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Catalysis Today
journal homepage: www.elsevier.com/locate/cattod

Methane dry reforming over ceria-zirconia supported Ni catalysts

Astrid Wolfbeisser a , Onsulang Sophiphun b , Johannes Bernardi c , Jatuporn Wittayakun b ,
Karin Föttinger a,∗ , Günther Rupprechter a
a
Institute of Materials Chemistry, Technische Universität Wien, Getreidemarkt 9, 1060 Vienna, Austria
b
School of Chemistry, Institute of Science, Suranaree University of Technology, 111 University Ave. Muang District, Nakhon Ratchasima, 300000, Thailand
c
University Service Center for Transmission Electron Microscopy, Technische Universität Wien, Wiedner Hauptstraße 8-10, Vienna, 1040, Austria

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

Article history: Nickel nanoparticles supported on Ce1-x Zrx O2 mixed oxides prepared by different synthesis methods, as
Received 11 January 2016 well as Ni-ZrO2 and Ni-CeO2 , were evaluated for their catalytic performance in methane dry reforming
Received in revised form 30 March 2016 (MDR). MDR is an interesting model reaction to evaluate the reactivity and surface chemistry of mixed
Accepted 19 April 2016
oxides. Textural and structural properties were studied by N2 adsorption and XRD. Mixed oxide prepa-
Available online xxx
ration by co-precipitation resulted in catalysts with higher surface area than that of pure ZrO2 or CeO2 .
XRD analysis showed the formation of different Ce1-x Zrx O2 solid solutions depending on using a surfac-
Keywords:
tant or not. The catalyst prepared by surfactant assisted co-precipitation was not active for methane dry
Methane dry reforming
Nickel nanoparticles
reforming most likely because of the encapsulation of Ni particles by ceria-zirconia particles, as revealed
Ceria-zirconia by TEM and H2 chemisorption. The catalytic activity of the catalyst prepared by co-precipitation without
Mixed oxides surfactant was comparable to Ni-ZrO2 . Clearly, catalyst activity strongly depends on preparation and on
Coke the resulting phase composition rather than on nominal composition. Compared to Ni-ZrO2 the ceria-
Coprecipitation zirconia supported Ni catalyst did not achieve higher activity or stability for methane dry reforming
but, nevertheless, the formation of filamentous carbon was strongly reduced (100 times less carbona-
ceous species). Consequently, using ceria-zirconia as a support material decreases the risk of reactor tube
blocking.
© 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license
(http://creativecommons.org/licenses/by/4.0/).

1. Introduction However, other possible reactions such as reverse water-

gas-shift RWGS (1.2), steam reforming of CH4 (1.3), methane
Methane dry reforming (MDR) has attracted attention in recent decomposition (1.4) and CO disproportionation (1.5) must be con-
years, not only because of synthesis gas production, but also due sidered, resulting in H2 :CO ratios different from 1 and leading to
to environmental aspects. The MDR reaction (1.1) directly converts carbon deposition on the catalyst.
the greenhouse gases CH4 and CO2 to synthesis gas. Since a lower
H2 :CO ratio is achieved by MDR than by methane steam reform- H2 + CO2 →
←− H2 O + CO H0r (25◦ C) = +41 kJmol−1 (1.2)
ing (MSR), synthesis gas produced by MDR is effective for olefins −1
H2 O + CH4 →
←− 3H2 + CO H0r (25◦ C) = +206 kJmol (1.3)
hydroformylation and carbonylation reactions. Additionally, MDR
has great potential to be used for energy transformation and storage CH4 →
←− 2H2 + C Hr0 (25◦ C) = +75 kJmol−1 (1.4)
due to its reversibility via methanation [1].
2CO→
←− C + CO2 H0r (25◦ C) = −171 kJmol−1 (1.5)
−1
CH4 + CO2 →
←− 2H2 + 2COH0r ◦
(25 C) = +247 kJmol (1.1) The effect of carbon deposition is a major problem and may lead
to catalyst deactivation [2,3], by decoration (poisoning) of the active
metallic sites and/or physical blockage of the tubes in fixed bed
reformers [4]. Hence, intense research efforts have been focused
∗ Corresponding author.
on the development of catalysts that show high activity but are
E-mail addresses: astrid.wolfbeisser@tuwien.ac.at (A. Wolfbeisser),
onsulang 111@hotmail.com (O. Sophiphun), bernardi@ustem.tuwien.ac.at
also resistant to carbon formation and sintering. Fischer and Trop-
(J. Bernardi), jatuporn@sut.ac.th (J. Wittayakun), karin.foettinger@tuwien.ac.at sch showed already in 1928 that most group VIII metals display
(K. Föttinger), guenther.rupprechter@tuwien.ac.at (G. Rupprechter). a significant activity for methane dry reforming [5]. Many years

http://dx.doi.org/10.1016/j.cattod.2016.04.025
0920-5861/© 2016 The Authors. Published by Elsevier B.V. This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).

