i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5

Available online at www.sciencedirect.com

ScienceDirect

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

Enhanced activity and stability of SO42¡/ZrO2 by

addition of Cu combined with CuZnOZrO2 for direct
synthesis of dimethyl ether from CO2
hydrogenation

Thongthai Witoon a,b,*, Thanapha Numpilai c, Napaphut Dolsiririttigul a,b,

Narong Chanlek d, Yingyot Poo-arporn d, Chin Kui Cheng e,
Bamidele Victor Ayodele f, Metta Chareonpanich a,b, Jumras Limtrakul g
a
Center of Excellence on Petrochemical and Materials Technology, Department of Chemical Engineering, Faculty of
Engineering, Kasetsart University, Bangkok, 10900, Thailand
b
Center for Advanced Studies in Nanotechnology for Chemical, Food and Agricultural Industries, KU Institute for
Advanced Studies, Kasetsart University, Bangkok, 10900, Thailand
c
Department of Environmental Science, Faculty of Science and Technology, Thammasat University, Pathumthani,
12120, Thailand
d
Synchrotron Light Research Institute, Nakhon Ratchasima, 30000, Thailand
e
Center for Catalysis and Separation (CeCaS), Department of Chemical Engineering, College of Engineering, Khalifa
University, P.O. Box 127788, Abu Dhabi, United Arab Emirates
f
Chemical Engineering Department, Universiti Teknologi PETRONAS, 32610 Seri Iskandar, Malaysia
g
Department of Materials Science and Engineering, School of Molecular Science and Engineering, Vidyasirimedhi
Institute of Science and Technology, Rayong, 21210, Thailand

highlights graphical abstract

The Cu addition on SO2

4 eZrO2

remarkably reduced the number of

strong acid sites.

Less amount of coke formation
was observed on Cu-modified SO2
4

eZrO2 catalysts.

Cu0 formed after H2 pretreatment
promoted undesired CH4.

Cu0 was converted to Cu2S during
the reaction which reduced the
CH4 formation.

The decrease of CH4 was accom-
panied by the increase of DME
formation.

* Corresponding author. Center of Excellence on Petrochemical and Materials Technology, Department of Chemical Engineering, Faculty
of Engineering, Kasetsart University, Bangkok, 10900, Thailand.
E-mail address: fengttwi@ku.ac.th (T. Witoon).
https://doi.org/10.1016/j.ijhydene.2022.03.150
0360-3199/© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5 41375

article info abstract

Article history: Cu-modified SO42/ZrO2 catalysts (XCu-SZ) with different Cu loading contents were pre-
Received 1 February 2022 pared by sulfation of ZrOCl2$8H2O with (NH4)2SO4 to form SO42/ZrO2 (SZ) followed by
Received in revised form impregnation of SZ with a Cu precursor. The resulting XCu-SZ catalysts combined with a
7 March 2022 CuOeZnOeZrO2 catalyst were tested for CO2 hydrogenation to dimethyl ether (DME). The
Accepted 15 March 2022 results indicated that the unmodified SZ catalyst exhibited the maximum DME yield (3.7%)
Available online 7 April 2022 which was 2.0e2.6 times higher than the DME yield of all XCu-SZ catalysts at the beginning
of reaction. However, the DME yield over the unmodified SZ catalyst rapidly decreased,
Keywords: while that of all XCu-SZ catalysts gradually increased during the time-on-stream experi-
Greenhouse gases ment. After 100 h, the 6 wt% Cu-modified SZ catalyst achieved the maximum DME yield of
CO2 utilization 3.2% at 260  C and 20 bar, while the DME yield of the unmodified SZ catalyst was only 2.5%.
CO2 hydrogenation The NH3-TPD and XPS analyses indicated that more strong acid sites were present on the
Dimethyl ether unmodified SZ catalyst, resulting in a coke formation and thus the rapid deactivation. For
Cu-modified sulfated zirconia the XCu-SZ catalysts, Cu0 was formed on the surface of SZ after the reduction with H2
which accounted for the active site of hydrogenolysis of methanol to methane. During the
time-on-stream experiment, Cu0 was progressively transformed to Cu2S through
poisoning, leading to the continued increase of DME yield.
© 2022 Hydrogen Energy Publications LLC. Published by Elsevier Ltd. All rights reserved.

