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Hydrogen production from CH4 dry reforming over bimetallic Ni-Co/Al2O3


catalyst

Article · June 2017


DOI: 10.1016/j.joei.2017.06.001

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Journal of the Energy Institute xxx (2017) 1e12

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institute

Hydrogen production from CH4 dry reforming over bimetallic


NieCo/Al2O3 catalyst
Tan Ji Siang a, Sharanjit Singh a, Osaze Omoregbe a, Long Giang Bach b,
Nguyen Huu Huy Phuc c, Dai-Viet N. Vo a, d, *
a
Faculty of Chemical & Natural Resources Engineering, Universiti Malaysia Pahang, Lebuhraya Tun Razak, 26300 Gambang, Kuantan, Pahang, Malaysia
b
Center for Advanced Materials Research, Nguyen Tat Thanh University, Ho Chi Minh City, Viet Nam
c
Department of Electrical and Electronic Information Engineering, Toyohashi University of Technology, 1-1 Hibarigaoka, Tempaku, Toyohashi,
Aichi 441-8580, Japan
d
Nguyen Tat Thanh University, 300A Nguyen Tat Thanh Street, Ward 13, District 4, Ho Chi Minh City, Viet Nam

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

Article history: Bimetallic 5%Nie10%Co/Al2O3 catalyst was synthesized using impregnation method and evaluated for
Received 21 April 2017 methane dry reforming reaction at different reaction temperatures. NiO, Co3O4 and spinal metal alu-
Received in revised form minates, namely, CoAl2O4 and NiAl2O4 phases were formed on g-Al2O3 support surface during calcina-
1 June 2017
tion process. 5%Nie10%Co/Al2O3 catalyst exhibited reasonable surface area of 86.93 m2 g1 with small
Accepted 1 June 2017
crystallite dimension of less than 10 nm suggesting that both Co3O4 and NiO phases were finely
Available online xxx
dispersed on the surface of support in agreement with results from scanning electron microscopy (SEM)
measurement. Temperature-programmed calcination measurement indicates the complete thermal
Keywords:
Bimetallic NieCo catalyst decomposition and oxidation of metal precursors, viz. Ni(NO3)2 and Co(NO3)2 to metal oxides and metal
Methane dry reforming aluminates at below 700 K. Both CH4 and CO2 conversions were stable over a period of 4 h on-stream and
Hydrogen attained an optimum at about 67% and 71%, respectively at 973 K whilst H2 selectivity and yield were
Syngas higher than 49%. The ratio of H2/CO was always less than unity for all runs indicating the presence of
reverse wateregas shift reaction. The activation energy for CH4 and CO2 consumption was computed as
55.60 and 40.25 kJ mol1, correspondingly. SEM micrograph of spent catalyst detected the formation of
whisker-like carbon on catalyst surface whilst D and G bands characteristic for the appearance of
amorphous and graphitic carbons in this order were observed on surface of used catalyst by Raman
spectroscopy analysis. Additionally, the percentage of filamentous carbon was greater than that of
graphitic carbon.
© 2017 Energy Institute. Published by Elsevier Ltd. All rights reserved.

1. Introduction

Increasing concerns about anthropogenic greenhouse gas emissions and the depletion of petroleum-based energy have renewed in-
terests in the study of natural gas reforming processes for hydrogen production. Hydrogen has been considered as a promising and green
energy for replacing fossil fuels since it exhibits superior energy capacity (ca. 120.7 kJ g1) to that of other common and alternative fuels [1]
and the combustion of H2 results in the formation of water as a sole by-product [2]. In addition, H2 is used as a building block for producing
synthetic fuel and valuable chemicals, namely, FischereTropsch synthesis (FTS) [3e5] and methanol production [6]. The conventional
approach for hydrogen production is methane steam reforming. However, this method generates H2/CO ratio of 3 unfavourable for FTS,
requires a higher H2O/CH4 ratio for increasing H2 yield and produces a considerable amount of greenhouse gas, CO2 [7]. Hence, dry
reforming of methane (DRM) has received significant attention since it converts CO2 to value-added products and forms syngas with H2/CO
ratio of less than unity favoured for downstream methanol and FT synthesis [8]. Co and Ni-based catalysts are conventionally employed for

