Romoting Effect of Fe On Supported Ni Catalysts in CO2methanation Byin situDRIFTS and DFT Study
Romoting Effect of Fe On Supported Ni Catalysts in CO2methanation Byin situDRIFTS and DFT Study
Romoting Effect of Fe On Supported Ni Catalysts in CO2methanation Byin situDRIFTS and DFT Study
Journal of Catalysis
journal homepage: www.elsevier.com/locate/jcat
a r t i c l e i n f o a b s t r a c t
Article history: Bimetallic NiFe catalysts have emerged as a promising alternative to the traditional Ni catalysts for CO2
Received 14 August 2020 methanation. However, the promoting effect of Fe on the bimetallic catalysts remains ambiguous. In this
Revised 12 October 2020 study, a series of NiFe catalysts derived from hydrotalcite precursors were investigated. In situ x-ray
Accepted 13 October 2020
diffraction (XRD) analysis revealed that small NiFe alloy particles were formed and remained stable dur-
Available online 29 October 2020
ing reaction. When Fe/Ni = 0.25, the alloy catalysts exhibited the highest CO2 conversion, CH4 selectivity
and stability in CO2 methanation at low temperature of 250–350 °C. The in situ diffuse reflectance infra-
Keywords:
red Fourier transform spectroscopy (DRIFTS) study indicated that the formate pathway was the most
CO2 methanation
NiFe
plausible reaction scheme on both Ni and NiFe alloy catalysts, while a moderate addition of Fe facilitated
In situ XRD the activation of CO2 via hydrogenation to *HCOO. Density functional theory (DFT) calculations further
In situ DRIFTS demonstrated that the overall energy barrier for CH4 formation was lower on the alloy surface.
DFT calculation Ó 2020 The Author(s). Published by Elsevier Inc. This is an open access article under the CC BY license
Reaction mechanism (http://creativecommons.org/licenses/by/4.0/).
https://doi.org/10.1016/j.jcat.2020.10.018
0021-9517/Ó 2020 The Author(s). Published by Elsevier Inc.
This is an open access article under the CC BY license (http://creativecommons.org/licenses/by/4.0/).
Huong Lan Huynh, J. Zhu, G. Zhang et al. Journal of Catalysis 392 (2020) 266–277
Ni-based catalysts to achieve the promoting effect appears to be Nitrogen physisorption was performed in a Tristar 3000
dependent on the support type and metal loading. Importantly, (Micromeritics) instrument at 196 °C. Prior to analysis, all samples
the amount of Fe addition plays a crucial role since a small amount were degassed at 150 °C under vacuum overnight. The specific sur-
of Fe boosted the production of CH4 while large amount of Fe pro- face area of the catalysts was calculated using Brunauer-Emmett-
moted the formation of CO via RWGS reaction [16]. NiFe catalysts Teller (BET) method, while the pore volume and pore size distribu-
prepared from layered double hydroxides (LDH) materials were also tions were evaluated using Barrett-Joyner-Halenda (BJH) models.
studied [17,18]. Overall, most of these studies have confirmed the Temperature-programmed reduction (TPR) of the calcined cata-
superiority of NiFe alloy catalysts in CO2 methanation compared to lysts and temperature-programmed desorption (TPD) of the
monometallic Ni catalysts. Regardless of metal loading or type of reduced catalysts were performed on AutoChem II 2920
supports, the optimal Fe content has been reported with a Fe/Ni (Micromeritics). In a typical measurement, 100 mg of calcined
molar ratio up to 1/3. Besides, the Ni3Fe/Al2O3 catalysts showed a sample was used to obtain reliable data [22]. The calcined catalysts
more stable performance compared to commercial Ni methanation were degassed, then the analysis was carried out by heating the
catalysts [19]. Based on kinetic measurements, Mutz et al. assumed sample from 50 °C to 950 °C at a heating rate of 10 K min1 in
the effect of Fe could be due to the synergetic effect of NiFe alloy [19]. 10 vol% H2/Ar (50 mL min1). Subsequently, the sample was
While the CO dissociation energy was used as a descriptor for CO and purged with He flow at 600 °C for 30 min and cooled down to
CO2 methanation activity [9,17], the binding energy of adsorbed CO 50 °C. Thereafter, the sample was exposed to a flow of 6 vol%
was proposed as the key descriptor for CO2 hydrogenation to CH4 CO2/Ar (50 mL min1) for 1 h, followed by purging in He for
(H2/CO2 = 2) [16]. An improvement in CO2 uptake capacity on alloy another 1 h to remove weakly adsorbed CO2. Finally, CO2-TPD data
surfaces corresponding to the promoted CH4 production has also were recorded by heating the sample to 800 °C at a heating rate of
been speculated [20]. Nevertheless, there is no consensus on the 10 K min1 in flowing He.
promotional effect of Fe on Ni, while the mechanism of CO2 metha- Hydrogen chemisorption analysis was conducted in ASAP 2020
nation on NiFe alloy catalysts is not clearly understood. Plus (Micromeritics) instrument at 35 °C. In a typical experiment,
Insights at the atomic scale of active intermediates and key ele- 200 mg of calcined catalyst was reduced in H2 flow at 600 °C for
mentary reaction steps are essential to unravel the reaction mech- 4 h with a heating rate of 5 K min1 and cooled down to 35 °C in
anism of catalytic reaction. In this work, we attempted to flowing He. It was assumed that the chemisorption of H2 occurred
understand the role of Fe and the reaction mechanism by in situ only on Ni atom with a dissociative mechanism because Fe is
X-ray diffraction (XRD) and in situ diffuse reflectance infrared Four- known to be inactive in H2 chemisorption.