Please cite this article in press as: A. Wolfbeisser, et al., Methane dry reforming over ceria-zirconia supported Ni catalysts, Catal. Today
(2016), http://dx.doi.org/10.1016/j.cattod.2016.04.025
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later various transition metals (Ni, Ru, Rh, Pd, Ir, and Pt) have been
tested [6–10]. Even though Rh was the most stable and active of
group VIII metals rather Pt catalysts have been developed as excel-
lent methane dry reforming catalysts [11–15]. Besides the highly
active noble metal catalysts, nickel based catalysts are the choice
for industrial applications, due to better availability, lower cost and
comparable activity [16]. Nevertheless, the active nickel particles
tend to form coke, leading to catalyst deactivation [17].
Nickel-based catalysts have been proven to be sensitive to dop-
ing and structure modification by other metals, such as Cu, which
affects the structure and morphology of the produced carbon [18].
We have studied CH4 reforming activities and selectivity on Ni and
CuNi-based catalyst systems by combining in situ spectroscopic
techniques such as near atmospheric pressure X-ray photoelectron
spectroscopy (NAP-XPS), Fourier transform infrared spectroscopy
(FTIR) and X-ray absorption spectroscopy (XAS) [19–21]. The for-
mation of CuNi alloy nanoparticles enhanced the stability against
carbon deposition, but the CuNi alloy showed limited stability (i.e.
Ni segregation) under reaction conditions [20,21]. For in situ studies
on other bimetallics (PdZn, Pd-Ga, Pd(Pt)-Cu) we refer to [22–26].
Boron promotion of Ni-based catalysts was also reported to inhibit
the formation of bulk carbide and weaken the on-surface carbon
binding energies [27].
Clearly, in addition to the metallic component of the cat-
alyst, the support material also plays an important role in
the catalytic activity and stability towards carbon deposition.
Indeed, nickel has been supported on various supports such as
MgO [3,16,28–30], Al2 O3 [3,30–34], SiO2 [3,16,35], TiO2 [3,16],
La2 O3 [31,32], CeO2 [30,32,36], ZrO2 [32,33,37,38] and Ce1-x Zrx O2
[39–49]. Ce1-x Zrx O2 solid solution is considered as a promising
support [39–46] for Ni-based MDR catalysts. Mixing ZrO2 and
CeO2 has been found to improve the thermal stability, catalytic
activity and oxygen storage capacity. The latter refers to the abil-
ity to deliver oxygen from the lattice to the gas phase or to
solid (adsorbed) carbon [39,46,50]. Several methods have been
used to prepare Ce1-x Zrx O2 solid solutions for catalytic applica-
tions. These include the high-temperature milling of a mixture of
the oxides [51], co-precipitation [39–41,44,50,52–56], surfactant-
assisted co-precipitation [42,43,45,57,58], thermal hydrolysis
[59–61], sol-gel [46,62,63] and pseudo-sol-gel techniques [47,48].
Among these methods, the surfactant-assisted co-precipitation
route has attracted considerable interest because of its effec-
tive soft-templating, reproducibility and simplicity [58]. However,
detailed correlations of MDR catalytic activity with the oxides
microstructures (e.g. determined by Raman spectroscopy or pow-
der XRD via the Rietvield analysis) are still lacking. In order to
understand the beneficial effect of the Ce1-x Zrx O2 support is of great
importance to establish relationships between the surface struc-
tural and physico-chemical properties with the catalytic activity.
Recent studies by Makri et al. [64] provided very important
insights into the carbon formation pathways and carbon reactiv-
ity over 5 wt% Ni/Ce0.8 Zr0.2 O2-␦ and 5 wt% Ni/Ce0.5 Zr0.5 O2-␦ MDR
catalysts. Using temperature-programmed methods and transient
isotopic experiments it was demonstrated that the reaction tem-
perature and support chemical composition had a strong effect of
on the relative contribution of the CH4 or the CO2 activation routes
towards carbon formation, as well as on the reactivity of the various
carbons towards H2 and O2 .
In this contribution we have revisited the mixed oxide sup-
port and have compared the catalytic activity, stability and
coke formation tendency of Ni based catalysts supported on
Ce0.6 Zr0.4 O2 (prepared by co-precipitation and surfactant assisted
co-precipitation) with those supported by the individual supports
ZrO2 and CeO2 . MDR is an interesting model reaction to compare
the reactivity and surface chemistry of different mixed oxides.
The main aim of this work was to understand some of the influ-
Please cite this article in press as: A. Wolfbeisser, et al., Methane dry reforming over ceria-zirconia supported Ni catalysts, Catal. Today
(2016), http://dx.doi.org/10.1016/j.cattod.2016.04.025
encing factors by correlating structure (governed mainly by the
synthesis procedure) with catalytic performance. Ce0.6 Zr0.4 O2 was
chosen since Kumar et al. [42] reported Ni-Ce0.6 Zr0.4 O2 to be the
most effective methane dry reforming catalyst, as its activity was
stable for up to 100 h at 650 and 700 ◦ C. We have tested these
catalysts during MDR at 600 ◦ C for up to 24 h and characterized
them carefully before and after exposure to the reaction mixture.
The mixed oxide catalysts prepared by different co-precipitation
methods showed very different catalytic behaviour. Even though
the catalytic activity of the active ceria-zirconia supported Ni cat-
alyst was not higher than that of Ni-ZrO2 , the Ce0.6 Zr0.4 O2 support
still strongly decreased deposition of carbonaceous species.
2. Experimental
2.1. Sample preparation
Ni-ZrO2 , Ni-CeO2 and two types of Ni-Ce0.6 Zr0.4 O2 catalysts
were prepared by different methods. ZrO2 was prepared from
Zr(OH)4 (MEL Chemicals, XZO 880/01) by heating from room
temperature (RT) to 650 ◦ C at a ramp of 2 ◦ C/min and kept at
650 ◦ C for 2 h. Commercial CeO2 (Schuchardt, CE026) was cal-
cined at 650 ◦ C at a ramp of 2 ◦ C/min and kept at 650 ◦ C for 2 h.
Two further binary ceria-zirconia materials were prepared by a
co-precipitation (cp) method, both Ce0.6 Zr0.4 O2 were composed
of 60 mol% CeO2 and 40 mol% ZrO2 . For preparation of the first
oxide support (labelled as Ce1−x Zrx O2 cp) stoichiometric quanti-
ties of zirconyl nitrate hexahydrate (ZrO(NO3 )2 ·6H2 O, Fluka) and
cerium(III) nitrate hexahydrate (Ce(NO3 )3 ·6H2 O, Aldrich) were dis-
solved in distilled water. The resulting solution was transferred to
a round bottom flask and stirred for 1 h at 80 ◦ C. Then, an aque-
ous solution of 20% w/w KOH was added drop-wise at 80 ◦ C with
constant stirring until a pH of 10.5 was reached. After digesting
the precipitate at 80 ◦ C for 72 h, it was filtrated and washed several
times with distilled water to remove any potassium impurity. Then,
it was air-dried for 72 h followed by drying at 120 ◦ C for 6 h. Finally,
the oxide was heated at a ramp of 2 ◦ C/min and kept at 650 ◦ C for 2 h.
The second mixed oxide, labelled as Ce1-x Zrx O2 ctab, was prepared
by surfactant-assisted co-precipitation with cetyltrimethylammo-
nium bromide (CTAB, Roth). The synthesis route was adapted from
Sunkonket et al. [45] with a molar ratio c(CTAB)/c(Ce + Zr) = 1 and
dropwise addition of aqueous ammonia for precipitation.
A nominal 5% w/w Ni was loaded over all supports by wet
impregnation, using nickel nitrate hexahydrate (Ni(NO3 )2· 6H2 O,
Merck) aqueous solution. After drying overnight at 100 ◦ C the cat-
alysts were calcined at 450 ◦ C for 2 h.
2.2. Catalyst characterization
2.2.1. X-ray diffraction measurements
Powder XRD patterns were recorded on a XPERT-PRO diffrac-
tometer with Cu K␣ radiation operating at 40 kV and 40 mA with a
2␪ scanning from 5 to 90◦ and a step size of 0.02◦ . The crystallite
size t was estimated from X-ray line broadening using the Scherrer’s
formula [65] t = 0.9·␭/(B · cos(␪)), where ␭ is the X-ray wavelength
(Cu K␣ radiation: 0.154 nm) and B the full-width half-maximum of
the Bragg diffraction angle ␪.
2.2.2. Surface area analysis
The Brunauer-Emmet-Teller (BET) specific surface areas for all
catalysts were obtained by N2 physisorption acquired at liquid N2
temperature using a Micromeritics ASAP 2020 apparatus. Prior to
analysis, all powders were outgassed at 300 ◦ C and <13 ␮bar for 1 h
prior to acquisition of the adsorption isotherm. The average pore
size and average pore volume were analysed by the BJH method
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using the adsorption branch of the N2 isotherm, as well as by NLDFT X-ray absorption data were processed and analysed using the
(model: cylindrical pores in an oxide surface). IFFEFIT [67] software package (version 0.9.21). With each recorded
XAS spectrum, the absorption edge position (E0 ) was set equal with
the position of the highest maximum of the 1st derivative of ␮(E)
2.2.3. Metal dispersion measurements
in the X-ray energy E. Data processing was done by fitting a linear
The metal dispersion and metallic surface area of the cata-
and a polynomial function to the pre- and post-edge region, respec-
lyst samples were estimated by H2 chemisorption at 35 ◦ C using
tively, resulting in a normalized ␮(E). Five ␮(E) data scans were
a Micromeritics ASAP 2020C instrument with 0.5 g catalyst. Prior
merged into one data file to improve the signal-to-noise ratio. The
to analysis, the samples were heated in an oxygen flow at 500 ◦ C
fraction of Ni present in reduced and used catalysts were deter-
for 1 h. After cooling down in vacuum to 300 ◦ C the samples
mined by fitting to linear combinations of reference spectra, i.e.
were reduced in hydrogen flow at 400 ◦ C. After 20 min reduction
normalized Ni K-edge XANES spectra of Ni foil and NiO references.
the samples were evacuated for 30 min at 400 ◦ C. Chemisorp-
Further details are given in the supporting information.
tion was performed at 35 ◦ C at hydrogen pressures between 75
and 775 mbar and repeated in order to isolate the chemisorp-
tion isotherm. The same analysis procedure was applied after 2.3. Catalytic testing
reducing at 600 ◦ C. The difference of the first isotherm data
(reversible + irreversible adsorption) and the repeated isotherm Activity studies of methane dry reforming (MDR) were carried
data (only reversible adsorption) was utilized to calculate the quan- out in a quartz flow reactor. 25 mg catalyst were mixed with 75 mg
tity of irreversibly adsorbed hydrogen [66,67] (for further details quartz sand and loaded into the glass reactor in-between two plugs
see Supporting information). of quartz wool. The catalysts were oxidized in 20 vol% O2 in Ar at
500 ◦ C for 30 min and reduced in 10 vol% H2 in Ar at 600 ◦ C for
30 min. Before exposure to the reaction mixture the sample was
2.2.4. Infrared spectroscopy
kept in Ar at 600 ◦ C for 30 min. Then, the sample was exposed to
The surface sites and oxidation states of the metals were inves-
a mixture of 10% CH4 , 10% CO2 and 80% Ar with a total flow of
tigated by FTIR spectroscopy of chemisorbed CO. IR spectra were
25 ml/min at 600 ◦ C for 24 h. For quantitative determination of the
recorded in transmission using a Bruker Vertex 70 spectrometer
reaction rates the reaction products were analysed under steady
with an MCT detector. Samples were pressed to small discs and
state conditions by a gas chromatograph equipped with a HP-PLOT
placed in the IR cell. All infrared spectra were collected at a resolu-
Q column, a thermal conductivity detector (TCD) and a flame ion-
tion of 4 cm−1 in the 4000–900 cm−1 range by averaging 128 scans
ization detector (FID).
to achieve good signal to noise ratios. The results shown herein are
After the MDR experiment the sample was cooled to room tem-
difference spectra with the spectrum of the clean sample was taken
perature in Ar. Subsequently, temperature programmed oxidation
as a background before adsorption. The pretreatment was carried
(TPO) was performed in 20% O2 in Ar applying a heating rate of
out in the IR cell by heating at 10 C/min from room temperature
5 ◦ C up to 900 ◦ C. The amount of CO2 formed by oxidation of C was
to 500 ◦ C under 100 mbar O2 pressure and holding that tempera-
monitored by mass spectrometry (Pfeiffer QMS 200) detection.
ture for 1 h, followed by a treatment in 5 mbar H2 and 900 mbar N2
at 400 ◦ C for 30 min. Then, the samples were outgassed at 400 ◦ C
below 10−5 mbar for 30 min. Spectra before and after exposure to 2.3.1. Equations used for calculation of catalytic results
5 mbar CO were recorded at 30 ◦ C. The CH4 and CO2 conversion, H2 formation rates, H2 :CO ratio,
carbon-balance, H2 selectivity and turn-over-frequency (TOF),
based on the metallic Ni surface area after reduction at 600 ◦ C, are
2.2.5. Transmission electron microscopy (TEM)
defined as follows:
TEM was utilized to obtain information about the size, morphol-    
ogy and distribution of the nickel particles on the oxide supports. f CH4,in − f CH4,out
Prior to microscopy the catalysts were oxidized at 500 ◦ C and % CH4 conversion : X CH4 =   × 100% (2.1)
f CH4,in
reduced at 600 ◦ C. To characterize the used catalysts, samples were
exposed to methane and carbon dioxide at 600 ◦ C for three hours.
   
