Journal of Catalysis 316 (2014) 78–92

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

Kinetic and mechanistic study of dry (CO2) reforming of methane over

Rh-substituted La2Zr2O7 pyrochlores
Devendra Pakhare a, Viviane Schwartz b, Victor Abdelsayed c,d, Daniel Haynes c, Dushyant Shekhawat c,
James Poston c, James Spivey a,⇑
a
Department of Chemical Engineering, Louisiana State University, Baton Rouge, LA 70803, USA
b
Center for Nanophase Material Science, Oak Ridge National Laboratory, Department of Energy, Oak Ridge, TN 37831, USA
c
National Energy Technology Laboratory, U.S. Department of Energy, Morgantown, WV 26507, USA
d
URS Corporation, 3610 Collins Ferry Rd, Morgantown, WV 26507, USA

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

Article history: The active sites and kinetics of dry reforming of methane (DRM) on lanthanum zirconate (LZ) pyrochlore
Received 9 January 2014 catalysts are studied as a function of Rh substitution, temperature, and partial pressures of CH4 and CO2.
Revised 8 April 2014 In this work, we focus specifically on determining the catalytic active sites for CH4 and CO2 activation and
Accepted 27 April 2014
their role in the DRM mechanism over the two Rh-substituted pyrochlores, i.e., 2 wt% Rh, designated
Available online 2 June 2014
L2RhZ and 5 wt% Rh, designated L5RhZ. Kinetic rate modeling suggests dual-site mechanism, where
CH4 and CO2 are activated on different sites (dual-site mechanism). Eleven different rate models were
Keywords:
tested against the kinetic rate data obtained over these two Rh pyrochlores. Statistical analysis shows
Dry reforming
La-oxycarbonates
valid and similar fits for only two of eleven models: one in which activation of CH4 is rate-determining
Pyrochlores and one in which CO2 activation is rate-determining. This dual-site mechanism is studied further in detail
Lattice oxygen to test the validity of the intermediate steps predicted by the kinetic model. CH4/CD4 isotope switching
Kinetic isotope effect shows a strong deuterium kinetic isotope effect on CH4 and CO2 conversion, suggesting that CH4 disso-
Transient pulsing ciation is the rate-determining step. Higher apparent activation energies of CH4 (Ea, CH4) versus CO2 (Ea, CO2)
on both catalysts also confirm that CH4 activation is rate-determining. Basic nature of La–O sites activates
mildly acidic CO2 to form La2O2CO3 complexes as confirmed by FTIR. From different polymorphs of La2-
O2CO3, the spectator and reactive species were distinguished by pulsing CH4 over La2O2CO3. Alternating
pulses (CH4/Ar ? CO2/Ar ? CH4/Ar) at 550 °C showed simultaneous formation of CO and H2, suggesting
that surface carbon, formed by CH4 decomposition, is oxidized by H2O; a crucial step in understanding
the catalytic behavior of pyrochlores in the reaction mechanism. These experiments were used to identify
the two types of sites taking part in the dual-site DRM mechanism. The work reported here helps in
determining a single set of kinetically significant steps that most closely represent the mechanistic
scheme of DRM over L2RhZ and L5RhZ.
Ó 2014 Elsevier Inc. All rights reserved.

1. Introduction attain equilibrium conversions, and deactivation by carbon deposi-

In the past decade, methane-reforming processes such as steam
reforming of methane (SRM), partial oxidation of methane (POM),
autothermal reforming of methane (ARM), and dry reforming of
methane (DRM) have been investigated. These processes differ in
the final H2/CO product ratio and energetics. From among these
reforming processes, DRM is shown to have lower operating cost
[1]. However, DRM has certain disadvantages such as high endo-
thermicity, requiring high reaction temperatures (900 °C) to
⇑ Corresponding author. Fax: +1 225 578 1476.
E-mail address: jjspivey@lsu.edu (J. Spivey).
tion and sintering [2,3].
CH4 þ CO2 ! 2CO þ 2H2 DHr ¼ þ59:1 kcal=mol
Thus, there is a need to develop catalysts that will resist deacti-
vation due to sintering and decrease carbon formation during DRM
[4–7]. A balance between formation and oxidation of surface
carbon is necessary for DRM catalyst stability. There are several
ways to increase deactivation resistance, such as increasing and
maintaining the dispersion of the active metal [8–10] improve
the oxidation rate of surface carbon by increasing the concentra-
tion of an oxidizing agent such as CO2 [11]. Since CO2 is mildly
acidic in nature, increasing the basicity of the catalyst will increase

http://dx.doi.org/10.1016/j.jcat.2014.04.023
0021-9517/Ó 2014 Elsevier Inc. All rights reserved.
 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92
CO2 activation and decrease carbon formation [12–14]. Addition of
basic promoters such as La2O3, CeO2, and alkaline earth metal oxi-
des such as MgO, CaO, and BaO help in CO2 activation, thus increas-
ing reactive oxygen for surface carbon oxidation [2,15–21]. Basic
promoters also help increase the active metal dispersion [13]. A
comprehensive review on DRM kinetics and mechanism by Pak-
hare and Spivey [22] suggests various ways to control deactivation
of DRM catalyst.
Activation of CH4 is a crucial step in DRM mechanism [17,22–24].
However, there is no consensus in the literature on the mechanism
of CH4 activation on catalytic sites, even on the same metal. For
example, Luntz and Winters [25] and Wei and Iglesia [26] proposed
that on Pt and Pd [27] clusters, the activation of CH4 occurs by direct
decomposition where all CAH bonds simultaneously dissociate
resulting in C(s) and evolution of H2(g). However, theoretical calcula-
tions by Seets et al. [28] suggest activation of CH4 by the formation of
reactive intermediates such as formates or CHx species. Yamaguchi
and Iglesia [27] observed that CAH bond activation in CH4 is struc-
ture sensitive and its rate increases with decreasing Pd clusters size.
For DRM, the activity decreases in the order Ru, Rh > Ir > Ni, Pt,
Pd > Co > Fe, Cu [29], with noble metals showing higher activity
and greater resistance to carbon deposition [30–33]. DRM has been
studied on various catalysts; however, we are aware of no papers
where pyrochlores have been studied for DRM other than those
reported by our group [34–36]. Pyrochlores are crystalline ther-
mally stable ternary metal oxides with a cubic unit cell and general
formula of A2B2O7. The A-site is usually a large cation (typically
rare earth elements) and the B-site cation has a smaller radius
(usually transition metal) [22,37]. These materials have two impor-
tant properties that make them interesting for this reaction. The
first is oxygen ion conductivity; vacancies at the O sites, created
during synthesis, facilitate oxygen ion migration, which minimizes
carbon deposition formed by CH4 dissociation [38]. The second is
the ability to isomorphically substitute catalytically active transi-
tion metals into the B-site, where they do not sinter at high DRM
temperatures. Candidate catalytically active transition metals for
B-site substitution include Ru, Rh, and Pt [34,35]. The most closely
related paper for DRM over pyrochlores is by Ashcroft et al. [39]
who studied Eu2Ir2O7 for DRM. However, the pyrochlore structure
in that study decomposed to Eu2O3 and metallic Ir under DRM
gases above 340 °C.
Here, we report a systematic study of the active sites and kinet-
ics of DRM on two Rh-substituted lanthanum zirconate [LZ]
pyrochlores: 2 wt% [L2RhZ] and 5 wt% [L5RhZ]. A detailed charac-
terization and activity study of these materials has been reported
in our earlier work [36] where we confirm the formation of the
pyrochlore phase and substitution of Rh at the B-site. Here, the
process of CH4 and CO2 activation as a function of temperature
and Rh substitution in the pyrochlore structure was studied by
Fourier transform infrared (FTIR) spectroscopy. The role of CH4 in
rate-limiting step in DRM mechanism is examined by studying
the CH4/CD4 kinetic isotope effect. The elementary steps involved
in oxidation of surface carbon were studied by transient pulsing
of CH4 and CO2 with Ar tracer. Kinetic rate models based on postu-
lated mechanisms were validated by statistically fitting the kinetic
data obtained over the L2RhZ and L5RhZ pyrochlores.
2. Experimental section
2.1. Catalyst synthesis
The LZ, L2RhZ, and L5RhZ pyrochlores studied in this work were
prepared by the modified Pechini method [40]. The metal precur-
sors of lanthanum nitrate hexahydrate [La(NO3)36H2O] (GFS
Chemicals, 99.9%), zirconium oxynitrate [ZrO(NO3)2xH2O] (Alfa
79
Aesar, 99.9%), and rhodium nitrate [Rh(NO3)32H2O] (Alfa Aesar,
99.9%) were used. The dissolved metal salts were combined in a
beaker with continuous stirring. Complexing agent citric acid
(CA) solution with molar CA:metal ion ratio of 1.2:1 was added
to the metal solution beaker and heated to 70 °C to which the poly-
merizing agent ethylene glycol (EG) was added with 1:1 M ratio of
EG:CA. The solution was stirred until a clear viscous gel remained
in the beaker. The gel was then heated to 130 °C to promote the
polyesterification reaction. The resulting amorphous polyester-
type resin was calcined at 1000 °C for 8 h to form pyrochlore
catalyst.
2.2. Activation energies
The activation energy was obtained in the AMI-200 Altamira
Instruments reactor using the catalyst:alumina of 1:10. Because
the activity of L5RhZ was higher than L2RhZ, the temperature
range chosen for L2RhZ (585–605 °C) was higher than that for
L5RhZ (520–560 °C) to limit the conversion in both cases and to
minimize any effects of concentration/temperature gradients
across the catalyst bed. Gas composition and flow was 10%
CH4/He and 10% CO2/He at 20 mL/min each.
2.3. Kinetic rate modeling
The equipment details and catalyst dilution ratio were the same
as reported previously (Section 2.2). The partial pressure depen-
dence of CH4/CO2 reaction rate was determined by keeping partial
pressure of one reactant (CH4 or CO2) constant at 0.05 atm and
varying that of the other (CO2 or CH4) as 0.03, 0.035, 0.04, and
0.045 atm (balance He). These set of experiments were performed
at 570 °C, 590 °C, and 610 °C for L2RhZ and at 520 °C, 540 °C, and
560 °C for L5RhZ. The conversion was kept below 15%, so as to
approach differential conditions.
2.4. CH4/CD4 kinetic isotope effect
Deuterium kinetic isotope effect was studied by using 10% of
CD4/He, 10% CH4/He, 10% CO2/He (all 99.99% pure). The reactor is
same as mentioned previously (Section 2.2). Before testing for
DRM, the catalysts were reduced in 4% H2/He by ramping from
25 °C to 600 °C and maintaining isothermal conditions at 600 °C
for 30 min then purged in He for 15 min. For testing the change
in the rate of consumption of CH4 and CD4, alternate cycles of
CH4/CO2/He and CD4/CO2/He of 30 min each were performed on
L2RhZ and L5RhZ.
2.5. In situ FTIR and transient pulsing
For in situ FTIR studies, a Thermo Electron Nexus 670 spectrom-
eter with a liquid N2 cooled MCT detector and a diffuse reflectance
infrared Fourier transform spectroscopy (DRIFTS) cell from Pike
Technologies was used. KBr beamsplitter provided spectra in the
wavenumber range of 4000–500 cm1. Prior to spectrum collec-
tion, catalysts were reduced in flowing 4% H2/He (20 mL/min) by
heating from 25 °C to 550 °C and maintaining at 550 °C for
30 min. The reduced catalysts were then flushed by He for
15 min for background collection. The DRIFTS cell was connected
to an 8-port valve which allowed rapid switching of gases without
interrupting the continuous He flow, thus avoiding pressure drop
across the cell. The valve was fitted with 0.5 cm3 loop, allowing
injection of known amount of reactant gas pulses in the continuous
He flow.
After background collection at 550 °C, the catalysts were treated
in flowing 10% CO2/He (20 mL/min). This resulted in the formation
of carbonate on the catalysts and the gas-phase CO2 was later
80 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92

