international journal of hydrogen energy xxx (xxxx) xxx

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Comparative study between supported and doped

MgO catalysts in supercritical water gasification for
hydrogen production

Mohd Sufri Mastuli a,b,c,d,*, Norlida Kamarulzaman c,

Muhd Firdaus Kasim c, Zulkarnain Zainal b, Yukihiko Matsumura e,
Yun Hin Taufiq-Yap a,b,**
a
Catalysis Science and Technology Research Centre, Faculty of Science, Universiti Putra Malaysia, UPM Serdang,
43400 Selangor, Malaysia
b
Department of Chemistry, Faculty of Science, Universiti Putra Malaysia, UPM Serdang 43400, Selangor, Malaysia
c
Centre for Nanomaterials Research, Institute of Science, Universiti Teknologi MARA, 40450 Shah Alam, Selangor,
Malaysia
d
School of Chemistry and Environment, Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah Alam,
Selangor, Malaysia
e
Department of Mechanical Science and Engineering, Hiroshima University, 1-4-1 Kagamiyama, Higashi-Hiroshima
739-8527, Japan

article info abstract

Article history: Different catalyst structures may influence the catalytic performance of catalysts in su-
Received 24 August 2018 percritical water gasification (SCWG). This study reports the catalytic activity of supported
Received in revised form (SP) and doped (DP) MgO catalysts in catalyzing the gasification of oil palm frond (OPF)
11 December 2018 biomass in supercritical water to produce hydrogen. Two types of supported catalysts,
Accepted 14 December 2018 labelled as Ni-SP (nickel supported MgO) and Zn-SP (zinc supported MgO), were synthe-
Available online xxx sized via impregnation method. Another two types of doped catalysts, labelled as Ni-DP
(nickel doped MgO) and Zn-DP (zinc doped MgO), were synthesized by using the self-
Keywords: propagating combustion method. All the synthesized catalysts were found to be pure
Catalyst with the doped catalysts exhibited small crystallites, in comparison to that produced by the
Hydrogen supported catalysts. The specific surface area increased in the order of Ni-DP
SCWG (67.9 m2 g
1) > Zn-DP (36.3 m2 g
1) > Ni-SP (30.1 m2 g
1) > Zn-SP (13.1 m2 g
1). Regardless
Supercritical water of supported or doped, the Ni-based catalysts always had larger specific surface area than
Gasification that in the Zn-based catalysts. Unexpectedly, the Zn-based catalysts with smaller surface
area for SCWG produced higher hydrogen (H2) yield from the OPF biomass. When
compared to the non-catalytic reaction, the H2 yield increased by 187.2% for Ni-SP, 269.0%
for Zn-SP, 361.7% for Ni-DP, and 438.1% for Zn-DP. Among the studied catalysts, the Zn-DP
displayed the highest H2 yield because it had the highest number of basic sites; approxi-
mately twenty-fold higher than that of the Zn-SP catalyst. The Zn-DP also proved to be the
most stable catalyst, as verified from the X-Ray photoelectron spectroscopy (XPS) results.
As such, this study concludes that the catalytic performances of the synthesized catalysts

* Corresponding author. School of Chemistry and Environment, Faculty of Applied Sciences, Universiti Teknologi MARA, 40450 Shah
Alam, Selangor, Malaysia.
** Corresponding author. Catalysis Science and Technology Research Centre, Faculty of Science, Universiti Putra Malaysia, UPM Serdang,
43400 Selangor, Malaysia.
E-mail address: taufiq@upm.edu.my (Y.H. Taufiq-Yap).
https://doi.org/10.1016/j.ijhydene.2018.12.102
0360-3199/© 2018 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.

Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102
2 international journal of hydrogen energy xxx (xxxx) xxx

do not only depend on the specific surface area, but they are also influenced by the number
of basic sites and the catalyst stability. It is trustworthy to note that this is the initial study
that associated SCWG with doped catalysts. The doped catalysts, hence, may serve as a
new catalyst system to generate SCWG reactions.
© 2018 Published by Elsevier Ltd on behalf of Hydrogen Energy Publications LLC.

