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ISSN 1000-6818CN 11-1892/O6CODEN WHXUEU
Acta Phys Chim Sin >> 2012,Vol.28>> Issue(03)>> 641-646     doi: 10.3866/PKU.WHXB201201161         中文摘要
CATALYSIS AND SURFACE SCIENCE
Effect of Fluoride Doping and Adsorption on the Photocatalytic Activity of TiO2
GAO Yue-Jun, XU Yi-Ming
Department of Chemistry, Zhejiang University, Hangzhou 310027, P. R. China
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It has been reported that bulk doping or surface modification of TiO2 with fluoride ions can enhance its photocatalytic activity for degradation of organic compounds in water. The effect of the former is ascribed to enhanced separation of photogenerated charge carriers through the surface-formed Ti3 + species, whereas that of the latter is ascribed to enhanced desorption of hydroxyl radicals through the interfacial fluoride ions. However, the difference in activity between two modified catalysts has not been investigated. In this work, different fluoride-doped samples were hydrothermally prepared from butyl titanate and NH4F. Their photocatalytic activities after addition of NaF or AgNO3 to the aqueous suspension were evaluated using phenol degradation as a model reaction. All the fluoride ions in the oxide lattices and in the outer and inner Helmholtz double layers of TiO2 were positive to phenol degradation, but the magnitude of their influences followed a decreasing order. Moreover, phenol degradation in the presence of both NaF and AgNO3 was much faster than the sum of their individual rates. These results indicate that combination of conduction band electron reduction and valence band hole oxidation is an effective way to improve the quantum yield of TiO2 photocatalysis.

Keywords: Photocatalysis   Titanium dioxide   Fluorine ion   Doping   Adsorption  
Received: 2011-09-25 Accepted: 2012-01-04 Publication Date (Web): 2012-01-16
Corresponding Authors: XU Yi-Ming Email: xuym@css.zju.edu.cn

Fund: The project was supported by the National Natural Science Foundation of China (20873124) and National Key Basic Research Program of China (973) (2011CB936003).

Cite this article: GAO Yue-Jun, XU Yi-Ming. Effect of Fluoride Doping and Adsorption on the Photocatalytic Activity of TiO2[J]. Acta Phys. -Chim. Sin., 2012,28 (03): 641-646.    doi: 10.3866/PKU.WHXB201201161
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77. LIN Cai-Fang, CHEN Xiao-Ping, CHEN Shu, SHANGGUAN Wen-Feng.Preparation of NiS-Modified Cd1-xZnxS by a Hydrothermal Method and Its Use for the Efficient Photocatalytic H2 Evolution[J]. Acta Phys. -Chim. Sin., 2015,31(1): 153-158
78. ZHANG Jian, WANG Yan-Juan, HU Shao-Zheng.Effect of K+ Doping on the Band Structure and Photocatalytic Performance of Graphitic Carbon Nitride Photocatalysts[J]. Acta Phys. -Chim. Sin., 2015,31(1): 159-165
79. REN Xiang-Zhong, LIU Tao, SUN Ling-Na, ZHANG Pei-Xin.Preparation and Electrochemical Performances of Li1.2Mn0.54-xNi0.13Co0.13ZrxO2 Cathode Materials for Lithium-Ion Batteries[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1641-1649
80. JIN Rui-Rui, YOU Ji-Guang, ZHANG Qian, LIU Dan, HU Shao-Zheng, GUI Jian-Zhou.Preparation of Fe-Doped Graphitic Carbon Nitride with Enhanced Visible-Light Photocatalytic Activity[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1706-1712
