核-壳结构多酸/磁性铈铁纳米复合氧化物@SiO2吸附-氧化脱硫性能

doi:10.11944/j.issn.1000-0518.2020.12.200152

摘要/Abstract

摘要： 水热法合成了铈铁纳米复合氧化物,采用化学沉积法在其表面包裹SiO₂制备核-壳结构磁性材料,以其为载体负载H₂O₂结合Keggin结构磷钼酸(HPMo)制备了HPMo-H₂O₂/CeFe_xO_y@SiO₂吸附-氧化脱硫催化剂。采用扫描电子显微镜(SEM)、透射电子显微镜(TEM)、傅里叶红外光谱(FT-IR)、X射线粉末衍射(XRD)、氮气吸附脱附(BET)、³¹P魔角核磁共振(MAS-NMR)和X射线光电子能谱(XPS)等对催化剂的结构进行表征。结果表明,SiO₂将CeFe_xO_y包裹形成核-壳结构纳米复合材料,以其为载体负载HPMo-H₂O₂后Keggin型多酸的骨架结构保持,并产生少量过氧化磷钼酸盐活性物种。不同催化剂对有机硫化物二苯并噻吩(DBT)的吸附脱硫和氧化脱硫性能,均呈现出HPMo-H₂O₂/CeFe_xO_y@SiO₂＞CeFe_xO_y@SiO₂＞CeFe_xO_y的活性顺序,多酸的引入大大提升了其对大分子有机硫化物的吸附和氧化脱除性能,催化氧化脱硫活性的提高源于多酸分子“假液相”反应过程的结果。在反应温度60 ℃,反应3 h,m(油)∶m(催化剂)=35∶1,n(O)∶n(S)=10∶1的条件下,对DBT氧化脱除率达到99.4%。制备的磁性核-壳结构氧化脱硫剂有理想的氧化脱除DBT的循环使用性能,并且可通过外加磁场进行简单分离,是一类制备方法简单、催化活性高且稳定性好的绿色环保型催化剂。

关键词: 吸附-氧化脱硫, 磷钼酸, 铈铁纳米复合氧化物, 二苯并噻吩

Abstract: The manganese-cerium mixed iron oxide nanocomposites were synthesized by hydrothermal synthesis method. The surface was wrapped by SiO₂ by chemical vapor deposition to prepare the core-shell magnetic material which was then loaded by H₂O₂ with Keggin structure phosphomolybdic acid (HPMo) to synthesize the HPMo-H₂O₂/CeFe_xO_y@SiO₂ adsorption-oxidative desulfurization catalyst. The catalyst was characterized by SEM, TEM, FT-IR, XRD, ³¹P MAS-NMR and XPS. The results of SEM, TEM and XPS characterization show that CeFe_xO_y is wrapped by SiO₂ to form core-shell nanocomposite material. The Keggin-type structure is retained after being loaded by HPMo-H₂O₂ and a little peroxophosphomolybdate active species are produced in this process. The active order of different catalysts on the adsorption and oxidation desulfurization presents as the following:HPMo-H₂O₂/CeFe_xO_y@SiO₂＞CeFe_xO_y@SiO₂＞CeFe_xO_y. The introduction of HPMo greatly improves the adsorption activity of organic sulfides, especially its remarkable performance in oxidative desulfurization. The improvement of the performance in oxidative desulfurization is due to the “pseudo-liquid phase” reaction process of polyoxometalate. The dibenzothiophene(DBT) oxidation removal rate reaches 99.4% under such conditions:m(oil)∶m(catalyst)=35∶1, n(H₂O₂)∶n(S)=10∶1 at 60 ℃ for 3 h. The prepared magnetic core-shell oxidative-desulfurization catalyst has ideal recycling performance for oxidative removal of DBT. HPMo-H₂O₂/CeFe_xO_y@SiO₂ catalyst becomes a kind of environmental-friendly catalysts with simple preparation method, high catalytic activity and good stability.

Key words: adsorption-oxidative desulfurization, phosphomolybdic acid, cerium-mixed iron oxide nanocomposites, dibenzothiophene

中图分类号:

O643

赵柳, 宋胜杰, 马康富, 王宏, 付丽华, 刘新阳, 陈立东, 成卫国. 核-壳结构多酸/磁性铈铁纳米复合氧化物@SiO₂吸附-氧化脱硫性能[J]. 应用化学, 2020, 37(12): 1457-1464.

