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Methanol synthesis via CO2 hydrogenation over CuO-ZrO2
prepared by Two-Nozzle Flame Spray Pyrolysis
Published on 20 March 2018. Downloaded by Fudan University on 20/03/2018 20:36:09.
Received 00th January 20xx,
Accepted 00th January 20xx Shohei Tada,a† Kim Larmier,a Robert Büchel,b* Christophe Copéret a
DOI: 10.1039/x0xx00000x
www.rsc.org/
Flame made CuO-ZrO2 catalysts for CO2 hydrogenation to
methanol were prepared such that only the Cu size was varied.
Smaller CuO clusters in CuO-ZrO2 showed a higher activity for
methanol synthesis via CO2 hydrogenation. Thus, the 2-FSP
technique is a promising one-step preparation process for CO2
hydrogenation catalysts.
Methanol, a key chemical intermediate of the petrochemical
industry, is produced by hydrogenation of carbon monoxide, since
Imperial Chemical Industries developed a CuO/ZnO/Al2O3 catalyst in
1 -1
the sixties. In view of the vast amount of CO2 liberated per year
and its contribution to global warming, the direct hydrogenation of
CO2 (in place of CO) to methanol has become an attractive field of
research as it would concur to allowing a closed carbon cycle,
provided high pressure H2 can be produced from renewable
resources; this approach constitutes the basis of the methanol
1-3
economy introduced by Olah and co-workers . Methanol
synthesis by CO2 hydrogenation is exothermic and the number of
2 20
product moles is lower than of the reactants (Eq. 1) . At high
temperature, the endothermic reverse water gas shift reaction
2
(RWGS reaction, Eq. 2) becomes dominant converting CO2 into CO,
hence low temperatures and high pressures are typically required
for the selective production of methanol.
Because conventional catalysts for CO-to-methanol hydrogenation
2
(Eq. 3) do not show enough activity for CO2-to-methanol
4
hydrogenation , it is important to develop specific catalyst for CO2-
to-methanol hydrogenation. Numerous experimental and
theoretical studies have been performed on Cu-based catalysts to
hydrogenate CO2 into methanol. Various supports and promoters
4-9 5, 10-15 16 17
have been reported e.g. ZnO, ZrO2, CeO2, and MgO .
Among the supports, ZrO2 is particularly promising because ZrO2-
containing catalysts led to highly active, selective and stable
† Present Address: Department of Materials and Life Science, Faculty of Science and
Technology, Seikei University, Kichijouji-kitamachi, Musashino-shi, 180-8633 Tokyo,
Japan
* Corresponding author: buechel@ptl.mavt.ethz.ch
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DOI: 10.1039/C8CY00250A
Catalysis Science & Technology Accepted Manuscript
5, 10-15 18
catalysts . According to our previous study , methanol
synthesis via CO2 hydrogenation over Cu/ZrO2 catalysts involves the
adsorption of CO2 and its conversion to formate and methoxy
species at the interface between ZrO2 and the Cu nanoparticles,
19
where H2 dissociatively adsorbs on Cu surface. Based on this
0
reaction scheme, the interface between Cu and ZrO2 plays a
12, 14, 15, 18
significant role in the CO2 hydrogenation to methanol .
Therefore, an intimate contact between Cu nanoparticles and ZrO2
could provide an ideal catalyst for selective methanol formation.
CO2 + 3H2 = CH3OH+ H2O ΔrH°298K = -49.5 kJ mol (1)
CO2 + H2 = CO + H2O ΔrH°298K = 41.2 kJ mol
-1
(2)
-1
CO + 2H2 = CH3OH ΔrH°298K = -90.6 kJ mol (3)
Here, we focused on a flame spray pyrolysis (FSP) approach as
catalyst preparation because FSP is an industrial process capable to
producing complex nanoparticle assemblies at several kg per
hour . Although several investigators developed CuO/ZnO/Al2O3
21-23
catalysts for methanol synthesis via syngas via FSP , no studies
have aimed to prepare the CO2-to-methanol hydrogenation
catalysts based on Cu and ZrO2. Here, we thus prepared CuO-ZrO2
catalysts with a two-nozzle flame spray pyrolysis (2-FSP) technique;
which allows the change of CuO-size without affecting the support
properties. The performance of these CuO-ZrO2 catalysts was tested
for CO2 hydrogenation to methanol, and compared to samples
prepared by physical mixture of CuO and ZrO2. The CuO-ZrO2
catalysts with smaller CuO particles exhibited higher performance
in CO2-to-methanol hydrogenation at a given selectivity. Such CuO-
ZrO2 catalysts showed higher selectivity in the CO2-to-methanol
hydrogenation than a commercial CuO/ZnO/Al2O3 catalysts.
24
CuO-ZrO2-A was prepared with a 2-FSP reactor (Figure 1) . The
precursors of Cu and Zr were copper (II) 2-ethylhexanoate (Sigma-
25
Aldrich), and zirconyl 2-ethylhexanoate in mineral spirits (STREM
Chemicals), respectively. Each metal precursor was dissolved in a
separate vessel with 2-ethylhexanoic acid (Sigma-Aldrich) and
xylene (Sigma-Aldrich) in a 1:1 volumetric ratio. The total metal
concentration of Cu and Zr was adjusted to 0.5 M. Each metal
-1
solution was pumped through a capillary at 5 mL min , and was
-1
dispersed with 5 L min of O2 into a fine spray. To ignite the spray, a
premixed CH4/O2 flame at a volume ratio of 1/2 was used (total
-1
flow rate of the flamelet: 3 L min ). In comparison to CuO-ZrO2-A
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(Figure 1a), CuO-ZrO2-B was prepared with a higher O2 dispersion prepared CuO-ZrO2 samples and the commercial catalyst have
gas flow of 10 L min-1 (instead of 5 L min-1) (Figure 1b) for the Cu comparable SSA of ca. 100 m2 g-1. The Cu loading for CuO-ZrO2