flushed by He. These carbonates were then reacted with 10%

CH4/He, 0.5 cm3 pulses with the help of the 8-port valve attached
to the DRIFTS cell. A total of 10 pulses of CH4/He separated by a
time gap of 10 min were injected in the continuous He flow over
the CO2-treated catalysts. After 10 pulses, the catalysts were again
treated in flowing 10% CO2/He (20 mL/min) for 15 min. Series spec-
tra were collected throughout the experiment with the resolution
of 4 cm1. The DRIFTS cell was connected to an on-line mass spec-
trometer to analyze the pulse product stream. The masses analyzed
were H2 (1), CH4 (15), H2O (18), CO (28), Ar (40), and CO2 (44). The
NIST web-book suggests that CO2 has a 10% (of mass 44) intensity
at mass 28. This information was used to correct CO concentration.

2.6. Temperature programmed reduction by CH4

The freshly calcined catalysts were dried in He at 200 °C and

then cooled to 30 °C. The dried catalysts were then heated from
30 °C to 950 °C at 5 °C/min in flowing (20 mL/min) 10% CH4/He.
Other equipment and experimental details are reported previously
[34] and in Section 2.2.

2.7. Transient pulsing

Here, we use single pulse format (SPF) where a single pulse of

known volume of CH4/Ar is introduced in the He carrier gas and
the time dependence of the product pulse was determined with
Ar as tracer. The transient pulsing experiments were conducted
in a non-steady-state reaction system comprised of DRIFTS cell
connected to an 8-port valve as discussed previously. The catalysts
were first reduced in 4% H2/He at 550 °C for 30 min and then
flushed with He. The pulse sequence used was 10% CH4/2% Ar/bal
He ? 10% CO2/2% Ar/bal He ? 10% CH4/2% Ar/bal He. Here, He
was used as carrier gas flowing continuously over the catalyst,
and mixture of 10% CH4/2% Ar/bal He or 10% CO2/2% Ar/bal He
was pulsed into the continuous stream of He. The product forma-
tion and the tailing process of each pulse were analyzed (in an
on-line Ametek quadrupole MS) separately and designated here
as CH4/Ar pulse 1 ? CO2/Ar pulse 2 ? CH4/Ar pulse 3.
Fig. 1. Arrhenius plot for CH4 and CO2 consumption over (a) L2RhZ and (b) L5RhZ.

3. Results and discussion

3.1. Activation energies Table 1

Summary of the activation energies calculated in this work and its comparison to that
reported in the literature.
The apparent activation energies for CH4 and CO2 disappearance
rates calculated from Arrhenius plot for L2RhZ and L5RhZ are Catalyst Apparent activation energy (kcal/ Reference
shown in Fig. 1. Table 1 shows the apparent activation energies mol)
for both CH4 and CO2. The activation energy for CH4 is higher than CH4 CO2
that for CO2 on both catalysts, which agrees well with the literature L2RhZ 34.2 ± 0.4 27 ± 0.2 This work
[14,29,41]. The CH4 and CO2 activation energies are significantly L5RhZ 21.8 ± 0.2 18.7 ± 0.1 This work
lower on L5RhZ than L2RhZ, suggesting a difference in active sites Rh (0.6%)/La2O3(27%)–SiO2 14.7 11.8 [42]
on L5RhZ than on L2RhZ. Rh (0.5%)/Al2O3–La2O3–BaO 22 19.28 [15]

The higher activation energies for CH4 (compared to CO2) on

both L2RhZ and L5RhZ show that the activation of CH4 is a slower
step than the activation of CO2 on both catalysts. A previous study
on Ni/La2O3 and BaO promoted catalysts suggests that basic sites
on these catalysts activate the mildly acidic CO2 [43]. Zhang and
Verykios [44] suggest that the presence of basic La–O sites cata-
lyzes CO2 conversion to lanthanum oxy-carbonates (La2O2CO3)
decreasing the apparent CO2 activation energy compared to that
of CH4.
3.2. Reaction mechanism
We are aware of no literature on the mechanism of the DRM
reaction over Rh-pyrochlore catalysts. Thus, the literature based
on catalysts containing Rh, La2O3, and ZrO2 [Table 2] as compo-
nents have been used to postulate DRM mechanistic steps for
kinetic rate modeling.
The most crucial step in DRM, which is also reported to be the
rds, is CH4 activation [18,19]. Mechanistic rate models with CH4
dissociation as rds were observed to fit the kinetic data of Souza
et al. [14], Erdohelyi et al. [41], Zhang and Verykios [44], and Mark
et al. [49]. However, Zhang et al. [50], and O’Connor et al. [51], sug-
gest that CO2 dissociation and surface carbon oxidation are slow
steps in the DRM mechanism. Kinetic study by Wei and Iglesia
[52,53], over Ni/Al2O3 and Rh/Al2O3 catalysts, showed that the
overall DRM rate or steam reforming (SR) is first order in CH4,
 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92 81

Table 2
Summary of key results used in formulating reaction mechanism.

