English

• 0.   Introduction

  Dimethyl carbonate (DMC) has been widely applied as a fuel additive, in electrochemistry and organic synthesis due to its environmental-friendly properties^[1-3]. Although many methods have been applied for DMC synthesis, such as phosgene method, transesterification method, urea alcoholysis method, epoxy alkane method, methanol, and CO₂ direct synthesis method, etc.^[4-6]. Direct synthesis of DMC from CO₂ and methanol has attracted great attention (Scheme 1)^[7]. The utilization of CO₂ as the carbon source instead of fossil feedstock may promote the sustainability of the chemical industry and terminate the greenhouse effect caused by excessive CO₂ emission. However, there are still some vital challenges such as low yield, deactivation of the catalyst, and thermodynamic limitations for this route^{[6, 8]}. Thus, designing novel catalysts and developing efficient water removing methods from the reaction mixture are crucial to overcoming the thermodynamic equilibrium of the reaction.

  Scheme 1

  

  Scheme 1.  Direct synthesis of DMC from CO₂ and methanol

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  Ceria-based nanomaterials have been widely studied in the direct synthesis of DMC from CO₂ and methanol. This is mainly due to its fascinating CO₂ capture ability which significantly affects the reaction efficiency. Inert CO₂ molecular in the gas phase needs to be adsorbed and activated by the surface oxygen vacancy sites and then can react with methanol to generate DMC^[9-12]. Doping metal ions while maintaining the fluorite crystalline structure of ceria is one of the effective ways to enhance the concentration of surface oxygen vacancy of CeO₂^{[9, 13-14]}. Because the impurity ions can reduce the crystalline size, generate more surface defects and boost the reducibility of surface oxygen^[15-16]. On another hand, the surface acid - base property of CeO₂ can be mediated by the doping method, which will further favor the formation of DMC to improve the selectivity^[9]. According to Scheme 1, the reaction equilibrium can shift toward the right side by water removal^[17]. Usually, inorganic dehydrating agents are introduced to physically remove water with limited effect due to the low dehydration capacity at reaction temperatures^[18-21]. While organic dehydrating agents are applied to remove water by chemical reactions which may form lots of by-products complicating the entire process^[22-25]. Coating the catalyst powder on the surface of cordierite honeycomb ceramics can improve the phase-phase mass transfer performance^[26-28]. Therefore, it is reasonable to expect an enhanced efficiency for water removal using a honeycomb structure catalyst, which will improve the DMC yield in return.

  In this contribution, Ce_1-xMg_xO₂ (x=0.05, 0.10, 0.15, 0.20) solid solutions with a variation of magnesium content were prepared by the co-precipitation method to find an optimal ratio. Mg ions doping in CeO₂ lattice adjusted the surface acid-base property and the surface oxygen vacancies. Among all the obtained catalytic materials, Ce_0.90Mg_0.10O₂ was found to show the best catalytic activity in the direct synthesis of DMC from methanol and carbon dioxide. Using a unique structure, monolithic catalyst produced by coating powder on cordierite honeycomb ceramics showed high effective and stable catalytic performance. At 140 ℃, 2.4 MPa, and 2 h continuous reaction, the yield of DMC over Ce_0.90Mg_0.10O₂ monolithic catalyst was the highest (20.21%).

