Citation: Yue-Ying YAN, Yue LI, Jie DENG, Xi ZHAO, Na TA, Yong-Dong CHEN. Direct Synthesis of Dimethyl Carbonate from CO₂ and Methanol by Mg-Doped Ceria Monolithic Catalyst[J]. Chinese Journal of Inorganic Chemistry, ;2022, 38(7): 1402-1410. doi: 10.11862/CJIC.2022.139 shu

Direct Synthesis of Dimethyl Carbonate from CO₂ and Methanol by Mg-Doped Ceria Monolithic Catalyst

Yue-Ying YAN ¹ ,
Yue LI ¹ ,
Jie DENG ¹ ,
Xi ZHAO ¹ ,
Na TA ^2,, ,
Yong-Dong CHEN ^1,,

1.
College of Chemistry and Chemical Engineering, Southwest Petroleum University, Chengdu 610500, China
2.
State Key Laboratory of Catalysis, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian, Liaoning 116023, China

Corresponding author: Na TA, tana@dicp.ac.cn Yong-Dong CHEN, yongdongchen@swpu.edu.cn
Received Date: 17 March 2022
Revised Date: 18 May 2022

Figures(10)

In this paper, Ce_1-xMg_xO₂ (x=0.05, 0.10, 0.15, 0.20) solid solution catalytic materials with different molar ratios were successfully synthesized by co-precipitation method. These materials were characterized by transmission electron microscope (TEM), X-ray diffraction (XRD), nitrogen adsorption-desorption test, Raman spectroscopy, X-ray photoelectron spectroscopy (XPS), CO₂ temperature-programmed desorption (CO₂-TPD) and other techniques. It was found that the particle size, specific surface area, surface defects, etc. of the prepared Ce_1-xMg_xO₂ catalytic materials can be tuned by regulating the content of Mg in the CeO₂ lattice. Among them, Ce_0.90Mg_0.10O₂ exhibited the best surface properties, with the smallest average particle size of about 5.8 nm, the largest specific surface area of about 136 m²·g^-1, and the highest surface oxygen content (31.98%). Ce_1-xMg_xO₂ catalytic material was coated on the cordierite honeycomb ceramic to make a monolithic catalyst, and its catalytic performance for the direct synthesis of dimethyl carbonate from CO₂ and CH₃OH was investigated. Under the conditions of 140℃, 2.4 MPa, and 2 h reaction, the yield of dimethyl carbonate on Ce_0.90Mg_0.10O₂ monolith catalyst was as high as 20.21%, and the catalytic activity was significantly higher than that of CeO₂ and other Ce_1-xMg_xO₂ (x=0.05, 0.15, 0.20) catalytic materials.
- CO₂ conversion,
- dimethyl carbonate,
- oxygen vacancies,
- monolithic catalyst,
- magnesium-cerium oxides
1. [1]
  Schifter I, Gonzalez U, Gonzalez-Macias C. Effects of Ethanol, Ethyl-tert-butyl Ether and Dimethyl Carbonate Blends with Gasoline on SI engine[J]. Fuel, 2016,183:253-261. doi: 10.1016/j.fuel.2016.06.051
2. [2]
  Tundo P, Musolino M, Aricò F. The Reactions of Dimethyl Carbonate and Its Derivatives[J]. Green Chem., 2018,20:28-85. doi: 10.1039/C7GC01764B
3. [3]
  Selva M, Perosa A, Fiorani G. Dimethyl Carbonate: A Versatile Reagent for a Sustainable Valorization of Renewables[J]. Green Chem., 2018,20:288-322. doi: 10.1039/C7GC02118F
4. [4]
  Keller N, Rebmann G, Keller V. Catalysts, Mechanisms and Industrial Processes for the Dimethyl Carbonate Synthesis[J]. J. Mol. Catal. A: Chem., 2010,317:1-18. doi: 10.1016/j.molcata.2009.10.027
5. [5]
  Saavalainen P, Kabra S, Turpeinen E, Oravisjärvi K, Yadav G D, Keiski R L, Pongrácz E. Sustainability Assessment of Chemical Processes: Evaluation of Three Synthesis Routes of DMC[J]. J. Chem., 2015:1-12.
6. [6]