* Corresponding author. Faculty of Chemical & Natural Resources Engineering, Universiti Malaysia Pahang, Lebuhraya Tun Razak, 26300 Gambang, Kuantan, Pahang,
Malaysia. Fax: þ60 9 549 2889.
E-mail address: vietvo@ump.edu.my (D.-V.N. Vo).

http://dx.doi.org/10.1016/j.joei.2017.06.001
1743-9671/© 2017 Energy Institute. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: T.J. Siang, et al., Hydrogen production from CH4 dry reforming over bimetallic NieCo/Al2O3 catalyst, Journal of
the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.06.001
2 T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12

hydrogen production in DRM owing to their high catalytic activity and selectivity [7,9]. However, these catalysts may be deteriorated by
carbon deposition and sintering during catalytic reaction [7]. CoeNi supported on TiO2 reportedly exhibited high catalytic performance and
resisted to coke formation due to the presence of NieCo alloy [10]. However, the synergetic effect and knowledge about bimetallic NieCo
catalyst are still limited for DRM. Particularly, the influence of operating parameters on catalytic performance, activation energy for product
formation and reactant consumption as well as the nature of carbonaceous deposition on catalyst surface are important knowledge for
kinetic studies and reactor design. Thus, the objective of this research was to investigate the physicochemical attributes of 5%Nie10%Co/
Al2O3 catalyst and examine the effect of reaction temperature on activity and selectivity of DRM.

2. Materials and methods

2.1. Catalyst preparation

Gamma-Al2O3 support supplied by SigmaeAldrich Chemicals was pretreated at 973 K in air for 5 h with a heating rate of 5 K min1 to
ensure thermal stability. Bimetallic 5%Nie10%Co/Al2O3 catalyst was prepared by co-impregnation method using calculated amounts of
Co(NO3)2$6H2O, Ni(NO3)2$6H2O precursor solutions and pretreat g-Al2O3 support. Both aqueous metal precursor solutions were simulta-
neously poured on the calcined g-Al2O3 support stored in a 150 ml glass beaker. Afterwards, the resulting slurry was magnetically stirred for
3 h under ambient conditions and subsequently dried for 24 h inside an oven (Carbolite) at 373 K. The dried solid was then calcined in air at
773 K for 5 h at a ramping rate of 10 K min1 in the same apparatus followed by crushing and sieving to the average particle size of 100 mm to
obtain 5%Nie10%Co/Al2O3 catalyst.

2.2. Catalyst characterization

Multi-point BET surface area measurements were determined using N2 physisorption at 77 K in a Thermo Scientific Surfer unit. The TGA
Q500 unit from TA Instruments was employed for temperature-programmed calcination (TPC) runs of uncalcined catalyst. Catalyst sample
was initially heated from ambient temperature to 373 K with a heating rate of 10 K min1 in N2 flow of 100 ml min1 and held isothermally
at this temperature for 30 min to remove moisture and volatile compounds. It was subsequently heated to 1023 K in 100 ml min1 flow of
20%O2/N2 mixture with different heating rates of 10e20 K min1. After keeping constantly at that temperature for 30 min, catalyst sample
was cooled down to room temperature in the same gas mixture. X-ray powder diffraction (XRD) measurements of g-Al2O3 support and 5%
Nie10%Co/Al2O3 catalyst were conducted in a Rigaku Miniflex II system using Cu target at 30 kV and 15 mA with wavelength, l ¼ 1.5418 Å.
  
Samples were scanned from 3 to 80 with a scan speed of 1 min1 and a step size of 0.02 . Scanning electron microscopy (SEM) mea-
surements were conducted for morphological analysis of both fresh and used 5%Nie10%Co/Al2O3 catalysts in a Carl Zeiss AG-EVO® 50 Series
unit. The accelerating voltage was kept at 7 kV whilst platinum holder was employed during analysis. Raman spectroscopy measurement of
spent catalyst was performed in a JASCO NRS-3100 system in ambient air with a 532 nm green laser and the laser power was kept at less
than 5 mW.