formation and thus lowering the methanol selectivity. As a

Introduction
The continued increase of CO2 concentration level in the at-
mosphere has been recognized as the main cause of climate
change [1,2]. CO2 is mainly released from coal burning power
plant, chemical industries, brewery, natural gas separation,
cement and steel plants [3]. The reduction of CO2 emissions
can be accomplished by improvement of energy efficiency,
use of renewable energy sources such as sunlight, wind and
water instead of coal combustion and implementation of
carbon capture utilization and storage (CCUS) [3,4]. The pro-
duction of electricity from the renewable energy sources
needs energy storage systems. However, there is a lack of
efficient energy storage technologies and efficient trans-
portation of stored energy. To overcome this problem in short-
term, the electricity can be converted to H2 via electrolysis of
water [5,6]. The produced H2 can be combined with the
released CO2 to form small molecules such as methanol and
dimethyl ether (DME) which can be transported and utilized
by using existing infrastructures. DME appears to be more
suitable as an alternative fuel because DME contains higher
lower heating value (28.62 MJ/kg) and cetane number (55e60)
compared to 19.99 MJ/kg and 5 of methanol [7,8], respectively,
which can attain a higher market value.
There are two main steps in the conversion of CO2 to DME.
The first step is the reaction of CO2 with H2 to produce
methanol (reaction 1) using methanol synthesis catalysts
which can be classified into low-temperature (Cu-based
catalysts) [9e11] and high-temperature methanol synthesis
catalysts (In2O3-based catalysts and ZnO-based catalysts)
[12e14]. As the CO2 conversion to methanol is exothermic
reaction, the thermodynamic equilibrium limited the meth-
anol formation at high reaction temperature. In addition,
reverse water gas shift (reaction 2), a side reaction, become
dominant which leads to a considerable increase of CO
result, Cu-based catalysts such as CuZnOAl2O3 and
CuZnOZrO2 are more suitable as the methanol synthesis
catalyst. The final step is the dehydration of produced
methanol to form DME (reaction 3) over acid catalysts such as
g-Al2O3 [15], zeolites [16e18], SO42/ZrO2 [19e21] and WOx/
ZrO2 [21,22]. Our previous work [19] compared two different
bifunctional catalysts including CuZnOZrO2eSO42/ZrO2 and
CuZnOZrO2eHZSM-5 for the production of DME from CO2
hydrogenation. The CuZnOZrO2eSO42/ZrO2 catalyst was
found to be more active than CuZnOZrO2eHZSM-5 catalyst at
the initial stage of time-on-stream experiment. However, the
CuZnOZrO2eSO42/ZrO2 catalyst showed a faster decline in
DME yield. It is postulated that a loss of sulfate ions on the
surface of ZrO2 by leaching with water vapor is a main reason
[19,23]. In addition, the deactivation of SO42/ZrO2 could be
caused by a coke formation [24]. Due to its high activity, the
improvement of the stability of SO42/ZrO2 is of great
interest.
Decoration of SO42/ZrO2 with transition metals could alter
the activity, selectivity and stability of reactions [25e27].
Alvarez et al. [27] reported that the addition of Pt onto SO42/
ZrO2 could alleviate the coke formation and thus enhancing
the stability in n-butane isomerization. Indovina et al. [25,28]
studied the effect of sulfate precursors including (NH4)2SO4,
Na2SO4 and CuSO4 in the preparation of SO42/ZrO2 for the
reduction of NO by propene under oxygen-rich system. Both
(NH4)2SO4/ZrO2 and CuSO4/ZrO2 were found to be active for
such reaction. However, compared to (NH4)2SO4/ZrO2, CuSO4/
ZrO2 exhibited several advantages including CO formed in less
amount, no coke formation and constant catalytic activity.
Due to the low-cost of Cu and its positive effects, it appeared
interesting to explore the behavior of Cu-modified SO42/ZrO2
catalysts for CO2 hydrogenation to dimethyl ether. In the
present work, SO42/ZrO2 catalyst was initially prepared by
sulfation of ZrOCl2$8H2O with NH2(SO)4 because this method
41376 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5

was simple and used no solvent [19]. The Cu-promoted SO42/
ZrO2 catalysts with different Cu loading contents (2e10 wt%)
were obtained by an impregnation of SO42/ZrO2 with Cu
precursor. The physicochemical properties of SO42/ZrO2 and
CueSO42/ZrO2 were thoroughly investigated. The resulting
CueSO42/ZrO2 catalysts were combined with a CuZnOZrO2
catalyst and their catalytic performance in CO2 hydrogenation
to dimethyl ether was examined.
Experimental
Catalyst preparation
Preparation of a CuOeZnOeZrO2 catalyst
A CuOeZnOeZrO2 catalyst with atomic Cu:Zn:Zr ratio of 4:3:3
was prepared by a reverse co-precipitation method as
described in our previous study [29]. The metal composition
(Cu:Zn:Zr) of the resulting catalyst examined with ICP tech-
nique was 4:3:3.47.
Preparation of SO42/ZrO2 (SZ) and Cu-modified SO42/ZrO2
catalysts (XCu-SZ)
Solvent-free method was employed for a SZ catalyst prepa-
ration [19]. In brief, ZrOCl2$8H2O and (NH4)2SO4 were put
together into agate mortar and ground for 20 min at room
temperature and further storing for 24 h. Subsequently, the
sample was calcined at 550  C for 5 h. A series of XCu-SZ
catalysts were prepared by impregnating SZ catalyst with
corresponding Cu(NO3)2$3H2O aqueous solution to yield the
desired Cu loading of 2, 4, 6, 8 and 10 wt%. The resulting slurry
was stirred at 60  C for 4 h, followed by drying at 100  C
overnight. At last, the sample was calcined at 550  C for 2 h.
Catalyst characterization
He (75 mL min1) for 1 h, followed by He flushing for 1 h to
evacuate the weakly adsorbed molecule. The NH3 desorption
profiles were recorded with TCD by raising the temperature to
500  C under He flow (75 mL min1) at a ramp rate of
10  C min1.
Cu K-edge (8979 eV) and S K-edge (2472 eV) X-ray absorp-
tion near-edge structure (XANES) spectra were acquired at
beamline 5.2 of the Synchrotron Light Research Institute
(SLIRI), Thailand. The data were taken in the transmission
mode using Ge (220) and InSb (111) monochromators for Cu K-
edge and S K-edge, respectively. The Cu foil, CuO, Cu2O, CuSO4
and Zr(SO4)2 were used as reference samples. The background
subtraction, spectra normalization, and linear-combination
fitting (LCF) analyses were processed using the ATHENA
software package.
X-ray photoelectron spectroscopy (XPS) analysis was
attained on a PHI 5000 Versa Probe II equipped with a mono-
chromated Al Ka excitation source (hn ¼ 1486.6 eV) at beam-
line 5.3 of the Synchrotron Light Research Institute (SLIRI),
Thailand. All of the obtained spectra were calibrated to the
binding energy of the C 1s signal at 284.8 eV.
Catalytic activity test
The direct CO2 hydrogenation to dimethyl ether was tested in
a fixed-bed tubular reactor containing two catalyst zones
(Fig. 1). The first zone on the top of reactor was contained a
physical mixture of 0.25 g of CuOeZnOeZrO2 (methanol syn-
thesis catalyst) and 0.75 g of SiO2 sand, while the second zone
was packed with 0.5 g of Cu-modified SO42/ZrO2 catalyst.
Prior to the reaction, pure N2 (60 mL min1) was fed into
the reactor and the reactor temperature was raised from
room temperature to 100  C and hold at that temperature for
30 min to remove a physical adsorption of moisture. Then
pure N2 was switched to pure H2 (60 mL min1) and the