  Tamboli A H, Chaugule A A, Kim H. Catalytic Developments in the Direct Dimethyl Carbonate Synthesis from Carbon Dioxide and Methanol[J]. Chem. Eng. J., 2017,323:530-544. doi: 10.1016/j.cej.2017.04.112
7. [7]
  Dabral S, Schaub T. The Use of Carbon Dioxide (CO₂) as a Building Block in Organic Synthesis from an Industrial Perspective[J]. Adv. Synth. Catal., 2019,361:223-246. doi: 10.1002/adsc.201801215
8. [8]
  Cai Q H, Lu B, Guo L J, Shan Y K. Studies on Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide[J]. Catal. Commun., 2009,10:605-609. doi: 10.1016/j.catcom.2008.11.002
9. [9]
  Liu B, Li C M, Zhang G Q, Yan L F, Li Z. Direct Synthesis of Dimethyl Carbonate from CO₂ and Methanol over CaO-CeO₂ Catalysts: The Role of Acidic-Basic Properties and Surface Oxygen Vacancies[J]. New J. Chem., 2017,41:12231-12240. doi: 10.1039/C7NJ02606D
10. [10]
  Marciniaka A A, Henriqueb F J F S, Limac A F F, Alvesd O C, Moreirae C R, Appele L G, Mota C J A. What are the Preferred CeO₂ Exposed Planes for the Synthesis of Dimethyl Carbonate? Answers from Theory and Experiments[J]. Mol. Catal., 2020,493111053. doi: 10.1016/j.mcat.2020.111053
11. [11]
  Fu Z W, Yu Y H, Li Z, Han D M, Wang S J, Xiao M, Meng Y Z. Surface Reduced CeO₂ Nanowires for Direct Conversion of CO₂ and Methanol to Dimethyl Carbonate: Catalytic Performance and Role of Oxygen Vacancy[J]. Catalysts, 2018,8164. doi: 10.3390/catal8040164
12. [12]
  Zhao S Y, Wang S P, Zhao Y J, Ma X B. An In Situ Infrared Study of Dimethyl Carbonate Synthesis from Carbon Dioxide and Methanol over Well-Shaped CeO₂[J]. Chin. Chem. Lett., 2017,28:65-69. doi: 10.1016/j.cclet.2016.06.003
13. [13]
  Tamboli A H, Chaugule A A, Gosavi S W, Kim H. Ce_xZr_1-xO₂ Solid Solutions for Catalytic Synthesis of Dimethyl Carbonate from CO₂: Reaction Mechanism and the Effect of Catalyst Morphology on Catalytic Activity[J]. Fuel, 2018,216:245-254. doi: 10.1016/j.fuel.2017.12.008
14. [14]
  Fu Z W, Zhong Y Y, Yu Y H, Long L Z, Xiao M, Han D M, Wang S J, Meng Y Z. TiO₂-Doped CeO₂ Nanorod Catalyst for Direct Conversion of CO₂ and CH₃OH to Dimethyl Carbonate: Catalytic Performance and Kinetic Study[J]. ACS Omega, 2018,3:198-207. doi: 10.1021/acsomega.7b01475
15. [15]
  Yu Q, Wu X X, Tang C J, Qi L, Liu B, Gao F, Sun K Q, Dong L, Chen Y. Textural, Structural, and Morphological Characterizations and Catalytic Activity of Nanosized CeO₂-MO_x (M=Mg²⁺, Al³⁺, Si⁴⁺) Mixed Oxides for CO Oxidation[J]. J. Colloid Interface Sci., 2011,354:341-352. doi: 10.1016/j.jcis.2010.10.043
16. [16]
  Kang K H, Joe W, Lee C H, Kim M, Kim D B, Jang B, Song I K. Direct Synthesis of Dimethyl Carbonate from Methanol and Carbon Dioxide Over CeO₂(X)-ZnO (1-X) Nano-Catalysts[J]. J. Nanosci. Nanotechnol., 2013,13:8116-8120. doi: 10.1166/jnn.2013.8177
17. [17]
  Sakakura T, Choi J, Saito Y, Sako T. Synthesis of Dimethyl Carbonate from Carbon Dioxide: Catalysis and Mechanism[J]. Polyhedron, 2000,19:573-576. doi: 10.1016/S0277-5387(99)00411-8
18. [18]
  Honda M, Tamura M, Nakagawa Y, Nakao K, Suzuki K, Tomishige K. Organic Carbonate Synthesis from CO₂ and Alcohol over CeO₂ with 2-Cyanopyridine: Scope and Mechanistic Studies[J]. J. Catal., 2014,318:95-107. doi: 10.1016/j.jcat.2014.07.022
19. [19]
  Stoian D, Medina F, Urakawa A. Improving the Stability of CeO₂ Catalyst by Rare Earth Metal Promotion and Molecular Insights in the Dimethyl Carbonate Synthesis from CO₂ and Methanol with 2-Cyanopyridine[J]. ACS Catal., 2018,8:3181-3225. doi: 10.1021/acscatal.7b04198