81. CHEN Ai-Min, BO Ying-Ying, SHAO Chen-Yi, WANG Jing, HU Jun.Synthesis of Single-Crystalline Cu3B2O6/CuB2O4 and Their Photocatalytic Degradation of Methylene Blue under Visible-Light Irradiation[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1713-1719
82. PENG San, GUO Hui-Lin, KANG Xiao-Feng.Preparation of Nitrogen-Doped Graphene and Its Electrocatalytic Activity for Oxygen Reduction Reaction[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1778-1786
83. ZHANG Jian-Fang, WANG Yan, SHEN Tian-Kuo, SHU Xia, CUI Jie-Wu, CHEN Zhong, WU Yu-Cheng.Visible Light Photocatalytic Performance of Cu2O/TiO2 Nanotube Heterojunction Composites Prepared by Pulse Deposition[J]. Acta Phys. -Chim. Sin., 2014,30(8): 1535-1542
84. TIAN Hong, WANG Hui-Xiang, SHI Wei-Mei, XU Yao.Microwave-Assisted Solvothermal Synthesis of In-Si Co-Modified TiO2 Photocatalysts with Enhanced Photocatalytic Activity[J]. Acta Phys. -Chim. Sin., 2014,30(8): 1543-1549
85. YAN Jing-Sen, WANG Hai-Yan, ZHANG Jing-Ru, XU Hui-Juan.Effect of TiO2-Al2O3 Support Preparation Technique on Hydrodenitrogenation of Ni2P/TiO2-Al2O3 Catalysts[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1309-1317
86. XU Ling-Ling, ZHANG Xiao-Hua, CHEN Jin-Hua.Synthesis and Electrochemical Supercapacitive Properties of Nitrogen-Doped Mesoporous Carbons[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1274-1280
87. WANG Li, MA Jun-Hong.Synthesis and Electrocatalytic Properties of Pt Nanoparticles on Nitrogen-Doped Reduced Graphene Oxide for Methanol Oxidation[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1267-1273
88. GAO Lin-Xin, JIANG Xin, GUO Sen.MnOx/CeO2/SiO2 Catalysts Prepared by Adsorption Phase Reaction Technique for Selective Catalytic Reduction of NOx at Low-Temperature[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1303-1308
89. HOU Na, LI Ying, WU Di, LI Zhi-Ru.Structures and Nonlinear Optical Properties of Alkali Metal-Doped t-Bu-calix[4]arene Molecules[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1223-1229
90. MI Chuan-Tong, LIU Guo-Ping, WANG Jia-Jia, GUO Xin-Li, WU San-Xie, YU Jin.First-Principles Calculations of the Adsorption of Au, Ag and Cu Atoms on Defected Graphene[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1230-1238
91. ZHAO Wei-Rong, SHI Qiao-Meng, LIU Ying.Performance, Deactivation and Regeneration of SnO2/TiO2 Nanotube Composite Photocatalysts[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1318-1324
92. HU Jing-Xiu, ZHANG Jing, ZOU Jian-Feng, XIAO Qiang, ZHONG Yi-Jun, ZHU Wei-Dong.Nitrogen-Rich Microporous Carbon Derived from Melamine-Based Porous Polymer for Selective CO2 Adsorption[J]. Acta Phys. -Chim. Sin., 2014,30(6): 1169-1174
93. FU Zhao-Ming, WANG Ming-Yang, ZHANG Yan-Xing, ZHANG Na, YANG Zong-Xian.First-Principles Study on the Microstructure of Triple-Phase Boundaries in the Ni/Yttria-Stabilized Zirconia Anode[J]. Acta Phys. -Chim. Sin., 2014,30(6): 1055-1060
94. ZHOU Ying, WANG Dao-Long, XIAO Nan, HOU Yu-Chen, QIU Jie-Shan.Influence of Heat Treatmecatalytic Activity[J]. Acta Phys. -Chim. Sin., 2015,31(12): 2349-2357
70. YANG Yi, YANG Zheng-Zheng, XU Hai-Di, XU Bao-Qiang, ZHANG Yan-Hua, GONG Mao-Chu, CHEN Yao-Qiang.Influence of La on CeO2-ZrO2 Catalyst for Oxidation of Soluble Organic Fraction from Diesel Exhaust[J]. Acta Phys. -Chim. Sin., 2015,31(12): 2358-2365
