Chemical Engineering Science 255 (2022) 117676

Contents lists available at ScienceDirect

Chemical Engineering Science

journal homepage: www.elsevier.com/locate/ces

Investigating the effects of synthesis procedures on textural and catalytic

properties of nickel/magnesium silicate catalyst in glycerol dry
reforming
Zahra Pirzadi a, Fereshteh Meshkani b,⇑
a
Catalyst and Advanced Materials Research Laboratory, Chemical Engineering Department, Faculty of Engineering, University of Kashan, Kashan, Iran
b
Institute of Nanoscience and Nanotechnology, University of Kashan, Kashan, Iran

h i g h l i g h t s g r a p h i c a l a b s t r a c t

The synthesis method affects the

structural properties of the Ni/MgO.
SiO2 catalyst.

The structural features of the Ni
catalyst affect catalytic performance
significantly.

The Ni/MgO.SiO2 catalyst prepared by
one-pot method showed better
performance.

The one-pot method has resulted in
the highest textural properties of the
Ni/MgO.SiO2.

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

Article history: Ni-based catalysts supported on magnesium silicate were synthesized using various synthesis procedures
Received 20 May 2020 and were then investigated for the first time in the glycerol-DR (dry reforming) process. In general, syn-
Received in revised form 20 March 2022 thesis procedures for catalyst supports included co-precipitation and hydrothermal, and nickel as active
Accepted 10 April 2022
metal was attached to the support simultaneously with support preparing and impregnation technique.
Available online 20 April 2022
The results of characterizations of Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), hydrogen
temperature-programmed reduction (TPR-H2), temperature-programmed oxidation (TPO), scanning elec-
Keywords:
tron microscopy (SEM), energy dispersive X-ray (EDX) element mapping, Fourier transform infrared
Dry reforming
Glycerol
(FTIR), thermogravimetric analysis (TGA-DTA), and the catalytic glycerol-DR reaction tests illustrated that
Synthesis the preparation route of Ni/MgO.SiO2 catalyst is effective in the structural and physicochemical features
Ni catalyst of the sample. It was observed that the catalysts with various synthesis methods exhibited different
Magnesium silicate activity and stability during the glycerol-DR reaction. However, the highest glycerol conversion (31–
50%) and the yield of both H2 and CO were achieved over the Ni/MgO.SiO2 (I) catalyst at all reaction tem-
perature ranges (600–750 °C). The high catalytic performance of the Ni/MgO.SiO2 (I) sample in the
glycerol-DR reaction was related to its textural properties such as surface area (411 m2 g1), the crystal-
lite size (8.5 nm), and active species dispersion, which were superior for this catalyst in comparison with
other samples. This sample also exhibited better catalytic stability during the reaction. Furthermore,

⇑ Corresponding author.
E-mail address: meshkani@kashanu.ac.ir (F. Meshkani).