20. [20]
  Wang S P, Zhou J J, Zhao S Y, Zhao Y J, Ma X B. Enhancements of Dimethyl Carbonate Synthesis from Methanol and Carbon Dioxide: The In Situ Hydrolysis of 2-Cyanopyridine and Crystal Face Effect of Ceria[J]. Chin. Chem. Lett., 2015,26:1096-1100. doi: 10.1016/j.cclet.2015.05.005
21. [21]
  Sakakura T, Saito Y, Okano M, Choi J C, Sako T. Selective Conversion of Carbon Dioxide to Dimethyl Carbonate by Molecular Catalysis[J]. J. Org. Chem., 1998,63:7095-7096. doi: 10.1021/jo980460z
22. [22]
  Marciniak A A, Alves O C, Appel L G, Mota C J A. Synthesis of Dimethyl Carbonate from CO₂ and Methanol over CeO₂: Role of Copper as Dopant and the Use of Methyl Trichloroacetate as Dehydrating Agent[J]. J. Catal., 2019,371:88-95. doi: 10.1016/j.jcat.2019.01.035
23. [23]
  Bansode A, Urakawa A. Continuous DMC Synthesis from CO₂ and Methanol over a CeO₂ Catalyst in a Fixed Bed Reactor in the Presence of a Dehydrating Agent[J]. ACS Catal., 2014,4:3877-3880. doi: 10.1021/cs501221q
24. [24]
  Han D M, Chen Y, Wang S J, Xiao M, Lu Y X, Meng Y Z. Effect of Alkali-Doping on the Performance of Diatomite Supported Cu-Ni Bimetal Catalysts for Direct Synthesis of Dimethyl Carbonate[J]. Catalysts, 2018,8:302-312. doi: 10.3390/catal8080302
25. [25]
  Santos B, Silva V, Loureiro J, Rodrigues A E. Adsorption of H₂O and Dimethyl Carbonate at High Pressure over Zeolite 3A in Fixed Bed Column[J]. Ind. Eng. Chem. Res., 2014,53:2473-2483. doi: 10.1021/ie403830r
26. [26]
  Chen Y D, Yang Y, Tian S L, Ye Z B, Li G. Highly Effective Synthesis of Dimethyl Carbonate over CuNi Alloy Nanoparticles@Porous Organic Polymers Composite[J]. Appl. Catal. A, 2019,587117275. doi: 10.1016/j.apcata.2019.117275
27. [27]
  Vita A, Italiano C, Pino L, Frontera P, Ferraro M, Antonucci V. Activity and Stability of Powder and Monolith-Coated Ni/GDC Catalysts for CO₂ Methanation[J]. Appl. Catal. B, 2018,226:384-395. doi: 10.1016/j.apcatb.2017.12.078
28. [28]
  Tsa S B, Ma H. A Research on Preparation and Application of the Monolithic Catalyst with Interconnecting Pore Structure[J]. Sci. Rep., 2018,816605. doi: 10.1038/s41598-018-35021-2
29. [29]
  Jin S, Bang G, Liu L, Lee C H. Synthesis of Mesoporous MgO-CeO₂ Composites with Enhanced CO₂ Capture Rate via Controlled Combustion[J]. Microporous Mesoporous Mater., 2019,288109587. doi: 10.1016/j.micromeso.2019.109587
30. [30]
  Matović B, Luković J, Stojadinović B, Aškrabić S, Zarubica A, Babić B, Dohčević-Mitrović Z. Influence of Mg doping on Structural, Optical and Photocatalytic Performances of Ceria Nanopowders[J]. Process. Appl. Ceram., 2017,11:304-310. doi: 10.2298/PAC1704304M
31. [31]
  Liu H, Zou W J, Xu X L, Zhang X L, Yang Y Q, Tian G, Feng S H. The Proportion of Ce⁴⁺in Surface of Ce_xZr_1-xO₂ Catalysts: The Key Parameter for Direct Carboxylation of Methanol to Dimethyl Carbonate[J]. J. CO₂ Util., 2017,17:43-49. doi: 10.1016/j.jcou.2016.11.006
32. [32]
  Alla S K, Mandal R K, Prasad N K. Optical and Magnetic Properties of Mg²⁺Doped CeO₂ Nanoparticles[J]. RSC Adv., 2016,6:103491-103498. doi: 10.1039/C6RA23063F
33. [33]
  Ma X, Lu P, Wu P. Structural, Optical and Magnetic Properties of CeO₂ Nanowires with Nonmagnetic Mg²⁺Doping[J]. J. Alloys Compd., 2017,734:22-28.
34. [34]
