孔道结构含多酸复合光催化材料的制备及其性能研究
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摘要
利用自组装技术、溶胶－凝胶和程序升温水热法，制备了三类具
有较高光催化活性、含多金属氧酸盐的新型固体光催化材料如杂化光
催 化 剂 K5M(H2O)PW11O39-APS-SiO2 （ M = Ni/Co ， APS =
(C2H5O)3SiCH2CH2CH2NH2，SiO2 = MCM-48，MCM-41，SIO-7）；介
孔复合材料 H3PW12O40/TiO2（无定形结构）以及 H6P2W18O62掺杂锐钛
矿纳米晶光催化材料 H6P2W18O62/TiO2。利用紫外漫反射光谱、红外光
谱、拉曼光谱、固体核磁共振波谱、电感耦合等离子原子发射光谱和
X-射线粉末衍射等手段，对这三类材料进行了组成和结构表征。结果
表明，上述光催化材料中，多酸仍保持着最初的基本结构。利用 N2吸
附测定和透射电子显微镜，对以上三类材料的孔道结构、表面物理性
质和形貌进行了分析。结果表明，这三类催化材料均具有孔结构。其
中，杂化材料 K5M(H2O)PW11O39-APS-SiO2表现为无定形介孔结构，平
均 孔 径 在 5.4-40.3 nm 。 通 过 溶 胶 － 凝 胶 合 成 的 复 合 材 料
H3PW12O40/TiO2 具有介孔结构，其平均孔径为 3.06 nm。H6P2W18O62
掺杂TiO2锐钛矿纳米晶光催化材料H6P2W18O62/TiO2具有微孔（0.6 nm）
和介孔（4.0 nm）双重孔径。与母体多金属氧酸盐相比，上述光催化
材料的 BET 比表面积均有了不同程度的提高。
通过对可溶性染料和杀虫剂（六氯苯和甲基对硫磷）的光催化降
解与矿化反应，研究了上述光催化材料在非均相体系中的光催化活
性。结果表明，K5M(H2O)PW11O39-APS-SiO2 在近紫外光能辐射下、
H3PW12O40/TiO2 和 H6P2W18O62/TiO2 在可见光照射下均具有较高的光
催化活性，可有效降解上述有机污染物。这些材料的光催化活性主要
来自于多金属氧酸盐本身的结构特征、孔结构材料优异的表面物理化
学性质、吸附在催化剂表面的染料分子的敏化作用以及多金属氧酸盐
与锐钛矿结构的 TiO2之间的协同作用。
Three types of the solid photocatalytic materials such as hybrid
catalyst K5M(H2O)PW11O39-APS-SiO2 (abbreviated PW11M-APS-SiO2，M
= Ni/Co，APS = (C2H5O)3SiCH2CH2CH2NH2，SiO2 = MCM-48，MCM-41，
SIO-7); mesoporous composite material H3PW12O40/TiO2 (amorphous) and
H6P2W18O62/TiO2(anatase phase) were prepared by the self-assembly
method, sol-gel and programmed temperature hydrothermal methods.
As-synthesized materials are novel, water-insoluble, photochemically
active and porous. UV-vis diffuse reflectance spectra (UV/DRS), infrared
(IR) spectra, raman spectra, 31P MAS NMR, ICP-AES, powder X-ray
diffraction (XRD), TEM and nitrogen adsorption analysis were used to
characterize the composition, structure, morphology and surface
physicochemical properties of as-prepared solid photocatalytic materials,
indicating that the primary polyoxometalate (POM) structures remained
intact in as-prepared composites, and the composites exhibited porous
structures. The average pore size of the hybrid catalyst PW11M-APS-SiO2
is 5.4-40.3 nm, the average pore size of the mesoporous composite material
H3PW12O40/TiO2 is 3.06 nm, and H6P2W18O62/TiO2 (anatase phase) have
bimodal pore systems (micro-mesoporosity) with pore size at 0.6 and 4.0
nm. In addition, compared with starting POMs, BET surface areas of the
solid photocatalytic materials have been improved in the different extents.
Photocatalytic activities of as-synthesized composites were studied
via the following model reactions, e.g., photodegradation of the aqueous
dye, the pesticide hexachlorobenzene (HCB) and methylparathion (MPT).
It has shown that aqueous organics can be degraded by the hybrid catalyst
PW11M-APS-SiO2 under near-UV irradition and by mesoporous
H3PW12O40/TiO2 (amorphous) and H6P2W18O62/TiO2 (anatase phase) under
visible-light irradition. The photocatalytic activity of the solid
photocatalytic materials is attributed to the structure of POMs, unique
３
东北师范大学硕士论文
physicochemical properties of the porous materials, sensitized effect of the
dye molecular adsorbed on the surface of the catalyst, and the synergistic
effect yielded by the combination of POM and TiO2.