https://doi.org/10.1016/j.ces.2022.117676
0009-2509/Ó 2022 Elsevier Ltd. All rights reserved.
Z. Pirzadi and F. Meshkani
synthesis gas (syngas) was produced for all catalysts with an H2/CO ratio of less than 1.6. These results
clearly show a significant impact of the sample synthesis procedure on the catalyst’s final physical and
chemical properties. The Ni/MgO.SiO2 catalyst prepared with a one-step method showed high potential
as a glycerol-DR catalyst for syngas production.
1. Introduction
Increasing problems caused by environmental pollution and
reserves depletion of fossil fuels have increased the need for alter-
native energy forms (Bobadilla, 2015; Dan et al., 2015; Sad et al.,
2015; Nanda et al., 2019; Liu et al., 2013). Hydrogen is a clean
and efficient chemical fuel and can be considered the future energy
carrier (Lee et al., 2015; Kim et al., 2015; Wess et al., 2015). Among
renewable candidates, glycerol (C3H8O3) is an excellent feedstock
to the production of hydrogen that is carried out through different
types of reforming techniques, including pyrolysis (Cheng, et al.,
2019), partial oxidation (Skrzyńska et al., 2019), autothermal
reforming (Liu et al., 2013), dry reforming (Bac, 2019), supercritical
water gasification (Li et al., 2019), and steam reforming (Gallegos-
Suárez, 2015). Dry reforming of glycerol is a beneficial method
among the various hydrogen/syngas production methods. Because
the CO2 greenhouse gas with the by-product of biodiesel converts
to the syngas in this green technique. Furthermore, this process’s
H2/CO ratio is suitable for Fischer-tropsch (FT) synthesis, methanol,
and dimethyl (Siew et al., 2014). Eq. (1) indicates the overall
glycerol-DR reaction:
C3 H8 O3 + CO2 $ 4CO + 3H2 + H2 O DH298K = 248.33 kJ mol1
ð1Þ
And side reactions:
C3 H8 O3 $ 3CO + 4H2 DH298K = 250 kJ mol1 ð2Þ
CO + H2 O $ H2 + CO2 DGo =  41.17 + (0.042) T ð3Þ
2CO $ C + CO2 DGo =  172.46 + (0.175) T ð4Þ
CO + 3H2 $ CH4 + H2 O DGo =  206.1 + (0.214) T ð5Þ
CO2 + 4H2 $ CH4 + 2H2 O DGo =  164.94 + (0.173) T ð6Þ
CH4 + CO2 $ 2CO + 2H2 DGo = 247.26 - (0.043) T ð7Þ
CH4 $ C + 2H2 DGo = 75 + (0.081) T ð8Þ
C + 2H2 O $ 2H2 + CO2 DGo = 90.13 + (0.092) T ð9Þ
The glycerol-DR process has investigated noble metals and nickel
as active metals. Harun et al. (2019) investigated the effect of Ag pro-
motion with different loading (1, 3, and 5 wt%) on the performance of
the Ni/Al2O3 catalyst in the glycerol-DR reaction. They reported that,
among all of the catalysts, the Ni/Al2O3 catalyst promoted with 3 wt
% Ag showed the highest conversion of glycerol (40.7%) and hydro-
gen yield (32%). In addition, the optimum conditions suggested by
this group include CO2 to glycerol (CGR) ratio of 1:1, 800 °C, and
1
gas hourly space velocity (GHSV): 3.6  104 mL g-1 cath . Bulutoglu
(2018) studied the performance of Rh/CeO2 and Rh/ZrO2 samples
in the glycerol-DR reaction. They reported that the Rh/ZrO2 catalyst
was more active in the reaction and produced syngas with a higher
yield, but the Rh/CeO2 sample showed higher catalytic stability. This
behavior was correlated with oxygen vacancies, mobile oxygen spe-
2
Chemical Engineering Science 255 (2022) 117676
Ó 2022 Elsevier Ltd. All rights reserved.
cies, and strong metal-support interactions of the Rh/CeO2 catalyst,
which improved its stability during 72 h reaction under the condi-
tion of CO2/glycerol: 4 and 750 °C. Furthermore, carbon formation
and Ru particle sintering caused the deactivation of the Rh/ZrO2 cat-
alyst. Mohd Arif et al. (2019) investigated glycerol-DR over 15 wt%
Ni/CaO and 5 wt% Re-Ni/CaO catalysts. It was reported that the opti-
mal conversion of glycerol (61%) and yield of H2 (56%) achieved over
the 5 wt% Re-Ni/CaO catalyst under optimal reaction condition of
1
GHSV: 3.6  104 mL g-1 cat s and 800 °C. In addition, optimal CGR
suggested by this group was 3 and 1 for 5 wt% Re-Ni/CaO and
15 wt% Ni/CaO, respectively. In this condition, glycerol conversion
and H2 yield for 15 wt% Ni/CaO catalyst were reported as 35% and
30%, respectively.
Although noble metals have a high performance in the reaction,
nickel catalysts are preferred as the main catalysts for the reform-
ing process due to the high capacity for cleavage of CAC bonds of
glycerol, extensive sources, and lower price. Notwithstanding, the
major drawback of Ni-catalysts is a high predisposition of carbon
formation, which would lead to deactivation in the reforming reac-
tion (Demsash et al., 2018; Wang, 2018; Arif, 2018; Mourhly, 2018;
Moura-Nickel et al., 2019; Zhou, 2019). Hence, many studies have
been conducted to enhance the stability and activity of Ni-catalysts
using different catalyst preparation procedures, choosing more
suitable catalyst support, and adding promoters (Ghods et al.,
2016; Zhang, 2013; Li and Rudolph, 2008). Magnesium oxide is
considered as an appropriate catalyst support or promoter for
metal catalysts. It increases resistance against carbon formation
on the catalyst surface and causes high thermal stability of the cat-
alyst. It can be due to the unique characteristics of MgO, e.g., high
thermal strength, high melting point, and strongly basic property
(Ghods et al., 2016; Rastegarpanah et al., 2017; Xu et al., 2001;
Paul et al., 2012). Although Ni/SiO2 catalyst exhibited excellent cat-
alytic performance in the reforming reaction, it deactivated readily
during the reaction at a high temperature (Mourhly, 2018; Lu et al.,
2018; Takahashi et al., 2004; Ghods et al., 2017). Therefore, MgO.
SiO2 combination as a suitable support for nickel-based catalyst
seems to lead to high activity and stability in the reforming pro-
cess. Zhang (2013) investigated the performance of Ni/Mg-SBA-
15 as the dry methane reforming (MDR) catalyst. They reported
that the addition of Mg to the support improved the activity and
stability of the catalyst. The Cu/MgSiO3 catalyst preparation with
the ammonia-evaporation method was investigated in the MDR
process by Qin et al. (2015). They revealed that the Cu/9MgO.
SiO2 catalyst has high catalytic performance due to its high Cu dis-
persion and great weak basic sites. Angelici et al. (2014) demon-
strated the synthesis method of MgO.SiO2 has a significant effect
on the morphology and performance of the catalyst. Ghods et al.
(2016) synthesized the MgSiO3 support by hydrothermal tech-
nique with high surface area (619 m2 g1) and then investigated
the activity of the prepared Ni/MgSiO3 catalyst in methane
steam/dry reforming reaction. They reported this catalyst’s good
excellent activity and stability during the reaction. Li and
Rudolph (2008) investigated the influence of different parameters,
including the type of SiO2 supports, loading methods, and precur-
sor salts, upon the activity of the MgO/SiO2 catalyst. They reported
that these variables except precursor salts are effective on catalytic
activity. Makshina et al. (2012) demonstrated that the synthesis
Z. Pirzadi and F. Meshkani
method for preparing MgO.SiO2 catalyst is effective on catalyst
performance; MgO.SiO2 sample was synthesized applying different
methods e.g., wet-kneading, co-precipitation, and hydrothermal
(Makshina et al., 2012; Da Ros et al., 2017; Narasimharao et al.,
2014). In the current study, for the first time, we employed the
MgO.SiO2 support for Ni-based catalyst in the glycerol-DR process.
We examined the correlation between the synthesis procedure and
the physicochemical properties and performance of Ni/MgO.SiO2
catalyst in the glycerol-DR reaction, such investigation has not
been reported in the glycerol-DR literature. For this purpose, differ-
ent methods were administered for the preparation of Ni/MgO.SiO2
catalyst. Generally, the catalyst supports were synthesized using
co-precipitation and hydrothermal methods, and catalyst samples
were prepared by one-step and impregnation routes. Analytical
techniques and catalytic tests (activity and stability) were then
employed for the investigation of physicochemical characteristics
and catalytic performance of the catalysts, respectively. Finally, a
method that led the better textural and structural properties as
well as the higher catalytic performance of Ni/MgO.SiO2 catalyst
in the dry reforming reaction was selected and was further inves-
tigated using FTIR, TGA-DTA, and TPD-CO2 analysis, and long-term
stability (25 h) test.
2. Experimental
2.1. Material
Ni (NO3)26H2O (98% from Centeral Drog House), Mg
(NO3)26H2O (99%, Centeral Drog House), sodium silicate (Na2SiO3,
Merck), tetraethyl orthosilicate (TEOS, Merck) were used as Ni, Mg,
and Si sources, respectively. Dodecylamine (DDA, Merk), Pluronic
P123 (Poly-(alkylene oxide) based Triblock copolymers (M.
W. = 5800), cetyltrimethylammonium bromide (CTAB, Merck),
and polyvinyl pyrrolidone (PVP, Merck) were used as surfactants.
Furthermore, ethanol (99% from Scharlau), HCl (65 wt%, Merck),
butanol (Merk), NH3 (25 wt%, Merk), NaOH (Merck) were also used
during catalysts synthesis.
2.2. Synthesis method
Six nickel/magnesium silicate mesoporous (labeled (I)-(VI)) cat-
alysts (with equal SiO2: MgO molar ratio) were prepared using dif-
ferent synthesis routes, as described below:
It is noticeable that, in the case of hydrothermal synthesis pro-
cedures, aging time, aging temperature, and silica source were dif-
ferent. Furthermore, the type of used surfactants for these methods
was different. So we distinguished the hydrothermal synthesis
methods with I-IV numbers in descriptions.
Synthesis of Ni/MgO.SiO2 (I):
Ni/MgO.SiO2 (I) sample was prepared using the one-step syn-
thesis method. In this method 1.2 g dodecylamine (DDA) surfactant
was added to a mixture containing distilled water and ethanol
(1:1), then 2.5 g tetraethyl orthosilicate (TEOS) was gradually
dropped to the mixture under the condition of vigorous stirring
and ambient temperature and was stirred about 1 h. After that,
the required amount (SiO2/MgO:1) of Mg (NO3)26H2O was added,
and the mixture was stirred for one more hour. After 1 h, the
desired amount of Ni (NO3)26H2O was added, and the solution
was kept stirring for 20 h. The obtained precipitate was then sep-
arated and washed with distilled water, dried at 80 °C, and finally
was calcined. We labeled the sample as Ni/MgO.SiO2 (I). It should
be mentioned that the MgO.SiO2 (I) support was obtained by elim-
inating the Ni addition step in the synthesis procedure.
3
Chemical Engineering Science 255 (2022) 117676
Synthesis of MgO.SiO2 (II):
MgO.SiO2 (II) sample was prepared by hydrothermal synthesis
method. At first, 1 g Pluronic P123 (Poly-(alkylene oxide) based Tri-
block copolymers) was dissolved in a mixture of 36 g distilled
water and 1.97 g HCl (2 M), then 1 g butanol was added to this
solution at 35 °C and was stirred for 1 h. Next, TEOS was added
with a slow dropping rate. Afterward, the required amount (SiO2/
MgO:1) of Mg (NO3)26H2O was added to it at 35 °C and was kept
stirring for 24 h at 35 °C. Next, the solution was transferred to an
autoclave and heated at 100 °C for 24 h. After 24 h, the autoclave
was cooled to ambient temperature. The obtained white precipi-
tate was separated by filtering dried in an oven at 90 °C. The tem-
plate was removed by extracting the dry sample in a solution of
ethanol and water and then was calcined.
Synthesis of MgO.SiO2 (III):
A co-precipitation synthesis technique was used for MgO.SiO2
(III) synthesis. First, 1.67 g cetyltrimethylammonium bromide
(CTAB) was dissolved in 500 mL distilled water under magnetic
stirring, after complete dissolution, Mg (NO3)26H2O and then
5 mL NH3 was added, then TEOS was slowly added to the solution
followed by stirring for 1 h. Eventually, the resulting precipitate
was filtered and washed until reaching pH 7, then dried in an air
oven at 85 °C and after that, the obtained powder was calcined.
Synthesis of MgO.SiO2 (IV):
For the synthesis of MgO.SiO2 (IV) sample, 2.58 g Mg (NO3)2-
6H2O was added to an aqueous solution containing Na2SiO3. The
pH was adjusted to 11 by NaOH (1 M). The solution was then
placed in an autoclave and heated at 180 °C for 15 h. The obtained
white precipitate was collected and washed several times via cen-
trifugation with distilled water, then dried overnight in an oven at
80 °C and after that, the resulted powder was calcined.
Synthesis of MgO.SiO2 (V):
The MgO.SiO2 (V) sample was synthesized by dissolving 1 g
polyvinyl pyrrolidone (PVP) in 120 mL distilled water under mag-
netic stirring, afterward 0.46 g NaOH was added. After dissolution,
1.4 g CTAB surfactant was added to the mixture. This procedure
was followed by adding Mg (NO3)26H2O Then continuous mag-
netic stirring was done for about 1 h. TEOS was then slowly
dropped to the solution. The resulting solution was stirred for
24 h. Then the solution was thermally treated in an autoclave at
85 °C for 48 h. The white solid product was separated and then
washed with distilled water to remove the residual ions. After that,
the sample was dried (85 °C) and calcined.
Synthesis of MgO.SiO2 (VI):
For the synthesis of MgO.SiO2 (VI) sample, each of Mg
(NO3)26H2O and Na2SiO3 were separately dissolved in 10 mL of
water. The two above solutions were then added dropwise into
the aqueous solution contained PVP. The pH of the solution was
adjusted at 10 using NaOH solution (0.5 M). Hydrothermal treat-
ment of solution was carried out using autoclave at 150 °C for
15 h. Hydrothermal treatment product was collected and washed
using a centrifuge with distilled water. At last, the sample was
dried at 80 °C overnight and then calcined.
All supports were calcined at 750 °C for 3 h in a programmable
furnace. The 10% Ni/MgO.SiO2 ((II)-(VI)) catalysts were prepared
via impregnating the supports with the appropriate concentration
of an aqueous solution of Ni (NO3)26H2O under stirring at room
Z. Pirzadi and F. Meshkani Chemical Engineering Science 255 (2022) 117676

temperature (RT) and then aged for 4 h. At last, the samples took in
an oven at 85 °C overnight and calcined at 550 °C for 4 h under air-
flow. The main parameters in each procedure are summarized in
Table 1.
2.3. Characterization
by passing the 30 mL min1 of O2/He (5:95) flow as an oxidizing gas
flow over the spent catalyst and increasing temperature linearly
from room temperature up to 900 °C with a rate of 10 °C min1.
The fresh and reacted Ni/MgO.SiO2 catalysts were examined for
morphological studying applying scanning electron microscopy
(SEM) technique and using a Nova NanoSEM 650.

