i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2

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Rh promoted and ZrO2/Al2O3 supported Ni/Co

based catalysts: High activity for CO2 reforming,
steameCO2 reforming and oxyeCO2 reforming
of CH4

Ahmed Al-Fatesh a,**, Sunit Kumar Singh b, G.S. Kanade b, Hanan Atia c,
Anis H. Fakeeha a, Ahmed A. Ibrahim a, Ahmed Mohamed El-Toni d,
Nitin K. Labhasetwar b,*
a
Chemical Engineering Department, College of Engineering, King Saud University, P.O Box 800, Riyadh 11421, Saudi
Arabia
b
Energy and Resource Management Division, CSIR-National Environmental Engineering and Research Institute,
Nagpur 440010, India
c
Leibniz Institute for Catalysis, Rostock, Germany
d
King Abdullah Institute for Nanotechnology, King Saud University, Riyadh 11421, Saudi Arabia

article info abstract

Article history: Ni (2.5 wt%) and Co (2.5 wt%) supported over ZrO2/Al2O3 were prepared by following a
Received 11 December 2017 hydrolytic co-precipitation method. The synthesized catalysts were further promoted by
Received in revised form Rh incorporation (0.01e1.00 wt%) and tested for their catalytic performance for dry CO2
6 April 2018 reforming, combined steameCO2 reforming and oxyeCO2 reforming of methane for pro-
Accepted 18 April 2018 duction of syngas. The catalysts were characterized by using N2 physical adsorption, XRD,
Available online xxx H2eTPR, SEM, CO2eTPD, NH3eTPD, TEM and TGA. The results revealed that ZrO2 phase
was in crystalline form in the catalysts along with amorphous Al oxides. Ni and Co were
Keywords: confirmed to be in their respective spinel phases that were reducible to metallic form at
CO2 reforming 800
C under H2. Ni and Co were well dispersed with their nano-crystalline nature. The
Catalyst catalyst with 0.2% loading of Rh showed superior performance in the studied reactions for
Dry CO2 reforming reforming of methane. This catalyst also showed good coke resistance ability for dry CO2
Combined steam-CO2 reforming reforming reaction with 3.8 wt% of carbon formation during the reaction as compared to
Oxy-CO2 reforming 11.6 wt% carbon formation over the catalyst without Rh. The catalyst performance was
Syngas stable throughout the reaction time for CH4 conversions, irrespective of carbon formation
with slight decline (~1%) in CO2 conversion. For dry CO2 reforming reaction, this catalyst
showed good conversion for both CH4 and CO2 (67.6% and 71.8% respectively) with a H2/CO
ratio of 0.84, while for the Oxy-CO2 reforming reaction, the activity was superior with CH4
and CO2 conversions (73.7% and 83.8% respectively) and H2/CO ratio of 1.05.
© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

* Corresponding author.
** Corresponding author.
E-mail addresses: aalfatesh@ksu.edu.sa (A. Al-Fatesh), nk_labhsetwar@neeri.res.in (N.K. Labhasetwar).
https://doi.org/10.1016/j.ijhydene.2018.04.152
0360-3199/© 2018 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