Catalyst Key result Reference

0.5% Rh/Al2O3  Langmuir–Hinshelwood redox model [45]
Rh/Al2O3  H2O formed in RWGS oxidizes C(s) formed from CH4 dissociation [46]
 CO2 dissociation is rate-determining step (rds)
Ni–Rh/Al2O3  Dissociative adsorption of CH4 and molecular adsorption of CO2 [47]
 Reaction between C(s) and CO2 is direct (without H2O formation) and is rds
Rh/La2O3  Dual-site mechanism where CH4 dissociates over Rh and CO2 reacts with La2O3 to form La2O2CO3 [48]
 CH4 dissociation and C(s) oxidation by La2O2CO3 as rds

i.e., r = k. PCH4, and is independent of the co-reactant partial pulsing experiments were performed. These experiments will also
pressure. However, studies by Munera et al. [42,48], Sierra Gallego help confirm the validity of important intermediate steps such as
et al. [54], Verykios [55], and Carrara et al. [16] suggest fractional oxidation of C(s) by H2O and dissociative adsorption of CH4.
order dependence on CO2 for La2O3-based catalysts.
Based on the mechanistic work reported in the literature, a series 3.3. CH4/CD4 kinetic isotope effect
of kinetically significant steps, with one of the steps being rate lim-
iting, is postulated here. This mechanistic sequence was then used to Activation energies (Table 1 and Fig. 1) show that CH4 dissocia-
derive the mathematical kinetic rate expressions. The assumptions tion is the rds during DRM on pyrochlores. In order to verify the
of kinetically significant steps were based on theoretical kinetic expected rate-limiting CAH bond cleavage in DRM, CH4/CD4
models such as Eley–Rideal and Langmuir–Hinshelwood (single kinetic isotope effect was studied. In this experiment, CH4/CD4
and dual site) mechanisms. Various possibilities of rds, including and CO2 consumption rates were measured before and after
CH4 and CO2 dissociation, oxidation of C formed from CH4 dissocia- switching of CH4 to CD4. Figs. 2 and 3 show the changes in CH4,
tion were assumed. The combinations of the theoretical models,
kinetically significant steps, and possible rds resulted in a matrix
of eleven kinetic rate models (details in Supplemental information),
out of which only two were statistically valid for the pyrochlores
studied in this work. The fitting parameters obtained from these
two models had (a) positive values, (b) 95% confidence intervals
did not include zero, (c) adsorption constants decreased with
increasing temperature, (d) and the rate constants increased with
increasing temperature. The reaction sequence for the two kinetic
models that resulted in a statistically valid fit to the kinetic data is
as follows:

CH4 þ S1 ¡CH4  S1 ð1Þ

CH4  S1 ¡C  S1 þ 2H2 ð2Þ

CO2 þ S2 ¡CO2  S2 ð3Þ

CO2  S2 ¡CO þ O  S2 ð4Þ

H2 þ O  S2 ¡H2 O þ S2 ð5Þ

C  S1 þ H2 O¡CO þ H2 þ S1 ð6Þ
The proposed mechanism is a dual-site mechanism, where CH4
activates on S1 and CO2 on S2. This mechanism predicts dissociative
adsorption of CH4 to form surface carbon (C(s)) and H2. The C(s) is
then oxidized by H2O formed from H2 and CO2–S2 reaction. This
is a very important step and will help in limiting carbon formation
of catalyst surface. The two rate models were derived using this
mechanism sequence, but differed in the rds. In the first model
(designated – dual site [1]), the irreversible CH4 dissociation (Eq.
(2)) was assumed to be rds, and in the second model (designated
– dual site [2]), CO2 dissociation (Eq. (4)) was assumed to be irre-
versible and rate determining. Of the eleven models tested, only
two resulted in statistically valid fit meeting criteria (a–d) men-
tioned above. Since multiple rate models resulted in a good statis-
tical fit, it is important to employ other experimental techniques to
distinguish between the 2 models and confirm the likelihood of
occurrence of the intermediate steps proposed in the mechanism.
To determine the active sites S1 and S2 further in detail and to con- Fig. 2. CH4/CD4 kinetic isotope effect on (a) CH4/CD4 conversion and (b) CO2
firm the rds, following CH4/CD4 kinetic isotope, FTIR, and transient conversion, observed in alternating cycles of CH4/CO2 and CD4/CO2 for L2RhZ.
82 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92
Fig. 3. CH4/CD4 kinetic isotope effect on (a) CH4/CD4 conversion and (b) CO2
conversion, observed in alternating cycles of CH4/CO2 and CD4/CO2 for L5RhZ.
CD4, and CO2 conversion over L2RhZ and L5RhZ, respectively. Dur-
ing the first 30-min cycle (i.e., t = 0–30 min) of CH4/CO2 at 600 °C,
significant CH4 and CO2 conversion (Figs. 2 and 3) was observed.
When CH4 was switched with CD4 in the next cycle, a strong deu-
terium isotope effect was apparent, where the CD4 conversion at
the time of switch (t = 30 min) was about 15% for L2RhZ and 30%
for L5RhZ and dropped to 0% and 10%, respectively, by the end of
30-min (i.e., t = 60 min) cycle. The CO2 conversion during this cycle
(t = 30–60 min) was lower as compared to that during the first
cycle (t = 0–30 min) for both catalysts, suggesting that deuterium
had a strong isotope effect on CO2 conversion as well. When the
reaction mixture was switched back to CH4/CO2 (t = 60–90 min),
the catalysts regained their first-cycle activity. In the next cycle
(t = 90–120 min) when CH4 was switched again with CD4, the exact
same decay of CD4 conversion with time observed in the first
switch was repeated.
Increasing the temperature from 600 °C to 620 °C resulted in
an increase in the CH4 and CO2 conversion (t = 120–150 min),
and the same isotope effect was observed for both the catalysts.
Finally, the conditions of the first cycle were repeated (600 °C)
and showed no deactivation of the catalyst over the 180 min of
the previous cycles.
The conversion of CH4 (or CD4) and CO2 over L5RhZ was greater
than L2RhZ in all cycles, and no conversion was observed over non-
substituted LZ pyrochlores. The XPS results reported earlier [36]
suggest that the surface concentration of Rh on L5RhZ is twice of
that on L2RhZ. Linic et al. [56] performed DFT calculations and
found that CH4 activation barrier on terrace sites is higher from
that on stepped sites and that uncoordinated metal sites assist in
CAH bond activation. Since the active site for CH4 activation is
Rh metal, the difference in CH4 conversion is attributed to greater
Rh surface concentration and presumably greater number of
stepped sites on L5RhZ pyrochlores compared to L2RhZ. When
CH4 was switched with CD4 in cycle 2, the drop in CD4 conversion
is consistent with the hypothesis that breaking the CAH bond in
methane is rate limiting suggesting occurrence of dual-site [1]
mechanism (Section 3.2). In the early part of the CD4 + CO2 cycle,
CD4 adsorbs on the Rh sites causing a high apparent CD4 conver-
sion even though it is not reacting. As time progresses, the slow
dissociation rate of CD4 prevents the turnover of CD4 and active
sites gradually get saturated with CD4. This gradual saturation of
Rh sites prevents further CD4 adsorption and results in a gradual
drop in the apparent CD4 conversion. When the CD4 is switched
back with CH4, a significant amount of CD4 from the previous cycle
desorbs and leaves the reactor along with the products of the suc-
ceeding CH4 cycle.
Higher activity of L5RhZ than L2RhZ could also be due to the dif-
ference in the mechanism of activation or the kinetics of CH4/CD4
activation over the two pyrochlores. Breaking of the CAH or CAD
bond in rds should result in an isotope effect factor (kCH4/CD4) value
of >1 [57]. In this case, it is evident that CD4 conversion is consis-
tently lower than CH4 conversion and kCH4/CD4 is >1 at all times.
Due to the lower vibrational frequency of CD4, it is less reactive
than CH4 [56,57] and the clear isotope effect shows that the rds
involves CAH (D) bond dissociation [56–58]. Wang and Au [57]
observed that over Ni/SiO2 deuterium (CD4) isotope had no effect
on CO2 conversion and the effect was less prominent on CO forma-
tion; thus, they proposed that the activation of CO2 is independent
of the activation rate of CH4. However, in this work, deuterium iso-
tope effect is observed on CO2 conversion, suggesting that the acti-
vation of CH4 and formation of H2 is essential for the conversion/
reduction of CO2. This dependence of CO2 reduction on H2 will be
studied in detail in CH4 TPR (Section 3.6) and transient (Section 3.7)
results reported later in this paper.
3.4. Theory of La-oxycarbonates (La2O2CO3)
La-oxycarbonates are polymeric complexes built up of slabs
forming layer-type structures [59] of La2O2+ 2
2 and CO3 ions formed
from the chemisorption of mildly acidic CO2 by basic La2O3 sites;
La2O3 + CO2 ? La2O2CO3 [44]. Depending on the positioning of
the La2O2+ 2 ions in the complex, three different crystalline poly-
morph types I, Ia, and II are defined (Fig. 4) [60]. Characterization
of these structures shows that there are no weight changes
recorded during type-I ? type-Ia ? type-II transformations, con-
firming that these types are polymorphs to each other [59].
Type-I form of La-oxycarbonates are square layers (Fig. 4) of
(La2O2+ 2
2 )n in a tetragonal crystalline form separated by CO3 ions.
Type-Ia form is the monoclinic distortion of type-I [61]. Type-II
carbonates are hexagonal unit cell crystallites found in A-form
sesquioxides with more than one local coordination of La [59,61].
Formation of these three polymorphs is a function of carbonation
temperature, the presence of H2O as an impurity, and heating/
cooling rate [62]. A detailed study of La-oxycarbonate formation
as a function of different pre-treatments is reported by Irusta
et al. [60]. These are the types of La-oxycarbonates that have been
reported to be formed on La2O3 supports; hence, it is important to
 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92
Fig. 4. Representation of the orientation of carbonate (CO2
3 ) ions in (a) type I, (b) type Ia, and (c) type II phases of La-oxide. The corners are represent La atoms and the O
associated with La is not shown. Adapted from [59].
acknowledge the possibility of minor differences in the La-oxycar-
bonates formed on lanthanum zirconate pyrochlores.
3.5. In situ FTIR and transient pulsing
3.5.1. Adsorbed La-oxycarbonates
In situ FTIR bands in the range 1000–1600 cm1 corresponding
to the formation of La-oxycarbonates observed on CO2 treated LZ,
L2RhZ, and L5RhZ (Fig. 5), suggesting strong CO2 chemisorption
[11]. Spectra in Fig. 5 are obtained after 15 min of CO2 flow fol-
lowed by 15 min of He flush, leaving only the strongly adsorbed
species on the surface. For determining the likelihood of adsorption
of CO2 on La2O3 and ZrO2, FTIR spectra for CO2 adsorption on La2O3
and ZrO2 standards were studied. No adsorbed CO2/carbonate
species were observed on ZrO2, but strong adsorption bands were
observed for La2O3, suggesting that La–O is the active site for the
activation of CO2 on the lanthanum zirconate pyrochlores. How-
ever, it is important to acknowledge that there could be differences
in the surface sites over La2O3 and LZ, L2RhZ, and L5RhZ pyrochlor-
es. Although ZrO2 did not show any activation of CO2, the presence
of Zr in the pyrochlore structure could contribute to the formation
of carbonates due to the difference in the structure of oxides such
as La2O3 (or ZrO2) and pyrochlores.
The carbonate bands (1100–1600 cm1) for all three catalysts
show a twofold splitting, suggesting more than one polymorph of
carbonate [63–65]. Carbonate (CO2 3 ) is a non-linear molecule,
and thus, it should have 3n  6 (i.e., 6) modes of vibration; how-
ever, due to the degeneracy of the modes and overlap with absorp-
tion bands of other surface species, not all modes of carbonate
vibrations appear in the spectra [61]. For LZ (Fig. 5a), peaks at
1066 and 1349 cm1 correspond to the presence of type-Ia poly-
morph of La-oxycarbonate [59,60,62]. The band at 1066 cm1
corresponds to symmetric stretching, and this mode is infrared
83
inactive for free ions but is active for crystalline complexes [59].
The distinct appearance of 1066 cm1 bands suggests that carbon-
ate is a part of the crystalline monoclinic tetragonal type-Ia struc-
ture and is closely associated with La ion. The peak at 1511 cm1
corresponds to m3 vibration of CO2 3 associated with type-II form
of oxycarbonate [63]. Taylor and Schrader [62] reported the pres-
ence of type-Ia at 1363 cm1 and type-II form of oxycarbonate at
1499 cm1 for La2O3. The shift in the peaks could be assigned to
the difference in the surface sites on LZ compared to that on
La2O3. Taylor and Schrader [62] also report the presence of bands
in the range of 500–1000 cm1 for La2O3 supports; however, these
bands are infrared inactive for the pyrochlores reported here. This
suggests a difference in the coordination of La ions on LZ (and other
reported pyrochlores) as compared to that over La2O3. A shoulder
at 1573 cm1 marks the presence of formates which is confirmed
by CAH stretching bands at 2834 cm1 [42,43,48,66]. A small peak
at 2163 cm1 is due to the presence of weakly linearly adsorbed
ionic CO as the band is at a higher wavenumber as reported in
the literature [43,55,67,68]. There are negative bands at 3631
and 3652 cm1, which correspond to stretching frequencies of
hydroxyl (OAH) species [29,43,59,60,66]. The negative absorbance
peaks suggest that there were chemisorbed hydroxyl species pres-
ent on LZ after reduction with H2 and were accounted for in the
background spectra. However, after reaction with CO2, these
hydroxyls are consumed to form formate species, resulting in a
negative peak at these wavenumbers [43,69].
The FTIR spectra for L2RhZ (Fig. 5b) show type-Ia oxycarbonate
peaks at 1068 cm1 and 1367 cm1 [48]. Presence of Rh in the
structure changes the electronic structure by adding an ionic char-
acter to type-Ia oxycarbonates, thus causing it to shift to a higher
wavenumber compared to LZ. Type-II oxycarbonate appears on
L2RhZ at wavenumber 1509 cm1, which corresponds to that
formed over LZ at 1511 cm1. Small shoulder at 1745 cm1
84 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92
Fig. 5. FTIR spectra after 15 min of CO2/He flow ? 15 min of He flush over reduced
(a) LZ, (b) L2RhZ, and (c) L5RhZ.
corresponds to the carbonyl group (˜C@O) of bidentate carbonate
species [11,43]. There are no CAH stretching or hydroxyl bands
observed over L2RhZ, unlike LZ. This is because the presence of
Rh inhibits hydration of the catalyst as reported by Irusta et al.
[60], over Rh/La2O3. The carbonate species observed over L5RhZ
(Fig. 5c) are very similar to that observed over L2RhZ with type-
Ia at 1072 and 1373, type-II at 1498 cm1. Heating of type-I oxy-
carbonate in air above 500 °C results in monoclinic distortion of
type-I to form type-Ia [59,63]. Since the experimental conditions
reported in this work are at 550 °C, there is the presence of only
two oxycarbonates polymorphs (type-Ia and II) and no type-I.
There is a clear difference between the wavenumbers of carbonates
on non-substituted LZ and Rh-substituted pyrochlores. This could
be due to higher electronegativity of Rh (2.28) compared to La
(1.1) and Zr (1.33), which has an effect on coordination of the
electron rich carbonates species with the lattice.
3.5.2. Reactive La-oxycarbonate species
In order to understand the mechanistic role of oxycarbonates in
DRM, it is important to distinguish the reactive oxycarbonate spe-
cies from the spectator ones. The changes in the FTIR spectra as a
result of 10 CH4/He pulses over oxycarbonates would help identify
the reactive oxycarbonates from the spectator ones. Following the
10 CH4/He pulses, CO2 was readsorbed to study the changes, if any,
in the oxycarbonate re-formation. The comparison of spectra for
freshly adsorbed oxycarbonates (Section 3.5.1), oxycarbonates
after 10 CH4/He pulses and readsorption of oxycarbonates is shown
in Fig. 6a, b, and c for LZ, L2RhZ, and L5RhZ, respectively.
For LZ (Fig. 6a), there is no apparent change in the spectra ‘‘after
10th CH4 pulse’’ compared to the ‘‘adsorbed CO2’’ spectra. Due to
the absence of Rh in LZ, no CH4 could react with the carbonates.
The spectra for ‘‘readsorbing CO2’’ are identical to that of ‘‘adsorbed
CO2,’’ suggesting the inactivity of LZ toward DRM, conforming
previously reported results [36].
Mass spectrometer analysis of the effluent gas showed that
there was CH4 consumption observed during CH4/He pulsing over
adsorbed oxycarbonates for L2RhZ and L5RhZ (Supplemental infor-
mation). Substitution of Rh on the B-site of the pyrochlore results
in the formation of sites that are not present in LZ. Significant
changes in IR spectra were observed after pulsing CH4 over
adsorbed oxycarbonates on L2RhZ and L5RhZ, and a clear distinc-
tion between the spectator and reactive species was achieved.
For L2RhZ (Fig. 6b), peaks at 1068, 1367, and 1745 cm1 are spec-
tator species which do not change as a result of CH4 pulse and upon
readsorption of CO2. However, the 1509 cm1 peak corresponding
to type-II oxycarbonate decreases significantly after the 10th CH4
pulse. This peak reappears upon readsorption of CO2, suggesting
that the oxycarbonates identical to the freshly adsorbed carbonates
are re-formed.
Table 3 shows that the ratio of the absorbance of oxycarbonate
peaks at 1367:1509 cm1 over L2RhZ and the closely related
1373:1498 cm1 peaks L5RhZ are essentially the same, indicating
that the same oxycarbonate species is reacting with CH4 on both
catalysts. For L5RhZ (Fig. 6c), species corresponding to 1072,
1373, 1749 cm1 are the spectator species and 1498 cm1 species
is dynamic or reactive (Table 3).
The ratio of type-Ia to type-II for L2RhZ increases from 1.26 to
8.71 and for L5RhZ from 1.3 to 8.05, suggesting a significant
decrease in the population of type-II oxycarbonates. This absor-
bance is regained after readsorption of CO2 where the ratio
decreases from 8.71 to 1.04 for L2RhZ and from 8.05 to 1.06 for
L5RhZ (Table 3), suggesting re-formation of the type-II oxycarbon-
ates. These type-II oxycarbonates were also formed over LZ at
1511 cm1 but were spectator species in that case. This confirms
that Rh increases the reactivity of type-II species. It can be postu-
lated that type-II oxycarbonates are formed irrespective of the
presence of Rh but only those at the Rh–La interface react with
CH4. Since the type-II oxycarbonates (1509 cm1 for L2RhZ and
1498 cm1 for L5RhZ) change only in absorbance and not in wave-
number, these species decrease in number but are structurally the
 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92
Fig. 6. FTIR spectra comparing the changes in the carbonates as a result of CH4
pulses over (a) LZ, (b) L2RhZ, and (c) L5RhZ.
same throughout the CH4 pulsing sequence. Type-Ia oxycarbonates
may be present on the Rh–La interface but are inactive toward
DRM. There is a small peak at 1866 cm1 for L2RhZ and L5RhZ,
and this is attributed to bridge adsorbed CO [70,71] which can be
85
Table 3
Summary of the change in the ratio of the absorbance of type-Ia peak to that of type-II
peak as a result of CH4 pulses and CO2 readsorption for L2RhZ and L5RhZ.
Catalyst/ Adsorbed After 10th CH4 pulse Readsorbing
treatment CO2 CO2
L2RhZ Ratio of peak 1367:1509
1.26 8.71 1.04
L5RhZ Ratio of peak 1373:1498
1.3 8.05 1.06
formed from either by oxidation of carbon (formed by CH4 dissoci-
ation) or from oxycarbonates reduction [42,48,66,72]. There were
no CAH stretching bands observed at about 2800 cm1 for L2RhZ
and L5RhZ, confirming dissociative adsorption of CH4. This agrees
with results reported in the literature [27,53].
3.6. Temperature Programmed Reduction (TPR) by CH4
The lattice oxygen in the pyrochlore crystals is reactive toward
surface carbon [40,73], especially at high temperatures. This phe-
nomenon is also observed in fluorite and perovskite catalysts
[2,18,19,74,75]. CH4-TPR was used to study pyrochlore lattice oxy-
gen reactivity. During CH4-TPR, CH4 adsorbs dissociatively forming
C(s) and H2. The pyrochlore lattice oxygen then oxidizes the surface
carbon forming mostly CO and some CO2. Fig. 7 shows the forma-
tion of H2, CO and CO2 during CH4 TPR of freshly calcined (a) L2RhZ
and (b) L5RhZ. MS signal showed that there was significant amount
of H2 formed at exact same temperature as CO during CH4-TPR.
This suggests a mechanism in which H2 reacts with lattice oxygen
to produce H2O, which then oxidizes the surface carbon forming
CO and H2 simultaneously. However, no observable signal for
H2O was observed in the MS during the experiment.
CH4-TPR of L2RhZ shows the formation of CO and H2 at 570 °C
(Fig. 7a) and a small but measurable quantity of CO2. The total
CO and CO2 formed corresponding to 36.7 mgO/gcat. For L5RhZ,
the peak temperature of CO formation was 415 °C with a shoulder
at 330 °C, which is much lower than that for L2RhZ pyrochlore
(Fig. 7b). The formation of CO and CO2 was greater for L5RhZ com-
pared to L2RhZ. The total amount of O reacting from the lattice of
L5RhZ was 60.4 mgO/gcat, which is greater than L2RhZ. The sum-
mary of the quantification of reactive oxygen for each catalyst is
shown in Table 4.
There are two further differences in CH4-TPR results for these
two catalysts. First, although both show multiple peaks, the lowest
significant TPR peak temperature for L5RhZ (415 °C versus 570 °C
for the L2RhZ) suggests greater lattice oxygen reactivity of
L5RhZ. Second, there are three high-temperature peaks for L2RhZ
(655, 770 and 950 °C), suggesting the presence of different species
of reactive oxygen within the lattice. These oxygen species have
different activation energies for diffusion to the pyrochlore surface
where they oxidize the carbon formed from CH4 activation. Hence,
there are different temperatures for CO and CO2 formation. These
different oxygen species are a characteristic of the metal substitu-
tion in the pyrochlore structure. Higher Rh substitution results in
lower activation barriers for the diffusion of reactive lattice oxygen
to the surface and enhances CH4 activation. When isothermal con-
ditions (950 °C) were maintained for 30 min (ISO-isothermal part
on the temperature axis in Fig. 7) in flowing CH4, the CO signal
did not return back to the baseline. If CH4 flow was continued at
this temperature for longer duration then, over a period of time,
the lattice oxygen would eventually deplete, and CO formation
would drop.
86 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92