Catalysis Science & Technology Accepted Manuscript

nozzle spray (all other characteristics of the Zr flame were kept the
same). The higher O2 flow increases the quenching of the ignited
spray of Cu precursor, leading to smaller CuO clusters. We prepared
separately ZrO2 and CuO particles using a one-nozzle flame spray
pyrolysis (1-FSP) reactor (Figure 1c), labeled as ZrO2 (FSP) and CuO
(FSP), respectively. We used 5 L min-1 O2 dispersion gas flow for
these samples (for all experiments the same Cu and Zr was used).
The physical mixture of those two 1-FSP samples are labeled as
Published on 20 March 2018. Downloaded by Fudan University on 20/03/2018 20:36:09.
catalysts were between 8 and 16 wt%. The CuZnAl has a reported
Cu loading of 50 wt%. Powder X-ray diffraction (PXRD) patterns of
the samples are shown in Figure S1a. The ZrO2 on CuO-ZrO2-A,
CuO-ZrO2-B, and ZrO2 (FSP) were mainly tetragonal-ZrO2 with
crystallite sizes of ca. 10 nm (Table 1), along with some amount of
monoclinic-ZrO2. The CuO peaks were observed in all Cu-containing
powders (Figure S1a).

CuO-ZrO2 (PM). Additionally, a commercial CuO/ZnO/Al2O3 was
tested as a benchmark catalyst (named as CuZnAl, Johnson Matthey
Catalysts, KATALCO 51-9s).
Figure 2 shows STEM pictures highlighting the positions of CuO
particles as obtained from EDX mapping. The ZrO2 particles in
Figure 2 are in the size range of ca. 10 nm, similar to the crystallite
size (Table 1). The size of CuO on CuO-ZrO2-B was slightly smaller
than that on CuO-ZrO2-A. With the 2-FSP technique the CuO size
was changed, without changing ZrO2 size (STEM and PXRD), nor
specific surface area (N2 adsorption). Accessible metallic Cu surface
area was measured by N2O titration. As summarized in Table 1, N2O
consumption amount for as-prepared CuO-ZrO2-A, and CuO-ZrO2-B
-1
were 642, and 800 μmol gCu , respectively. Also, the Cu dispersion
(= the ratio of exposed Cu amount to the total number of Cu) of
CuO-ZrO2-B (5.1%) was larger than that of CuO-ZrO2-A (4.1%).

The reducibility of the prepared catalysts was evaluated by

Figure 1. Schematics of (a, b) two-nozzle flame spray pyrolysis
(2-FSP) and (c) one-nozzle flame spray pyrolysis (1-FSP). The CuO
clusters in (a) are bigger compared to (b) since in (b) a higher O2
dispersion flow is used on the CuO side, cooling the CuO-producing-
flame leading to a shorter residence time of the CuO clusters in the
hot zone of the flame.
temperature programmed reduction by H2 (Figure S2). No peak
appeared for ZrO2 (FSP) while broad peaks appeared for Cu-
containing samples in the temperature range 150-350 °C, therefore
mainly CuO was reduced. The CuO (FSP) was reduced between 150
and 300 °C. Since CuO-ZrO2-A and CuO-ZrO2-B were reduced at
lower temperatures than CuO (FSP), the interaction between Cu
26, 27
species and ZrO2 facilitates the reduction of CuO.

Table 1 summarizes the main characteristics of the investigated

2 -1
samples. Pure ZrO2 powder (ZrO2 (FSP)) had a SSA of 126 m g . The

Table 1. Summary of the characteristics of FSP and commercial catalysts.