X-ray diffraction (XRD) of calcined SZ and XCu-SZ catalysts

were collected on a Bruker D8 Advance powder diffractometer
with Cu Ka radiation (l ¼ 1.5406
A). The 2q range was scanned
over the range 10  2q  75 with a step size of 0.02 .
Scanning electron microscope (FEI Quanta 450) and trans-
mission electron microscope (JEOL JSM-2100) were used to
examine the morphological structure and Cu distribution of
SZ and 6Cu-SZ catalysts.
H2 temperature-programmed reduction (H2-TPR) was pro-
ceeded in a U-tube quartz reactor on an AutoChem II 2920
Micromeritics analyzer equipped with a thermal conductivity
detector (TCD). Initially, 0.1 g of sample was heated from room
temperature to 150  C in a flowing stream of high-purity Ar
(50 mL min1) and held for 30 min. After cooling to 50  C, a flow
of 10% H2/Ar gas (50 mL min1) was introduced, and the
temperature was simultaneously raised to 550  C with a
heating rate of 10  C min1.
The catalyst acidity was examined by temperature pro-
grammed desorption of ammonia (NH3-TPD) in the same
apparatus of the H2-TPR experiment. For each measurement,
0.1 g of sample was heated up to 550  C in a He flow
(75 mL min1) at a ramping rate of 10  C min1, and remained
for 1 h to clean the catalyst surface. After lowering the tem- Fig. 1 e Schematic illustration of a fixed-bed tubular reactor
perature to 100  C, the sample was exposed to 0.2% v/v NH3 in packed with two catalyst zones.
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5
reactor temperature was increased from 100  C to 300  C and
hold at that temperature for 4 h under atmospheric pressure
to reduce CuOeZnOeZrO2 catalyst. Subsequently, the
reactor temperature was cooled down to 260  C and pure H2
gas was altered to a gas mixture (67.5 mL min1) containing
H2/CO2/N2 in the molar ratio of 3:1:0.5, and the reactor was
gradually pressurized to 20 bar. Two gas chromatographs
(GC) were used for analyzing the exit gas stream. GC-14B
installed with a thermal conductivity detector was
employed to detect CO2, CO, H2 and N2. GC-8A connected
with a flame ionization detector was used to analyze
methanol, DME and other hydrocarbons. The catalytic per-
formance data was determined based on a carbon balance
using an average of three independent measurements. The
CO2 conversion, selectivity of CO, methanol, DME and CH4
and yield of CO, methanol, DME and CH4 are defined ac-
cording to the equations (1)e(6):
nproducts  100
CO2 conversionð%Þ ¼
nproducts þ moles CO2;out
X
n function of time-on-stream experiment which was accom-
nproducts ¼ moles COout þ moles CH4;out þ i
i¼1
 moles of oxygenatei;out ; i
¼ atomic number of carbon
moles COout  100
SCO ð%Þ ¼
nproducts
moles CH4;out  100
SCH4 ð%Þ ¼
nproducts
i  moles of oxygenatei;out  100
Soxygenatei ð%Þ ¼
nproducts
Yield of Producti ¼ CO2 conversion  Sproducti  100
where S is the selectivity of products.
Results and discussion
Catalytic activity test
As shown in Fig. 1, CO2 was converted to CH3OH and CO over
CueZnOeZrO2 catalyst (zone 1) according to CO2 hydroge-
nation to methanol (reaction 1) and reverse water gas shift
reaction (reaction 2), respectively. The CO and CH3OH prod-
ucts and remaining CO2 and H2 from the catalyst zone 1
underwent to the catalyst zone 2, which could be catalyzed
by metallic and acid functions of Cu-modified SO24 /ZrO2 to
form many products as shown in Reactions (2)e(6). Reactions
3, 4, 5 and 6 were CH3OH dehydration, CO methanation,
CH3OH decomposition and hydrogenolysis of CH3OH to CH4
[30], respectively.
CO2 þ 3H2 /CH3 OH þ H2 O
41377
CO2 þ H2 /CO þ H2 O (Reaction 2)
2CH3 OH / CH3 OCH3 þ H2 O (Reaction 3)
CO þ 2H2 /CH4 þ H2 O (Reaction 4)
CH3 OH / CO þ 2H2 (Reaction 5)
CH3 OH þ 2H2 /CH4 þ 2H2 O (Reaction 6)
Fig. 2 shows yields of different products including DME
(Fig. 2a), CH3OH (Fig. 2b), CO (Fig. 2c) and CH4 (Fig. 2d) derived
from CO2 hydrogenation over two catalyst zones containing
CuOeZnOeZrO2 (zone 1) and different XCu/SO42eZrO2 cata-
lysts (zone 2). Because the zone 1 used the identical
CuOeZnOeZrO2 catalyst for all experiments, the difference in
the catalytic performance was attributed to the XCu/
SO42eZrO2 catalysts. As shown in Fig. 2a, the SO42eZrO2
(1)
catalyst (SZ) provided the highest DME yield of 3.7% at the
initial reaction. However, the DME yield steadily declined as a
panied by an increase of CH3OH yield (Fig. 2b), indicating the
deterioration of the acid function of the SO42eZrO2 catalyst.
After 100 h time-on-stream experiment, the DME yield
(2)
reduced to 2.5%.
Incorporating Cu into SO42eZrO2 catalyst remarkably
changed the DME yield as a function of time-on-stream. At the
(3)
beginning of the reaction, the DME yield of 2Cu-SZ, 4Cu-SZ,
6Cu-SZ, 8Cu-SZ and 10Cu-SZ was found to be 1.6%, 1.3%, 1.8%,
1.8%, and 1.8%, respectively, which were lower than that of
(4)
the unmodified SO42eZrO2 catalyst (SZ). However, the DME
yield of all Cu/SO42eZrO2 catalysts gradually increased with
time-on-stream experiment and tended to be stable after 40 h
(5)
time-on-stream experiment. After 100 h time-on-stream
experiment, the DME yield of all Cu/SO42eZrO2 catalysts
(6) (except that of 2Cu-SZ) was higher than that of the SZ catalyst,
and the maximum DME yield of 3.2% was achieved over the
6Cu-SZ catalyst. In addition, the formation of CH4 was
observed for the Cu-modified SO42eZrO2 catalysts at Cu
loading content higher 2 wt% (Fig. 2c). The amount of pro-
duced CH4 at the beginning of the reaction increased with
ascending the Cu loading contents and declined as a function
of time-on-stream. Since CH3OH was the intermediates for
both DME (reaction 3) and CH4 (reaction 6) production, the
increased DME (Fig. 2a) in an expense of CH3OH (Fig. 2b) and
CH4 (Fig. 2c) indicates the transformation of active sites for
CH4 production to DME production during the reaction.
Fig. 2d depicts the CO yield over CuOeZnOeZrO2 catalyst
(zone 1) connected with different XCu/SO42eZrO2 catalysts
(zone 2). The SZ catalyst exhibited the lowest CO yield in the
catalyst series. In fact, most CO was produced via reverse
water gas shift reaction (reaction 2) over CuOeZnOeZrO2
catalyst. The higher CO formation was likely associated with
the enhancement of side reactions, e.g., CH3OH decomposi-
tion (reaction 5) and reverse water gas shift reaction (reaction
(Reaction 1) 2) over Cu/SO42eZrO2 catalysts.
41378 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5

