MOF-derived/zeolite hybrid catalyst for the production of light olefins from CO2

Article abstract of DOI:10.1002/cctc.202001109

In this contribution we propose an alternative catalytic system based on MOF derivatives and small pore zeolites for the selective conversion of CO₂ into light olefins, using the lowest metal loadings and highest GHSV reported in literature. The catalyst synthesis involves deriving In?Zr oxides from MOFs containing these metals in their structure, i. e. (Zr)UiO-67-bipy-In, via direct calcination in the presence of the zeolite, avoiding co-precipitation, washing and mixing steps. This effectively creates a truly bifunctional In?Zr zeolite catalyst, opposed to physical mixtures of two catalysts using different precursors. The good dispersion and low loadings of the MOF-derived In?Zr oxide supplemented with the strong acidity of chabazite-type zeolites allows to couple the activation of CO₂ with C?C coupling, obtaining space time yields of 0.1 mol of CO₂ converted to light olefins per gram of In per hour at 375 °C, under the GHSV conditions employed.

Full text of DOI:10.1002/cctc.202001109

The European Society Journal for Catalysis
Supported by
Accepted Article
Title: MOF-derived/zeolite hybrid catalyst for the production of light
olefins from CO2
Authors: Nuria Martín, Ander Portillo, Ainara Ateka, Francisco G
Cirujano, Lide Oar Arteta, andrés aguayo, and michiel
dusselier
This manuscript has been accepted after peer review and appears as an
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of the final Version of Record (VoR). This work is currently citable by
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1/2020

ChemCatChem
10.1002/cctc.202001109
FULL PAPER
MOF-derived/zeolite hybrid catalyst for the production of light
olefins from CO
2
[
a] ‡
[b]‡
[b]
[c]
[b]
Nuria Martín, * Ander Portillo, Ainara Ateka, Francisco G. Cirujano, Lide Oar-Arteta, Andrés T.
[
b]
[a]
Aguayo, * and Michiel Dusselier *
[
[
[
a]
b]
c]
Dr. N. Martín, Prof. M. Dusselier
Center for Sustainable Catalysis and Engineering (CSCE)
KU Leuven
Celestijnenlaan 200F, 3001 Leuven, Belgium
E-mail: nuria.martin@kuleuven.be; michiel.dusselier@kuleuven.be
Ander Portillo, Dr. Ainara Ateka, Dr. Lide Oar-Arteta, Prof. Andrés T. Aguayo
Department of Chemical Engineering
University of the Basque Country UPV/EHU
P.O. Box 644, 48080 Bilbao, Spain
E-mail: andrestomas.aguayo@ehu.eus
Dr. F. G. Cirujano
Instituto de Ciencia Molecular (ICMol)
Universitat de Valencia
Catedrático José Beltrán Martínez nº 2, 46980 Paterna, Valencia, Spain
‡
These authors contributed equally to this work
Supporting information for this article is given via a link at the end of the document.
metal/oxide interface.[7] Due to the stoichiometry of the gas-phase
reaction and its exothermic nature (CO + 3H  CH OH + H O,
ΔHT=298K = -49.3 kJ/mol), both the increase in reaction pressure
Abstract: In this contribution we propose an alternative catalytic
2
2
3
2
system based on MOF derivatives and small pore zeolites for the
2
selective conversion of CO into light olefins, using the lowest metal
and decrease in reaction temperature, respectively, could favor
loadings and highest GHSV reported in literature. The catalyst
synthesis involves deriving In-Zr oxides from MOFs containing these
metals in their structure, i.e. (Zr)UiO-67-bipy-In, via direct calcination
in the presence of the zeolite, avoiding co-precipitation, washing and
mixing steps. This effectively creates a truly bifunctional In-Zr zeolite
catalyst, opposed to physical mixtures of two catalysts using different
precursors. The good dispersion and low loadings of the MOF-
derived In-Zr oxide supplemented with the strong acidity of chabazite-
CO
2
conversion and subsequent methanol formation. However
the yield of methanol synthesized from CO
kinetically limited at low temperatures (<300 °C), requiring
catalytic promotion.[
Among recent metal- and reducible oxide-based catalysts for the
2 3
selective synthesis of methanol, In O has been reported as a
highly efficient catalytic system, avoiding side products such as
CO from reverse water gas shift (RWGS), hydrocarbons, higher
2 2 3
alcohols, etc. In the hydrogenation of CO to methanol, this In O
2
hydrogenation is
8-10]
type zeolites allows to couple the activation of CO
2
with C-C coupling,
catalyst achieves near 100% of selectivity and outstanding activity
under (industrially) relevant conditions (T = 200–300 ºC, P = 1.0–
5.0 MPa, and gas hourly space velocities (GHSV=16ꢀ000–48ꢀ000
obtaining space time yields of 0.1 mol of CO converted to light olefins
2
per gram of In per hour at 375ºC, under the GHSV conditions
employed.
−1 [11]
h ). These authors also showed that it is possible to increase
the amount of active vacancies by adding CO to the gas feed or
using the electronically interacting ZrO
2
as support for In
2
O
3
,
resulting in a highly active and stable supported In
catalyst.
