Journal of CO₂ Utilization 24 (2018) 509–515

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Journal of CO2 Utilization

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CO2 reforming of methane over Ni-Ru supported catalysts: On the nature of T

active sites by operando DRIFTS study
⁎
A. Álvarez M., L.F. Bobadilla , V. Garcilaso, M.A. Centeno, J.A. Odriozola
Instituto de Ciencia de Materiales de Sevilla, Centro mixto Universidad de Sevilla-CSIC, 49 Av. Américo Vespucio, 41092 Sevilla, Spain

A R T I C L E I N F O A B S T R A C T

Keywords: The present paper addresses the nature of the active sites of a bimetallic Ni-Ru supported catalyst on the dry
Dry reforming of methane reforming of methane (DRM). The structural characterization by XRD and Raman spectroscopy, along with the
Ni-Ru bimetallic reducibility study (TPR-H2) of the samples, evidenced the existence of a strong Ni–Ru interaction in the bime-
Operando DRIFTS tallic system. We have assumed that Ru atoms block the most reactive Ni sites (step-edge sites) leaving less
reactive centers for methane activation (terraces). In this way, operando DRIFTS measurements revealed that Ru
decreases the catalytic activity but favors the carbon gasification and prevents the CO dissociation.

1. Introduction formation of coke in oxide supports is the result of the acid-catalyzed

cracking and polymerization reactions between the coke precursors
CO2 conversion into value-added chemicals such as syngas, me- [6,7]. Wang at al. [8] reported that the addition of basic elements as Na
thanol or dimethylether (DME) is considered as the ideal route for or Mg reduce the carbon formation in a 13.4%. Horiuchi et al. [9] re-
dealing with global warming, energy crisis, and energy storage [1–3]. ported that the addition of Na, K, and Mg decreases the carbon for-
Therefore, any efficient reactions using CO2 as a reagent have positive mation owed to the lower catalyst capacity to adsorb dissociatively
effects towards carbon management. CH4. Bobadilla et al. [10] established an optimum quantity of MgO in
Among the different possible reactions, the transformation of CO2 10 wt.% that allowed the modification of the support acidity and im-
with CH4 (Eq. (1)) stands out due to the abundance of these reactants proved the Ni dispersion. In addition, other strategies have been ad-
and the possibility of their transformation towards H2 and/or synthesis dressed regarding the active phase modification. Trimm [11,12] pro-
gas (syngas). posed the formation of Ni-M (M = Sn, Ge…) alloys where,
hypothetically, the 3d electrons of Ni are interacting with the 2p elec-
CH4 + CO2 → 2CO + 2H2 (1)
trons of the alloying metal (M), avoiding in this way the formation
This reaction, known as CO2 or dry reforming of methane (DRM), is nickel carbide, which they propose, is the main precursor in coke for-
highly endothermic and thus require high operating temperatures to mation. The addition of noble metals is another strategy to improve the
reach high conversions of the reactants. However, these high tem- resistance to deactivation. Pt [13,14], Rh [15,16] or Ru [17,18], have
peratures result in catalyst deactivation by coke deposition, mainly due been successful approached. Additionally, besides improving the cata-
to the deep cracking of methane [4,5]. Hence, it is a major challenge to lyst resistance towards coke deposition, the addition of noble metals
develop highly thermal resistant catalysts which can inhibit carbon enhances the catalytic activity. Nevertheless, when Ni catalysts are
deposition effectively. modified with small amounts of another metal, a lot of attention have
Noble metal-based and Ni-based catalysts are the most widely used been paid to the preparation method. In this sense, we have previously
for DRM. From the industrial standpoint, nickel is more attractive since demonstrated how the metal order addition have a huge influence in a
it is more accessible and less expensive, so high loadings are feasible in bimetallic Ni-Ru catalyst when performing the combined steam-dry
order to achieve a high catalytic performance. Nevertheless, Ni-based reforming of methane [19].
catalysts get easily deactivated by sintering, coke deposition and Ni In the last decades, numerous efforts have been focused in the
oxidation. Several approaches have been demonstrated to be feasible in elucidation of the reaction mechanism and the elementary steps of dry
order to increase its stability. For instance, the modification of the reforming of methane. However, the nature of the adsorbed species, as
support acid-base properties is a plausible alternative since the well as the key reaction intermediates is still controversial. To gain a
more comprehensive vision of the role of the involved species during