Fig. 2 e Yield of DME (a), CH3OH (b), CH4 (c) and CO (d) over two catalyst zones containing CuOeZnOeZrO2 and different XCu/
SO2¡
4 eZrO2 catalysts.

Catalyst characterization
Fig. 3 shows the XRD pattern of the different XCu/SO42eZrO2
catalysts. The XRD pattern of SZ catalyst exhibited mixed
tetragonal and monoclinic ZrO2 phases. Impregnating Cu at
2e4 wt% into SZ (2Cu-SZ and 4Cu-SZ) enhanced the forma-
tion of monoclinic ZrO2 phase. However, the tetragonal ZrO2
phase became more dominant when Cu loading content
>4 wt% (6Cu-SZ, 8Cu-SZ and 10Cu-SZ). The diffraction lines
of Cu compounds were not visible for 2e8 wt% Cu-loaded
SO42eZrO2, suggesting that Cu species was highly
dispersed on the catalyst surface. However, the diffraction
lines corresponding to CuSO4 appeared for 10 wt% Cu-loaded
SO42eZrO2, suggesting that a part of sulfate groups was
unbound from the ZrO2 surface, which was then reacted with
Cu species to form CuSO4.
The tangible structure of SZ and representative 6Cu-SZ
samples was revealed by means of SEM and TEM. As shown in
Fig. 4, SEM image of SZ displayed a rough surface with an
abundance of voids. Impregnating Cu onto SZ did not notably
make alterations to the morphological structure of the SZ
catalyst. The dispersion of Cu over the surface of SZ was
further examined with SEM-EDS analysis (Fig. 5). It was found
that the Cu element was well-dispersed throughout the sur-
face of 6Cu-SZ sample. TEM image (Fig. 6) of SZ showed a
lattice fringe with a spacing of 0.295 nm which could be
indexed to the 1 0 1 plane of tetragonal ZrO2. In addition to the
tetragonal ZrO2, lattice fringes with spacing of 0.318 nm and
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5
Fig. 3 e XRD pattern of calcined SZ and XCu/SO2¡
4 eZrO2
catalysts.
0.234 nm matched to the 1 3 1 plane of CuSO4 and 1 1 1 plane of
CuO could be visible after impregnation of SZ with Cu (6Cu-
SZ).
In order to investigate the Cu species especially for 2e8 wt
% Cu-loaded SO42eZrO2 catalysts, X-ray absorption near edge
structure (XANES) was performed. The Cu K-edge XANES
spectra of all Cu-loaded SO42eZrO2 catalysts, CuO, Cu2O and
CuSO4 are presented in Fig. 7a. The Cu K-edge XANES spec-
trum of 2Cu-SZ, 4Cu-SZ and 6Cu-SZ resembled that of CuSO4
reference. Further increasing Cu loading contents (8Cu-SZ and
10Cu-SZ) altered the Cu K-edge XANES spectra as the white
Fig. 4 e SEM images of SZ and 6Cu-SZ catalysts.
41379
line intensity decreased and the edge position shifted towards
that of CuO. Linear combination fitting (LCF) using CuO, Cu2O
and CuSO4 as references was used to determine the Cu species
content for each sample. As shown in Fig. 7b, CuSO4 was
found to be predominant phase (95%) for 2 wt% Cu-loaded
SO42eZrO2 and it gradually decreased with increasing Cu
loading content. This was accompanied by an increase of CuO
phase.
The temperature programmed reduction of SZ and XCu/
SO42eZrO2 catalysts with H2 was performed to investigate
the reducibility of Cu species in the XCu/SO42eZrO2 cata-
lysts (Fig. 8). The H2-TPR signal ranging from 200 to 550  C of
SZ sample was found to be almost zero, suggesting that there
was no H2 consumption for SO42eZrO2 as well as sulfate
ions bounded to ZrO2 were not reduced by H2. After modifi-
cation of SO42eZrO2 with 2 wt% Cu (2Cu-SZ), a small amount
of H2 consumption ranging from 380 to 420  C was observed
which could be assigned to a reduction of CuSO4 to Cu0 [31]. A
prominent H2 consumption was visible at a temperature
higher than 500  C, which was likely associated with the
removal of sulfate ions bounded to ZrO2. The result suggests
that the presence of Cu0 can catalyze the reduction of
SO42eZrO2 to occur at a lower temperature compared to that
of the unpromoted SO42eZrO2 (SZ). Increasing Cu loading
content to 4 wt% (4Cu-SZ) displayed an additional H2 con-
sumption peak at 280e300  C. This peak became more pre-
dominant with increasing Cu loading contents which was
strongly related to the increase of CuO phase as indicated by
XANES analysis (Fig. 7b). Note that the amount of CuO phase
in the 2Cu-SZ sample was too low to display a clear peak in
H2-TPR analysis. Because CuOeZnOeZrO2 (zone 1) and SZ
and XCu/SO42eZrO2 (zone 2) were reduced with H2 at 300  C
for 4 h, the CuO phase in XCu/SO42eZrO2 (zone 2) was
converted to Cu0 prior to the reaction, while CuSO4 remained
unchanged.
The sulfur K-edge XANES was used to examine the sulfate
species of calcined SO42eZrO2 and Cu-decorated SO42eZrO2
catalysts (solid lines); the results are depicted in Fig. 9. The
white line position of Zr(SO4)2 and CuSO4 showed at 2483 eV.
The white line of all calcined samples (solid lines) appeared at
the same position with that of Zr(SO4)2 and CuSO4, suggesting
the sulfur species of the calcined samples were present in the
form of sulfate groups (SO42). After 100 h time-on-stream
41380 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5

Fig. 5 e SEM-EDS analysis of 6Cu-SZ catalyst.