  1.   Experimental

  1.1   Materials preparations

  The preparation of Ce_0.90Mg_0.10O₂ by the coprecipitation method is described as an example. We weighed 15.000 0 g (NH₄)₂Ce(NO₃)₆, 0.779 5 g Mg(NO₃)₂ ·6H₂O, and 70.000 0 g urea (CH₄N₂O) and dissolved them completely with 500 mL deionized water under stirring. The mixture was transferred to a 1 000 mL three - neck flask and gradually heated to 90 ℃ under mechanical stirring (600 r·min^-1) for 5 h. After the reaction, the product was cooled to room temperature naturally, the precipitate was filtered and washed with water (over 4 000 mL) and absolute ethanol (about 300 mL), dried overnight at 80 ℃, and calcined at 400 ℃ for 4 h in the air to obtain the target product. The obtained Ce_1-xMg_xO₂ powder was ground with the required deionized water to obtain a slurry, which was coated on a cordierite honeycomb ceramics (64 cells per cm², Φ: 10 mm, L: 25 mm). The load was maintained at 0.5 g, and the excess slurry was blown away. Finally, the coated catalyst was dried overnight at 80 ℃ and calcined at 400 ℃ for 4 h in the air to obtain a Ce_0.90Mg_0.10O₂ monolithic catalyst. The preparation method of Ce_0.95Mg_0.05O₂, Ce_0.85Mg_0.15O₂, and Ce_0.80Mg_0.20O₂ monolithic catalysts were the same as above, only the mass of Mg(NO₃)₂·6H₂O was changed.

  1.2   Catalytic tests

  The catalytic activity of the prepared catalyst for the direct synthesis of DMC from CO₂ and methanol was evaluated in a continuous fixed-bed reactor. Water was the main disadvantageous factor for the formation of DMC in the synthesis reaction. The flow of the reaction system can remove the water vapor well and detect the reaction products online. A typical procedure was to place the prepared Ce_1-xMg_xO₂ monolith catalyst in a stainless steel reaction tube. The reactor was sealed and purged with a CO₂ stream for 30 min to drain the internal air. When the reaction system reached the required temperature, a mixed gas stream of CH₃OH (0.145 mL·min^-1) and CO₂ (40 mL·min^-1) (n_CH3OH∶n_CO2=2∶1) was introduced. Then the reaction was carried out at 140 ℃, 2.4 MPa, and 2 880 h^-1 of gas hourly space velocity (GHSV). The outlet component after the reaction was analyzed online using gas chromatography (Agilent 7890B) equipped with a hydrogen flame ionization detector. The calculation formula for CH₃OH conversion and DMC selectivity is as follows:

  $ {\rm{Conversion}} = \frac{{2{c_{{\rm{DMC}}}} + {c_{{\rm{HCHO}}}} + 2{c_{{\rm{DME}}}}}}{{{c_{{\rm{C}}{{\rm{H}}_3}{\rm{OH}}}} + 2{c_{{\rm{DMC}}}} + 2{c_{{\rm{DME}}}} + {c_{{\rm{HCHO}}}}}} \times 100\% $

  (1)

  $ {\rm{Selectivity}} = \frac{{{c_{{\rm{DMC}}}}}}{{{c_{{\rm{DMC}}}} + {c_{{\rm{DME}}}} + {c_{{\rm{HCHO}}}} + {c_{{\rm{CO}}}}}} \times 100\% $

  (2)

  Where c_i represents the concentration of a component (i).

  2.   Results and discussion

  2.1   Characterization of as-prepared solid solutions

  Fig. 1 shows the X - ray diffraction (XRD) patterns of the prepared Ce_1-xMg_xO₂ composite oxides (Detailed characterization conditions can be found in Supporting Information). CeO₂ samples showed typical diffraction lines of cubic fluorite structure (PDF No. 43-1002). Besides, it can be seen that the catalyst doped with Mg²⁺ still maintained the characteristic peak of cubic fluorite ceria after calcination, no diffraction line representing MgO or any other impurities was detected. Compared with pure CeO₂, the (111) plane peak shifted to a higher angle with increased Mg concentration (Fig. 1b), indicating a lattice contraction. The calculated lattice constant decreased from 0.541 8 nm for CeO₂ to 0.540 6 nm for Ce_0.80Mg_0.20O₂ (Table 1) because the ionic radius of Mg²⁺ (0.089 nm) is smaller than that of Ce⁴⁺ (0.097 nm). The XRD patterns imply that the Mg²⁺ incorporate into the CeO₂ lattice forming no MgO species and part of them substitutes the Ce⁴⁺ leading to lattice contraction. These results are in good agreement with previous reports^{[15, 29-30]}. The calculated grain size from (111) for all samples ranges from 5.8 to 6.1 nm and the specific surface area is basically the same, indicating that the addition of Mg has little influence on the micro-textural property.

