双酸体系下有序介孔SO42-/ZrO2-SiO2材料的合成

引用本文: 于峰, 郭敏, 王旭, 潘大海, 李瑞丰. 双酸体系下有序介孔SO₄^2-/ZrO₂-SiO₂材料的合成[J]. 燃料化学学报, 2013, 41(4): 456-462. shu

Citation: YU Feng, GUO Min, WANG Xu, PAN Da-hai, LI Rui-feng. Synthesis of well-ordered SO₄^2-/ZrO₂-SiO₂ materials in bi-acid system[J]. Journal of Fuel Chemistry and Technology, 2013, 41(4): 456-462. shu

双酸体系下有序介孔SO₄^2-/ZrO₂-SiO₂材料的合成

于峰 ^1, ,
郭敏 ^1, ,
王旭 ^1, ,
潘大海 ^1, ,
李瑞丰 ^{1,2,
,}

通讯作者: LI Rui-feng, E-mail: rfli@tyut.edu.cn.

基金项目:
Supported by the Natural Science Foundation of China (NSFC, 50772070, 51172154) (NSFC, 50772070, 51172154)

the Research Fund for the Doctoral Program of Higher Education (20121402120011) (20121402120011)

the Science and technological program of Shanxi Province (20110008) (20110008)

摘要: 采用一锅合成法通过调变自组装过程中硫酸和盐酸的体积比,成功制备了系列介孔SO₄^2-/ZrO₂-SiO₂固体酸材料(Zr/Si物质的量为1.1).XRD、UV-Vis DRS、HR-TEM等表征结果表明,所得材料均具有高度有序的二维介孔结构及四方相氧化锆的晶体结构.氮吸附和FT-IR表征结果进一步发现,通过改变硫酸/盐酸体积比可有效调变材料比表面积、孔容、孔径及表面L酸与B酸的相对强度.与纯硅介孔分子筛SBA-15不同,此系列SO₄^2-/ZrO₂-SiO₂固体酸材料均在正戊烷的异构化反应中表现出较高的催化活性和稳定性.其原因在于,在合成过程中硫酸的加入不仅促使了酸基的形成,而且稳定了催化剂的晶体结构;盐酸的存在则保持了有序的介孔结构.由此可见,混酸合成体系有望制备出结构有序、酸性可调、催化性能优越的新型催化材料,并在众多酸催化反应中取得应用.

关键词:

English

Synthesis of well-ordered SO₄^2-/ZrO₂-SiO₂ materials in bi-acid system

YU Feng ^1, ,
GUO Min ^1, ,
WANG Xu ^1, ,
PAN Da-hai ^1, ,
LI Rui-feng ^{1,2,
,}

1.
1. College of Chemistry and Chemical Engineering, Taiyuan University of Technology, Taiyuan 030024, China;

Corresponding author: LI Rui-feng, E-mail: rfli@tyut.edu.cn.

Received Date: 17 December 2012
Fund Project:
Supported by the Natural Science Foundation of China (NSFC, 50772070, 51172154)

the Research Fund for the Doctoral Program of Higher Education (20121402120011)

the Science and technological program of Shanxi Province (20110008)

Abstract: A series of solid acid SO₄^2-/ZrO₂-SiO₂ catalysts with a fixed Zr/Si molar ratio of 1.1 were successfully synthesized in one-pot through changing the H₂SO₄/HCl volume ratio during the self-assembly process. X-ray diffraction (XRD), UV-visible DRS, and high resolution transmission electron microscopy (HRTEM) results demonstrate that all the resultant catalysts exhibit a highly ordered 2D hexagonal mesostructures with zirconia particles of homogenously distributed tetragonal nanocrystallites in mesoporous walls. N₂ adsorption and pyridine in-situ Fourier-transformed infrared spectra (FT-IR) further reveal that the surface area, pore volume, pore diameter and the relative strength of Lewis and Brønsted acidic sites of resultant catalysts can be controlled by tuning the H₂SO₄/HCl volume ratio during the synthesis. Different from pure mesoporous SBA-15 material, the mesoporous SO₄^2-/ZrO₂-SiO₂ materials prepared in this work exhibit high structural stability and catalytic activity in n-pentane isomerization, which is attributed not only to hydrochloric acid that facilitates the formation of mesoporous silica but also to sulfuric acid that helps to stabilize the structure of catalysts and produce acid sites. The methods proposed in this work provide an important approach to synthesize ordered solid acid catalysts with high stability and potential applications in various acidic-catalyzed reactions.