71. HE Zhi-Qiao, TONG Li-Li, ZHANG Zhi-Peng, CHEN Jian-Meng, SONG Shuang.Ag/Ag2WO4 Plasmonic Catalyst for Photocatalytic Reduction of CO2 under Visible Light[J]. Acta Phys. -Chim. Sin., 2015,31(12): 2341-2348
72. XING Jian-Dong, JING Fang-Li, CHU Wei, SUN Hong-Li, YU Lei, ZHANG Huan, LUO Shi-Zhong.Improvement of Adsorptive Separation Performance for C2H4/C2H6 Mixture by CeO2 Promoted CuCl/Activated Carbon Adsorbents[J]. Acta Phys. -Chim. Sin., 2015,31(11): 2158-2164
73. YANG Jie-Yang, HUANG Zhang-Gen, HAN Xiao-Jin, JING Wen, ZENG Ze-Quan.Effect of Activated Carbon Pore Structure on the Adsorption of Pb(II) from Aqueous Solution[J]. Acta Phys. -Chim. Sin., 2015,31(10): 1956-1962
74. LIU Chun-Mei, ZHANG Guo-Ying, ZHANG Xin, XU Yan-Yan, GAO Dong-Zhao.Hydrothermal Synthesis of Ag3PO4 Polyhedrons with Oriented {110} Facets and Visible-Light-Driven Photocatalytic Activity[J]. Acta Phys. -Chim. Sin., 2015,31(10): 1939-1948
75. YU Chang-Lin, WEI Long-Fu, LI Jia-De, HE Hong-Bo, FANG Wen, ZHOU Wan-Qin.Preparation and Characterization of GO/Ag3PO4 Composite Photocatalyst and Its Visible Light Photocatalytic Performance[J]. Acta Phys. -Chim. Sin., 2015,31(10): 1932-1938
76. YE Huang-Qing, DENG Yong-Hong, YAN Yan, ZHANG Mei-Jie, QIAN Yong, QIU Xue-Qing.Influence of Soldium Lignosulfonate with Different Molecular Weights on the Dispersion of Multiwalled Carbon Nanotubes[J]. Acta Phys. -Chim. Sin., 2015,31(10): 1991-1996
77. LIN Cai-Fang, CHEN Xiao-Ping, CHEN Shu, SHANGGUAN Wen-Feng.Preparation of NiS-Modified Cd1-xZnxS by a Hydrothermal Method and Its Use for the Efficient Photocatalytic H2 Evolution[J]. Acta Phys. -Chim. Sin., 2015,31(1): 153-158
78. ZHANG Jian, WANG Yan-Juan, HU Shao-Zheng.Effect of K+ Doping on the Band Structure and Photocatalytic Performance of Graphitic Carbon Nitride Photocatalysts[J]. Acta Phys. -Chim. Sin., 2015,31(1): 159-165
79. REN Xiang-Zhong, LIU Tao, SUN Ling-Na, ZHANG Pei-Xin.Preparation and Electrochemical Performances of Li1.2Mn0.54-xNi0.13Co0.13ZrxO2 Cathode Materials for Lithium-Ion Batteries[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1641-1649
80. JIN Rui-Rui, YOU Ji-Guang, ZHANG Qian, LIU Dan, HU Shao-Zheng, GUI Jian-Zhou.Preparation of Fe-Doped Graphitic Carbon Nitride with Enhanced Visible-Light Photocatalytic Activity[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1706-1712
81. CHEN Ai-Min, BO Ying-Ying, SHAO Chen-Yi, WANG Jing, HU Jun.Synthesis of Single-Crystalline Cu3B2O6/CuB2O4 and Their Photocatalytic Degradation of Methylene Blue under Visible-Light Irradiation[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1713-1719
82. PENG San, GUO Hui-Lin, KANG Xiao-Feng.Preparation of Nitrogen-Doped Graphene and Its Electrocatalytic Activity for Oxygen Reduction Reaction[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1778-1786
83. ZHANG Jian-Fang, WANG Yan, SHEN Tian-Kuo, SHU Xia, CUI Jie-Wu, CHEN Zhong, WU Yu-Cheng.Visible Light Photocatalytic Performance of Cu2O/TiO2 Nanotube Heterojunction Composites Prepared by Pulse Deposition[J]. Acta Phys. -Chim. Sin., 2014,30(8): 1535-1542
84. TIAN Hong, WANG Hui-Xiang, SHI Wei-Mei, XU Yao.Microwave-Assisted Solvothermal Synthesis of In-Si Co-Modified TiO2 Photocatalysts with Enhanced Photocatalytic Activity[J]. Acta Phys. -Chim. Sin., 2014,30(8): 1543-1549