On top of novel methanol synthesis catalysts using CO , there has
2
2
O
3
/ZrO
2
Introduction
been an increased interest in the direct transformation of
methanol into base petrochemicals, as methanol is a platform
chemical that can be generated from non-petrol-derived
feedstocks (e.g. coal, natural gas or biomass), through
Climate and pollution concerns, feedstock availability and
geopolitical issues increase the need for alternative sustainable
processes for the production of chemicals and fuels. In this
context, the utilization of CO
2
as a feedstock (from carbon capture
[12]
intermediate syngas. Among those petrochemicals, light olefins
or concentrated point-sources) for making valuable compounds
or intermediates, preferably containing more than one carbon, is
a grand challenge of our time.[1-3] Among different strategies that
(
such as ethylene and propylene) are important building blocks in
the chemical industry, with worldwide production in the range of
[13]
200 million tons per year (mainly from steam cracking today).
aim to use CO
2
as a carbon feedstock, e.g. solar or
When methanol is activated in the presence of acid catalysts such
as zeolites, it can be transformed into different hydrocarbons,
depending on the porous structure of the molecular sieve in which
electrochemical, classic thermo-catalytic methods certainly
[4-5]
deserve their place.
The hydrogenation of CO
such a route, provided one has a point source of CO
2
to methanol (C1 product) presents
, e.g. from
[14]
the active proton site is located.
2
In this sense, small pore zeotypes and zeolites (3.5-4Å) with large
industry or power plant flue gases (e.g. 10% pure), and
[15-18]
cavities, e.g. CHA, AEI, DDR,
are able to convert methanol
sustainable hydrogen, e.g. from solar water splitting.6 Reported
to light olefins (C2, C3 and some C4 alkene building blocks for
plastics). The large cavities allow the formation of the intermediate
hydrocarbon pool and favor the diffusion of the produced light
olefins out of the small pores, avoiding their further
systems for such CO
of CO + syngas (CO/CO
catalyst based on Cu/ZnO/Al
2
conversion, or the conversion of mixtures
/H ), often make use of a classic redox
, with a crucial role for the
2
2
2
2
O
3
1
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ChemCatChem
10.1002/cctc.202001109
FULL PAPER
oligomerization and cracking.[19] Although still not a mature
decrease the In content and outperforms certain state-of-the art
technology, the direct hydrogenation of the CO
2
to methanol
catalysts in terms of (CO
2
-to-) olefins space time yield.
combined with further C-C coupling into value-added products
with two or more carbons, i.e. ethylene or propylene, is a very
promising gas-to-liquid process.[20] This direct strategy allows for
obtaining light olefins with a reduced number of steps and
minimized chemical waste, while, most importantly, offering the
prospect of fossil-fuel independent olefins production, hopefully
In-Zr MOF
In3+
Zr
4+
OH-
with the net consumption of greenhouse gas CO
An industrially viable heterogeneous catalyst is highly desired,
however, this is challenging due to the inertness of CO , the
2
.
In-Zr oxide
2
combination of two sets of reaction conditions and the activation
barriers of C-C coupling. On the one hand, the first step requires


High In-Zr
dispersion
Low In-Zr
loading
CHA zeolite
 Low In-Zr
active metal or metal oxide species able to selectively reduce CO
into C1 oxygenate intermediates (e.g. methanol or CHO ),
2
dispersion
 High In-Zr
loading
x
avoiding undesired CO (from RWGS reaction) or the
accumulation of methanol. On the other hand, the second
transformation from the C1 oxygenate intermediates requires an
acid catalyst with sufficient activity and selectivity during the C-C
bond formations towards the desired light olefins. Note that in
(
In-Zr)MOF/CHA
In-Zr/CHA
2
another route, i.e. CO to syngas followed by Fisher-Tropsch
chemistry, CO can be the desired intermediate, but not for the
zeolite based C-C coupling.[21,22]
For the methanol route, the state-of-the-art so far has focused
mainly on physically mixing two types of solid catalysts (redox,
In-Zr Oxide
acid) in a single reactor vessel for both reductive and C-C
coupling steps.[
23-25]
In this sense there are several reports
combining the In-Zr oxides with oxygen vacancies (as methanol
synthesis catalyst) and zeotype SAPO-34, based on its good
performance in the methanol-to-olefins (MTO) process.[26-29] Such
catalyst combination favors both the methanol generation on the
2 3 2
Figure 1. Different synthetic procedures for the obtention of In O /ZrO -CHA,
either through physical mixture of the oxides and zeolite, or via co-calcination of
the zeolite with (Zr)UiO-67-bipy-In MOF. The resulting hydrogenation/acid
bifunctional catalysts are applied in the direct production of light olefins from
CO2.
2 3 2
surface of In O /ZrO , and the in situ conversion into light olefins,
with high selectivities (80-90% in the hydrocarbon fraction),
shifting the equilibrium towards methanol in the first reaction and
avoiding the undesired CH
surface polymerization of CH
4
fraction or even uncontrollable
Results and Discussion
(x = 1–3) on the metal surface.[
26]
x
However, the metal oxides obtained through co-precipitation
methods requires the use of stoichiometric amount of base, which
a cost, safety and corrosion (handling-neutralization) concern.
