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Direct synthesis of dimethyl carbonate from CO2

and methanol over CaO–CeO2 catalysts: the role
Cite this: New J. Chem., 2017,
41, 12231 of acid–base properties and surface oxygen
vacancies
Bin Liu, Congming Li,* Guoqiang Zhang, Lifei Yan and Zhong Li *

Received 18th July 2017,
Accepted 30th August 2017
DOI: 10.1039/c7nj02606d
rsc.li/njc
Herein, the direct synthesis of dimethyl carbonate (DMC) from CO2 and methanol was investigated over
a series of CeO2-based catalysts promoted by variable amounts of CaO. The catalysts were synthesized
by a co-precipitation method and fully characterized by powder X-ray diffraction (XRD), N2 adsorption/
desorption, transmission electron microscopy (TEM), Raman spectroscopy, X-ray photoelectron
spectroscopy (XPS), and NH3-TPD and CO2-TPD techniques. The results demonstrated that the addition
of different amounts of CaO could affect the structure and surface properties of the obtained catalysts.
The acid–base properties and amount of surface oxygen vacancies on the surface of the catalysts were
improved due to the interaction between CaO and CeO2, and the oxygen vacancies enhanced the
adsorption of CO2. The synthesis of DMC from CO2 and methanol was studied in a slurry bed reactor at
3 MPa and 140 1C. The results revealed that the acid–base properties and oxygen vacancies play a crucial
role in promoting the formation of DMC. Among all the bimetallic and pure CeO2 catalysts, the Ca1.5Ce
sample showed the maximum DMC yield (2.47 mmol g1) due to the modification of the acid–base proper-
ties of the catalyst and the existence of higher concentration of oxygen vacancies on the CeO2 surface.

1 Introduction As a green chemical substitute, DMC is not only a very

The chemical industry is committed to develop or improve the
hazardous traditional processes, responsible for the environ-
mental problems such as emissions of greenhouse gases, parti-
cles, and toxic compounds, via more sustainable alternatives.1
Carbon dioxide is regarded as the main greenhouse gas leading
to global warming. Therefore, CO2 capture or chemical conver-
sion of CO2 has been considered as a promising method to
reduce CO2 levels.2 It is generally known that CO2 hydrogenation
to formic acid or methanol is one of the effective ways to produce
high-value chemicals. However, this process normally requires
high temperatures and pressures to achieve a satisfactory CO2
conversion.3,4 Another current research focus is to produce
organic carbonates from CO2,5 which might be classified into
two types: cyclic carbonates (such as glycerol carbonate, butylene
carbonate, etc.) and linear carbonates (such as diethyl carbonate,
dimethyl carbonate, etc.). Among them, DMC, the simplest
organic carbonate, plays an important role in the chemical
industry due to its remarkable properties.
Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi
Province, Taiyuan University of Technology, Taiyuan 030024, Shanxi, China.
E-mail: licongming0523@163.com, lizhong@tyut.edu.cn
important intermediate in organic synthesis, which is widely
used in carboxylation and methylation reactions, but also a fuel
additive owing to its non-toxicity.6–8 Before 1980, DMC was
synthesized via the phosgenation of methanol; this method
involved the use of phosgene, a very toxic compound. Then,
several advanced methods such as transesterification route,
oxidative carboxylation of methanol, and direct synthesis from
methanol and CO2 have been applied to produce DMC. The
direct synthesis of DMC from methanol and CO2 is considered as
a promising method due to its non-toxicity and the abundance of
reactants as compared to the other routes.9
Recently, homogeneous or heterogeneous catalysts have been
applied in this synthesis method. Among the reported catalysts,
Ni(CH3COO)2, zirconia, CeO2, CeO2–ZrO2, CexTi1xO2, and
(H3PW12O40/CexTi1xO2) presented reasonable activity.10–13
Furthermore, ceria-based catalysts have attracted significant
attention due to their high catalytic activity and selectivity.14
CeO2 possesses acid–base and redox properties that are favorable
for the activation of CO2 and methanol. Santos et al.15 reported
the kinetics for the direct synthesis of dimethyl carbonate over
CeO2 and developed a kinetic model for this reaction. It is
accepted that the addition of some metal oxide promoters to
the CeO2 catalyst can greatly modify the support texture, regulate
the particle size, and modulate the redox property to enhance