Key words:

1. [1] KRESGE C T, LEONOWICZ M E, ROTH W J, VARULI J C, BECK J S. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism[J]. Nature, 1992, 359: 710-712.[1] KRESGE C T, LEONOWICZ M E, ROTH W J, VARULI J C, BECK J S. Ordered mesoporous molecular sieves synthesized by a liquid-crystal template mechanism[J]. Nature, 1992, 359: 710-712.
2. [2] CORMA A. From microporous to mesoporous molecular sieve materials and their use in catalysis[J]. Chem Rev. 1997, 97(6): 2373-2419.[2] CORMA A. From microporous to mesoporous molecular sieve materials and their use in catalysis[J]. Chem Rev. 1997, 97(6): 2373-2419.
3. [3] ZHAO D, FENG J, HUO Q, MELOSSH N, FREDRICKSON G H, CHMELKA B F, STUCKY G D. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores[J]. Science, 1998, 279(5350): 548-552.[3] ZHAO D, FENG J, HUO Q, MELOSSH N, FREDRICKSON G H, CHMELKA B F, STUCKY G D. Triblock copolymer syntheses of mesoporous silica with periodic 50 to 300 angstrom pores[J]. Science, 1998, 279(5350): 548-552.
4. [4] CHEN X R, JU Y H, MOU C Y. Direct synthesis of mesoporous sulfated silica-zirconia catalysts with catalytic activity for biodiesel via esterification[J]. J Phys Chem C, 2007, 111(50): 18731-18737.[4] CHEN X R, JU Y H, MOU C Y. Direct synthesis of mesoporous sulfated silica-zirconia catalysts with catalytic activity for biodiesel via esterification[J]. J Phys Chem C, 2007, 111(50): 18731-18737.
5. [5] HWANG C C, MOU C Y. Alumina-promoted sulfated mesoporous zirconia catalyst[J]. J. Phys. Chem. C, 2009, 113(13): 5212-5221.[5] HWANG C C, MOU C Y. Alumina-promoted sulfated mesoporous zirconia catalyst[J]. J. Phys. Chem. C, 2009, 113(13): 5212-5221.
6. [6] WANG Y, LEE K Y, CHOI S, LIU J, WANG L Q, PEDEN C H F, Grafting sulfated zirconia on mesoporous silica[J]. Green Chem, 2007, 9(6): 540-544.[6] WANG Y, LEE K Y, CHOI S, LIU J, WANG L Q, PEDEN C H F, Grafting sulfated zirconia on mesoporous silica[J]. Green Chem, 2007, 9(6): 540-544.
7. [7] CHEN C, LI T, CHENG S, LIN H, BHONGALE C J, MOU C Y, Direct impregnation method for preparing sulfated zirconia supported on mesoporous silica[J]. Micropor Mesopor Mater, 2001, 50(2-3): 201-208.[7] CHEN C, LI T, CHENG S, LIN H, BHONGALE C J, MOU C Y, Direct impregnation method for preparing sulfated zirconia supported on mesoporous silica[J]. Micropor Mesopor Mater, 2001, 50(2-3): 201-208.
8. [8] CHANG B B, FU J, TIAN Y L, DONG X P. Mesoporous solid acid catalysts of sulfated zirconia/SBA-15 derived from a vapor-induced hydrolysis route[J]. Appl Catal A, 2012, 437-438: 149-154.[8] CHANG B B, FU J, TIAN Y L, DONG X P. Mesoporous solid acid catalysts of sulfated zirconia/SBA-15 derived from a vapor-induced hydrolysis route[J]. Appl Catal A, 2012, 437-438: 149-154.
9. [9] LI F X, YU F, LI Y L, LI R F, XIE K C. Direct synthesis of Zr-SBA-15 mesoporous molecular sieves: characterization and catalytic activities after sulfated[J]. Micropor Mesopor Mater, 2007, 101(1-2): 250-255.[9] LI F X, YU F, LI Y L, LI R F, XIE K C. Direct synthesis of Zr-SBA-15 mesoporous molecular sieves: characterization and catalytic activities after sulfated[J]. Micropor Mesopor Mater, 2007, 101(1-2): 250-255.
10. [10] LI R F, YU F, LI F X, ZHOU M M, XU B S, XIE K C. One-pot synthesis of superacid catalytic material SO₄^2-/ZrO₂-SiO₂ with thermostable well-ordered mesoporous structure[J]. J Solid State Chem, 2009, 182(5): 991-994.[10] LI R F, YU F, LI F X, ZHOU M M, XU B S, XIE K C. One-pot synthesis of superacid catalytic material SO₄^2-/ZrO₂-SiO₂ with thermostable well-ordered mesoporous structure[J]. J Solid State Chem, 2009, 182(5): 991-994.
11. [11] CIESLA U, FRBA M, STUCKY G, SCHVTH F. Highly ordered porous zirconias from surfactant-controlled syntheses: Zirconium oxide-sulfate and zirconium oxo phosphate[J] Chem Mater, 1999, 11(2): 227-234.[11] CIESLA U, FRBA M, STUCKY G, SCHVTH F. Highly ordered porous zirconias from surfactant-controlled syntheses: Zirconium oxide-sulfate and zirconium oxo phosphate[J] Chem Mater, 1999, 11(2): 227-234.