  Figure 1

  

  Figure 1.  (a) XRD patterns of Ce_{1 -x}Mg_xO₂ composite oxides and (b) zoomed-in view of the (111) plane peak

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  Table 1

  

  Table 1.  Structural and textural properties of Ce_1-xMg_xO₂ composite oxides

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  Catalyst	(111) plane		Lattice parametera / nm	Particle sizeb / nm	SBET / (m2·g-1)	VPore / (m3·g-1)
  	2θ / (°)	d / nm
  CeO2	28.510	0.312 8	0.541 8	8.6	133	0.131
  Ce0.95Mg0.05O2	28.709	0.311 3	0.540 5	6.7	129	0.142
  Ce0.90Mg0.10O2	28.730	0.310 0	0.540 1	5.8	136	0.188
  Ce0.85Mg0.15O2	28.770	0.310 1	0.539 8	6.1	117	0.129
  Ce0.80Mg0.20O2	28.757	0.310 2	0.540 6	6.3	126	0.168
  a Calculated using Vegard′s law; b Estimated by TEM.

  The N₂ adsorption - desorption isotherms and pore size distributions of Ce_{1 -x}Mg_xO₂ catalyst are shown in Fig.S1. As shown in Fig.S1, all catalysts obtained type Ⅳ isotherms with clear H3 hysteresis lines, indicating typical mesoporous materials. In Fig. S2, all catalysts contain mesopore pore size distributions with pore sizes ranging from 2 to 20 nm. The above results show that the Mg²⁺ content has a significant effect on the pore size distribution. The BET (Brunauer - Emmett - Teller) surface area and pore volume of the synthesized Ce_1-xMg_xO₂ catalyst are summarized in Table 1. It can be observed that Ce_0.90Mg_0.10O₂ composite oxide possesses the highest specific surface area of 136 m²·g^-1 and pore volume of 0.188 cm³·g^-1.

  Transmission electron microscope (TEM) images (Fig. 2) of as-prepared Ce_1-xMg_xO₂ composite oxides indicated that all samples were in irregular spherical shape exposing no specific facets. The average particle size of as - prepared Ce_1-xMg_xO₂ is consistent with the grain size.

  Figure 2

  

  Figure 2.  (a-e) TEM images of Ce_1-xMg_xO₂ composite oxides; (f) Size distribution of Ce_0.90Mg_0.10O₂

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  There are two bands observed in Raman spectra (Fig. 3). The vibration peak around 461 cm^-1 can be attributed to the F_2g vibrational mode of Ce—O, which usually shows a sharp and symmetric band at 466 cm^{-1[9, 31]}. Considering the high specific surface area of the prepared material, the peak shifted to low frequency and showed asymmetric character, which are mainly attributed to the small particle size. Compared with asprepared CeO₂ nanoparticles, the F_2g band gradually blue-shifted with increased Mg²⁺ content, which demonstrates the decreased average length of Ce—O bond and lattice contraction further. Therefore, it is reasonable to deduce that smaller Mg²⁺ cations substitute some Ce⁴⁺ ions in the fluorite lattice. It is also noted that the intensity of F_2g decreased with increased Mg²⁺ content, revealing structural distortion^[32-33]. Another band near 596 cm^-1 is related to the oxygen vacancies caused by the Ce³⁺ ion in the CeO₂ lattice (Fig. 3b)^[34]. The intensity of this mode increased with an increase of Mg²⁺ content, pointing at increased intrinsic oxygen vacancy concentration. No Raman shifts of MgO were observed in Ce_1-xMg_xO₂, which further infers Ce_1-xMg_xO₂ prefers a solid solution state.