Brunauer–Emmett–Teller (BET) and Barrett-Joyner Halenda 2.4. Catalytic evaluation

(BJH) methods were used for estimating the mean pore diameter,
specific surface area, total pore volume, and pore size distribution
(PSD) by N2 adsorption–desorption analysis and using a BELSORP-
mini II analyzer. The calculation of the particle size was performed
using the Eq. (10):
D ¼ 6000=q  SBET
Which q is powder skeletal density, SBET is the BET surface area.
The X-ray diffraction (XRD) analysis of all prepared samples was
done using a PANalytical X’Pert-Pro diffractometer in a step-scan
mode at 10–80°. The Scherrer equation (Eq. (11)) was also used
for calculating the average crystallite sizes of the catalysts.
0:9k
D ¼
cosh
where k is the crystallite sizes, b and h are the Bragg angle and line
broadening at half of the maximum intensity (FWHM), respectively.
Bahr STA 503 system was used for both TGA (thermogravimetric
analysis) and DTA (derivative thermogravimetry) analysis. The cat-
alyst sample was annealed in an air atmosphere from ambient tem-
perature to about 800 °C with a rate of 10 °C min1. FTIR
transmittance spectra of the samples were analyzed using a
Nicolet-Impact 400D spectrophotometer in the range of 400–
4000 cm1. The surface morphology of the prepared catalysts was
investigated using scanning electron microscopy (SEM) and energy
dispersive X-ray (EDX) element mapping analysis through a Nova
NanoSEM 650 and a VEGA TESCAN microscope. The surface chemi-
cal analysis of the samples for the metal-containing particles of Si,
Mg, O, and Ni was characterized via energy dispersive X-ray
(EDX) analysis. Investigating the reduction behavior of the fresh
samples to identify the metal-carrier interaction and reducibility
degree of the samples was conducted via H2 temperature-
programmed reduction (TPR-H2) technique using a micrometrics
chemisorb 2750 apparatus connected to a TCD detector. Calcined
samples (0.1 g) were degassed with Ar at 200 °C for 1 h. After being
reduced under 25 mL min1 gaseous stream of the 10% H2/Ar mix-
ture and temperature range of 30–850 °C, were subjected to a heat-
ing ramp rate of 10 °C min1. The basic property of the catalyst was
analyzed by programmed temperature with CO2 (TPD-CO2) analy-
sis. This analysis was done on the mentioned equipment as TPR
experiment. The gaseous flow (30 mL min1) of the 10% CO2/Ar
mixture was introduced over calcined samples (0.1 g) and heated
then from 30 °C to 850 °C with a rate of 10 °C min1. Characteriza-
tion of the deposited carbon over the reacted catalyst was studied
by temperature-programmed oxidation with O2 (TPO-O2). A chemi-
sorb 2750 micrometric apparatus was also used for TPO-O2 analysis
In order to evaluate the catalytic performance of catalysts in the
glycerol-DR process, catalytic reaction tests were carried out in a
quartz vertical fixed-bed reactor with an inner diameter of 8 mm
and a length of 60 cm, under atmospheric pressure.
All catalysts were activated at 700 °C under a 25 mL min1 of
ð10Þ
pure H2 flow for 4 h, before reaction. The bed temperature was
then cooled down to the desired temperature. The catalytic perfor-
mance was measured in the range of 600–750 °C with CO2 to glyc-
erol ratio of unity. Liquid glycerol was pumped using an HPLC
pump and evaporated in the heating zone upstream of the reactor.
The total inlet flow contains CO2 and glycerol as reactant gas and
nitrogen carrier gas as a diluent was fixed at 7.2  104 mL g-cat
1 1
ð11Þ h . Reactor outlet gaseous product was separated from the con-
densable products by passing through two cold traps. The dried gas
was analyzed using a gas chromatograph (Teif gostar) with a TCD
capillary columns detector and HP-MOLSIV.
Conversion of C3H8O3 to gaseous products (Xgly) was calculated
based on H balance (Eq. (12)), as commonly done in other similar
investigations in literature (Siew et al., 2015; Siew et al., 2015;
Lee et al., 2014; Mohd Arif et al., 2016; Ayodele et al., 2016; Siew
et al., 2014; Harun et al., 2016; Tavanarad et al., 2018; Tavanarad
et al., 2018).
2  F H2 þ 4  F CH4
Xgly ¼  100 ð12Þ
8  F C 3 H8 O3
Hydrogen yield (Y H2 ) and carbon monoxide yield (Y CO ) were
evaluated using the following equations:
F CO
YCO ¼  100 ð13Þ
3  F C 3 H 8 O3
2  F H2
Y H2 ¼  100 ð14Þ
8  F C 3 H 8 O3
3. Results and discussion
3.1. Structural properties
3.1.1. BET analysis results
The porous structure properties (surface area, pore volume, and
average pore size) of different magnesium silicate supports and Ni
catalysts are tabulated in Tables 2 and 3, respectively. As can be
seen in Table 2, different types of magnesium silicate support,
despite having the same composition, create various surface areas,

Table 1
Sample labels and summary of different catalyst preparation methods in this study.

Label Method preparation Si source Mg source Solvent Surfactant Aging condition Dry/calcination (°C)
(temperature/ time) (°C /h)
Ni/MgO.SiO2 (I) One-step SiC8H20O4 Mg(NO3)26H2O Water + ethanol DDA RT/20 80/750
Ni/MgO.SiO2 (II) Hydrothermal (I) SiC8H20O4 Mg(NO3)26H2O Water P123 35/24, 100/24 90/750
Ni/MgO.SiO2 (III) Co-precipitation SiC8H20O4 Mg(NO3)26H2O Water CTAB RT/1 80/750
Ni/MgO.SiO2 (IV) Hydrothermal (II) Na2SiO3 Mg(NO3)26H2O Water None 180/15 80/750
Ni/MgO.SiO2 (V) Hydrothermal (III) SiC8H20O4 Mg(NO3)26H2O Water PVP, CTAB RT/24, 85/48 85/750
Ni/MgO.SiO2 (VI) Hydrothermal (IV) Na2SiO3 Mg(NO3)26H2O Water PVP 150/15 80/750

4
Z. Pirzadi and F. Meshkani Chemical Engineering Science 255 (2022) 117676

Table 2 the lowest surface area and pore volume were observed in MgO.
Surface texture of catalyst supports preparation by different route. SiO2 (IV) catalyst supports. Fig. 1a, b, c, and d depict the pore size
Catalyst BET surface area Pore volume Pore size distributions and the nitrogen adsorption and desorption iso-
(m2 g1) (cm3 g1) (nm) therms of the MgO.SiO2 supports and Ni/MgO.SiO2 catalysts,
MgO.SiO2 (I) 847 0.38 3.43 respectively. As visible in Fig. 1c, N2 adsorption–desorption iso-
MgO.SiO2 (II) 521 0.33 7.05 therms type for all catalyst supports was similar; type IV. This type
MgO.SiO2 (III) 245 0.37 97.78 of isotherm is relevant to the mesoporous structure (Ghani et al.,
MgO.SiO2 (IV) 88 0.15 9.23
MgO.SiO2 (V) 425 0.15 2.43
2019). Nonetheless, the curve of distribution pore size for MgO.
MgO.SiO2 (VI) 338 0.24 3.43 SiO2 (III) and MgO.SiO2 (II) samples showed a peak in the region
higher than 50 nm, which indicated the presence of macropores
in their structure (Fig. 1a). The hysteresis loops in N2 desorption
demonstrated H2 type except for the MgO.SiO2 (III) sample, regard-
pore volume, and pore size. The highest surface area of catalyst ing this hysteresis loop type, the mesoporous materials contain
supports was 847 m2 g1 and belonged to the MgO.SiO2 (I) sample channel/ink bottle-like pore with non-uniform size. The ring shape
with the highest pore volume of about 0.38cm3 g1. Additionally, for the MgO.SiO2 (III) sample followed H3 type, indicating the

Table 3
Surface texture of catalysts preparation by different routes.

Catalyst BET surface area (m2 g1) Pore volume (cm3 g1) Pore size (nm) Crystal size DXRD (nm) Particle size (nm)
10 %Ni/MgO.SiO2 (I) 411 0.32 2.43 8.5 4
10 %Ni/MgO.SiO2 (II) 275 0.32 4.69 9.91 6.03
10 %Ni/MgO.SiO2 (III) 93 0.28 97.78 10.6 17.8
10 %Ni/MgO.SiO2 (IV) 29 0.03 26 48.1 57.3
10 %Ni/MgO.SiO2 (V) 59 0.05 24.49 14.1 28.17
10 %Ni/MgO.SiO2 (VI) 22 0.03 9.23 26.86 74.3

Fig. 1. (a): Pore size distributions of MgO.SiO2 supports prepared by different routes, (b): Pore size distributions of 10% Ni/MgO.SiO2 catalysts prepared by different routes,
(c): N2 adsorption/desorption isotherms of supports and (d): N2 adsorption/desorption isotherms of 10% Ni/MgO.SiO2 catalysts prepared by different routes.