⁎
Corresponding author.
E-mail address: bobadilla@icmse.csic.es (L.F. Bobadilla).

https://doi.org/10.1016/j.jcou.2018.01.027
Received 22 November 2017; Received in revised form 30 January 2018; Accepted 31 January 2018
Available online 15 March 2018
2212-9820/ © 2018 Elsevier Ltd. All rights reserved.
A.Á. M. et al. Journal of CO₂ Utilization 24 (2018) 509–515

the DRM it is necessary to make use of spectroscopic techniques under reduction (TPR) measurements were performed by means of a
reaction conditions, i.e., in situ and operando characterization methods. Micromeritics AutoChem II 2920 equipment with a TCD detector. The
The purpose of the operando spectroscopy is to determine the active analysis was carried out using 100 mg of fresh catalyst under
sites of the catalyst and the spectator species present during the reac- 25 mL min−1 of a 10% H2/Ar mixture. The temperature was increased
tion under working conditions. Diffuse reflectance infrared Fourier from room temperature to 950 °C with a rate of 10° min−1. The H2
transform spectroscopy (DRIFTS) has been widely employed as a useful consumption was continuously monitored on a thermal conductivity
tool to investigate the adsorbed species during the reaction and to detector (TCD). CuO powder was used as standard for calibrating the H2
elucidate the mechanism by correlating the structure of the catalyst and consumption. The degree of reducibility was estimated assuming that
intermediates with the catalytic activity/selectivity. The present paper only Ni2+ and/or Ru2+ were present like reducible species in the
deals with a comprehensive study to understand the nature of the active samples before the reduction pretreatment.
sites of a Ni-Ru/MgO/Al2O3 catalyst in the DRM reaction and clarify
why the Ni-Ru combination increases the resistance towards carbon 2.3. Activity measurements
deposition under reaction conditions.
The dry reforming of methane was carried out in a commercial
2. Experimental computerized Microactivity Reference Catalytic Reactor from PID Eng&
Tech, employing a stainless steel reactor with 9 mm internal diameter.
2.1. Catalysts preparation A catalytic bed of 0.32 cm3 composed by 50 mg of catalyst diluted in
SiC (both sieved in 100–200 μm) was placed in the center of the reactor.
The MgO/Al2O3 support was prepared from a commercial γ- Prior to the reaction, the catalyst was reduced in 50% H2/N2 at 750 °C
Alumina (Spheralite SCS505) sieved between 100–200 μm by impreg- for 3 h (100 mL min−1). After the pretreatment, a feed mixture of CO2/
nating an alcoholic solution of Mg(NO3)2·6H2O (Aldrich) in order to CH4/N2 (2:2:1) with a CH4/CO2 = 1 M ratio at a total flow rate of
obtain a 10 wt.% of MgO. In previous works [10,20] we established that 115 mL min−1 was introduced into the reactor. The total space velocity
this quantity of MgO is the most adequate in order to assure an optimal was equal to 150 L h−1 g−1. The reforming tests were performed at 650,
acidity/basicity of the support and guarantee a good Ni dispersion. 600 and 550 °C in decreasing order maintaining each temperature for
After impregnation, the solid was dried overnight at 100 °C and then 2 h to achieve steady-state conditions. The effluent gases were analyzed
calcined for 12h at 850 °C. This modified Al2O3 support was named on line by using a micro Gas Chromatograph (Varian 4900 model)