有较高光催化活性、含多金属氧酸盐的新型固体光催化材料如杂化光
催 化 剂 K5M(H2O)PW11O39-APS-SiO2 （ M = Ni/Co ， APS =
(C2H5O)3SiCH2CH2CH2NH2，SiO2 = MCM-48，MCM-41，SIO-7）；介
孔复合材料 H3PW12O40/TiO2（无定形结构）以及 H6P2W18O62掺杂锐钛
矿纳米晶光催化材料 H6P2W18O62/TiO2。利用紫外漫反射光谱、红外光
谱、拉曼光谱、固体核磁共振波谱、电感耦合等离子原子发射光谱和
X-射线粉末衍射等手段，对这三类材料进行了组成和结构表征。结果
表明，上述光催化材料中，多酸仍保持着最初的基本结构。利用 N2吸
附测定和透射电子显微镜，对以上三类材料的孔道结构、表面物理性
质和形貌进行了分析。结果表明，这三类催化材料均具有孔结构。其
中，杂化材料 K5M(H2O)PW11O39-APS-SiO2表现为无定形介孔结构，平
均 孔 径 在 5.4-40.3 nm 。 通 过 溶 胶 － 凝 胶 合 成 的 复 合 材 料
H3PW12O40/TiO2 具有介孔结构，其平均孔径为 3.06 nm。H6P2W18O62
掺杂TiO2锐钛矿纳米晶光催化材料H6P2W18O62/TiO2具有微孔（0.6 nm）
和介孔（4.0 nm）双重孔径。与母体多金属氧酸盐相比，上述光催化
材料的 BET 比表面积均有了不同程度的提高。
通过对可溶性染料和杀虫剂（六氯苯和甲基对硫磷）的光催化降
解与矿化反应，研究了上述光催化材料在非均相体系中的光催化活
性。结果表明，K5M(H2O)PW11O39-APS-SiO2 在近紫外光能辐射下、
H3PW12O40/TiO2 和 H6P2W18O62/TiO2 在可见光照射下均具有较高的光
催化活性，可有效降解上述有机污染物。这些材料的光催化活性主要
来自于多金属氧酸盐本身的结构特征、孔结构材料优异的表面物理化
学性质、吸附在催化剂表面的染料分子的敏化作用以及多金属氧酸盐
与锐钛矿结构的 TiO2之间的协同作用。
Three types of the solid photocatalytic materials such as hybrid
catalyst K5M(H2O)PW11O39-APS-SiO2 (abbreviated PW11M-APS-SiO2，M
= Ni/Co，APS = (C2H5O)3SiCH2CH2CH2NH2，SiO2 = MCM-48，MCM-41，
SIO-7); mesoporous composite material H3PW12O40/TiO2 (amorphous) and
H6P2W18O62/TiO2(anatase phase) were prepared by the self-assembly
method, sol-gel and programmed temperature hydrothermal methods.
As-synthesized materials are novel, water-insoluble, photochemically
active and porous. UV-vis diffuse reflectance spectra (UV/DRS), infrared
(IR) spectra, raman spectra, 31P MAS NMR, ICP-AES, powder X-ray
diffraction (XRD), TEM and nitrogen adsorption analysis were used to
characterize the composition, structure, morphology and surface
physicochemical properties of as-prepared solid photocatalytic materials,
indicating that the primary polyoxometalate (POM) structures remained
intact in as-prepared composites, and the composites exhibited porous
structures. The average pore size of the hybrid catalyst PW11M-APS-SiO2
is 5.4-40.3 nm, the average pore size of the mesoporous composite material
H3PW12O40/TiO2 is 3.06 nm, and H6P2W18O62/TiO2 (anatase phase) have
bimodal pore systems (micro-mesoporosity) with pore size at 0.6 and 4.0
nm. In addition, compared with starting POMs, BET surface areas of the
solid photocatalytic materials have been improved in the different extents.
Photocatalytic activities of as-synthesized composites were studied
via the following model reactions, e.g., photodegradation of the aqueous
dye, the pesticide hexachlorobenzene (HCB) and methylparathion (MPT).