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the DMC yield.16,17 Hence, ceria-based catalysts doped with
different metal oxides have been extensively studied. According to
previous studies conducted by Hye Jin Lee et al.,18 gallium oxide
supported on CexZr1xO2 catalysts can modify the acidity and
basicity of the support. The yield of DMC over XGa2O3/Ce0.6Zr0.4O2
catalysts was significantly improved by increasing both acidity
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and transformed to O2. The role of CaO in the CaO–CeO2
catalysts for the DMC synthesis has yet to be investigated in detail.
Therefore, it is worthwhile to study the effect of CaO on the surface
properties of CaO–CeO2 catalysts and the catalytic effectiveness of
these catalysts for DMC synthesis from CO2 and methanol.
In this study, a series of CeO2 catalysts promoted by CaO

and basicity of the catalysts. Furthermore, some researchers
prepared Al2O3-modified CeO2 catalysts, which exhibited higher
stability as compared to CeO2 due to the addition of Al2O3 that
promoted the reduction of Ce(IV) to Ce(III).17
Generally, the addition of alkali and alkaline earth metals to
catalysts can modify the catalyst structure and improve the
catalytic activity. Tamao Ishida and co-workers19 found that the
Na promoter led to a decrease in the particle size of Co nano-
particles and an increase in the surface basicity of the catalyst,
which was helpful for the catalytic performance in the Fischer–
Tropsch synthesis (FTS). Moreover, it has been reported that the
introduction of Ca2+ into ZrO2 can effectively improve the thermal
stability of the CaO–ZrO2 catalyst.20 Similarly, the addition of Ca to
CeO2-based catalysts was shown to promote the production of
biodiesel due to the favorable interactions between calcium and
cerium species in the solid catalyst.21,22 Kumar et al.23 reported that
the CaO–CeO2 catalysts prepared by the surfactant-template method
were used for the direct synthesis of DMC from CO2 and methanol.
The author used sieve 3 A as a dehydrating agent, the Ce1–Ca1
catalyst exhibited the best activity, and the DMC yield reached
2.96 mmol g1. Santos et al.24 also used sieve 3 A as a dehydrating
agent and studied the adsorption of DMC and water on a fixed-bed
column. The authors have found that to enhance the DMC yield,
the removal of water from the reaction mixture is a crucial factor
for the development of novel synthetic methods in this regard.
It is generally believed that oxygen vacancies play a critical
role by accommodating the oxygen generated from the cleavage
of CQO bonds25 and the oxide catalysts; thus, the presence of
oxygen vacancies on the catalyst surface is expected to have a
significant impact on the activation and conversion of CO2.26 It
has been reported that CeO2 and ceria-based catalysts have fine
redox property and high oxygen storage capacity.27,28 However,
there has been limited studies reporting the effect of oxygen
vacancies on the reaction performance. Liu and co-workers29
have researched the soot oxidation over CeO2 and Ag/CeO2
catalysts and found that a suitable number of surface oxygen
vacancies on the Ag/CeO2 catalyst results in a 10-fold increase
in the soot oxidation activity since O can be readily regenerated
were synthesized with a mass fraction of Ca between 0 and
4.9 wt% using a co-precipitation method, and their catalytic
performance for DMC synthesis from CO2 was evaluated. In
addition, the relationship between the physicochemical proper-
ties and the catalytic activity was investigated in detail. The
focus of this study was to evaluate the surface oxygen vacancies
of the catalysts as a function of the CaO content, which were
directly related to the resulting reaction performance.
2 Experimental
2.1 Materials
Cerium(III) nitrate hexahydrate (Ce(NO3)3, 99.9%, AR) and calcium
nitrate (Ca(NO3)2, 99.0%, AR) were purchased from Tianjin
Guang Fu Fine Chemical Research Institute (Tianjin, China),
and ammonia (NH3H2O, 25%, AR) was obtained from Feng
Chuan Chemical Reagent Co., Ltd (Tianjin, China). All reagents
were used as received without any further purification.
2.2 Catalyst preparation
The CaO/CeO2 catalyst was prepared via a co-precipitation method.
All mixed oxides were designed to obtain a CaxCe solid solution,
where x is the weight percentage of Ca in the catalysts. Typically, a
300 mL aqueous solution containing cerium nitrate and calcium
nitrate with different Ca/Ce mass ratios and 100 mL ammonia
solution of 1.0 M were mixed in a dropwise fashion in a 2 L beaker.
After the precipitation was completed, the precipitates were aged for
2 h at room temperature. Subsequently, the precipitate was filtered
and washed several times with deionized water. The precipitate
was washed until the conductivity of the filtrate was similar to
that of deionized water. The washed solid was dried at 100 1C
overnight and then calcined at 700 1C for 3 h. Other catalysts
(Table 1) were prepared following a similar procedure.
2.3 Characterization
2.3.1 Temperature-programmed desorption of CO2/NH3
(CO2-TPD and NH3-TPD). Temperature-programmed desorption