f CO2,in − f CO2,out
For TEM measurements the samples were suspended in ethanol % CO2 conversion : X CO2 =   × 100% (2.2)
and deposited on carbon coated Cu grids. TEM was performed on f CO2,in
an analytical TECNAI F20 field emission TEM operated at 200 kV
H2 production rate : r H2 = FT × yH2 (2.3)
equipped with an energy dispersive X-ray detector (EDX). EDX was
used to identify the Ni particles on the support materials. The struc- CO production rate : r CO = FT × yCO (2.4)
tural analysis of the recorded images has been performed using
ImageJ 1.48. The digital diffractograms reported herein correspond rH2
H2 : CO ratio : R = (2.5)
to the log- scaled power spectrum of the corresponding fast Fourier rCO
transforms.    
f CH4,out + f CO2,out + f (COout )
Carbon ratio : C balance =     (2.6)
2.2.6. X-ray absorption spectroscopy (XAS): data acquisition and f CH4,in + f CO2,in
analysis  
f H2,out
XAS spectra were recorded at the Ni K-edge (E0 = 8333 eV) at % H2 selectivity : S H2 =      × 100% (2.7)
Beamline 8 of the Synchrotron Light Research Institute, Thailand. 2 f CH4,in − f CH4,out
Spectra of catalysts reduced in 20 vol% H2 in Ar at 600 ◦ C (labelled
as: “red.”) and samples after exposure to the MDR-reaction mix- NH2
Turn-over-frequency : TOF = (2.8)
ture (10 vol% CH4 , 10 vol% CO2 and 80 vol% Ar) at 600 ◦ C for 3 h NNi
(labelled as: “used”) were recorded at room temperature in fluo-
rescence mode. Each sample was pressed into a frame covered by Number of produced H2 molecules per s : N H2
polyimide tape and mounted onto a sample holder. The experi-  
mental setup and the measurement procedure were described in f H2,out ×  (H2 )
[66]. = × NA (2.9)
M (H2 )

