2018, Liu Et Al., Oxygen Vacancy Promoting Dimethyl Carbonate Synthesis From CO2 and Methanol Over Zr-Doped CeO2 Nanorods
2018, Liu Et Al., Oxygen Vacancy Promoting Dimethyl Carbonate Synthesis From CO2 and Methanol Over Zr-Doped CeO2 Nanorods
2018, Liu Et Al., Oxygen Vacancy Promoting Dimethyl Carbonate Synthesis From CO2 and Methanol Over Zr-Doped CeO2 Nanorods
ABSTRACT: The synthesis of dimethyl carbonate (DMC) from CO2 and methanol by
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Zr-doped CeO2 nanorods with different ratios of Zr/Ce has been studied at 6.8 MPa and 140 °C.
The catalysts were characterized extensively by TEM, XRD, N2 adsorption, Raman spectroscopy,
UV−vis spectroscopy, XPS, CO2-TPD, and in situ FTIR techniques. Doping of Zr atoms into the
ceria lattice produced a fluorite-like solid solution, promoting the formation of oxygen vacancy
sites. Zr-doped CeO2 nanorods exhibited significantly more oxygen vacancy sites than pure CeO2
nanorods. Zr0.1Ce nanorods which exhibited DMC synthesis activity also possess the highest concentration of oxygen vacancy sites.
In situ FTIR studies further revealed that CO2 can adsorb on the oxygen vacancy to form bidentate carbonate and as intermediate
to participate in the reaction. This study presents a strategy to design a high-efficiency CeO2-based catalysts by controlling the
concentration of the surface oxygen vacancies.
KEYWORDS: Zr-doped CeO2 nanorods, oxygen vacancy, CO2 adsorption, dimethyl carbonate, bidentate carbonate
Scheme 1. Schematic Illustration of the Synthesis Process of the Zr-Doped CeO2 Nanorods
compared to pure CeO2 nanorods because of the presence of a Specific surface area measurement was carried out by a
high concentration of oxygen vacancies on the doped CeO2 Beishide 3H-2000PS2 surface analyzer using nitrogen adsorp-
nanorods.31 According to these previous studies, oxygen vacan- tion at liquid-nitrogen temperature (77 K). Before the test, the
cies could play a significant role in the direct synthesis of DMC sample was degassed in situ at 250 °C for 4 h. The surface
on CeO2-based catalysts.32,33 However, the effect of the surface areas of the catalysts were estimated by the Brunauer−
oxygen vacancy on this reaction is poorly understood. Emmett−Teller (BET) method, and the pore size distributions
In this work, the CeO2 nanorods with various Zr content were calculated from analysis of the desorption branch of the
were prepared and their activity in DMC synthesis from CO2 isotherm via the conventional the Barrett−Joyner−Halenda
and methanol was investigated. It was found that the surface (BJH) model.
oxygen vacancy concentration and CO2 adsorption varied with The contents of Ce and Zr were determined by inductively
Zr content, which are crucial to determine the catalytic activity coupled plasma atomic emission spectroscopy (ICP-AES).
of direct synthesis of DMC from methanol and CO2. Before analysis, 2 mL of concentrated HF was used to dissolve
80 mg of the samples, followed by adding 2 mL of 30 wt %
2. EXPERIMENTAL SECTION H2O2, and then the solution was diluted to 1000 mL with
deionized water. Elemental analysis was performed.
2.1. Materials. Cerium(III) nitrate hexahydrate (Ce(NO3)3· Raman spectra were recorded by a Renishaw in ViainVia
6H2O, 99.9%, AR) and zirconium nitrate (Zr(NO3)4·5H2O, micro laser Raman spectrometer (U.K.), Ar+ laser (514.5 nm
99.0%, AR) were purchased from Tianjin Guangfu Fine wavelength), with an output power of 4 mW. The UV−vis
Chemical Research Institute (Tianjin, China); sodium hydrox- spectra of the catalyst samples were obtained by a PerkinElmer
ide (NaOH, 99%, AR) was obtained from Feng Chuan Lambda 900 UV−vis/NIR spectrophotometer.
Chemical Reagent Co, Ltd. (Tian jin, China). All reagents X-ray photoelectron spectroscopy (XPS) data were obtained
were used as received without further purification. by an ESCALab220i-XL electron spectrometer (VG, UK)
2.2. Catalyst Preparation. The nanorods were synthesized using 300 W Al Kα radiation. The samples were compressed
by the hydrothermal process based on a previous report.34 into a pellet of 2 mm thickness and then mounted on a sample
Typically (shown in Scheme 1), Zr(NO3)4·5H2O and holder by utilizing double-sided adhesive tape for XPS analysis.