  Liu B, Li C M, Zhang G, Yao X, Chuang S, Li Z. Oxygen Vacancy Promoting Dimethyl Carbonate Synthesis from CO₂ and Methanol over Zr-Doped CeO₂ Nanorods[J]. ACS Catal., 2018,8:10446-10473. doi: 10.1021/acscatal.8b00415
35. [35]
  Chen Y D, Wang H, Qin Z, Tian S, Li G. Ti_xCe_1-xO₂ Nanocomposites: A Monolithic Catalyst for Direct Conversion of Carbon Dioxide and Methanol to Dimethyl Carbonate[J]. Green Chem., 2019,21:4642-4649. doi: 10.1039/C9GC00811J
36. [36]
  Pu Y F, Xuan K, Wang F, Li A X, Zhao N, Xiao F K. Synthesis of Dimethyl Carbonate from CO₂ and Methanol over a Hydrophobic Ce/SBA-15 Catalyst[J]. RSC Adv., 2018,8:27216-27226. doi: 10.1039/C8RA04028A
37. [37]
  Bustamante F, Orrego A F, Villegas S, Villa A L. Modeling of Chemical Equilibrium and Gas Phase Behavior for the Direct Synthesis of Dimethyl Carbonate from CO₂ and Methanol[J]. Ind. Eng. Chem. Res., 2012,51:8945-8956. doi: 10.1021/ie300017r
1. [1]
  Renshu Huang , Jinli Chen , Xingfa Chen , Tianqi Yu , Huyi Yu , Kaien Li , Bin Li , Shibin Yin . Synergized oxygen vacancies with Mn2O3@CeO2 heterojunction as high current density catalysts for Li–O2 batteries. Chinese Journal of Structural Chemistry, 2023, 42(11): 100171-100171. doi: 10.1016/j.cjsc.2023.100171
2. [2]
  Zhenjie Yang , Chenyang Hu , Xuan Pang , Xuesi Chen . Sequence design in terpolymerization of ε-caprolactone, CO₂ and cyclohexane oxide: Random ester-carbonate distributions lead to large-span tunability. Chinese Chemical Letters, 2024, 35(5): 109340-. doi: 10.1016/j.cclet.2023.109340
3. [3]
  Bei Li , Zhaoke Zheng . In situ monitoring of the spatial distribution of oxygen vacancies at the single-particle level. Chinese Journal of Structural Chemistry, 2024, 43(10): 100331-100331. doi: 10.1016/j.cjsc.2024.100331
4. [4]
  Mengjun Zhao , Yuhao Guo , Na Li , Tingjiang Yan . Deciphering the structural evolution and real active ingredients of iron oxides in photocatalytic CO2 hydrogenation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100348-100348. doi: 10.1016/j.cjsc.2024.100348
5. [5]
  Zixuan Zhu , Xianjin Shi , Yongfang Rao , Yu Huang . Recent progress of MgO-based materials in CO₂ adsorption and conversion: Modification methods, reaction condition, and CO₂ hydrogenation. Chinese Chemical Letters, 2024, 35(5): 108954-. doi: 10.1016/j.cclet.2023.108954
6. [6]
  Shu-Ran Xu , Fang-Xing Xiao . Metal halide perovskites quantum dots: Synthesis, and modification strategies for solar CO2 conversion. Chinese Journal of Structural Chemistry, 2023, 42(12): 100173-100173. doi: 10.1016/j.cjsc.2023.100173
7. [7]
  Li Li , Fanpeng Chen , Bohang Zhao , Yifu Yu . Understanding of the structural evolution of catalysts and identification of active species during CO₂ conversion. Chinese Chemical Letters, 2024, 35(4): 109240-. doi: 10.1016/j.cclet.2023.109240
8. [8]
  Tingting Liu , Pengfei Sun , Wei Zhao , Yingshuang Li , Lujun Cheng , Jiahai Fan , Xiaohui Bi , Xiaoping Dong . Magnesium doping to improve the light to heat conversion of OMS-2 for formaldehyde oxidation under visible light irradiation. Chinese Chemical Letters, 2024, 35(4): 108813-. doi: 10.1016/j.cclet.2023.108813
9. [9]
  Haodong Wang , Xiaoxu Lai , Chi Chen , Pei Shi , Houzhao Wan , Hao Wang , Xingguang Chen , Dan Sun . Novel 2D bifunctional layered rare-earth hydroxides@GO catalyst as a functional interlayer for improved liquid-solid conversion of polysulfides in lithium-sulfur batteries. Chinese Chemical Letters, 2024, 35(5): 108473-. doi: 10.1016/j.cclet.2023.108473