Therefore, catalyst modification is required when nickel is

Introduction
Without any doubt, hydrogen is the future energy carrier for
the transportation sector upon success of hydrogen fuel cell
technology [1]. The production of hydrogen from biomass
makes it a renewable and sustainable resource [2]. The com-
bustion of hydrogen in fuel cell produces only water as its by-
product, unlike fossil fuels that emit carbon dioxide (CO2) that
promotes global warming. The potential of hydrogen as an
alternative fuel minimizes the dependency on conventional
fuels and can cater to the escalating energy demands. As such,
numerous advanced technologies have been developed for
the conversion of biomass into combustible hydrogen [3e5].
The SCWG refers to a promising technology that generates
hydrogen from biomass. Biomass, which usually contains
high moisture content, can be employed directly in SCWG
without any costly drying pre-treatment because supercritical
water (Tc > 374  C, Pc > 22.1 MPa) is applied as the reaction
medium to produce hydrogen [6]. Additionally, hydrogen,
which is produced at high pressure, requires less energy to
pressurize the hydrogen in storage tank [7]. Tar and char is-
sues can be suppressed during the biomass SCWG [8].
Nevertheless, the SCWG product is not limited to H2 alone as it
generates carbon monoxide (CO), carbon dioxide (CO2), and
methane (CH4) gases with varied ratios. This gas mixture is
also called syngas (synthesis gas). Therefore, the addition of
catalyst in the SCWG process is vital to alleviate H2 yield and
to suppress the formation of other gases.
Several review papers have published the role of catalysts
in SCWG reactions [9e11]. The gas product can be either H2
rich syngas or CH4 rich syngas, depending on the type of
catalysts used. Mostly, Ni-based catalysts enhance hydrogen
production. For example, nickel metal and Raney nickel have
been widely used in SCWG due to comparable catalytic per-
formances to that of noble metal catalysts [12,13]. These cat-
alysts are also relatively lower in cost. Nickel catalysts
promote the hydrogenation reaction to form H2 and CO from
the biomass, which in turn, can generate CH4 and CO2 via
methanation reaction. A. Sinag et al. [14] catalyzed the SCWG
of glucose using Raney nickel and K2CO3. They discovered that
the Raney nickel increased CH4 yield, but not H2 yield. The H2
yield was only increased when K2CO3 was used as the catalyst.
A significant increment of H2 yield was also observed when
NaOH and KOH were used as the catalysts for SCWG of sug-
arcane bagasse [15]. As explained in Ref. [9], the Raney nickel
catalyst strongly promotes the CeO cleavage and reacts with
some the produced H2; resulting in CH4 rich syngas. Alkali
catalysts are favorable to produce hydrogen due to their ba-
sicity properties that are crucial in increasing H2 yield via
water-gas shift reaction.
considered as the catalyst for SCWG of biomass. One common
way to modify the catalyst is by supporting the nickel onto
metal oxide. Most nickel-supported catalysts were synthe-
sized via impregnation method. Among them, the nickel
supported onto MgO has received greater attention for SCWG
due to its highly basic active sites [16e22]. The catalytic ac-
tivity of the nickel supported MgO catalyst can be further
increased through the addition of other non-noble metals,
such as copper and zinc [23e25]. In fact, our previous work
compared the catalytic performances of Ni, Cu, and Zn oxides
that were supported onto MgO in SCWG of OPF biomass for
hydrogen production [26]. The H2 yield increased in the order
of Zn-supported MgO > Ni-supported MgO > Cu-supported
MgO. The catalytic performances of these supported catalysts
were mainly controlled by the basicity properties and the
catalyst stability. It is also believed that the stability of the
catalyst can be improved by doping (instead of supported) the
active metal into the crystal structure of MgO. The doped
catalyst can be synthesized by using the self-propagating
combustion method [27,28]. Varied catalyst structures (sup-
ported and doped) may influence their catalytic performances
in SCWG reactions. In this study, two groups of catalysts;
supported and doped Ni and Zn onto/into MgO, were syn-
thesized and characterized. The catalyst properties and cat-
alytic performances of the synthesized catalysts in SCWG of
OPF biomass for H2 rich syngas are discussed in detail.
Materials and methods
Materials
All the chemicals used were analytical grade and directly
used as received without further purification. High purity of
nickel (II) nitrate hexahydrate (Ni(NO3)2$6H2O, 98% purity),
zinc (II) nitrate hexahydrate (Zn(NO3)2$6H2O, 98% purity),
magnesium (II) nitrate hexahydrate (Mg(NO3)2$6H2O, 98%
purity), magnesium oxide (MgO, > 99.5% purity), and citric
acid (C6H8O7, >99.5% purity) were used for the synthesis of
catalysts. All these chemicals were procured from Sigma-
Aldrich Co., St. Louis, MO, USA. The ultra-pure deionized
water (EDI: 15e10 MU cm) used in this study was obtained
from TKA Labtower. The OPF biomass was used as feedstock
for SCWG to produce hydrogen. The preparation and the
properties of the feedstock are given in Ref. [26].
Catalysts synthesis
Two groups of catalysts were synthesized and the related
details are summarized in Table 1. The first group refers to

Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102
 international journal of hydrogen energy xxx (xxxx) xxx
the supported catalysts (Ni-SP and Zn-SP) that were syn-
thesized via impregnation method and the details are as
described in our previous work [26]. Meanwhile, the second
group is the doped catalysts that were synthesized by using
the self-propagating combustion method. Stoichiometric
amount of metal salts (20 wt% of Ni or Zn, and 80 wt% of Mg)
were dissolved in minimal amount of deionized water. Citric
acid as an oxidizing agent (also known as a combustion
agent) was added slowly into the aqueous metal solution
under vigorous stirring to form a homogeneous mixture. The
ratio between metal salt and oxidizing agent was 1:1. After
that, the solution mixture was heated at 350  C without
stirring until it combusted and produced dried powders. Note
that the combustion process took place rapidly within a few
minutes. The obtained powders were grounded before
calcined at 600  C for 6 h, which was similar to that per-
formed on the supported catalysts, thus forming the doped
catalysts (Ni-DP and Zn-DP).
Catalysts characterization
Various characterization techniques were used to study the
properties of both supported and doped catalysts. The for-
mation of these catalysts was confirmed by using X-Ray
diffraction (XRD; PANalytical X'Pert Pro MPD) that was oper-
ated at 45 kV and 40 mA using Bragg-Brentano configuration
for data collection. Their morphology and elemental compo-
sition were investigated by using field emission scanning
electron microscope integrated with energy dispersive X-Ray
(FESEM-EDX; JEOL JSM-7600F). The morphology of the cata-
lysts was also examined under high resolution of trans-
mission electron microscope (HRTEM; JEOL JEM-2100 F). The
nitrogen (N2) adsorption-desorption isotherms of the catalysts
were measured by using BELSORP-mini II instrument from
BEL Japan Inc. Additionally, Brunauer-Emmett-Teller (BET)
and Barrett-Joyner-Halenda (BJH) methods were employed to
calculate the specific surface area and the distribution of pore
size. Temperature programmed desorption of carbon dioxide
(TPD-CO2: Thermo Finnigan TPDRO 1100) that was equipped
with a thermal conductivity detector had been applied to
measure the strength and the amount of basicity of the cat-
alysts. The chemical environment, such as binding energy (BE)
and oxidation state of the synthesized catalysts, were studied
via XPS (JEOL JPS-9200).
Catalytic SCWG
The catalytic performances of the supported and doped cat-
alysts were investigated in SCWG of OPF biomass to generate
hydrogen. The SCWG experiments were conducted by using a
Table 1 e Details of synthesized catalysts.
Catalyst Composition Catalyst group Synthesis method
Ni-SP 20NiO/MgO Supported catalyst Impregnation
Zn-SP 20ZnO/MgO Supported catalyst Impregnation
Ni-DP Ni0$2Mg0$8O Doped catalyst SPC
Zn-DP Zn0$2Mg0$8O Doped catalyst SPC
SPC: self-propagating combustion.
Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102
3
batch reactor system, as schematically illustrated in Fig. 1.
The reactor was made of stainless steel tubing (SS316, OD ¼ 3/
8 in., ID ¼ 7.44 mm, length ¼ 13 cm) with an internal volume of
6.2 ml. A ball valve (SS-4SKPS4) was connected to one end of
the reactor tube through another stainless steel tubing (SS316,
OD ¼ 1/16 in., ID ¼ 1 mm, length ¼ 35.5 cm) to collect the
generated gas. As for the non-catalytic SCWG, 0.0402 g of OPF
biomass was added into the reactor tube together with 1.3 ml
of deionized water to make 3 wt% suspension of biomass in
water. On the other hand, for the catalytic SCWG, 0.0020 g of
the synthesized catalysts, which is 5% from the weight of OPF
biomass used, was added into the reactor tube together with
the biomass suspension, and the reactor tube was closed
tightly. The batch reactor was immersed into molten salt bath
at 400  C to raise its pressure to 25 MPa and this temperature
was retained for 30 min. After that, the reactor was withdrawn
from the molten salt bath and cooled down immediately to
room temperature using cold water. The collected gas was
transferred into a gas bottle and its volume was measured by
using the water displacement method.
Gas products analysis
The gas products were analyzed via gas chromatography (GC;
Shimadzu GC-14B) that was equipped with a thermal con-
ductivity detector (TCD) and a flame ionization detector (FID).
The yield and the composition of the gas products, such as H2,
CO, CO2, CH4, C2H6, and C2H4, were quantified. GC-TCD was
used to detect H2, CO, and CO2 gases with helium (He) as the
carrier gas for H2 analysis, while N2 as the carrier gas for CO
and CO2 analyses. Meanwhile, CH4, C2H6, and C2H4 gases were
detected by using GC-FID with He as the carrier gas. A stan-
dard gas mixture of H2, CO, CO2, CH4, C2H6, and C2H4 was used
for GC calibration and determination of gas composition.
