多孔结构Bi2WO6光催化剂的制备及其模拟燃油催化氧化脱硫活性

doi:10.3724/SP.J.1077.2013.13043

无机材料学报 ›› 2013, Vol. 28 ›› Issue (10): 1079-1086.DOI: 10.3724/SP.J.1077.2013.13043

多孔结构Bi₂WO₆光催化剂的制备及其模拟燃油催化氧化脱硫活性

王丹军^{1, 2}, 岳林林¹, 郭莉¹, 付峰¹, 薛岗林²

(1. 延安大学化学与化工学院, 陕西省化学反应工程重点实验室, 延安 716000; 2. 西北大学化学与材料科学学院, 西安 710069)

收稿日期:2013-01-17 修回日期:2013-03-03 出版日期:2013-10-20 网络出版日期:2013-09-18
基金资助:
国家自然科学基金重点项目(20973133); 陕西省教育厅自然科学基金(12JK0597); 陕西省科技厅工业攻关项目(2013k11-08); 延安市工业攻关项目(2011kg-13)

Synthesis of Porous-Bi₂WO₆ and Its Photocatalytic Oxidative Desulfurization (Photo-ODS) Activity of Simulation Fuel

WANG Dan-Jun^{1, 2}, YUE Lin-Lin¹, GUO Li¹, FU Feng¹, XUE Gang-Lin²

(1. College of Chemistry & Chemical Engineering, Yan'an University, Shaanxi Key Laboratory of Chemical Reaction Engineering, Yan'an 716000, China; 2. College of Chemistry & Materials Science, Northwest University, Xi’an 710069, China)

Received:2013-01-17 Revised:2013-03-03 Published:2013-10-20 Online:2013-09-18
Supported by:
National Natural Science Foundation of China (20973133); Natural Science Program of Education Department of Shaanxi Province (12JK0597); science and Technology Department of Shaanxi Province (2013k11-08); Key Industry Plan of Yan’an City(2011kg-13)

摘要/Abstract

摘要： 采用水热法合成了多孔结构Bi₂WO₆光催化剂, 借助X射线衍射(XRD)、场发射扫描电子显微镜(FESEM)、透射电子显微镜(TEM)、X射线能量色散谱(EDS)、紫外-可见漫反射(UV-Vis-DRS)、N2吸附/脱附等测试手段对样品的物相组成、形貌、比表面-孔径分布和光吸收特性等进行了表征。考察了水热温度、水热反应时间对Bi₂WO₆的形貌、比表面-孔径分布和光吸收特性影响, 并探讨了Bi₂WO₆光催化剂对模拟燃油的脱硫活性。结果表明, 在强酸性条件下水热温度和水热时间对Bi₂WO₆的形貌、比表面积和催化活性影响显著, 190℃水热反应2 h所得Bi₂WO₆为新颖的鸟巢状微晶, 且鸟巢状Bi₂WO₆由片层状二级结构组装而成。XRD和EDS表明, 鸟巢状结构的Bi₂WO₆为正交晶系, 纯度较高。N₂吸附-脱附测试结果表明, 鸟巢状Bi₂WO₆具有多孔结构, 孔主要分布在10 nm, 比表面积大约为17.49 m²/g。催化活性测试结果表明, 三维介孔结构Bi₂WO₆具有较好的模拟燃油脱硫效果, 在空气流量为100 mL/min, 催化剂加入量为1.2 g/L, 可见光照射180 min, 模拟汽油脱硫率高达91.2%, 且催化剂的稳定性能较好。

关键词: 水热法, 三维多孔Bi₂WO₆, 光催化氧化, 模拟燃油脱硫

Abstract: Porous-Bi₂WO₆ was synthesized by a hydrothermal process. The phase composition, morphology, surface area/pore size distribution and optical properties of as-synthesized Bi₂WO₆ sample were investigated by X-ray diffraction (XRD), filed-scanning electron microscope (FE-SEM), transmission electron mcroscope (TEM), energy dispersive spectrometer (EDS), UV-Vis absorption spectrum (UV-Vis-DRS), and low-temperature N₂ adsorption/desorption techniques. Furthermore, the photocatalytic oxidative desulfurization (Photo-ODS) activity of as-synthesized Bi₂WO₆ samples was also investigated. The experimental results reveal that reaction temperature and reaction time have a significant effect on the morphology and structure of Bi₂WO₆ under the strong acidic medium. After 2 h of reaction at 190℃, the as-obtained sample exhibits a novel nest-like 3D Bi₂WO₆ microcrystal with scales of 3-4 μm. HR-SEM reveals that the 3D nest-like Bi₂WO₆ microcrystal composes of many small secondary nanoplates. XRD and EDS results confirm that the as-synthesized D nest-like Bi₂WO₆ microcrystal is orthorhombic pure-Bi₂WO₆. N₂ adsorption/desorption isotherms and the pore distribution result show that nest-like 3D Bi₂WO₆ microcrystal has pores in the size of 6-8 nm and the BET surface area is calculated to be as much as 17.49 m²/g. The photocatalytic experimental result illustrates that as-synthesized 3D nest-like porous Bi₂WO₆ microcrystals exhibit an excellent photocatalytic performance to photocatalytic oxidative desulfurization for simulated fuel oil under sun-like light irradiation. Under the conditions of 100 mL/min air flow, 1.2 g/L photocatalyst amount, and visible-light irradiation for 180 min, the desulfurization rate of simulated fuel oil reaches 91.2%, and the stability of photoctalyst is also good.