ier transform spectroscopy (DRIFTS) study combined with DFT The morphology and particle size of the reduced-passivated and
simulations. To the best of our knowledge, this is the first com- spent catalysts were revealed by transmission electron microscopy
bined experimental and theoretical study on NiFe alloy catalysts (TEM) analysis using JEM-2100 Plus (JEOL) microscope operating at
for the Sabatier reaction. We prepared a series of NiFe on (Mg,Al) 200 kV. The calcined catalysts were reduced in 50 vol% H2/N2
Ox supported catalysts derived from hydrotalcite (HT) precursors (100 mL min1, STP) at 600 °C for 4 h (heating rate of 5 K min1)
in order to study the impact of Fe content on the physicochemical in a fixed-bed reactor. The sample was cooled down in a flowing
properties and catalytic performance in CO2 methanation. The for- N2 to room temperature before being passivated by adding syn-
mation of NiFe alloy upon reduction, as well as the structural thetic air to the gas mixture. The oxygen content was adjusted to
changes during reaction was investigated by in situ XRD analysis. 0.1 vol% and slowly increased to 1 vol%.
Table 1
Elemental compositions and textural properties of calcined catalysts.
2.4. In situ XRD study specified. K-points were sampled using the 4 4 1
Monkhorst-Pack mesh for Ni and NiFe alloys.
In situ XRD diffractograms were collected on a SmartLab 9 kW All the transition states (TS) were determined using the linear
(Rigaku) diffractometer equipped with an XRK900 reactor chamber synchronous transit (LST) and quadratic synchronous transit
and a 1D/Dtex detector to improve the signal-to-noise ratio. The (QST) methods. The TS structures were confirmed by using a local
diffractometer was operated at 45 kV and 200 mA using CuKa radi- minimum search (after a small distortion of each TS in the reaction
ation source. About 50 mg of calcined catalyst was loaded in the coordinate direction) to reach the reactants and products [26]. The
sample holder and heated up to 600 °C at a heating rate of desorption energy (Edes) of adsorbed species was calculated with
10 K min1 under a flow of pure H2 (30 mL min1) for reduction Eq. (5), where Eads and Esurf are the total energies of the isolated
at atmospheric pressure. The diffractograms were subsequently adsorbates in vacuum and the clean surface, respectively. Eads_surf
recorded at 100–600 °C at a scanning speed of 8° min1 (hold for is the total energy of the adsorbed system.
5 min at each temperature). When the temperature reached
600 °C, the data were collected every 15 min for 90 min. The Edes = Esurf + Eads Eadssurf ð5Þ
in situ XRD measurement was also conducted under reaction con-
ditions. A gas mixture of CO2/H2/N2 = 17/69/14 (30 mL min1) was
introduced after cooling the reduced sample down to 200 °C. The 3. Results and discussion
XRD diffractograms were continuously recorded at elevated
temperatures. 3.1. Physicochemical properties
268
Huong Lan Huynh, J. Zhu, G. Zhang et al. Journal of Catalysis 392 (2020) 266–277
the rock-salt-type phase (NiO or MgO) was observed while crys- Ni(2 0 0) was detected at 2h of 51.4° (JCPDS 03–065-2865) after the
talline spinels (e.g., MgAl2O4) would be formed at above 800 °C sample reached 600 °C for 15 min. The intensity of this line grad-
[27]. Therefore, it is assumed that the support was in the mixed ually increased during 90 min of reduction, indicating the growth
oxide phase (Mg,Al)Ox. Notably, the increase of Fe resulted in of Ni particle from 5.3 nm to 9.1 nm (Table S2). Besides, the mixed
poorer crystallinity with slightly smaller crystallite sizes of the oxides phases (Mg,Al)Ox remained unchanged, demonstrating their
oxide catalysts, as can be seen by the reduced intensity of the irreducible nature. As for the NiFe-0.25 and NiFe-0.5 catalysts, the
diffraction lines (Fig. 1). characteristic peak shifted to a lower angle of 50.85° and 50.75°,
Elemental analysis by ICP-OES of the calcined catalysts reveals respectively. Correspondingly, the d-spacing obtained from the
the actual metal loading and Fe/Ni molar ratio, which was close (2 0 0) reflection was in a linear correlation with the molar ratio
to the nominal values (Table 1). It could be assumed that Ni and of Ni/(Ni + Fe) (Figure S4) [34]. The lattice parameter appeared to
Fe ions were successfully precipitated. be increased with increasing Fe content. The shift in peak position
The N2 physisorption analysis of calcined catalysts shows that could confirm the formation of Ni-rich NiFe fcc alloy upon reduc-
all isotherms were type IV with hysteresis loop at high P/Po range tion of NiFe-0.25 and NiFe-0.5 catalysts at 600 °C [19,34–36].
(Figure S2), attributed to mesoporous materials according to Moreover, the alloy crystals were smaller in size (5–6 nm) than
IUPAC classification [28]. The pore size distribution of calcined cat- Ni crystals (9 nm) (Table S2).
alysts (Figure S3) further confirmed that the calcined catalysts had
mesopores in the range of 10–15 nm. In general, all HT-derived cat- 3.3. Metal surface area and basicity of the reduced catalysts
alysts had a relatively high surface area of 200–250 m2 g1 and a
large pore volume of 0.7–0.8 cm3 g1 (Table 1). Interestingly, the The maximum Ni surface area of 5.52 m2 g1 was obtained from
increase of Fe content did not significantly affect the mesoporous NiFe-0 catalyst based on H2 chemisorption analysis. With increas-
texture of the catalysts. ing Fe content, the Ni surface area dramatically dropped to 0.1 m2
g1 for NiFe-0.5 catalyst although the Ni loading was kept constant
3.2. Temperature programmed reduction and in situ XRD study at 20 wt% (Table 2). These results further confirmed the formation
of NiFe alloy which is inactive in H2 chemisorption [34].
