MeCeOx(Me=In,Zr)固溶催化剂制备及催化合成碳酸二甲酯研究

人工晶体学报 ›› 2021, Vol. 50 ›› Issue (1): 113-121.

MeCeO_x(Me=In,Zr)固溶催化剂制备及催化合成碳酸二甲酯研究

王逸舟^1,2, 刘飞^1,2, 赵天翔^1,2, 曹建新^1,2, 许芳³

1.贵州大学化学与化工学院,贵阳 550025;
2.贵州大学,贵州省绿色化工与清洁能源技术重点实验室,贵阳 550025;
3.贵州民族大学材料科学与工程学院,贵阳 550025

收稿日期:2020-08-19 出版日期:2021-01-15 发布日期:2021-03-01
通讯作者: 刘飞,教授。E-mail:ce.feiliu@gzu.edu.cn
曹建新,教授。E-mail:jxcao@gzu.edu.cn
作者简介:王逸舟(1995—),男,湖北省人,硕士研究生。E-mail:1063505411@qq.com
基金资助:
国家自然科学基金(21666007);贵州省百层次创新型人才专项(黔科合平台人才5655);贵州省科技创新人才团队(黔科合平台人才5607);贵州省科技计划项目(黔科合平台人才5788号,5781号);教育厅青年科技人才成长项目(黔教合KY字147)

Preparation of MeCeO_x(Me=In, Zr) Solid Solution Catalyst for the Application in the Synthesis of Dimethyl Carbonate

WANG Yizhou^1,2, LIU Fei^1,2, ZHAO Tianxiang^1,2, CAO Jianxin^1,2, XU Fang³

1. School of Chemistry and Chemical Engineering, Guizhou University, Guiyang 550025, China;
2. Guizhou Key Laboratory for Green Chemical and Clean Energy Technology, Guizhou University, Guiyang 550025, China;
3. School of Material Science and Engineering, Guizhou Minzu University, Guiyang 550025, China

Received:2020-08-19 Online:2021-01-15 Published:2021-03-01

摘要/Abstract

摘要： 采用液相共沉淀法制备了MeCeO_x(Me=In,Zr)双金属氧化物固溶催化剂。借助X射线衍射(XRD)、X射线光电子能谱(XPS)、程序升温还原(H₂-TPR)、程序升温脱附(CO₂-TPD、CH₃OH-TPD)及漫反射傅里叶变换红外光谱(DRIFTS)等手段对催化剂物化性质进行了分析表征。在系统考察不同金属氧化物种类和掺杂量的基础上,对比研究了不同金属氧化物掺杂改性CeO₂制得固溶催化剂的结构性质及催化行为。结果表明:不同金属氧化物掺杂改性制得的MeCeO_x(Me=In,Zr)双金属氧化物,由于形成的固溶结构增大了氧空位缺陷浓度;InCeO_x具有最大的氧空位缺陷浓度和CO₂、CH₃OH分子化学吸附量;在反应压力1.0 MPa、反应温度140 ℃,反应空速(GHSV)3 600 mL/(g·h)、V(CO₂)/V(CH₃OH)/V(N₂)=4∶1∶5条件下,InCeO_x表现出优异的催化性能,碳酸二甲酯(DMC)选择性91.3%,CH₃OH转化率8.4%,碳酸二甲酯STY(时空产率)达0.11 g_DMC·h^-1·g^-1_cat。原位红外分析进一步揭示了氧空位活化CO₂及中间体单配位甲氧基的形成是碳酸二甲酯高选择性的关键。