Ce(NO3)3·6H2O with different mole ratios were dissolved in The sample holder was then placed into a fast entry air load-
30 mL of deionized water under vigorous stirring until com- lock chamber without exposure to air and evacuated under
pletely dissolved. Simultaneously, 84.0 g of NaOH was dis- vacuum (<10−6 Torr) overnight. Finally, the sample holder was
solved in 210 mL of deionized water. Then the two solutions transferred to the analysis chamber for XPS study. The base
were mixed together and kept stirring for 30 min. The obtained pressure inside the analysis chamber was usually maintained at
mixed slurry was transferred into a 300 mL stainless steel <10−10 Torr. The binding energies were referenced to the C 1s
autoclave and kept at 100 °C for 24 h. After the autoclave was line of adventitious carbon at 284.6 eV.
cooled down to room temperature, the products were washed Temperature-programmed desorption (TPD) was carried
with deionized water until the pH reaches 7 and then washed out on a Micromeritics Autochem II 2920 analyzer. A 0.1 g
several times with ethanol. The resulting product was dried at amount of sample was pretreated at 200 °C for 1 h under N2.
80 °C overnight and then calcined at 600 °C for 5 h in a muffle CO2 (NH3) adsorption was performed at 25 °C by switching
furnace to obtain ZrxCe nanorods, where x is the mole ratio of He flow to a stream of 15 vol % CO2 (NH3)−He (40 mL·
Zr to Ce in the catalysts. The Zr/Ce mole ratio was controlled min−1) and maintaining the temperature for 60 min. The
in the range from 0 to 0.3 in order to keep the morphology sample was purged with He (40 mL·min−1) for 2 h in order to
of nanorods. For comparison, the pure ZrO2 were synthesized remove the physically adsorbed CO2 (NH3). TPD test was carried
by the same process. To highlight the important role of hydro- out under the condition of a constant flow of He (40 mL·min−1)
thermal synthesis in the preparation of nanorod catalyst, we from 50 to 600 °C at a heating rate of 10 °C·min−1. The con-
also prepared CeO2 particles for XPS and catalyst activity centration of CO2 (NH3) in the tail gas was continuously
studies (SI, Activity and Characterization of CeO2 particles monitored by a TCD detector.
prepared by coprecipitation). The IR measurements were performed on a Nicolet 6700
2.3. Material Characterization. The morphology of FTIR spectrometer (Thermo-Nicolet) with a DRIFTS (diffuse
the obtained powder of CeO2, ZrxCe nanorods, and ZrO2 reflectance fourier-transform spectroscopy) reactor by the fol-
was characterized by a JEOL JEM-2100 transmission electron lowing procedures.35−37
microscope operated at an accelerating voltage of 200 kV.
Samples for TEM analyses were prepared by dispersing the (1) Pretreatment: 10 mg of catalyst powder was placed in
powdered products in ethanol and then deposited on a carbon the cell, and the catalyst was heated at 200 °C for 10 min
film coated on a copper grid. in an argon environment. Part of the preadsorbed water
The powder X-ray diffraction patterns of the investigated and CO2 were removed.
catalysts were obtained from an X-ray diffractometer equipped (2) CO2 adsorption: Argon was flowed in the IR cell (flow
with a Cu Kα radiation source (in the 2θ range 10−85° with a of Ar is 40 mL·min−1). After 1 min, the flowing gas was
scanning speed of 8°/min). switched to CO2 with the flow 40 mL·min−1.