Fig. 6 e TEM images of SZ and 6Cu-SZ catalysts.

Fig. 7 e Cu K-edge XANES of calcined XCu/SO42¡eZrO2 catalysts (a) and corresponding Cu species quantitatively determined
by LCF with CuSO4, CuO and Cu2O references (b).
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5
Fig. 8 e H2-TPR of calcined SZ and XCu/SO42¡eZrO2
catalysts.
experiment (dash line), an additional broad peak ranging from
2472 to 2479 eV was visible for all spent samples, which could
be attributed to the presence of sulfur species with a lower
oxidation state than SO42 such as sulfite [32,33], sulfide [32,33]
and protonated sulfate [34,35].
In order to further confirm the sulfur species, the calcined
and spent samples were analyzed using XPS technique. As
shown in Fig. 10, the S2p XPS spectrum of calcined SZ, 2Cu-SZ,
6Cu-SZ and 10Cu-SZ samples exhibited one prominent peak at
169.5 eV corresponding to the presence of sulfate groups
(SO2
4 ). For the spent samples, a small S2p peak at 162.6 eV
assigned to metal sulfide [36] was observed for 6Cu-SZ and
10Cu-SZ, suggesting a transformation of Cu0 to Cu2S during
the reaction. The surface chemical compositions of all fresh
and spent catalysts are shown in Table 1.
The surface acidity of unpromoted sulfated zirconia (SZ)
and Cu-promoted sulfated zirconia (6Cu-SZ) before and after
reaction was determined with NH3-TPD technique. As shown
in Fig. 11, the NH3-TPD profiles of all samples can be decon-
voluted into three peaks including a, b and g assigned to weak,
medium and strong acid sites [37], respectively. The amount
of acid sites is listed in Table 2. The SZ sample showed the
highest amount of weak, medium and strong acid sites with
the total amount of acid sites of 540.02 mmol g1. Impregnation
of SZ with Cu (6Cu-SZ) caused a slight decrease of weak and
medium acid sites but drastic reduction of strong acid sites.
41381
Fig. 9 e Sulfur K-edge XANES of XCu/SO42¡eZrO2 catalysts,
CuSO4 and Zr(SO4)2. The solid and dash lines represented
the calcined and spent catalysts.
Previous works indicated that zirconium atoms (eZrþe)
adjacent with sulfate groups could act as Lewis acid sites,
while Bronsted acid sites (eZreOH) could be formed due to a
strong electron-withdrawing of sulfate groups. As a result, the
reduction of acid sites after Cu impregnation could be attrib-
uted to the interaction of Cu with sulfate groups to form
CuSO4 species, reducing the inductive effect of sulfate groups
and the deposition of Cu species on the ZrO2 surface, reducing
the available oxygen atoms for the formation of -Zr-OH (see
Scheme 1). Subsequent to the reaction, the total acid sites of
SZ (Spent SZ) and 6Cu-SZ (Spent 6Cu-SZ) were found to be
223.45 and 326.50 mmol g1 which were 70% and 92% of their
initial acidity, respectively. As indicated by XPS analysis
(Table 1), the significant reduction in acidity of the SZ catalyst
could be attributed to the carbonaceous deposit which
blocked the acid sites. The presence of Cu species abated the
carbonaceous formation, maintaining the surface acidity
close to their initial values.
Scheme 1 proposes the promotional effect of Cu addition
on activity and stability of 6Cu-SZ catalyst based on the
characterization results obtained so far. As discussed above in
XRD and Cu K-edge XANES results, CuO and CuSO4 species
were formed on the surface of sulfated zirconia after
impregnation and calcination at 550  C for 2 h. Subsequent to
the reduction with H2 at 300  C for 4 h, only CuO phase was
41382 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5

Fig. 10 e S 2p XPS spectra of calcined and spent SZ (a), 2Cu-SZ (b), 6Cu-SZ (c) and 10Cu-SZ (d) catalysts.

portion of CH3OH to CH4 (reaction 6). Nevertheless, the notable

Table 1 e Surface chemical compositions determined by increase of the DME yield of XCu-SZ catalysts was observed as
XPS analysis of all catalysts before and after reaction. the time-on-stream experiment prolonged to 40 h. Ng and
Samples Chemical compositions (wt%) Horva t [38] reported that a small amount of H2S could be
Cu Zr S C O evolved from the surface of SO42eZrO2 during the treatment
with H2. In our catalytic system, hydrogen was used as one of
SZ e 42.73 10.19 9.98 37.1
Spent SZ e 31.21 5.06 32.28 31.45 the reactants which could be the source of H2S generation.
2Cu-SZ 1.61 34.01 7.82 16.75 39.81 The produced H2S during the reaction could react Cu0 to form
Spent 2Cu-SZ 1.43 39.93 8.01 16.83 33.8 Cu2S as confirmed by XPS analysis (Fig. 10) which then
4Cu-SZ 3.54 34.3 8.46 16.17 37.53 disabled the hydrogenation function of Cu0. Note that the 6Cu-
Spent 4Cu-SZ 3.6 38.48 8.75 16.36 32.81 SZ catalyst achieved the maximum DME yield in the series of
6Cu-SZ 5.54 39.85 10.02 8.09 36.5
XCu-SZ catalysts. At higher Cu loading contents (8Cu-SZ and
Spent 6Cu-SZ 5.87 44.17 9.75 8.52 31.69
8Cu-SZ 7.8 38.61 9.75 11.94 31.9
10Cu-SZ), Cu0 still existed on the catalysts surface which led to
Spent 8Cu-SZ 7.87 35.6 7.98 12.1 36.45 the competitive CH3OH conversion to DME and CH4.
10Cu-SZ 8.63 38.38 10.08 9.18 33.73 After 40 h (Fig. 2a), the DME yield of XCu-SZ catalysts was
Spent 10Cu-SZ 9.07 40.44 8.91 9.50 32.08 not altered, indicating their high stability compared to the
unpromoted SZ catalyst. A possible reason for the continuous
decline in DME yield of the unpromoted SZ catalyst can be the
transformed to Cu0. The initial DME yield (Fig. 2a) of XCu-SZ different strong acid sites. The higher quantity of strong acid
catalysts was lower than that of unpromoted SZ catalyst sites over the unpromoted SZ catalyst causes the remarkable
because the presence of Cu0 facilitated the hydrogenolysis of a carbonaceous contents covered on its surface as indicated by
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5 41383