Results and discussion
Physicochemical properties of supported and doped MgO
catalysts
In this study, two types of catalyst structures; supported and
doped, were synthesized and characterized. Additionally,
their catalytic performances in SCWG were compared for the
first time. Fig. 2(a) shows the schematic illustration of crystal
Fig. 1 e Experimental apparatus for batch SCWG reactor.
4 international journal of hydrogen energy xxx (xxxx) xxx
Fig. 2 e (a) Schematic illustration for crystal structure and
(bec) XRD patterns of supported and doped catalysts.
structure for both types of catalysts. One can observe that the
active metal (Ni or Zn) is formed either outside (for supported
catalyst) or inside (for doped catalyst) the cubic structure of
MgO, depending on the synthesis method.
The XRD was used to confirm the formation of the syn-
thesized catalysts, as displayed in Fig. 2(b) and (c). All the
catalysts showed the XRD peaks of MgO that well-matched
our previous work [29]. As for the Ni-SP catalyst, the NiO and
MgO diffraction patterns seemed to coincide with each other
due to their similar crystal structures of cubic. Nonetheless,
no XRD peak coincidence was noted for Zn-SP catalyst
because ZnO has a different crystal structure, which is
Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102
hexagonal [30]. As reported in the literature, the supported
catalysts with mixed phase of XRD peaks verified the active
metal formed outside the crystal structure of the support
[31e33]. Kamarulzaman et al. synthesized various types of
doped metal oxides for electrical and electrochemical appli-
cations, such as Hf-doped Al2O3 [28], Cr-doped Al2O3 [27], Cu-
doped ZnO [34], Mn-doped ZnO [35], and Li-doped MgO [36]. All
these doped materials portrayed single phase of XRD peaks
that revealed the dopant was actually located inside the
crystal structure. This means; Ni and Zn substituted the Mg
position in the cubic structure for Ni-DP and Zn-DP catalysts.
The XRD results suggest that all the synthesized supported
and doped MgO catalysts are indeed pure without any
impurity.
Fig. 3 illustrates the FESEM micrographs for the synthe-
sized catalysts. The doped catalysts are smaller than the
supported catalysts. As exhibited in Fig. 3(a) and (b), the sup-
ported catalysts have irregular particles shapes that are flaky
for Ni-SP and spherical for Zn-SP. Meanwhile, the morphology
for the doped catalysts is not clearly discernible due to the
minute crystallites, as shown in Fig. 3(c) and (d). This required
observation under higher resolution of TEM. The HRTEM mi-
crographs (Fig. 3(e) and (f)) clearly display the shapes of Ni-DP
and Zn-DP catalysts. Both have spherical shape with crystal-
lite sizes below 50 nm. In addition, the dispersion of the doped
catalysts is better than that of the supported catalysts, which
is an important factor to be highly active in catalytic reaction
[37,38].
The Ni and Zn elemental analysis was carried out by using
FESEM-EDX measurement. The metal loading for Ni-SP, Zn-SP,
Ni-DP, and Zn-DP catalysts is 13.0 wt%, 17.8 wt%, 20 wt%, and
16.9 wt%, respectively. This means; the doped catalysts
formed the highest metal loading, when compared to the
supported catalysts. During the synthesis process, the metal
salt of Ni nitrate or Zn nitrate was combusted simultaneously
with Mg nitrate to form Ni-DP and Zn-DP catalysts, thus
resulting smaller crystallite sizes with higher metal loading.
Nonetheless, as for the supported catalysts, a bulk MgO was
directly used during the impregnation method to limit the
formation of Ni or Zn onto the surface of MgO. The bulk MgO is
large in size and thermally stable. Other researchers reported
that the crystallite size of the supported catalysts derived
from the impregnation method are usually larger than those
synthesized using other synthesis methods, such as sol-gel
[39], precipitation [40], and template [41].
Fig. 4 shows the N2 adsorption-desorption isotherms and
the pore size distribution of the synthesized catalysts. Based
on the classification standard of International Union of Pure
and Applied Chemistry (IUPAC), the adsorption isotherms can
be classified as Type II (Fig. 4(a) and (b)) for the supported
catalysts, while Type IV (insert Fig. 4(a) and (b)) for the doped
catalysts. This means; both Ni-SP and Zn-SP catalysts are
macroporous, whereas Ni-DP and Zn-DP are mesoporous. The
pore size distribution of the doped catalysts was determined
by employing the Barrett-Joyner-Halenda (BJH) method. The
pore size distribution for the Ni-DP catalyst appeared to be
narrower than that of the Zn-SP catalyst with centered at
4.8 nm and 11.0 nm, respectively. The Ni-DP catalyst displayed
smaller pore size, when compared to the Zn-DP catalyst, and
agreed to the average pore diameter tabulated in Table 2.
 international journal of hydrogen energy xxx (xxxx) xxx 5