10447 DOI: 10.1021/acscatal.8b00415
ACS Catal. 2018, 8, 10446−10456
ACS Catalysis Research Article
Table 1. Interplanar Spacing, Lattice Parameters, Specific CeO2 lattice. The ID/IF2g values indicate the amounts of defects
Surface Area, and Pore Volume of the Catalysts in the catalysts.28,42 The ID/IF2g values of CeO2 and ZrxCe
catalysts are shown in Figure S1 in the Supporting Information,
interplanar lattice SBET Vpore
2θ spacing (Å) parameterb (m2/g) (cm3/g) which increased in the following order: CeO2 < Zr0.05Ce <
Zr0.1Ce < Zr0.2Ce < Zr0.3Ce, indicating that the amounts of
CeO2 28.64 3.11 5.39 75 0.51
defects in the catalysts increased with the Zr contents. No
Zr0.05Ce 28.76 3.10 5.38 83 0.65
Raman shifts of ZrO2 are observed in ZrxCe, which indicated
Zr0.1Ce 28.79 3.10 5.37 76 0.52
ZrO2 and CeO2 formed a solid solution in line with XRD
Zr0.2Ce 28.88 3.09 5.36 72 0.51
results. For the pure ZrO2, the bands at 146, 266, 319, 461, and
Zr0.3Ce 28.94 3.08 5.35 59 0.45
643 cm−1 could be assigned to tetragonal ZrO2.43,44
ZrO2 30.38 3.07 3.58 46 0.34
a
The introduction of Zr species into CeO2 increases the
Calculated by the (111) plane from XRD. bCalculated for ZrxCe absorbance in the visible light region (see the UV−vis spectra
catalysts by the cubic phase and for ZrO2 by tetragonal.
in Figure S2 in Supporting Information). The adsorption edge
of ZrxCe catalysts slightly shifted to the higher wavenumbers,
CeO2, Zr0.05Ce, Zr0.1Ce, Zr0.2Ce, Zr0.3Ce, and ZrO2, are 5.39, increasing the absorption intensity in the range of 200−500 nm.
5.38, 5.37, 5.36, 5.35, and 3.58 Å, respectively (Table 1). The Thus, the results indicate that the substitution of Ce4+ with Zr
lattice parameter decreased with the Zr content because the species facilitates the formation of Ce3+ ions, leading to a rise
ionic radius of Zr4+ (0.84 Å) is smaller than that of Ce4+ of oxygen vacancy concentration in Zr-doped CeO2 nanorods
(0.97 Å). These results confirmed the incorporation of Zr4+ through distorting the lattice structure.45
into the lattice of CeO2, resulting in the formation of a solid 3.4. Concentration of the Surface Oxygen Vacancies
solution accompanied by the shrinking interplanar spacing, and Chemical States of the Catalysts. Figure 4 shows the
which decreased from 3.11 to3.08 Å.37 The ZrO2 catalyst only XPS spectra of the catalysts. The characters V and U are
showed the tetragonal phase (t-ZrO2), which differs from the related to the spin−orbit splitting of Ce 3d5/2 and Ce 3d3/2.46
structure of pure CeO2 and ZrxCe nanorods.39 In Figure 4a, Ce 3d spectra can be deconvoluted into eight
The XRD patterns in Figure 2 and lattice parameters in peaks: U‴ (∼916.8 eV), U″ (∼907.4 eV), U′ (∼903.4 eV),
Table 1 agree with those disclosed by Liu et al.31 Figure 2 also U (∼900.9 eV), V‴ (∼898.3 eV), V″ (∼888.9 eV),
shows that ZrxCe gave broader peaks than CeO2, suggesting V′ (∼884.9 eV), and V (∼882.4 eV). The four U bands repre-
that Zr doping decreases the crystallite size of nanorods. sent the Ce 3d3/2, and the other V bands represent the Ce
3.3. Raman Spectra. The Raman spectra in Figure 3 3d5/2. The 3d104f 0 state of Ce4+ species is labeled as U‴, U″, U,
further confirmed the formation of ceria−zirconia solid V‴, V″, and V, whereas the 3d104f1 state of Ce3+ species is
labeled as U′ and V′. The V′ and U′ peaks can be used to
quantitatively estimate the concentration ratio of Ce3+ by
calculating the ratio between the area of V′, U′ peaks and the
total area of V, V″, V‴, U, U″, and U‴ peaks based the
following equation
A Ce3+
C[Ce3 +]% = × 100%
A Ce3+ + A Ce4+
Figure 4. (a) Ce 3d and (b) O 1s XPS spectra of CeO2, ZrxCe nanorods, and ZrO2.