Please cite this article in press as: Al-Fatesh A, et al., Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2
reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
10.1016/j.ijhydene.2018.04.152
2 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2
Introduction
Carbon-rich fossil fuels such as coal, petroleum oil, and nat-
ural gas have long been utilized to meet the worldwide energy
demand covering over 80% of the energy needs. However, long
history of utilization of these fossils fuels has resulted in
enormous anthropogenic addition of CO2 as a greenhouse gas
to the earth's atmosphere leading to serious environmental
consequences. It has therefore raised alarming responses
among the scientific community to investigate, develop and
introduce novel greener technological ways of meeting the
energy demands. At the same time it is become even more
vital to explore transformation of CO2 to other useful chem-
icals or fuels to achieve negative carbon emissions. CO2 cap-
ture and storage technologies such as pre-combustion
capture, post-combustion capture and oxyfuel combustion
have been extensively explored to capture CO2 emissions
produced from combustion of fossil fuels in power generation
and other industrial processes, thus preventing CO2 from
entering the atmosphere [1]. This provides ample future
availability of captured CO2 for which better and novel tech-
nological ways are required to make its useful transformation
to some form of cleaner energy. Also, methane is known to be
the second most potential greenhouse gas [2]. CO2 reforming
of methane for synthetic gas (H2 þ CO or syngas) production is
one of best ways to bring back the CO2 to energy cycle. This
process along with CCS (carbon capture and sequestration)
processes can provide an ideal way for utilization of carbon-
rich fossil fuels in an environmentally safe manner. Conver-
sion of natural gas with higher carbon dioxide content to
valuable syngas and removal of greenhouse gases (CO2 and
CH4) offer valuable environmental benefits through dry
reforming of methane, and therefore a topic of extreme rele-
vance [3,4].
CO2 reforming of methane or dry reforming of methane
(DRM) was first studied in 1928 by Fisher and Tropsch, and
later became one of the most important reactions known as
FT synthesis. They performed this reaction over Ni and Co
catalysts and observed significant carbon depositions over the
catalyst leading to severe deactivation of the catalysts [5]. The
carbon deposition is mainly induced either due to methane
decomposition (MD, Eq. (1)) [6] or CO disproportionation
(Boudouard reaction: BR, Eq. (2)) [7]. DRM is an extremely
endothermic reaction (Eq. (3)), hence requires high opera-
tional temperatures for high equilibrium conversion of re-
actants and production of syngas [8,9]. DRM reaction (Eq. (3))
thermodynamically proceeds in forward direction at temper-
atures greater than 640
C [9] and can produce syngas with
stoichiometric ratio of H2/CO of 1. However, due to parallel
occurrence of reverse water gas shift reaction, RWGS (Eq. (4)),
the ratio of H2/CO decreases to <1 [10,11]. Thermodynami-
cally, RWGS has been inferred to occur only up to 820
C and
for MD and BR, the temperatures required are above 557
C
and below 700
C window [9]. Carbon formation results in
significant increase in H2/CO ratio higher than 1 due to
decrease in CO formation. High syngas yields are observed
with increase in reaction temperature up to 900
C and carbon
formation, though not thermodynamically favoured, is
unavoidably accompanied at such high temperatures. Also, at
Please cite this article in press as: Al-Fatesh A, et al., Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2
reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
10.1016/j.ijhydene.2018.04.152
high temperatures, the supported metal suffers deactivation,
or reduction in the activity, due to sintering of metal particles
over the support and irreversible metal support reactions, for
example, the formation of inactive spinels [12e14].
CH4 4C þ 2H2 DHo298 K ¼ 75:0kJ=mol (Eq. 1)
2CO4C þ CO2 DHo298 K ¼ 172:0kJ=mol (Eq. 2)
CH4 þ CO2 /2CO þ 2H2 DHo298 K ¼ 247kJ=mol (Eq. 3)
CO2 þ H2 /CO þ H2 O DHo298 K ¼ 41:2kJ=mol (Eq. 4)
Thus, developing a catalyst that avoids deactivation by
resisting carbon formation and sintering, along with high
thermal stability, is a challenging issue taken up by re-
searchers worldwide. Ni has been widely reported for its cat-
alytic activity in DRM reaction on supports such as geAl2O3
[15e17], MgO [18,19], SiO2 [20], ZrO2 [21], MgOeSiO2 [22], and
others [23]. Among non-noble metals, apart from Ni, Co have
been studied and showed considerable activity for DRM re-
action [24e26]. However, despite of their good catalytic ac-
tivity and use of low cost non-noble metals, such as Ni, Co, Fe,
there were challenges in terms of their deactivation due to the
carbon formation and sintering of active metal. Noble metals
(Pt, Rh, Ru, Pd) are, however, known for their resistance to-
wards carbon formation and sintering. Among these Rh is
found to be the most active metal for DRM reaction with
alumina as support [13,27,28]. Ni based catalysts with noble
metals as promoters have shown better activity than Ni alone
and are more resistant to carbon deposition and sintering
[29e32]. Potential industrial application for DRM have been
shown by bimetallic NiePt supported on ZrO2 with high sta-
bility towards prolonged reaction time exposure [33]. It is re-
ported that noble metals increase the catalytic activity and
stability of Ni in reduced form through hydrogen spill over
mechanisms [34]. Similar observation was reported for Co/
TiO2 catalyst, where Rh and Pt as promoters enhanced the
activity and stability of Co by avoiding deactivation due to its
oxidation in the reaction [35,36].
Steam reforming of methane (SRM) has also been a
prominent reaction for syngas production with H2/CO ratio of
3 as shown in Eq. (5) [37,38]. Water gas shift reaction Eq. (6)
contributes to additional hydrogen produced in SRM. Com-
bined reaction of DRM and SRM (Combined SteameCO2
reforming, CSCRM) has also attracted researchers for the
inherent advantage of less coke formation and production of
syngas with H2/CO ratio of 2 [39,40]. Thus, in CSCRM by
adjusting the feed ratios, syngas with suitable molar ratio can
be produced for FishereTropsch synthesis of clean fuels
[41,42]. However, alike to both SRM and DRM, CSCRM is also
highly endothermic and demands high energy costs at in-
dustrial scale. Hence, addition of oxidants in DRM such as
oxygen (OxyeCO2 methane reforming, OCRM) in the feed was
explored, so that exothermicity of the partial (Eq. (7)) or
complete (Eq. (8)) oxidation of methane can supply the
necessary heat required for the DRM reaction [43e45]. OCRM
has been a topic of interest due to energy cost advantages at
industrial scale, which are low compared to SRM, DRM and
CSCRM. Also, oxygen in the reactant feed reduces/avoids the
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2 3