Fig. 3 e FESEM ((a) Ni-SP, (b) Zn-SP, (c) Ni-DP, (d) Zn-DP) and HRTEM ((e) Ni-DP, (f) Zn-DP) micrographs of the synthesized
catalysts.

Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102
6 international journal of hydrogen energy xxx (xxxx) xxx

Fig. 4 e (aeb) N2 adsorption-desorption isotherms, (ced) pore size distributions and (eef) illustration of pore trapping and
pore blockages by oxide clusters.

The specific surface area, the total pore volume, and the
average pore diameter for all the synthesized catalysts
calculated using the BET method are presented in Table 2. The Table 2 e Textural properties of supported and doped
doped catalysts have larger specific surface area than the catalysts.
supported catalysts in the following order: Ni-DP > Zn- Catalyst SBET Total pore Average pore
DP > Ni-SP > Zn-SP. These findings are in agreement with the (m2 g
1) volume (cm3 g
1) diameter (nm)
outcomes derived from FESEM and HRTEM. The smallest Ni-SP 30.1 0.4541 50.3
crystallite gives the largest specific surface area. The BET Zn-SP 13.1 0.1372 41.9
analysis also revealed that the catalyst structure (supported or Ni-DP 67.9 0.1412 10.8
doped) affected the aspect of porosity. It is believed that for Zn-DP 36.3 0.3320 36.6

Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102
 international journal of hydrogen energy xxx (xxxx) xxx
the supported catalysts, some Ni and Zn oxides possess a
greater tendency to enter the pores and block the pore en-
trances, which may reduce the total pore volume and the
average pore diameter. These drawbacks, however, cannot be
avoided for the supported catalysts [42e44]. It is noteworthy to
highlight that the trapping and blocking of pores by the oxide
clusters may not occur for the doped catalysts, mainly
because the Ni and Zn elements are positioned within the
cubic MgO crystals. Fig. 4(e) and (f) show the pore illustration
for all supported and doped catalysts. It appears that the
doped catalysts have larger specific surface area, higher total
pore volume, and smaller average pore diameter to benefit the
catalytic reaction.
The TPD-CO2 was applied to determine the strength and
the amount of basicity of the synthesized catalysts. The
basicity strength can be expressed in terms of CO2 desorp-
tion temperature, as recorded by the TPD-CO2 profiles and
presented in Fig. 5. The CO2 desorption peaks for the cata-
lysts ranged between 300 and 600  C, which can be said to
have medium basic strength, with the doped catalysts
slightly higher than the supported catalysts. Table 3 shows
that the doped catalysts have greater amount of basicity
than that of the supported catalysts. The amount of basicity
increased in the following order: Zn-SP < Ni-SP < Ni-
DP < Zn-DP. The Zn-DP catalyst displayed the highest
amount of active basic sites with more than twenty-fold
increment than the Zn-SP catalyst. This shows that the
catalyst structure has greatly influenced both the strength
and the amount of the basicity properties. Hence, it is more
interesting to examine the catalytic performances of both
supported and doped catalysts.
Catalytic SCWG of OPF biomass
The catalytic performances between supported (Ni-SP and Zn-
SP) and doped (Ni-DP and Zn-DP) MgO catalysts were
compared by catalyzing the SCWG of OPF biomass to produce
syngas with high H2 yield. For each SCWG experimental run,
the reaction was performed at 400  C and 25 MPa for 30 min
with 5 wt% of the synthesized catalyst. Without catalyst, the
Fig. 5 e TPD-CO2 profiles of (a) Ni-SP, (b) Zn-SP, (c) Ni-DP
and (d) Zn-DP catalysts.
Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102
7
Table 3 e Basicity of supported and doped catalysts.
Catalyst CO2 desorption Amount of CO2
temperature ( C) desorbed (mmol g
1)
Ni-SP 344 794.4
Zn-SP 386 345.9
Ni-DP 469 5740.9
Zn-DP 437 7252.6
OPF biomass produced a gas yield of 142.6 ml g
1, which
further increased by 28.5%, 32.0%, 35.7%, and 55.0% with the
addition of Ni-SP, Zn-SP, Ni-DP, and Zn-DP catalysts, respec-
tively, during the SCWG reactions. The outcomes suggest that
the lignocellulosic waste, such as OPF biomass, can be gasified
at a lower temperature by using catalytic SCWG. Similar
findings are reported in the literature with various nickel
supported catalysts [45e47]. Herein, for the first time, the
catalytic activity of doped catalysts is studied in SCWG. Sur-
prisingly, the doped catalysts (Ni-DP and Zn-DP) gave higher
gas yields than those of the supported catalysts (Ni-SP and Zn-
SP). All the synthesized catalysts accelerated the steam
reforming reactions of Eqs. (1) and (2), apart from generating
syngas with various gas compositions [48]. The x and y refer to
the elemental molar ratios of H/C and O/C in the biomass,
respectively.
CHxOy þ (1
y)H2O / (1
y þ x/2)H2 þ CO (1)
CHxOy þ (2
y)H2O / (2
y þ x/2)H2 þ CO2 (2)
Fig. 6 illustrates the effects of supported and doped MgO
catalysts on the composition of gas products. For non-
catalytic SCWG, the produced gas contained 41.1 vol% of CO,
29.2 vol% of CO2, 14.6 vol% of CH4, 10.6 vol% of H2, 3.8 vol% of
C2H6, and 0.7 vol% of C2H4. CO emerged as the main gas
product, followed by CO2, CH4, and H2 gases. Other hydro-
carbon gases, such as C2H6 and C2H4, were also detected at
very minimal amount. Nevertheless, the CO yield decreased
with the addition of synthesized catalysts during SCWG of OPF
biomass. It is believed that the added catalysts promoted the
water-gas shift reaction, which promoted H2 yield in each gas
product. The findings also showed that the CH4 yield
remained constant although with the presence of catalysts.
This means; both supported and doped catalysts were only
Fig. 6 e Effects of supported and doped catalysts on gas
composition for catalytic SCWG of OPF biomass.
8 international journal of hydrogen energy xxx (xxxx) xxx
active for the water-gas shift reaction (Eq. (3)), but appeared to
be inactive for the methanation reaction (Eqs. (4) and (5)).
CO þ H2O / H2 þ CO2 (3)
CO þ 3H2 / CH4 þ H2O (4)
CO2 þ 4H2 / CH4 þ 2H2O (5)
Fig. 7 displays the impacts of each catalyst on the indi-
vidual gas yield. It seemed that H2 yield increased tremen-
dously with the decreasing yield of other gases. When
compared to those without any catalyst, the supported cata-
lysts; Ni-SP and Zn-SP increased the H2 yield by 187.2% and
269.0%, respectively. These H2 yields momentously increased
when the doped catalysts were applied, wherein increment up