2.3. Methane dry reforming experiment

Reaction runs were performed in a temperature-controlled tubular fixed-bed reactor (L ¼ 17 in and O.D. ¼ 3/8 in) with CO2:CH4 ratio of
1:1 at temperature range of 923 Ke973 K and atmospheric pressure. About 0.1 g of catalyst with average catalyst particle size of 100 mm
mounted by quartz wool in the middle of stainless steel reactor was used per run. Gas hourly space velocity (GHSV) was maintained constant
at 36 L g1
cat h
1
for all runs to minimize transport-disguised kinetics. Before conducting methane dry reforming evaluation, catalyst was
reduced in situ in 50%H2/N2 mixture of 60 ml min1 at 973 K with a ramping rate of 5 K min1 and kept isothermally at this temperature for
2 h. Gaseous products were measured in an Agilent 6890 Series gas chromatograph equipped with both thermal conductivity (TCD) and
flame ionization (FID) detectors.
The catalyst performance was evaluated in terms of reactant conversion (XCH4 and XCO2 ), consumption rate (rCH4 ), selectivity (Si, i: H2 or
CO) and yield of products (Yi) as provided in Eqs. (1)e(5).

FjIn  FjOut
Xj ð%Þ ¼  100%ðj : CH 4 or CO2 Þ (1)
FjIn

  F In  F Out
j j
rn mol g 1 s1 ¼ (2)
WCat:

ri
Si ð%Þ ¼ P  100% (3)
i¼H 2 ;CO ri

FHOut
YH2 ð%Þ ¼ 2
 100% (4)
2F In
CH4

Please cite this article in press as: T.J. Siang, et al., Hydrogen production from CH4 dry reforming over bimetallic NieCo/Al2O3 catalyst, Journal of
the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.06.001
T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12 3

Out
FCO
YCO ð%Þ ¼  100% (5)
In
FCH 4
þ FCO
In
2

where FjIn and FjOut are inlet and outlet molar flow rates (mol s1), respectively and WCat. is the weight of catalyst (g).

3. Results and discussion

3.1. Textural properties

As seen in Table 1, it was inevitable that the impregnation of active metals on support surface led to a reduction in surface area, average
pore volume and pore diameter in comparison with that of calcined g-Al2O3 support. This observation was rationally due to the successful
incorporation of both Ni and Co metal oxides on the porous structure of g-Al2O3 support and hence decreasing its textural parameters,
namely, average pore volume and pore diameter. The drop in BET surface area of catalyst was also owing to the presence of metal particles on
the pore entrance of support. However, 5%Nie10%Co/Al2O3 catalyst still exhibited reasonable surface area of 86.93 m2 g1 with average pore
volume and pore diameter of 0.20 cm3 g1 and 11.21 Å, respectively comparable with other studies [11,12].

3.2. Temperature-programmed calcination

Fig. 1 shows the derivative weight profile during temperature-programmed calcination of uncalcined catalyst with different heating rates
of 10e20 K min1. The derivative weight profiles was stable beyond 700 K indicating the complete thermal decomposition and oxidation of
Ni(NO3)2 and Co(NO3)2 metal precursors to metal oxides and metal aluminates.
As seen in Fig. 1, each thermal profile has 2 characteristic peaks (P1 and P2) located at different temperatures regardless of ramping rates.
The high intensity peak located at low temperature of about 478 K was due to the decomposition of metal nitrates to metal oxides during
calcination (see Eqs. (6) and (7)).

1
NiðNO3 Þ2 /NiO þ 2NO2 þ O2 (6)
2

1
CoðNO3 Þ2 /CoO þ 2NO2 þ O2 (7)
2
The second peak (P2) was assigned to the subsequent oxidation of CoO and NiO phases to Co3O4 and NiCo2O4, respectively at about 558 K
as given in the corresponding Eqs. (8) and (9). In fact, this observation is in line with the report from Foo et al. [8].

Table 1
Summary of textural properties of g-Al2O3 support and 5%Nie10%Co/Al2O3 catalyst.

Sample BET surface area (m2 g1) Average pore volume (cm3 g1) Average pore diameter (Å)
Calcined g-Al2O3 174.13 ± 1.53 0.38 ± 0.003 54.56 ± 0.48
5%Nie10%Co/Al2O3 86.93 ± 0.66 0.20 ± 0.001 11.21 ± 0.09

Fig. 1. Derivative weight profiles of 5%Nie10%Co/Al2O3 catalyst during temperature-programmed calcination at different heating rates.

