Chinese Chemical Letters 28 (2017) 65–69

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Chinese Chemical Letters

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

Original article

An in situ infrared study of dimethyl carbonate synthesis

from carbon dioxide and methanol over well-shaped CeO2
Shu-Yang Zhao, Sheng-Ping Wang *, Yu-Jun Zhao, Xin-Bin Ma
Key Laboratory for Green Chemical Technology, School of Chemical Engineering and Technology, Tianjin University; Collaborative Innovation Center of
Chemical Science and Engineering, Tianjin 300072, China

A R T I C L E I N F O A B S T R A C T

Article history: The mechanism of dimethyl carbonate (DMC) formation from CO2 and methanol is investigated using
Received 27 April 2016 three well-shaped CeO2 catalysts, nanorod, nanocube and octahedron, which are packed with different
Received in revised form 14 May 2016 crystal planes. In situ Fourier Transform Infrared Spectroscopy (FTIR) is employed to probe each reaction
Accepted 23 May 2016
step in the DMC synthesis. The number of –OH groups and the species of CO2 adsorptions on ceria surface
Available online 8 June 2016
have significant influence on the activity of ceria with different morphologies. Rod-ceria has favorable
catalytic activity because of the large amount of –OH groups and the formation of bidentate carbonate
Keywords:
species.
Dimethyl carbonate
CeO2
ß 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences.
–OH Published by Elsevier B.V. All rights reserved.
Bidentate carbonate
Crystal planes

1. Introduction analyze the nature of the active sites needed for every step and
explain the different catalytic performance on different crystal
CeO2 is known for its widely application in heterogeneous planes.
catalysis, either as the catalyst or the support [1–3], because of its
low redox potential [4], versatile acid and base properties [5] and 2. Experimental
high oxygen storage capability [6]. Three low-index crystal planes
({1 1 1}, {1 0 0} and {1 1 0}) exposed on ceria are affected by its Catalyst preparation: Cerium oxides were prepared by a
morphology [7–13]. hydrothermal method. 480 mmol NaOH and 4 mmol
The direct synthesis of DMC from CO2 and methanol over the Ce(NO3)36H2O were dissolved in 70 and 10 mL of deionized
ceria catalyst appears to be a promising pathway because of its water. The mixed solution was stirred for 30 min to produce a
implications in CO2 fixation and sustainable development [12, purple slurry. Then the slurry was transferred into a Teflon-lined
14,15]. Some researchers [16,17] have proposed a mechanism of stainless autoclave and heated at 373 K and 453 K for 24 h. After
mono-dentate methyl carbonate (MMC) as an intermediate the hydrothermal treatment, precipitates were collected by
product. Michele Aresta [18] thought the CO2 reacts directly with filtration, washed with deionized water and ethanol several
the methoxy group on the catalyst, while B.A.V. Santos [19] times and dried at 353 K for 24 h. The samples were labeled as rod
believed both CO2 and CH3OH are adsorbed on the ceria surface and cube, respectively. For CeO2 octahedron, 0.15 mmol Na3PO4
before they react with each other. It is worth noting that the and 20 mmol Ce(NO3)36H2O were used, and the hydrothermal
latter viewpoint was supported by kinetic studies but no other temperature was changed to 433 K. The sample was labeled as
characterizations for the reaction or catalyst were reported. octa.
In this paper, three well-shaped cerium oxides exposing Catalyst characterization: The morphology of CeO2 samples was
different surfaces were prepared to investigate the mechanism characterized through TEM and HRTEM operated at an accelerating
of DMC synthesis using CO2 and methanol. In situ FTIR was used to voltage of 200 kV. FTIR measurements were performed on a Nicolet
6700 spectrometer (Thermo Fisher Scientific) equipped with an
MCT detector. Four scans were averaged at a resolution of
* Corresponding author. 4 cm1. The sample was pressed into a disk and put into a
E-mail address: [email protected] (S.-P. Wang). homemade reaction cell with ZnSe windows. The cell temperature