5
Z. Pirzadi and F. Meshkani Chemical Engineering Science 255 (2022) 117676

slit-like pores formed by platy particles (Sing, 1985; Adam and

Iqbal, 2010). In this way, the effect of sample preparation on the
size and shape of the pores is significant.
The BET surface area and pore volume for nickel-supported cat-
alysts are lower than the catalyst support, which is observable in
Table 3. It is visible that the highest surface area (411 m2 g1)
and pore volume (0.32 cm3 g1) still belonged to the prepared cat-
alyst using the one-step synthesis method. In the case of the MgO.
SiO2 (I) sample, the reduction in the BET surface area and pore vol-
ume could be attributed to the inclusion of the Ni species (as the
active metal for glycerol-DR) within the pore walls of the support,
which leads to a decrease in both the BET surface area and pore
volume. In the other catalysts, the difference in the BET surface
area could be because of the mesopores blockage in the impregna-
tion step effect.
In addition to the aforementioned, re-calcination of samples can
be contributed to the reduction of the surface area and pore vol-
ume. The effect of adding nickel species on the catalyst textural
properties is visible in the distribution pore size curves (Fig. 1b).
NiO cluster penetration into the pores was lead to the destruction
of some mesopores and the formation of macropores. As can be
seen in Fig. 1b, the peak intensity was decreased substantially in
the mesoporous region and a new peak appeared in the macro-
range (>50 nm). Moreover, the addition of nickel to the catalyst
support caused a change in the pore shape of Ni/MgO.SiO2 (VI),
Ni/MgO.SiO2 (IV), and Ni/MgO.SiO2 (V) catalysts, such that the type
of hysteresis ring was changed from H2 type to H4 type (Fig. 1d).
The H4 type loop is relevant to narrow slit-shaped pores (Sing,
1985). Furthermore, the smallness of the cycle isotherms could
be because of the lower rate of N2 desorption than absorption rate,
which can be in turn related to the effects of the percolation on
porous structures (Charisiou et al., 2017).

3.1.2. XRD
The powder X-ray diffractograms of the calcined magnesium
silicate supports and nickel/ magnesium silicate catalysts with var-
ious synthesis procedures are displayed in Fig. 2a and b, respec-
tively. Fig. 2a demonstrates that the corresponding patterns of
the catalyst supports were approximately similar, except for the
sample with the hydrothermal (II) synthesis procedure. The XRD
results of all the catalyst supports, except the hydrothermal (IV)
method, confirmed the existence of MgO.SiO2 phase. The MgO.
SiO2 phase (JCPDS code N. 01-082-1644) was identified and
detected at 2h = 19.9°, 22.8°, and 43.1° for MgO.SiO2 with the co-
precipitation (MgO.SiO2 (III)), one-step (MgO.SiO2 (I)), and
hydrothermal (I; MgO.SiO2 (II)) synthesis methods, and also for
the hydrothermal (IV) method at 2h = 27.5° and 28.1° (JCPDS code
N. 01-082-1235). Nevertheless, the reflections belong to crystalline
MgO.SiO2 could not be observed in the XRD profile. This phe-
nomenon can be due to the broadened reflection peaks at 2h rang-
ing between 20° and 40°, which were created because of the
presence of amorphous silica (Angelici et al., 2014; Janssens
et al., 2015; Das et al., 2019; Jan et al., 2019). The MgO.SiO2 (III)
sample was also included the Orthorhombic Mg2SiO4 phase (JCPDS
code N.01-087-2039), which reflection spectrums overlapped with
MgO peaks at 2h = 43.6°, 53.5°, and 63.1°. The catalyst support pre-
pared by hydrothermal (II) synthesis method indicated the Mg2-
SiO4 (forsterite) phase (JCPDS code N.00-003-1118) as the
principal phase with clear reflectance peaks at 2h position between
23° and 73.2° (Zhu et al., 2017). It is noteworthy that, for both MgO.
SiO2 (IV) and MgO.SiO2 (III) supports the diffraction signals at
36.9°, 42.9°, and 62.2° of 2h position were attributed to MgO phase
with the JCPDS code N. 01-071-1176 (Janssens et al., 2015).
Fig. 2b depicts the broad X-ray diffraction spectra of a series of
nickel/magnesium silicate catalysts with various synthesis proce-
dures and an equal and fixed Ni content. The new diffraction
Fig. 2. (a): X-ray diffraction patterns of the magnesium silicate supports prepared
by different routes, (b): X -ray diffraction patterns of (I): 10% Ni/MgO.SiO2 (I), (II):
10% Ni/MgO.SiO2 (II), (III): 10% Ni/MgO.SiO2 (III), (IV): 10% Ni/MgO.SiO2 (IV), (V):
10% Ni/MgO.SiO2 (V), (VI): 10% Ni/MgO.SiO2 (VI).
spectrums at the 2h position of 37.26°, 43.3°, 62.89°, 75.43°, and
79.4° were detected for all Ni catalysts, which is attributed to the
NiO (JCPDS code N. 01-078-0643) phase (Zhang, 2013). The cata-
lyst with the one-step synthesis method had the lowest NiO peak
intensity compared to other samples. The higher dispersion of
NiO upon carrier surface could be a cause of the descent in the
intensity of NiO peaks compared to other catalysts. It may be in
connection with the higher surface area of the MgO.SiO2 (I) support
that confirmed by the BET analysis. Indeed, the higher surface area
of the catalyst support can be a reason for the improvement of the
dispersion of active metals on the catalyst surface area (Chen et al.,
2018). In addition, the smallest nickel crystal size obtained from
the Scherrer formula (Eq. (11)) can be another reason for the
decrease of NiO peaks intensity and high dispersion of NiO. In
two cases of Ni/MgO.SiO2 (IV) and Ni/MgO.SiO2 (VI), a solid solu-
tion of MgNiO2 was formed but was not visible on their patterns
due to overlapping with NiO diffractions. In principle, Ni (II) ions
can strongly interact with the MgO species as a component of
the support composition and form the MgNiO2 solid solution
(Zhang, 2013; Thyssen et al., 2019). According to the obtained

6
Z. Pirzadi and F. Meshkani Chemical Engineering Science 255 (2022) 117676

results, the sample preparation procedures concretely influence

the textural (surface area, particle size, pore volume, shape, pore
diameter) and structural features of the catalyst (Angelici et al.,
2014; Albarazi et al., 2015).

3.1.3. TGA-DTA
To check the thermal behavior of the sample, thermal analyses
such as Thermogravimetric (TGA) and differential thermal (DTA)
analysis were performed. As visible from Fig. 3, the weight of the
sample was gradually reduced from approximately 35 to 750 °C.
The first weight change (14%) occurred in the range of 30–
220 °C, which was attributed to ethanol/water desorption
(Mourhly, 2018; Lin et al., 2006; Yin et al., 2009). The DTA curve
also indicated this event in a first endothermic peak at about
97 °C (Fig. 3). The next thermal event at about 220–430 °C was
attributed to the combustion of remaining organic groups and also
leaving a low amount of carbon. Additionally, in this range of tem-
perature, the decomposition of nitrate and OH groups occur (Lin
et al., 2006; Douy, 2002). The sample weight was decreased
approximately 21% in this range. Another weight loss (7.5 %)
was occurred at above 430 °C. This was attributed to the conden-
sation reactions that could occur between AOH groups (Douy,
2002). These results were consistent with the FTIR analysis for
the aforementioned groups. At high-temperature ranged 530–
750 °C; the tiny amplitude of continuous mass loss (about 6%)
could be attributed to the dehydroxylation of the sample’s struc-
ture layers (Pongjanyakul et al., 2009). These endothermal events
are consistent with the DTA curve.

3.1.4. FTIR
For Ni/MgO.SiO2 (I) sample the FTIR transmittance spectra are
demonstrated in Fig. 4a and b. The sample contains various groups
that produce different bonds. Before calcination, a broad absorp-
tion band was seen in the 3600 and 3200 cm1 wavenumber range.
It could be attributed to the overlapping of such groups as hydroxyl
(AOH) stretching vibration spectra of silanols group and adsorbed
water (Yin et al., 2009; Pongjanyakul et al., 2009; Klapiszewski,
2018). The next small signal with a shoulder in the 2971–
2783 cm1 range was assigned to CAH stretching groups (ACH3,
ACH2) (Pongjanyakul et al., 2009; Klapiszewski, 2018; Ma et al.,
2015). A medium signal located at 1634 cm1 can be ascribable
to the hydroxyl stretch and bend modes of adsorbed water associ-
ated with silicate (Sun et al., 2018). The vibration of NO–3 derived of
nickel nitrate was visible at 1384 cm1 (Zhu et al., 2017; Ikuhara
Fig. 3. TGA/DTA curves for 10% Ni/MgO.SiO2 catalysts prepared by one-step
synthesis procedure.
Fig. 4. FTIR spectra for 10% Ni/MgO.SiO2 (I) catalysts (a): fresh catalyst before
calcination and (b): catalyst calcined at 750 °C for 3 h.
et al., 2012). The spectra for symmetric stretching vibration of
the network SiAOASi bond were observed in the positions of
467, 800, and 1057 cm1 (Mourhly, 2018; Zhu et al., 2017; Sun,
2014; Liu, 2012). The signal centered at 663 cm1 was attributed
to the CH bands (Goel et al., 2009). Additionally, the signal located
at a wavenumber of 467 cm1 was also reported for the MgAO
stretch vibration band (Ma et al., 2015).
FTIR reflection spectra for nickel/magnesium silicate sample
after calcination are visible in Fig. 4b. As can be seen, absorption
spectra of nitrate and carboxylate groups were not observed. In
other words, the reflection spectrum of NO–3 and CH bands was
destroyed. This phenomenon occurs because of the calcination pro-
cess. The absence of nitrate groups can be due to the thermal
decomposition of nickel nitrate and magnesium nitrate, which
can release as the gaseous species of NOx and CH groups and
decompose during the calcination process at 750 °C. These results
were confirmed by the lost weight in the range of 220–420 °C in
the TGA analysis. Hydroxyl groups’ relative amount was decreased
upon heating during the calcination process. It also appeared with
less intensity in the FTIR spectrum. The TGA calcined sample indi-
cated the advent of a new peak centered at 809 cm1, which was

7
Z. Pirzadi and F. Meshkani Chemical Engineering Science 255 (2022) 117676

assigned to the SiAOASi bond-stretch vibration (Zhu et al., 2017).