“MgAl”. Ni-Ru bimetallic catalyst was prepared by incipient wetness equipped with two columns: Poraplot Q and Molecular Sieve 5A.
impregnation of both alcoholic solutions of Ni(NO3)2.6H2O (Panreac)
and Ru(NO)(NO3)3 (Aldrich) mixed and impregnated simultaneously 2.4. Operando DRIFTS study
onto the support. After drying in air at 120 °C overnight, the catalysts
were calcined in air at 500 °C for 5 h. Ni and Ru monometallic catalysts Operando DRIFTS measurements were performed in a high-tem-
were prepared by simple impregnation following an analogous proce- perature environmental reaction cell supported in a Praying Mantis
dure. The nickel and ruthenium contents were fixed at 15 wt.% and (Harrick) optical system with ZnSe windows. The spectra were recorded
0.5 wt.%, respectively. Bimetallic catalyst was denoted as NiRu/MgAl on a Thermo Nicolet Nexus FTIR spectrometer equipped with a liquid
while the Ni and Ru monometallic catalysts were labelled as Ni/MgAl N2 cooled MCT detector at 4 cm−1 of resolution and an average of 64
and Ru/MgAl, respectively. scans. About 50 mg of catalyst was loaded in the cell for each experi-
ment. Prior to the measurements, the catalyst was activated in situ at
2.2. Characterization techniques 750 °C in 50% H2/Ar with a total flow of 50 mL min-1. The reaction was
performed by feeding a mixture of 10% of CH4 and 10% of CO2 in argon
Metal content of the catalysts was determined by X-ray fluorescence balance for a total flow rate of 50 mL min-1 into the DRIFTS cell. The
spectrometry (XRF) in a PAnalytical AXIOS PW440 sequential spec- temperature was increased from 550 °C to 700 °C with intervals of 50 °C
trophotometer with a rhodium tube as source of radiation. Textural and each temperature was maintained for 30 min to achieve steady-
properties of calcined catalysts were investigated by nitrogen adsorp- state conditions. For the experiment of CO2 adsorption, a total flow rate
tion experiments at liquid nitrogen temperature. The measurements of 50 mL min−1 of 10% CO2 in Ar was introduced into the IR cell for
were performed using a Micromeritics ASAP 2010 equipment. Prior to 30 min under isothermal conditions at 550 °C. Typically, 64 scans were
the analysis, the samples were degassed for 2 h at 250 °C in vacuum to collected at 4 cm−1 resolution in the range of 400 – 4000 cm−1. In both
remove surface impurities. The structure of the catalysts was analyzed experiments, the concentration of CO2 was measured by time-resolved
by X-ray diffraction (XRD) on an X’Pert Pro PANalytical Diffractometer. analysis by using a VAISALA CO2 analyzer and all DRIFT spectra of the
Diffraction patterns were recorded with Cu Kα radiation (40 mA, 45 kV) adsorbed species on the catalyst surface were obtained by subtracting
over a 2θ range of 10–80° and a position-sensitive detector using a step the spectrum of the catalyst after reduction pretreatment.
size of 0.05° and a step time of 1 s. Raman spectra were collected on a
dispersive Horiba Jobin Yvon LabRam HR800 microscope with a 3. Results and discussion
20 mW He–Ne green laser (532.14 nm) operating at 5 mW and with a
600 g mm−1 grating. A 50X objective (Olympus) was used for both 3.1. Structural analysis and textural properties
focusing the excitation beam on the sample and collecting the scattered
light with a confocal pinhole of 1000 μm. Temperature programmed XRF results (Table 1) show that the metal content of Ni and Ru are

