王伟,沈祖德,孟心宇,王其瑞

• 1:常州大学 环境科学与工程学院， 江苏 常州 213164

摘要(Abstract)：

为了明确金属氧化物上酯类挥发性污染物催化燃烧的构效关系与反应机理。采用简单热解法制备了一系列金属氧化物MO_x(M= Ce、Co、Al、Mg、V、W)催化剂，通过不同的表征手段，探究它们的表面性质与乙酸乙酯(EA)催化燃烧性能之间的关系。结果表明，CeO₂呈现最优的EA降解活性和产物选择性。CeO₂的表面羟基有利于EA的水解，同时，其表面适度的酸性，减弱了乙醇等中间产物的强烈吸附。重要的是，CeO₂具有优异的表面晶格氧迁移能力，有利于气相产物以及表面水解物种(乙酸盐/乙醇盐)的快速氧化分解。

关键词(KeyWords)： 金属氧化物;催化燃烧;乙酸乙酯;氧化铈;表面性质

Abstract:

Keywords:

基金项目(Foundation): 国家自然科学基金青年项目(22106010)；常州市领军型创新人才引进培育项目(CQ20210108)。

作者(Author): 王伟,沈祖德,孟心宇,王其瑞

DOI: 10.3969/j.issn.1003-9015.2024.04.008

参考文献(References)：

• [1] 徐思遥, 李森, 彭东辉, 等. Cu-Co催化剂中Ce、La的添加对催化燃烧降解正庚烷性能的影响 [J]. 高校化学工程学报, 2018, 32(5): 1153-1163. XU S Y, LI S, PENG D H, et al. Effects of Ce and La in Cu-Co catalysts on catalytic combustion of n-heptane [J]. Journal of Chemical Engineering of Chinese Universities, 2018, 32(5): 1153-1163.
  [2] 马洪玺, 何双荣, 杨座国. 油烟气催化氧化净化过程研究 [J]. 高校化学工程学报, 2019, 33(1): 228-236. MA H X, HE S R, YANG Z G. Study on catalytic combustion of cooking fume [J]. Journal of Chemical Engineering of Chinese Universities, 2019, 33(1): 228-236.
  [3] HE C, CHENG J, ZHANG X, et al. Recent advances in the catalytic oxidation of volatile organic compounds: A review based on pollutant sorts and sources [J]. Chemical Reviews, 2019, 119(7): 4471-4568.
  [4] ZHAO Q, LI Y J, CHAI X L, et al. Interaction of inhalable volatile organic compounds and pulmonary surfactant: Potential hazards of VOCs exposure to lung [J]. Journal of Hazardous Materials, 2019, 369: 512-520.
  [5] GUO Y L, WEN M C, LI G Y, et al. Recent advances in VOC elimination by catalytic oxidation technology onto various nanoparticles catalysts: A critical review [J]. Applied Catalysis B: Environmental, 2021, 281: 119447.
  [6] YANG Y X, XU X L, SUN K P. A highly efficient copper supported catalyst for catalytic combustion of ethyl acetate [J]. Catalysis Communications, 2006, 7(10): 756-760.
  [7] MA R H, SU X W, JIN L Y, et al. Preparation and characterizations of Ce-Cu-O monolithic catalysts for ethyl acetate catalytic combustion [J]. Journal of Rare Earths, 2010, 28(3): 383-386.
  [8] SHEN Z D, GAO E H, MENG X Y, et al. Mechanistic insight into catalytic combustion of ethyl acetate on modified CeO₂ nanobelts: Hydrolysis–oxidation process and shielding effect of acetates/alcoholates [J]. Environmental Science & Technology, 2023, 57(9): 3864-3874.
  [9] YUAN H J, CHEN Y Q, YU F, et al. Hydrothermal synthesis and chromic properties of hexagonal WO₃nanowires [J]. Chinese Physics B, 2011, 20(3): 036103.
  [10] KHATKO V, LLOBET E, VILANOVA X, et al. Gas sensing properties of nanoparticle indium-doped WO₃ thick films [J]. Sensors and Actuators B: Chemical, 2005, 111/112: 45-51.
  [11] MOHAMMED A A, KHODAIR Z T, KHADOM A A. Preparation and investigation of the structural properties of α-Al₂O₃nanoparticles using the sol-gel method [J]. Chemical Data Collections, 2020, 29: 100531.