Gases were pulsed into continuous He flow to avoid any pressure

drop across the catalyst bed. The (a) rate at which pulses exit the
reactor, (b) the pulse response with respect to that of Ar tracer,
and (c) the relative product yields is a function of diffusion, adsorp-
tion, reaction selectivity and desorption of the gas over the catalyst
surface [76]. These transient experiments can elucidate details of
the surface reaction intermediates, provided that the intermediate
reactions are not undetectably fast [2,17,76].
Figs. 8 and 9 show the response of the pulse scheme CH4/Ar
pulse 1 ? CO2/Ar pulse 2 ? CH4/Ar pulse 3 for L2RhZ and L5RhZ,
respectively. For each pulse, the reactant gas mixture was pulsed
at t = 0 (x-axis); however, there was a slight delay in the appear-
ance of the unreacted reactant and Ar tracer in the MS signal
(Figs. 8a and 9a) due to minimal dead volume between the reactor
bed and the MS. The MS signal was then normalized so that the
normalized intensities represent the time-dependent response
and not the actual product yield (Figs. 8b and 9b). Yield of Ar
was almost 100% in all pulses and it diffused through the catalyst
bed without significant interaction with the catalytic surface. Blank
experiments confirmed that the interaction of Ar with the catalyst
surface was insignificant.