http://dx.doi.org/10.1016/j.cclet.2016.06.003
1001-8417/ß 2016 Chinese Chemical Society and Institute of Materia Medica, Chinese Academy of Medical Sciences. Published by Elsevier B.V. All rights reserved.
66 S.-Y. Zhao et al. / Chinese Chemical Letters 28 (2017) 65–69

was controlled by a programmable temperature controller. Before are shown at 3691, 3654 and 3590 cm1 associated with terminal,
the exposure to an adsorbent, the disk with catalyst was pretreated bibridged, and tribridged –OH groups [21], respectively. Because –
at 673 K in flowing He stream (15 mL/min) for 1 h and then cooled OH groups are on ceria surface originally, the bands associated
to 413 K (reaction temperature). CH3OH was brought into the cell with –OH stretching are included in the background that the FTIR
with 15 mL/min He stream for 0.5 h through a saturator, which spectra are based on. As being exposed to ceria, CH3OH reacts with
was kept at 278 K during the adsorption of methanol, followed by surface –OH groups, which leads to the consumption of –OH
pure He stream for 0.5 h for the desorption of methanol. DMC was groups on ceria samples. And as a result, negative peaks in –OH
injected into the reaction cell using a syringe (0.2 mL). The flow stretching region are observed. In the y(CO) region, three bands
rate of CO2 and He was set as 10 mL/min and 15 mL/min, grow at 1095, 1043 and 1010 cm1, associated with on-top
respectively, controlled by a mass flow controller. He was methoxy, bridging methoxy and three-coordinate methoxy
deoxidized by a deoxidizing tube and passed through molecular species, respectively [22]. Upon adsorption, methanol reacts with
sieves to remove water. The whole process was conducted at the surface hydroxyl groups to form methoxy groups and release of
atmospheric pressure. And all infrared spectra exhibited were water. This process is widely believed to be the first step in this
difference spectra referenced to the background spectrum reaction. Large negative peaks at 35003800 cm1 and three peaks
collected at 413 K after pretreatment. around 1001100 cm1 represent the –OH groups consumed and
The synthesis of DMC from CH3OH and CO2: In a typical methoxy groups produced on cube and rod ceria surface. While for
procedure of DMC synthesis, 15 mL CH3OH and 0.1 g catalyst the octa, only a very small negative peak is observed at 3672 cm1
were put into a stainless steel autoclave. Then the autoclave was with a band showing up at 1060 cm1. It is speculated that there
filled with 5 MPa CO2. The reactor was heated and stirred at are not enough –OH groups on the octahedron ceria surface that
413 K for 3 h. After the reaction, 1-propanol was added as a can activate methanol to form methoxy groups. CO2 reacts with
standard substance to quantify the mixture when the reactor insufficient number of methoxy groups, leading to the low activity
was cooled to room temperature. Products were then analyzed of octahedron for DMC formation.
by GC (Agilent 4890 D) analysis. DMC was the only product The distribution and assignment of CO2 adsorption species on
observed in our work. three samples are shown in Fig. 2, based on both the IR
experiment of CO2 (CO) adsorptions on ceria [23–26] and
3. Results and discussion computational modeling studies [27,28]. Generally, CO2 reacts
with –OH groups on the surface and adsorbs as bicarbonates
3.1. Structural and morphological of catalysts (1600, 1398, and 1215 cm1), and CO2 can also react with surface
lattice oxygen to mono-dentate (1353, 1465 cm1), bridged
As shown and discussed in our previous study [20], all the (1242, and 1651 cm1) and bidentate (1580, 1292 cm1)
cerium oxide samples are of high purity, and the crystal planes carbonates. A small peak at 1693 cm1 is associated with
exposed on different morphology ceria samples are determined. carboxylic acid. Because of the diverse atomic arrangement on
Only {1 1 1} crystal plane is observed on octa surface and only the surface of different morphology ceria, the same type of
{1 0 0} on cube surface. Both {1 1 1} and {1 1 0} crystal planes are carbonate species can also show slightly different vibrational
exposed on rod surface. frequencies when CO2 is conducted to different ceria nanoshapes
[24]. Mono-dentate carbonate, bidentate carbonate and bicar-
3.2. Catalytic activities of different ceria catalysts bonate species can form on all the three samples. As number
of –OH groups on ceria octahedron surface is much fewer than
Also shown in our previus work [20], the order of catalytic that on cube and rod, correspondingly, bicarbonates on ceria
activity in DMC formation was summarized as: rod>octa>cube, octahedron surface occupies less than that on cube and rod. It is
and the rod showed much higher activity than other two samples. noted that bidentate carbonates account for a large proportion
It is speculated that the different crystal planes play the most on rod and octa, while only a small amount of bidentate
important role in this phenomenon. carbonates can be observed on nanocube ceria. Because rod and
octa ceria expose a large number of {1 1 0} and {1 1 1} planes,
3.3. In situ Fourier transform infrared spectroscopy comparing with cubes exposing dominant {1 0 0} crystal planes.
It is hypothesized that bidentate carbonates adsorb on ceria
Fig. 1 shows the different IR spectra when methanol is used as a {1 1 0} and {1 1 1} crystal plane instead of {1 0 0}. On the other
probe to different samples. For rod and cube, three negative peaks hand, bridged carbonates are merely observed on cube with