  Figure 3

  

  Figure 3.  (a) Raman spectra of Ce_1-xMg_xO₂ composite oxides and (b) zoomed-in view of the peak attributed to oxygen vacancies

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  To elaborate on changes in the CeO₂ chemical state after Mg doping, X -ray photoelectron spectroscopy (XPS) analysis was carried out. The XPS spectra of Ce3d (Fig. 4a) exhibit complex features with eight peaks. U and V represent spin - orbits of Ce3d_3/2 and Ce3d_5/2, respectively. Spin-orbit doublet (V‴ ca. 898.3 eV and U‴ ca. 916.8 eV, V″ ca. 888.9 eV and U″ ca. 907.4 eV, V ca. 882.4 eV and U ca. 900.9 eV) are attributed to the Ce⁴⁺ species, while (V′ ca. 884.9 eV and U′ ca. 903.4 eV) are assigned to the Ce³⁺ species^{[29, 31]}. Then the concentration of Ce³⁺ can be estimated by taking the ratio of the area of the integrated peak corresponding to Ce³⁺ to the total area of fitted peaks. It is shown that Mg doping has enhanced the concentration of Ce³⁺ on the surface remarkably, and the maximum ratio (19.42%) has been obtained when 10% Mg doping. The O1s XPS spectra (Fig. 4b) of Ce_1-xMg_xO₂ composite oxides can be deconvoluted into 3 surface oxygen species: lattice oxygen (O_L ca. 529.3 eV), surface oxygen vacancies (O_V ca. 530.5 eV); and chemisorption oxygen species (O_C) at the highest binding energy (ca. 532.2 eV)^[35]. The intensity ratio of surface oxygen vacancies to the sum of all oxygen species was summarized in Table 2. It was observed that the incorporation of Mg²⁺ can effectively increase the number of surface oxygen species (O_V+O_C). These results confirm that there are enhanced mobility and availability of lattice oxygen species due to the synergistic effect between MgO and CeO₂.

  Figure 4

  

  Figure 4.  (a) Ce3d and (b) O1s XPS spectra of Ce_1-xMg_xO₂ composite oxides

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  Table 2

  

  Table 2.  Relative ratio of Ce³⁺ species and oxygen vacancies on the surface

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  Catalyst	Surface content of Ce3+ / %	Surface content of OV+OC / %	Total amount of adsorbed CO2a / (mmolCO2·gcat-1)
  CeO2	1.34	24.97	0.787
  Ce0.95Mg0.05O2	11.57	30.85	0.794
  Ce0.90Mg0.10O2	19.42	31.98	0.845
  Ce0.85Mg0.15O2	15.18	25.06	0.808
  Ce0.80Mg0.20O2	15.40	23.19	0.771
  aDetermined using the CO2 temperature-programmed desorption (CO2-TPD) analysis in Fig.S3.

  Fig. 5 shows the temperature - programmed reduction by hydrogen (H₂-TPR) profile of as-prepared Ce_1-xMg _xO₂ composite oxides. The TPR of pure CeO₂ showed a broad peak starting at 500 ℃ and one peak at 825 ℃, representing the surface and the bulk reduction process, respectively. The surface reduction initiated around a lower temperature 500 ℃ after Mg²⁺ ions (less than 20%) were introduced, which means the reducibility of surface oxygen species has been significantly improved. Meanwhile, the area of this broad peak increased gradually with higher Mg concentration as well, indicating the lattice oxygen in bulk can move to the surface and participate in chemical reactions at a relatively lower temperature. Thus not only the reducibility of surface oxygen but also the mobility of lattice have activated due to Mg²⁺ introduction, resulting in more oxygen vacancies, probably by reducing the interaction between Ce— O with a distorted crystalline structure. This feature will facilitate chemical reactions whose reactants would be activated by oxygen vacancies. According to the related literature, the oxygen vacancy is crucial for activating carbon dioxide in the direct synthesis of DMC from CO₂ and methanol^{[11, 34, 36]}.