Structural and physico-chemical properties
First, different aluminosilicates as potential acid catalysts for the
second C-C coupling step (MTO) were prepared.[
41,42]
Two
Moreover, the use of silico-alumino phospates as MTO catalysts
often suffer from low stability and/or acid strength.[30]
zeolites with chabazite (CHA) structure and different acid
contents (Si/Al = 15 and 30) were synthesized (see supporting
information for synthesis details on all zeolites/zeotypes). A
sample of benchmark SAPO-34, the commercial catalysts
In this work we propose, on the one hand, the use of
aluminosilicate zeolites with the same CHA topology as zeotype
SAPO-34, but with different acid strengths, and we compare their
catalytic performances for the direct transformation of CO into
2
light olefins. On the other hand, we focus our attention on the use
of In-Zr mixed metal organic frameworks (MOFs) as precursors of
[
43]
employed for this process, was also prepared. Additionally the
SSZ-39 small-pore zeolite with the AEI structure was prepared,
given its good MTO performance, in order to compare possible
effects of the cage structure (similar to CHA with small pores and
redox active and robust supported (In-Zr)O
x
nanoparticles
large cavities) on the catalytic performance.[
15,44]
The microporous
uniformly distributed in (or on) the aluminosilicate phase (i.e.
SSZ-13), after its thermal decomposition (see Fig. 1). These
MOFs could be cost-efficient since they can be potentially
prepared from commercially available precursors using
inexpensive, environmentally benign and scalable strategies,
nature of the silicoaluminophosphate (SAPO-34) and zeolites was
confirmed by N physisorption, showing a higher porosity for the
CHA zeolites (690 m g ) with respect to the SAPO-34 (563 m g
2
2
-1
-1
2 -
1
2
)
or SSZ-39 (457 m g ) samples, (see Fig. S2 and Table S1 in
the supporting information). The high external surface area of the
employing water as solvent, room temperature conditions or even
2
-1
2 -1
rapid and clean mechanosynthesis.[31-33]
chabazites (̴ 150 m g ) with respect to the SAPO-34 (̴ 10 m g )
indicates the nanosized nature of the zeolite crystals. This was
confirmed by transmission electronic microscopy (TEM). The
crystal sizes of the samples increase in the order: CHA < SAPO-
Furthermore, MOFs are an interesting alternative to the use of co-
precipitated bulk metal oxides due to the fact that the metal (oxide
precursor) sites are atomically dispersed in a metal organic
crystalline framework and thus, it should produce less
34 < SSZ-39 (see Fig. S6 and S7 in the supporting information).
The different zeolites were mixed with In-Zr oxides (prepared via
hydrothermal co-precipitation, see supporting information for
details) in order to obtain the physically combined In-Zr/zeolites
powder with a mass ratio 1:2 (zeolite/oxide). For that, In-Zr oxides
and the corresponding zeolite were crushed together, pelletized
and sieved (particle size of 0.25 - 0.5 mm). The In-Zr bulk oxide
was characterized by an In content of 15.4 wt% (see Table S2 in
the supporting information).
agglomerated and smaller nanoparticles after thermal
decomposition of the linker in the close vicinity of the zeolite.[34-40]
Recently, some of the authors here used this concept to create
Zn and Cu oxide clusters on FAU zeolites for C-C and C-N
couplings during the synthesis of fine chemical intermediates.[34]
Moreover, different groups have employed MOFs or MOF derived
catalysts in the hydrogenation of CO into hydrocarbons (Fischer-
Tropsch) and hydrogenation of CO
2
into methanol or methane.[
35-
4
0]
Secondly, we prepared a sample of (Zr)UiO-67-bipy-In MOF by
Here, we describe the possibility to use In-Zr-based MOFs as
pre-catalysts in the presence of acid CHA zeolites, to yield truly
bifunctional materials for the direct transformation of CO into
olefins (see (In-Zr)MOF/CHA in Figure 1). This strategy allowed to
solvothermal reaction between ZrOCl
,5'dicarboxylic acid and biphenyl-5,5'-dicarboxylic acid. The
anchoring of In(III) to the bipyridine groups of the MOF is achieved
2 2
·8H O, 2,2'-bipyridine-
5
2
2
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10.1002/cctc.202001109
FULL PAPER
by soaking the MOF in an ethanolic solution of In(NO
3
)
3
H
2
O (11
CO
2
starts to be converted at temperatures higher than 350 ºC,
wt.% of In respect to the total MOF weight). The MOF structure
and composition was confirmed by XRD, liquid H-NMR and TGA
with almost no conversion at lower temperatures, under the
reaction conditions employed (see Fig. 3a). In our hands, the
benchmark physically mixed In-Zr/SAPO-34 sample, shows an In-
1
(
see Figures S3 and S4 in the supporting information). In order to
obtain the MOF-derived In-Zr oxides, we have employed a
recently reported methodology based on the use of metal-organic
frameworks (MOFs) as precursors of metal oxide nanoparticles
after thermal treatment at high temperature.[34-40] To the best of
our knowledge, this MOF derived method has not been reported
for In-Zr oxides in this particular catalytic application. Specifically,
we have co-calcined the (Zr)UiO-67-bipy-In MOF (7 wt.% In) in
the presence of the CHA30 zeolite with a MOF/zeolite mass ratio
of 0.5/1. The resulting (In-Zr) oxide-zeolite hybrid material should
have a mass ratio of 7/1 zeolite/oxide of 7:1, based on the metal
based reaction rate (amount of CO
2
converted per bulk indium
weight and time) that increases in parallel with the reaction
-
4
-1 -1
-4
temperature (from 1·10 molCO2·gIn ·s at 375 °C to 9·10
-1
-1
molCO2·gIn ·s at 450 °C), as shown in Fig.3a. The In−Zr oxide
mixed with the CHA30 zeolite with high Si/Al ratio of 30, shows an
In-based conversion rate higher to that of the CHA15 with Si/Al
ratio of 15 (1.3·10-4 vs.7.9·10 molCO2·gIn ·s , respectively) at
375 °C. This either highlights a remarkable contribution of strong
acid sites (for the same type and content of mixed In-Zr oxides in
-5
-1 -1
2
both zeolite samples) to the hydrogenation of CO or, alternatively,
III
content of the MOF and stoichiometric oxide formation of In and
that the zeolite-based differences in MTO chemistry affect the
equilibrium or conversion rate of the first step. The latter seems
more plausible, i.e. the CHA with a higher Si/Al ratio induces a
IV
Zr
after co-calcination. The detailed synthesis and
characterization of the MOF is described in section 1 of the
supporting information). Importantly, the In content in the final
composite was only 2.3 wt% (see the ICP analysis in table S2 of
the supporting information).