It has shown that aqueous organics can be degraded by the hybrid catalyst
PW11M-APS-SiO2 under near-UV irradition and by mesoporous
H3PW12O40/TiO2 (amorphous) and H6P2W18O62/TiO2 (anatase phase) under
visible-light irradition. The photocatalytic activity of the solid
photocatalytic materials is attributed to the structure of POMs, unique
３
东北师范大学硕士论文
physicochemical properties of the porous materials, sensitized effect of the
dye molecular adsorbed on the surface of the catalyst, and the synergistic
effect yielded by the combination of POM and TiO2.
引文
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[3] Katsoulis D. E. A survey of applications of polymetalates, Chem.Rev.,
1998,98, 359-367.
[4]毛萱,殷元骐 杂多酸催化研究新进展,分子催化,2000,14(6),483-489.
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Tetrakis(tetrabutylammonium) decatungstate(Ⅵ)and catalytic hydrogen
evolution from alcohols, J.Chem.Soc.Dalton Trans.1984,793-199.
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organic substrate by polyoxometalates, J.Am.Chem.Soc.1985,107, 5148-
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degradation of N-methylpyrrolidinone in the presence of CS3PW12O40 and
TiO2 colloid photocatalysts, Environ.Sci.Technol.1999,33,3193-3198.
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Water: An Aid to Environmental Preservation.Pure &Appl Chem,1992,
64,1285.
[14] Mills A, Davies R H, Worsley D,Water Purification by Semiconductor
６５
东北师范大学硕士论文
Photocatalysis.Chem Soc Rev, 1993,22,417~425.
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TiO2/SiO2 photocatalyst, Appl.Catal.B, 2001,35,95-105.
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东北师范大学硕士论文
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derivatives of polyoxometalates, Chem.Rev., 1998,98,77-111.
[2]王恩波,胡长文,许林 多酸化学导论,化学工业出版社,1998(第一
版).1-3
[3] Katsoulis D. E. A survey of applications of polymetalates, Chem.Rev.,
1998,98, 359-367.
[4]毛萱,殷元骐 杂多酸催化研究新进展,分子催化,2000,14(6),483-489.
[5]泉有亮 化学總说 1993,20,112.
[6]吴跃 催化化学，科学出版社,1998(第二版).
[7] Fujishima A, Honda K. Electrochemical photolysis of water at a
Semiconductor Electrocle, Nature, 1972,238,37-38.
[8] Anpo M, Surface photochemistry, John Willey & Sons, 1996.
[9] Yamase T., Takabayashi N., Kaji M. Solution Photochemistry of
Tetrakis(tetrabutylammonium) decatungstate(Ⅵ)and catalytic hydrogen
evolution from alcohols, J.Chem.Soc.Dalton Trans.1984,793-199.
[10] Hill C.L., Bouchard D.A. Catalytic photochemical dehydrogenation of
organic substrate by polyoxometalates, J.Am.Chem.Soc.1985,107, 5148-
5157.
[11] Papaconstantinou E. Photochemistry of polyoxometalaes of
molybdenum and tungsten and/or vanadium, Chem.Soc.Rev.1989,18,1-31.
[12] Friesen D.A., Headley J.V., Langford C.H. The photooxidative
degradation of N-methylpyrrolidinone in the presence of CS3PW12O40 and
TiO2 colloid photocatalysts, Environ.Sci.Technol.1999,33,3193-3198.
[13] Matthews R W. Photocatalytic Oxidtion of Organic Contaminants in
Water: An Aid to Environmental Preservation.Pure &Appl Chem,1992,
64,1285.
[14] Mills A, Davies R H, Worsley D,Water Purification by Semiconductor
６５
东北师范大学硕士论文
Photocatalysis.Chem Soc Rev, 1993,22,417~425.
[15] Hoffmann, Application of Semiconductor Photocatalysis.Chem
rev,1995,95,69~96.
[16]沈伟韧,赵文宽,贺飞 TiO2光催化反应及其在废水处理中的应用,化
学进展,1998,10,349.
[17]韩兆慧,赵化侨 半导体多相光催化应用研究进展,化学进展,1999，
11,1-10.
[18]王九思,赵红花 负载型纳米TiO2光催化降解活性艳红X-3B染料,应
用化学,2002,19(8),792-794.
[19] Hu Chun, Wang Yiahong, Tang Hongxiao, Influence of adsorption on
the photodegradation of various dyes using surface bond-conjugated
TiO2/SiO2 photocatalyst, Appl.Catal.B, 2001,35,95-105.
[20] Giuseppe P. Lepore, Lalchan Persaud, Cooper H.Langford, Supporting
titanium dioxide photocatalysts on silica gel and hydrophobically modified
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