12. [12] ZHAO D, HUO Q, FENG J, CHMELKA B, STUCKY G. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures[J]. J Am Chem Soc, 1998, 120: 6024-6036.[12] ZHAO D, HUO Q, FENG J, CHMELKA B, STUCKY G. Nonionic triblock and star diblock copolymer and oligomeric surfactant syntheses of highly ordered, hydrothermally stable, mesoporous silica structures[J]. J Am Chem Soc, 1998, 120: 6024-6036.
13. [13] TUEL A, GONTIE S, TEISSIER R. Zirconium containing mesoporous silicas: New catalysts for oxidation reactions in the liquid phase[J]. Chem Commun, 1996, (5): 651-652.[13] TUEL A, GONTIE S, TEISSIER R. Zirconium containing mesoporous silicas: New catalysts for oxidation reactions in the liquid phase[J]. Chem Commun, 1996, (5): 651-652.
14. [14] LI M, FENG Z, XIONG G, XIONG G, YING P, XIN Q, LI C. Phase transformation in the surface region of zirconia detected by UV raman spectroscopy[J]. J Phys Chem B, 2001, 105(34): 8107-8111.[14] LI M, FENG Z, XIONG G, XIONG G, YING P, XIN Q, LI C. Phase transformation in the surface region of zirconia detected by UV raman spectroscopy[J]. J Phys Chem B, 2001, 105(34): 8107-8111.
15. [15] FERNNDEZ L[WTBZ][WTB1]PEZ E, ESCRIBANO V S, PANIZZA M, CARNASCIALI M, BUSCA G. Vibrational and electronic spectroscopic properties of zirconia powders[J]. J Mater Chem, 2001, 11(7): 1891-1897.[15] FERNNDEZ L[WTBZ][WTB1]PEZ E, ESCRIBANO V S, PANIZZA M, CARNASCIALI M, BUSCA G. Vibrational and electronic spectroscopic properties of zirconia powders[J]. J Mater Chem, 2001, 11(7): 1891-1897.
16. [16] YAMAGUCHI T. Recent progress in solid superacid[J]. Appl Catal, 1990, 61(1): 1-25.[16] YAMAGUCHI T. Recent progress in solid superacid[J]. Appl Catal, 1990, 61(1): 1-25.
17. [17] BAERTSCH C D, SOLED S L, IGLESIA E. Isotopic and chemical titration of acid sites in tungsten oxide domains supported on zirconia[J]. J Phys Chem B, 2001, 105(7): 1320-1330.[17] BAERTSCH C D, SOLED S L, IGLESIA E. Isotopic and chemical titration of acid sites in tungsten oxide domains supported on zirconia[J]. J Phys Chem B, 2001, 105(7): 1320-1330.
18. [18] WANG W, WANG J H, CEHN C L. n-Pentane isomerization over promoted SZ/MCM-41 catalysts[J]. Catal Today, 2004, 97(4): 307-313.[18] WANG W, WANG J H, CEHN C L. n-Pentane isomerization over promoted SZ/MCM-41 catalysts[J]. Catal Today, 2004, 97(4): 307-313.
19. [19] WANG J H, MOU C Y, Alumina-promoted mesoporous sulfated zirconia: A catalyst for n-butane isomerization[J]. Appl Catal A, 2005, 286(1): 128-136.[19] WANG J H, MOU C Y, Alumina-promoted mesoporous sulfated zirconia: A catalyst for n-butane isomerization[J]. Appl Catal A, 2005, 286(1): 128-136.
20. [20] TANABE K, HATTORI H, YAMAGUCHI T. Crit Rev Surf Chem, 1990, 1: 1.[20] TANABE K, HATTORI H, YAMAGUCHI T. Crit Rev Surf Chem, 1990, 1: 1.
21. [21] RISCH M A, WOIF E E. Characterization and n-butane isomerization activity of high surface area sulfated zirconia catalysts[J]. Appl Catal A, 1998, 172: L1-L5.[21] RISCH M A, WOIF E E. Characterization and n-butane isomerization activity of high surface area sulfated zirconia catalysts[J]. Appl Catal A, 1998, 172: L1-L5.
22. [22] HAMMACHE S, GOODWIN J G. Characteristics of the active sites on sulfated zirconia for n-butane isomerization[J]. J Catal, 2003, 218(2): 258-266.[22] HAMMACHE S, GOODWIN J G. Characteristics of the active sites on sulfated zirconia for n-butane isomerization[J]. J Catal, 2003, 218(2): 258-266.
23. [23] CORMA A, GARCIA H. Lewis Acids: From conventional homogeneous to green homogenerous and heterogeneous catalysis[J]. Chem Rev, 2003, 103(11): 4307-4365.[23] CORMA A, GARCIA H. Lewis Acids: From conventional homogeneous to green homogenerous and heterogeneous catalysis[J]. Chem Rev, 2003, 103(11): 4307-4365.

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1.
沈阳化工大学材料科学与工程学院沈阳 110142

双酸体系下有序介孔SO₄^2-/ZrO₂-SiO₂材料的合成

通讯作者: LI Rui-feng, E-mail: rfli@tyut.edu.cn.

English

Synthesis of well-ordered SO₄^2-/ZrO₂-SiO₂ materials in bi-acid system

Corresponding author: LI Rui-feng, E-mail: rfli@tyut.edu.cn.

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