In addition, little change was visible in the SiAOASi spectrum,
implying the existence of the SiAOASi network with high heat
resistance in the structure after calcination treatment.

3.1.5. Temperature programmed reduction analysis (TPR-H2)

Fig. 5 presents the Ni/MgO.SiO2 samples reduction curves. As
can be observed, reduction peaks have appeared at three distinct
temperature regions, indicating the existence of oxide species of
nickel that interacted in varying degrees with MgO.SiO2 carrier. A
signal above 600 °C, which is visible in all curves, can be assigned
to the reduction of nickel (II) with moderate/strong interaction
with MgO.SiO2 support (Thyssen et al., 2019; Thyssen et al.,
2017). In the Ni/MgO.SiO2 (I) sample, the advent of the shoulder
peak at 730 °C could be ascribed to the reduction of NiO phase
interacting strongly with the carrier (Zhang, 2013). It inhibits the
nickel species accumulation and migration and increases its dis-
persion in the magnesium silicate support (Thyssen et al., 2017).
Ni/MgO.SiO2 (IV), Ni/MgO.SiO2 (V) and Ni/MgO.SiO2 (IV) profiles
showed small peaks at elevated temperatures in the range of
800–900 °C. It could be related to the reduction of the NiO phase
Fig. 6. TPD-CO2 spectra of Ni/SiO2 and Ni/MgO.SiO2 (I) catalysts.
that has an intense interaction with MgO species present in the
carrier composition; via the formation of MgNiO2 as a solid solu-
tion, as confirmed with the results of the XRD analysis (Thyssen 130 °C was attributed to the weak basic strength, and another wide
et al., 2019; Thyssen et al., 2017). A small hump at 400 °C in the desorption hump broadened in the temperature range of 350–
Ni/MgO.SiO2 (II) profile could be due to the nickel oxides reduction 500 °C could be attributed to basic sites with moderate strength.
in the bulk form or NiO that has a weak interaction with the mag- The last wide peak at above 500 °C was appeared due to the pres-
nesium silicate support (Lu et al., 2018; Bacariza et al., 2018). ence of the strong basic sites on the catalyst (Ge et al., 2013). These
Higher H2-consumption of the Ni/MgO.SiO2 (I) sample indicated three types of basic sites were also observed over the Ni/MgO.SiO2
higher reducible nickel species and higher reducibility degree of (I) sample, but all peaks appeared in higher temperature with the
the catalyst (Rastegarpanah et al., 2017). These results are consis- higher intensity. A shift to the higher temperature and higher
tent with the results described from the XRD experiment that CO2 desorption peak area of the Ni/MgO.SiO2 (I) catalyst was due
revealed higher dispersion and amount of NiO on the catalyst sur- to the introduction of magnesium as an alkaline metal to the cata-
face for Ni/MgO.SiO2 (I) sample. As it is clear in TPR results, the lyst support formulation, which can enhance the strength and con-
sample preparation procedure can affect the reducibility of the centration of the basic site. Therefore, it was concluded that the
samples by influencing the metal oxides-support interaction. basic properties of Ni/MgO.SiO2 (I) catalyst was significantly higher
than the Ni/SiO2 catalyst. Indeed, alkaline earth metals can thwart
3.1.6. Temperature programmed reduction analysis (TPD-CO2) acidic sites and enhance the basic properties, thereby enhance CO2
In order to compare the basicity properties of the Ni/MgO.SiO2 absorption and reducing the coke production over the catalyst sur-
(I) with Ni/SiO2 catalyst, the TPD-CO2 experiment was undertaken, face in dry reforming reactions (Charisiou et al., 2019).
and the results are compiled as two desorption patterns in Fig. 6.
TPD patterns of the two catalysts are similar in shape. For the
Ni/SiO2 pattern, the intense CO2 desorption hump centered at 3.2. Catalytic performance

The effect of the synthesis procedure for the preparation of cat-

alysts on their performance and stability in the glycerol-DR reac-
tion was investigated under harsh conditions, as described in
Section 2.3. Fig. 7a demonstrates that glycerol conversion continu-
ously increases in the investigated temperature region from 600 to
750 °C, mainly because the glycerol-DR is an endothermic reaction.
As depicted in Fig. 7a, nickel/magnesium silicate catalysts illus-
trated a different activity in the reaction. The performance of two
catalysts prepared by one-step and hydrothermal (I) procedures
was higher than other catalysts. However, the one-step method
was the better procedure in which glycerol conversion was
obtained about 50% at 750 °C. It can be explained by a higher
reducibility degree, higher BET surface area (411 m2 g1), and
small crystallite size (8.5 nm) in this sample compared to other
catalysts, which facilitates the diffusion of the molecules to and
from existing active sites in the catalyst. In addition, nickel is the
active site for glycerol-DR and can break down the CAC, CAH,
and CAO bonds well, so higher nickel dispersion leads to a greater
number of active sites available for reactants on the catalyst sur-
face and thus can increase catalyst activity and stability (Thyssen
et al., 2017; Carrero et al., 2017; Zamzuri et al., 2017). Low activity
Fig. 5. TPR-H2 profiles of the Ni/MgO.SiO2 catalysts. of the Ni/MgO.SiO2 catalysts synthesized by co-precipitation,
8
Z. Pirzadi and F. Meshkani Chemical Engineering Science 255 (2022) 117676

Fig. 7. Catalytic performances in glycerol-DR reaction: (a): Glycerol conversion, (b): H2/CO molar ratio, (c): H2 Yield, (d): CO Yield, (e): stability test at 750 °C for 10% Ni/MgO.
SiO2 catalysts prepared by different synthesis routes (reaction conditions: CO2/Glycerol = 1; GHSV = 7.2  104 mL h1 g-1 cat), (f): effect of CGR and GHSV and CGR on the glycerol
conversion of 10% Ni/MgO.SiO2 (I) catalysts and (j): long time stability test at 750 °C for 10% Ni/MgO.SiO2 (I) catalyst.

hydrothermal (II and IV) procedures, in addition to their low textu-
ral properties, might be related to the pore shape of these catalysts.
In principle, the geometric limitations lead to the reactants shape
selectivity (Bartholomew and Farrauto, 2011), so the narrow slit-
shaped of the catalysts synthesized by co-precipitation, hydrother-
mal (II and IV) procedures might limit access to glycerol large
molecules to the pores and thus activate sites. This can be a reason
for the low activity of these catalysts. These results are confirmed
by XRD and BET analysis. Fig. 7b shows the syngas ratios (H2/CO)
for catalysts with various synthesis routes in the glycerol-DR reac-
tion. As can be observed, the syngas ratios reduced when the reac-
tion temperature increased from 600 to 750 °C. It might be related
to the exothermic water–gas-shift (WGS) reaction (Tavanarad
et al., 2018). The H2/CO ratio produced in the gaseous products is
a critical key factor for the application in FT synthesis. It is note-
worthy that, the amount of synthesis gas ratio was less than 2,
which is proper for the Fischer-Tropsch synthesis feed.
Fig. 7c and d illustrate that the yield of both H2 and CO, progres-
sively raised with temperature, because dry reforming of glycerol
is an endothermic reaction and high temperature is in favor of
glycerol decomposition (Eq. (2)), methane dry reforming (Eq. (7)),
and methane steam reforming (Eq. (6)) (Bulutoglu, 2018). At the
first investigated temperature (600 °C), the yield of hydrogen
was higher than the CO yield, while at higher temperatures, due
to the effect of reverse water gas shift (RWGS) reaction, the CO
yield became higher than H2 yield (Tavanarad et al., 2018).
The thermal stability of catalysts with various synthesis routes
is shown in Fig. 7e. The stability analysis results confirm that the
thermal stability of the catalysts is affected by the preparation
method of the catalyst. The one-step synthesis method resulted
in the catalyst with high deactivation resistance and subsequently
higher stability throughout the glycerol-DR reaction (5) h on
stream. It is appreciable that the catalyst activity was just dropped
4% after 5 h in one-step synthesis, while in the co-precipitation
procedure, the activity was reduced by about 10%. This could be
related to the superior textural properties of Ni/MgO.SiO2 (I) cata-
lyst compared to other catalysts (Carrero et al., 2017).
The effect of gas hourly space velocity (GHSV) and inlet
CO2/glycerol molar ratio (CGR) on the glycerol conversion of the
Ni/MgO.SiO2 (I) catalyst was investigated and the results are
shown in Fig. 7f. The results clearly showed a downward trend in
glycerol conversion with increasing GHSV value, indicating a