higher CO
acidity favours a quicker conversion of the methanol produced
(pulling it away from its CO hydrogenation equilibrium), into light
2
conversion rate, pointing to the fact that the strong
2
For both co-calcined MOF-zeolite and co-precipitated oxide-
zeolites, the PXRD patterns of the final In-Zr/zeolites mixtures
show the preservation of the zeolite crystalline structure, and the
presence of the In-Zr oxide phase reflections at 2θ= 30, 35 and
olefins (with respect to other hydrocarbons), rather than
accumulating oxygenated intermediates. The latter occurs with
SAPO-34, as we will further discuss when analysing product
distributions.
5
0 degrees (see Fig. 2 a). NH
Desorption (NH -TPD) indicates a higher total amount of acid
sites in the case of the physically-mixed In-Zr/CHA sample (136
mmol NH /g) with In /ZrO , with respect to the (In-Zr)MOF/CHA
101 mmol NH /g) with the MOF derived In /ZrO prepared by
co-precipitation in the presence of the zeolite (see Fig. 2b). The
incorporation of MOF-derived In /ZrO in close contact with the
3
-Temperature-Programmed
Given the good performance of the In-Zr/CHA30 sample, we
decide to investigate routes to decrease the In-Zr loading, while
maintaining or improving the good catalytic performance of using
a zeolite (instead of a SAPO). The MOF-derived sample
described previously fulfils this requirements, and, in fact, the (In-
3
3
2
O
3
2
(
3
2
O
3
2
2
Zr)MOF/CHA30 exhibit the highest CO conversion values per gIn at
-
3
-1 -1
2
O
3
2
temperatures higher than 425 °C (1·10 molCO2·gIn ·s ).At lower
temperatures comparable conversions to that of In-Zr/CHA30 are
observed (see Fig. 3a). The In-based reaction rate per g of indium
(as metal, but present in oxide form) obtained with the sample of
In-Zr/SAPO-34 prepared in this work, is different than the
zeolite slightly decreases the number of acid sites and affects
their strength distribution as well, as described for CuO/ZnO on
FAU zeolite.[
34]
Finally, the TEM images indicate a better
dispersion of the In
the In-Zr /CHA physical mixture. For the latter, the higher loading
of In-Zr, in accord with the ICP results, is clear from TEM as well
2
O
3
/ZrO in the (In-Zr)MOF/CHA with respect to
2
previously reported ones (2·10-4 vs. 1·10 molCO2·gIn ·s at
-4
-1 -1
400°C, 3MPa, H
employed here, 78300 vs. 9000 ml·gcat ·h (expressed as the
space time velocity in ml·gcat ·h ).
2 2
/CO = 3/1), probably due to the high GHSV
-
1
-1
(
see Table S2 in the supporting information).
-
1
-1 [23]
A high space velocity is
Catalytic properties
The performance of the different samples for the hydrogenation
of CO at different temperatures was studied. The tests were
2
industrially interesting if the conversions rate can remain high,
since it allows minimizing the amount of catalyst or contact time,
which results in a faster and cheaper catalytic system.
2 2
conducted with a H /CO feed gas ratio of 3/1. For all samples,
a)
b) 100
In-Zr
-3
-4
a)
(In-Zr)MOF/CHA30
In-Zr/CHA30
b)
In-Zr/CHA30
1x10
7
5
In-Zr/CHA15
In-Zr/SSZ-39
(In-Zr)MOF/CHA30
*
In-Zr/SAPO-34
In-Zr/SAPO-34
In-Zr/SSZ-39
In-Zr/CHA15
In/Zr-CHA30
(In/Zr)MOF-CHA30
8
4
x10
x10
*
*
50
-
4
2
5
0
0
3
50
375
400
425
450
350
375
400
425
o
450
o
Temperature ( C )
Temperature ( C )
c)
d)
1
0
20
30
40
50
60
150 200 250 300 350 400 450 500 550
100
100
80
60
40
20
0
10
8
2
 (degree)
0
Temperature/
C
8
6
4
2
0
c)
d)
0
0
0
0
6
4
(
In-Zr)MOF
2
CHA30
0
9
15
30 /CHA30
MOF
34 SZ-39
In-
15
30
CHA30
Zr/CHA Zr/CHA
APO- Zr/S
Zr/CHA Zr/CHA
In-
/
Zr/SAPO-3 4Z r/SSZ- 3I n-
In-
In-
-Zr)
Zr/S
In-
(In-Zr)MOF
In-
(In
In-
Figure 3. Conversion
equation 푟 = 퐹푙표푤퐶푂2 · 2
ꢀ
r
ꢁ
a
푛
t
푣
e
.