[(Fig._1)TD$IG]
0.7
1043

0.0 rod
0.6 cube
3672

octa
Absorbance (a.u.)

-0.1 0.5
Absorbance (a.u.)

1095

rod
0.4
3590

cube
-0.2 octa
3691

0.3
1010

0.2
-0.3
1060

0.1
3654

-0.4 0.0
3800 3750 3700 3650 3600 3550 3500 1120 1100 1080 1060 1040 1020 1000 980
-1
Wavenumber (cm ) -1
Wavenumber (cm )

Fig. 1. IR spectra following methanol desorption for 0.5 h on ceria catalysts at 413 K.
[(Fig._2)TD$IG] S.-Y. Zhao et al. / Chinese Chemical Letters 28 (2017) 65–69 67

0.5 condition. Thus, it can be assumed that bicarbonate, mono-dentate

rod

1398
carbonate and bridged carbonate species on CeO2 cube cannot

1580
1600
cube react with –OCH3 groups to form any intermediate products.

1651
0.4

1292
octa*5 For rod ceria in Fig. 3b, bands associated with –HCO3 (1600,
1693 1398, and 1215 cm1) disappear immediately under CH3OH

1465
0.3 condition and new bands are observed. At the same time, two
Absorbance (a.u.)

1242
bands associated with bidentate carbonate (1292 and 1576 cm1)