9
Z. Pirzadi and F. Meshkani
Fig. 8. TPO-O2 analysis for the Ni/MgO.SiO2 catalysts.
negative effect of this parameter on catalytic activity. This phe-
nomenon can be due to decreasing in the time of contact between
active sites and reactants.
As is evident, increasing CO2 entrance molecules resulted in
reducing the conversion of glycerol. It can be explained by RWGS
reaction (Eq. (3)), in which increasing CO2 content in the inlet feed
is beneficial for this reaction. However, the RWGS reaction caused
the consumption of H2 and so reducing glycerol conversion.
Fig. 9. SEM analysis of (a): calcined and (b): spent Ni/MgO.SiO2 (I) catalyst.
10
Chemical Engineering Science 255 (2022) 117676
The long-term stability (25 h) test was conducted over the Ni/
MgO.SiO2 (I) catalyst at 750 °C within 25 h of glycerol-DR
(Fig. 7j). The results show that the catalyst stability was relatively
high until the initial 5 h of the glycerol-DR reaction and then grad-
ually declined with time on stream. It can be related to carbon
accumulation and growth of filaments on the catalyst surface with
time on stream, which led to a decrease in catalyst activity.
4. Characterization of spend catalysts
4.1. Temperature programmed oxidation (TPO-O2) analysis:
The carbon deposition investigation was undertaken on the
reacted catalysts following the glycerol-DR tests by TPO-O2.
Fig. 8 indicates the representative TPO profiles. Relatively similar
profiles were observed for all samples with a difference in the oxi-
dation peak area. TPO profiles revealed two distinct oxidation
regions, which were characterized by a broad hump and one main
oxidation signal. The humps below 350 °C were attributed to the
active type of carbon species (Zhang et al., 2017). This type of car-
bon was not observed in Ni/MgO.SiO2 (IV and V) samples. Major
oxidation peaks situated in the range of 680–700 °C belong to
the nanofilamentous (NF, whisker-like) carbon (Amin et al.,
2017). Therefore, the formed carbon deposits upon the spent Ni/
MgO.SiO2 catalysts were mainly in the form of inert graphitic car-
bon and the highest oxidation peak area (highest carbon amount)
was related to the Ni/MgO.SiO2 (I) sample. On the other hand, from
catalytic and stability experiments’ results, Ni/MgO.SiO2 (I) exhib-
ited higher activity and maintained its catalytic stability during the
reaction better. It seems unlikely. It can be explained by deposited
Z. Pirzadi and F. Meshkani
Fig. 10. EDX spectra and EDX mapping of calcined Ni/MgO.SiO2 (I) catalyst.
carbon species nature. Indeed, NF carbon does not cause the cata-
lyst to deactivate rapidly, because the NF does not encapsulate the
active sites (Ni0 atoms) and reactants can still access them
(Luisetto, 2015). In addition, from the literature (Zhou et al.,
2015; Charisiou et al., 2019), the high-temperature oxidation
signal has been suggested for the carbonaceous species in the form
of transitory intermediate with less toxicity, forming gradually via
transformation of C a and C b species to C c carbon. Mentioned spe-
cies are commonly in the nanofilaments form. As was reported in
the glycerol-DR literature (Charisiou et al., 2019; Wang et al.,
2009), these carbonaceous species do not necessarily cause the
deactivation of the catalyst but could improve catalyst perfor-
mance (Alberton et al., 2007). As can be observed, the type and
amount of deposited carbon over the reacted catalysts differed.
Indeed, the synthesis method can also control the amount and nat-
ure of carbon produced during the reaction by affecting the physic-
ochemical properties and catalytic efficiency.
4.2. SEM/EDX analysis
Representative SEM images of calcined and reacted Ni/MgO.
SiO2 (I) catalysts are presented in Fig. 9. The calcined sample image
(Fig. 9a) exhibited the flat-like nanoscale particles with the shape
of irregular discs placed on each other. As presented in Fig. 9b,
the reacted sample contained two kinds of carbonaceous species;
amorphous carbon with almost spherical form and nanofilaments
carbon, which are seen as intertwined. These results are well con-
sistent with the TPO results. It is also noticeable that, bright points
located at the tip of the filaments were due to nickel species, sug-
gesting filamentous carbon mainly formed via the tip growing
mechanism (Venugopal, 2007). Furthermore, Fig. 9b shows no
change in the surface morphology. EDX element mapping images
and EDX spectrum corresponding to the fresh Ni/MgO.SiO2 (I) cat-
alyst are compiled in Fig. 10. The elemental examination indicated
that Ni, Mg, and Si elements were present in the sample and also
confirmed the high distribution of the Ni nanoparticles on the sur-
face of MgO.SiO2 (V) substrate. These results affirmed the findings
of XRD results.
5. Conclusion
In the present study, the influence of various synthesis routes of
Ni-based catalyst supported on magnesium silicate upon the struc-
tural and physicochemical features was evaluated and led to an
effective procedure. Overall, co-precipitation and hydrothermal
methods were used for preparing catalyst supports and Ni was
attached to the supports with the impregnation technique as well
as simultaneously with preparing support. According to the char-
acterization results, it was concluded that the synthesis method
was a significant effect on the type of porous structure and textural
11
Chemical Engineering Science 255 (2022) 117676
properties of the catalyst. The highest specific surface area and
pore volume belonged to the one-step procedure. On the other
hand, XRD patterns of the mentioned catalyst revealed that the
active species were well dispersed on the surface of the support
with the smallest nickel crystal size in comparison with the other
catalysts. It can be due to the high surface area of its support. The
performance of the catalyst in the glycerol-DR reaction was then
investigated and the results showed different activity and stability
for the catalysts with various synthesis methods. As expected, the
catalyst synthesized by means of one-step method revealed the
excellent performance under the harsh reaction conditions
(GHSV = 7.2  104 mL h1 g-1 cat); higher conversion of glycerol to
gaseous products (50% glycerol conversion at 750 °C), higher yield
toward H2, and higher catalytic stability. The reason could be
related to the high degree of reducibility, higher BET surface area
(411 m2 g1), higher pore volume (0.32 cm3 g1), the small crystal-
lite size (8.5 nm), and high active phase dispersion in this sample
surface. Furthermore, synthesis gas was produced for all catalysts
with an H2/CO ratio of less than 1.6. Ultimately, the one-step syn-
thesis method is an effective procedure for preparing Ni/MgO.SiO2
catalyst and catalyst produced via this method is an appropriate
catalyst for the glycerol-DR process.
Declaration of Competing Interest
The authors declare that they have no known competing finan-
cial interests or personal relationships that could have appeared
to influence the work reported in this paper.
Acknowledgment
The authors gratefully acknowledge the financial support from
the University of Kashan (Grant No. 573921/1).
References
Adam, F., Iqbal, A., 2010. The oxidation of styrene by chromium–silica
heterogeneous catalyst prepared from rice husk. Chem. Eng. J. 160 (2), 742–750.
Albarazi, A., Gálvez, M.E., Da Costa, P., 2015. Synthesis strategies of ceria–zirconia
doped Ni/SBA-15 catalysts for methane dry reforming. Catal. Commun. 59, 108–
112.
Alberton, A.L., Souza, M.M.V.M., Schmal, M., 2007. Carbon formation and its
influence on ethanol steam reforming over Ni/Al2O3 catalysts. Catal. Today 123
(1-4), 257–264.
Amin, R., Liu, B., Ullah, S., Biao, H.Z., 2017. Study of coking and catalyst stability over
CaO promoted Ni-based MCF synthesized by different methods for CH4/CO2
reforming reaction. Int. J. Hydrogen Energy 42 (34), 21607–21616.
Angelici, C., Velthoen, M.E.Z., Weckhuysen, B.M., Bruijnincx, P.C.A., 2014. Effect of
preparation method and CuO promotion in the conversion of ethanol into 1, 3-
Butadiene over SiO2–MgO Catalysts. ChemSusChem 7 (9), 2505–2515.