85. YAN Jing-Sen, WANG Hai-Yan, ZHANG Jing-Ru, XU Hui-Juan.Effect of TiO2-Al2O3 Support Preparation Technique on Hydrodenitrogenation of Ni2P/TiO2-Al2O3 Catalysts[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1309-1317
86. XU Ling-Ling, ZHANG Xiao-Hua, CHEN Jin-Hua.Synthesis and Electrochemical Supercapacitive Properties of Nitrogen-Doped Mesoporous Carbons[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1274-1280
87. WANG Li, MA Jun-Hong.Synthesis and Electrocatalytic Properties of Pt Nanoparticles on Nitrogen-Doped Reduced Graphene Oxide for Methanol Oxidation[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1267-1273
88. GAO Lin-Xin, JIANG Xin, GUO Sen.MnOx/CeO2/SiO2 Catalysts Prepared by Adsorption Phase Reaction Technique for Selective Catalytic Reduction of NOx at Low-Temperature[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1303-1308
89. HOU Na, LI Ying, WU Di, LI Zhi-Ru.Structures and Nonlinear Optical Properties of Alkali Metal-Doped t-Bu-calix[4]arene Molecules[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1223-1229
90. MI Chuan-Tong, LIU Guo-Ping, WANG Jia-Jia, GUO Xin-Li, WU San-Xie, YU Jin.First-Principles Calculations of the Adsorption of Au, Ag and Cu Atoms on Defected Graphene[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1230-1238
91. ZHAO Wei-Rong, SHI Qiao-Meng, LIU Ying.Performance, Deactivation and Regeneration of SnO2/TiO2 Nanotube Composite Photocatalysts[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1318-1324
92. HU Jing-Xiu, ZHANG Jing, ZOU Jian-Feng, XIAO Qiang, ZHONG Yi-Jun, ZHU Wei-Dong.Nitrogen-Rich Microporous Carbon Derived from Melamine-Based Porous Polymer for Selective CO2 Adsorption[J]. Acta Phys. -Chim. Sin., 2014,30(6): 1169-1174
93. FU Zhao-Ming, WANG Ming-Yang, ZHANG Yan-Xing, ZHANG Na, YANG Zong-Xian.First-Principles Study on the Microstructure of Triple-Phase Boundaries in the Ni/Yttria-Stabilized Zirconia Anode[J]. Acta Phys. -Chim. Sin., 2014,30(6): 1055-1060
94. ZHOU Ying, WANG Dao-Long, XIAO Nan, HOU Yu-Chen, QIU Jie-Shan.Influence of Heat Treatmeynthesis of Single-Crystalline Cu3B2O6/CuB2O4 and Their Photocatalytic Degradation of Methylene Blue under Visible-Light Irradiation[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1713-1719
82. PENG San, GUO Hui-Lin, KANG Xiao-Feng.Preparation of Nitrogen-Doped Graphene and Its Electrocatalytic Activity for Oxygen Reduction Reaction[J]. Acta Phys. -Chim. Sin., 2014,30(9): 1778-1786
83. ZHANG Jian-Fang, WANG Yan, SHEN Tian-Kuo, SHU Xia, CUI Jie-Wu, CHEN Zhong, WU Yu-Cheng.Visible Light Photocatalytic Performance of Cu2O/TiO2 Nanotube Heterojunction Composites Prepared by Pulse Deposition[J]. Acta Phys. -Chim. Sin., 2014,30(8): 1535-1542
84. TIAN Hong, WANG Hui-Xiang, SHI Wei-Mei, XU Yao.Microwave-Assisted Solvothermal Synthesis of In-Si Co-Modified TiO2 Photocatalysts with Enhanced Photocatalytic Activity[J]. Acta Phys. -Chim. Sin., 2014,30(8): 1543-1549
85. YAN Jing-Sen, WANG Hai-Yan, ZHANG Jing-Ru, XU Hui-Juan.Effect of TiO2-Al2O3 Support Preparation Technique on Hydrodenitrogenation of Ni2P/TiO2-Al2O3 Catalysts[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1309-1317
86. XU Ling-Ling, ZHANG Xiao-Hua, CHEN Jin-Hua.Synthesis and Electrochemical Supercapacitive Properties of Nitrogen-Doped Mesoporous Carbons[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1274-1280