Key words: hydrothermal three-dimensional porous Bi₂WO₆, photocatalytic oxidation, desulfurization of simiulated fuel oil

中图分类号:

TQ174

王丹军, 岳林林, 郭莉, 付峰, 薛岗林. 多孔结构Bi₂WO₆光催化剂的制备及其模拟燃油催化氧化脱硫活性[J]. 无机材料学报, 2013, 28(10): 1079-1086.

WANG Dan-Jun, YUE Lin-Lin, GUO Li, FU Feng, XUE Gang-Lin. Synthesis of Porous-Bi₂WO₆ and Its Photocatalytic Oxidative Desulfurization (Photo-ODS) Activity of Simulation Fuel[J]. Journal of Inorganic Materials, 2013, 28(10): 1079-1086.

参考文献

[1] Zhu S B, Xu T G, Fu H B, et al. Synergetic effect of Bi2WO6 photocatalyst with C60 and enhanced photoactivity under visible irradiation. Environ. Sci. Technol., 2007, 41(17): 6234–6239.

[2] Zhang L S, Wang W Z, Chen Z G, et al. Fabrication of flower-like Bi2WO6 superstructures as high performance visible-light driven photocatalysts. J. Mater. Chem, 2007, 17(24): 2526–2532.

[3] Li Y Y, Liu J P, Huang X T, et al. Hydrothermal synthesis of Bi2WO6 uniform hierarchical microspheres.-Cryst.-Growth-Des., 2007, 7(7): 1350–1355.

[4] Liu S W, Yu J G. J. Cooperative self-construction and enhanced optical absorption of nanoplates-assembled hierarchical Bi2WO6 flowers. J. Solid State Chem., 2008, 181(5): 1048–1055.

[5] Shi R, Huang G L, Lin J, et al. Photocatalytic activity enhancement for Bi2WO6 by fluorine substitution. J. Phys. Chem. C, 2009, 113(45): 19633–19638.

[6] Li Y, Huang X, Liu J, et al. Self-assemly of Bi2WO6 square nanoplates into hierarchical structure. Journal of Nanoscience and Nanotechnology, 2009, 9(2): 1530–1534.

[7] Shang M, Wang W Z, Xu H L. New Bi2WO6 nanocages with high visible-light-driven photocatalytic activities prepared in refluxing EG. Crystal Growth & Design, 2009, 9(2): 991–996.

[8] Zhang G K, Lü F, Li M, et al. Synthesis of nanometer Bi2WO6 synthesized by Sol–Gel method and its visible-light photocatalytic activity for degradation of 4BS. J. Phys. Chem. Solids, 2010, 71 (4): 579–582.

[9] Huang Y, Ai Z H, Ho W K, et al. Ultrasonic spray pyrolysis synthesis of porous Bi2WO6 microspheres and their visible- light-induced photocatalytic removal of NO. J. Phys. Chem. C, 2010, 114(14): 6342–6349.

[10] Wu L, Bi J H, Li Z H, et al. Rapid preparation of Bi2WO6 photocatalyst with nanosheet morphology via microwave-assisted solvothermal synthesis.-Catalysis Today, 2008, 131(1-4): 15–20.

[11] Xie H D, Shen D Z, Wang X Q, et al. Microwave hydrothermal synthesis and visible-light photocatalytic activity of Bi2WO6 nanoplates. Mater. Chem.Phys., 2007, 103(2/3): 334–339.

[12] Zhang C, Zhu Y. Synthesis of square Bi2WO6 nanoplates as high-activity visible-light-driven photocatalysts. Chem. Mater., 2005, 17(13): 3537–3543.

[13] Liu S W, Yu J G. Cooperative self-construction and enhanced optical absorption of nanoplates-assembled hierarchical Bi2WO6 flowers. J. Solid State Chem., 2008, 181(5): 1048–1055.