ꢀꢂꢃ(r) of CO
2
per In weight, obtained from the
1
00
(a) and selectivity to CO (b) at different
2.4 푔.퐼푛
temperatures for the series of catalysts. Selectivity of products: olefins (red),
paraffins (black), methane (magenta) and oxygenates (blue); with respect to the
selectivity of CO (grey) at 375ºC (c). The product distribution without considering
Figure 2. (a) PXRD patterns of the catalyst samples employed in this work. (b)
NH -TPD of the (In-Zr)MOF/CHA (red) and In-Zr/CHA (black) catalysts. (c) TEM
image of (In-Zr)MOF/CHA. (d) TEM image of In-Zr/CHA.
CO is shown in part (d), together with the C
dots), both at T= 375ºC.
2 4
-C olefin/paraffin ratio (see green
3
3
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However, for temperatures higher than 400 ºC, the major part of
modified CHA versus when using the standard co-precipitated
approach. This could be related to the slightly altered and lower
amount of acid sites in the MOF-derived sample, as seen from
the CO
2
is hydrogenated into CO, through the favoured
(
endothermic) reverse water gas shift reaction (see Fig. 3b and c).
The selectivity of hydrocarbons with respect to that of CO at the
edge temperature of 375ºC is 10% higher for the MOF-based
hybrid sample with respect to the co-precipitated oxides mixed
NH
3
-TPD in Fig. 2b. Based on the reaction pathway of CO
firstly
2
hydrogenation over oxide/zeolite mixed catalysts, CO
2
hydrogenates to the methanol intermediate on the metal oxide
phase, and then the intermediate transfers to the acid sites of the
zeolite for C–C coupling to generate hydrocarbons. The proximity
of these two types of active sites can play an important role in
giving a high selectivity for desired light olefins (mainly ethylene
and propylene, as shown in Figure S9c). In the case of the well-
dispersed MOF derived hybrid (In-Zr)MOF/CHA30, the distances
between the In-Zr sites and the acid sites are likely shorter
(tentative in Fig. 2c), favouring the transformation of methanol or
CO intermediates into the desired hydrocarbons.
In order to put our work in context, the values of space-time yield
obtained with the samples prepared in this work (entries 8-12 in
Table S5) were compared with those reported in literature (entries
1-7 in Table S5). In general, it is clear from these two groups of
results that the use of a higher GHSV results in a higher amount
of olefins produced per hour and gram of catalyst (STYolefins).
̴
1·10- molCO2·gIn
4
-
with CHA, at comparable CO
·
2
conversion rate (
s ). This indicates that the MOF derived sample promotes to a
higher extent the hydrogenation (at the well-dispersed In-Zr MOF-
derived oxides) of CO into CH O intermediates that further
1
-1
2
x
migrate to the nearby strong Brønsted acid sites of the CHA,
resulting in the corresponding hydrocarbons (see Fig. 3c). The
CH O species likely run through methanol synthesis and with
x
transformation of the methanol into light olefins. This is
corroborated by the product slate of the In-Zr/SAPO-34 where the
oxide part of the physically mixed catalyst generated methanol
with 13% selectivity in the hydrocarbon fraction at 375 ºC (see
blue bar in Fig. 3d).
In the case of In-Zr/SAPO-34, the olefin selectivity at 375 °C in
the hydrocarbon phase (see Fig. 3d) is significantly lower with
respect to the (In-Zr)MOF/CHA30 (69 vs. 87%), highlighting the
importance of the strong acidity in the conversion of the methanol
produced into light olefins and avoiding the accumulation of
oxygenated intermediates. Zeolites allow performing MTO at
slightly lower temperature than SAPO zeotypes. The co-
precipitated In-Zr/CHA30 selectivity is lower than the MOF derived
one (76%), although still higher than samples with a less well
performing acid component (see Fig. 3d), e.g. In-Zr/CHA15 (45%),
In-Zr/SSZ-39 (49%) and In-Zr/SAPO-34 (69%) at 375ºC, for
Despite the good selectivities to olefins in most cases, the CO
2
conversions are below the reported values obtained for lower
GHSV, likely the effect of the shorter contact times in our case.
The best performing catalyst is the one containing SSZ-13 (CHA,
Si/Al=30), with a productivity per gram of catalyst one order of
magnitude higher (entry 10 in Table S5) than state-of-the-art In/Zr
containing catalysts. Both the MOF- derived In-Zr (entry 11) and
the co-precipitated In-Zr physical mixed one (entry 10) with the
CHA30 zeolite show the best performances on an In-Zr oxide basis,
with the highest productivity found for the MOF-derived one (see
Figure 4a). This material allows to decrease the In-Zr content,
4
-1 -1
comparable CO
2
rate (̴
1·10- molCO2·gIn ·s ). The lower
selectivity obtained with In-Zr/CHA15 containing a high amount of
Brønsted acid sites originates partially from its higher CO
selectivity, but may also be due to the favoured oligomerisation
and cracking of the lower olefins in the more aluminous zeolite,
with generation of coke. In fact the lower Si/Al ratio results in SSZ-
resulting in a more economic catalyst for the process of CO
2
hydrogenation, maintaining one of the highest selectivities to
olefins (26% when including CO, see entry 11), reported to date.