  Figure 5

  

  Figure 5.  H₂-TPR profiles of CeO₂ and Ce_1-xMg_xO₂ composite oxides

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  2.2   Catalytic performance

  Fig. 6a illustrates photographs of as-prepared monolithic catalyst. A scanning electron microscope (SEM) image (Fig. 6) revealed that the average thickness of the catalyst coating was ca. 60 μm. Well uniform coating layers were found, as evidenced in the corner, inner, and frontal channel views from the energy dispersion X-ray spectrum (EDS) mappings of Ce_0.90Mg_0.10O₂ -coated monolithic catalyst. The abnormal distribution of Mg is due to a small amount of Mg in cordierite. It also demonstrates that Ce_0.90Mg_0.10O₂- coated monolithic catalyst can be insufficient contact with the reaction gas stream to promote the conversion and the yield of the product^[37]. Catalyst activity of monolithic and particulate (40-60 mesh) Ce_0.90Mg_0.10O₂ catalyst was comparatively studied (Fig. 7). It is easy to conclude this monolithic do have enhanced the DMC yield and methanol conversion even though both were carried out in the same fixed bed reactor. Therefore, it is probable that the unique structure of the monolithic catalyst accelerates the water removal and shifts the reaction equilibrium successfully. Fig. 8 shows the performance of Ce_1-xMg_xO₂ monolithic catalysts on direct DMC synthesis. The optimum temperature and optimum pressure can be obtained from Fig.S4 and S5. The activity of the catalyst was Ce_0.90Mg_0.10O₂ > Ce_0.95Mg_0.05O₂ > CeO₂ > Ce_0.85Mg_0.15O₂ > Ce_0.80Mg_0.20O₂. When x=0.10, the yield of DMC reached the maximum of 20.21% and decreased with a higher doping concentration. It is mainly reflected in the decrease of DMC selectivity and the increase of HCHO and DME selectivity.

  Figure 6

  

  Figure 6.  (a) Photographs, (b) SEM image, and (c-e) EDS element mappings on Ce_0.90Mg_0.10O₂-coated monolithic catalyst

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  Figure 7

  

  Figure 7.  Catalytic activity of monolithic and particulate Ce_0.90Mg_0.10O₂ catalyst

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  Figure 8

  

  Figure 8.  Catalytic performance of Ce_1-xMg_xO₂ monolithic catalysts

  Reaction conditions: catalyst: 500 mg, GHSV: 2 880 mL·g_cat^-1·h^-1, n_CH3OH∶n_CO2=2∶1, temperature: 140 ℃, pressure: 2.4 MPa

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  According to our previous studies, there are the following reaction processes in this process: (Ⅰ) 2CH₃OH → CH₃OCH₃+H₂O; (Ⅱ) 2CH₃O+CO₂ → HCHO+CO+H₂O^[35]. It can be seen that the doping of Mg can promote the process of (Ⅰ) and (Ⅱ), which leads to a decrease in the selectivity of DMC.

  Figure 9

  

  Figure 9.  Durability test of Ce_0.90Mg_0.10O₂ monolithic catalyst

  Reaction conditions: catalyst: 500 mg, GHSV: 2 880 mL·g_cat^-1·h^-1, n_CH3OH∶n_CO2=2∶1, temperature: 140 ℃, pressure: 2.4 MPa

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  To provide referable information for the industry, we examined the stability of Ce_0.90Mg_0.10O₂ monolithic catalyst at 140 ℃ and 2.4 MPa. There is little deactivation for this catalyst (DMC yield from 20.21% to 19.56%) during the 50 h durability test implies it is a quite promising application for the direct synthesis of DMC from CO₂ and methanol.