Please cite this article in press as: A. Wolfbeisser, et al., Methane dry reforming over ceria-zirconia supported Ni catalysts, Catal. Today
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cerium and zirconium precursor during co-precipitation. The sup-

Fig. 1. XRD patterns of Ni-ZrO2 , Ni-CeO2 , Ni-Ce1-x Zrx O2 cp and Ni-Ce1-x Zrx O2 ctab
after ex-situ reduction. ZrO2 exhibits characteristics of monoclinic zirconia, CeO2
and Ce1-x Zrx O2 ctab show characteristics of cubic CeO2 or cubic Ce-Zr-oxide and
Ce1-x Zrx O2 cp shows reflections of both cubic and tetragonal Ce-Zr-oxides.
Number of surface Ni atoms : NNi = mcat × ANi × NNi/m2 (2.10)
for f (iin ) and f (iout ) being the volume flow rates of each component
in the feed or effluent in m3 /s, FT being the total molar flow rate
(in mol/s) measured at room T and 1 atm, yH2 is the mole fraction of
hydrogen and yCO that of CO in the product gas mixture,  (H2 ) the
density of hydrogen, M (H2 ) the molar mass of hydrogen, mcat is the
mass of the catalyst in the reactor of 0,025 g, ANi is the Ni surface
area (m2 /g of catalyst), and NNi/m2 is the number of surface nickel
atoms per square meter of catalyst.
port prepared by co-precipitation with CTAB as surfactant consists
of a single cubic ceria-zirconia-mixed oxide phase with a lattice
parameter of 530 pm and a Ce:Zr ratio of 60:40. Broader reflections
indicate smaller ceria-zirconia crystallites compared to the other
samples. The average crystallite sizes of the support materials esti-
mated by using the Scherrer-equation are given in Table 1. We also
performed the Rietveld refinement for CeO2 as well and obtained
lower crystallite size (12 nm as compared to 30 nm according to
the Scherrer equation). Thus, the absolute values have to be treated
with care and we focus our discussion on and potential reaction-
induced changes. The reflection positions at about 38◦ , 43◦ and 63◦
2␪ of cubic NiO are marked in Fig. 1 and are observed as small reflec-
tions on all samples. Since the samples were exposed to air between
ex-situ reduction and XRD measurements, the Ni particles were
(partially) re-oxidized to NiO. The average crystallite sizes of NiO
estimated by the Scherrer-equation are 27 nm on Ni-ZrO2 , 21 nm on
Ni-CeO2 and 16 nm on both ceria-zirconia supported catalysts. For
all samples the presence of additional amorphous phases cannot
be excluded, however.
Surface area analysis by nitrogen physisorption was carried out
for the samples ZrO2 , CeO2 , Ce1−x Zrx O2 cp and Ce1-x Zrx O2 ctab.
The results of the calculations of the specific surface areas using
the method of Brunauer, Emmet and Teller (BET) and of the pore
size and pore volume using the method of Barret, Joyner and Hal-
enda (BJH) [68] as well as a comparison to the pore size and pore
volume obtained by NLDFT are included in Table 1. The specific
surface area of both oxides prepared by co-precipitation was sig-
nificantly higher than that of pure CeO2 and ZrO2 . The mesopores
volume reached the highest value for the ceria-zirconia supports
while the lowest value was obtained for ZrO2 . The average pore
size of ZrO2 of 21 nm is clearly larger than that of the other sam-
ples. In general, all the samples are mesoporous, and hardly any
micropores were detected.

3. Results 3.2. TEM study

3.1. Textural and structural properties
The crystalline structure of the samples was determined by XRD.
The X-ray diffractograms of Ni-ZrO2 , Ni-CeO2 , Ni-Ce1-x Zrx O2 cp
and Ni-Ce1-x Zrx O2 ctab after ex-situ reduction at 600 ◦ C are shown
in Fig. 1. The ZrO2 supported catalyst shows reflections assigned to
monoclinic ZrO2 while the diffractogram of Ni-CeO2 shows reflec-
tions assigned to cubic CeO2 . The ceria-zirconia mixed oxides vary
in their phase composition: The support material prepared by co-
precipitation without surfactant is composed of a mixture of a cubic
ceria-rich mixed oxide phase and a tetragonal zirconia-rich mixed
oxide phase. The lattice parameter of the cubic phase is 539 pm,
indicating a Ce:Zr ratio of 90:10 and the lattice parameters of the
tetragonal phase are 363 pm and 522 pm, indicating a Ce:Zr ratio
of 12:88. The phase separation indicates insufficient mixing of the
Fig. 2 shows representative TEM images of a) Ni-ZrO2 , b) Ni-
Ce1-x Zrx O2 cp and c) Ni-Ce1−x Zrx O2 ctab. The samples were ex-situ
reduced at 600 ◦ C prior to the microscopy but exposure to air during
sample transport led to (partial) re-oxidation of the Ni particles.
On Ni-ZrO2 , Ni or NiO particles of 10–30 nm diameter were iden-
tified as displayed in Fig. 2a. On Ni-Ce1-x Zrx O2 cp, besides rather
large 50 nm Ni or NiO particles, mainly particles of about 10 nm size
were detected, as shown in Fig. 2b. According to elemental maps
(shown in the Supporting information) Ni particles were located
both on ceria- enriched and zirconia-enriched grains of the mixed
oxide support. On Ni-Ce1-x Zrx O2 ctab, Ni was again detected by
EDX analysis but, in contrast to the other catalysts, no Ni or NiO par-
ticles could be found on the border of the agglomerates (even after
intensive search). Thus, it seems that these particles are well dis-
persed and in strong interaction with the mixed oxide support (or