Please cite this article in press as: T.J. Siang, et al., Hydrogen production from CH4 dry reforming over bimetallic NieCo/Al2O3 catalyst, Journal of
the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.06.001
4 T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12

1
3CoO þ O2 /Co3 O4 (8)
2

1
NiO þ 2CoO þ O2 /NiCo2 O4 (9)
2
The small intensity peaks observed at high temperature range of 600e700 K suggested the formation of metal aluminates [13] may be
described by:

CoO þ Al2 O3 /CoAl2 O4 (10)

NiO þ Al2 O3 /NiAl2 O4 (11)


In addition, Fig. 2 shows that peak temperature for both P1 and P2 shifted linearly to higher temperature with increasing heating rate and
the derivative weight profiles exhibited similar shapes for all ramping rates. This would suggest that the decomposition and oxidation
reactions followed the same reaction mechanism irrespective of heating rates [14]. Thus, activation energy, Ea (kJ mol1) and associated pre-
exponential factor, A (s1) for the production of metal oxides and metal aluminates may be estimated from Kissinger equation [14] in order
to examine the activity of these solid decomposition and oxidation reactions:
!  
b AR Ea
ln ¼ ln  (12)
Tp2 Ea RTp

with b, Tp and R being heating rate, peak temperature and universal gas constant, respectively. The linear regressions of experimental data to
Kissinger equation (12) exhibited a reasonable fit with correlation coefficient of essentially unity. Thus, the associated Arrhenius parameters
can be estimated from the slope and intercept of the plots for lnðb=Tp2 Þ vs: ð1=Tp Þ (see Fig. 3) and are summarized in Table 2. The activation
energy was about 89.51 and 80.03 kJ mol1 for peaks P1 and P2, respectively. The relatively low activation energy for peaks P1 and P2 would
suggest the facile decomposition and oxidation processes of Ni(NO3)2 and Co(NO3)2 metal precursors to the corresponding final metal
oxides and metal aluminates.

3.3. X-ray diffraction measurement

The XRD patterns of calcined Al2O3 support and 5%Nie10%Co/Al2O3 catalyst are shown in Fig. 4. The Joint Committee on Powder
Diffraction Standards (JCPDS) database was employed for analysing X-ray diffractograms [15]. X-ray diffraction measure was conducted for
 
calcined Al2O3 support for comparison purpose. As seen in Fig. 4a, g-Al2O3 phase was detected with typical peaks at 2q of 19.28 , 32.50 ,
     
37.16 , 45.84 , 60.22 and 66.94 . The discrete peaks located at 2q ¼ 19.28 and 31.46 corresponded to the formation of Co3O4 phase whilst
  
NiO phase was detected at 36.98 and 65.34 . The characteristic peak observed at 2q of 31.46 for bimetallic 5%Nie10%Co/Al2O3 catalyst was
   
ascribed to the formation of NiCo2O4 phase. The peaks belonging to spinal NiAl2O4 (2q ¼ 36.98 , 45.00 and 59.66 ) and CoAl2O4 (2q of 31.46 ,
   
36.98 , 45.00 , 59.66 and 65.34 ) phases were also observed consistent with other studies [8,12]. Additionally, XRD results are in agreement
with the results obtained from temperature-programmed calcination as seen in Fig. 1.
The crystallite sizes of Co3O4 and NiO phases were estimated from Scherrer equation (see Eq. (13)) [16] as about 7.65 and 7.75 nm,
respectively. Both Co3O4 and NiO phases possessed small crystallite size of less than 10 nm indicating the fine metal dispersion on support
surface.

Fig. 2. Peak temperature versus heating rates during temperature-programmed calcination of 5%Nie10%Co/Al2O3 catalyst.

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T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12 5

Fig. 3. Estimated activation energy for the formation of metal oxides and NiCo2O4 phases over 5%Nie10%Co/Al2O3 catalyst during temperature-programmed calcination.

Table 2
Summary of activation energy, Ea and pre-exponential factor, A values for peak P1 and P2.

Peak 1 (P1) Peak 2 (P2)


Ea (kJ mol1) A (s1) Ea (kJ mol1) A (s1)
89.51 ± 0.02 97.2 ± 0.02  108 80.03 ± 0.38 4.03 ± 0.02  107

Fig. 4. X-ray diffractograms of (a) calcined alumina support and (b) 5%Nie10%Co/Al2O3 catalyst.

0:94l
dp ¼ (13)
Bcosq
with dp being crystallite dimension whilst l, B and q are wavelength, peak width and Bragg angle, respectively.