carbon deposition over catalyst and thereby avoiding deacti- prepared. For every loading, we used 3 g support (calcined at
vation due to the coke formation. 800
C) and 3 g solution (with different Rh concentration) as
shown in Table 1. The solution was mixed with the support
CH4 þ H2 O/CO þ 3H2 DHo298 K ¼ 206kJ=mol (Eq. 5)
and homogenized with a spatula, dried and then calcined at
800
C.
CO þ H2 O/CO2 þ H2 DHo298 K ¼ 41:2kJ=mol (Eq. 6)
Catalyst characterization
CH4 þ 1 2O2 /CO þ 2H2
=
DHo298 K ¼ 36kJ=mol (Eq. 7)
Micromeritics Tristar II 3020 surface area and porosity
CH4 þ 2O2 /CO2 þ 2H2 O DHo298 K ¼ 803:0kJ=mol (Eq. 8) analyzer was used to determine the specific surface area, pore
volume and pore diameter values by following BET-BJH
With the background of these observations and literature, method. For each analytical run, 90 min degassing was per-
in this work, we have explored Ni/Co supported over Al2O3e formed for about 0.2 g of the catalyst at 200
C before quan-
ZrO2 with Rh loading in the range 0.00e1.00 wt% as catalysts tification. The Temperature Programmed Reduction (TPR) of
for the DRM reaction and compared the performance of same the fresh calcined catalysts was measured by using a Micro-
catalysts for CSCRM and OCRM reactions as well with some meritics Auto Chem II machine. About 70 mg of a sample was
interesting findings. taken for analysis. Samples were pre-heated in Argon (99.9%)
at 150
C for 30 min, and then the samples were cooled to
25
C. The sample was then heated to 1000
C at 10
C min1
Experimental section with 10% H2/Ar gas mixture flowing at 40 mL min1. The H2
consumed was determined by using a thermal conductivity
Materials detector (TCD). Carbon formation on the spent catalysts was
analyzed by thermogravimetric analysis (Shimadzu TGA-51)
AR grades Cobalt(II)-acetate tetrahydrate [Co(ac)2*4H2O, by heating the sample from 25
C to 1000
C in air. The rate
Aldrich], Nickel(II)-acetate tetrahydrate [Ni(ac)2*4H2O, of heating was adjusted to 20
C min1.
Aldrich], Aluminium tri-sec-butoxide [Al(sec.-BuO)3, Merck], The morphology of the calcined catalysts was studied by
Zirconium (IV)-butoxide [Zr(BuO)4, 80 wt% solution in 1- Scanning electron microscopy (SEM). JSM-7500F (Japan, JEOL
butanol, Aldrich] and Ammonium hexachlororhodate(III) Ltd.) instrument was used to collect SEM images of the used
[(NH4)3[RhCl6], Aldrich] were used. catalysts. SEM was also used to investigate the presence of
The salts were dried at 110
C for 24 h in a drying oven to get carbon on the used catalysts. Transmission Electron Micro-
the water free salts. The weight loss should be similar to the scope (JEOL JEM-2100F, USA) operated at 120 KV accelerating
water content, to be sure, there is no decomposition. Before voltages was used to examine the shape, morphology and
their use, salts were ground using a mortar pestle and sieved microstructure of the catalysts studied.
through a 100 mm sieve. These salts were used as precursors The CO2-TPD measurements (Micromeritics Auto Chem II
for Co and Ni. 2910, USA) were accomplished on fresh calcined catalysts.
Physically adsorbed species were removed by heating 70 mg of
Catalyst preparation sample at 200
C for 1 h under flowing He. CO2/He mixed gas
(volume ratio, 10/90) was then passed over sample at 50
C for
In a 3 neck round bottom glass flask (250 mL) equipped with 30 min (flow rate: 30 mL min1) to carry out the CO2 adsorp-
reflux condenser and magnetic stirrer, 48 g of the Zirconium tion. Temperature was then linearly increased up to 800
C
(IV)-butoxide and 25 g of the Aluminium tri-sec-butoxide were (heating rate: 10
C min1) and TPD signals were recorded with
heated under stirring up to 130
C. Then 2.59 g of the dried thermal conductivity detector (TCD) detector. The NH3-TPD
Co(II)-acetate and 2.59 g of Ni(II) acetate were added. After measurements (Micromeritics Auto Chem II 2910, USA) were
2 h at 130
C, the content of the glass flask was poured inside accomplished on fresh calcined catalysts. Same pre-
75 g of isopropanol in a 500 mL beaker. The residual butoxides treatment was given to sample as mentioned in CO2-TPD to
from the round bottom flask were transferred with another remove physically adsorbed and/or weakly bound species.
portion of 75 g of iso-propanol to the beaker. Now, 27 g of
distilled water was added within 1 min under intensive stir-
ring and refluxed for 1 h. The beaker was covered with a round
Table 1 e Rh incorporation procedure on catalyst.
bottom flask that contains some water, to prevent a loss of iso-
Catalyst Rh wt% Amount of Amount of Solution
propanol. After cooling it to room temperature, the precipitate
Support taken
was separated from the liquid phase with a glass frit. After
drying at room temperature overnight (as prepared), the solid NC0.01 0.01% Rh 3.00 g 0.03 g of solution#1 and
2.97 g water
was calcined at 800
C for 5 h, following a heating rate of
NC0.05 0.05% Rh 3.00 g 0.15 g of solution#1 and
2
C min1. The molar ratio of Zr:Al was 1.23:1 with Ni and Co 2.85 g water
loading of 2.5 wt% each with Ni:Co ¼ 1:1. This catalyst was NC0.10 0.10% Rh 3.00 g 0.30 g of solution#1 and
abbreviated as NC0 in further discussions. 2.70 g water
Incorporation of Rh in the catalyst was carried out by NC0.20 0.20% Rh 3.00 g 0.60 g of solution#1 and
incipient wetness method. An aqueous solution of 180 mg 2.40 g water
NC1.00 1.00% Rh 3.00 g 3.00 g of solution#1
(NH4)3[RhCl6] dissolved in 4.82 g water (5 g solution #1) was