Table 1
BET surface area, BJH average pore size and volume, mean pore size and total pore volume obtained by NLDFT, and average support and metal crystallite size (estimated by
using Scherrer’s equation) of Ni-ZrO2 , Ni-CeO2 , Ni-Ce1-x Zrx O2 cp and Ni-Ce1-x Zrx O2 ctab.

sample BET surface BJH average pore BJH average pore NLDFT mean pore NLDFT total pore Oxide structure Average NiO
area (m2 /g) size (nm) volume (cm3 /g) size (nm) volume (cm3 /g) and average crystallite size
crystallite size (nm)
(nm)

ZrO2 37 21 0.023 16 0.016 Monoclinic: 36 27

CeO2 56 7 0.074 6.7 0.059 cubic: 30 21
Ce1-x Zrx O2 cp 91 7 0.13 7.8 0.15 tetragonal: 9 16
cubic: 19
Ce1-x Zrx O2 93 9 0.25 10.1 0.11 cubic: 10 16
ctab

Please cite this article in press as: A. Wolfbeisser, et al., Methane dry reforming over ceria-zirconia supported Ni catalysts, Catal. Today
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Fig. 2. TEM images of a) Ni-ZrO2 b) Ni-Ce1-x Zrx O2 cp and c) Ni-Ce1-x Zrx O2 ctab.

Table 2 Table 3
Ni dispersion and Ni surface area of Ni-ZrO2 , Ni-CeO2 , Ni-Ce1-x Zrx O2 cp and Ni- Turn-over frequencies for H2 production normalized by the number of surface nickel
Ce1-x Zrx O2 ctab after reduction at 400 ◦ C and 600 ◦ C, based on H2 chemisorption. atoms after reduction at 600 ◦ C during MDR at 600 ◦ C.

sample Ni dispersion (%) Ni surface area (ANi ) sample turn-over frequency (TOF) (s−1 )
(m2 /g of catalyst)
initial after 3 h after 24 h
400 ◦ C red. 600 ◦ C red. 400 ◦ C red. 600 ◦ C red.
Ni-ZrO2 1.2 1.2 1.0
Ni-ZrO2 4.7 1.75 1.57 0.58 Ni-CeO2 0.8 0.8 0.5
Ni-CeO2 2.6 1.4 0.88 0.46 Ni-Ce1-x Zrx O2 cp 1.8 1.6 0.9
Ni-Ce1-x Zrx O2 cp 3.3 1.0 1.08 0.34
Ni-Ce1-x Zrx O2 ctab 0.1 – 0.03 –

2131–2145 and ␯as (CO) at 2100–2083 cm−1 ) [75,77–79] and tri-

even partly encapsulated which would decrease the accessibility of
nickel; see below).
3.3. Adsorption properties
3.3.1. H2 -chemisorption
The accessible nickel surface area was determined by selective
chemisorption of H2 . The nickel dispersion and metallic nickel sur-
face area per gram of sample after reduction at 400 ◦ C and 600 ◦ C
are shown in Table 2. The highest Ni surface area upon reduction
at 400 ◦ C is observed on the zirconia supported Ni catalyst while
on Ni-Ce1-x Zrx O2 ctab only very little H2 adsorbs. The very small
uptake of hydrogen by the Ni-Ce1-x Zrx O2 ctab catalyst could be due
to activated H2 chemisorption or to a strong SMSI effect after oxi-
dation at 500 ◦ C and reduction at 400 ◦ C, induced by the specific
interactions of Ni with this support (we will discuss the origin of
this effect later in Section 4). After reduction at 600 ◦ C the nickel
surface area decreases suggesting sintering of the supported nickel
particles. TPR confirmed that Ni reduction was complete at 600 ◦ C
for all catalysts. The metallic Ni surface area decreases more on Ni-
ZrO2 than on Ni-CeO2 indicating that the ceria support increases
the stability of Ni against sintering.
carbonyls (2156, 2124 and 2109 cm−1 ) [75] with Ni+ . This unusual
oxidation state is stabilized by CO. The stretching vibrations of
linear adsorbed CO on metallic nickel appear at 2050–2094 cm−1
[72,78–84] and bridged carbonyls are observed below 1960 cm−1
[72,80,84].
On Ni-ZrO2 and Ni-Ce1-x Zrx O2 cp, Ni2+ -CO is observed as a
shoulder of the larger Zr4+ -CO peak at 2177 and 2171 cm−1 , respec-
tively. The peaks of CO adsorbed as mono-, di- or tricarbonyls on
surface-Ni+ can be observed on Ni-ZrO2 and the mixed oxide sup-
ported samples but not on Ni-CeO2 . On all catalysts CO peaks of
linear and bridged adsorbed CO on metallic nickel are present. On
Ni-CeO2 CO only adsorbs on metallic nickel which indicates that all
the Ni on the surface is fully reduced at 400 ◦ C. The ability of Ni-
Ce1-x Zrx O2 ctab to adsorb CO but not H2 (cf. Table 3) is currently
not understood.
After evacuation Ni+ -CO as well as linear and bridged CO on Ni0
remain on the surface of Ni-ZrO2 . On Ni-CeO2 a rather high amount
of linear and bridged CO on Ni0 remains on the surface in contrast
to the Ce1-x Zrx O2 supported samples, where only little CO remains
on the reduced Ni surface.
3.4. Catalyst performance evaluation