Table 1 Acidity and basicity of the CaxCe catalysts

Basicitya (mmol g1) Acidityb (mmol g1)

Weak Moderate Strong Weak Moderate Strong
(o200 1C) (200–400 1C) (4400 1C) Total (o200 1C) (200–400 1C) (4400 1C) Total
Ca0Ce 0.185 0.134 0.007 0.326 0.188 0.069 0.026 0.283
Ca0.5Ce 0.195 0.144 0.010 0.349 0.194 0.075 0.032 0.301
Ca1.5Ce 0.221 0.160 0.017 0.398 0.219 0.083 0.048 0.350
Ca3.6Ce 0.116 0.028 0.024 0.168 0.072 0.055 0.038 0.165
Ca4.9Ce — 0.009 0.037 0.046 0.059 0.049 0.03 0.138
a b
Calculated by CO2-TPD. Calculated by NH3-TPD.

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(TPD) was carried out using a Micromeritics Autochem II 2920
analyzer. Typically, 60 mg sample was pretreated at 500 1C
for 1 h under N2. After cooling, CO2 or NH3 adsorption was
performed by switching the He flow with a stream of 15 vol%
CO2 (NH3)–He (40 mL min1) and maintained at this tempera-
ture for 30 min. The sample was purged with He (40 mL min1)
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for 2 h to remove the physically adsorbed CO2 (NH3). The TPD
test was carried out under a constant flow of He (40 mL min1)
from 50 1C to 500 1C at a rate of 10 1C min1. The concentration
of CO2 (NH3) in the tail gas was continuously measured using a
TCD detector.
2.3.2 Powder X-ray diffraction (XRD). The powder X-ray diffrac-
tion patterns of the investigated catalysts were obtained using a
German Bruker D4 (40 kV, 30 mA) X-ray diffractometer equipped
with a Cu Ka radiation source (l = 0.15406 nm) and a nickel filter in
the 2y range of 201–851 at a scanning speed of 81 min1.
2.3.3 Atomic absorption spectroscopy (AAS). Atomic absorp-
tion spectroscopy (AAS) was conducted to determine the actual Ca
loading of the as-prepared catalysts by a SpectrAA-220 AAS analyzer.
Particularly, 25 mg of fresh catalyst was dissolved in 10–15 mL of
concentrated hydrochloric acid solution, and the mixture was
diluted with distilled water. Then, the solution was transferred to
a 250 mL volumetric flask and again diluted to 250 mL with
distilled water. After this, 5 mL of the abovementioned solution
was transferred to a 100 mL flask and diluted to 100 mL using
distilled water again (making sure that the Ca solution concen-
tration was 1–5 mg L1 for the AAS analysis). Finally, 50 mL of this
solution was obtained to measure the Ca content.
2.3.4 N2 adsorption–desorption measurement. The N2
adsorption–desorption measurements were carried out via a
Beishide 3H-2000PS2 apparatus using nitrogen at liquid-
nitrogen temperature (77 K). Prior to the test, the sample was
degassed in situ at 200 1C for 3 h. The specific surface areas of
the samples were calculated by the Brunauer–Emmett–Teller
(BET) method, and the pore size distribution was measured
using the Barrett–Joyner–Halenda (BJH) model.
2.3.5 Transmission electron microscopy (TEM). Transmission
electron microscopy (TEM) images were obtained using a JEOL
JEM-2100 transmission electron microscope operated at an
accelerating voltage of 200 kV. The samples for TEM analyses
were prepared by dispersing the powder products as a slurry in
ethanol and then depositing on a carbon film coated on a
copper grid.
2.3.6 Raman spectra. Raman spectra were acquired in the
scanning range of 100–1000 cm1 using a Renishaw inVia micro
laser Raman spectrometer (UK) and an Ar+ laser (514.5 nm
wavelength) with an output power of 4 mW.
2.3.7 X-ray photoelectron spectroscopy (XPS). X-ray photo-
electron spectroscopy (XPS) data were obtained via an
ESCALab220i-XL electron spectrometer (VG, UK) using 300 W
Al Ka radiation. Typically, the samples were compressed into
pellets of 2 mm thickness and then mounted on a sample
holder utilizing double-sided adhesive tape for XPS analysis.
The sample holder was then placed in a fast entry air load-lock