  3.   Conclusions

  In conclusion, doping Mg in CeO₂ lattice can enhance the catalytic performance on the direct formation of DMC from methanol and CO₂. Since Mg²⁺ ions play an important role in the activation of oxygen species in CeO₂ lattice, which favors the oxygen vacancies formation. At the same time, the honeycomb structure of the monolithic catalyst greatly improves the removal of reaction products, overcoming thermodynamic limitations to some extent. Consequently, the yield of DMC and the stability of the catalyst can be improved.

  Supporting information is available at http://www.wjhxxb.cn

  
  Acknowledgments: We acknowledge XIAO Yong - Li, JIANG Lan for their aid in this work.
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  Scheme 1  Direct synthesis of DMC from CO₂ and methanol

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  Figure 1  (a) XRD patterns of Ce_{1 -x}Mg_xO₂ composite oxides and (b) zoomed-in view of the (111) plane peak

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  Figure 2  (a-e) TEM images of Ce_1-xMg_xO₂ composite oxides; (f) Size distribution of Ce_0.90Mg_0.10O₂

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  Figure 3  (a) Raman spectra of Ce_1-xMg_xO₂ composite oxides and (b) zoomed-in view of the peak attributed to oxygen vacancies

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  Figure 4  (a) Ce3d and (b) O1s XPS spectra of Ce_1-xMg_xO₂ composite oxides

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  Figure 5  H₂-TPR profiles of CeO₂ and Ce_1-xMg_xO₂ composite oxides

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  Figure 6  (a) Photographs, (b) SEM image, and (c-e) EDS element mappings on Ce_0.90Mg_0.10O₂-coated monolithic catalyst

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  Figure 7  Catalytic activity of monolithic and particulate Ce_0.90Mg_0.10O₂ catalyst

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  Figure 8  Catalytic performance of Ce_1-xMg_xO₂ monolithic catalysts

  Reaction conditions: catalyst: 500 mg, GHSV: 2 880 mL·g_cat^-1·h^-1, n_CH3OH∶n_CO2=2∶1, temperature: 140 ℃, pressure: 2.4 MPa

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  Figure 9  Durability test of Ce_0.90Mg_0.10O₂ monolithic catalyst

  Reaction conditions: catalyst: 500 mg, GHSV: 2 880 mL·g_cat^-1·h^-1, n_CH3OH∶n_CO2=2∶1, temperature: 140 ℃, pressure: 2.4 MPa

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  Table 1.  Structural and textural properties of Ce_1-xMg_xO₂ composite oxides

  Catalyst	(111) plane		Lattice parametera / nm	Particle sizeb / nm	SBET / (m2·g-1)	VPore / (m3·g-1)
  	2θ / (°)	d / nm
  CeO2	28.510	0.312 8	0.541 8	8.6	133	0.131
  Ce0.95Mg0.05O2	28.709	0.311 3	0.540 5	6.7	129	0.142
  Ce0.90Mg0.10O2	28.730	0.310 0	0.540 1	5.8	136	0.188
  Ce0.85Mg0.15O2	28.770	0.310 1	0.539 8	6.1	117	0.129
  Ce0.80Mg0.20O2	28.757	0.310 2	0.540 6	6.3	126	0.168
  a Calculated using Vegard′s law; b Estimated by TEM.

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  Table 2.  Relative ratio of Ce³⁺ species and oxygen vacancies on the surface

  Catalyst	Surface content of Ce3+ / %	Surface content of OV+OC / %	Total amount of adsorbed CO2a / (mmolCO2·gcat-1)
  CeO2	1.34	24.97	0.787
  Ce0.95Mg0.05O2	11.57	30.85	0.794
  Ce0.90Mg0.10O2	19.42	31.98	0.845
  Ce0.85Mg0.15O2	15.18	25.06	0.808
  Ce0.80Mg0.20O2	15.40	23.19	0.771
  aDetermined using the CO2 temperature-programmed desorption (CO2-TPD) analysis in Fig.S3.

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