3.4. Methane dry reforming evaluation

The transient profiles of CH4 and CO2 conversions for methane dry reforming at different reaction temperatures from 923 to 973 K with
CO2/CH4 ¼ 1 are shown in Fig. 5. It is apparent that catalyst performance was stable within 4 h on-stream for all reaction temperatures. Both
CH4 and CO2 conversions were improved from 48% to 67% and 56% to 71% with increasing temperature, respectively. In addition, CO2

Please cite this article in press as: T.J. Siang, et al., Hydrogen production from CH4 dry reforming over bimetallic NieCo/Al2O3 catalyst, Journal of
the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.06.001
6 T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12

Fig. 5. Effect of reaction temperature on (a) CH4 and (b) CO2 conversions at CO2/CH4 ¼ 1:1.

conversion was always greater than that of CH4 regardless of reaction temperature suggesting that CO2 was simultaneously consumed by the
reverse wateregas shift and/or CO2 gasification reactions (Eqs. (14) and (15), respectively) during dry reforming of methane reaction [9].

CO2 þ H2 %CO þ H2 O (14)

C þ CO2 %2CO (15)


In fact, the general mechanistic pathway for methane dry reforming reaction is reportedly a two-step process, in which H2 is initially
generated via CH4 dehydrogenation into carbonaceous CxH1x (x  1) species (see Eq. (16)) subsequently gasified by CO2 reactant for
producing CO gas as shown in Eq. (17) [17,18].

Table 3
Summary of catalytic activity for dry reforming of methane over Ni- and Co-based catalysts reported in literature.

Catalysts Operating conditions CH4 conversion (%) CO2 conversion (%) References

T (K) CH4:CO2 ratio TOSa (h)


4%Ni/Al2O3 973 1:1 n.m.b 60 56 [19]
5%Co/ZrO 923 1:1 4 52 52 [20]
0.4%Pte4%Ni/Al2O3 973 1:1 n.m. 69 76 [19]
0.5%Mne14% Ni/Al2O3 1023 1:1 5 61 77 [21]
5%Nie10%Co/Al2O3 973 1:1 4 67 71 This study
a
TOS: time-on-stream.
b
n.m.: not mentioned.

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T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12 7

 
5x  1
xCH 4 /Cx H1x þ H2 (16)
2
 
1x
C x H 1x þ xCO2 /2xCO þ H2 (17)
2
In order to assess the efficiency of this bimetallic NieCo/Al2O3 catalyst, the catalytic performance of several Ni- and Co-based
catalysts is summarized in Table 3 for comparison purpose. The bimetallic NieCo/Al2O3 catalyst in this study exhibited superior CH4
and CO2 conversions to those of monometallic Ni-based and Co-based catalysts. Additionally, in comparison with Pt-promoted and Mn-
promoted Ni/Al2O3 catalysts, the bimetallic NieCo/Al2O3 catalyst showed a comparable catalytic activity. This observation could reveal
its potential and promising use for replacing noble metal catalysts in large-scale methane dry reforming production from an economic
standpoint.
The selectivity and yield of hydrogen were also stable with time-on-stream as shown in Fig. 6. It is apparent that an increase in reaction
temperature from 923 to 973 K significantly enhanced YH2 by up to 60% (see Fig. 6b) whilst the slight improvement of SH2 was observed as
seen in Fig. 6a. Temperature of 973 K seems to be the optimal reaction temperature within temperature range of 923e973 K since it
possessed greatest reactant conversions and exhibited the highest H2 selectivity and yield of about 49.5% and 58.0%, respectively.
Figs. 7 and 8 show the effect of reaction temperature on the corresponding reactant consumption rates and formation rates of gaseous
product at CO2/CH4 ¼ 1. It is evident that consumption and formation rates increased with growing reaction temperature. Hence, the

Fig. 6. Effect of reaction temperature on (a) selectivity and (b) yield of H2 at CO2 to CH4 ratio of 1:1.

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8 T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12

Fig. 7. Effect of reaction temperature on consumption rates of CH4 and CO2 at CO2:CH4 ¼ 1:1.

Fig. 8. Effect of reaction temperature on formation rates of H2 and CO at CO2:CH4 ¼ 1:1.

Fig. 9. Estimation of Arrhenius parameters for methane dry reforming at CO2:CH4 ¼ 1:1.