chamber without exposure to air and evacuated under vacuum
(o106 Torr) overnight. Finally, the sample holder was transferred
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to the analysis chamber for XPS study. The base pressure
inside the analysis chamber was usually maintained at better
than 1010 Torr. The binding energies were referenced to the
C 1s line at 284.6 eV from adventitious carbon.
2.4 Catalytic performance evaluation
To evaluate the catalytic performance of the as-prepared cata-
lysts, the DMC synthesis was conducted on a slurry bed reactor
under continuous mechanical stirring; typically, the catalyst
(1 g) and CH3OH (35 mL) were placed inside the batch reactor,
and the mixture was purged with CO2 several times to remove
the air. Then, the reactor was purged with CO2 to a certain
pressure, and the reaction was carried out at 140 1C for 3 h. After
the reaction, the reactor was cooled down to room temperature,
and then, 1-propanol (CH3CH2CH2OH) was added as an internal
standard substance. The products were further analyzed by a gas
chromatograph (FID-GC, O Hua 9160). It was noted that DMC
was the only product, and no other by-products were formed
during the reaction process.
The mass of DMC was calculated by the GC, and the catalyst
activity was calculated by the following equation:
nðDMCÞ=mmol
Catalyst activity ¼
mðcatalystÞ=g
3 Results
3.1 Catalytic activity
Fig. 1 shows the DMC yield over the pure CeO2 and the CaxCe
samples for the synthesis of DMC from methanol and CO2.
Obviously, it was observed that the DMC yield reached a
maximum value of 2.47 mmol g1 when the Ca content was
increased from 0 to 1.5 wt%, and thereafter, it decreased with
the further increase in the Ca content. It was also noted that
the DMC yield obtained over the Ca1.5Ce sample was 1.2 times
higher than that obtained with the pure CeO2 sample.
3.2 CO2-TPD and NH3-TPD
CO2-TPD and NH3-TPD analysis were conducted to investigate
the effect of Ca content on the acid–base properties of the
CaxCe catalysts. Fig. 2(a) shows the CO2-TPD profiles of the
Fig. 1 Catalytic activity of the CaxCe catalysts. Reaction conditions: catalyst
mass: 1 g; temperature: 140 1C; pressure: 3 MPa; reaction time: 3 h.
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Fig. 2 (a) CO2-TPD and (b) NH3-TPD profiles of the CaxCe catalysts.
CaxCe catalysts from 50 1C to 500 1C, and the total basicity of
the CaxCe catalysts calculated from the CO2-TPD peak area is
summarized in Table 1. It revealed that all the CaxCe catalysts,
except the Ca4.9Ce sample, contained the same types of basic
sites. The desorption peaks appearing in the lower temperature
range below 200 1C can be assigned to the interaction between
CO2 and weakly basic sites. The Ca1.5Ce sample exhibits highest
adsorption capacity, and the quantity of CO2 adsorbed is
0.398 mmol g1. Furthermore, it was found that the Ca1.5Ce
sample had the largest number of basic sites, and the total
basicity of the catalysts decreased in the following order:
Ca1.5Ce 4 Ca0.5Ce 4 Ca0Ce 4 Ca3.6Ce 4 Ca4.9Ce; this trend
is in good agreement with the catalytic activity results. It
was also found that the adsorption of CO2 increased with the
increasing Ca content at the strong basic sites, which was
confirmed by the previous literature.30 Furthermore, Ca1.5Ce
showed a higher basicity than bulk CeO2; this may be ascribed
to the synergic effect between CaO and CeO2. Indeed, some
authors have reported that doping another metal into a metal
oxide can affect the textural and surface properties due to their
synergic effect between the metal and the metal oxide.30–32
However, interestingly, the basicity of the catalysts decreased
with the increasing Ca content, which was consistent with the