The reduction behavior of calcined catalysts was investigated CO2-TPD analysis showed that the alloy catalysts exhibited
by H2-TPR analysis (Fig. 2). For the monometallic NiFe-0 catalyst, stronger basicity than monometallic catalyst, due to the larger
only a single reduction peak at 810 °C was observed, corresponding integrated area of the desorption profiles (Figure S5). It reveals
to the reduction of NiO to metallic Ni. In fact, the reduction tem- that Fe addition could enhance the total basicity of the catalysts.
perature of pure NiO is at 290–340 °C [29]. Other types of Ni2+ However, the impact of different basic types (i.e., weak, medium,
cations such as NiO aggregates or freely bounded NiO were not and strong) on the catalytic activity in CO2 methanation remains
depicted. It has been suggested that Ni was embedded in the disputable [37,38].
MgO-Al2O3 structure, thus it was harder to be reduced [29,30].
For bimetallic NiFe catalysts, the sequential reduction of Fe2O3 3.4. CO2 methanation activity tests
was not observed due to low Fe content [31,32], and only small
peaks at 350–400 °C were observed in Fe-rich catalysts. This could
be ascribed to the partial reduction of Fe2O3 to Fe3O4 [19,33], 3.4.1. Temperature-programmed reaction study
whereas the reduction of Fe3O4 to Fe and NiO to Ni was overlapped The catalytic behavior of different NiFe catalysts was firstly
at higher temperatures [31,32]. The main reduction peaks of Ni studied in temperature-programmed reaction at atmospheric pres-
species shifted to lower temperatures with increasing Fe content. sure. It shows that NiFe alloy catalysts were more active than
Therefore, it can be suggested that Fe enhanced the reducibility monometallic Ni catalysts in CO2 methanation at low tempera-
of the NiFe alloy catalysts. tures, particularly at 260–290 °C (Fig. 4.a). NiFe-0.25 achieved
The in situ XRD diffractograms of NiFe-0, NiFe-0.25, and NiFe- the highest CO2 conversion of 53% at 270 °C. As the temperature
0.5 catalysts during reduction are shown in Fig. 3. For the increased to 450 °C, a decline of activity for all catalysts was
monometallic catalyst, the diffraction line associated with metallic observed.
During CO2 methanation, the simultaneous RWGS reaction led
to a competition between CO and CH4 formation. At 250 °C, the
highest CH4 selectivity was obtained from the NiFe-0 catalyst
(Fig. 4.b). However, at 270–400 °C, NiFe alloy catalysts exhibited
better CH4 selectivity, particularly for NiFe-0.25 with SCH4 greater
than 97%. At a higher temperature of 400–450 °C, a decrease of
SCH4 was observed because the endothermic RWGS reaction was
favored. Moreover, the addition of too large amount of Fe facili-
tated the formation of CO for NiFe-0.33 and NiFe-0.5. It has been
reported that although Fe/(Mg,Al)Ox catalysts had very low activity
in CO2 methanation, the CO selectivity was very high (~100%) [17].
Fe-rich Ni/ZrO2 catalysts have also been found to significantly pro-
mote the RWGS reaction rather than CO2 methanation [16]. Hence,
it could be concluded that a high CH4 yield could only be achieved
over a suitable composition of Ni and Fe, particularly the NiFe-0.25
catalyst in the low-temperature region.
Fig. 3. In situ XRD diffractograms of (a) NiFe-0, (b) NiFe-0.25, and (c) NiFe-0.5 catalysts during reduction in pure H2 at increasing temperatures and time.
1
Fig. 4. (a) CO2 conversion and (b) CH4 selectivity as a function of reaction temperature in CO2 methanation (H2/CO2/N2 vol.% = 64/16/20, WHSV = 43,200 mLCO2 g-1
cat h ).
270
Huong Lan Huynh, J. Zhu, G. Zhang et al. Journal of Catalysis 392 (2020) 266–277
Fig. 7. In situ DRIFTS spectra of (a) NiFe-0 and (b) NiFe-0.25 catalysts under CO2 adsorption condition (CO2/N2 vol.% = 1/5) at increasing temperatures.
Fig. 8. In situ DRIFTS spectra of (a) NiFe-0 and (b) NiFe-0.25 catalysts under CO2 methanation condition (CO2/H2/N2 vol.% = 1/4/5) at increasing temperatures.
assumed to follow the decomposition *HCO3 M *HCOO+*O. It is could be the key to decipher the promoting effect of Fe in the NiFe
also possible that CO2 was directly hydrogenated *CO2+*H M alloy catalysts.