to 361.7% and 438.1% had been recorded for Ni-DP and Zn-DP.
In fact, two important findings need to be highlighted. First,
the doped catalysts performed better than the supported
catalysts. This suggests that the position of active element (Ni
or Zn), regardless of outside or inside the cubic structure of the
MgO, influenced the catalytic performances. Second, the Zn-
based catalysts always gave higher H2 yields than that of the
Ni-based catalysts. The catalytic activity of the synthesized
catalysts is in the order of Zn-DP > Zn-SP > Ni-DP > Ni-SP.
The promotional effects of all the catalysts toward water-
gas shift reaction had been verified by the reduction of CO
yield in each gas product. This means; the CO yield decreased
as the H2 yield increased. Among the catalysts, the Zn-DP
displayed the highest reduction of CO yield with 82.4%
decrement as it produced the highest H2 yield by more than
four times over Ni-SP, Zn-SP, and Ni-DP catalysts. Unfortu-
nately, the CO2 yield did not adhere to the expected trend.
During the water-gas shift reaction, as the produced CO
reacted with water, both H2 and CO2 yields should be
increased simultaneously. However, the CO2 yield in this
study decreased in the range of 24.8%e41.9% although the
added catalysts promoted the water-gas shift reaction, hence
indicating that some CO2 could have been absorbed on the
catalyst surfaces, as explained in our previous works [49,50].
The ability of the synthesized catalysts to absorb the produced
CO2 is an advantage for the catalytic SCWG of OPF biomass to
Fig. 7 e Increment or decrement of gas composition after
the addition of supported and doped catalysts for catalytic
SCWG of OPF biomass.
Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102
produce H2 rich syngas. Another advantage is that all the
synthesized catalysts did not catalyze the methanation reac-
tion as the undesired CH4 gas was formed with constant gas
yield. Hence, one can conclude that the supported and doped
Ni and Zn on the MgO-based catalysts are active for water-gas
shift reaction, but inactive for methanation reaction. The
doped catalyst of Zn-DP caused the SCWG of OPF biomass to
produce syngas with the highest H2 yield and the lowest CH4
yield, in comparison to other synthesized catalysts.
Relationship between catalyst properties and catalytic
performances in SCWG reactions
As depicted, varied catalyst structures (supported and doped)
can significantly influence the catalytic performances of the
synthesized catalysts. As reported previously [26], for the
supported catalysts, the Zn-based catalyst exhibited the
highest H2 yield from the OPF biomass even though it has the
smallest specific surface area. The main reason for the Zn-
based catalyst to perform better during the SCWG reaction is
due to the higher catalyst stability, as confirmed in the XPS
outcomes. The ZnO that was supported on the MgO surface
increased the strength of OeMg bond, which further increased
the stability of the catalyst. Therefore, the stability of the
catalyst is an important factor to be considered while
designing a new catalyst system for the SCWG reaction. It is
believed that the catalyst stability can be further improved by
inserting (or doped substitutionally) the active metal into the
crystal structure of the catalyst. Next, comparisons were
made for the catalyst properties and the catalytic perfor-
mances between supported and doped Ni and Zn onto/into
MgO catalysts.
The catalyst properties of both supported (Ni-SP and Zn-
SP) and doped (Ni-DP and Zn-DP) catalysts differed from
each other. All the synthesized catalysts were highly pure, as
indicated by the XRD patterns with mixed phase for the
supported catalysts and the single-phase for the doped cat-
alysts. The doped catalysts have very small crystallites, as
compared to the supported catalysts, as observed vividly
from the FESEM and HRTEM micrographs. These results are
further confirmed using the BET analyses with the Ni-DP and
Zn-DP catalysts showing larger specific surface area than the
Ni-SP and Zn-SP catalysts. The smaller crystallite size pro-
vides larger specific surface area. Furthermore, the doped
catalysts attained higher metal loading with higher active
basic sites at medium basic strength. Interestingly, the
doped catalysts had managed to catalyze the SCWG of OPF
biomass effectively by increasing the H2 yield up to 361.7%
and 438.1% for Ni-DP and Zn-DP catalysts, respectively.
Although the Zn-DP catalyst has slightly smaller surface area
than the Ni-DP catalyst, it has the highest number of active
basic sites that are crucial to promote catalytic reaction. The
basic catalysts possess greater tendency in promoting the
water-gas shift reaction to increase the production of
hydrogen [51,52]. The effectiveness of the doped catalysts for
SCWG reaction was further influenced by catalyst stability,
which was elucidated via XPS measurements.
To better understand the chemical environment of both
supported and doped catalysts, XPS investigation was per-
formed. The BE values for all the elements are listed in Table 4.
 international journal of hydrogen energy xxx (xxxx) xxx 9