Table 1
Metal loading, textural properties and reducibility of the catalysts prepared.

Sample Ni wt.% Ru wt.% SBET m2 g−1 Pore volume cm3 g−1 Pore size nm Reducibility %

MgAl support – – 123 0.37 9.5 –

Ni/MgAl 17.2 – 106 0.30 8.7 62
Ru/MgAl – 0.41 118 0.35 9.3 82
Ni-Ru/MgAl 15.2 0.35 102 0.28 8.6 80

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A.Á. M. et al. Journal of CO₂ Utilization 24 (2018) 509–515

Fig. 2. Raman spectra of the fresh catalysts and support.

Fig. 1. X-ray diffraction patterns of catalysts and support.

cause this variation in the Raman spectra. This behavior has been
close to the desired values (15 wt.% of Ni and 0.5 wt.% of Ru) in all previously reported by our group and denotes a high RuO2-NiO inter-
catalysts prepared. Regarding the textural properties, all solids are action [19].
mesoporous (adsorption and desorption isotherms are Type IV, not The reducibility of Ni2+ and RuO2 species supported on MgAl was
shown), and the textural properties are mainly governed by the support. investigated by H2-TPR measurements. Their profiles are reported in
However, there is a slight decrease in the SBET area, pore volume and Fig. 3. Regarding the monometallic samples, the Ru/MgAl present an
pore size when Ni and/ or Ru are added, indicating a slight blocking of unique peak at 200 °C attributed to the reduction of Ru+4 to metallic Ru
the porosity by the metal addition (Table 1). [30,31] while the Ni/MgAl catalyst present a broad peak around 600 °C
Fig. 1 presents the XRD patterns of the calcined catalysts as well as and a smaller one at very high temperature (∼850 °C). The broad peak
that of support. As observed, the principal and more intense peaks can be ascribed to the reduction of Ni2+ to Ni° in isolated NiO [32]
correspond to the MgAl2O4 spinel (JCPDS 00-021-1152). The coex- whereas the small shoulder at higher temperature can be attributed to
istence of MgAl2O4 with a minor amount of NiAl2O4 spinel should not the reduction of Ni in strong interaction with the support, forming
be discarded, although at the temperature at which the catalysts have probably the NiAl2O4 spinel as we suggested above. Considering that
been calcined (500 °C) thermodynamically is favoured the preferential the amount of MgO added to the initial alumina support was of 10 wt.%
formation of MgAl2O4 [20]. The absence of peaks associated to MgO and that the total available tetrahedral sites available in the γ-Al2O3
phase implies that the impregnation of 10 wt.% of MgO and subsequent accounts for 28 wt.%, there are still “free” tetrahedral sites which Ni
calcination, results into the total insertion of Mg2+ into the tetrahedral can occupy and form the Ni-Al spinel (NiAl2O4). In good agreement, the
sites of the initial alumina. The formation of MgAl2O4 has been widely Ni reduction in the NiAl2O4 spinel has been widely studied and has
studied as a beneficial aspect in reforming catalysts since it enhances Ni been reported to present Ni reduction peaks around 800 °C [33–35].
dispersion, decreases the alumina acidity and increases the CO2 ad- Likewise, it is worth to notice the shape of the reduction peaks between
sorption capacity [21–23]. Regarding the metal phases, Ni is evidenced 400 and 650 °C of the bimetallic sample. When Ru is present, the
as NiO (JCPDS 00-047-1049) and Ru as RuO2 (JCPDS 01-070-2662). maximum reduction temperature of Ni shifts toward lower values,
Scherrer calculation of the NiO crystallite size indicates no great dif-
ferences between the samples, finding an average size of 5–6 nm. Re-
garding Ru, Scherrer crystallite size calculations denote a size around
30 nm for the Ru/MgAl sample whereas for the NiRu/MgAl no signs of
RuO2 are evidenced. This could be owed to a high dispersion of RuO2 or
even to a possible NiO-RuO2 mixed-oxide.
In order to clarify the RuO2-NiO interaction, a Raman analysis of the
calcined samples was performed (Fig. 2). The bands at 410 and
711 cm−1, characteristic of the Eg and A1g vibration modes of MgAl2O4,
validate the formation of the MgAl2O4 spinel [24]. Regarding the
monometallic samples, the Ru/MgAl present the characteristic bands of
RuO2, at 510, 625, and 700 cm−1, corresponding to the Eg, A1g and B2g
vibration modes, respectively [25,26]. Meanwhile, the Ni/MgAl sample
presents a broad band around 550 cm−1 that can be related to two
overlapping bands attributed to first order transverse optical (TO) and
longitudinal (LO) phonon modes of NiO [27–29]. As it can be noted, the
bimetallic sample present a different behavior. Noteworthy that the
wide band around 550 cm−1 comprises the LO phonon mode of NiO
and the Eg mode of RuO2. Nevertheless, the A1g mode of RuO2 in this
sample is very weak. It has been described that the variation of the
lattice parameters of RuO2 may cause stress and limit the A1g mode,
weakening this band. The structural modification owed to the variation Fig. 3. H2-temperature programmed reduction (TPR) profiles of Ni-Ru/MgAl, Ni/MgAl
of particle size, or even de insertion of Ni2+ into the RuO2 lattice could and Ru/MgAl catalysts.