*HCOO at elevated temperature, thus *HCO3 formation was
bypassed. *HCOO and *HCO could be the key intermediates in 3.6. DFT simulations
the reaction pathway of CO2 methanation, while the RWGS could
occur via direct CO2 dissociation since gaseous CO species was To further unravel the reaction mechanisms and the higher
found on Fe-rich (NiFe-0.5) catalyst during CO2 adsorption and activity of NiFe alloy compared to monometallic Ni catalysts in
methanation (Figure S8 and S9). Based on the relative intensity CO2 methanation, DFT calculations were performed on the Ni
of in situ DRIFTS spectra, it further revealed that NiFe alloy could (1 1 1) and Ni4Fe(1 1 1) (representing NiFe-0 and NiFe-0.25 cata-
accelerate the formation of *HCOO and *HCO intermediates com- lysts, respectively, as shown in Figure S11). Energetics of elemen-
pared to the monometallic (NiFe-0) catalyst (Figure S10). *HCOO tary reactions and the desorption energy of adsorbed species are
formation rate would be promoted by increasing Fe content presented in Table S3 and Table S4, together with the stable
(NiFe-0.5 > NiFe-0.25 > NiFe-0). However, the production rate of geometries of reaction intermediates and its coordinates (Fig-
*HCO and CH4 did not follow this trend (NiFe-0.25 > NiFe-0.5 > Ni ure S12 and S13 and Table S5).
Fe-0). Moreover, because Fe-based catalysts are active for the
RWGS reaction [49,50], tuning Fe content is therefore of great 3.6.1. H2 dissociation and diffusion
importance to achieve the best performance of NiFe alloy catalysts The dissociation of H2 and diffusion of *H atom on the surface of
for CO2 methanation. The transformation of *HCOO?*HCO?*CH4 catalyst directly determine whether the catalyst can provide
272
Huong Lan Huynh, J. Zhu, G. Zhang et al. Journal of Catalysis 392 (2020) 266–277
enough *H atom for CO2 methanation. Our calculation shows that The energy diagram of *HCO formation via COOH route with a
the activation energy (Ea) for the dissociation of H2 on Ni(1 1 1) partial contribution from direct CO2 dissociation is presented in
and Ni4Fe(1 1 1) was estimated to be 1.6, 2.3 (H2 adsorbed on Fe), Fig. 11. On Ni surface, the energy barrier for *COOH formation from
and 4.7 (H2 adsorbed on Ni) kcal mol1, respectively (Fig. 9.a). This *CO2 was calculated to be 12.3 kcal mol1, while it required
implies that H2 dissociation was facile on these two catalysts. The 23.9 kcal mol1 for the splitting of *CO and *O. In contrast, *COOH
reaction energy (DE) for H2 dissociation was between 19.2 to formation had a higher energy barrier (Ea = 20 kcal mol1) than
30 kcal mol1, thus it can be speculated that the formed *H atoms that of *CO2 direct dissociation on Ni4Fe surface (Ea = 16.3 kcal mo
were relatively stable on both catalysts. The diffusion barriers for l1). Therefore, the NiFe alloy surface promoted the dissociation of
*H atom on Ni(1 1 1) and Ni4Fe(1 1 1) were estimated to be 12.0 *CO2, consistent with Kim et al. [34] and the in situ CO2 adsorption
and 16.0 kcal mol1, respectively (Fig. 9.b). This indicates that study.
the diffusion of *H atoms was relatively easy on both catalysts, sug- However, the subsequent hydrogenation of *O at (*CO+*O) state
gesting the sufficient availability of *H atoms for CO2 methanation. was difficult on both surfaces (Ea of 31.1 and 37.6 kcal mol1 for Ni
and Ni4Fe, respectively). Therefore, *CO2?*CO?*HCO transforma-
3.6.2. CO2 methanation on Ni and NiFe alloy surface tion can occur easier via the COOH pathway rather than via the
Based on the in situ DRIFTS observation and literature data [51], direct dissociation. *CO+*HM*HCO was the rate-determining step
possible pathways for CO2 hydrogenation to CH4 and CO are pro- (RDS) for the formation of *HCO via COOH route. The activation
posed in Fig. 10. The initial step of CO2 hydrogenation could occur energy of this reaction was 37.7 kcal mol1 on Ni and
on either O-terminal to produce *COOH (carboxyl pathway) or C- 39.5 kcal mol1 on Ni4Fe catalysts. Notably, the hydrogenation of
terminal to produce *HCOO (formate pathway). In the carboxyl *CO was much less favorable compared to the reverse reaction
pathway, *COOH was dissociated into *CO and *OH, which could on both surfaces. The *HCO intermediate was not stable and pre-
be further hydrogenated to produce water or to yield *HCO inter- ferred to decompose back to *CO since the energy barrier of
mediates. In the formate pathway, *HCOO could directly dissociate *HCO formation was much higher than its dissociation. It suggests
to *HCO and *O. The direct dissociation of CO2 to *CO and *O is also that the RWGS reaction has likely occurred following the COOH
possible. The C-O bond of *CO2 could split to form adsorbed *CO pathway. However, the desorption energy of *CO was calculated
and *O, which underwent hydrogenation to either *HCO+*O fol- to be 59.7 kcal mol1 on Ni and 58.1 kcal mol1 on Ni4Fe surface.
lowing the formate pathway or *CO+*OH following the carboxyl Hence, CO desorption was very difficult due to the strong binding
pathway. It is noteworthy that *COH can also be formed from of *CO to the metallic surfaces. While steadily adsorbed *CO would
*CO hydrogenation. However, it was not included in our study not contribute to the production of CH4 via *HCO, it would occupy
because *HCO (also written as *CHO) formation was more favor- the active sites, consequently, cause catalytic deactivation during
able [52]. It could be assumed that *HCO is the key intermediate reaction. In our study, *CO was formed and desorbed easier on NiFe
in the initial hydrogenation of CO2, in agreement with literature alloy compared to the Ni surface in both experimental and theoret-
and the in situ DRIFTS study [16,53]. ical studies. This could explain the more stable performance of
*HCO intermediate can transform to *CHOH, *H2CO, or *CH as NiFe-0.25 compared to NiFe-0 catalyst in the long-term test.