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T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12 9

activation energy, Ea and pre-exponential, A can be computed from Arrhenius plots (as seen in Fig. 9) with correlation coefficient, R2 of
0.90e0.99. As seen in Table 4, activation energy for both reactants and products was relatively low and varied from 40 to 63 kJ mol1.
Fig. 10a shows H2:CO ratio at different reaction temperatures and the constant feed composition of CO2:CH4 ¼ 1:1. Regardless of reaction
temperature, it is evident that H2/CO ratio was less than unity appropriate for using as feedstock for FT synthesis to generate long-chain
hydrocarbons reasonably owing to the reverse wateregas shift reaction given in Eq. (14) [9]. In fact, the ratio of H2 production rate to
CH4 consumption rate (rH2 =rCH4 ) was inferior to two (see Fig. 10b) suggesting the formation of other hydrogen-containing products, viz.
H2O arising from the reverse wateregas shift reaction. The ratio of H2/CO also increased with rising temperature and approached to nearly
unity at 973 K. The enhancement of H2/CO ratio was possibly due to the increasing rate of CH4 dehydrogenation reaction given by;

Table 4
Arrhenius parameters for methane dry reforming reaction at CO2:CH4 ¼ 1:1.

Species Activation Energy, Ea (kJ mol1) Pre-exponential factor, A (s1)


CH4 55.60 ± 0.14 0.13 ± 0.003
CO2 40.25 ± 2.20 0.02 ± 0.001
H2 62.58 ± 0.40 0.55 ± 0.003
CO 48.08 ± 2.50 0.09 ± 0.004

Fig. 10. Effect of reaction temperature on (a) H2:CO ratio and (b) rH2 =rCH4 of methane dry reforming at CO2:CH4 ¼ 1:1.

Please cite this article in press as: T.J. Siang, et al., Hydrogen production from CH4 dry reforming over bimetallic NieCo/Al2O3 catalyst, Journal of
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10 T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12

Fig. 11. Raman spectrum of spent 5%Nie10%Co/Al2O3 catalyst at 973 K and CO2/CH4 ¼ 1:1.

CH 4 /C þ 2H2 (18)

3.5. Raman spectroscopy analysis

In order to study the type of carbonaceous deposition on catalyst surface during methane dry reforming reaction, Raman measurement
was conducted for spent 5%Nie10%Co/Al2O3 catalyst from catalytic evaluation at 973 K and CO2:CH4 ¼ 1:1. As seen in Fig. 11, two absorption
peaks, P1 and P2 at low bands of 547.9 and 1064.5 cm1, respectively resulted from the oscillation of NieO [22]. The bands detected at high
Raman shift of 1349.2 (P3) and 1592.5 (P4) cm1 were due to the stretching mode of carbon sp2 bonds [23] which is commonly used for
identifying the type of carbon produced during dry reforming of methane. In fact, peak P3 belonged to D band associated with the defects or
the formation of carbon nanoparticles and amorphous carbon whilst band P4 was assigned to G band indicating the presence of an ordered
carbon structure, viz. graphite [24]. The existence of D and G bands suggested the heterogeneity of carbon deposition on catalyst surface.
However, in terms of degree of graphitization, the ratio of integrated areas of D to G bands, ID/IG was estimated as 1.32 superior to unity
further confirming that the proportion of amorphous carbon was greater than that of crystalline carbon. This nano-whisker carbon was
reportedly not prone to rapid catalyst deterioration since it was highly reactive and readily eliminated from catalyst surface by CO2 reactant
via reverse-Boudouard reaction [25]. Additionally, Christensen et al. found that the growth of carbon nanofiber did not encapsulate or block
the access to active metal but lifted it up to the tip of filaments [26]. Hence, the higher percentage of reactive and non-deactivating fila-
mentous carbon would explain why 5%Nie10%Co/Al2O3 catalyst did not experience catalyst deactivation over a period of 4 h on-stream due
to carbonaceous deposition from Eq. (18).

3.6. Scanning electron microscopy measurement

Fig. 12a shows the SEM image of fresh 5%Nie10%Co/Al2O3 catalyst. It is noticeable that the plate-like NiO particles were finely dispersed
on g-Al2O3 support surface. The fine metal dispersion corroborates the aforementioned small crystallite sizes for both Co3O4 and NiO forms
of about 7.65 and 7.75 nm, respectively. The morphology of used catalyst was also observed by SEM micrograph as seen in Fig. 12b. It is
apparent that carbon nanofilament or whisker-like (blue circle) and graphitic (red rectangle) carbons were present on the surface of catalyst.
This observation was consistent with the result from Raman spectrum. In fact, whisker-like carbon was also detected on Ni-based catalysts
during dry reforming of hydrocarbons in other studies [10,27].