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studied. We note that Ni/MgAl catalyst exhibits the most optimal cat-
alytic performance whereas monometallic Ru sample is the less active.
H2/CO molar ratios lower than one were observed during methane dry
reforming in the three cases. This is attributed to the reverse water-gas
shift (RWGS) reaction (Eq. (2)), in which part of the hydrogen produced
is consumed in the reaction with CO2.

CO2 (g) + H2 (g) ↔ CO (g) + H2O (g) (2)

We would like to emphasize here the rate for RWGS is higher than
methane decomposition, and thus the RWGS reaction achieve rapidly
the equilibrium [37].
This order for DRM reactivity is opposite to the results previously
reported for the combined steam-dry reforming in which the bimetallic
Ni-Ru catalyst presented the highest catalytic activity [19]. It is gen-
erally accepted that the reaction of steam reforming of methane (SRM)
proceeds via dehydrogenation of methane to form surface carbon which
is oxidized by adsorbed oxygen generated from water dissociation [38]
The thermodynamics of SRM favors the formation of nickel oxide and
the role of Ru on the Ni-Ru alloy is to activate the hydrogen produced
by the dehydrogenation of CH4 through a spillover effect enhancing the
reduction of Ni2+ species originally present or formed over the catalysts
[39]. Moreover, the presence of water enhances the gasification of
carbonaceous deposits and it is well known the presence of Ru favors
this reaction [40]. By contrast, the DRM reaction occurs via decom-
position of methane to generate surface carbon and hydrogen species
followed by the subsequent reaction of surface carbon with CO2 to
produce CO (Boudouard reaction) [41]. In this case, the thermo-
dynamics of DRM favor the formation of nickel carbide or carbon, and
the role of ruthenium has not been completely clarified. Our results
show that the addition of ruthenium decreases the DRM intrinsic ac-
tivity of monometallic Ni catalyst, and it could be caused by local
changes in the electronic structure. Typically, the nickel surfaces pre-
sent two types of active sites: terraces and edge-step sites. From a
theoretical point of view, the reactivity of catalytic surfaces is often
dominated by very reactive low-coordinated atoms such as step-edge
sites [42]. Different studies on model surfaces have concluded that
activation of methane depends sensitively on surface structure; speci-
fically, surface steps and kinks are much more active than atoms on
Fig. 4. Catalytic performance for methane and CO2 conversion together with the corre-
sponding H2/CO molar ratio as a function of time-on stream and the temperature for the terraces [43]. Although additional characterization such as XPS would
three catalysts. Reaction conditions: GHSV = 150 L g−1 h−1, atmospheric pressure, and be necessary to be confirmed, we believe that the subsequent addition
CH4/CO2 = 1. of Ru decreases the activity because of atoms of Ru are located on the
step-edge sites of Ni particles and the blockage of these reactive step-
indicating a positive effect of Ru in the reduction of Ni, probably owed edge sites on Ni surfaces shifts the active centers for methane activation
to spillover phenomena. Enger et al. [36] describe that noble metals are from step sites to less reactive terrace sites as have been previously
able to promote the reduction of Ni owed to the electronic effects and reported for other analogous cases like the combination Ni-Ag [44] or
spillover phenomenon indicating that an intimate contact between both Ni-Au [45]. We have assumed the atoms of Ru are located on the step-
metals should exist in order to observe these effect. This statement is in edge sites considering the limited solubility between nickel and ru-
agreement with the results observed in the bimetallic catalyst where a thenium. Consequently, although the concentration of Ru is very low it
major percentage of Ni is reduced at lower temperature compared to can be sufficient to block the Ni active sites.
the Ni/MgAl monometallic sample. Equally, when comparing the ex-
perimental H2 consumed with the theoretical values, a higher percen-
3.3. Operando DRIFTS study of dry reforming reaction
tage of reducibility is observed for this sample (Table 1). The increase in
the reducibility percentage as well as the shift toward lower tempera-
Operando DRIFTS was used to investigate the nature of the active
ture in the TPR profile, besides the strong evidence of higher Ni-Ru
sites and the adsorbed species on the catalyst surface during the DRM
interaction observed by Raman spectroscopy, suggest that the presence
reaction in the temperature range of 550–700 °C. Fig. 5 shows the
of Ru could promote the formation of a Ni-Ru alloy and increase the Ni
spectra recorded under steady-state conditions over the mono- and bi-
dispersion, although there is no full evidences of possible Ni-Ru alloy
metallic Ni-Ru catalysts after stabilization of the reaction mixture at
formation.
550, 600, 650 and 700 °C. IR spectra of the catalysts taken under re-
action conditions present bands in two regions, one set appearing be-
3.2. Comparative catalytic performance for the DRM reaction tween 3600 and 2700 cm−1 and another set appearing between 2600
and 1200 cm−1. The bands in the first of these regions are associated
Catalytic activity for Ni, Ru and Ni-Ru supported on MgAl was with hydroxyls groups and hydrocarbons where slight perturbations
evaluated for the DRM reaction in the temperature range of 650-550 °C. were observed due to the possible formation of water and methane in
Fig.4 shows the CO2-CH4 conversions and the H2/CO molar ratio ob- gas phase, respectively. The bands appearing in the second region are
tained as a function of time at each temperature for the three catalysts due to CO2 and CO gas, carbonyl and carbonate species. The effects of