  [12] REIKOWSKI F, MAROUN F, PACHECO I, et al. Operando surface X-ray diffraction studies of structurally defined Co₃O₄ and CoOOH thin films during oxygen evolution [J]. ACS Catalysis, 2019, 9(5): 3811-3821.
  [13] DHACHAPALLY N, KALEVARU V N, MARTIN A. Ammoxidation of 2-methylpyrazine to 2-cyanopyrazine over Nb–V oxides: Marked effect of the Nb/V ratio on the catalytic performance [J]. Catalysis Science & Technology, 2014, 4(9): 3306-3316.
  [14] SREENIVASULU K V, ROTTE N K, SRIKANTH V V S S, et al. Non-collinear ferromagnetic short range order in MgO decked multi-layered graphene [J]. Physical Chemistry Chemical Physics, 2017, 19(1): 854-862.
  [15] LEE J, RYOU Y, CHAN X J, et al. How Pt interacts with CeO₂ under the reducing and oxidizing environments at elevated temperature: The origin of improved thermal stability of Pt/CeO₂ compared to CeO₂ [J]. The Journal of Physical Chemistry C, 2016, 120(45): 25870-25879.
  [16] ZHAO T Q, GAO Q, LI H J, et al. Catalytic decomposition of N₂O over Y-Co₃O₄ composite oxides prepared by one-step hydrothermal method [J]. Journal of Fuel Chemistry and Technology, 2019, 47(4): 446-454.
  [17] LU S H, WANG F, CHEN C C, et al. Catalytic oxidation of formaldehyde over CeO₂-Co₃O₄ catalysts [J]. Journal of Rare Earths, 2017, 35(9): 867-874.
  [18] PENG Y, LI J H, CHEN L, et al. Alkali metal poisoning of a CeO₂–WO₃ catalyst used in the selective catalytic reduction of NO_x with NH₃: An experimental and theoretical study [J]. Environmental Science & Technology, 2012, 46(5): 2864-2869.
  [19] BRODSKIY A, YASKEVICH V, KHUSSAIN B, et al. Studies of the reduction process of the Fe/γ-Al₂O₃ catalytic system [J]. EurAsian Journal of BioSciences, 2020, 14(1): 823-828.
  [20] HU X C, WANG W W, SI R, et al. Hydrogen production via catalytic decomposition of NH₃ using promoted MgO-supported ruthenium catalysts [J]. Science China Chemistry, 2019, 62(12): 1625-1633.
  [21] CHEN X R, CHEN C L, XU N P, et al. Al- and Ga-promoted WO₃/ZrO₂strong solid acid catalysts and their catalytic activities in n-butane isomerization [J]. Catalysis Today, 2004, 93/94/95: 129-134.
  [22] 黄秀兵, 王鹏, 陶进长, 等. CeO₂修饰Mn-Fe-O复合材料及其NH₃-SCR脱硝催化性能 [J]. 无机材料学报, 2020, 35(5): 573-580. HUANG X B, WANG P, TAO J Z, et al. CeO₂ modified Mn-Fe-O composites and their catalytic performance for NH₃-SCR of NO [J]. Journal of Inorganic Materials, 2020, 35(5): 573-580.
  [23] LI L L, JI J W, TAN W, et al. Enhancing low-temperature NH₃-SCR performance of Fe–Mn/CeO₂ catalyst by Al₂O₃ modification [J]. Journal of Rare Earths, 2022, 40(9): 1454-1461.
  [24] SU Z A, SI W Z, LIU H, et al. Boosting the catalytic performance of CeO₂in toluene combustion via the Ce–Ce homogeneous interface [J]. Environmental Science & Technology, 2021, 55(18): 12630-12639.
  [25] SUN Y G, LI N, XING X, et al. Catalytic oxidation performances of typical oxygenated volatile organic compounds (acetone and acetaldehyde) over MAlO (M = Mn, Co, Ni, Fe) hydrotalcite-derived oxides [J]. Catalysis Today, 2019, 327: 389-397.