关键词: InCeO_x催化剂, 双金属氧化物, 固溶结构, 氧空位, 碳酸二甲酯

Abstract: MeCeO_x (Me=In, Zr) bimetallic oxide catalysts were prepared by liquid-phase co-precipitation method with a matrix of CeO₂. The physiochemical properties of MeCeO_x were characterized by X-ray diffraction (XRD), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction(H₂-TPR), temperature programmed desorption(CO₂-TPD, CH₃OH-TPD), and diffuse reflectance infrared fourier transform spectroscopy (DRIFTS) techniques. Based on the systematic investigation of the types and doping amounts of various metal oxides, the structure properties and catalytic behavior of solid solution catalysts prepared by doping CeO₂ with different metal oxides were comparatively studied in this paper. The results show that the solid solution structure formed by MeCeO_x bimetal oxide catalysts increases the concentration of oxygen vacancy defects. The InCeO_x solid solution catalyst exhibit the largest concentration of oxygen vacancy defects, resulting in the improve chemical adsorption for CO₂ and CH₃OH molecules. Under the condition of reaction pressure 1.0 MPa, reaction temperature 140 ℃, reaction space velocity (GHSV) 3 600 mL/(g·h) and V(CO₂)/V(CH₃OH)/V(N₂)=4∶1∶5, the InCeO_x shows the excellent catalytic performance with dimethyl carbonate selectivity of 91.3%, CH₃OH conversion of 8.4%, and dimethyl carbonate STY(Space Time Yield) of 0.11 g_DMC·h^-1·g^-1_cat. In addition, further in-depth DRIFTS study show that activation of CO₂ with oxygen vacancies and the formation of terminal methoxy as the intermediate are the crucial to the enhance selectivity of dimethyl carbonate.

Key words: InCeO_x catalyst, bimetallic oxide, solid solution structure, oxygen vacancy, dimethyl carbonate

中图分类号:

O643.3

王逸舟, 刘飞, 赵天翔, 曹建新, 许芳. MeCeO_x(Me=In,Zr)固溶催化剂制备及催化合成碳酸二甲酯研究[J]. 人工晶体学报, 2021, 50(1): 113-121.

WANG Yizhou, LIU Fei, ZHAO Tianxiang, CAO Jianxin, XU Fang. Preparation of MeCeO_x(Me=In, Zr) Solid Solution Catalyst for the Application in the Synthesis of Dimethyl Carbonate[J]. JOURNAL OF SYNTHETIC CRYSTALS, 2021, 50(1): 113-121.