intermediates, which could be further hydrogenated to CH4. It Fig. 12 illustrates the energy diagram of *HCO formation via
was reported that *HCO dissociation (*HCOM*CH+*O) was the HCOO route and direct CO2 dissociation pathway. In the dissocia-
most favorable pathway amongst others [16,52]. As illustrated in tion pathway, the hydrogenation of *CO to *HCO had a very high
Fig. 10, *CH species underwent sequential hydrogenation reactions energy barrier for both Ni (Ea = 38.6 kcal mol1) and Ni4Fe cata-
to *CH2, *CH3 and eventually *CH4. Likewise, surface *O removal lysts (Ea = 39.3 kcal mol1). Indeed, *CO hydrogenation was rather
was carried out by two steps of hydrogenation to water. Finally, difficult via either COOH or direct dissociation pathway with Ea of
*H2O and *CH4 desorbed as gaseous products. Beside CO2 methana- roughly 38–40 kcal mol1. It is also noticeable that the reaction
tion, the RWGS reaction can occur simultaneously and its mecha- was not facilitated on Ni4Fe alloy surface. In contrast, *CO2 was
nism can also be understood by DFT calculations. The side more likely to be hydrogenated to *HCOO with a moderate Ea of
reaction could follow either carboxyl pathway or direct CO2 disso- 15.2–16.0 kcal mol1 on both surfaces. For the C-O bond cleavage
ciation pathway since the dissociated *CO species (cyan route in of *HCOO to *HCO, an energy barrier of 32.3 kcal mol1 was needed
Fig. 10) could desorb as a gaseous product while surface *O and to overcome for monometallic Ni, but it required only 8.5 kcal mol1
*OH were removed as water. for Ni4Fe alloy. Therefore, the transformation of *CO2?*HCOO?
Fig. 9. (a) H2 dissociation pathway and (b) *H diffusion pathway on Ni and Ni4Fe surface.
273
Huong Lan Huynh, J. Zhu, G. Zhang et al. Journal of Catalysis 392 (2020) 266–277
Fig. 11. Energy diagram for the formation of *HCO via COOH pathway and CO2 direct dissociation pathway on Ni(1 1 1) and Ni4Fe(1 1 1).
*HCO was more facile than that of *CO2?*CO?*HCO regardless of Finally, *CH4 was desorbed to gaseous CH4 as product with a
the catalytic systems, and *HCO was formed much easier on Ni4Fe desorption energy of 8.27 and 19.14 kcal mol1 from Ni and Ni4Fe
alloy surface than on Ni surface. *HCOO appeared to be more stable surface, respectively. Indeed, *CH4 was more strongly bound on
on Ni surface and could be detected experimentally [6], while Ni4Fe alloy surface than on Ni surface. According to Young, reac-
Ni4Fe alloy was more active to produce *HCO. This could explain tions with a barrier of 21 kcal mol1 or less can readily occur at
the higher formation rate of *HCOO and *HCO observed in the room temperature [54]. Accordingly, CH4 could easily desorb from
in situ DRIFTS study. both catalytic surfaces. The energy diagram for water produced
Fig. 13 illustrates the energy diagram of *HCO?*CH4 transfor- from *O at (*CH4+*O) state is also presented in Figure S14 (orange
mation for both catalyst surfaces. It shows that the decomposi- pathway). The removal of *O by two steps hydrogenation is crucial
tion of *HCO occurred with a moderate Ea of 23.5 kcal mol1 because not only the active sites would be free from occupied *O,
on Ni surface and 22.6 kcal mol1 on Ni4Fe surface. Alloy surface but *H2O would also be produced as a product from both RWGS
promoted the formation of *CH and *O better than Ni surface. and CO2 methanation. The formation of *H2O via *OH+*H M *H2O
When (*CH+*O) reacted with *H, either *CH2 or *OH could be required significantly high activation energy compared to the for-
formed. While *CH further yielded *CH4 (Fig. 13), water could mation of *CH4, which agreed with Zhang et al. [55]. However,
also be produced (Figure S14, gray pathway). *CH and *CH3 were *H2O could also be formed via *OH+*OH M *H2O+*O at very low
other stable adsorbed species on the metal surfaces. *CH could activation energy of 3.4 kcal mol1 and 1.2 kcal mol1 on Ni and
easily overcome small barriers of approximately 15 kcal mol1 Ni4Fe surface, respectively.
to form *CH2 and *CH3, while the formation of *CH4 from *CH3 Microkinetic modeling on Ni(1 1 1) surface reported that
required very high activation energy of 26.2–26.9 kcal mol1 HCO*MCH*+O* was the main RDS for CO2 methanation [56]. As
on both surfaces, which could be assumed to be the RDS of mentioned above, the decomposition of *HCO was better facilitated
*HCO?*CH4 transformation. on Ni4Fe than on Ni surface due to a lower energy barrier. Accord-
274
Huong Lan Huynh, J. Zhu, G. Zhang et al. Journal of Catalysis 392 (2020) 266–277
Fig. 12. Energy diagram for the formation of *HCO via HCOO pathway and CO2 direct dissociation pathway on Ni(1 1 1) and Ni4Fe(1 1 1).