literature.30 In Fig. 2(a), it was seen that the Ca3.6Ce and Ca4.9Ce
samples almost had no obvious adsorption peak. Thus, the
basicity of these two catalysts was even lower than that of pure
CeO2. In the previous reports,33,34 CaO-based solid adsorbents
have been identified as the most promising candidates, which
are widely used for CO2 capture. The results indicated that the
introduction of an appropriate amount of Ca into CeO2 could
increase the number of basic sites in the catalyst, whereas an
excessive amount of Ca could lead to a decrease in the amount
of basic sites. The reduction in the amount of basic sites may be
due to the aggregation of CaO.35
Fig. 2(b) also shows the NH3-TPD profiles of the CaxCe
catalysts. It was found that NH3-TPD and CO2-TPD results
exhibited the same trend of variation. This revealed that all
CaxCe catalysts, except Ca4.9Ce, mainly consisted of same acidic
sites below 200 1C. The desorption peak for Ca4.9Ce sample can
hardly be seen in the temperature range below 200 1C; this
indicates a weak acidity. The Ca4.9Ce catalyst had no obvious
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TCD signals, and this probably represented that the NH3
adsorption sites were covered by Ca2+. The acidity of the CaxCe
catalysts was calculated based on the NH3-TPD peak area
percentage, as listed in Table 1. It was obvious that the acidity
of the Ca1.5Ce catalyst is higher than that of other CaxCe catalysts
and the adsorption quantity of NH3 is 0.350 mmol g1. The
total acidity of the catalysts decreased in the following order:
Ca1.5Ce 4 Ca0.5Ce 4 Ca0Ce 4 Ca3.6Ce 4 Ca4.9Ce. This trend is
in good agreement with the catalytic activity results. Moreover,
the trend for the adsorption strength (weak, moderate, and
strong) is the same as the trend for the total acidity.
3.3 Textural properties of the Ca(x)Ce catalysts
The N2 adsorption/desorption isotherms and pore size distri-
butions of the CaxCe catalysts are presented in Fig. 3. As shown
in Fig. 3(a), a type IV isotherm with a clear H2 hysteresis loop is
obtained for all catalysts except the Ca4.9Ce catalysts, indicating
typical mesoporous materials. In Fig. 3(b), the pore size dis-
tribution calculated by the BJH method from the desorption
branch of the isotherm revealed that all the catalysts, except the
Ca4.9Ce catalyst, contained mesoporous pore distribution with
a pore size of 2–15 nm. In Table 2, it can be seen that the pore
size of the Ca4.9Ce catalyst is higher than that of other catalysts;
however, the surface area of the Ca4.9Ce catalyst is lower
than that of the other catalysts; this may be attributed to the
formation of piled pores in the aggregated particles. The above-
mentioned results indicated that the Ca content had a signifi-
cant effect on the pore size distribution. The BET surface
areas and pore volumes of the synthesized CaxCe catalysts are
summarized in Table 2. It can be seen that the Ca1.5Ce catalyst
possesses the highest specific surface area of 36 m2 g1 and pore
volume of 0.14 cm3 g1, whereas Ca4.9Ce presents the lowest
specific surface area of only 1 m2 g1 and pore volume of
0.035 cm3 g1. It is noted that there is a correlation between
the total adsorption capacity of CO2 and NH3 and the specific
surface area. Thus, an increase in the specific surface area (from
1 to 36 m2 g1) with a suitable content of Ca may provide more
available acidic and basic active sites on the catalyst surface. On
the other hand, an excessive amount of Ca led to a decrease of
the specific surface area and pore size, in turn decreasing the
CO2 adsorption capacity, as confirmed by the CO2-TPD results.
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Fig. 3 (a) N2 adsorption/desorption isotherms and (b) pore size distributions of the CaxCe catalysts.