Please cite this article in press as: Al-Fatesh A, et al., Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2
reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
10.1016/j.ijhydene.2018.04.152
4 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2
This was followed by NH3 adsorption at 50
C for 30 min by
passing NH3/He mixed gas (volume ratio, 10/90) at a flow rate
of 30 mL min1. The TPD signals were recorded by TCD with a
linear temperature increase up to 800
C at a heating rate of
10
C min1.
Rigaku (Miniflex-Japan) diffractometer was used for
recording XRD diffractograms of catalysts. The operating
conditions were: Cu Ka radiation operated at 40 kV and 40 mA,
scanning range (10e85
) with step size (0.02
). X'pert high
score plus software was used to analyze the raw data file. The
peak intensities were measured and ASCII files were gener-
ated at granularity 8, bending factor 5, minimum peak sig-
nificance 1, minimum peak width 0.40, maximum tip width 1
and peak base width 2 by minimum second derivatives.
Different phases with their scores were matched using JCPDS
data bank and X'pert high score plus software.
Catalytic activity test
The dry reforming of methane with CO2 (DRM) reaction was
performed in a fixed-bed tubular micro reactor (ID ¼ 9 mm,
length ¼ 30 cm) at atmospheric pressure. The setup was sup-
plied by PID Eng and Tech, Spain. Prior to DRM reaction, 0.10 g
catalyst was reduced in situ under H2 flow (30 mL min1) at
800
C for 60 min. Then the reactor was flushed with N2 for
15 min. After that, the reactants CH4, CO2 and N2 were simul-
taneously introduced at flow rates of 35, 35 and 5 mL min1
respectively. The catalyst was run at 700
C for 400 min. During
the reaction, 10 mL min1 of water vapor or oxygen was added
in some of the samples, accordingly to reaction feed compo-
sitions. The temperature, pressure and reaction variables were
monitored through the automated reactor panel. The GC
attached was equipped with a thermal conductivity detector.
Porapak Q and Molecular Sieve 5A columns were used in se-
ries/bypass connections for the complete analysis of the re-
action products. The conversion values of CH4 and CO2 were
determined using the following equations, respectively.
4  CH4
CHIN OUT
CH4 %Conversion ¼  100
CHIN
4 different in the case of NC0 and NC0.20 catalysts (Table 2). CO2
2  CO2
COIN OUT
CO2 %Conversion ¼ IN
 100
CO2
Fig. 1 e A) CH4 conversions and B) CO2 conversions in DRM reaction w.r.t. Reaction time using catalysts with different Rh
loading.
Please cite this article in press as: Al-Fatesh A, et al., Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2
reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
10.1016/j.ijhydene.2018.04.152
Results and discussion
Catalyst activity
As mentioned earlier, the catalyst was reduced at 800
C in H2
flow of 30 mL min1 for 60 min before reaction and activity of
catalysts for DRM reactions was tested at a reaction temper-
ature of 700
C with CH4:CO2:N2 ¼ 35:35:5 and Weight Hourly
Space velocity (WHSV) ¼ 45000 mL g1 h1. Fig. 1A shows the
CH4 conversions observed with reaction time up to 400 min.
The performance of catalysts for CH4 conversions was stable
for the range of reaction time studied. NC0 catalyst showed
minimum CH4 conversions of ~50.6%. It was observed that
with increasing Rh loading, the catalytic conversion increased
from ~51.6% (NC0.01 catalyst) to ~68.5% (NC1.00 catalyst).
However, the conversions with NC0.20 and NC1.00 were
comparable with ~67.6% and ~68.5% values respectively.
Similar trends (Fig. 1B) were recorded for CO2 conversions
with minimum ~62.3% (NC0 catalyst) and increased from
~65.0% (NC0.01 catalyst) to ~71.8% (NC0.20 catalyst) and
~72.8% (NC1.00 catalyst).
Hence, NC0 and NC0.20 catalysts, as can be clearly inferred
from Table 2, were considered for comparison of DRM reaction
with CSCRM and OCRM reaction. The reaction temperature for
the later reactions were similar to DRM reaction (700
C)
except for the change in feed ratio and WHSV, which was
CH4:CO2:N2:H2O/O2 ¼ 35:35:5:10 and Weight Hourly Space
Velocity (WHSV) ¼ 51000 mL g1 h1 respectively. The activity
of catalysts (NC0 and NC0.20) was observed to be stable for
both CH4 and CO2 conversions within the reaction time
studied for each reaction (Fig. 2A and Fig. 2B). CH4 conversion
with NC0 catalyst was lower in DRM reaction (~50.6%), which
was increased for CSCRM reaction (~55.5%) with highest
conversion for OCRM reaction as 63.1%, as shown in Table 2.
Similar trends of CH4 conversion were observed in case of
NC0.20 catalyst, where the conversion was ~67.6% for DRM
reaction, ~70.9% for CSCRM reaction and ~73.7% for OCRM
reaction. However, trends for CO2 conversions were quite
conversions were highest in DRM reaction (~62.3%) followed
by OCRM reaction (~55.6%) and CSCRM reaction (~52.9%) using
NC0 catalyst. Similarly, CO2 conversions were highest in DRM
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2 5