Table 4 e Binding energy (BE) for Ni-SP, Ni-DP, Zn-SP and

Zn-DP catalysts.
Catalyst Component BE (eV) %
Ni-SP Mg 2p 48.86
Ni 2p3/2 Ni2þ 852.16 75.5
Ni3þ 853.37 24.5
Ni 2p1/2 869.62
O 1s OeMg 530.06
OeNi 527.98
Ni-DP Mg 2p 48.98
Ni 2p3/2 Ni2þ 852.85 77.2
Ni3þ 854.07 22.8
Ni 2p1/2 870.30
O 1s OeMg 530.02
OeNi 528.33
Zn-SP Mg 2p 49.14
Zn 2p3/2 Zn2þ 1017.13 100
Zn 2p1/2 1040.14
O 1s OeMg 530.27
OeZn 528.29
Zn-DP Mg 2p 49.23
Zn 2p3/2 Zn2þ 1018.05 100
Zn 2p1/2 1040.98
O 1s OeMg 530.31
OeZn 528.35

All the BEs are corrected based on the C 1s peak (BE ¼ 284.2 eV)
as depicted in Ref. [53], while Shirley background was applied
for peak fitting. The BE values are also in agreement with the
NIST database. Fig. 8 illustrates the XPS narrow scans of Mg 2p
and O 1s for both supported and doped catalysts. As shown in
Fig. 8(a), all the synthesized catalysts have symmetrical Mg 2p
peaks; indicating only one oxidation state of þ2 present for Mg
in each catalyst. Besides, the BE values of the Mg 2p retrieved
for doped catalysts appeared to be higher than those obtained
for supported catalysts (refer to Table 4). Regardless of sup-
ported or doped structures, the Zn-based catalysts shifted the
Mg 2p peaks to higher BE values, as compared to the Ni-based
catalysts. This phenomenon is believed to occur due to the
bonding character of ionic bonds in the MgO. It is well known
that in ionic bonding, the positions of cation (Mg2þ) and anion
(O2
) are locked by a strong electrostatic attraction force be-
tween the ions. When larger ionic radius of Zn2þ (0.74  A) is
supported or doped onto/into the MgO crystal lattice, a greater
electron repulsion is felt by the electron clouds surrounding
the ions (Mg2þ and O2
) that pushes the electrons into each Mg
and O orbital closer to their nucleus. Note that the ionic radius
of Mg2þ is 0.72  A. This explains why the BEs of Mg 2p peak for
both Zn-SP and Zn-DP catalysts are higher, as compared to
those of Ni-SP and Ni-DP catalysts, which have smaller ionic
radius of Ni2þ (0.69 A). The ionic radii for all the cations adhere
to the coordination number 6 of the cubic structure [54]. Be-
tween the Zn-based catalysts, the Zn-DP displayed the highest
BE value for the Mg 2p peak than the Zn-SP. This can be further
explained by examining the crystal structure of the catalysts,
as illustrated in Fig. 2 (a). As for the supported catalyst, the
active metal of Zn was only formed on the MgO surface. In
contrast, for the doped catalyst, the Zn2þ took place in the
Mg2þ site at the MgO lattice structure. The incorporation of
Zn2þ into the MgO host lattice can cause the surrounding
atoms (Mg and O) to experience more electron repulsion from
Fig. 8 e XPS narrow scans for (a) Mg 2p and (b) O 1s of the
supported and doped catalysts.
the electron cloud of Zn2þ than being only supported on the
MgO surface. The greater electron repulsion leads the elec-
trons in each orbital of Mg and O ions to move closer to their
nucleus, which can result in higher BE values. This is well
supported with the BE value of O 1s for the Zn-DP catalyst (see
Table 4). In Fig. 8(b), the BE of O 1s for Zn-DP shifted to a higher
value; indicating that its OeMg bond is stronger (shorter dis-
tance) than the other catalysts. The shorter distance between
OeMg bond implies that more energy is needed to break this
bond. Hence, it is can be concluded that the Zn-DP catalyst has
higher stability of catalyst structure, when compared to the
rest.
Fig. 9 illustrates the XPS narrow scans of the active metals
(Ni and Zn) for both supported and doped catalysts. The doped
catalysts recorded higher BE values than the supported cata-
lysts. This is mainly because the Ni and Zn ions took place in
the Mg2þ sites in the MgO lattice. In Fig. 9(a), both the Ni-
supported and doped catalysts possess asymmetry shape of
Ni 2p3/2 peaks, which reflect the existence of more than one
oxidation state for Ni cations. The deconvolution on Ni 2p3/2
peak was performed for both catalyst structures. An example
of deconvolution of Ni 2p3/2 peak for Ni-DP catalyst is shown in
Fig. 10. The analysis revealed that the Ni-based catalysts have
mixture of Ni2þ and Ni3þ, as tabulated in Table 4. On the
contrary, Fig. 9(b) presents that both the Zn-supported and
doped catalysts have symmetrical Zn 2p3/2 peaks. This implies

Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102
10 international journal of hydrogen energy xxx (xxxx) xxx
Fig. 9 e XPS narrow scans for active metal of (a) Ni and (b)
Zn of the supported and doped catalysts.
that only one oxidation state exists for the Zn cation, which is
þ2. This is further confirmed by the energy splitting of
approximately 23 eV between Zn 2p1/2 and Zn 2p3/2 peaks. This
finding is in line with the NIST database. Based on these re-
sults, the active element (Ni or Zn) and the catalyst structure
(supported or doped) are greatly affected by the chemical
environments, such as BE and oxidation state of the
Fig. 10 e The deconvolution for Ni 2p3/2 peak of Ni-DP
catalyst.
Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102
synthesized catalysts. The doped catalysts are more stable
than the supported catalysts with the Zn-based catalysts al-
ways being more reactive than the Ni-based catalysts during
the SCWG of OPF biomass. The catalytic performances of the
synthesized catalysts are given in the following order: Zn-
DP > Zn-SP > Ni-DP > Ni-SP. This means; the doped catalysts
can be considered as new promising catalysts for SCWG
reactions.
Conclusion
Supported (Ni-SP and Zn-SP) and doped (Ni-DP and Zn-DP)
catalysts were synthesized successfully and catalyzed the
SCWG of OPF biomass for hydrogen production. The study
outcomes revealed that the doped catalysts have larger spe-
cific surface area than the supported catalysts with Zn-DP
catalyst, which led to the highest H2 yield up to 438.1% of
increment, when compared to that without catalyst. The
catalytic activity of the doped catalysts seemed to be affected
by the active basic sites and the catalyst stability. The Zn-
based catalysts generated the highest H2 yield, when
compared to the Ni-based catalysts for each supported and
doped catalysts. In future work, the compositions of Ni-DP
and Zn-DP will be varied and used as new promising cata-
lysts to catalyze the SCWG reactions.
Acknowledgement
This work was supported by the Malaysian Ministry of Higher
Education (MOHE) through Fundamental Research Grant
Scheme (600-RMI/FRGS5/3(13/2013)). M. S. Mastuli would like
to thank to MOHE for the PhD scholarship.
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Please cite this article as: Mastuli MS et al., Comparative study between supported and doped MgO catalysts in supercritical water
gasification for hydrogen production, International Journal of Hydrogen Energy, https://doi.org/10.1016/j.ijhydene.2018.12.102