Table 2 Structure and physical parameters of various samples 3.4 TEM images
Ca loadinga SBET/ Vp Pore Particle Mean Fig. 5 shows the TEM images of the as-prepared catalysts. It was
Sample (wt%) m2 g1 (cm3 g1) size (nm) sizeb (nm) sizec (nm) noted that the particle size was in the range of 10–40 nm in all the
Ca0Ce — 23 0.074 8.0 22 23 cases. This value was in good agreement with the diameter range
Ca0.5Ce 0.5 26 0.11 10.0 20 21 calculated from the XRD data (15–23 nm). In addition, it can be
Ca1.5Ce 1.5 36 0.14 11.0 17 18 seen that with the increase of Ca contents, the particle size of the
Ca3.6Ce 3.6 8 0.049 8.7 16 18
Ca4.9Ce 4.9 1 0.035 25.3 14 15 catalysts decreased, in good line with the XRD results. The above-
a mentioned results indicated that the Ca content had a significant
Determined by AAS. b Calculated for about 100 nanoparticles from
the TEM images. c Estimated by the Scherrer equation, applied to the effect on the particle size of the catalysts, and the Ca1.5Ce catalyst
(111) reflection of fluorite CeO2. possessed the smaller mean size of about 17 nm. In Fig. 5, we can
also see that the Ca4.9Ce catalyst has the smaller mean size of about
14 nm, and the catalyst particles are severely agglomerated.
The XRD patterns of the CaxCe catalysts are presented in
Fig. 4. All the peaks of the samples can be indexed to the face-
centered cubic fluorite structure (JCPDS-ICDD 34-0394). The 3.5 Raman spectra analysis
peaks at 28.51, 33.01, 47.51, 56.51, 59.31, and 69.61 were ascribed The structures of the representative CaxCe samples were
to the (111), (200), (220), (311), (222), and (420) planes of CeO2, studied by Raman spectroscopy (Fig. 6). Ca0Ce exhibits a strong
according to PDF#34-0394.36 After the introduction of Ca F2g vibrational peak at 461 cm1 and a weak oxygen vacancy
species, no new diffraction peaks corresponding to the CaO defect-induced vibrational peak at 602 cm1, ref. 22. The addi-
phase (at around 381 and 541) were observed. This may be tion of Ca2+ species to ceria led to an increase of bandwidth of
attributed to the incorporation of Ca2+ species into the ceria the F2g mode; this suggested that there was a strong interaction
lattice and their high dispersion as a result of their small between CaO and CeO2. The results indicated the creation of
diameter. The mean crystallite size, as calculated by the Scherrer new oxygen vacancies via doping of the CeO2 catalyst with CaO.39
equation, was 23 nm for Ca0Ce, 21 nm for Ca0.5Ce, 18 nm for In addition, this peak exhibited a red shift as the content of CaO
Ca1.5Ce, 18 nm for Ca3.6Ce, and 15 nm for Ca4.9Ce (Table 2). increased; this indicated the incorporation of Ca2+ into the
It indicated that the decline of the crystallite size with the lattice of the resulting catalyst, which was in agreement with
increasing content of CaO could be related to the distortion of that observed via XRD analyses. Furthermore, a weak oxygen
the CeO2 structure due to the incorporation of CaO.37,38 vacancy defect-induced vibrational peak centered at 602 cm1
was observed. Because Ce ion has a valence of 4 or 3, and Ca ion
has only a valence of 2, some vacancies have been created during
the ion substitution process to maintain charge neutrality in
the ionic crystal (Ce4+ + O2 2 Ca2+ + VO, VO: oxygen vacancy).
These vacancies induced lattice distortions to form defects that
were favorable for heterogeneous catalysis. The intensity ratio
between the 602 (ID) and 464 cm1 (If2g) bands was used to
estimate the oxygen vacancy concentration. The ID/If2g values
rapidly increased as the Ca loading increased and followed the
trend Ca4.9Ce 4 Ca1.5Ce 4 Ca0Ce. These results suggested that a
larger amount of oxygen vacancies were created after the addition
of CaO.37,40 Moreover, the weaker band at 255 cm1 was observed
for Ca4.9Ce that belonged to the transverse acoustic (TA) mode.
Fig. 4 XRD patterns of the CaxCe catalysts. It implied that there existed some interaction between CaO and