Appendix A. Supplementary data [26] M.V. Frash, V.B. Kazansky, A.M. Rigby, R.A. van Santen, Cracking of
Hydrocarbons on Zeolite Catalysts: Density Functional and HartreeFock
Calculations on the Mechanism of the b-Scission Reaction, J. Phys. Chem. B 102
Supplementary data to this article can be found online at (1998) 2232–2238.
https://doi.org/10.1016/j.jcat.2020.10.018. [27] K. Mette, S. Kühl, H. Düdder, K. Kähler, A. Tarasov, M. Muhler, M. Behrens,
Stable Performance of Ni Catalysts in the Dry Reforming of Methane at High
Temperatures for the Efficient Conversion of CO2 into Syngas, ChemCatChem 6
References (2014) 100–104.
[28] K.S. Sing, D.H. Everett, R.A. Haul, L. Moscou, R.A. Pierotti, R. J., T. Siemieniewska,
Reporting Physisorption Data for Gas/Solid Systems, in: Handbook of
[1] J. Artz, T.E. Müller, K. Thenert, J. Kleinekorte, R. Meys, A. Sternberg, A. Bardow,
Heterogeneous Catalysis, 2008.
W. Leitner, Sustainable Conversion of Carbon Dioxide: An Integrated Review of
[29] D. Beierlein, D. Häussermann, M. Pfeifer, T. Schwarz, K. Stöwe, Y. Traa, E.
Catalysis and Life Cycle Assessment, Chem. Rev. 118 (2018) 434–504.
Klemm, Is the CO2 methanation on highly loaded Ni-Al2O3 catalysts really
[2] P. Sabatier, J.-B. Senderens, Nouvelles syntheses du methane, Comptes Rendus
structure-sensitive?, Appl. Catal. B 247 (2019) 200–219.
Des Séances De L‘Académie Des Sciences, Section VI –, Chimie 134 (1902) 514–
[30] M.-M. Millet, A.V. Tarasov, F. Girgsdies, G. Algara-Siller, R. Schlögl, E. Frei,
516.
Highly Dispersed Ni0/NixMg1–xO Catalysts Derived from Solid Solutions: How
[3] C. Vogt, M. Monai, G.J. Kramer, B.M. Weckhuysen, The renaissance of the
Metal and Support Control the CO2 Hydrogenation, ACS Catal. 9 (2019) 8534–
Sabatier reaction and its applications on Earth and in space, Nat. Catal. 2 (2019)
8546.
188–197.
[31] S.-H. Kang, J.-H. Ryu, J.-H. Kim, S.-J. Seo, Y.-D. Yoo, P.S. Sai Prasad, H.-J. Lim, C.-
[4] M. Bailera, P. Lisbona, L.M. Romeo, S. Espatolero, Power to Gas projects review:
D. Byun, Co-methanation of CO and CO2 on the NiX-Fe1X/Al2O3 catalysts;
Lab, pilot and demo plants for storing renewable energy and CO2, Renew.
effect of Fe contents, Korean J. Chem. Eng. 28 (2011) 2282–2286.
Sustain. Energy Rev. 69 (2017) 292–312.
[32] R. Brown, M.E. Cooper, D.A. Whan, Temperature programmed reduction of
[5] S. Rönsch, J. Schneider, S. Matthischke, M. Schlüter, M. Götz, J. Lefebvre, P.
alumina-supported iron, cobalt and nickel bimetallic catalysts, Applied
Prabhakaran, S. Bajohr, Review on methanation – From fundamentals to
Catalysis 3 (1982) 177–186.
current projects, Fuel 166 (2016) 276–296.
[33] X. Ge, M. Li, J. Shen, The Reduction of Mg–Fe–O and Mg–Fe–Al–O Complex
[6] E. Vesselli, M. Rizzi, L. De Rogatis, X. Ding, A. Baraldi, G. Comelli, L. Savio, L.
Oxides Studied by Temperature-Programmed Reduction Combined with in
Vattuone, M. Rocca, P. Fornasiero, A. Baldereschi, M. Peressi, Hydrogen-
Situ Mössbauer Spectroscopy, J. Solid State Chem. 161 (2001) 38–44.
Assisted Transformation of CO2 on Nickel: The Role of Formate and Carbon
[34] S.M. Kim, P.M. Abdala, T. Margossian, D. Hosseini, L. Foppa, A. Armutlulu, W.
Monoxide, The Journal of Physical Chemistry Letters 1 (2010) 402–406.
van Beek, A. Comas-Vives, C. Copéret, C. Müller, Cooperativity and Dynamics
[7] M.A.A. Aziz, A.A. Jalil, S. Triwahyono, A. Ahmad, CO2 methanation over
Increase the Performance of NiFe Dry Reforming Catalysts, J. Am. Chem. Soc.
heterogeneous catalysts: recent progress and future prospects, Green Chem.
139 (2017) 1937–1949.
17 (2015) 2647–2663.
[35] D. Pandey, G. Deo, Promotional effects in alumina and silica supported
[8] M. Younas, L. Loong Kong, M.J.K. Bashir, H. Nadeem, A. Shehzad, S. Sethupathi,
bimetallic Ni–Fe catalysts during CO2 hydrogenation, J. Mol. Catal. A: Chem.
Recent Advancements, Fundamental Challenges, and Opportunities in Catalytic
382 (2014) 23–30.
Methanation of CO2, Energy Fuels 30 (2016) 8815–8831.