Table 2. Relative Ratios of the Surface Concentration of ZrxCe catalysts exhibit two Zr 3d peaks at 181.8 and 184.2 eV
Ce3+ and Oxygen Vacancy Based on XPS Analysis that could be related to the Zr 3d3/2 and 3d5/2 spin−orbit
splitting. The binding energy of Zr 3d in the ZrxCe catalysts
catalyst CeO2 Zr0.05Ce Zr0.1Ce Zr0.2Ce Zr0.3Ce ZrO2
(182.1 and 184.5 eV) was higher than that in ZrO2.52 These
surface content of 17.9 20.7 21.5 19.8 18.7 results further confirmed that Zr4+ entered into the CeO2
Ce3+
lattice and formed the solid solutions, as shown by the results
surface content of 7.1 9.4 10.4 8.8 7.7 6.0
OV (%) of XRD and TEM.49,52
bulk atomic ratio 0.039 0.13 0.24 0.37 3.5. TPD Analysis of the Catalysts. It has been reported
Zr/Ce (%)a that the surface oxygen vacancy acts as Lewis acid sites and
surface atomic ratio 0.059 0.11 0.27 0.47 plays a key role in the adsorption of CO2.13 Thus, we further
Zr/Ce (%)b
a
studied the nature of the catalyst surface by CO2-TPD. The
Determined by ICP. bDetermined by XPS. results are shown in Figure 5. The amount of CO2 desorbed
The surface acid properties of the catalysts were investigated increasing Zr/Ce ratios. In Figure S6 the yields increased from
by NH3-TPD, and the results are exhibited in Figure S5. The 7.2 to 12.1 mmol/g for CeO2 and from 10.2 to 14.9 mmol/g
amount of NH3 of all of the catalysts is calculated from the for Zr0.1Ce with increasing reaction time. It is also noted that
TPD peak area and also displayed in Figure S5. It is observed further increasing the reaction time has not exhibited an
from FigureS5 that the CeO2, ZrxCe nanorods, and ZrO2 obvious increase of the yields for the Zr0.1Ce catalyst. These
catalyst contained the same types of acidic sites: the desorption results indicated that the reaction may reach a plateau state
peaks in the range of 50−200, 200−400, and 400−600 °C can after 6 h reaction time for Zr0.1Ce catalyst because of the
be assigned to weak, moderate, and strong adsorption, respec- accumulation of water.
tively. The amount of NH3 desorbed from these sites is cal- According to the reaction equation of the DMC synthesis
culated and summarized in Table S3. It is noted that the acid from carbon dioxide and methanol, the thermodynamic infor-
properties of the catalysts were strongly affected after doping mation about this reaction was calculated by the thermody-
Zr into CeO2. The Zr0.1Ce has the highest acidic sites density namic data of various substances.55 The ΔGΘ298K and ΔHΘ298K
compared to other samples, and the adsorption quantity of values are 26.21 and −27.90 kJ/mol, respectively. The ΔG of
NH3 is 0.54 mmol/g−1, which indicated that Zr0.1Ce sample this reaction in our reaction conditions is about 32.95 kJ/mol.
has the largest number of acidic sites. The amount of adsorp- It can be seen that the Gibbs free energy of this reaction at
tion NH3 for all catalysts showed a volcano-shaped curve with ambient temperature is higher than 0, which indicated that this
respect to Zr content and followed the order Zr0.1Ce > reaction does not occur spontaneously at 413 K. However, we
Zr0.05Ce > Zr0.2Ce > CeO2 > Zr0.3Ce > ZrO2. It has to be can see from the estimated result that the ΔG (413 k, 6.8 MPa)
emphasized that the total acidity of ZrxCe nanorods catalysts is smaller than ΔGΘ413K, which indicates that an increase in the
was higher than pure CeO2 and ZrO2 catalysts (except Zr0.3Ce), pressure of the reaction is in favor of the formation of the DMC.
which may be ascribed to a synergic effect between ZrO2 and We also found that ΔG (413 k, 6.8 MPa) is still larger than
CeO2. At the same time, the findings also showed that the ΔGΘ298K; this is due to ΔHΘ413K < 0; hence, the higher temper-
acidity of Zr0.3Ce nanorods was lower than the acidity of CeO2 ature is not in favor of the formation of the DMC.
nanorods. It may be due to the BET surface and pore volume The stability is one of the most important concerns of the
of Zr0.3Ce nanorods (59 m2/g) being lower than pure CeO2 heterogeneous catalyst. The reusability of the catalysts in the
nanorods (74 m2/g) and exposed less acidic sites. Similar to DMC synthesis was tested with six reaction cycles under identical
CO2-TPD results, for all ZrxCe catalysts, weak and moderate reaction as mentioned in the Experimental Section. The results
acidic sites increased first and then decreased with higher Zr are shown in Figure S7 in the Supporting Information. The
content. It can be found that the Zr0.1Ce nanorods possess the activity from these catalysts decreased slightly after six cycles.
largest amount of acidic sites. By doping oxides the surface However, the activity of Zr0.1Ce remained the highest among all
acid−base sites of CeO2 will be varied and will bring about the samples. The activities of the catalysts were reduced by 21%, 24%,
performance differences; similar results were obtained by pre- 22%, 26%, 19%, and 68% after six cycle times corresponding to
vious reports.53,54 CeO2, Zr0.05Ce, Zr0.1Ce, Zr0.2Ce, Zr0.3Ce, and ZrO2, respectively.