1353
become higher. As the reaction proceeds, four bands (1292, 1346,

1215
0.2
1461, and 1576 cm1) grow together to the highest (line 1 to 4) and
decrease together too (line 4 to 7). Bands at 1461 and 1346 cm1
0.1 are associated with MMC [14,21], and in some literatures [15,18],
the band at 1576 cm1 also was assigned to MMC. It is possible that
bands at 1576 and 1292 cm1 all stand for MMC as they grow and
0.0
reduce together with bands at 1461 and 1346 cm1. The decrease
of four bands (1292, 1346, 1461, and 1576 cm1) from line 4 to 7 in
-0.1 Fig. 3b is because MMC is unstable under this condition and
1800 1700 1600 1500 1400 1300 1200 dissociates to form carbonate and methanol quickly. It is clear that
-1 some CO2 adsorpted on rod surface reacts with surface –OCH3 to
Wavenumber (cm )
form intermediate product MMC. Bands associated with bidentate
Fig. 2. IR spectra following CO2 adsorption for 0.5 h on ceria catalysts at 413 K. carbonate show a slight excursion when growing, which can be
explained by the interaction between bidentate carbonates and –
OCH3 groups. From Fig. 3a, bicarbonates and mono-dentate
{1 0 0} crystal plane, meaning that bridged carbonates adsorb carbonates are unable to react with –OCH3 groups to form
only on ceria {1 0 0} crystal planes. MMC. It is hypothesized that bidentate carbonates are necessary
Fig. 3a-3d demonstrates the evolution of CO2 adsorptions when for MMC formation. Also in Fig. 3a, only a small peak of bidentate
CeO2 cube, rod and octa pre-adsorbed CO2 are exposed to CH3OH. carbonates (1292 cm1) is observed on cube surface, which is
For cube ceria in Fig. 3a, all large bands associated with different necessary for MMC formation. As a result, bands associated with
kinds of CO2 adsorptions (bicarbonate: 1200, 1399, 1600 cm1, MMC on cube surface are barely observed.
bridged carbonate: 1242, 1651 cm1, mono-dentate carbonate: Fig. 3 C D demonstrates the evolution of CO2 adsorptions
1343, 1465 cm1) disappear or reduce as CH3OH adsorbs on cube when CeO2 octahedron pre-adsorbed CO2 is exposed to CH3OH. In
(line 1 to 7). It is noted that only a small band at 1346 cm1 showed Fig. 3c, all bands change similarly as bands in Fig. 3b. Two peaks
up, meaning little intermediate product is formed under this associated with MMC (1461 and 1352 cm1) are observed, and

[(Fig._3)TD$IG]
0.4
1651
1600

cube rod 1
0.6
1576

1 (A) (B) 2
1398

0.3 3
1693

2
0.5 4
1292
3
1346
1242
Absorbance (a.u.)

1461

4 5
1600
1200

0.4
Absorbance (a.u.)

0.2 5 6
1292
1465

1399

6 7
1343

7 0.3
0.1
1215

0.2
0.0
0.1

-0.1 0.0

1800 1700 1600 1500 1400 1300 1200 -0.1

1800 1700 1600 1500 1400 1300 1200
Wavenumber (cm ) Wavenumber (cm )
octa 1 0.14
1581

0.14 octa 1
1561
1292

(C) 2
1354

(D) 2
3 0.12
1371

0.12 3
1592

4
1352

4
5 0.10
0.10 5
Absorbance (a.u.)

Absorbance (a.u.)

6
1292
1461

6
0.08 0.08

0.06 0.06

0.04 0.04

0.02 0.02

0.00 0.00
1700 1600 1500 1400 1300 1200 1700 1600 1500 1400 1300 1200
Wavenumber (cm ) Wavenumber (cm )

Fig. 3. IR spectra taken during exposure of ceria pre-adsorbed CO2 to CH3OH at 413 K with (a) for cube, (b) for rod, (c) and (d) for octa. (As time goes by, the line in Fig. 3a and 3b
changes from number 1 to number 7 and in Fig. 3c and Fig. 3d from 1 to 6. In Fig. 3a and 3b, the time scale from line 1 to line 7 is 0 s!2 min 17 s!2 min 25 s!3 min!6 min
54 s!9 min 8 s!30 min. The time scale from line 1 to 6 in Fig. 3c is 0 s!2 min 17 s!2 min 25 s!3 min!4 min 11 s!5 min 32 s and then in Fig. 3d from line 1 to 6 is 5 min
32 s!5 min 41 s!6 min 7 s!11 min 40 s!19 min 15 s!30 min. Line 6 in Fig. 3c and line 1 in Fig. 3d are the same one. Fig. 3d was obtained just after Fig. 3c in time scale).
68 [(Fig._4)TD$IG]
S.-Y. Zhao et al. / Chinese Chemical Letters 28 (2017) 65–69

two original peaks associated with bidentate carbonate and MMC 0.8
1

1292
(1292 and 1581 cm1) increase with the middle two bands at 2
1464 and 1340 cm1 (Fig. 3c: line 1 to 6). After reaching the
0.7
3
highest position, all these four peaks (1292, 1352, 1461, and 0.6 4
1581 cm1) become smaller. However, they reduce slightly and 5