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Fig. 5. DRIFT spectra obtained during DRM reaction in the temperature range of 550–700 ºC on the three catalysts. Reaction conditions: total flow rate of 50 mL min−1 and CH4/CO2 = 1.

the reaction temperature on the spectra of the adsorbed species present

on the surface of the metal and/or support and the bands associated
with the gas phase were evaluated with detail to identify the stability
and reactivity of these species in the DRM reaction.
The bands appearing at 1637, 1590 and 1377 cm−1 are character-
istic of carbonates with different degree of coordination on the
MgAl2O4 support [46]. These species are formed by direct adsorption of
CO2 on the support towards the interaction with the hydroxyl groups
and they are present in the three samples in all the range of temperature
investigated. The intense bands observed in the 2100–1900 cm-1 range
correspond to metallic carbonyl species. The band observed at
2020–2030 cm−1 is characteristic of CO coordinated linearly on metal
sites (Ni°-CO), whereas the vibrational mode at 1910 cm−1 indicate the
formation of bridging carbonyls ((Ni°)x-CO) [47]. However, the absence
of bands associated with Ru carbonyls in the monometallic catalyst is
evidenced. Likewise, the shift in the frequencies of Ni carbonyls in the
Ni-Ru/MgAl catalyst, associated to the Ni-Ru interaction is not ob-
served. This fact is due to the high Ni/Ru ratio (Ni∼15%; Ru∼0,5%) in
the bimetallic catalyst where the effects are masked. On the other hand,
the monometallic Ru catalyst present a band at 1980 cm−1 that is ty- Fig. 6. CO2 conversion against the temperature measured in the DRIFTS cell under re-
pical of bridging-bonded CO on Ru zerovalent sites with a slightly action conditions (total flow rate of 50 mL min−1 and CH4/CO2 = 1).
different energy and could be attributed to the decrease in the CO
surface coverage, which allows the transformation of linearly to
the band associated to gas phase CO against the CO2 rate consumption
bridged bonded sites at higher temperatures [48]. This suggest that CO2
for both Ni- and NiRu catalysts (Fig. 7a and b, respectively). It is evi-
is dissociated on Ru sites forming CO linearly bonded on Ru that rapidly
denced that a linear correlation exists between the CO produced in gas
are desorbed to gas phase CO and only remain on the catalyst surface
phase and the CO2 dissociated to CO linear species in both catalysts.
the Ru bridged-adsorbed CO species. As can be observed, by increasing
Aditionally, a clear deviation of the slope in the CO production and the
the reaction temperature the band areas of gas phase CO2 and CH4 are
linear carbonyls representation is evidenced for the monometallic
decreased whereas the CO produced is increased. Fig. 6 shows the CO2
sample, suggesting that the reaction proceeds with another reaction
conversion measured during the operando DRIFTS experiments for the
path at greater temperatures.
three catalysts. We observe that the values found of CO2 conversion in
Between the expected reactions in the catalyst surface, the
the DRIFTS cell are consistent with the values obtained in the chemical
Bouduard reaction (Eq. (3)) and the RWGS reaction (Eq. (2)) are the
reactor indicating that the operando methodology used involves true
main responsible for the increase of CO2 rate and CO production.
catalytic kinetic conditions.
Ni is more active than Ru for the CO2 dissociation. Nevertheless, CO CO2 (g) + C(s) ↔ 2CO (g) (3)
can be desorbed from Ru sites before further decomposition whereas
Between 500 °C and 600 °C, the RWGS reaction begins to be ther-
may be decomposed into carbon on Ni before desorption [49]. This
modynamically favorable and the CO production is mainly associated to
implies that the Ni-catalyst can be rapidly deactivated by coke de-
this reaction. However, in this range of temperature the carbon de-
position. Although the combination Ni-Ru is less active for the DRM
position is increased due to the reverse Boudouard reaction, which is
activation, we believe that the presence of ruthenium in intimal contact
highly exothermic and present a greater preference towards carbon
with the active nickel helps to mitigate the carbon formed avoiding the
deposition at low temperature [50,51]. From 600 °C to 700 °C, the
formation of nickel carbide. The role of Ru is to decrease the diffusion
carbon deposition decreases due to an increase in the thermodynamic
rate of carbon into the metallic nickel particle avoiding the growth of
favorability of the Boudouard reaction. At higher temperatures, the
the carbon nanotubes [7].
methane decomposition is very favored but the carbon formed reacts
In order to confirm this assumption we have represented the evo-
with the CO2 producing CO. This reaction is thermodynamically very
lution of the band associated to CO linearly adsorbed and the area of
favorable around 700 °C and the CO2 consumption and the CO

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Fig. 7. Correlation of band area of CO gas (left) and the band height associated to metallic carbonyl species as function of the CO2 rate consumption on Ni/MgAl and Ni-Ru/MgAl
catalysts. Reaction conditions: total flow rate of 50 mL min−1 and CH4/CO2 = 1.