[36] S.A. Theofanidis, V.V. Galvita, H. Poelman, G.B. Marin, Enhanced Carbon-
[9] M.P. Andersson, T. Bligaard, A. Kustov, K.E. Larsen, J. Greeley, T. Johannessen, C.
Resistant Dry Reforming Fe-Ni Catalyst: Role of Fe, ACS Catal. 5 (2015) 3028–
H. Christensen, J.K. Nørskov, Toward computational screening in
3039.
heterogeneous catalysis: Pareto-optimal methanation catalysts, J. Catal. 239
[37] L. He, Q. Lin, Y. Liu, Y. Huang, Unique catalysis of Ni-Al hydrotalcite derived
(2006) 501–506.
catalyst in CO2 methanation: cooperative effect between Ni nanoparticles and
[10] A.L. Kustov, A.M. Frey, K.E. Larsen, T. Johannessen, J.K. Nørskov, C.H.
a basic support, Journal of Energy Chemistry 23 (2014) 587–592.
Christensen, CO methanation over supported bimetallic Ni–Fe catalysts:
[38] P.A.U. Aldana, F. Ocampo, K. Kobl, B. Louis, F. Thibault-Starzyk, M. Daturi, P.
From computational studies towards catalyst optimization, Appl. Catal. A
Bazin, S. Thomas, A.C. Roger, Catalytic CO2 valorization into CH4 on Ni-based
320 (2007) 98–104.
ceria-zirconia, Reaction mechanism by operando IR spectroscopy, Catalysis
[11] J. Sehested, K.E. Larsen, A.L. Kustov, A.M. Frey, T. Johannessen, T. Bligaard, M.P.
Today 215 (2013) 201–207.
Andersson, J.K. Nørskov, C.H. Christensen, Discovery of technical methanation
[39] M.B. Jensen, S. Morandi, F. Prinetto, A.O. Sjåstad, U. Olsbye, G. Ghiotti, FT-IR
catalysts based on computational screening, Top. Catal. 45 (2007) 9–13.
characterization of supported Ni-catalysts: Influence of different supports on
[12] S. Hwang, U.G. Hong, J. Lee, J.H. Baik, D.J. Koh, H. Lim, I.K. Song, Methanation of
the metal phase properties, Catal. Today 197 (2012) 38–49.
Carbon Dioxide Over Mesoporous Nickel–M–Alumina (M = Fe, Zr, Ni, Y, and
[40] K. Hadjiivanov, Chapter Two - Identification and Characterization of Surface
Mg) Xerogel Catalysts: Effect of Second Metal, Catal. Lett. 142 (2012) 860–868.
Hydroxyl Groups by Infrared Spectroscopy, in: F.C. Jentoft (Ed.), Advances in
[13] D. Pandey, G. Deo, Effect of support on the catalytic activity of supported Ni–Fe
Catalysis, Academic Press, 2014, pp. 99–318.
catalysts for the CO2 methanation reaction, J. Ind. Eng. Chem. 33 (2016) 99–
[41] J.I. Di Cosimo, V.K. Díez, M. Xu, E. Iglesia, C.R. Apesteguía, Structure and Surface
107.
and Catalytic Properties of Mg-Al Basic Oxides, J. Catal. 178 (1998) 499–510.
[14] J. Ren, X. Qin, J.-Z. Yang, Z.-F. Qin, H.-L. Guo, J.-Y. Lin, Z. Li, Methanation of
[42] F. Solymosi, A. Erdöhelyi, T. Bánsági, Infrared study of the surface interaction
carbon dioxide over Ni–M/ZrO2 (M=Fe Co, Cu) catalysts: Effect of addition of a
between H2 and CO2 over rhodium on various supports, J. Chem. Soc., Faraday
second metal, Fuel Process. Technol. 137 (2015) 204–211.
Trans. 1 F 77 (1981) 2645–2657.
[15] D. Pandey, K. Ray, R. Bhardwaj, S. Bojja, K.V.R. Chary, G. Deo, Promotion of
[43] G. Busca, V. Lorenzelli, Infrared spectroscopic identification of species arising
unsupported nickel catalyst using iron for CO2 methanation, Int. J. Hydrogen
from reactive adsorption of carbon oxides on metal oxide surfaces, Materials
Energy 43 (2018) 4987–5000.
Chemistry 7 (1982) 89–126.
[16] B. Yan, B. Zhao, S. Kattel, Q. Wu, S. Yao, D. Su, J.G. Chen, Tuning CO2
[44] S.R. Tong, L.Y. Wu, M.F. Ge, W.G. Wang, Z.F. Pu, Heterogeneous chemistry of
hydrogenation selectivity via metal-oxide interfacial sites, J. Catal. 374 (2019)
monocarboxylic acids on alpha-Al2O3 at different relative humidities, Atmos.
60–71.
Chem. Phys. 10 (2010) 7561–7574.
[17] C. Mebrahtu, F. Krebs, S. Perathoner, S. Abate, G. Centi, R. Palkovits,
[45] Y. Wang, Y. Su, M. Zhu, L. Kang, Mechanism of CO methanation on the Ni4/c-
Hydrotalcite based Ni–Fe/(Mg, Al)Ox catalysts for CO2 methanation –
Al2O3 and Ni3Fe/c-Al2O3 catalysts: A density functional theory study, Int. J.
tailoring Fe content for improved CO dissociation, basicity, and particle size,
Hydrogen Energy 40 (2015) 8864–8876.
Catal. Sci. Technol. 8 (2018) 1016–1027.