3.7.1. L2RhZ, CH4 pulse 1

The MS signal response for the three consecutive pulses over
L2RhZ is shown in Fig. 8a and the normalized pulse response in
Fig. 8b. During CH4/Ar pulse 1, the MS signal (Fig. 8a) shows
response pulse for significant amounts of H2, CO, unreacted CH4,
Ar, and negligible amounts of CO2. Quantification of the MS signals
suggests that about 55% of CH4 was converted to primarily CO and
H2 (and an insignificant amount of CO2) during CH4/Ar pulse 1
(Table 5). The H2 formed during this pulse was about 83.1% of
the theoretical value calculated from CH4 conversion and a small
H2O peak was also observed (Supplemental information). A carbon
balance suggests that only 53.1% of the carbon from CH4 activation
could be accounted by the formation of CO and CO2. Thus, CO and
CO2 are formed by the reaction between surface carbon and lattice
oxygen, as found in CH4-TPR (Fig. 7). During DRM, carbon deposi-
tion is primarily due to decomposition of CH4 [77,78]. The remain-
Fig. 7. TPR by CH4 of freshly calcined (a) L2RhZ and (b) L5RhZ from 50 °C to 950 °C
ing carbon that could not be accounted in CO and CO2 formation is
at the ramp rate of 5 °C/min. (ISO represents that the conditions were isothermal at
950 °C for 30 min.) The plot of each catalyst differs in y-axis scale. likely solid surface carbon that remains on the catalyst. Normalized
response for the components formed during CH4 pulse 1 can be
compared to the response for Ar.
Table 4
First, it is important to note that the residence time distribution
Summary of the reactive oxygen from the lattice of the pyrochlores. of the gas in the catalyst bed is dependent on (a) the interaction
(adsorption/desorption) of the gas with the catalyst and on (b)
Catalyst Amount of Amount of Amount of Percentage of the
CO formed CO2 formed reactive total lattice
the gas diffusivity [76,79]. Thus, if there is no interaction of the
(mgCO/gcat) (mgCO2/gcat) lattice O oxygen reacted gas with the catalyst, the gases will exit the reactor in the order
(mgO/gcat) (%) of decreasing diffusivities, i.e., increasing molecular weights. In
L2RhZ 48 12 36.7 17.4 case of diffusion controlled pulse response, the order of gas exiting
L5RhZ 98 13 60.4 27.7 the reactor would be H2, CH4, CO, Ar, and lastly CO2. Any change in
this order would be due to interaction of the gas with the catalyst
surface. For normalized CH4 pulse 1 (Fig. 8b), CH4 is observed to
exit the reactor faster than Ar, due to greater diffusivity of CH4
3.7. Transient pulsing compared to Ar. Molecules of CO and H2 are much smaller (thus
greater diffusivity) than Ar and would be expected to exit before
Steady-state reaction provides useful information, but does not Ar. However, the response for CO and H2 was observed to be much
allow insight that can be gained by transient pulsing. In these SPF slower than Ar response. This is because either, CO and H2 both
experiments, CH4 pulse is followed by a CO2 pulse and time-depen- interact strongly with the catalyst surface, or the rate of reac-
dent product response is measured (details in Section 2.7). This tion-forming CO and H2 is much slower than diffusion of Ar. It is
gives insight into the diffusion of chemisorbed species between important to note that the response curve for CO is quite close to
different active sites, reaction between chemisorbed species, and that of H2, suggesting that CO and H2 are formed from a common
desorption of products. Detecting chemisorbed surface species surface reaction.
and studying their interaction with catalytic active sites is essential
in understanding the overall mechanistic scheme of the reaction. 3.7.2. L2RhZ CO2 pulse 2
The non-steady-state reaction setup allowed rapid pulsing of There are two possible mechanisms for the activation of CH4;
known volume and composition of gas mixture over the catalyst. direct dissociation [25,80], in which all four CAH bonds are cleaved
 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92 87

Fig. 8. Response for pulse scheme CH4/Ar ? CO2/Ar ? CH4/Ar for L2RhZ, (a) MS signal response and (b) normalized pulse response.