Arif, N.N.M. et al., 2018. Hydrogen production via CO2 dry reforming of glycerol over
ReNi/CaO catalysts. Int. J. Hydrogen Energy.
Z. Pirzadi and F. Meshkani
Ayodele, B.V., Khan, M.R., Cheng, C.K., 2016. Production of CO-rich hydrogen gas
from methane dry reforming over Co/CeO2 catalyst. Bull. Chem. Reaction Eng.
Catal. 11 (2), 210–219.
Bac, S. et al., 2019. Exceptionally active and stable catalysts for CO2 reforming of
glycerol to syngas. Appl. Catal. B: Environ. 256, 117808.
Bacariza, M.C., Graça, I., Bebiano, S.S., Lopes, J.M., Henriques, C., 2018. Micro-and
mesoporous supports for CO2 methanation catalysts: A comparison between
SBA-15, MCM-41 and USY zeolite. Chem. Eng. Sci. 175, 72–83.
Bartholomew, C.H., Farrauto, R.J., 2011. Fundamentals of Industrial Catalytic
Processes. John Wiley & Sons.
Bobadilla, L. et al., 2015. Glycerol steam reforming on bimetallic NiSn/CeO2–MgO–
Al2O3 catalysts: Influence of the support, reaction parameters and deactivation/
regeneration processes. Appl. Catal. A: General 492, 38–47.
Bulutoglu, P.S. et al., 2018. Dry reforming of glycerol over Rh-based ceria and
zirconia catalysts: New insights on catalyst activity and stability. Appl. Catal. A:
General 564, 157–171.
Carrero, A., Vizcaíno, A.J., Calles, J.A., García-Moreno, L., 2017. Hydrogen production
through glycerol steam reforming using Co catalysts supported on SBA-15
doped with Zr, Ce and La. J. Energy Chem. 26 (1), 42–48.
Charisiou, N.D., Siakavelas, G., Papageridis, K.N., Baklavaridis, A., Tzounis, L.,
Polychronopoulou, K., Goula, M.A., 2017. Hydrogen production via the
glycerol steam reforming reaction over nickel supported on alumina and
lanthana-alumina catalysts. Int. J. Hydrogen Energy 42 (18), 13039–13060.
Charisiou, N.D., Papageridis, K.N., Siakavelas, G., Sebastian, V., Hinder, S.J., Baker, M.
A., Polychronopoulou, K., Goula, M.A., 2019. The influence of SiO2 doping on the
Ni/ZrO2 supported catalyst for hydrogen production through the glycerol steam
reforming reaction. Catal. Today 319, 206–219.
Charisiou, N.D., Papageridis, K.N., Tzounis, L., Sebastian, V., Hinder, S.J., Baker, M.A.,
AlKetbi, M., Polychronopoulou, K., Goula, M.A., 2019. Ni supported on CaO-
MgO-Al2O3 as a highly selective and stable catalyst for H2 production via the
glycerol steam reforming reaction. Int. J. Hydrogen Energy 44 (1), 256–273.
Chen, M., Wang, Y., Yang, Z., Liang, T., Liu, S., Zhou, Z., Li, X., 2018. Effect of Mg-
modified mesoporous Ni/Attapulgite catalysts on catalytic performance and
resistance to carbon deposition for ethanol steam reforming. Fuel 220, 32–46.
Cheng, C.K., et al., 2019. Synthesis and characterization of a LaNi/aAl2O3 catalyst
and its use in pyrolysis of glycerol to syngas.
Da Ros, S., Jones, M.D., Mattia, D., Schwaab, M., Barbosa-Coutinho, E., Rabelo-Neto, R.
C., Noronha, F.B., Pinto, J.C., 2017. Microkinetic analysis of ethanol to 1, 3-
butadiene reactions over MgO-SiO2 catalysts based on characterization of
experimental fluctuations. Chem. Eng. J. 308, 988–1000.
Dan, M., Mihet, M., Lazar, M.D., 2015. Catalytic glycerol steam reforming for
hydrogen production. In: AIP Conference Proceedings. AIP Publishing.
Das, S., Shah, M., Gupta, R.K., Bordoloi, A., 2019. Enhanced dry methane reforming
over Ru decorated mesoporous silica and its kinetic study. J. CO2 Utiliz. 29, 240–
253.
Demsash, H.D., Kondamudi, K.V.K., Upadhyayula, S., Mohan, R., 2018. Ruthenium
doped nickel-alumina-ceria catalyst in glycerol steam reforming. Fuel Process.
Technol. 169, 150–156.
Douy, A., 2002. Aqueous syntheses of forsterite (Mg2SiO4) and enstatite (MgSiO3). J.
Sol-Gel Sci. Technol. 24 (3), 221–228.
Gallegos-Suárez, E. et al., 2015. Efficient and stable Ni–Ce glycerol reforming
catalysts: chemical imaging using X-ray electron and scanning transmission
microscopy. Appl. Catal. B: Environ. 165, 139–148.
Ge, J., Zeng, Z., Liao, F., Zheng, W., Hong, X., Tsang, S.C.E., 2013. Palladium on iron
oxide nanoparticles: the morphological effect of the support in glycerol
hydrogenolysis. Green Chem. 15 (8), 2064. https://doi.org/10.1039/c3gc40712h.
Ghani, N.N.M., Jalil, A.A., Triwahyono, S., Aziz, M.A.A., Rahman, A.F.A., Hamid, M.Y.S.,
Izan, S.M., Nawawi, M.G.M., 2019. Tailored mesoporosity and acidity of shape-
selective fibrous silica beta zeolite for enhanced toluene co-reaction with
methanol. Chem. Eng. Sci. 193, 217–229.
Ghods, B., Meshkani, F., Rezaei, M., 2016. Effects of alkaline earth promoters on the
catalytic performance of the nickel catalysts supported on high surface area
mesoporous magnesium silicate in dry reforming reaction. Int. J. Hydrogen
Energy 41 (48), 22913–22921.
Ghods, B., Rezaei, M., Meshkani, F., 2017. Ni catalysts supported on mesoporous
nanocrystalline magnesium silicate in dry and steam reforming reactions.
Chem. Eng. Technol. 40 (4), 760–768.
Goel, A., Tulyaganov, D.U., Shaaban, E.R., Knee, C.S., Eriksson, S., Ferreira, J.M.F.,
2009. Structure and crystallization behaviour of some MgSiO3-based glasses.
Ceram. Int. 35 (4), 1529–1538.
Harun, N., Gimbun, J., Azizan, M.T., Abidin, S.Z., 2016. Characterization of Ag-
promoted Ni/SiO2 catalysts for syngas production via carbon dioxide (CO2) dry
reforming of glycerol. Bull. Chem. Reaction Eng. Catal. 11 (2), 220. https://doi.
org/10.9767/bcrec.11.2.553.220-229.
Harun, N., Abidin, S.Z., Osazuwa, O.U., Taufiq-Yap, Y.H., Azizan, M.T., 2019.
Hydrogen production from glycerol dry reforming over Ag-promoted Ni/
Al2O3. Int. J. Hydrogen Energy 44 (1), 213–225.
Ikuhara, Y.H., Saito, T., Takahashi, S., Sasaki, Y., Hirayama, T., Gur, T., 2012. Synthesis
and microstructural analysis of homogeneously dispersed nickel nanoparticles
in amorphous silica. J. Am. Ceram. Soc. 95 (2), 524–529.
Jan, O., Song, K., Dichiara, A., Resende, F.L.P., 2019. Oligomerization of supercritical
ethylene over nickel-based silica-alumina catalysts. Chem. Eng. Sci. 197, 212–
222.
Janssens, W., Makshina, E.V., Vanelderen, P., De Clippel, F., Houthoofd, K., Kerkhofs,
S., Martens, J.A., Jacobs, P.A., Sels, B.F., 2015. Ternary Ag/MgO-SiO2 Catalysts for
the Conversion of Ethanol into Butadiene. ChemSusChem 8 (6), 994–1008.
12
Chemical Engineering Science 255 (2022) 117676
Kim, T.-W., Kim, M.-C., Yang, Y.-C., Kim, J.-R., Jeong, S.-Y., Kim, C.-U., 2015. Hydrogen
production via the aqueous phase reforming of polyols over CMK-9 mesoporous
carbon supported platinum catalysts. Int. J. Hydrogen Energy 40 (44), 15236–
15243.
Klapiszewski, L. et al., 2018. Magnesium silicate conjugated with calcium
lignosulfonate: In situ synthesis and comprehensive physicochemical
evaluations. Physicochem. Problems Mineral Process. 54 (3), 793–802.
Lee, H.-J., Shin, G.S., Kim, Y.-C., 2015. Characterization of supported Ni catalysts for
aqueous-phase reforming of glycerol. Korean J. Chem. Eng. 32 (7), 1267–1272.
Lee, H.C., Siew, K.W., Gimbun, J., Cheng, C.K., 2014. Synthesis and characterisation of
cement clinker-supported nickel catalyst for glycerol dry reforming. Chem. Eng.
J. 255, 245–256.
Li, E., Rudolph, V., 2008. Transesterification of vegetable oil to biodiesel over MgO-
functionalized mesoporous catalysts. Energy Fuels 22 (1), 145–149.
Li, S., Savage, P.E., Guo, L., 2019. Stability and activity maintenance of sol-gel Ni-
MxOy (M= Ti, Zr, Ta) catalysts during continuous gasification of glycerol in
supercritical water. J. Supercritical Fluids 148, 137–147.
Lin, L., Min, Y., Chaoshu, S., Weiping, Z., Baogui, Y., 2006. Synthesis and
luminescence properties of red phosphors: Mn2+ doped MgSiO3 and Mg2SiO4
prepared by sol-gel method. J. Rare Earths 24 (1), 104–107.
Liu, Z. et al., 2012. Highly dispersed nickel loaded on mesoporous silica: One-spot
synthesis strategy and high performance as catalysts for methane reforming
with carbon dioxide. Appl. Catal. B: Environ. 125, 324–330.
Liu, Y., Farrauto, R., Lawal, A., 2013. Autothermal reforming of glycerol in a dual
layer monolith catalyst. Chem. Eng. Sci. 89, 31–39.
Lu, Y., Guo, D., Ruan, Y., Zhao, Y., Wang, S., Ma, X., 2018. Facile one-pot synthesis of
Ni@ HSS as a novel yolk-shell structure catalyst for dry reforming of methane. J.
CO2 Utiliz. 24, 190–199.