3.6. Catalytic Activity. Figure 6 shows the catalyst per- 3.7. Characterization of the Used Catalyst. To deter-
formance over the catalysts. The ZrxCe nanorods gave higher mine the deactivation mechanism, we compared the TEM,
XRD, and XPS results of the fresh and used Zr0.1Ce nanorods.
The TEM results and the XRD patterns of the fresh Zr0.1Ce
and used Zr0.1Ce nanorods are shown in Figure S8 in the
Supporting Information. The TEM images of the morpholo-
gies of Zr0.1Ce nanorods showed that the fresh and used
Zr0.1Ce have the same morphologies after six cycles. However,
the used Zr0.1Ce nanorods had a mean diameter of ∼10 nm
and an average length of ∼46 nm; it appears that the used
Zr0.1Ce nanorods become a little wider and longer than fresh
Zr0.1Ce nanorods (∼9 and ∼40 nm). After six cycles, the used
Zr0.1Ce catalysts still display the characteristic diffraction peaks
corresponding to the cubic fluorite structure, which is fully
consistent with the TEM results.
Figure 7a and 7b compares the deconvoluted Ce 3d and
Figure 6. Catalytic performance of the CeO2, ZrxCe nanorods and O 1s XPS spectra of fresh and used Zr0.1Ce. The relative
ZrO2 catalysts. Methanol conversion = 2nDMC/nCH3OH × 100%. Error abundances of the Ce3+ and Ov of the samples, listed in Figure 7,
bars represent one standard deviation (n = 5). showed that the content of Ce3+ and the surface oxygen
vacancy decreased from 21.5% to 17.4% and from 10.4% to
activity than CeO2 and ZrO2. The yield reached a maximum 7.1%, respectively. This decrease could be attributed to partial
value of 14.2 mmol/g at Zr/Ce = 0.1 and then decreased with filling of surface oxygen vacancy with the O atom of adsorbed
further increasing Zr/Ce ratios. The activity of Zr0.1Ce is 1.3 CO2.56 A number of DFT studies have indicated that the sur-
and 6.7 times higher than that of the pure CeO2 and ZrO2, face oxygen vacancy is thermodynamically unstable and highly
respectively. The activity of the catalysts decreased in the order reactive; experimental studies also showed that the surface
Zr0.1Ce > Zr0.05Ce > Zr0.2Ce > Zr0.3Ce > CeO2 > ZrO2, which oxygen vacancy can interact with O from adsorbed CO2.57,58
followed the trend of the surface oxygen vacancy concen- 3.8. Effect of the Surface Vacancy Concentrations on
trations and the capacity of CO2 adsorption. Meanwhile, it can the CO2 Adsorption and Activity of Catalysts. The
be observed that the methanol conversion reached a maximum surface oxygen vacancy on the catalyst surface could serve as
value of 0.65% at Zr/Ce = 0.1 and then decreased with further Lewis acid sites that promote CO2 adsorption.13,33 Thus, we
10451 DOI: 10.1021/acscatal.8b00415
ACS Catal. 2018, 8, 10446−10456
ACS Catalysis Research Article
further investigated the relationship between the surface because the surface of CeO2 nanorods is more defective.
oxygen vacancy, CO2 adsorption capacity, and catalyst activity In CO2 methanation,15,61 some authors proposed that the sur-
in Figure 8. The adsorption capacity of CO2 of the catalysts face oxygen vacancy played an important role in the reduction
of CO2 to CO and proved that the surface oxygen vacancy cata-
lyzed the rate-determining step with a much lower activation
temperature. According to the previous reports and the obtained
results in this work, doped Zr into CeO2 lattice resulted in more
oxygen vacancies on the CeO2 surface serving as the active sites,
which can promote the interaction between CO2 and ZrxCe
nanorods.
3.9. In Situ FTIR Study. We have further employed in situ
FTIR to characterize the structure of adsorbed species and the
nature of the active sites. Figure 9a shows that CO2 adsorption
on CeO2 produced carbonate and bicarbonate.64,65
Zr doping decreased the IR intensity of bidentate carbonate.