Fig. 9. Pulse response for scheme CH4/Ar ? CO2/Ar ? CH4/Ar for L5RhZ, (a) mass spec signal response and (b) normalized pulse response.
88 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92
Table 5
Summary of the quantification of the MS signal pulse during transient experiments.
Pulse L2RhZ
a b
CH4/CO2 conversion (%) H2 yield CO yield CO2 yield
CH4 pulse 1 55 83.1 50.2 2.9
CO2 pulse 2 33.7 – 19.1 – –
CH4 pulse 3 48.1 81.3 60.6 3.4
a
(Moles of H2 formed/(2  moles of CH4 converted))  100.
b
(Moles of CO or CO2 formed/moles of CH4 converted)  100.
c
(Moles of CO2 + CO formed/moles of CH4 or CO2 converted)  100.
to produce a surface carbon, and precursor-mediated activation
[28], in which CH4 forms adsorbed intermediates such as CHx or
formates. During CO2 pulse 2, the MS signal showed no traces of
CH4 and H2 (Fig. 8a) suggesting no CHx, adsorbed formates, or
adsorbed H2 intermediates were present on the catalyst from
previous CH4/Ar pulse 1. This would mean that the activation of
CH4 is by direct dissociation over pyrochlores, where it decom-
poses completely to C(s) and H2. About 33.7% of CO2 is converted
during the CO2 pulse 2, but only 19.1% of the CO2 converted
resulted in CO formation (Table 5). The rest of the CO2 likely forms
surface carbonates. The normalized response for CO2 in pulse 2
suggests simultaneous exit of CO and CO2, which is slower than
diffusion of Ar (Fig. 8b). This suggests that CO is a product of either
the reduction of CO2 or the oxidation of surface carbon by CO2 or
both. The next CH4 pulse (pulse 3 below) provides insight into
the mechanism of the formation of CO and oxidation of the surface
carbon.
3.7.3. L2RhZ CH4 pulse 3
The MS signal intensity for H2 in CH4 pulse 3 is smaller than in
CH4 pulse 1 (Fig. 8a). Quantification suggests that only 48.1% of CH4
was converted in CH4 pulse 3 as opposed to 55% in CH4 pulse 1
(Table 2), possibly due to carbon (formed during CH4 pulse 1)
blocking the active sites. The H2 selectivity, however, remains
essentially the same at 81.3% in CH4 pulse 3 (compared to 83.1%
in CH4 pulse 1). Carbon balance suggests that there was an increase
in CO formed during CH4 pulse 3 compared to CH4 pulse 1. About
64% of carbon converted in CH4 could be accounted for by CO and
CO2 formation. The carbon in CO and CO2 could be from the CH4
activated in CH4 pulse 3, reduction of the carbonates formed during
CO2 pulse 2, and oxidation of the carbon formed during CH4 pulse
1. It is important to note that carbon yield and formation of CO in
the CH4 pulses is significantly greater than the CO2 pulse 2. This
suggests that the presence of H2 has a positive effect on the forma-
tion of CO.
Consider the normalized CH4 pulse 3 to understand the role of
H2 in CO formation (Fig. 8b). H2 and CO exit the reactor simulta-
neously in spite of large differences in their molecular diffusivities,
suggesting that both H2 and CO are produced in a same slow surface
reaction [81]. Based on this, it can be postulated that H2 formed
from dissociation of CH4 does not desorb immediately but reacts
with oxygen associated with either surface carbonates or with the
pyrochlore lattice to form H2O. If this H2 bonds with carbonate oxy-
gen, it would reduce the carbonates to CO and if it reacts with lattice
oxygen, it would reduce the pyrochlore (see Section 3.6). This H2O
then oxidizes the carbon formed from CH4 activation (C(s) + H2-
O ? CO + H2), liberating CO and H2 simultaneously. Osaki et al.
[82] observed the same trend of delayed H2 and CO response over
Ni/SiO2 catalyst and proposed that oxidation of carbon by H2O is
the rate-limiting step in the mechanism. This step of carbon oxida-
tion by H2O over pyrochlores here must be a slow step in order to
cause a delay in the response of H2 and CO with respect to Ar
[83]. The presence of strong CH4/CD4 isotope effect (as will be seen
L5RhZ
b c
C bal (%) CH4/CO2 conversion (%) H2 yielda CO yieldb CO2 yieldb C bal (%)c
53.1 64.3 82.5 34.3 27.4 61.8
32.7 – 22 – –
64 58.8 81.3 46.6 22.1 68.8
later) results suggests that carbon oxidation step is not rate deter-
mining, but is slow enough to be detected in the transient pulse
experiments. Oxidation of surface carbon is a crucial step in the
DRM mechanism and is greatly influenced by the activation of CH4.
3.7.4. L5RhZ CH4 pulse 1
The process of methane activation appears to be occurring to a
greater extent on the L5RhZ compared to the L2RhZ due to greater
Rh content. The MS signal for CH4 pulse 1 over L5RhZ (Fig. 9a) sug-
gests significant amounts H2 and CO formation. In addition, CO2
formation is an order of magnitude greater than that over L2RhZ.
During this pulse, 64.3% of CH4 was converted, which is greater
than that (55%) observed over L2RhZ. The experimental H2
produced is about 82.5% of theoretical value calculated from CH4
conversion (Table 5). The carbon balance computed from CO and
CO2 formation accounts for about 61.8% of carbon reacted in CH4
pulse 1. The remaining carbon likely remains on the catalyst as
solid adsorbed carbon, C(s). The carbon balance is greater for
L5RhZ (61.8%) compared to L2RhZ (53.1%). The normalized
response suggests that the CH4 response is faster than Ar response
(Fig. 9b). H2 and CO formation are simultaneous, similar to what
was observed in L2RhZ CH4 pulse 1. The response for CO2 is slower
than CO and H2; also there is a shift in the peak of CO2. The result-
ing CO2 response curve has a higher residence time over the cata-
lyst than any other component. This could be either due to lower
diffusivity or increased interaction with the catalyst surface. The
response of CO2 during the blank experiment was observed to be
much faster than the CO2 response over L5RhZ; thus, the delay in
the CO2 response curve is due to interaction/slow surface reaction
[84] and not due to lower diffusivity value of CO2. The fact that the
peak for CO2 appears later than the peak for CO and H2 suggests
that CO2 might be formed from further oxidation of CO. A delay
in the response curve would also mean that the catalyst has
strongly adsorbing CO2 sites, which increases its residence time
over the catalyst [76].
3.7.5. L5RhZ CO2 pulse 2
The CO2 pulse 2 for L5RhZ (Fig. 9) is qualitatively and quantita-
tively very similar to that observed for L2RhZ (Fig. 8). Conversion of
CO2 was about 32.7%, and no H2 and CH4 were observed in the MS
signal suggesting the absence of any CHx or H2 species. Thus, CH4
activates on L5RhZ by direct dissociation mechanism forming C(s)
and H2. About 22% of the CO2 converted resulted in CO formation;
the remaining 78% of the converted CO2 presumably results in car-
bonate formation and could not be completely reduced to CO due
to the absence of H2. The normalized response of CO is accompa-
nied by that of CO2, suggesting that this limited amount of CO is
formed either from the reduction of CO2 or from the oxidation of
C(s) formed in the CH4 pulse 1.
3.7.6. L5RhZ CH4 pulse 3
During the CH4 pulse 3, the CH4 conversion dropped to 58.8%
compared to 64.3% in CH4 pulse 1. As the carbon balance during
 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92
CH4 pulse 1 suggested substantial carbon formation, this presum-
ably blocked the active sites and resulted in lower CH4 activation.
The H2 yield was 82.5% which is nearly the same as that in CH4
pulse 1 (Table 5). The carbon balance improved in CH4 pulse 3 to
about 68.8% as compared to 61.8% for CH4 pulse 1. Some of the car-
bonates formed during CO2 pulse 2 were reduced to CO during CH4
pulse 3, which resulted in an improved carbon balance. The nor-
malized response for CH4, H2, and CO during CH4 pulse 3 is very
similar to that during CH4 pulse 1. Simultaneous exit of H2 and
CO suggests oxidation of the surface carbon by H2O. However,
there is a difference in the normalized CO2 response during the
two CH4 pulses. The CO2 normalized response during CH4 pulse 3
is delayed compared to CH4 pulse 1, likely due to increased catalyst
interaction of CO2. Also, there are multiple peaks observed in pulse
3. The multiple peaks suggest multiple reactions with varying rates
of CO2 formation [76]. The peak broadness suggests the presence of
different types of CO2 adsorbing sites on the catalyst surface, as
reported by others [9,84]. For L5RhZ, the mechanism of CH4 activa-
tion and product formation during CH4 pulse 1 differs from that
during CH4 pulse 3 as seen by the difference in the CO2 response
curve. This difference could also be present for L2RhZ but was
not clearly apparent due to limited CO2 formation.
Increased CH4 conversion over L5RhZ compared to L2RhZ sug-
gests that the active site for CH4 is Rh. Also, L5RhZ showed better
carbon balance numbers suggesting that Rh plays an important
role in the surface carbon oxidation. Considering that CO2 activa-
tion is primarily by La sites on pyrochlores [11,60,85], the oxida-
tion of the surface carbon could be occurring at Rh–La interface.
This is in agreement with the transient experiments where
L5RhZ having higher surface Rh concentration had higher carbon
oxidation rate as seen by higher carbon balance. This greater num-
ber of Rh–La interfacial sites on L5RhZ compared to L2RhZ leads to
greater rates of surface carbon oxidation.
3.8. Kinetic rate modeling
The rate expression derived for the proposed mechanistic
sequence is given in Eq. (7). Using this expression and kinetic data,
the adsorption and rate constants giving the best statistical fit were
determined.
 