Scheme 1 e Proposed promotional effect of Cu addition on

SO42¡/ZrO2 acid catalyst for methanol dehydration to DME.

Conclusions

In summary, the addition of Cu on SO42/ZrO2 catalysts

remarkably altered the properties of the bare SO42/ZrO2 cata-
lyst and determined the catalytic activity and stability. At Cu
loading content of 2 wt%, Cu species were predominantly
formed as CuSO4 (95%) with the small amount of CuO (5%). With
increasing Cu loading content, the amount of CuO progressively
increased accompanied by decreasing CuSO4 phase. The pres-
ence Cu species on the surface of SO42/ZrO2 drastically
decreased the number of strong acid sites in comparison to the
bare SO42/ZrO2 catalyst lessening the coke formation. Never-
theless, Cu0 formed by the reduction of CuO after H2 pretreat-
ment accelerated the hydrogenolysis of methanol intermediates
to methane, resulting in a lower DME yield at the initial activity.
During the reaction, Cu0 was poisoned by H2S to form Cu2S
which was inactive for hydrogenation reaction, turning off the
hydrogenation ability of the catalyst, resulting in a lower
Fig. 11 e NH3-TPD profiles of SZ, spent SZ, 6Cu-SZ and methane yield accompanied by the increase of DME yield. The
spent 6Cu-SZ catalysts. Cu-modified SO42/ZrO2 catalyst with the optimum Cu loading
content of 6 wt% exhibited the highest DME yield of 3.2% at
260  C and 20 bar after 100 h time-on-stream experiment.

the XPS analysis (Table 1), leading to the catalyst deactivation.

The addition of Cu onto SZ catalyst notably decreases strong
acid sites (Table 2), weakening the interaction of carbon
molecules with the surface of XCu-SZ catalysts, extenuating
the carbon deposition. In addition, the H2 dissociation and
hydrogenation ability of Cu can resist the coke deposition
[39e41], resulting in the stable DME yield after 40 h time-on-
stream experiment.
Table 2 e Surface acidic properties of unpromoted
sulfated zirconia (SZ) and Cu-promoted sulfated zirconia
(6Cu-SZ) before and after reaction.
Samples Amount of acid sites (mmol g1)
Credit authorship contribution statement
Thongthai Witoon: Investigation, Conceptualization, Meth-
odology, Writing-Original draft preparation, Writing-
Reviewing and Editing. Thanapha Numpilai: Investigation,
Validation, Writing-Original draft preparation, Writing-
Reviewing and Editing. Napaphut Dolsiririttigul: Investiga-
tion, Writing-Reviewing and Editing. Narong Chanlek: Inves-
tigation and Validation. YingYot Poo-arporn: Investigation
and Validation. Chin Kui Cheng: Visualization, Writing-
Reviewing and Editing. Bamidele Victor Ayodele: Visualiza-
tion, Writing-Reviewing and Editing. Metta Chareonpanich:
Visualization, Writing-Reviewing and Editing. Jumras Lim-
trakul: Supervision.

