide-induced rise in the reductive potential of
the atmosphere was detrimental for the activity is a clear indication that such reduced Zn-species
are not critical to the support effect from ZnO. In a further experiment Cu/ZnO/Al2O3 was at high
space velocity (low conversion) exposed to a H2/He/CO2 gas mixture with an excess of CO2
compared to H2 i.e. a nominally oxidizing atmosphere. Once activity had stabilized, the He was
replaced with an equal concentration of CO, which changed the atmosphere into a nominally
reducing gas. Again the effect of CO was purely inhibiting. The fact that CO is also detrimental at
such oxidizing conditions is a further indication that reduced Zn-sites may not be involved in
creating the beneficial synergy between Cu and ZnO.

Acknowledgements
This work was supported by a research grant (9455) from VILLUM FONDEN. We thank Saint
Gobain for providing the SiO2 support.

21
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