4. Conclusions

The 5%Nie10%Co/Al2O3 catalyst was evaluated for dry reforming of methane at varying reaction temperature of 923e973 K and at-
mospheric pressure. TPC and XRD measurements identified the presence of NiO, Co3O4, NiCo2O4, CoAl2O4 and NiAl2O4 phases on g-Al2O3
support surface. The fine dispersion of both NiO and Co3O4 phases was observed by SEM morphology. 5%Nie10%Co/Al2O3 catalyst exhibited
stable catalytic performance with 4 h on-stream and the conversions of CH4 and CO2 were about 67e71% at 973 K whilst H2 yield was
superior to 50%. The activation energy estimated from Arrhenius plots for reactants and gaseous products varied from 40 to 63 kJ mol1. The
reverse wateregas shift reaction simultaneously occurred during methane dry reforming reaction over NieCo catalyst. Raman spectroscopy
and SEM measurements observed the existence of both whisker-like and graphitic carbons. However, the amorphous carbon seemed to be
dominant on spent catalyst surface explaining the catalytic stability with TOS.

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the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.06.001
T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12 11

Fig. 12. SEM micrographs of (a) fresh 5%Nie10%Co/Al2O3 catalyst and (b) spent 5%Nie10%Co/Al2O3 catalyst at 973 K and CO2/CH4 ¼ 1:1.

Acknowledgements

The authors would like to appreciate UMP Research Grant Scheme (RDU170326) for the financial support of this study. The author, Dai-Viet
N. Vo is also grateful to the Foundation for Science and Technology Development Nguyen Tat Thanh University for partial financial support.

References

[1] A. Haryanto, S. Fernando, N. Murali, S. Adhikari, Current status of hydrogen production techniques by steam reforming of ethanol: a review, Energy Fuels 19 (2005)
2098e2106.
[2] M. Ni, D.Y.C. Leung, M.K.H. Leung, A review on reforming bio-ethanol for hydrogen production, Int. J. Hydrogen Energy 32 (2007) 3238e3247.
[3] D.-V.N. Vo, T.-H. Nguyen, E.M. Kennedy, B.Z. Dlugogorski, A.A. Adesina, Fischer-tropsch synthesis: effect of promoter type on alumina-supported Mo carbide catalysts,
Catal. Today 175 (2011) 450e459.

Please cite this article in press as: T.J. Siang, et al., Hydrogen production from CH4 dry reforming over bimetallic NieCo/Al2O3 catalyst, Journal of
the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.06.001
12 T.J. Siang et al. / Journal of the Energy Institute xxx (2017) 1e12