参考文献

[1] GIBSON D H. Carbon dioxide coordination chemistry: metal complexes and surface-bound species. What relationships?[J]. Coordination Chemistry Reviews, 1999, 185: 335-355.
[2] JACOBSON M Z. Review of solutions to global warming, air pollution, and energy security[J]. Energy Environ Sci, 2009, 2(2): 148-173.
[3] ARESTA M, DIBENEDETTO A, ANGELINI A. Catalysis for the valorization of exhaust carbon: from CO₂ to chemicals, materials, and fuels. Technological use of CO₂[J]. Chemical reviews, 2014, 114(3): 1709-1742.
[4] ONO Y. Catalysis in the production and reactions of dimethyl carbonate, an environmentally benign building block[J]. Applied Catalysis A General, 1997, 155(2): 133-166.
[5] ONO Y. Dimethyl carbonate for environmentally benign reactions[J]. Catalysis Today, 1997, 35(1/2): 15-25.
[6] KELLER N, REBMANN G, KELLER V. Catalysts, mechanisms and industrial processes for the dimethylcarbonate synthesis[J]. Journal of Molecular Catalysis A: Chemical, 2010, 317(1/2): 1-18.
[7] KING S T. Reaction mechanism of oxidative carbonylation of methanol to dimethyl carbonate in Cu-Y zeolite[J]. Journal of Catalysis, 1996, 161(2): 530-538.
[8] TATSUMI T, WATANABE Y, KOYANO K A. Synthesis of dimethyl carbonate from ethylene carbonate and methanol using TS-1 as solid base catalyst[J]. Chemical Communications, 1996(19): 2281.
[9] DELLEDONNE D, RIVETTI F, ROMANO U. Developments in the production and application of dimethylcarbonate[J]. Applied Catalysis A: General, 2001, 221(1/2): 241-251.
[10] TOMISHIGE K, SAKAIHORI T, IKEDA Y, et al. A novel method of direct synthesis of dimethyl carbonate from methanol and carbon dioxide catalyzed by zirconia[J]. Catalysis Letters, 1999, 58(4): 225-229.
[11] BIAN J, XIAO M, WANG S J, et al. Highly effective synthesis of dimethyl carbonate from methanol and carbon dioxide using a novel copper-nickel/graphite bimetallic nanocomposite catalyst[J]. Chemical Engineering Journal, 2009, 147(2/3): 287-296.
[12] CHEN H L, WANG S J, Xiao M, et al. Direct synthesis of dimethyl carbonate from CO₂ and CH₃OH using 0.4 nm molecular sieve supported Cu-Ni Bimetal catalyst[J]. Chinese Journal of Chemical Engineering, 2012, 20(5): 906-913.
[13] ZHOU Y J, WANG S J, XIAO M, et al. Novel Cu-Fe bimetal catalyst for the formation of dimethyl carbonate from carbon dioxide and methanol[J]. RSC Advances, 2012, 2(17): 6831-6837.
[14] ARESTA M, DIBENEDETTO A, PASTORE C, et al. Cerium(IV)oxide modification by inclusion of a hetero-atom: a strategy for producing efficient and robust nano-catalysts for methanol carboxylation[J]. Catalysis Today, 2008, 137(1): 125-131.
[15] KANG K H, LEE C H, KIM D B, et al. NiO/CeO₂-ZnO nano-catalysts for direct synthesis of dimethyl carbonate from methanol and carbon dioxide[J]. Journal of Nanoscience and Nanotechnology, 2014, 14(11): 8693-8698.
[16] ZHANG M, XIAO M, WANG S J, et al. Cerium oxide-based catalysts made by template-precipitation for the dimethyl carbonate synthesis from carbon dioxide and methanol[J]. Journal of Cleaner Production, 2015, 103: 847-853.
[17] KUMAR P, WITH P,SRIVASTAVA V C, et al. Dimethyl carbonate synthesis from carbon dioxide using ceria-zirconia catalysts prepared using a templating method: characterization, parametric optimization and chemical equilibrium modeling[J]. RSC Advances,2016,6(111): 110235-110246.
[18] LI A X, PU Y F, LI F, et al. Synthesis of dimethyl carbonate from methanol and CO₂ over Fe-Zr mixed oxides[J]. Journal of CO₂ Utilization, 2017, 19: 33-39.
[19] FU Z Z, ZHONG Y Y, YU Y H, et al. 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(1): 198-207.
[20] 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 Catalysis, 2018, 8(4): 3181-3193.
[21] CHEN Y D, WANG H, QIN Z X, et al. Ti_xCe_1-xO₂ nanocomposites: a monolithic catalyst for the direct conversion of carbon dioxide and methanol to dimethyl carbonate[J]. Green Chemistry, 2019, 21(17): 4642-4649.
[22] SCHMITT R, NENNING A, KRAYNIS O, et al. A review of defect structure and chemistry in ceria and its solid solutions[J]. Chemical Society Reviews, 2020, 49(2): 554-592.
[23] YE J Y, LIU C J, MEI D H, et al. Active oxygen vacancy site for methanol synthesis from CO₂ hydrogenation on In₂O₃(110):a DFT study[J]. ACS Catalysis, 2013, 3(6): 1296-1306
[24] WANG J J, TANG C Z, LI G N, et al. High performance MaZrO_x (Ma=Cd, Ga) solid solution catalysts for CO₂ hydrogenation to methanol[J]. ACS Catalysis, 2019, 9(11): 10253-10259.
[25] CHEN T Y, CAO C, CHEN T, et al. Unraveling highly tunable selectivity in CO₂ hydrogenation over bimetallic In-Zr oxide catalysts[J]. ACS Catalysis, 2019, 9(9): 8785-8797.
[26] LIU B, LI C M, ZHANG G Q. Oxygen vacancy promoting dimethyl carbonate synthesis from CO₂and methanol over Zr-doped CeO₂ nanorods[J]. ACS Catalysis, 2018, 8(11): 10446-10456.