3.3.2. Infrared spectroscopy of CO adsorption
IR spectra of room temperature CO adsorption on reduced Ni-
ZrO2 , Ni-CeO2 , Ni-Ce1-x Zrx O2 cp and Ni-Ce1-x Zrx O2 ctab are shown
in Fig. 3. Note that reduction was carried out directly in the IR
cell prior to adsorption without air exposure, in contrast to XRD
and TEM measurements. According to literature data [15,33,69–71]
adsorption of CO on ZrO2 results in a band at about 2190 cm−1
which can be observed on Ni-ZrO2 as well as on the mixed oxide
supported samples. Different oxidation states of Ni can be dis-
tinguished by the vibrational frequency of adsorbed CO. Bands
attributed to Nin+ -CO surface complexes cover a broad spectral
range, such as linear monocarbonyls but also bridged di- and
tricarbonyl species. The weak adsorption band of CO on Ni2+ is
observed around 2150–2180 cm−1 [33,70,72–74]. CO forms stable
monocarbonyls (2160–2100 cm−1 ) [75–78], dicarbonyls (␯s (CO) at
The results obtained for methane dry reforming at 600 ◦ C for
24 h are presented in Fig. 4. Concerning stability, it can be stated
that the CH4 and CO2 conversion over Ni-ZrO2 hardly changed with
time while the conversion over Ni-CeO2 rapidly decreased and that
over Ni-Ce1-x Zrx O2 cp continuously decreased. Ni-Ce1-x Zrx O2 ctab
was hardly active during the first 30 min and then completely deac-
tivated. The oxide support materials without nickel were inactive
under these conditions, too.
In agreement with the reactant conversions, the H2 and CO
production rates were stable over Ni-ZrO2 and decreased with
time on stream over Ni-CeO2 and Ni-Ce1-x Zrx O2 cp. Over Ni-
Ce1-x Zrx O2 ctab only little initial H2 and CO production was
observed before the catalyst was completely inactive for methane
dry reforming. The H2 selectivity was around 75% both for Ni-ZrO2
and Ni-Ce1-x Zrx O2 cp during the entire reaction time indicating

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Fig. 3. IR spectra of a) 5 mbar CO adsorbed on reduced Ni-ZrO2 , Ni-CeO2 , Ni-Ce1-x Zrx O2 cp and Ni-Ce1−x Zrx O2 ctab at room temperature and b) after evacuation below
10−5 mbar.

Fig. 4. Screening of Ni-ZrO2 , Ni-CeO2 , Ni-Ce1-x Zrx O2 cp and Ni-Ce1-x Zrx O2 ctab catalysts for methane dry reforming reaction at 600 ◦ C; feed composition:
CH4 :CO2 :Ar = 10/10/80; feed flow rate = 25 ml/min.

RWGS during reaction, whereas over Ni-CeO2 the H2 selectivity
strongly changed with time.
The H2 :CO ratio achieved was below 1 due to H2 O production
by reverse water gas shift as a side reaction. The highest value was
obtained for Ni-CeO2 but it strongly decreased with time on stream.
The C-balance, being an indicator for coke formation when below
1, was increasing to (nearly) 1 within the first 2 h.
The turn-over-frequencies (TOF) for H2 production based on the
metallic Ni surface area after reduction at 600 ◦ C and normalized
to the number of surface nickel atoms assuming 1.59·1019 nickel
atoms/m2 [85] are presented in Table 3. Reporting TOF values is in
general a difficult matter because the nature and amount of active
sites and the reaction mechanism would have to be exactly known.
CO2 activation likely occurs on the support and/or metal-oxide
interface [64,86]. Recently, Makri et al. [64] performed a detailed
mechanistic study and reported that MDR on Ni/Ce1−x Mx O2−␦
(M = Zr4+ , Pr3+ ) very likely follows a bi-functional mechanism. CH4
activation is suggested to occur practically only on the Ni surface,
whereas CO2 activation is proposed to proceed both on Ni but also
on oxygen vacancies at the Ni-support interface. There is, however,
broad agreement that CH4 activation on Ni is the rate determining
step in MDR. Therefore, we normalized the rate of H2 production
by the accessible Ni sites to be able to compare the catalysts, taking
into account the different Ni particle sizes. Nevertheless, the TOF
values have to be considered with care.