2 -1 a e
Sample Composition Preparation SSA / m g Cu loading Dt-ZrO2 N2O cons. TOFMeOH
/ wt% / nm / μmol gCu
-1
/h
-1

Fresh Spent Fresh Spent

CuO-ZrO2-A CuO/ZrO2 2-FSP 106 94 11 11 642 709 5.1
CuO-ZrO2-B CuO/ZrO2 2-FSP 114 97 14 10 800 511 10.7
ZrO2(FSP) ZrO2 1-FSP 126 119 - 11 - - -
b
CuO(FSP) CuO 1-FSP 48 6 80 - - N. D. -
CuO-ZrO2(FSP) CuO/ZrO2 Physical 16 c - - - -
112 -
mixing
CuZnAl Cu-Zn-Al Commercial 94 - 50 - - 628 7.0

a
Crystallite size of t-ZrO2 estimated by XRD. b % Cu in pure CuO. c Based on the mixing ratio. d Commercial catalyst KATALCO 51-9 by
e -1
Johnson Matthey. Turnover frequency of MeOH production. Reaction condition: CO2/H2/N2 = 1/3/1, W/F = 480 mgcat mL s, reaction
temperature = 270 °C, pressure = 20 bar.

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Figure 2. STEM image of (a) CuO-ZrO2-A, and (b) CuO-ZrO2-B.
Highlighted areas are Cu-rich zones from EDX mapping, particles not
highlighted have been identified as ZrO2. STEM images of (c) CuO-
ZrO2-A, and (d) CuO-ZrO2-B without Cu mapping.
Methanol production rates for the prepared catalysts and CuZnAl
are summarized in Figure 3a. The order of the methanol production
rate per copper mass (gCu) was CuO-ZrO2-B > CuZnAl > CuO-ZrO2-A
> CuO (FSP) > CuO-ZrO2 (PM). The ZrO2 (FSP) as well as CuO-ZrO2
(PM) were inactive for methanol production (less than 0.1 mL(stp)
-1 -1
min gCu ). Figure 3b shows the methanol selectivity at different
CO2 conversion. The CO2 conversion was adjusted by changing W/F
-1
ratio from 10 to 480 mgcat mL s. At low CO2 conversion, methanol
production was dominant, and the methanol selectivity decreased
15, 18
with higher CO2 conversion, comparable to previous reports
For CuO (FSP), methanol selectivity decreased from 62 to 41% with
increasing CO2 conversion (when the methanol selectivity
decreased the CO and H2O increased instead). The methanol
selectivity for the CuO-ZrO2-A, CuO-ZrO2-B and CuZnAl was much
higher than that for CuO (FSP). CuO-ZrO2 (PM) had very low activity
and therefore the selectivity could not be determined reliably and
was therefore excluded in Figure 3a. The selectivity-conversion
trend for CuO-ZrO2-A followed a similar trend like the commercial
CuZnAl, while the selectivity for CuO-ZrO2-B was higher at the same
CO2 conversion compared to the other here investigated catalysts.
Besides, improving the selectivity is challenging, particularly at
higher CO2 conversions (5-10 %) under low pressure CO2
hydrogenation. In that respect, the performances of our best
catalyst are significantly improved by comparison with the
reference catalysts (from 29 to 45 % at 5.9 % CO2 conversion).
Figure S3 shows Cu K-edge XANES spectra for CuO-ZrO2-A and CuO-
ZrO2-B under the CO2-to-methanol hydrogenation condition (20 bar,
230 °C, CO2/H2/N2 = 1/3/1). These spectra are identical to that of Cu
foil and show a first inflexion point at 8979 eV assignable to Cu0,
indicating that Cu species on CuO-ZrO2-A and CuO-ZrO2-B were
mainly metallic during the CO2 hydrogenation. This is in accordance
with our previous report, where the main active sites for CO2-to-
methanol hydrogenation are located at the interface between Cu0
18
and ZrO2. In contrast to this, the CuO (FSP) as well as CuO-ZrO2
(PM) sample showed only little MeOH production (Figure 3a).
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Catalysis Science & Technology Accepted Manuscript
Figure 3. (a) Methanol production rate for three types of CuO-ZrO2,
CuO (FSP), and CuZnAl catalysts. (b) Methanol selectivity at
different CO2 conversion for prepared catalysts and commercial
CuZnAl. The CO2 conversion was varied by changing W/F ratio from
-1
10 to 480 mgcat mL s. Reaction condition: CO2/H2/N2 = 1/3/1,
reaction temperature = 270 °C, pressure = 20 bar. Before the
reaction test, all catalysts were reduced at 300 °C in 17%H2/N2 (60
mL min-1) for 30 min under 1 bar.
The SSA of the spent catalysts are rather constant, albeit decreasing
slightly (Table 1), showing that the catalysts were stable under the
reaction conditions. The ZrO2 phase of prepared CuO-ZrO2 catalysts
did not change during catalysts testing, as evidenced by PXRD
patterns (Figure S1b). After reaction, no CuO species were detected
in the spent CuO (FSP) catalysts, but metallic Cu was found instead.