production depend essentially on this reaction, but the rate reduces Ni4(CO) [54] while the band at 1910 cm−1 associated to bridging-
when CO2 is the limiting reactant [52]. This explains the slight devia- carbonyls is apparently absent. We believe that CO2 dissociation occurs
tion of the slopes observed for CO production and linearly adsorbed CO on the edge-sites of the metal particle and the formed CO migrates to
on the monometallic Ni catalyst. It can be inferred from these ob- the terraces where it interacts with the atoms forming polynuclear
servations that the results obtained are consistent with the thermo- carbonyl species. The absence of these species during the DRM reaction
dynamic and kinetic predictions. Noteworthy that this deviation is not may be due to the presence of carbon adsorbed species that restrain the
observed in the Ni-Ru bimetallic catalyst. To understand the effect of Ru interaction of CO with a maximum of two atoms. Comparing both
it must be considered the others reaction involved in the process such as mono- and bimetallic samples, the position of the IR bands appeared are
the carbon gasification (Eq. (4) and Eq. (5)): identical, although noteworthy that the proportion of carbonyls with
respect to carbonates is significantly major in the bimetallic catalyst.
C (s) + H2O (g) ↔ CO (g) + H2 (g) (4)
This indicates that the presence of highly dispersed Ru interacting
C (s) + 2H2O (g) ↔ CO2 (g) + 2H2(g) (5) strongly with the nickel particles on the edge sites favors the CO2 dis-
sociation. In a recent theoretical study, it was calculated that on Ru
The water formed in the RWGS reaction can react with the carbon (0001) surface the direct dissociation of CO2 is thermodynamically fa-
adsorbed species producing COx and hydrogen. This reaction requires vorable although with a significant activation barrier, suggesting the
the activation of the water molecules and the presence of Ru promotes direct CO2 dissociation does not readily takes place on close-packed Ru
this step. Since the electronic density of ruthenium is higher than of surfaces that are abundant in large Ru particles [55]. It should be
nickel, the Ni-Ru interaction results in the modification of the oxidation mentioned that during the DRM reaction the CO2 conversion was su-
state of Ni and Ru, respectively. The nickel on the coordination sphere perior on monometallic Ni catalyst. This apparent inconsistency can be
of the Ru atoms acquires a higher electronic density, thus decreasing understood considering that monometallic Ni catalyst favors the me-
the number of coordination and consequently the surface energy. This thane decomposition reaction increasing the CO2 conversion via Bou-
suggests that Ru addition decreases the stability of the Ni neighboring douard reaction, but in absence of methane CO2 dissociation is more
sites and thus the stability of the adsorbed carbon species. On the other favored on bimetallic Ni-Ru catalyst.