This high selectivity, together with the better catalytic activity
results in an outperformance of the rate of olefins produced per In
weight (see Figure 4b). Indeed, the STYs on a bulk In basis is 1.4
times higher in the case of the MOF derived hybrid catalyst (98
mmololefins·gIn ·h ), with respect to the co-precipitated InZr/CHA30
mixture (72 mmololefins·gIn ·h ) and more than two times higher
than state-of-the-art In-Zr/SAPO-34 physical mixtures, in our
setup (43 mmololefins·gIn ·h ). Both MOF derived hybrid and co-
precipitated catalysts show an optimal stability under the different
reaction temperatures, as indicated by the stable conversion
values over time (see Figures S8 and S9).
13 samples with more than one Al per cavity (i.e. Al pairs) which
is reported to be correlated with both coke species formation and
rapid deactivation.[45-47] Moreover, the reduced Brønsted acidity of
CHA(Si/Al=30) also inhibits H-transfer reactions (and
consequently oligomerization) giving additional light olefins at the
expense of longer chain hydrocarbons, thus increasing the
selectivity towards olefins with respect to CHA(Si/Al=15), as has
been recently proposed for ZSM-5 (see Figure S11 for the
analysis of coke formation on the used catalyst, c.a. 4 wt.%).[48]
Beside coke formation and blocking of acid sites in the zeolite,
indium (III) cation migration during the reaction may exchange
with the zeolite protons, further decreasing the acidity (see Figure
S12). A similar catalyst behaviour is observed for the In-Zr/SSZ-
-
1
-1
-
1
-1
-
1
-1
a)
b)
39 sample with similar acidity (Si/Al ratio). The olefin/paraffin
2
0
6
100
80
60
40
20
0
ratios plotted in Figure 3d corroborate this interpretation (see C2-
C4 olefin/paraffin in green). In general, for the best samples, i.e.
1
(
In-Zr) MOF /CHA30 and In-Zr/CHA30, it can be hypothesized that
12
8
the small size of the CHA zeolite crystals (estimated at 50-100 nm
by TEM analysis, see Fig. 2c and Fig. S6) favours the fast
4
transformation of CH
the favoured diffusion (of the CH
x
O intermediates into hydrocarbons due to
O intermediates generated at
0
x
O-
34
Z-39
In-Z
15
30
30
O-
34
Z-39
In-Z
15
30 MOF/CHA
r/CHA r/CHA
In-Z
Zr)
(In-
30
r/CHA r/CHA MOF/CHA
In-Z
Zr)
r/SAP
r/SS
r/SAP
r/SS
In-Z
In-Z
(In-
In-Z
In-Z
the In-Zr oxide particles) to the acid sites in the nanocrystals. This
partially suppresses the undesired RWGS side-reaction to CO
and possibly avoids excessive olefinoligomerisation and cracking
further impeded by relatively low Al-content. Similar results have
been recently reported for nanosized CHA or SAPO-34 in MTO,
Figure 4. Production rate (Space Time Yields) for C2-C4 olefins per In-Zr oxide
weight (a) or In weight (b) at 375 ºC with the samples prepared in this work. A
feed of CO
and H
2
with a flow of 60 ml·min-1 (H
2
/CO = 3/1) was employed at
2
2
30 bar, using 46 mg of catalysts. Note that the STYs are calculated on a mmol
and also for different In-Zr/SAPO-34 catalysts in CO
2
conversion.[
27, 28]
2
CO -to- olefins basis.
There, small crystal sizes are indeed deemed
interesting to shorten the diffusion path of the methanol
=
= [30]
intermediates and enhance the selectivity of C
2 4
-C .
As pointed out earlier, the C –C olefin/paraffin (o/p) ratios
2
4
Conclusion
significantly augments with the Si/Al ratio (from 15 to 30), and with
the use of MOF-derived In-Zr oxides instead of co-precipitated
ones (see Fig. 3d). The latter is intriguing and indicates favouring
the generation of olefins over paraffins, by avoiding (or reducing)
hydrogen transfer reactions at the acid sites present in the
Herein, we have reported for the first time the use of small pore
zeolites, opposed to zeotypes, as acid catalysts in the preparation
of physically mixed In-Zr oxide/zeolite cocktail catalysts for the
4
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ChemCatChem
10.1002/cctc.202001109
FULL PAPER
upgrading of CO
This demonstrated the importance of acid strength and controlling
the acidity by varying the Si/Al ratio for the catalytic CO -to-
methanol-to-olefins cascade. Moreover, this contribution has
shown that it is possible to decrease the number of redox active
sites needed (e.g. on an Indium basis, which is a costly metal) for
the hydrogenation of CO into light olefins via a MOF-derived
2
approach in order to prepare novel bifunctional hydrogenation-
acid tandem catalysts.
2
into valuable chemicals, such as light olefins.