The spent CuO-ZrO2, however, showed neither Cu nor CuO (Figure
S1b), probably because crystallite sizes of Cu species were smaller
than the detection limit for PXRD. As described above, the Cu
.
species on CuO-ZrO2-A and CuO-ZrO2-B were metallic Cu (Figure S3).
Figure S4 shows STEM pictures of spent CuO-ZrO2-B highlighting Cu
species obtained from EDX mapping. The Cu particle size was in the
range of 10-20 nm. In PXRD (Figure S1b) neither Cu nor CuO was
observed for the spent CuO-ZrO2-B, in spite of the fact that the Cu
species particle size (10-20 nm) was larger than the detection limit
for PXRD (less than 5 nm), as shown in Figure S4. Thus, the Cu
clusters with less than 5 nm aggregated with each other on ZrO2,
resulting in the formation of Cu clusters of 10-20 nm in the spent
CuO-ZrO2-B.
The amount of surface Cu for the spent CuO-ZrO2-A and CuO-ZrO2-
B were measured by N2O titration to be 708 and 511 μmol gCu-1,
respectively, as shown in Table 1. The corresponding Cu dispersion
(= the ratio of exposed Cu amount to the total number of Cu) for
the spent catalysts was CuO-ZrO2-A (4.5%) > CuO-ZrO2-B (3.3%). We
note that the Cu dispersion of the spent CuO-ZrO2-B (3.3%) was
smaller than that of the spent CuO-ZrO2-A (4.5%), in spite the as
prepared CuO-ZrO2-B showed higher Cu dispersion than the as
prepared CuO-ZrO2-A. The turnover frequency (TOF) of methanol
production per exposed Cu sites was calculated according to Eq. S5
(see ESI) and summarized in Table 1. The turnover frequency for
CuO-ZrO2-B was higher than those for CuO-ZrO2-A and CuZnAl
catalysts. However, as we discussed in our previous publication on
the topic 18 (and also reported in other papers 5, 12, 14), the most
active sites in this type of systems are likely located at the interface
between metal and the oxide. Thus, all surface copper sites are not
equally active. Smaller particle size can translate into high
dispersion (= copper atoms exposed at the surface) but also to a
28-31
higher number of interfacial sites . Thus, the fact that we
calculate different TOF values for the two 2-FSP catalysts likely
Catal. Sci. Technol., 2017, 00, 1-3 | 3
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means that CuO-ZrO2-B contains in proportion more interfacial sites
vs. copper surface sites than CuO-ZrO2-A, in line with the smaller Cu
particle size observed by mapping on the former.
In conclusion, we made CuO-ZrO2 catalysts with flame spray
pyrolysis for methanol synthesis via CO2 hydrogenation. The CuO
size was varied for CuO-ZrO2 without changing the ZrO2 morphology
and size. A CuO-ZrO2 catalyst with smaller CuO particles had higher
selectivity towards methanol at a given CO2 conversion compared
to commercial CuO/ZnO/Al2O3, and CuO-ZrO2 with large CuO
particles. The resulting catalyst also had a higher activity,
Published on 20 March 2018. Downloaded by Fudan University on 20/03/2018 20:36:09.
normalized by mass of surface exposed copper, than the other
catalysts studied - including the commercial CuO/ZnO/Al2O3 catalyst.
During the MeOH production at 20 bar at 230 °C the CuO was
completely reduced to metallic Cu according to XANES
measurements. Overall, flame pyrolysis approach provides a
scalable access to efficient CO2 hydrogenation catalysts, and we are
currently exploring ways to further improve their catalytic efficiency.
Supporting Information
Experimental details, PXRD patterns, H2-TPR results, XANES data,
STEM imaging.
Funding Sources
The research leading to these results has received funding from the
SCCER (REF-115-40004), European Research Council under the
European Union's Seventh Framework Program (FP7/2007-2013) /
ERC grant agreement n° 247283, and ETH. S.T. were also supported
by the Japan Society for the Promotion of Science (JSPS, No.
15J10157).
Conflicts of interest
The authors declare no conflicts.
Acknowledgement
TEM studies were conducted at ScopeM at ETH Zürich by Frank
Krumeich. XAS measurements were carried out at the SuperXAS
beamline at the Swiss Light Source (SLS; Paul Scherrer Institut,
Villigen, Switzerland). We are grateful to Dr. Olga Safonova and Dr.
Maarten Nachtegaal, Paul Scherrer Institut, for their kind help with
XAS.
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