Table 2 e CH4 conversions, CO2 conversions and H2/CO ratios in DRM, CSCRM and OCRM reactions.
Reaction Catalysts CH4 Conversions (A) CO2 Conversions (B) Difference in Conversions (AeB) H2/CO Ratio
DRM NC0 50.6 62.3 11.7 0.80
DRM NC0.01 51.6 65.0 13.4 0.81
DRM NC0.05 55.0 66.2 11.2 0.82
DRM NC0.10 63.7 69.1 5.4 0.83
DRM NC0.20 67.6 71.8 4.2 0.84
DRM NC1.00 68.5 72.8 4.3 0.84
CSCRM NC0 55.5 52.9 2.6 1.52
OCRM NC0 63.1 55.6 7.5 1.10
CSCRM NC0.20 70.9 59.9 11.0 1.45
OCRM NC0.20 73.7 63.8 9.9 1.05

Fig. 2 e A) CH4 conversions and B) CO2 conversions in DRM, CSCRM and OCRM reactions w.r.t. Reaction time using catalyst
with 0% and 0.2% Rh loading.

reaction (~71.8%) followed by OCRM reaction (~63.8%) and
CSCRM reaction (~59.9%) using NC0.20 catalyst.
H2/CO ratios in the product stream were stable during the
reaction time of 400 min for all the catalysts studied in DRM
reaction. The H2/CO was recorded to be stable at 0.80e0.84 for
NC0 to NC1.00 catalysts (Fig. 3A and Table 2). As compared to
DRM reaction, H2/CO ratio was enhanced in OCRM reaction,
where it was 1.1 for NC0 catalyst and 1.05 for NC0.20 catalyst.
In CSCRM, H2/CO ratio was highest 1.52 for NC0 catalyst and
1.45 for NC0.20 catalyst (Fig. 3B and Table 2).
In case of DRM reaction, it was observed that the CH4
conversions were less than that of the CO2 conversions for all
the catalysts tested and the difference in CH4 and CO2 con-
version was reduced with increase in Rh loading (Table 2).
Steven et al. [46] observed similar conversion on Rh/Al2O3
catalysts at 700
C, while Li et al. [47] also reported higher CH4
conversions on NieMo/CeZreMgAl(O) catalysts. This can be
explained by the mechanism suggested for this reaction in the
literature [48e50]. DRM reaction mechanism is bi-functional
with CH4 activation on metal sites and CO2 activation on

Fig. 3 e A) H2/CO ratio in the product stream in DRM reaction w.r.t. Reaction Time using catalysts with different Rh loadings.
B) H2/CO ratio in DRM, CSCRM and OCRM reactions w.r.t. Reaction time using catalyst with 0% and 0.2% Rh loadings.

Please cite this article in press as: Al-Fatesh A, et al., Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2
reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
10.1016/j.ijhydene.2018.04.152
6 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2
acidic/basic support. CO2 is activated on acidic sites by gen-
eration of formates species, while on basic sites by formation
of oxy-carbonates [5,51]. Activation mechanism is mono-
functional on inert support such as SiO2, where both CH4
and CO2 are activated on metal sites [5,23]. Theoretically, as
studied by quantum models and by experiments, CH4 is acti-
vated first on metal sites generating hydrogen and CHx species
(where x is 0e3). The hydrogen generated is spilled over to the
support and activates the adsorbed CO2 for the production of
CO and hydroxyl groups. The hydroxyl groups generated re-
acts back with CHx species for the production of CO and
hydrogen. This mechanism results in reaction of CH4 with CO2
(in a ratio 1:1) for the production of H2 and CO with ratio 1:1
(Eq. (3)). When this reaction is followed by RWGS reaction (Eq.
(4)), which thermodynamically occurs up to 820
C [9], CO2
conversions are increased with decreased H2/CO ratio in the
product stream. This was exactly observed in this case, where
we have used catalysts with 0% Rh to 1% Rh loading (NC0 e
NC1.00), with higher CO2 conversion and H2/CO ratio 0.8e0.84.
With increasing Rh loading, it was observed that CH4 and CO2
conversions were increased, which was due to increased
adsorption of methane. This also resulted in a decrease in the
differences observed between CH4 and CO2 conversion and
increase in H2/CO ratio (Table 2). This observation showed
that the oxidation of CHx species with hydroxyl groups was
accelerated with Rh loading [56].
For CSCRM and OCRM reactions on the same catalysts (NC0
and NC0.20 i.e. 0% Rh and 0.2% Rh loading over Ni/Co/Al2O3/
ZrO2), compared to DRM, the conversion trends were reversed
with higher methane conversions than CO2 conversions. The
additional conversions of methane were due to SRM (Eq. (5))
and oxidation (Eq. (7) and Eq. (8)) of methane in CSCRM and
OCRM reactions respectively. SRM in CSCRM resulted in the
formation of higher H2 as product and is the reason for
observed higher H2/CO ratio (1.45e1.52) as shown in Table 2
[52]. SRM proceeds with adsorption of H2O on both metallic
and acidic sites followed by subsequent transfer of O from H2O
to CHx species. This pathway obstructs the hydrogen spill over
to CO2 adsorptive sites; hence resulting in lower CO2 conver-
sion. Besides, introduction of H2O in feed stream also restricts
the RWGS reaction which occurred in case of dry reforming at
this operating temperature. Similarly, partial oxidation of CH4
(Eq. (7)) in OCRM provides additional CH4 conversion along
Fig. 4 e H2 and CO yields of the performed DRM, CSCRM and OCRM reforming reactions.
Please cite this article in press as: Al-Fatesh A, et al., Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2
reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
10.1016/j.ijhydene.2018.04.152
with DRM and results in enhancement of H2/CO ratio (1.05e1.1)
reducing the hydrogen spill over to basic sites leading low CO2
conversions and high CH4 conversions. (Table 2).
It was observed that 0.2% Rh loading over the catalyst
(NC0.20) results in highest CH4 and CO2 conversion in OCRM
reaction with H2/CO ratio nearly unity. This indicated that the
synthesized catalyst is the superior candidate for OCRM re-
action as compared to DRM and CSCRM reactions. Fig. 4 shows
the H2 and CO yield of DRM, OCRM and CSCRM reactions. It
was observed that H2 production was considerably higher in
DRM reaction with NC0.2 (with Rh) catalyst than NC0 (without
Rh); the H2 yield observed was 46.2% and 42.5% respectively.
This clearly indicated the promotional effect of Rh in this re-
action due to enhanced adsorption of CH4 and its consecutive
dissociation to produce H2. In case of OCRM with NC0.2 cata-
lyst, additional H2 production (50.3% H2 yield) was observed
due to parallel partial oxidation of CH4 [55] H2 production was
also higher in case of CSCRM reaction (49.5% H2 yield) with
NC0.2 catalyst and almost comparable with OCRM reaction. If
we observe the CO yield with NC0.2 catalyst in case of OCRM
(50.3% CO yield) and CSCRM (50.3% CO yield) as compared to
DRM (50.3% CO yield) reaction, low CO yield is observed in case
CSCRM reaction. This indicated that parallel water-gas shift
reaction occurred in this case which added to higher H2 yield
and thus lower CO yield. The stability of the optimum catalyst
NC0.2 is compared with other catalysts reported in literature
[5,56] in Table 3.
Catalyst characterization
XRD diffractograms of the prepared catalysts are shown in
Fig. 5. All the catalysts exhibited similar diffraction patterns
with peaks at 30
, 35
, 52
, 62
, and 83
. The peak positions
(from low angle to high angle with decreasing intensity)
clearly indicated presence of high symmetry lattice structure
of the crystalline phase present in the catalyst series. These
peaks inferred the presence ZrO2 phase as crystalline phase
with high symmetry orthorhombic lattice, as also matched
with ICDD reference code 01-079-1796. The peaks were
indexed to 30
(111), 35
(200), 52
(022), 62
(311), and 83
(313)
for the ZrO2 phase. There was no evidence of crystalline Al
oxides in the XRD diffractograms. This is an indication for the
amorphosity of the Al oxides phase, which can also be
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2 7