Bidentate carbonate and bidentate bicarbonate can be assigned
to CO2 adsorbed on the surface oxygen vacancy sites. CO2 may
adsorb on the surface oxygen vacancy site through inserting
Figure 8. Relationship between catalyst activity, CO2 adsorption one O atom in the vacancy site on the surface of the catalysts.
amount, and concentration of the surface oxygen vacancy. The C atoms bind the O atom of the catalyst surface to form
the carbonate. A number DFT studies have demonstrated that
increased with the surface oxygen vacancy concentrations, the surface oxygen vacancy assists CO2 activation and adsorp-
indicating that surface oxygen vacancies promote CO2 adsorp- tion.57,59,66 This proposition is further supported by our XPS
tion. Oxygen vacancies can be associated with Ce3+. XRD, and CO2-TPD results.
Raman, and XPS results in Figures 2, 3, and 4 showed that Zr Figure 9b shows that the adsorption of methanol on CeO2
doping led to the formation of Ce3+ in the fluorite structure of produced terminal methoxy (1106 cm−1) and bridged methoxy
CeO2. The Lewis acid nature of oxygen vacancy allowed it (1052 cm−1) on Ce4+. Zr doping produced a methoxy
to interact with nonbonding electrons in the O atom of CO2 (1156 cm−1) on Zr4+. The formation of these positive methoxy
through Lewis acid−base interactions.13 A number of theo- bands is accompanied by an increase in the H2O band in the
retical and experimental studies suggest that the surface oxygen 3300−3400 cm−1 region and the negative OH band at 3674 cm−1.
vacancy allows inserting one of the O atoms of CO2 into the This observation has also been reported by former studies on
oxygen vacancy, forming a bent CO2− intermediate.59,60 Marco the interaction of alcohol with the surface hydroxyl groups of
Fronzi et al.60 suggested that a higher energy is needed to form metal oxides.67,68 This interaction allowed the transfer of the
an oxygen vacancy reflecting a higher reactivity of a reduced H atom from methanol’s OH to a coordinately unsaturated
nanocluster toward CO2. Our results showed ZrxCe nanorods O2− center on the catalyst surface, producing a bridging OH
with increasing surface oxygen vacancy concentration exhibited group. The H in methanol’s OH could also react the surface
a propensity to increase CO2 adsorption. OH group to produce surface water (Figure S9).69 Accordingly,
Figure 8 also shows that the catalytic activity of ZrxCe the whole process is summarized in Scheme S1.
catalysts increased with the surface oxygen vacancy concen- Because of its high activity, we have further studied the
tration. Among these catalysts, the Zr0.1Ce nanorods which interaction of CO2 with adsorbed methoxy species on Zr0.1Ce,
exhibited the highest activity among the investigated samples shown in Figure 10a. Exposure of adsorbed methoxy species
possessed the highest concentration of surface oxygen vacancy. to CO2 resulted in a rapid decrease in a terminal methoxy at
Oxygen vacancies promote the direct DMC synthesis from 1106 cm−1 and the formation of monomethyl carbonate. The
CO2/methanol. On the basis of the previous reports,61,62 CO2 IR spectra of monomethyl carbonate were further verified by
could be adsorbed and activated on the oxygen vacancy sites the adsorption of DMC on the catalysts in Figure 10b. Mono-
over the defect surface of metal oxide. In DFT studies, the methyl carbonate has been considered to be the reaction inter-
CO bond cleavage of CO2 is achieved by using one of the mediate of direct synthesis of DMC from CO2 and methanol.
O atoms to fill the oxygen vacancy with a small barrier, which Adsorption of DMC on Zr0.1Ce produced not only monomethyl
is easier than that on the metal surface.60 Wu et al.63 studied carbonate species but also adsorbed methoxy species. Adsorbed
the CeO2 nanocrystals with different morphology (rod, cube, DMC was not detected because the low-pressure condition used
octahedral) and found CeO2 nanorods bind CO2 strongly favors its conversion to monomethyl carbonate.69
10452 DOI: 10.1021/acscatal.8b00415
ACS Catal. 2018, 8, 10446−10456
ACS Catalysis Research Article
■
work, based on the XPS, CO2-TPD, and FTIR results, it can be
found that CO2 and methanol interact with the surface oxygen
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■ NOTE ADDED AFTER ASAP PUBLICATION
This paper published ASAP on October 18, 2018 with errors in
the Supporting Information file. The corrected paper reposted
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