hand, the Ni-Ru interaction decreases the electronic density on Ru sites Fig. 9 presents the temporal evolution of the IR band area of car-
and therefore increases its oxophilicity favoring the water dissociation. bonyls and carbonates species and the concentration of gaseous CO2
A similar case have been already reported by ourselves for a bimetallic analyzed online. It can be appreciated in both samples that initially an
Ni-Au catalyst [53]. Therefore, is precise to suggest that the presence of important amount of gaseous CO2 is trapped on the catalyst surface
Ru favors the carbon gasification implied in the DRM reaction. forming carbonate species until the saturation is reached and another
part of CO2 is dissociated forming carbonyls species. As can be ob-
served, the production of carbonyls is superior over the Ni-Ru catalyst
3.4. DRIFTS study of CO2 adsorption
showing that this catalyst favors the CO2 dissociation. On the other
hand, is noteworthy that the carbonyls curve reaches a maximum value
In order to explore details of the CO2 activation, we performed an
and decreases till increases again slightly. This feature can be attributed
experiment of CO2 adsorption at 550 °C on both monometallic Ni and
to the dissociation of CO and subsequent reaction of carbon with CO2
the bimetallic Ni-Ru catalysts. Fig. 8 shows the IR spectra of the surface
via Boudouard, and the effect is more pronounced on the monometallic
species formed in both catalysts during CO2 exposure. We can note that
catalyst. We can conclude that the presence of Ru favors the CO2 dis-
the adsorption of CO2 at 550 °C leads to the appearance of several
sociation but prevents the CO dissociation.
bands. Carbonates on the support are evidenced in the
1800–1350 cm−1 range, carbonyl species on the metallic sites are
shown on the 2000–1800 cm-1 range and gas phase CO2 is evidenced at 4. Conclusions
2349 cm-1 (not shown). The presence of carbonyls evidences that dis-
sociative adsorption of CO2 takes place on the Ni-Ru sites whereas the The role of Ni and Ru in a bimetallic Ni-Ru catalyst on the dry re-
formation of carbonates likely occurs on the basic sites of the support. It forming of methane reaction has been explored. The results of struc-
should be noted that on both samples appears the band ascribed to CO tural characterization and reducibility suggest that exist a strong in-
linearly adsorbed on Ni sites and a new band at 1830 cm−1 that is teraction between both metals. Considering the low solubility between
characteristic of Ni multicentered carbonyl species of type Ni3(CO) and nickel and ruthenium, we have assumed the atoms of Ru are located on

514
A.Á. M. et al. Journal of CO₂ Utilization 24 (2018) 509–515

Fig. 8. Evolution of DRIFTS spectra with the time on Ni/MgAl and Ni-Ru/MgAl catalysts during the adsorption of CO2 at 550 °C (10 vol.% CO2 in Ar, 50 mL min−1). The black line
represents the last spectra obtained in each case.

Hydrogen Energy 39 (2014) 5704–5712.

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