2 2 3 2
CHA30: SiO /0.017Al O //0.4TMAdaOH/0.2NaOH/15H O
The homogeneous gel was transferred to a 40mL Teflon lined
stainless steel autoclave (Parr Instruments) and heated at 160 °C
in an oven for 10 days. The final products were centrifuged,
washed with abundant water and dried at 100°C. All samples
were calcined in air with a heating ramp of 3 °C/min to 580 °C for
2
5
hours to remove organic template. The sodium‐containing
materials were mixed with a 1ꢀM aqueous solution of ammonium
nitrate and the mixture was stirred at 80ꢀ°C for 2 h. The solid
product was filtered, washed with abundant water, and dried at
This synthesis method allows to prepare In-Zr oxides derived from
MOFs, containing these metals in its structure, via direct co-
calcination in the presence of the zeolite, avoiding co-precipitation
and washing and mixing steps. In this manner, a truly In-Zr/zeolite
bifunctional catalyst can be created, opposed to physical mixtures
of two catalysts using different precursors. A comparison of
olefins space-time yields was made, and in our conditions of high
space velocity, the productivity of the MOF-derived catalytic
system seems among the highest reported, with 18
1
00ꢀ°C. Finally, the solid was calcined in air at 500ꢀ°C for 4 h.
[16]
Synthesis of SSZ-39 zeolite: The synthesis of SSZ-39 zeolite
(AEI) was achieved in the presence of N,N-dimethyl-3,5-
dimethylpiperidinium as organic structure directing agent. N,N-
dimethyl-3,5-dimethylpiperidinium (DMP) cation was synthesized
starting from 15g of 3,5-dimethylpiperidine (C
Aldrich, ≥99%, cis-trans mixture) dissolved in 140 mL of methanol
CH OH, Acros Organics, 99.99%) in presence of 20g of
potassium carbonate (KHCO , Sigma Aldrich, 99.7%). 55g of
7
H15N, Sigma
(
3
3
-
1
-1
-1 -1
mmololefins·gInZrOx ·h and 98 mmololefins·gIn ·h . The MOF-derived
methyl iodide (CH I, Sigma Aldrich, 99.9%) were added dropwise
3
In-Zr/CHA
severely
outperforms
benchmark
to the previous solution. Then the resultant mixture was
maintained under stirring for 6 days. After this time, MeOH was
partially removed under vacuum, and the iodide salt was
precipitated by addition of diethyl ether. For preparing the
corresponding hydroxide form, the iodide salt was dissolved in
water in the presence of a commercially available hydroxide ion
exchange resin, and it was maintained under stirring overnight.
The final solution was filtered obtaining an aqueous solution
containing the N,N-dimethyl-3,5-dimethylpiperidinium hydroxide.
For the SSZ-39 synthesis, 3.4g of aqueous solution of DMP (35%)
and 1.5g of 20ꢀwt% aqueous solution of sodium hydroxide
silicoaluminophosphates physically mixed with co-precipitated In-
Zr oxides. Overall, absolute olefin yields (here and in the art)
remain low in this cascade, highlighting one of the major
2
challenges in direct CO -to-olefins catalysis still ahead.
Experimental Section
Synthesis of the catalysts
2 3 2
Obtention of In O /ZrO
by coprecipitation method:[26] On the
(
2
Sigma–Aldrich) were mixed. Then 6.7g of deionized water and
g of commercial Faujasite (FAU, CBV-720, Zeolyst) were added
one hand, the coprecipitation of indium and zirconium oxides was
carried out starting from 3.9 g of indium nitrate and 17.6 g
zirconium nitrate dissolved in a mixture of 50 mL of deionized
water and 150mL of ethanol. On the other hand, a solution
to the previous solution achieving the final gel with the following
molar composition:SSZ-39:
2 2 3 2
SiO /0.033Al O /0.2 DMP /0.2NaOH/15H O.
containing 34 mL of ammonia hydroxide (NH
4
OH 28-30 wt% in
The homogeneous gel was transferred to a 20mL Teflon lined
stainless steel autoclave (Parr Instruments) and heated at 140 °C
in an oven for 10 days. The final product was centrifuged, washed
with abundant water and dried at 100°C. The samples was
calcined in air with a heating ramp of 3 °C/min to 580 °C for 5
hours to remove organic template. The sodium‐containing
material was mixed with a 1ꢀM aqueous solution of ammonium
nitrate and the mixture was stirred at 80ꢀ°C for 2 h. The solid
product was filtered, washed with abundant water, and dried at
H
2
O, Sigma Aldrich) in 110 mL of ethanol was added dropwise
over the previous mixture. The product was aged at 80°C for 30
min and then filtered, washed with deionized water, dried
[23]
overnight at 60°C and calcined in air at 500°C for 5h.
Synthesis of SAPO-34:[26] The silicoaluminophosphate SAPO-
4 (CHA) was prepared mixing 1,9g of aluminium hydroxide
Al(OH) , ≥64% Al , Sigma-Aldrich) with 2.1g of phosphoric
PO , 85 wt%. Sigma Aldrich) in 2.8g of deionized water
3
(
3
2 3
O
acid (H
3
4
(
(
18.2 MΩ cm). Finally, 8.5g of tetraethylammonium hydroxide
TEAOH, 35wt%. Sigma Aldrich) and 0.7g of colloidal suspension
100ꢀ°C. Finally, the solid was calcined in air at 500ꢀ°C for 4 h.