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Fig. 5 TEM images of the CaxCe catalysts.

CeO2 due to the more vacancies created by the substitution affected the synergistic interactions between the CaO and
of Ca2+ in CeO2.41,42 Therefore, the doped Ca significantly CeO2 nanostructures.

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Fig. 6 Raman spectra of Ca0Ce0, Ca1.5Ce, and Ca4.9Ce.
3.6 XPS analysis
Fig. 7 presents the XPS spectra of Ce 3d and O 1s for CaxCe
samples. The chemical states of the Ce species on the surface of the
catalysts are obviously related to the concentration of CaO. The Ce
3d spectra can be deconvoluted into eight peaks:43 V (B882.5 eV),
V0 (B884.1 eV), V00 (B888.4 eV), V0 0 0 (B898.0 eV), U (B899.8 eV),
U0 (B901.6 eV), U00 (B907.5 eV), and U0 0 0 (B916.5 eV). The four U
bands represent Ce 3d3/2, and the four V bands represent Ce 3d5/2.
The 3d104f0 state of the Ce4+ species was labeled as U, U00 , U0 0 0 , V,
V00 , and V0 0 0 , whereas the 3d104f1 state of the Ce3+ was labeled as U0
and U0 . The calculated Ce3+ concentration of the catalyst CaCe-x
was semi-quantitatively analyzed using the integrated peak area of
the respective valence states via the following equation
 3þ  ACe3þ
Ce % ¼  100%
ACe3þ þ ACe4þ
ACe3+: photoelectron peaks areas of Ce3+; ACe4+: photoelectron
peaks areas of Ce4+.
Fig. 7 XPS spectra of Ce 3d (a) and O 1s (b) for the CaxCe catalysts ((a) Ca0Ce, (b) Ca0.5Ce, (c) Ca1.5Ce, (d) Ca3.6Ce, (e) and Ca4.9Ce).
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As listed in Table 3, the percentages of Ce3+ were estimated
to be 19%, 24%, 27%, 17%, and 16% for Ca0Ce, Ca0.5Ce, Ca1.5Ce,
Ca3.6Ce, and Ca4.9Ce, respectively. This trend is exactly the
same as that for the N2 adsorption data. Ca4.9Ce presents the
lowest Ce3+ concentration, whereas Ca1.5Ce presents the highest
concentration. Combining the XPS results with the N2 adsorp-
tion data and Raman spectra, the fact that Ca4.9Ce had the
lowest Ce3+ concentration indicated that Ca2+ may be incorpo-
rated into the bulk of the CeO2 lattice due to the smallest BET
specific surface area of the CaO particles. The percentage of Ce3+
of the Ca1.5Ce sample with the highest BET specific surface area
reaches the maximum value of 27%. In general, the chemical
valence of Ce ion is 3 or 4, but Ca ion has only 2 valence; thus,
some vacancies are generated upon substitution to keep charge
neutrality in the ionic crystal, and these vacancies are favorable
for heterogeneous catalysis.21,31,44 Oxygen vacancy-associated
exposed ions on CeO2 are potentially potent surface sites in the
titled activation of CO2.45,46 Herein, combining the N2 adsorp-
tion data, Raman spectra, and XPS results, it was concluded
that the chemical states of the CaxCe samples were clearly
affected by the amount of CaO added, which also affected the
structural properties.
The O 1s spectra of the CaxCe samples clearly showed three
states of surface oxygen (Fig. 7, O 1s): lattice oxygen (OL), at a lower
binding energy (B529.0 eV); weakly bonded oxygen species and/or
chemisorbed oxygen (OC) (B531.0 eV); and surface oxygen (OS)
at the highest binding energy (B532.5 eV).47–49 The calculated
OL concentration in the CaxCe catalysts was semi-quantitatively
estimated from the integrated peak area using the following
equation:
AOL
½OL % ¼  100%
AOC þ AOL þ AOS
AOL: photoelectron peaks areas of lattice oxygen; AOC: photo-
electron peaks areas of chemisorbed oxygen; and AOS: photo-
electron peaks areas of surface oxygen.
As shown in Table 3, the ratio of OL to OT (OT = OL + OC + OS)
for all samples was calculated. It was observed that the incor-
poration of Ca2+ can effectively increase the amount of lattice
oxygen (OL) on the surface of the CaxCe catalysts. These results
confirmed that there was an enhanced mobility and availability
of lattice oxygen species due to the synergistic effect between
CaO and CeO2.50
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Table 3 Concentrations of Ce3+ (%) and OL estimated by XPS form of CaCO3 and could not effectively react with CO2; this led to
a decline in catalytic activity.35 Consequently, a suitable degree of
Catalyst Ca0Ce Ca0.5Ce Ca1.5Ce Ca3.6Ce Ca4.9Ce
basicity and acidity is necessary for the catalysts to adsorb CO2
OL (%) 0.42 0.50 0.55 0.48 0.37 and CH3OH and ultimately promote the formation of DMC.
Ce3+ (%) 0.19 0.24 0.27 0.18 0.16

4.2 The role of surface oxygen vacancies

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4 Discussion As seen in Fig. 9, the catalytic activity of the CaxCe catalysts