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Fig. 5. Temperature Programmed Oxidation with 20% O2 in Ar, performed after 24 h
methane dry reforming at 600 ◦ C.
3.5. Post-reaction characterization
Temperature programmed oxidation (TPO) was performed to
characterize coke formation after 24 h reaction in CH4 and CO2 . The
amount of carbon dioxide formed during TPO quantifies the amount
of coke formed during the reaction and the temperature needed to
burn off the carbon is characteristic for the carbon bond strength to
the catalyst’s surface. Fig. 5 shows the production of carbon diox-
ide during TPO in 20% O2 in Ar after MDR. Over Ni-ZrO2 clearly the
highest amount of coke was formed and temperatures of 600 ◦ C are
needed to oxidize most of it. We compared TPO measurements after
3 h and after 24 h of reaction time. Interestingly, we observed that
most of the coking occurs during the first three hours over Ni-ZrO2
and Ni-Ce1-x Zrx O2 cp. Longer reaction times did not significantly
increase the amount of carbonaceous species deposited on these
samples (Fig. S4 in the Supporting information). The small maxi-
mum of CO2 evolution at 300 ◦ C over the Ni-CeO2 catalyst can be
assigned to the oxidation of amorphous carbon [87,88] and around
500 ◦ C graphitic carbon is oxidized [16]. The CO2 evolution around
600 ◦ C can be assigned to the oxidation of whisker type carbon
which does not deactivate the nickel surface but rather causes a
breakdown of the catalyst by pore plugging [10].
In addition to carbon oxidation, carbonates can also contribute
to the CO2 TPO signal at temperatures ≥ 600 ◦ C (i.e. the temperature
at which we purged the samples in Ar after reaction). This would
lead to an overestimation of the amount of carbon. Therefore, we
rather focus on the relative difference in the amount of carbon-
containing species over the various samples. Nevertheless, most
of the CO2 produced during TPO is attributed to carbon oxidation,
because O2 consumption (also detected by mass spec) occurred at
the same temperature as CO2 production. Furthermore, reference
experiments using Ar instead of O2 /Ar indicated the absence of CO2
evolution in the absence of O2 , which excludes a significant TPO
contribution by carbonate decomposition (Fig. S5 in Supporting
information).
The amount of CO2 formed over Ni-ZrO2 is about 20 times
more than on Ni-CeO2 and about 200 times more than on Ni-
Ce1-x Zrx O2 cp (note the logarithmic scale). When the overall
amount of carbon converted within 24 h reaction time is consid-
ered (i.e. 67.1 mmol C converted over Ni-ZrO2 , 33.4 mmol C over
Ni-CeO2 , and 34.2 mmol C over Ni-Ce1-x Zrx O2 cp) somewhat lower
but nevertheless considerable differences in the amount of car-
bonaceous species deposited on the catalysts were observed: the
amount of CO2 formed in TPO over Ni-ZrO2 is about 10 times
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7
higher than over Ni-CeO2 and about 100 times more than on
Ni-Ce1-x Zrx O2 cp. This is clearly a huge advantage of the Ni-
Ce1-x Zrx O2 cp catalyst over Ni-ZrO2 (even though the large amount
of carbonaceous species formed during 24 h reaction hardly affects
the Ni-ZrO2 activity), since the major problem of carbon deposition
in a continuous flow reactor is the possibility of physical block-
ing of the tube reactor. Such “clogging” was indeed observed when
the amount of catalyst used for catalytic tests was increased. Thus,
using a mixed oxide support for the Ni particles is beneficial for
the MDR performance. As expected, on Ni-Ce1-x Zrx O2 ctab hardly
any CO2 is formed during TPO, not surprising in light of its almost
inactivity.
Fig. 6 shows TEM images of Ni-ZrO2 (a) and Ni-Ce1-x Zrx O2 cp (b)
after dry reforming at 600 ◦ C for 3 h. On both catalysts filamentous
carbon has formed and some Ni particles are on top of these carbon
nanofibers, tubes or rods. On Ni-CeO2 and Ni-Ce1-x Zrx O2 ctab no
filamentous carbon was detected.
Fig. 7 shows XRD patterns of the samples after reaction at 600 ◦ C,
for the range of 20−55◦ 2␪. In contrast to the XRD patterns shown
in Fig. 1, the reflections of NiO have disappeared or − in case of Ni-
CeO2 decreased in intensity, and the reflection of Ni(111) at 44.3
2␪ is observed on Ni-CeO2 and the mixed oxide supported samples.
On Ni-ZrO2 this reflection is overlapping with one of monoclinic
ZrO2 . The crystallite sizes calculated with Scherrer’s equation are
27 nm, 23 nm and 21 nm on Ni-CeO2 , Ni-Ce1-x Zrx O2 cp and Ni-
Ce1-x Zrx O2 ctab, respectively, and thus not much larger than the
NiO crystallites of the catalysts after ex-situ reduction. The reflec-
tion at 26.1 2␪ in the diffractogram of the used Ni-ZrO2 catalyst is
assigned to graphite. On the other samples much less carbon was
observed by TPO and it may be rather amorphous. The XRD pat-
terns of the used Ni-Ce1-x Zrx O2 catalysts indicate no change of the
lattice parameters of the cubic phases and thus of the Ce/Zr ratios
of the catalysts.
Fig. 8 shows graphical representations of the Ni K-edge normal-
ized ␮(E) in the XANES region a) and the first derivative of the ␮(E)
data in the XANES region b).The latter reveal several local maxima
with two larger ones around 8333 eV and/or 8343 eV. The position
of the largest maximum value with the first derivative of the ␮(E)
data was chosen as the value of E0. With the Ni fcc reference foil
the first maximum at 8333 eV is the highest one. With NiO refer-
ence and the reduced samples the highest maximum is apparently
at 8343 eV and with the used samples it is also at 8343 eV.
The XANES spectra of the catalysts reduced ex situ in a H2 /Ar
mixture at 600 ◦ C for 30 min resemble that of the NiO reference.
Linear combination analysis of the spectra shown in Fig. 8 confirms
that the Ni on all catalysts after ex situ H2 reduction is in the oxi-
dized state. This proves that these catalysts are fully re-oxidized
after exposure to air.
Linear combination analysis of the used catalysts, which were
also exposed to air in between reaction and XAS measurement,
revealed an amount of metallic nickel of 86%, 84%, 78% and
70% in Ni-ZrO2 , Ni-CeO2 , Ni-Ce1-x Zrx O2 cp and Ni-Ce1-x Zrx O2 ctab,
respectively. In contrast to the reduced samples most of the Ni has
remained metallic and did not get re-oxidized upon air exposure.
Since the Ni particles analysed by TEM and XRD were not signifi-
cantly larger after reaction than before, sintering can be excluded.
Possible explanations for the XANES spectra can be either that the
carbon (which has formed during reaction and was deposited on
the catalyst) stabilizes the metallic state of nickel (e.g. by decorat-
ing sites at which O2 dissociation and oxidation would initiate).
Alternatively, a nickel carbide phase may have formed. The XANES
spectrum of Ni3 C would resemble the XANES of metallic Ni rather
than NiO but shows significant differences in the Fourier transforms
of the ␹(k). Ni3 C was obtained and detected by XAS during Ni car-
burization [89,90] and during low temperature steam reforming
of ethanol over a ceria supported Ni catalyst [91]. Besides carbon,
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Fig. 6. TEM images of a) Ni-ZrO2 and b) Ni-Ce1-x Zrx O2 cp after exposure to methane and carbon dioxide at 600 ◦ C for 3 h.

Fig. 7. XRD patterns of the Ni-ZrO2 , Ni-CeO2 , Ni-Ce1-x Zrx O2 cp and Ni-Ce1-x Zrx O2 ctab after MDR for 3 h at 600 ◦ C.

Table 4 place, since the carbon signal from the first Ni-C coordination shell
Structural parameters of the first Ni–Ni coordination shell resulting from multiple
at the phase-uncorrected distance of R ∼1.2 Å is missing.
shell fits in R-space to EXAFS data of Ni foil and post-reaction Ni supported catalysts.

sample R(Å) CN ␴2 (Å2 ) R factor

4. Discussion
Ni foil 2.46 ± 0.00 12 a
0.006 0.087
Ni-ZrO2 2.52 ± 0.05 9.6 0.005 0.073
Ni-CeO2 2.51 ± 0.05 11.1 0.006 0.084 We have characterized nickel-based catalysts, including ceria-
Ni-Ce1-x Zrx O2 cp 2.55 ± 0.05 11.1 0.007 0.072 zirconia mixed oxide supports prepared by different synthesis
Ni-Ce1-x Zrx O2 ctab 2.53 ± 0.05 10.9 0.006 0.065 methods. The catalysts were evaluated for their catalytic perfor-
a
Constrained for Ni foil. mance in methane dry reforming. Large differences in the catalytic
performance of the two mixed oxide supported Ni catalysts of
the same nominal elemental composition were observed. The
catalyst prepared by surfactant assisted co-precipitation showed
nickel carbide formation is favoured in a dry mixture of methane promising textural properties such as high surface area which is
and carbon dioxide [1] and Ni3 C formation was indeed observed by often connected with a good metal dispersion. Nevertheless, after
Swaan et. al [92]. However, Goula et. al [93] discarded the hypothe- reduction at 600 ◦ C hardly any H2 adsorbed, as shown by hydro-
sis of bulk nickel carbide formation during methane dry reforming. gen chemisorption measurements, indicating (partly) inaccessible
The k2 -weighted k and r space EXAFS with their respective fits (encapsulated) nickel on this catalyst. Since the surfactant CTAB
are shown in Fig. 9 and the best fitting structural parameters are was used for the synthesis of the mixed oxide support material,
presented in Table 4. According to these fittings, all samples are residual bromide was considered to potentially affect the catalytic
well fitted by using fcc Ni. The formation of Ni3 C seems not to take activity. Residual chloride from Cl-containing Pt precursors was

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Fig. 8. a) Normalized XANES spectra of reference samples and reduced and used samples and b) first derivative of the spectra shown in a). The dashed lines in b) mark the
positions of two local maxima at 8333 eV and 8343 eV. The asterisk (*) labels the absolute maximum.