This Work
Ref.
[57]
[58]
[59]
[60]
[61]

[62]
[57]

[61]
[63]
Metal wt% (Promoter wt%) Temperature (
C) CH4 Conversion % CO2 conversion %
75
89
96
88
96

72
80

76
73
72
69
90
94
79
95

53
73

74
78
68

Fig. 5 e XRD Diffractograms of freshly prepared catalysts

after calcination at 800
C.
800
800
800
800
800

750
800

750
800
800

observed by SEM micrograph of NC0 catalyst (Fig. 6A). SEM

micrographs showed that the particle size is noneuniform
and agglomerated, however, with high porosity. TEM micro-
graphs analysis showed presence of crystalline ZrO2 phase
with d-spacing 0.29 nm, corresponding to (111) plane, along
0.075e7.425e92.5 mol%

0.075e7.425e92.5 mol%

with amorphous areas (Fig. 6B). Additionally, there were no

peaks (XRD) for Ni and Co oxides in the fresh calcined cata-
lysts, which may be either due to these oxides being in
nanosized form or due to their amorphosity. However, in XRD
2.5/2.5 (0.2)

diffractograms of NC0 and NC0.20 catalysts after reduction

0.75e2.25
Table 3 e Comparison of optimum catalyst with other reported catalyst in literature.

with hydrogen (Fig. 7), there are no peaks observed even for
15e10
10 (5)

10 (1)
12.5

the reduced metallic form of Ni and Co. This suggests that

2

metallic Ni and Co formed after reduction are either amor-

phous or nano-crystalline.
Co0.075Ni7.425Mg92.5O e n/a e n/a
Metal - support - promoter

The N2 adsorptionedesorption studies of catalysts showed

that the surface area, pore volume and pore diameter of the
synthesized catalysts do not show any trend or significant
NieMgO e Ce0.8Zr0.2O2

Fixed-bed tubular Incipient wetness Impregnation Ni/CoeZrO2/Al2O3eRh

Incipient wetness Impregnation PteRu e gAl2O3 e n/a

IreCe0.9Zr0.1O2 e n/a

change with increasing Rh loading from 0% to 1% (Table 4).