[4] B. Todic, L. Nowicki, N. Nikacevic, D.B. Bukur, FischereTropsch synthesis product selectivity over an industrial iron-based catalyst: effect of process conditions, Catal.
Today 261 (2016) 28e39.
[5] S.S. Ail, S. Dasappa, Biomass to liquid transportation fuel via Fischer Tropsch synthesis e technology review and current scenario, Renew. Sustain. Energy Rev. 58 (2016)
267e286.
[6] A. Riaza, G. Zahedic, J.J. Klemesd, A review of cleaner production methods for the manufacture of methanol, J. Clean. Prod. 57 (2013) 19e37.
[7] M. Usman, W.M.A.W. Daud, H.F. Abbas, Dry reforming of methane: influence of process parameters e a review, Renew. Sust. Energy Rev. 45 (2015) 710e744.
[8] S.Y. Foo, C.K. Cheng, T.-H. Nguyen, A.A. Adesina, Oxidative CO2 reforming of methane on alumina-supported Co-Ni catalyst, Ind. Eng. Chem. Res. 49 (2010) 10450e10458.
[9] M.C.J. Bradford, M.A. Vannice, CO2 reforming of CH4, Catal. Rev. Sci. Eng. 41 (1999) 1e42.
[10] X. You, X. Wang, Y. Ma, J. Liu, W. Liu, X. Xu, H. Peng, C. Li, W. Zhou, P. Yuan, X. Chen, Ni-Co/Al2O3 bimetallic catalysts for CH4 steam reforming: elucidating the role of Co
for improving coke resistance, Chem. Cat. Chem. 6 (2014) 3377e3386.
[11] H. Ay, D. Üner, Dry reforming of methane over CeO2 supported Ni, Co and NieCo catalysts, Appl. Catal. B Environ. 179 (2015) 128e138.
[12] S.Y. Foo, C.K. Cheng, T.-H. Nguyen, E.M. Kennedy, B.Z. Dlugogorski, A.A. Adesina, Carbon deposition and gasification kinetics of used lanthanide-promoted Co-Ni/Al2O3
catalysts from CH4 dry reforming, Catal. Commun. 26 (2012) 183e188.
[13] B. Vos, E. Poels, A. Bliek, Impact of calcination conditions on the structure of alumina-supported nickel particles, J. Catal. 198 (2001) 77e88.
[14] M.E. Brown, Introduction to thermal analysis: techniques and application, Kluwer Academic Publishers, The Netherlands, 2001.
[15] JCPDS Powder Diffraction File, International Centre for Diffraction Data, PA, 2000.
[16] A.L. Patterson, The scherrer formula for x-ray particle size determination, Phys. Rev. 56 (1939) 978e982.
[17] S.Y. Foo, C.K. Cheng, T.H. Nguyen, A.A. Adesina, Kinetic study of methane CO2 reforming on CoeNi/Al2O3 and CeeCoeNi/Al2O3 catalysts, Catal. Today 164 (2011) 221e226.
[18] O. Omoregbe, H.T. Danh, C. Nguyen-Huy, H.D. Setiabudi, S.Z. Abidin, Q.D. Truong, D.-V.N. Vo, Syngas production from methane dry reforming over Ni/SBA-15 catalyst:
effect of operating parameters, Int. J. Hydrogen Energy 42 (2017) 11283e11294.
[19] M. García-Die guez, I.S. Pieta, M.C. Herrera, M.A. Larrubia, L.J. Alemany, Nanostructured Pt-and Ni-based catalysts for CO2-reforming of methane, J. Catal. 270 (2010)
136e145.

[20] Ş. Ozkara-Aydıno lu, A.E. Aksoylu, Carbon dioxide reforming of methane over Co-X/ZrO2 catalysts (X ¼ La, Ce, Mn, Mg, K), Catal. Commun. 11 (2010) 1165e1170.
g
[21] A.E.C. Luna, M.E. Iriarte, Carbon dioxide reforming of methane over a metal modified Ni-Al2O3 catalyst, Appl. Catal. A Gen. 343 (2008) 10e15.
[22] C. Luo, D. Li, W. Wu, Y. Zhang, C. Pan, Preparation of porous microenano-structure NiO/ZnO heterojunction and its photocatalytic property, RSC Adv. 4 (2014)
3090e3095.
[23] A. Zawadzki, J.D.A. Bellido, A.F. Lucredio, E.M. Assaf, Dry reforming of ethanol over supported Ni catalysts prepared by impregnation with methanolic solution, Fuel
Process. Technol. 128 (2014) 432e440.
[24] A.M. da Silva, K.R. de Souza, G. Jacobs, U.M. Graham, B.H. Davis, L.V. Mattos, F.B. Noronha, Steam and CO2 reforming of ethanol over Rh/CeO2 catalyst, Appl. Catal. B
Environ. 102 (2011) 94e109.
[25] R. Yang, C. Xing, C. Lv, L. Shi, N. Tsubaki, Promotional effect of La2O3 and CeO2 on Ni/g-Al2O3 catalysts for CO2 reforming of CH4, Appl. Catal. A Gen. 385 (2010) 92e100.
[26] K.O. Christensen, D. Chen, R. Lødeng, A. Holmen, Effect of supports and Ni crystal size on carbon formation and sintering during steam methane reforming, Appl. Catal. A
Gen. 314 (2006) 9e22.
[27] W. Chen, G. Zhao, Q. Xue, L. Chen, Y. Lu, High carbon-resistance Ni/CeAlO3-Al2O3 catalyst for CH4/CO2 reforming, Appl. Catal. B Environ. 136e137 (2013) 260e268.

Please cite this article in press as: T.J. Siang, et al., Hydrogen production from CH4 dry reforming over bimetallic NieCo/Al2O3 catalyst, Journal of
the Energy Institute (2017), http://dx.doi.org/10.1016/j.joei.2017.06.001
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