  [26] YANG Y, LI Y Z, ZHANG Q, et al. Novel photoactivation and solar-light-driven thermocatalysis on ε-MnO₂ nanosheets lead to highly efficient catalytic abatement of ethyl acetate without acetaldehyde as unfavorable by-product [J]. Journal of Materials Chemistry A, 2018, 6(29): 14195-14206.
  [27] TAYRABEKOVA S, MÄKI-ARVELA P, PEURLA M, et al. Catalytic dehydrogenation of ethanol into acetaldehyde and isobutanol using mono- and multicomponent copper catalysts [J]. Comptes Rendus Chimie, 2018, 21(3/4): 194-209.
  [28] PSARRAS A C, MICHAILOF C M, ILIOPOULOU E F, et al. Acetic acid conversion reactions on basic and acidic catalysts under biomass fast pyrolysis conditions [J]. Molecular Catalysis, 2019, 465: 33-42.
  [29] WANG F, JIANG J Z, WANG B. Recent in situ/operando spectroscopy studies of heterogeneous catalysis with reducible metal oxides as supports [J]. Catalysts, 2019, 9(5): 477.
  [30] LAO Y J, JIANG X X, HUANG J, et al. Catalytic oxidation of ethyl acetate on Ce–Mn–O catalysts modified by La [J]. Rare Metals, 2021, 40(3): 547-554.
  [31] DEY S, DHAL G C. The catalytic activity of cobalt nanoparticles for low-temperature oxidation of carbon monoxide [J]. Materials Today Chemistry, 2019, 14: 100198.
  [32] ZHANG X D, LI H X, YANG Y, et al. Facile synthesis of new efficient Cu/MnO₂ catalysts from used battery for CO oxidation [J]. Journal of Environmental Chemical Engineering, 2017, 5(5): 5179-5186.
  [33] ZHANG X D, ZHANG X L, SONG L, et al. Enhanced catalytic performance for CO oxidation and preferential CO oxidation over CuO/CeO₂catalysts synthesized from metal organic framework: Effects of preparation methods [J]. International Journal of Hydrogen Energy, 2018, 43(39): 18279-18288.
  [34] MAIRA A J, CORONADO J M, AUGUGLIARO V, et al. Fourier transform infrared study of the performance of nanostructured TiO₂particles for the photocatalytic oxidation of gaseous toluene [J]. Journal of Catalysis, 2001, 202(2): 413-420.
  [35] PILKENTON S, HWANG S J, RAFTERY D. Ethanol photocatalysis on TiO₂-coated optical microfiber, supported monolayer, and powdered catalysts: An in situ NMR study [J]. The Journal of Physical Chemistry B, 1999, 103(50): 11152-11160.
  [36] MARTIN C, MARTIN I, RIVES V. Fourier-transform infrared study of the oxidation of ethene on MoO₃/TiO₂catalysts doped with alkali metals [J]. Journal of the Chemical Society, Faraday Transactions, 1993, 89(22): 4131-4135.
  [37] RODRÍGUEZ J L, PASTOR E, XIA X H, et al. Reaction intermediates of acetaldehyde oxidation on Pt(111) and Pt(100). An in situ FTIR study [J]. Langmuir, 2000, 16(12): 5479-5486.
  [38] YEE A, MORRISON S J, IDRISS H. A study of the reactions of ethanol on CeO₂ and Pd/CeO₂ by steady state reactions, temperature programmed desorption, and in situ FT-IR [J]. Journal of Catalysis, 1999, 186(2): 279-295.
  [39] YEE A, MORRISON S J, IDRISS H. The reactions of ethanol over M/CeO₂ catalysts: Evidence of carbon–carbon bond dissociation at low temperatures over Rh/CeO₂ [J]. Catalysis Today, 2000, 63(2/3/4): 327-335.