Weak Medium Strong Total acid sites

(a) (b) (g)
Declaration of competing interest
SZ 40.91 349.24 149.87 540.02
6Cu-SZ 32.40 321.96 27.76 382.12
Spent SZ 23.04 186.59 13.82 223.45 The authors declare that they have no known competing
Spent 6Cu- 36.69 299.44 15.42 351.55 financial interests or personal relationships that could have
SZ appeared to influence the work reported in this paper.
41384 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5
Acknowledgments
This research was financially supported by the National
Research Council of Thailand (N41A640081) and the Kasetsart
University Research and Development Institute (KURDI)
through its program of Development of Advance Researcher
Competence System for Competitiveness in Agriculture and
Food (FF(KU)25.64).
references
[1] Dowell NM, Fennell PS, Shah N, Maitland GC. The role of CO2
capture and utilization in mitigating climate change. Nat
Clim Change 2017;7:243e9. https://doi.org/10.1038/
nclimate3231.
[2] Wei YM, Kang JN, Liu LC, Li Q, Wang PT, Hou JJ, Liang QM,
Liao H, Huang SF, Yu B. A proposed global layout of carbon
capture and storage in line with a 2  C climate target. Nat
Clim Change 2021;11:112e8. https://doi.org/10.1038/s41558-
020-00960-0.
[3] Hepburn C, Adlen E, Beddington J, Carter EA, Fuss S,
Dowell NM, Minx JC, Smith P, Williams CK. The technological
and economic prospects for CO2 utilization and removal.
Nature 2019;575:87e97. https://doi.org/10.1038/s41586-019-
1681-6.
[4] Olajire AA. CO2 capture and separation technologies for end-
of-pipe applications e a review. Energy 2010;35:2610e28.
https://doi.org/10.1016/j.energy.2010.02.030.
[5] Ahmed SF, Mofijur M, Nuzhat S, Rafa N, Musharrat A,
Lam SS, Boretti A. Sustainable hydrogen production:
technological advancements and economic analysis. Int J
Hydrogen Energy 2022;47:37227e55.
[6] Wang R, Inoguchi K, Ohashi M, Someya S, Munakata T,
Ishida M, Ito H. Effect of catalyst distribution and structural
properties of anode porous transport electrodes on the
performance of anion exchange membrane water
electrolysis. Int J Hydrogen Energy 2021;46:37757e67. https://
doi.org/10.1016/j.ijhydene.2021.09.078.
[7] Semelsberger TA, Borup RL, Greene HL. Dimethyl ether (DME)
as an alternative fuel. J Power Sources 2006;156:497e511.
https://doi.org/10.1016/j.jpowsour.2005.05.082.
[8] Ruina L, Zhong W, Peiyong N, Yang Z, Mingdi L, Lilin L.
Effects of cetane number improvers on the performance of
diesel engine fuelled with methanol/biodiesel blend. Fuel
2014;128:180e7. https://doi.org/10.1016/j.fuel.2014.03.011.
[9] Godini HR, Kumar SR, Tadikamalla N, Gallucci F.
Performance analysis of hybrid catalytic conversion of CO2 to
dimethyl ether. Int J Hydrogen Energy 2022;47(21):11341e58.
https://doi.org/10.1016/j.ijhydene.2021.11.073.
[10] Numpilai T, Cheng CK, Limtrakul J, Witoon T. Recent
advances in light olefins production from catalytic
hydrogenation of carbon dioxide. Process Saf Environ Protect
2021;151:401e27. https://doi.org/10.1016/j.psep.2021.05.025.
[11] Witoon T, Numpilai T, Phongamwong T, Donphai W,
Boonyuen C, Warakulwit C, Chareonpanich M, Limtrakul J.
Enhanced activity, selectivity and stability of a CuO-ZnO-
ZrO2 catalyst by adding graphene oxide for CO2
hydrogenation to methanol. Chem Eng J 2018;334:1781e91.
https://doi.org/10.1016/j.cej.2017.11.117.
[12] Numpilai T, Kidkhunthod P, Cheng CK, Wattanakit C,
Chareonpanich M, Limtrakul J, Witoon T. CO2 hydrogenation
to methanol at high reaction temperatures over In2O3/ZrO2
catalysts: influence of calcination temperatures of ZrO2
support. Catal Today 2021;375:298e306. https://doi.org/
10.1016/j.cattod.2020.03.011.
[13] Akkharaphatthawon N, Chanlek N, Cheng CK,
Chareonpanich M, Limtrakul J, Witoon T. Tuning adsorption
properties of GaxIn2-xO3 catalysts for enhancement of
methanol synthesis activity from CO2 hydrogenation at high
reaction temperature. Appl Surf Sci 2019;489:278e86. https://
doi.org/10.1016/j.apsusc.2019.05.363.
[14] Temvuttirojn C, Poo-arporn Y, Chanlek N, Cheng CK,
Chong CC, Limtrakul J, Witoon T. Role of calcination
temperatures of ZrO2 support on methanol synthesis from
CO2 hydrogenation at high reaction temperatures over ZnOx/
ZrO2 catalysts. Ind Eng Chem Res 2020;13:5525e35. https://
doi.org/10.1021/acs.iecr.9b05691.
[15] Sahebdelfar S, Bijani PM, Yaripour F. Deactivation kinetics of
g-Al2O3 catalyst in methanol dehydration to dimethyl ether.
Fuel 2022;310:122443. https://doi.org/10.1016/
j.fuel.2021.122443.
[16] Ateka A, Portillo A, Sa  nchez-Contador M, Bilbao J,
Aguayo AT. Macro-kinetic model for CuO-ZnO-ZrO2@SAPO-
11 core-shell catalyst in the direct synthesis of DME from CO/
CO2. Renew Energy 2021;169:1242e51. https://doi.org/
10.1016/j.renene.2021.01.062.
[17] Ateka A, Eren ~ a J, Pe
rez-Uriarte P, Aguayo AT, Bilbao J. Effect
of the content of CO2 and H2 in the feed on the conversion of
CO2 in the direct synthesis of dimethyl ether over a CuO-
ZnO-Al2O3/SAPO-18 catalyst. Int J Hydrogen Energy
2017;42:27130e8. https://doi.org/10.1016/
j.ijhydene.2017.09.104.
[18] Bonura G, Todaro S, Frusteri L, Majchrzak-Kuce˛ba I,
Wawrzyn  czak D, Pa  szti Z, Ta
 las E, Tompos A, Ferenc L,
Solt H, Cannilla C, Frusteri F. Inside the reaction mechanism
of direct CO2 conversion to DME over zeolite-based hybrid
catalysts. Appl Catal B Environ 2021;294:120255. https://
doi.org/10.1016/j.apcatb.2021.120255.
[19] Witoon T, Permsirivanich T, Kanjanasoontorn N,
Akkaraphataworn C, Seubsai A, Faungnawakij K,
Warakulwit C, Chareonpanich M, Limtrakul J. Direct
synthesis of dimethyl ether from CO2 hydrogenation over
Cu-ZnO-ZrO2/SO2 4 eZrO2 hybrid catalysts: effects of sulfur-