Absrobance (a.u.)
then spectra become different compared to CO2 adsorbed on 0.5 6

1560
1570
rod, and peaks associated with MMC is disturbed by other 7
species. As observed in Fig. 3d, the peak at 1292 cm1 continues
0.4
to reduce, while the bands between 1350 cm1 to 1400 cm1 and

1461

1346
1781
0.3

1354
1767

1371
1550 cm1 to 1600 cm1 grow for the second time. Bands around
1354, 1371, 1561, and 1592 cm1 can be assigned to a single and 0.2
a two-fold coordinated formate species (m-OHCO and b-OHCO)
[15,21]. It can be explained that on the ceria octahedron surface, 0.1
CO2 adsorbs as bidentate carbonates and mono-dentate carbo- 0.0
nates, and only the former species can react with –OCH3 groups
on octahedron surface to form intermediate product MMC. At the 1800 1700 1600 1500 1400 1300 1200
same time, formate species (Ce-OCHO) are formed in agreement Wavenumber (cm )
-1

with the reduction of ceria and four other bands (1354, 1371,
1561, and 1592 cm1) grow again and cover the former ones. As Fig. 4. IR spectra taken during exposure of rod to DMC at 413 K. (As time goes by the
no other bands are found on ceria rod and cube surface, it is line changes from number 1 to number 7, the number 2 line is obtained just after
DMC was injected into the reaction cell.).
possible that the formation of formates is more easily on
octahedron surface, {1 1 1} crystal planes. Formate species
(Ce-OCHO) are unstable under 413 K conditions, and the
formates dissociate on the octahedron surface quickly, as a Bands related to bicarbonate (1215, 1400, and 1600 cm1) are
result bands associated with formates reduce with CH3OH observed immediately and bands of formate (1354, 1371, and
steam pumping in. 1560 cm1) show up quite late (line 7).
Two bands at 1767 and 1781 cm1 are characteristics of C=O Therefore, the small number of –OH groups on octahedron
groups in DMC. As no bands around 1770 cm1 can be observed surface can only activate limited CH3OH to form –OCH3 groups on
in Fig. 3 during CO2 and CH3OH adsorption, it is obvious that its {1 1 1} crystal planes and release H2O, so CO2 adsorptions can
the reaction between MMC with another CH3OH to form DMC is only react with these insufficient number of methoxy groups to
the rate-determining step in the synthesis. Ceria nanorods, form intermediate product MMC. As a result, the catalytic activity
which show the highest catalytic activity, are exposed to the of octahedron is low. Ceria cubes have a large number of –OH
final product, DMC, to study the reverse reaction. In Fig. 4, species on surface, but bidentate carbonate cannot be formed
bands at 1292, 1767 and 1781 cm1 are associated with under CO2 adsorptions on its {1 0 0} crystal planes. CO2 partici-
physically absorbed DMC, and all of these bands reduce pates in this reaction only when it adsorbs on ceria as bidentate
immediately after DMC is injected in, which means DMC carbonate species, so the cube scarcely catalyzes the reaction. Ceria
dissociate immediately on ceria nanorods. However, the peak rods possess sufficient number of –OH groups and bidentate
at 1292 cm1 still exists when peaks around 1767 and carbonates, leading to the highest catalytic capacity. The dissoci-
1781 cm1 already disappeared, at the same time other bands ated adsorption of DMC is quite effortless, which means its reversal
associated with MMC (1346, 1461, and 1570 cm1) show up and process, MMC reacts with CH3OH to DMC is the rate-determining
increase (line 2-7). It appears that the band at 1292 cm1 is step for this whole reaction. The proposed reaction mechanism is
associated with DMC and DMC dissociative adsorption, MMC. illuminated in Fig. 5.

[(Fig._5)TD$IG]

Fig. 5. The mechanism of direct synthesis of DMC from methanol and CO2 over different ceria catalysts.
 S.-Y. Zhao et al. / Chinese Chemical Letters 28 (2017) 65–69 69

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