ZHAO Liu, SONG Shengjie, MA Kangfu, WANG Hong, FU Lihua, LIU Xinyang, CHEN Lidong, CHENG Weiguo. Adsorption-Oxidative Desulfurization Performance of Core-Shell Polyoxometalate/Magnetic Cerium-Iron Nanocomposite Oxide@SiO₂[J]. Chinese Journal of Applied Chemistry, 2020, 37(12): 1457-1464.

参考文献

[1] Song C S. An Overview of New Approaches to Deep Desulfurization for Ultra-clean Gasoline, Diesel Fuel and Jet Fuel[J]. Catal Today,2003,86(1/2/3/4):211-263.
[2] Julião D,Mirante F,Ribeiro S O,et al. Deep Oxidative Desulfurization of Diesel Fuels Using Homogeneous and SBA-15-Supported Peroxophosphotungstate Catalysts[J]. Fuel,2019,241:616-624.
[3] Bazyari A,Khodadadi A A,Mamaghani A H,et al. Microporous Titania-Silica Nanocomposite Catalyst Adsorbent for Ultra-deep Oxidative Desulfurization[J]. Appl Catal B: Environ,2016,180(1):65-77.
[4] Hou L,Zhang Y Q,Hu Z F,et al. Reduced Phosphomolybdate Hybrids as Efficient Visible-Light Photocatalysts for Cr(VI) Reduction[J]. Inorg Chem,2019,58(24):16667-16675.
[5] SONG Fangyuan,DING Yong,ZHAO Congchao. Progress in Polyoxometalates-Catalyzed Water Oxidation[J]. Acta Chim Sin,2014,72(2):133-144(in Chinese).
宋芳源,丁勇,赵崇超. 多金属氧酸盐催化的水氧化研究进展[J]. 化学学报,2014,72(2):133-144.
[6] Zhang X M,Zhang Z H,Zhang B H,et al. Synergistic Effect of Zr-MOF on Phosphomolybdic Acid Promotes Efficient Oxidative Desulfurization[J]. Appl Catal B:Environ,2019,256(1):117804.
[7] Xu J J,Zhu Z G,Su T,et al. Green Aerobic Oxidative Desulfurization of Diesel by Constructing an Fe-Anderson Type Polyoxometalate and Benzene Sulfonic Acid-Based Deep Eutectic Solvent Biomimetic Cycle[J]. Chinese J Catal,2020,41(5):868-876.
[8] MA Kangfu,TONG Huan,LIAO Lin,et al. Efficient Shape-Selective Oxidative Desulfurization by Phosphotungstic Acid/Nanocrystalline Catalyst TS-1[J]. Pet Process Petrochem,2019,50(8):38-45 (in Chinese).
马康富,佟欢,廖林,等.磷钨酸/纳米晶TS-1催化剂高效择形催化氧化脱硫[J].石油炼制与化工,2019,50(8):38-45.
[9] SONG Shengjie,ZHAO Liu,TONG Huan,et al. Effect of Polyoxometalate Structure on Catalytic Oxidative Desulfurization Performance of Nano-TS-1 Zeolite[J]. Chinese J Appl Chem,2020,37(8):952-959(in Chinese).
宋胜杰,赵柳,佟欢,等. 多酸结构对纳米TS-1沸石催化氧化脱硫性能的影响[J]. 应用化学,2020,37(8):952-959.
[10] Guo P,Huang F,Huang Q,et al. Optimization of Biodiesel Production Using a Magnetically Stabilized Fluidized Bed Reactor[J]. J Am Oil Chem Soc,89(3):497-504.
[11] Chaudhuri R G,Paria S. Core/Shell Nanoparticles:Classes, Properties, Synthesis Mechanisms, Characterization, and Applications[J]. Chem Rev,2012,112(4):2373-2433.
[12] Wang C X,Zhong H L,Wu W J,et al. Fe₃O₄@C Core-Shell Carbon Hybrid Materials as Magnetically Separable Adsorbents for the Removal of Dibenzothiophene in Fuels[J]. ACS Omega,2019,4(1):1652-1661.
[13] Li S W,Wang W,Zhao J S. Magnetic-Heteropolyacid Mesoporous Catalysts for Deep Oxidative Desulfurization of Fuel:The Influence on the Amount of APES Used[J]. J Colloid Interface Sci,2020,57:337-347.