to-zirconia ratios. Catal Sci Technol 2015;5:2347e57. https://
doi.org/10.1039/C4CY01568A.
[20] Temvuttirojn C, Chuasomboon N, Numpilai T,
Faungnawakij K, Chareonpanich M, Limtrakul J, Witoon T.
Development of SO2 4 eZrO2 acid catalysts admixed with a
CuO-ZnO-ZrO2 catalyst for CO2 hydrogenation to dimethyl
ether. Fuel 2019;241:695e703. https://doi.org/10.1016/
j.fuel.2018.12.087.
[21] Ramos FS, Duarte de Farias AM, Borges LEP, Monteiro JL,
Fraga MA, Sousa-Aguiar EF, Appel LG. Role of dehydration
catalyst acid properties on one-step DME synthesis over
physical mixtures. Catal Today 2005;101:39e44. https://
doi.org/10.1016/j.cattod.2004.12.007.
[22] Witoon T, Kidkhunthod P, Chareonpanich M, Limtrakul J.
Direct synthesis of dimethyl ether from CO2 and H2 over
novel bifunctional catalysts containing CuO-ZnO-ZrO2
catalyst admixed with WOx/ZrO2 catalysts. Chem Eng J
2018;348:713e22. https://doi.org/10.1016/j.cej.2018.05.057.
[23] Saravanan K, Tyagi B, Bajaj HC. Sulfated zirconia: an efficient
solid acid catalyst for esterification of myristic acid with
short chain alcohols. Catal Sci Technol 2012;2:2512e20.
https://doi.org/10.1039/C2CY20462B.
[24] Kim SY, Goodwin Jr JG, Galloway D. n-Butane isomerization
on sulfated zirconia: active site heterogeneity and
deactivation. Catal Today 2000;63:21e32. https://doi.org/
10.1016/S0920-5861(00)00442-9.
[25] Indovina V, Campa MC, Pietrogiacomi D. Sulphated-ZrO2
prepared by impregnation with ammonium, sodium, or
 i n t e r n a t i o n a l j o u r n a l o f h y d r o g e n e n e r g y 4 7 ( 2 0 2 2 ) 4 1 3 7 4 e4 1 3 8 5
copper sulphate: catalytic activity for NO abatement with
propane in the presence of oxygen. Stud Surf Sci Catal
2000;130:1439e44. https://doi.org/10.1016/S0167-2991(00)
80402-4.
[26] Vera CR, Yori JC, Parera JM. Redox properties and catalytic
activity of SO2
4 eZrO2 catalysts for n-butane isomerization: role
of transition metal cation promoters. Appl Catal A Gen
1998;167:75e84. https://doi.org/10.1016/S0926-860X(97)00301-3.
[27] Alvarez WE, Liu H, Resasco DE. Comparison of the different
promoting effects of Fe-Mn, Ni and Pt on the n-butane
isomerization activity of sulfated zirconia catalysts. Appl
Catal A Gen 1997;162:103e19. https://doi.org/10.1016/S0926-
860X(97)00088-4.
[28] Indovina V, Campa MC, Pietrogiacomi D. Sulphated-ZrO2
prepared by impregnation with ammonium, sodium, or
copper sulphate: catalytic activity for NO abatement with
propane in the presence of oxygen. Stud Surf Sci Catal
2000;130:1439e44. https://doi.org/10.1016/S0167-2991(00)
80402-4.
[29] Witoon T, Kachaban N, Donphai W, Kidkhunthod P,
Faungnawakit K, Chareonpanich M, Limtrakul J. Tuning of
catalytic CO2 hydrogenation by changing composition of CuO-
ZnO-ZrO2 catalysts. Energy Convers Manag 2016;118:21e31.
https://doi.org/10.1016/j.enconman.2016.03.075.
[30] Numpilai T, Wattanakit C, Chareonpanich M, Limtrakul J,
Witoon T. Optimization of synthesis condition for CO2
hydrogenation to light olefins over In2O3 admixed with
SAPO-34. Energy Convers Manag 2019;180:511e23. https://
doi.org/10.1016/j.enconman.2018.11.011.
[31] Habashi F, Mikhail SA. Reduction of binary sulfate mixtures
containing CuSO4 by H2. Can J Chem 1976;4:3561e7. https://
doi.org/10.1139/v76-525.
[32] Kumar P, Nagarajan R, Sarangi R. Quantitative X-ray
absorption and emission spectroscopies: electronic structure
elucidation of Cu2S and CuS. J Mater Chem C 2013;1:2448e54.
https://doi.org/10.1039/C3TC00639E.
[33] McKeown DA, Muller IS, Gan H, Pegg IL, Stolte WC.
Determination of sulfur environments in borosilicate waste
41385
glasses using X-ray absorption near-edge spectroscopy. J
Non Cryst Sold 2004;333:74e84. https://doi.org/10.1016/
j.jnoncrysol.2003.09.035.
[34] Liu C, Bolin T, Northrup P, Lee S, McEnally C, Kelleher P,
Pfefferle L, Haller GL. Combined Zr and S XANES analysis on
S-ZrO2/MWCNT solid acid catalyst. Top Catal
2014;57:693e705. https://doi.org/10.1007/s11244-013-0226-8.
[35] Pin S, Huthwelker T, Brown MA, Voger F. Combined sulfur
K-edge XANES-EXAFS study of the effect of protonation on
the sulfate tetrahedron in solids and solutions. J Phys
Chem A 2013;117:8368e76. https://doi.org/10.1021/
jp404272e.
[36] Kurmaev EZ, Fedorenko VV, Galakhov VR, Bartkowski S,
Uhlenbrock S, Neumann M, Slater PR, Greaves C, Miyazaki Y.
Analysis of oxyanion (BO3 2 2 3 4
3 , CO3 , SO4 , PO4 , SeO4 )
substitution in Y123 compounds studied by X-ray
photoelectron spectroscopy. J Supercond 1996;9:97e100.
https://doi.org/10.1007/BF00728433.
[37] Cheng YW, Chong CC, Cheng CK, Ng KH, Witoon T, Juan JC.
Ethylene production from ethanol dehydration over
mesoporous SBA-15 catalyst derived from palm oil clinker
waste. J Clean Prod 2020;249:119323. https://doi.org/10.1016/
j.jclepro.2019.119323.
[38] Ng FTT, Horva  t N. Sulfur removal from ZrO2/SO24 during n-
butane isomerization. Appl Catal A Gen 1995;123:L197e203.
https://doi.org/10.1016/0926-860X(95)00025-9.
[39] Chen F, Tao Y, Ling H, Zhou C, Liu Z, Huang J, Yu A. Ni-Cu
bimetallic catalysts on Yttria-stabilized zirconia for
hydrogen production from ethanol steam reforming. Fuel
2020;280:118612. https://doi.org/10.1016/j.fuel.2020.118612.
[40] Wu Y, Zhang H, Yan Y. High efficiency of phenol oxidation in
a structured fixed bed over Cu-ZSM-5/PSSF prepared by ion-
exchanged method. Chem Eng J 2020;380:122466. https://
doi.org/10.1016/j.cej.2019.122466.
[41] Li Y, Zhang C, Liu Y, Tang S, Chen G, Zhang R, Tang X. Coke
formation on the surface of Ni/HZSM-5 and Ni-Cu/HZSM-5
catalysts during bio-oil hydrodeoxygenation. Fuel
2017;189:23e31. https://doi.org/10.1016/j.fuel.2016.10.047.