Luisetto, I. et al., 2015. Ni/CeO2–Al2O3 catalysts for the dry reforming of methane:
the effect of CeAlO3 content and nickel crystallite size on catalytic activity and
coke resistance. Appl. Catal. A: General 500, 12–22.
Ma, W., Meng, F., Cheng, Z., Xin, G., Duan, S., 2015. Synthesis of macroporous silica
biomass nanocomposite based on XG/MgSiO3 for the removal of toxic ions.
Bioresour. Technol. 186, 356–359.
Makshina, E.V., Janssens, W., Sels, B.F., Jacobs, P.A., 2012. Catalytic study of the
conversion of ethanol into 1, 3-butadiene. Catal. Today 198 (1), 338–344.
Mohd Arif, N.N., Vo, D.-V., Azizan, M.T., Abidin, S.Z., 2016. Carbon dioxide dry
reforming of glycerol for hydrogen production using Ni/ZrO2 and Ni/CaO as
catalysts. Bull. Chem. Reaction Eng. Catal. 11 (2), 200. https://doi.org/10.9767/
bcrec.11.2.551.200-209.
Mohd Arif, N.N., Abidin, S.Z., Osazuwa, O.U., Vo, D.-V., Azizan, M.T., Taufiq-Yap, Y.H.,
2019. Hydrogen production via CO2 dry reforming of glycerol over ReNi/CaO
catalysts. Int. J. Hydrogen Energy 44 (37), 20857–20871.
Moura-Nickel, C.D., Tachinski, C.G., Landers, R., De Noni, A., Virmond, E., Peterson,
M., Moreira, R.d.F.P.M., José, H.J., 2019. Syngas production by dry reforming of
methane using lyophilized nickel catalysts. Chem. Eng. Sci. 205, 74–82.
Mourhly, A. et al., 2018. New low cost mesoporous silica (MSN) as a promising
support of Ni-catalysts for high-hydrogen generation via dry reforming of
methane (DRM). Int. J. Hydrogen Energy.
Nanda, S., Rana, R., Hunter, H.N., Fang, Z., Dalai, A.K., Kozinski, J.A., 2019.
Hydrothermal catalytic processing of waste cooking oil for hydrogen-rich
syngas production. Chem. Eng. Sci. 195, 935–945.
Narasimharao, K., Ali, T.T., Bawaked, S., Basahel, S., 2014. Effect of Si precursor on
structural and catalytic properties of nanosize magnesium silicates. Appl. Catal.
A: General 488, 208–218.
Paul, M., Pal, N., Mondal, J., Sasidharan, M., Bhaumik, A., 2012. New mesoporous
magnesium–aluminum mixed oxide and its catalytic activity in liquid phase
Baeyer-Villiger oxidation reaction. Chem. Eng. Sci. 71, 564–572.
Pongjanyakul, T., Khunawattanakul, W., Puttipipatkhachorn, S., 2009.
Physicochemical characterizations and release studies of nicotine–magnesium
aluminum silicate complexes. Appl. Clay Sci. 44 (3-4), 242–250.
Qin, H., Guo, C., Sun, C., Zhang, J., 2015. Influence of the support composition on the
hydrogenation of methyl acetate over Cu/MgO-SiO2 catalysts. J. Mol. Catal. A:
Chem. 409, 79–84.
Rastegarpanah, A., Meshkani, F., Rezaei, M., 2017. Thermocatalytic decomposition of
methane over mesoporous nanocrystalline promoted Ni/MgOAl2O3 catalysts.
Int. J. Hydrogen Energy 42 (26), 16476–16488.
Rastegarpanah, A., Meshkani, F., Rezaei, M., 2017. COx-free hydrogen and carbon
nanofibers production by thermocatalytic decomposition of methane over
mesoporous MgOAl2O3 nanopowder-supported nickel catalysts. Fuel Process.
Technol. 167, 250–262.
Sad, M.E., Duarte, H.A., Vignatti, C.h., Padró, C.L., Apesteguía, C.R., 2015. Steam
reforming of glycerol: Hydrogen production optimization. Int. J. Hydrogen
Energy 40 (18), 6097–6106.
Siew, K.W., Lee, H.C., Gimbun, J., Cheng, C.K., 2014. Characterization of La-promoted
Ni/Al2O3 catalysts for hydrogen production from glycerol dry reforming. J.
Energy Chem. 23 (1), 15–21.
Siew, K.W., Lee, H.C., Gimbun, J., Cheng, C.K., 2014. Production of CO-rich hydrogen
gas from glycerol dry reforming over La-promoted Ni/Al2O3 catalyst. Int. J.
Hydrogen Energy 39 (13), 6927–6936.
Siew, K.W., Lee, H.C., Khan, M.R., Gimbun, J., Cheng, C.K., 2015. CO2 reforming of
glycerol over La-Ni/Al2O3 catalyst: A longevity evaluative study. J. Energy Chem.
24 (3), 366–373.
Siew, K.W., Lee, H.C., Gimbun, J., Chin, S.Y., Khan, M.R., Taufiq-Yap, Y.H., Cheng, C.K.,
2015. Syngas production from glycerol-dry (CO2) reforming over La-promoted
Ni/Al2O3 catalyst. Renew. Energy 74, 441–447.
Z. Pirzadi and F. Meshkani
Sing, K.S., 1985. Reporting physisorption data for gas/solid systems with special
reference to the determination of surface area and porosity (Recommendations
1984). Pure Appl. Chem. 57 (4), 603–619.
Skrzyńska, E., El Roz, A., Paul, S., Capron, M., Dumeignil, F., 2019. Glycerol Partial
Oxidation over Pt/Al2O3 Catalysts under Basic and Base-Free Conditions—Effect
of the Particle Size. J. Am. Oil. Chem. Soc. 96 (1), 63–74.
Sun, W.W. et al., 2014. Double Sealing of Ultrasonic Micro-arc Oxidation Coating on
Pure Magnesium by Nano-SiO2 particles and SiO2 Sol Sealing Agent. Advanced
Materials Research. Trans Tech Publ.
Sun, P., Xu, L., Li, J., Zhai, P., Zhang, H., Zhang, Z., Zhu, W., 2018. Hydrothermal
synthesis of mesoporous Mg3Si2O5(OH) 4 microspheres as high-performance
adsorbents for dye removal. Chem. Eng. J. 334, 377–388.
Takahashi, R., Sato, S., Sodesawa, T., Yoshida, M., Tomiyama, S., 2004. Addition of
zirconia in Ni/SiO2 catalyst for improvement of steam resistance. Appl. Catal. A:
General 273 (1-2), 211–215.
Tavanarad, M., Meshkani, F., Rezaei, M., 2018. Synthesis and application of Noble
metal Nanocatalysts supported on MgAl2O 4 in glycerol dry reforming reaction.
Catal. Lett. 148 (1), 164–172.
Tavanarad, M., Meshkani, F., Rezaei, M., 2018. Production of syngas via glycerol dry
reforming on Ni catalysts supported on mesoporous nanocrystalline Al2O3. J.
CO2 Utiliz. 24, 298–305.
Thyssen, V.V., Georgetti, F., Assaf, E.M., 2017. Influence of MgO content as an
additive on the performance of Ni/MgOSiO2 catalysts for the steam reforming of
glycerol. Int. J. Hydrogen Energy 42 (27), 16979–16990.
Thyssen, V.V., Sartore, D.M., Assaf, E.M., 2019. Effect of preparation method on the
performance of Ni/MgOSiO2 catalysts for glycerol steam reforming. J. Energy
Inst. 92 (4), 947–958.
Venugopal, A. et al., 2007. Hydrogen production by catalytic decomposition of
methane over Ni/SiO2. Int. J. Hydrogen Energy 32 (12), 1782–1788.
Wang, Y. et al., 2018. Bimetallic Ni-M (M= Co, Cu and Zn) supported on attapulgite
as catalysts for hydrogen production from glycerol steam reforming. Appl. Catal.
A: General 550, 214–227.
13
Chemical Engineering Science 255 (2022) 117676
Wang, X., Li, M., Wang, M., Wang, H., Li, S., Wang, S., Ma, X., 2009. Thermodynamic
analysis of glycerol dry reforming for hydrogen and synthesis gas production.
Fuel 88 (11), 2148–2153.
Wess, R., Nores-Pondal, F., Laborde, M., Giunta, P., 2015. Single stage H2 production,
purification and heat supply by means of sorption-enhanced steam reforming of
glycerol. A thermodynamic analysis. Chem. Eng. Sci. 134, 86–95.
Xu, B.-Q., Wei, J.-M., Wang, H.-Y., Sun, K.-Q., Zhu, Q.-M., 2001. Nano-MgO: novel
preparation and application as support of Ni catalyst for CO2 reforming of
methane. Catal. Today 68 (1-3), 217–225.
Yin, A., Guo, X., Dai, W.-L., Fan, K., 2009. The nature of active copper species in Cu-
HMS catalyst for hydrogenation of dimethyl oxalate to ethylene glycol: New
insights on the synergetic effect between Cu0 and Cu+. J. Phys. Chem. C 113 (25),
11003–11013.
Zamzuri, N.H., Mat, R., Saidina Amin, N.A., Talebian-Kiakalaieh, A., 2017. Hydrogen
production from catalytic steam reforming of glycerol over various supported
nickel catalysts. Int. J. Hydrogen Energy 42 (14), 9087–9098.
Zhang, H. et al., 2013. Structure and catalytic performance of Mg-SBA-15-supported
nickel catalysts for CO2 reforming of methane to syngas. Chem. Eng. Technol. 36
(10), 1701–1707.
Zhang, L.i., Wang, X., Chen, C., Zou, X., Ding, W., Lu, X., 2017. Dry reforming of
methane to syngas over lanthanum-modified mesoporous nickel aluminate/c-
alumina nanocomposites by one-pot synthesis. Int. J. Hydrogen Energy 42 (16),
11333–11345.
Zhou, R. et al., 2019. On the reactivity of carbon formed from CO CVD over Ni (1 1 1)/
TiO2. Chem. Eng. Sci. 194, 22–28.
Zhou, L.u., Li, L., Wei, N., Li, J., Basset, J.-M., 2015. Effect of NiAl2O4 formation on Ni/
Al2O3 stability during dry reforming of methane. ChemCatChem 7 (16), 2508–
2516.
Zhu, Q., Wang, B., Tan, T., 2017. Conversion of ethanol and acetaldehyde to
butadiene over MgO–SiO2 catalysts: effect of reaction parameters and
interaction between MgO and SiO2 on catalytic performance. ACS Sustain.
Chem. Eng. 5 (1), 722–733.