Preparation of physical mixtures: The different zeolites were
physically mixed with In-Zr oxides in order to obtain the
bifunctional catalyst with a mass ratio 2/1. For that In-Zr oxides
and the corresponding zeolite were together crushed, pelletized
and sieved (particle size of 0.25 – 0.5 mm).
of silica in water (40ꢀwt%, LUDOX‐AS, Sigma–Aldrich) were
introduced in the gel and the mixture was stirred for 30 min. The
resulting get was transferred to an autoclave with a Teflon liner
(
Parr Instruments), and heated at 160 °C during 5 days.[23] The
molar composition of the final gel was:
Synthesis and characterization of the novel In-Zr MOFs: The
solvothermal synthesis of UiO-67 MOFs starts by mixing 400 mg
0
.44 SiO : Al : P 5 : 1.6 TEAOH : 40 H O
2
2
O
3
2
O
2
2 2
ZrOCl ·8H O, 300 mg Bipy (2,2'-bipyridine-5,5'dicarboxylic acid)
The final products were centrifuged, washed with abundant water
and dried at 100°C. All samples were calcined in air with a heating
ramp of 3 °C/min to 580 °C for 5 hours to remove organic template.
Synthesis of CHA zeolites:[43] The synthesis of SSZ-13 zeolites
and 100 mg BPDC (biphenyl-5,5'-dicarboxylic acid) in 10 mL DMF
and 1 mL HAc in a 100 mL pyrex Schott bottle. This solution is put
in an ultrasound bath for 10 min, until all reactants are fully
dissolved. After one day in a conventional synthesis oven at
(
CHA) was achieved using N,N,N-trimethyladamantammonium
as organic structure directing agent. The required amounts of a
5ꢀwt% aqueous solution of N,N,N-trimethyladamantammonium
TMAdaOH, 25 wt%. Sachem) and a 20ꢀwt% aqueous solution of
sodium hydroxide (Sigma–Aldrich) were mixed. Then the required
amounts of alumina (Al , Sigma Aldrich) and a colloidal
120°C, a gel phase has formed. The final crystal form is reached
by utilizing the Büchner filtration method accompanied by
consecutively washing with copious amounts of DMF and EtOH.
The anchoring of In(III) to the bipy groups of the MOF is achieved
2
(
through the following procedure: 300 mg of In(NO
dissolved in ml of EtOH and added to 1g of
Zr (OH) 11wt.% In respect to the MOF).
3 3 2
) H O were
2
O
3
7
suspension of silica in water (40ꢀwt%, LUDOX‐AS, Sigma–
Aldrich) were added and the resultant mixture was stirred for the
time required to evaporate the excess of water until achieving the
desired gel concentration. The final molar batch compositions
were:
6
O
4
4
[BPDC]2.28[Bipy]3.72 (̴
After stirring at 30 °C overnight, the solid was recover by
centrifugation and washed three times with fresh EtOH. The
sample was dried at 60 ºC overnight under vacuum.
Synthesis of the novel In-Zr MOF derived oxides in zeolites:
Briefly, 1g of zeolite (e.g. CHA) was physically mixed with 0.5g of
2 2 3 2
CHA15: SiO /0.033Al O /0.4TMAdaOH/0.2NaOH/15H O
5
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ChemCatChem
10.1002/cctc.202001109
FULL PAPER
UiO-67-bipy-In (containing a 7%wt. of In) in a moulter, and
subsequently calcined at 580ºC during 5h. The amount of In in
the final mixture was 2.5 %wt.
Characterization of the catalysts
X-ray powder diffraction (XRD) patterns were acquired on a STOE
acknowledged for funding (CTQ2016-77812-R).
F.G.C.
acknowledge that the project leading to these results has received
funding from “la Caixa” Foundation (ID 100010434), under
agreement < LCF/BQ/PI19/11690011>. SACHEM is thanked for
providing the TMAdaOH organic structure directing agent for
SSZ-13. M.D. acknowledges KU Leuven Internal Funds and BOF.
We are grateful to Cristina Almansa for performing the TEM
analysis of the samples at the research technical services of the
University of Alicante in Spain.
stadi MP using Cu K-α radiation. Nitrogen-sorption (N
was measured with a Micromeritics TriStar 3000 instrument at 77
K. Samples were pretreated overnight under a N flow at 573 K
2
-sorption)
2
before the measurements. The surface area was calculated by
the BET method. The t-plot method was used to determine the
micropore volume. The amount of In and Zr as well as the Si/Al
ratio in the solid catalysts was determined by ICP Optical
Emission Spectroscopy (Varian 720-ES). Ammonia temperature-
2
Keywords: CO hydrogenation • zeolites • MOFs • olefins
programmed desorption (NH
apparatus with a mass spectrometer for the desorbed gas (NH
After pretreatment of the samples (100 mg) in helium flow at 673
K for 2 h, adsorption of NH was conducted at 473 K for 0.5 h.
Afterward, the sample was flushed by helium for 0.5 h at 473 K.
NH -TPD profiles were obtained by heating the sample in a
3
-TPD) was measured in a flow
3
).
3
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This article is protected by copyright. All rights reserved.

ChemCatChem
10.1002/cctc.202001109
FULL PAPER
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ChemCatChem
10.1002/cctc.202001109
FULL PAPER
Entry for the Table of Contents
In-Zr MOF co-calcined along with small pore zeolites (i.e. SSZ-13) is more efficient than the physically mixed (co-precipitated) In-Zr
oxides in the direct transformation of CO2 into light olefins, obtaining 100 mmol of light olefins per gram of In and hour.
Institute and/or researcher Twitter usernames: @ZEOCO2, @dusselierem
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