Co0.075Ni7.425Mg92.5O
Ni e g-Al2O3eCeO2
Ni e SBA-15 e n/a

This may be due to the small Rh content and its higher

Incipient wetness Impregnation NiOeMgO e n/a
Incipient wetness Impregnation NieGd e ZrO2

dispersion on catalyst surface as well as reasonably higher

e n/a e n/a

surface area of catalysts making no noticeable change after Rh

incorporation. The catalysts showed overall increased BET
e n/a

surface area in the range 77.4e94.7 m2 g1 with high pore

volume (0.31e0.32 cm3 g1) and pore diameters (14.4e16.2 nm).
This along with the adsorptionedesorption isotherms (Type II,
Fig. 8) of the catalyst clearly inferred to macroporosity of the
Preparation method

Deposition Precipitation

catalysts. The N2 adsorptionedesorption studies of catalysts

(NC0 and NC0.20) after reduction with hydrogen at 800
C
showed increase in surface area (13% and 28% respectively),
Co-precipitation

pore volume (32% and 36% respectively) and pore diameters

Impregnation

Impregnation
Solvothermal

Solvothermal

(6% and 3% respectively). These increases in parameters can be

explained considering the presence of Ni and Co in spinel
phases as also supported by H2-TPR discussed later. The
reduction of these spinels at high temperature resulted in
structural changes leading to expansion of pore volumes and
micro reactor
Quartz reactor
Reactor type

pore diameters. This suggested that most of Ni and Co resides

at internal surfaces of the pores and pore openings [64].
Fixed Bed
Fixed Bed
Fixed Bed

Fixed Bed

Fixed Bed
Fixed Bed

Fixed Bed
Fixed Bed

H2-TPR of NC0 catalyst showed reduction peak at high

temperature (846.6
C). Oxides of Ni and Co (pure phases)
generally show reduction peaks at lower temperature

Please cite this article in press as: Al-Fatesh A, et al., Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2
reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
10.1016/j.ijhydene.2018.04.152
8 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2

Fig. 6 e A) SEM B) TEM micrographs of 0% Rh catalyst.

Fig. 7 e XRD Diffractograms of catalysts after reduction

with H2 at 800
C.

Fig. 8 e N2 AdsorptioneDesorption Isotherms for the

(<500
C). The occurrence of reduction at 846.6
C (Fig. 9A)
indicated that Ni and Co are not present in their individual
oxide phases, and instead some mixed metal oxide phases of
Ni and Co were present, such as spinels, which were likely to
be formed considering high temperature synthesis and pres-
ence of Al. [53,54] However, as discussed earlier, these phases
were not detected in XRD analysis, probably due to their low
concentration and higher dispersion. The significantly higher
amount of hydrogen consumption during TPR analysis for this
sample therefore suggested the reduction of relatively higher
quantity of metals for this particular catalyst. Thus, higher
synthesized catalysts.
dispersion of Ni and Co sites in NC0 catalyst can be inferred for
this catalyst, which can be expected from the synthesis pro-
cedure followed for preparation of catalyst. The addition of Rh
on the catalyst (NC0.1) showed increase in the hydrogen
consumed with an almost same degree of reduction (Table 4).
This indicated that Rh was well dispersed without much
coverage of NieCo active metal sites in this catalyst. However,
increase in the Rh content (0.2 and 1% i.e. NC0.20 and NC1.00)

Table 4 e Physiochemical characteristics of prepared catalysts.

Catalysts N2 adsorptionedesorption H2-TPR CO2-TPD NH3-TPD


SBET P. V. P. D. TMax Quantity Degree of TMax ( C) Quantity TMax (
C) Quantity
(m2/g) (cm3/g) (nm) (
C) (mmol/g) Reduction % (mmol/g) (mmol/g)
0% Rh 84.3 0.31 15.8 846.6 604.5 53.2 n.d. n.d. 99.8/272.0 81.4/84.6
0.01% Rh 94.7 0.34 15.1 n.d. n.d. n.d. 87.5/255.3 39.2/119.1 107.1/271.7 50.9/108.1
0.05% Rh 77.4 0.32 15.9 n.d. n.d. n.d. 86.8/262.9 47.9/129.1 n.d. n.d.
0.1% Rh 80.6 0.31 16.0 852.4 615.6 53.5 86.7/257.4 32.7/113.9 103.8/271.7 54.2/90.3
0.2% Rh 81.3 0.33 16.2 844.5 532.6 45.6 84.4/253.4 31.9/92.1 105.7/273.7 50.3/104.2
1% Rh 89.2 0.34 14.4 812.1 555.0 43.1 86.7/258.5 40.8/101.8 103.8/277.1 52.7/83.1

P.V. BJH adsorption cumulative volume of pores between 1.700 nm and 300 nm diameter.
P.D. BJH adsorption average pore diameter (4v/A).

Please cite this article in press as: Al-Fatesh A, et al., Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2
reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
10.1016/j.ijhydene.2018.04.152
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2 9

Fig. 9 e (A) H2-TPR, (B) NH3-TPD and (C) CO2-TPD of fresh calcined catalysts.

acidic and basic sites. The peak at low desorption temperature

indicate presence of weak/lewis sites and peak at higher
desorption temperature indicate presence of strong/bro € nsted
sites (Fig. 9B and C) [23].