k2 PCO PH2
r CH4 ¼ PCH4 1 þ K 1 PCH4 þ
K1 K 6 P H2 O
K3
P H2 O ¼ K 5 P H2 PCO2 PCO
K4
The two models giving a valid statistical fit had the same mech-
anistic sequence but differed in the assumed rate-limiting step, i.e.,
either dissociation of CO2 or dissociation of CH4. The kinetics
isotope effect results (Section 3.3 above) clearly showed a strong
deuterium isotope effect when CH4 was replaced with CD4. Pres-
ence of alkaline and alkaline earth metals such as La, Mg, Ce, Ca,
and Sr adds to the basicity of the catalysts, which helps in the
Table 6
Summary of the statistical fitting parameters for L2RhZ and L5RhZ obtained by fitting the kinetic data to the derived rate expression.
Parameters L2RhZ
570 °C 590 °C
K1 (atm1)  102 11.6 ± 1.8 10.3 ± 1.4
k2 (mol s1 g1)  104 6.7 ± 3.1 16.1 ± 4.9
K3 (atm1)  103 857 ± 2.4 808 ± 15.9
K4 (atm)  103 762 ± 2.1 718 ± 14.1
K5  103 666 ± 1.89 628 ± 12.4
K6 (atm)  103 571 ± 1.6 538 ± 10.6
The parameter values are reported as ±95% confidence interval.
89
activation of mildly acidic CO2 and accelerates the rate of carbon-
ate formation, consistent with the literature [2,15,43,60,86]. The
presence of La–O on the L2RhZ and L5RhZ surface increases the
rate of CO2 activation to form carbonates (Section 3.5). These
results suggest that the rds is activation or dissociation of CAH
bond in CH4.
Oxidation of carbon formed from CH4 activation is also an
important step. From CH4 TPR (Section 3.6) and transient pulsing
experiments (Section 3.7), it was observed that surface carbon is
oxidized by carbonates via H2O formation. This is an intermediate
step assumed in the postulated mechanism. Thus, the most proba-
ble DRM mechanism over L2RhZ and L5RhZ would be the dual-site
[1] mechanism i.e., steps (1–6) and step (2) as an irreversible
rate-determining step.
The statistical fitting parameters K1, k2, K3–K6 determined by fit-
ting the kinetic data for L2RhZ and L5RhZ to the above rate expres-
sion are shown in Table 6. The parameters were estimated by using
the function minimization Marquardt’s algorithm [47].
Here, K1 and K3 are adsorption constants for CH4 and CO2
adsorption, respectively. The rate constant for the rate-limiting
dissociation of CH4 is given by k2, other constants K4–K6 are equi-
librium constants for the Steps 4–6. Note that for large values of K6
(reaction of steam with surface carbon) and small values of K1
(adsorption of CH4, Step 1), the rate becomes first order in meth-
ane, as observed on other catalysts reported in the literature
[26,27,52,53].
The parity plots (Fig. 10) for L2RhZ and L5RhZ show reasonable
agreement of the predicted reaction rate of CH4 consumption and
the experimental reaction rate, over both L2RhZ compared to
L5RhZ based on the adjusted R2 values. It can be concluded that
a Langmuir–Hinshelwood dual-site mechanism with dissociative
adsorption of CH4 as rds is consistent with the kinetic measure-
ments, and also with the transient pulsing results. Differences in
the rates of the DRM reaction on the two catalysts are due to
differences in the nature of the surface Rh sites. Specifically, the
L5RhZ contains surface Rh sites that activate CH4 via a lower
energy transition state (Eapp = 21.8 kcal/mol) than L2RhZ
(Eapp = 34.2 kcal/mol).
3.9. Summary of the DRM reaction mechanism
A detailed characterization and activity study of L2RhZ and
L5RhZ has been reported in our previous work [36]. The character-
ization results suggested higher surface coverage of Rh on L5RhZ
ð7Þ compared to L2RhZ. Also, CH4 and CO2 conversion was observed
to be greater for L5RhZ than L2RhZ as suggested by the activity
results. To study the catalytic active sites responsible for dissocia-
tion of CH4/CO2 and formation of H2 and CO, a detailed study of the
activation of CH4 and CO2 is reported here. This study showed
strong deuterium (CH4/CD4) isotope effect suggesting that break-
ing of the CAH bond in CH4 is the rds. CH4 is activated on Rh sites
on both catalysts, although these sites appear to be different on
L2RhZ compared to L5RhZ.
L5RhZ
610 °C 520 °C 540 °C 560 °C
9.1 ± 1.2 10.3 ± 1.4 9.8 ± 1.4 8.7 ± 1.2
34.2 ± 8.4 12.7 ± 3.4 18.6 ± 5.9 36.8 ± 9.6
745 ± 29.3 839 ± 13.8 815 ± 14.5 759 ± 27.6
662 ± 26 746 ± 12.3 725 ± 12.9 675 ± 24.5
579 ± 22.7 653 ± 10.7 634 ± 11.3 590 ± 21.4
496 ± 19.5 560 ± 9.25 543 ± 9.6 506 ± 18.4
90 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92
Fig. 10. Statistical fit of the postulated kinetic model showing the comparison of
the rate predicted by the model to the experimental rate for (a) L2RhZ and (b)
L5RhZ.
Based on our previous work and the results reported here, a
sequence of mechanistic steps for DRM over Rh-substituted
pyrochlores can be derived. The most important step in the DRM
mechanism is activation of CH4 which occurs solely on the Rh site
in L2RhZ and L5RhZ (Step 1 in Fig. 11). Activation of CH4 occurs via
dissociative adsorption (Step 2 in Fig. 11) as suggested by the
absence of CAH stretching bands in the IR spectra during CH4
pulsing and transient pulsing studies (Sections 3.5.2 and 3.7) and
as seen in the literature [26,52]. The dissociation of CAH bond is
the rds as seen from strong deuterium isotope effect (Section 3.3).
This was also confirmed by the fact that activation energy for CH4
consumption was greater than that for CO2, suggesting slower
kinetics for CH4 activation (Section 3.1). This rate-limiting dissocia-
tive adsorption of CH4 results in formation of surface carbon and
hydrogen. The activation of mildly acidic CO2 occurs at La–O sites
(Section 3.5.1) which result in formation of La-oxycarbonates (La2-
O2CO3) (Steps 3 and 4 in Fig. 11). In transient pulsing of CH4/Ar
mixture over reduced L2RhZ and L5RhZ catalysts, simultaneous
evolution of H2 and CO was observed which was much slower than
evolution of Ar. This observation suggests that hydrogen (formed
from CH4 activation on the Rh site) reacts with adsorbed La-oxy-
carbonates (Step 5 in Fig. 11), perhaps by diffusion from Rh to
the La–Rh interface, forming H2O and reducing carbonates to CO.
This H2O later reacts with surface carbon at the La–Rh interface
evolving CO and H2 simultaneously (Steps 6 and 7 in Fig. 11). Since
H2 and CO are observed to evolve much later than Ar, either the
surface diffusion of H2 or the oxidation of surface carbon is a slow
step. This delay in the formation of H2 and CO compared to Ar
could also be due to slow activation of CH4, which is rds. Since
CH4 and Ar are pulsed simultaneously, a slow CH4 dissociation
would result in slower formation of H2 and thus a further delay
in the H2O formation and subsequent oxidation of carbon. Oxida-
tion of surface carbon via H2O formation is an important step in
understanding DRM mechanism over these pyrochlores. In the pre-
vious rate modeling Section 3.8, a dual-site mechanism was consis-
tent with our kinetic data. These two types of sites that are
responsible for CH4 and CO2 activation have been clearly identified
as Rh and La respectively. Hence the previously reported reaction
mechanism can be restated as follows:
CH4 þ Rh¡CH4  Rh
CH4  Rh ! C  Rh þ 2H2 . . . rate-limiting step
CO2 þ La2 O3 ¡La2 O2 CO3
La2 O2 CO3 þ H2 ¡La2 O3 þ CO þ H2 O
C  Rh þ H2 O¡CO þ H2 þ Rh
4. Conclusion
The two lanthanum zirconate pyrochlores containing different
levels of Rh substitution shows significantly different kinetic
behaviors toward DRM. The different levels of Rh (2% and 5%) pro-
duced catalytically different materials as measured by CH4-TPR
and activation energy. Increasing the Rh content facilitates CH4
activation by decreasing CH4 apparent activation energy, clearly
suggesting a difference in the nature of the surface Rh sites on
the two catalysts. Increasing the Rh content also increases the oxy-
gen reactivity, as measured by CH4-TPR, and thus the reducibility
of the pyrochlore.
The primary site for CH4 activation and dissociation is Rh, as
shown by transient pulsing of CH4 over La2O2CO3. This was also
confirmed by isotope studies in which there is a direct correlation
between CH4 (CD4) conversion and Rh content of the catalyst. A
strong deuterium kinetic isotope effect was apparent on CH4 and
CO2 conversion suggesting that dissociation of CAH (D) bond is
the rds in DRM mechanism over both pyrochlores. A correspond-
ingly strong deuterium isotope effect on the CO2 conversion indi-
cates that the CH4 activation (or the products formed from CH4
activation) is essential for CO2 conversion. This mechanistic step
is elucidated by transient experiments where H2 from CH4 reacts
with the carbonates formed from CO2, reducing them to CO, result-
ing in simultaneous formation of H2 and CO. Absence of H2 would
cause a decrease in the CO2 conversion, as observed in isotope
effect and transient pulsing results. The delayed response in H2
and CO relative to Ar suggests (a) a slower rate of formation of
CO and H2 and (b) simultaneous formation of H2 and CO.
Activation of CO2 takes place on La site by formation of 3 poly-
morphs (type I, Ia and II) of La2O2CO3, out of which only type II is
reactive. Keeping in view that CH4 dissociates on Rh; the oxidation
of C(s) could be occurring at the Rh–La interface. Higher surface Rh
concentration on L5RhZ compared to L2RhZ (as shown by
CH4-TPR), would produce greater number of Rh–La interfacial sites
and thus enhanced surface carbon oxidation. This is in agreement
with the carbon balance obtained during the transient pulse exper-
iments. This is the first time that the kinetics of DRM has been
reported on pyrochlore catalysts.
 D. Pakhare et al. / Journal of Catalysis 316 (2014) 78–92
Fig. 11. Pictorial representation of the mechanistic steps of DRM over Rh-substituted pyrochlores. (This cycle is for graphical presentation purpose and does not necessarily
suggest the exact location of the surface atoms or the exact sequence of reaction steps.)
Acknowledgments
This material is based upon work supported as part of the Center
for Atomic Level Catalyst Design, an Energy Frontier Research Center
funded by the U.S. Department of Energy, Office of Science, Office of
Basic Energy Sciences under Award Number DE-SC0001058. [A
portion of] this research was conducted at the Center for Nanophase
Materials Sciences, which is sponsored at Oak Ridge National
Laboratory by the Scientific User Facilities Division, Office of Basic
Energy Sciences, U.S. Department of Energy.
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.jcat.2014.04.023.
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