4.1 The role of basicity–acidity increased with the increasing concentration of Ce3+ on the surface.
Generally, both basic and acidic sites are necessary for the Obviously, the catalytic activity depended on the concentration of
direct synthesis of DMC from methanol and carbon dioxide.13 Ce3+ on the catalyst surface. Among all catalysts, the Ca1.5Ce
Therefore, the total basicity and acidity of the CaxCe catalysts catalyst, with the highest concentration of Ce3+ on the surface,
determined the yield of DMC. As seen in Fig. 8(a), we observed exhibited the best catalytic performance. This indicated that more
that changes from weak to moderate basicity were consistent oxygen vacancies are beneficial for this reaction. According to the
with the activity of the catalysts; however, the changes from previous DFT studies, CO2 could be activated in the oxygen
moderate to strong basicity were not. The improved weak and vacancies on the defective surface of the metal oxide.57 However,
moderate basicity could be ascribed to the synergic effect on perfect metal surfaces, CO2 was very weakly adsorbed and
between CaO and CeO2. The strongly basic sites were caused activated via the Eley–Rideal mechanism.57–60 It was also shown
by the introduction of Ca2+ into CeO2. However, a higher that increasing the content of oxygen vacancies on the CeO2
number of strongly basic sites did not favor this reaction, surface could enhance the adsorption of CO2 and improve the
which was consistent with a previous report.51 As shown in interactions between CO2 and CeO2.61,62 As is well known,
Fig. 8(b), it was observed that more acidic sites were favorable
for increasing the DMC yield. The acidity of the catalysts
increased as the content of Ca increased, whereas the acidity
decreased at an excessive amount of Ca. Calcium oxide is an
alkaline oxide and therefore, an excessive amount of Ca in the
catalysts may result in a decrease of ammonia adsorption.
Ca1.5Ce showed the best DMC yield than other catalysts
due to its higher CO2 and NH3 adsorption capacity. Based
on previous literature reports,52–54 methanol was activated to
methyl and methoxy species at the acidic and basic sites of the
catalyst, and then, the methoxy species reacted with CO2 on the
basic sites of the catalyst to form the methoxy carbonate anion,
which finally reacted with the methyl species to generate DMC.
The adsorption at weakly and moderately basic sites was
enhanced due to the synergistic effect between CaO and
CeO2. However, at strongly basic sites, CO2 could interact with Fig. 9 Correlation between the concentration of Ce3+ (%) and catalytic
CaO to generate calcium carbonate due to the strong basicity of activity. Reaction conditions: catalyst mass of 1 g, temperature of 140 1C,
the catalyst.55,56 Therefore, some active CaO still existed in the pressure of 3 MPa, and reaction time of 3 h.

Fig. 8 Correlation between (a) basicity, (b) acidity, and catalytic activity of catalysts. Reaction conditions: catalyst mass of 1 g, temperature of 140 1C,
pressure of 3 MPa, and reaction time of 3 h.

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Fig. 10 Putative mechanism for the formation of DMC from CO2 and
methanol at the surface oxygen vacancies over the CaxCe catalysts.
oxygen vacancies are Lewis sites and therefore, a higher number
of oxygen vacancies favors CO2 adsorption. Thus, a high concen-
tration of Ce3+ helped to produce more oxygen vacancies, which
in turn favored the activation of CO2, thus improving the overall
reaction performance.
4.3 Proposed mechanism for DMC formation over the
surfaces of CaxCe catalysts
On the basis of literature reports and our results, synthesis
mechanism of DMC at the surface oxygen vacancies over the
CaxCe catalysts was proposed. As shown in Fig. 10, many oxygen
vacancies on the surface of CaxCe samples and metal ions (Ce3+
and Ca2+) acted as Lewis acid sites.63 First, CO2 molecules were
adsorbed onto oxygen vacancies through the interaction of oxygen
atoms of CO2 with the oxygen vacancies. Subsequently, methanol
molecules were adsorbed at a metal ion site adjacent to the oxygen
vacancy through the interactions of oxygen atoms with the metal
atom because metal ions constituted Lewis acid sites that could
interact with the oxygen atom of the methanol molecules;
afterwards, another methanol molecule was adsorbed at
another metal ion adjacent to an oxygen vacancy to form an
intermediate. The O atoms in carbon dioxide molecule as Lewis
base sites subtract H atom from methanol molecules to form
water and an intermediate. Finally, after the surface reaction
was completed, the intermediate converted into DMC, whereas
the oxygen vacancy was regenerated.
5 Conclusions
In this study, a series of CaxCe catalysts with different contents
of Ca were prepared by a co-precipitation method. The addition
of CaO to the CeO2 catalyst had a significant impact on the
acid–base properties and amounts of oxygen vacancies in the
catalyst, as demonstrated by CO2-TPD, NH3-TPD and XPS.
The Raman results also demonstrated that the interactions
between CaO and CeO2 generated more oxygen vacancies.
Furthermore, it was observed that a higher number of oxygen
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Paper
vacancies favored CO2 adsorption and improved the catalytic
performance for the synthesis of DMC from CO2 and methanol.
Under the catalytic reaction conditions of 140 1C, 3 MPa, and 2 h
reaction time, the highest DMC yield of 2.47 mmol g1 could be
obtained over the Ca1.5Ce catalyst. Based on the obtained results,
a reaction route for DMC synthesis from CO2 and methanol over
the CaxCe catalysts was proposed.
Conflicts of interest
There are no conflicts to declare.
Acknowledgements
This work was supported by the National Natural Science
Foundation of China (grants U1510203, 21676176), the National
Science Foundation of the Shanxi Province, China (grant
201601D011016), and the fund of State Key Laboratory of Catalysis
in DICP (grant N-15-05).
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