Coke formation

The catalysts were investigated for possible coke deposition

Fig. 10 e Thermogravimetric analysis of different catalysts
after reaction.
resulted in significant decrease in the hydrogen consumed
(Table 4). This suggested that active metal surface area of Nie
Co was reduced with increased loading of Rh beyond 0.1%.
However, 0.2% Rh and 1% Rh loading over catalyst (NC0.20 and
NC1.00) increased the CH4 and CO2 conversion by more than
15% and 10% respectively, which clearly indicated high ac-
tivity of Rh for DRM reaction as compared to Ni and Co. CO2
TPD indicated presence of two types of basic sites and simi-
larly NH3 TPD also indicated two types of acidic sites for all the
synthesized catalysts as shown in Table 4. The CO2 and NH3
desorption temperature for all catalysts were observed at
~100
C and ~300
C indicating that there are two types of
using thermogravimetric analysis with heating temperature
range from 50 to 1000
C. Fig. 10 shows the TGA graphs ob-
tained for % wt loss as a function of temperature for 0% and
0.2% Rh catalysts (NC0 and NC0.20) in DRM reaction as well as
0.2% Rh (NC0.20) in OCRM and CSCRM reactions. The weight
loss in the temperature range up to 300
C can be attributed to
moisture and other volatile contents. Weight loss beyond
300
C extending up to 720
C was attributed to oxidation of
carbon deposited over catalysts during reaction. It was
observed that catalyst without Rh (0% Rh; NC0) showed
highest amount of carbon deposition (through TG weight loss
measurement) during the reaction, which reached to about
11.9 wt% of the catalyst (Table 5). Catalyst with 0.2% Rh
loading (NC0.20) showed significantly lower amount of carbon
deposition with about 3.9 wt% of the catalyst. This may be due
to better metal support interaction with Rh that results in
increased spill over of hydrogen (generated by decomposition
of methane on metal sites) on to the CO2 adsorption sites on
the support. Consequently, it resulted in increment of the spill
over that generates more H2O by reduction of CO2 to CO,
which in turn results in oxidation of CHx species over metal
sites with H2O. Due to this mechanism, carbon formation and
deposition over metal sites was reduced, which also results in
decrease in the difference of CH4 and CO2 conversions with

Table 5 e N2 adsorption and desorption results of catalysts after reduction with H2 at 800
C and thermogravimetric
analysis data of used catalyst.
Catalysts Reaction N2 adsorptionedesorption after Reduction TGA after reaction
2
SBET (m /g) P. V. (cm /g)3
P. D. (nm) Temperature (
C) % Wt Loss
0% Rh DRM 95.1 0.41 16.8 300e750 11.9
0.2% Rh DRM 104.1 0.45 16.7 300e750 3.9
0.2% Rh OCRM n.d. n.d. n.d. 300e750 1.1
0.2% Rh CSCRM n.d. n.d. n.d. 300e750 2.3

Please cite this article in press as: Al-Fatesh A, et al., Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2
reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
10.1016/j.ijhydene.2018.04.152
10 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y x x x ( 2 0 1 8 ) 1 e1 2
increasing Rh loading as observed in Table 2. Coke deposition
was even more diminished in the presence of oxygen and
steam as evidenced from OCRM and CSCRM reaction (Table 5).
Such behaviour may be due to direct oxidation of CHx species
generated over metallic sites with oxygen and steam resulting
in avoidance of coke formation to minimum level. A mini-
mum of ~1.1% and ~2.3% was observed in OCRM and CSCRM
reaction respectively with NC0.20 catalyst. Attempts have
been made to identify the presence of carbon on catalysts
surface after exposure to reaction mixture, using SEM images,
however, it was not possible to find reliable evidences of the
carbon presence.
Conclusions
The catalysts were prepared by hydrolytic coeprecipitation of
metal alkoxides of Zr, Al, Ni and Co. Calcination of these
precipitates at 800
C resulted in catalysts with ZrO2 in crys-
talline form and Al oxides in amorphous one. Ni and Co were
confirmed to be in spinel phases (NiAl2O4 and CoAl2O4). These
phases were reducible in hydrogen at 800
C and resulted in
formation of metallic sites of Ni and Co with high degree of
reduction. The catalyst without and with Rh incorporation (up
to 1% Rh) were studied in DRM, CSRCRM and OCRM reaction
for their catalytic activity. The catalysts with 0.2% Rh (NC0.20)
over 2.5%Ni/2.5%CoeZrO2/Al2O3 was found to have better
performance for these reactions. In DRM, this catalyst showed
good conversion for both CH4 and CO2 (67.6% and 71.8%
respectively) with a H2/CO ratio of 0.84 at appreciably high
space velocity of 45000 mL g1 h1. This catalyst also showed
appreciable coke resistance with only 3.8 wt% carbon forma-
tion in the reaction time of 400 min. The performance of this
catalyst was superior for OCRM reaction where CH4 and CO2
conversions (73.7% and 83.8% respectively) with an excellent
H2/CO ratio of 1.05 at appreciably high space velocity of
51000 mL g1 h1. The results show that this catalyst presents
a potential candidate for DRM as well as OCRM reaction.
Acknowledgements
The authors extend their appreciation to the International
Scientific Partnership Program ISPP at King Saud University
for funding this research work through ISPP# 0057.
CSIR NEERI KRC no.: CSIR-NEERI/KRC/2017/AUG/ERMD/1.
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reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
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Please cite this article in press as: Al-Fatesh A, et al., Rh promoted and ZrO2/Al2O3 supported Ni/Co based catalysts: High activity for CO2
reforming, steameCO2 reforming and oxyeCO2 reforming of CH4, International Journal of Hydrogen Energy (2018), https://doi.org/
10.1016/j.ijhydene.2018.04.152