[14] Yu J G, Xiong J F, Cheng B, et al. Hydrothermal preparation and visible-light photocatalytic activity of Bi2WO6 powders. J. Solid State Chem., 2005, 178(6): 1968–1972.

[15] Fu H B, Yao W Q, Zhang L W, et al. The enhanced photoactivity of nanosized Bi2WO6 catalyst for the degradation of 4-chlorophenol. Mater. Res. Bull., 2008, 43(10): 2617–2625.

[16] Tailleur R G, Ravigli J, Quenza S, et al. Catalytic for ultra-low sulfur and aromatic diesel. Appl. Catal. A-Gen., 2005, 282(1/2): 227-235.

[17] Stumpf A, Tolfaj K, Juhasa M. Detailed analysis of sulfur compounds in gasoline range prtroleum products with high-resolution gas chromatography-atomtic emission detection using proup-selective chemical treatment. J. Chroma. A, 1998, 819 (1/2): 67–74

[18] Hatanaka S. Hydrodesulfurziation of catalytic cracked gasoline- inhibiting effects of olefins on HDS of alkyl(benzo) thiophene contained in catalytic cracked gasoline. Ind. Eng. Chem. Res., 1997, 36(3): 1519–1523.

[19] Nocca J L, Cosyns j, Debuisschert Q, et al. The Domino Interaction of Refinery Processes for Gasoline Quality Attainment. NRPRRA Annual Meeting, Texas, 2000, AM-00-61.

[20] Gyanesh P. Desulfurization with Zinc Titanate Sorbents. US. patent 6338794, 2002.

[21] Shiraishi Y, Hirai T, Komasawa I. Photochemical desulfurization of light oils using oil/hydrogen peroxide aqueous solution extraction system: application for high sulfur content straight-run light gas oil and aromatic rich light cycle oil. J. Chem. Eng. Japan, 1999, 32(1): 158–161.

[22] Hirai T, Shirai T, Ogawa K, et al. Effect of photosensitizer and hydrogen peroxide on desulfurization of light oil by photochemical and liquid-liquid extraction. Ind. Eng. Chem. Res., 1997, 32(1): 158–161.

[23] Donald R. Sorbent Composition US patent: 6350422, 2002-2-26.

[24] Khare G. P. Desulfurization Process and Novel Bimetallic Sorbents systems for Same US patent: 6274533, 2001-08-14.

[25] Haji S, Erkey C. Removal of dibenzothiophene from model diesel by adsorption on carbon aerogels for fuel cell application. Ind. Eng. Chem. Res. 2003, 42(26): 6933–6937.

[26] Sami H A, Dina M H, Bader H A, et al. Removal of dibenzothiophenes from fuel by oxy-desulfurization. Energy Fuels, 2009, 23(12): 5986-5994.

[27] Sampanthar J T, Huang X, Jian D, et al. A novel oxidative desulfurization process to remove refractory sulfur compounds from diesel fuel. Appl. Catal. B: Environ., 2006, 63(1/2): 85-93.

[28] Campos-Martin J M, Capel-Sanchez M C, Fierro J L G. Highly efficient deep desulfurization of fuels by chemical oxidation. Green Chem., 2004, 6(11): 557–562.

[29] Ali M F, Al-Malki A, El-Ali B, et al. Deep desulphurization of gasoline and diesel fuels using non-hydrogen consuming techniques. Fuel, 2006, 85(8): 1354–1363.

[30] Song C S, Ma X L. New design approaches to ultra-clean diesel fuels by deep desulfurization. Appl. Catal. B, 2003, 41(1/2): 207–238.

[31] Te M, Fairbridge C, Ring Z. Oxidation reactivities of dibenzothiophenes in polyoxometalate/H2O2 and formic acid/H2O2. Appl. Catal. A, 2001, 219(1/2): 267–280.

[32] Chica A, Gatti G, Moden B, et al. Selective catalytic oxidation of organosulfur compounds tert-butyl hydroperoxide. Chem. Eur. J., 2006, 12(7): 1960–1967.

[33] Prasad V V D N, Jeong K E, Chae H J, et al. Oxidative desulfurization of 4, 6-dimethyl dibenzothiophene and light cycle oil over supported moybdenum oxide catalysts. Catal. Commun., 2008, 9(10): 1966–1969.

[34] Li H M, Jiang X, Zhu W S, et al. Deep oxidative desulfurization of fuel oils catalyzed by decatungstates in the ionic liquid of [Bmin]PF6. Ind. Eng. Chem., 2009, 48(19): 9034-9039.

[35] Chen X, Lou Y B, Samia A C S, et al. Formation of oxynitride as the photocatalytic enhancing site in nitrogen-doped titania nanocatalysts: comparison to a commercial nanopowder. Adv. Funct. Mater., 2005, 15(1): 41-49.