Fig. 9. k2 -weighted EXAFS functions ␹(k) and magnitude and imaginary part of Fourier transforms (uncorrected for phase shifts) of ␹(k) of Ni foil and the supported nickel
catalysts after methane dry reforming reaction at 600 ◦ C. Solid lines: experimental data, hollowed spheres: fits in R-space and back transformed into k-space.

reported to have an enormous effect on the selectivity of the
catalyst [94], thus a similar effect of bromide is possible. Even
though no bromide was detected by elemental analysis, an addi-
tional catalyst was prepared by impregnating the co-precipitation
support with ammonium bromide (Merck) before adding Ni. The
amount of Br was the same as used for the preparation of Ni-
Ce1-x Zrx O2 ctab assuming the maximum theoretical loading. The
methane conversion over this brominated catalyst was about the
same as over Ni-Ce1−x Zrx O2 cp, i.e. 56.7% initially (57.4% over Ni-
Ce1-x Zrx O2 cp) and 46.5% after 3 h time on stream (47.7% over
Ni-Ce1-x Zrx O2 cp). Therefore, a negative effect due to the utiliza-
tion of the bromide containing surfactant can be excluded. Thus,
a reasonable explanation for the lack of catalytic activity or the
extremely fast deactivation of Ni-Ce1-x Zrx O2 ctab is mostly inac-
cessible Ni particles, based on the extremely low Ni surface area
observed by H2 chemisorption and the TEM observation that Ni par-

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ticles were always surrounded by the mixed oxide support which
has a structure different from Ce1-x Zrx O2 cp. Considering the active
Ni-Ce1-x Zrx O2 cp catalyst, no advantage compared to Ni-ZrO2 in
terms of conversion or H2 selectivity was observed but the forma-
tion of filamentous carbon was strongly suppressed (100 times).
As reported in literature, the ceria-zirconia support material leads
to acceleration of gasification of coke deposits on metal particles
which is related to the increase of the oxygen accessibility/mobility
on the surface [95] and the higher surface density of active sites on
the ternary catalyst [41].
Recently, Makri et al. [64] reported important insights into
the carbon chemistry of 5 wt% Ni/Ce0.8 Zr0.2 O2-␦ and 5 wt%
Ni/Ce0.5 Zr0.5 O2-␦ MDR catalysts. Using temperature-programmed
methods and transient isotopic experiments they demonstrated
that the relative amount of the carbon species (formed either via
the CH4 or the CO2 activation routes) as well as the reactivity of the
various carbons towards H2 and O2 were strongly influenced by the
support chemical composition (Ce/Zr ratio). In addition, the support
composition affected the nickel particle size, which in turn influ-
enced the origin and the reactivity of carbon deposited under MDR
conditions. Particularly, the metal-oxide interface was suggested
to play an important role for reacting off carbon. While CH4 acti-
vation is found to occur only on Ni, CO2 is activated also at oxygen
vacancies at and/or near the Ni-oxide interface. Thus, the amount
of vacancies near the interface and an improved rate of oxygen
transfer towards the interface strongly affect the catalytic prop-
erties and carbon accumulation during MDR [64]. In view of the
work of Makri et al., the huge differences in MDR catalytic activity,
which we observed for Ni supported on the two differently pre-
pared ceria-zirconia materials, may also be explained by an effect
of the different oxide compositions on the abundance of oxygen
vacancies and on the participation of labile surface/subsurface lat-
tice oxygen around the Ni particles, which may be key for the
removal of carbon near or at the metal-support interface.
5. Conclusions
In this study we have prepared two different ceria-zirconia
mixed oxide support materials which were impregnated with
nickel and compared with zirconia and ceria supported nickel
catalysts in terms of textural and adsorption properties, catalytic
behaviour during methane dry reforming and post-reaction prop-
erties. Both ceria-zirconia supported catalysts showed promising
high surface area. Ni was accessible by CO adsorption on all catalysts
after reduction. Nevertheless, the catalyst prepared by surfactant
assisted co-precipitation (Ni-Ce1-x Zrx O2 ctab) was not active for
methane dry reforming while the activity of the one prepared by
co-precipitation without surfactant (Ni-Ce1-x Zrx O2 cp) was com-
parable to Ni-ZrO2 , which was the most active and most stable of
the tested catalysts.
The inactivity of the Ni-Ce1-x Zrx O2 ctab catalyst is most likely
explained by the inaccessibility of metallic Ni for hydrogen adsorp-
tion after reduction at 600 ◦ C and by the TEM observation of Ni
particles being covered by ceria-zirconia particles. Thus, as gener-
ally accepted, catalyst activity depends strongly on the preparation.
Alternatively, the differing compositions of the ceria-zirconia
phases obtained by the respective preparation routes may affect
the presence of oxygen vacancies and of labile surface/subsurface
lattice oxygen around the Ni particles which may be essential for
the removal of carbon near/at the metal-support interface.
Considering the active Ni-Ce1-x Zrx O2 cp catalyst no improve-
ment of catalytic activity was observed when compared to Ni-ZrO2 ,
but the stability against filamentous coke formation was signifi-
cantly increased. Consequently, the risk of reactor tube blockage
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in a flow system can be decreased which justifies using mixed
ceria-zirconia as a support material.
Acknowledgements
This work was supported by the Austrian Science Fund (FWF) via
SFB FOXSI (F4502-N16) and project DryRef (I 942-N17). We thank
Dr. Klaudia Hradil and DI Werner Artner (X-ray center at TUW) for
assistance with the XRD measurements and data evaluation. We are
grateful to the Synchrotron Light Research Institute (SLRI), Thailand
for providing beamtime at Beamline 8 for X-ray absorption analysis.
A.W. acknowledges the ASEA-UNINET for a travelling grant.
Appendix A. Supplementary data
Supplementary data associated with this article can be found,
in the online version, at http://dx.doi.org/10.1016/j.cattod.2016.04.
025.
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