10. [10]
  Peng Wang , Daijie Deng , Suqin Wu , Li Xu . Cobalt-based deep eutectic solvent modified nitrogen-doped carbon catalyst for boosting oxygen reduction reaction in zinc-air batteries. Chinese Journal of Structural Chemistry, 2024, 43(1): 100199-100199. doi: 10.1016/j.cjsc.2023.100199
11. [11]
  Yu-Hang Li , Shuai Gao , Lu Zhang , Hanchun Chen , Chong-Chen Wang , Haodong Ji . Insights on selective Pb adsorption via O 2p orbit in UiO-66 containing rich-zirconium vacancies. Chinese Chemical Letters, 2024, 35(8): 109894-. doi: 10.1016/j.cclet.2024.109894
12. [12]
  Muhammad Humayun , Mohamed Bououdina , Abbas Khan , Sajjad Ali , Chundong Wang . Designing single atom catalysts for exceptional electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(1): 100193-100193. doi: 10.1016/j.cjsc.2023.100193
13. [13]
  Hong Dong , Feng-Ming Zhang . Covalent organic frameworks for artificial photosynthetic diluted CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(7): 100307-100307. doi: 10.1016/j.cjsc.2024.100307
14. [14]
  Ping Wang , Tianbao Zhang , Zhenxing Li . Reconstruction mechanism of Cu surface in CO2 reduction process. Chinese Journal of Structural Chemistry, 2024, 43(8): 100328-100328. doi: 10.1016/j.cjsc.2024.100328
15. [15]
  Hanqing Zhang , Xiaoxia Wang , Chen Chen , Xianfeng Yang , Chungli Dong , Yucheng Huang , Xiaoliang Zhao , Dongjiang Yang . Selective CO2-to-formic acid electrochemical conversion by modulating electronic environment of copper phthalocyanine with defective graphene. Chinese Journal of Structural Chemistry, 2023, 42(10): 100089-100089. doi: 10.1016/j.cjsc.2023.100089
16. [16]
  Kunyao Peng , Xianbin Wang , Xingbin Yan . Converting LiNO₃ additive to single nitrogenous component Li₂N₂O₂ SEI layer on Li metal anode in carbonate-based electrolyte. Chinese Chemical Letters, 2024, 35(9): 109274-. doi: 10.1016/j.cclet.2023.109274
17. [17]
  Yatian Deng , Dao Wang , Jinglan Cheng , Yunkun Zhao , Zongbao Li , Chunyan Zang , Jian Li , Lichao Jia . A new popular transition metal-based catalyst: SmMn₂O₅ mullite-type oxide. Chinese Chemical Letters, 2024, 35(8): 109141-. doi: 10.1016/j.cclet.2023.109141
18. [18]
  Wenlong LI , Xinyu JIA , Jie LING , Mengdan MA , Anning ZHOU . Photothermal catalytic CO₂ hydrogenation over a Mg-doped In₂O_3-x catalyst. Chinese Journal of Inorganic Chemistry, 2024, 40(5): 919-929. doi: 10.11862/CJIC.20230421
19. [19]
  Tianbo Jia , Lili Wang , Zhouhao Zhu , Baikang Zhu , Yingtang Zhou , Guoxing Zhu , Mingshan Zhu , Hengcong Tao . Modulating the degree of O vacancy defects to achieve selective control of electrochemical CO₂ reduction products. Chinese Chemical Letters, 2024, 35(5): 108692-. doi: 10.1016/j.cclet.2023.108692
20. [20]
  Yufei Jia , Fei Li , Ke Fan . Surface reconstruction of Cu-based bimetallic catalysts for electrochemical CO2 reduction. Chinese Journal of Structural Chemistry, 2024, 43(3): 100255-100255. doi: 10.1016/j.cjsc.2024.100255

Get Citation

PDF

XML

Metrics

PDF Downloads(10)
Abstract views(639)
HTML views(151)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142

Direct Synthesis of Dimethyl Carbonate from CO2 and Methanol by Mg-Doped Ceria Monolithic Catalyst

Metrics

通讯作者: 陈斌, bchen63@163.com

Direct Synthesis of Dimethyl Carbonate from CO₂ and Methanol by Mg-Doped Ceria Monolithic Catalyst