[36] Wang C Y, Zhang H, Li F, et al. Degradation and mineralization of Bisphenol A by mesoporous Bi2WO6 under simulated solar light irradiation. Environ. Sci. Technol., 2010, 44(17): 6843-6848.

[37] Sing K S W, Everett D H, Haul R A W, et al. Reporting physisorption data for gas/solid system with special reference to the determination of surface area and porosity. Pure Appl. Chem., 1985, 57(4): 603-619.

[38] Ren J, Wang W Z, Sun S M, et al. Enhance photocatalytic activity of Bi2WO6 loaded with Ag nanoparticles under visible light irradiation. Appl. Catal. B: Environ., 2009, 92(1/2): 50-55.

多孔结构Bi₂WO₆光催化剂的制备及其模拟燃油催化氧化脱硫活性

Synthesis of Porous-Bi₂WO₆ and Its Photocatalytic Oxidative Desulfurization (Photo-ODS) Activity of Simulation Fuel

RichHTML

PDF (PC)

可视化

被引次数

摘要/Abstract

引用本文

使用本文

参考文献

相关文章 15

编辑推荐

Metrics

本文评价

[1]	姚仪帅, 郭瑞华, 安胜利, 张捷宇, 周国治, 张国芳, 黄雅荣, 潘高飞. 原位负载Pt-Co高指数晶面催化剂的制备及其电催化性能[J]. 无机材料学报, 2023, 38(1): 71-78.
[2]	张弦, 张策, 姜文君, 冯德强, 姚伟. 四元BiMnVO₅的合成、电子结构与可见光催化性能研究[J]. 无机材料学报, 2022, 37(1): 58-64.
[3]	肖昱旻, 李彬, 覃礼钊, 林华, 李庆, 廖斌. 用CuCl₂为铜源高效制备形貌可控CuGeO₃的研究[J]. 无机材料学报, 2021, 36(1): 69-74.
[4]	王举汉,文雄,刘成超,张煜华,赵燕熹,李金林. 多级孔Co/Al-SiO₂催化剂制备及其费-托合成催化性能[J]. 无机材料学报, 2020, 35(9): 999-1004.
[5]	王金敏, 于红玉, 马董云. 纳米二氧化锰的制备及其应用研究进展[J]. 无机材料学报, 2020, 35(12): 1307-1314.
[6]	李孟夏, 陆越, 王利斌, 胡先罗. Mn₃O₄@ZnO核壳结构纳米片阵列的可控合成及其在水系锌离子电池中的应用[J]. 无机材料学报, 2020, 35(1): 86-92.
[7]	许云青,王海增. EDTA辅助水热法制备不同形貌的氟化镁钠[J]. 无机材料学报, 2019, 34(9): 933-937.
[8]	苟生莲, 乃学瑛, 肖剑飞, 叶俊伟, 董亚萍, 李武. 碱式氯化镁晶须制备纳米氧化镁热分解动力学研究[J]. 无机材料学报, 2019, 34(7): 781-785.
[9]	刘伟, 郑凯, 王东红, 雷忆三, 范怀林. Co₃O₄纳米线阵列@活性炭纤维复合材料的水热合成及电化学应用[J]. 无机材料学报, 2019, 34(5): 487-492.
[10]	王伟, 罗世阶, 鲜聪, 肖群, 杨洋, 欧云, 刘运牙, 谢淑红. 水热合成BiCl₃/Bi₂S₃复合材料的热电性能[J]. 无机材料学报, 2019, 34(3): 328-334.
[11]	蒋海燕, 夏云生, 李育珍. 多孔棒状FeVO₄的制备及可见光催化性能研究[J]. 无机材料学报, 2018, 33(9): 949-955.
[12]	张国雄, 陈月梅, 何臻妮, 林川, 陈益钢, 郭海波. 表面活性剂对NiCo₂S₄纳米薄膜的电化学性能影响的研究[J]. 无机材料学报, 2018, 33(3): 289-294.
[13]	曾燕飞, 辛国祥, 布林朝克, 张邦文. 一步法制备三维还原氧化石墨烯/NiO超级电容器电极材料及其性能研究[J]. 无机材料学报, 2018, 33(10): 1070-1076.
[14]	杨坤坤, 杨少华, 赵平, 赵彦龙. FeS₂/RGO纳米复合材料的制备及热电池放电性能[J]. 无机材料学报, 2017, 32(7): 691-698.
[15]	杨敏, 贾晓鹏, 李秉轲, 邓国伟, 王琪慧, 刘晓旸. Zn₂GeO₄微米球的一步合成及其光催化制氢活性[J]. 无机材料学报, 2017, 32(2): 141-147.