[46] K. Ito, H.J. Bernstein, The Vibrational Spectra Of The Formate, Acetate, And
[18] T. Burger, F. Koschany, A. Wenng, O. Thomys, K. Köhler, O. Hinrichsen,
Oxalate Ions, Can. J. Chem. 34 (1956) 170–178.
Simultaneous activity and stability increase of co-precipitated Ni–Al CO2
[47] J. Raskó, J. Kiss, Adsorption and surface reactions of acetaldehyde on alumina-
methanation catalysts by synergistic effects of Fe and Mn promoters, Catal. Sci.
supported noble metal catalysts, Catal. Lett. 101 (2005) 71–77.
Technol. 8 (2018) 5920–5932.
[48] J. Coates, Interpretation of Infrared Spectra, A Practical Approach, in:
[19] B. Mutz, M. Belimov, W. Wang, P. Sprenger, M.-A. Serrer, D. Wang, P. Pfeifer, W.
Encyclopedia of Analytical Chemistry, Wiley, 2006.
Kleist, J.-D. Grunwaldt, Potential of an Alumina-Supported Ni3Fe Catalyst in
[49] D.H. Kim, S.W. Han, H.S. Yoon, Y.D. Kim, Reverse water gas shift reaction
the Methanation of CO2: Impact of Alloy Formation on Activity and Stability,
catalyzed by Fe nanoparticles with high catalytic activity and stability, J. Ind.
ACS Catal. 7 (2017) 6802–6814.
Eng. Chem. 23 (2015) 67–71.
[20] T. Burger, F. Koschany, O. Thomys, K. Köhler, O. Hinrichsen, CO2 methanation
[50] C.-S. Chen, W.-H. Cheng, S.-S. Lin, Study of iron-promoted Cu/SiO2 catalyst on
over Fe- and Mn-promoted co-precipitated Ni-Al catalysts: Synthesis,
high temperature reverse water gas shift reaction, Appl. Catal. A 257 (2004)
characterization and catalysis study, Appl. Catal. A 558 (2018) 44–54.
97–106.
[21] H.L. Huynh, W.M. Tucho, X. Yu, Z. Yu, Synthetic natural gas production from
[51] S. Kattel, P. Liu, J.G. Chen, Tuning Selectivity of CO2 Hydrogenation
CO2 and renewable H2: Towards large-scale production of Ni–Fe alloy
Reactions at the Metal/Oxide Interface, J. Am. Chem. Soc. 139 (2017)
catalysts for commercialization, J. Cleaner Prod. 121720 (2020).
9739–9754.
[22] D.A.M. Monti, A. Baiker, Temperature-programmed reduction. Parametric
[52] E.B. Sterk, CO2 methanation over Ni and its structure sensitivity. A
sensitivity and estimation of kinetic parameters, J. Catal. 83 (1983) 323–335.
computational study, Inorganic Chemistry and Catalysis, Utrecht University,
[23] B. Delley, An all-electron numerical method for solving the local density
2018.
functional for polyatomic molecules, J. Chem. Phys. 92 (1990) 508–517.
[53] W. Zhen, F. Gao, B. Tian, P. Ding, Y. Deng, Z. Li, H. Gao, G. Lu, Enhancing
[24] B. Delley, From molecules to solids with the DMol3 approach, J. Chem. Phys.
activity for carbon dioxide methanation by encapsulating (111) facet Ni
113 (2000) 7756–7764.
particle in metal–organic frameworks at low temperature, J. Catal. 348
[25] J.P. Perdew, K. Burke, M. Ernzerhof, Generalized Gradient Approximation Made
(2017) 200–211.
Simple, Phys. Rev. Lett. 77 (1996) 3865–3868.
276
Huong Lan Huynh, J. Zhu, G. Zhang et al. Journal of Catalysis 392 (2020) 266–277
[54] D. Young, Finding Transition Structures, in: Computational Chemistry: A [57] C. Mebrahtu, S. Perathoner, G. Giorgianni, S. Chen, G. Centi, F. Krebs, R.
Practical Guide for Applying Techniques to Real World Problems, John Wiley & Palkovits, S. Abate, Deactivation mechanism of hydrotalcite-derived Ni–AlOx
Sons, Inc., 2002, pp. 145-158. catalysts during low-temperature CO2 methanation via Ni-hydroxide
[55] M. Zhang, B. Zijlstra, I.A.W. Filot, F. Li, H. Wang, J. Li, E.J.M. Hensen, A formation and the role of Fe in limiting this effect, Catal. Sci. Technol. 9
theoretical study of the reverse water-gas shift reaction on Ni(111) and Ni (2019) 4023–4035.
(311) surfaces, The Canadian Journal of Chemical Engineering 98 (2020) 740– [58] G. Giorgianni, C. Mebrahtu, M.E. Schuster, A.I. Large, G. Held, P. Ferrer, F.
748. Venturini, D. Grinter, R. Palkovits, S. Perathoner, G. Centi, S. Abate, R. Arrigo,
[56] C. Vogt, M. Monai, E.B. Sterk, J. Palle, A.E.M. Melcherts, B. Zijlstra, E. Elucidating the mechanism of the CO2 methanation reaction over Ni–Fe
Groeneveld, P.H. Berben, J.M. Boereboom, E.J.M. Hensen, F. Meirer, I.A.W. hydrotalcite-derived catalysts via surface-sensitive in situ XPS and NEXAFS,
Filot, B.M. Weckhuysen, Understanding carbon dioxide activation and carbon– PCCP (2020).
carbon coupling over nickel, Nat. Commun. 10 (2019) 5330.
277