[14] LIU Di,TONG Huan,YUAN Linjie,et al. Preparation of High Activity Oxidative Desulfurization Catalyst from Phosphomolybdic Acid and Titania Silica Nanocomposite[J]. Chinese J Appl Chem,2018,35(11):1351-1356(in Chinese).
刘迪,佟欢,袁琳杰,等. 磷钼酸和钛硅纳米复合氧化物构筑高活性氧化脱硫催化剂[J]. 应用化学,2018,35(11):1351-1356.
[15] Li X H,Zhang J,Zhou F,et al. Oxidative Desulfurization of Dibenzothiophene and Diesel by Hydrogen Peroxide:Catalysis of H₃PMo₁₂O₄₀ Immobilized on the Ionic Liquid Modified SiO₂[J]. Mol Catal,2018,452:93-99.
[16] Xi Z W,Zhou N,Sun Y,et al. Reaction-Controlled Phase-Transfer Catalysis for Propylene Epoxdation to Propylene Oxide[J]. Science,2001,292(11):1139-1141.
[17] Jiang F, Wang X, Wu D. Design and Synthesis of Magnetic Microcapsules Based on n-Eicosane Core and Fe₃O₄/SiO₂ Hybrid Shell for Dual-Functional Phase Change Materials[J]. Appl Energy,2014,134:456-468.
[18] Zhu W,Zhu G,Li H,et al. Oxidative Desulfurization of Fuel Catalyzed by Metal-Based Surfactant-Type Ionic Liquids[J]. J Mol Catal A:Chem,2011,347(1/2):8-14.
[19] Laguna O H,Centeno M A,Boutonnet M,et al. Fe-Doped Ceria Solids Synthesized by the Microemulsion Method for CO Oxidation Reactions[J]. Appl Catal B:Environ,2011,106(3/4):621-629.
[20] Levebyre F.³¹P MAS-NMR Study of H₃PW₁₂O₄₀ Supported on Silica:Formation of (SiOH₂)⁺(H₂PW₁₂O₄₀) [J]. J Chem Soc Chem Commun,1992,(10):756-757.
[21] Huang Y W,Wang Y J,Wei S C,et al. Preparation of Graphene/Fe₃O₄/Ni Electromagnetic Microwave Absorbing Nano-Composite Materials[J]. Int J Mod Phys B,2019,33:1-3.
[22] Ahmidou L,Vincent P,Ahmed B,et al. Reduction of CeO₂ by Hydrogen-Magnetic-Susceptibility and Fourier-Transform Infrared Ultraviolet and X-Ray Photoelectron-Spectroscopy Measurements[J]. J Chem Soc Faraday Trans,1991,87(10):1601-1609.
[23] Xu J,Li H C,Wang S T,et al. Ultra-deep Desulfurization via Reactive Adsorption on Peroxophosphomolybdate/Agarose Hybrids[J]. Chemosphere,2014,111:631-637.
[24] Xu L L,Li W,Hu J L,et al. Transesterification of Soybean Oil to Biodiesel Catalyzed by Mesostructured Ta₂O₅-Based Hybrid Catalysts Functionalized by Both Alkyl-Bridged Organosilica Moieties and Keggin-Type Heteropoly Acid[J]. J Mater Chem,2009,19(45):8571-8579.
[25] Hernández-Maldonado A J,Yang R T. Desulfurization of Commercial Liquid Fuels by Selective Adsorption via π-Complexation with Cu(I)-Y Zeolite[J]. Ind Eng Chem Res,2003,42(13):3103-3110.
[26] LIU Chang,YAN Zhiyi,LI Qiaoling,et al. Research Progress of Selective Adsorption Desulfurization[J]. Chem Ind Eng Prog,2019,38(11):5114-5126(in Chinese).
刘畅,闫志义,李巧灵,等. 选择吸附脱硫研究进展[J]. 化工进展,2019,38(11):5114-5126.
[27] Misono M. Unique Acid Catalysis of Heteropoly Compounds (Heteropolyoxometalates) in the Solid State[J]. Chem Commum,2001,(13):1141-1153.

核-壳结构多酸/磁性铈铁纳米复合氧化物@SiO₂吸附-氧化脱硫性能

Adsorption-Oxidative Desulfurization Performance of Core-Shell Polyoxometalate/Magnetic Cerium-Iron Nanocomposite Oxide@SiO₂

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