87. WANG Li, MA Jun-Hong.Synthesis and Electrocatalytic Properties of Pt Nanoparticles on Nitrogen-Doped Reduced Graphene Oxide for Methanol Oxidation[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1267-1273
88. GAO Lin-Xin, JIANG Xin, GUO Sen.MnOx/CeO2/SiO2 Catalysts Prepared by Adsorption Phase Reaction Technique for Selective Catalytic Reduction of NOx at Low-Temperature[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1303-1308
89. HOU Na, LI Ying, WU Di, LI Zhi-Ru.Structures and Nonlinear Optical Properties of Alkali Metal-Doped t-Bu-calix[4]arene Molecules[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1223-1229
90. MI Chuan-Tong, LIU Guo-Ping, WANG Jia-Jia, GUO Xin-Li, WU San-Xie, YU Jin.First-Principles Calculations of the Adsorption of Au, Ag and Cu Atoms on Defected Graphene[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1230-1238
91. ZHAO Wei-Rong, SHI Qiao-Meng, LIU Ying.Performance, Deactivation and Regeneration of SnO2/TiO2 Nanotube Composite Photocatalysts[J]. Acta Phys. -Chim. Sin., 2014,30(7): 1318-1324
92. HU Jing-Xiu, ZHANG Jing, ZOU Jian-Feng, XIAO Qiang, ZHONG Yi-Jun, ZHU Wei-Dong.Nitrogen-Rich Microporous Carbon Derived from Melamine-Based Porous Polymer for Selective CO2 Adsorption[J]. Acta Phys. -Chim. Sin., 2014,30(6): 1169-1174
93. FU Zhao-Ming, WANG Ming-Yang, ZHANG Yan-Xing, ZHANG Na, YANG Zong-Xian.First-Principles Study on the Microstructure of Triple-Phase Boundaries in the Ni/Yttria-Stabilized Zirconia Anode[J]. Acta Phys. -Chim. Sin., 2014,30(6): 1055-1060
94. ZHOU Ying, WANG Dao-Long, XIAO Nan, HOU Yu-Chen, QIU Jie-Shan.Influence of Heat Treatment Temperature on the Structure and Electrochemical Performance of Asphaltene-Based B/N Co-Doped Porous Carbons[J]. Acta Phys. -Chim. Sin., 2014,30(6): 1127-1133
95. YIN Hai-Feng, ZHANG Hong, YUE Li.Near-Infrared Plasmon Study on N-Doped Hexagonal Graphene Nanostructures[J]. Acta Phys. -Chim. Sin., 2014,30(6): 1049-1054
96. RUAN Lin-Wei, ZHU Yu-Jun, QIU Ling-Guang, LU Yu-Xiang.First-Principles Calculations of Optical and Elastic Properties of Carbon-Doped α-S8[J]. Acta Phys. -Chim. Sin., 2014,30(5): 845-854
97. WANG Shi-Mao, DONG Wei-Wei, FANG Xiao-Dong, DENG Zan-Hong, SHAO Jing-Zhen, HU Lin-Hua, ZHU Jun.Modification of Single-Crystal TiO2 Nanorod Arrays and Its Application in Quantum Dot-Sensitized Solar Cells[J]. Acta Phys. -Chim. Sin., 2014,30(5): 873-880
98. AO Ping, XU Xiang-Sheng, XU Xiao-Xiao, LI Jia-Heng, YAN Xin-Huan.Low-Temperature Total Oxidation of Toluene over Assembled Pt/TiO2 Catalyst[J]. Acta Phys. -Chim. Sin., 2014,30(5): 950-956
99. FU Ping-Feng, ZHANG Peng-Yi.Low-Temperature Electrostatic Self-Assembly of Noble Metals on TiO2 Nanostructured Films with Enhanced Photocatalytic Activity[J]. Acta Phys. -Chim. Sin., 2014,30(5): 965-972
100. WANG Juan, XIA Shu-Wei, YU Liang-Min.Adsorption Mechanism of Hydrated Pb(OH)+ on the Kaolinite (001) Surface[J]. Acta Phys. -Chim. Sin., 2014,30(5): 829-835
101. YANG Fan, ZHANG Jing, WU Wei-Cheng.Hydrogenation Study of Benzene over a Mo2C/γ-Al2O3 Catalyst by In situ IR Spectroscopy[J]. Acta Phys. -Chim. Sin., 2014,30(5): 943-949
102. LI Jing-Zhe, KONG Fan-Tai, WU Guo-Hua, CHEN Wang-Chao, HUANG Yang, FANG Xia-Qin, DAI Song-Yuan.Di-n-alkylphosphinic Acid with a Long Alkyl Chain as a Coadsorbent for Modifying TiO2 Photoanodes[J]. Acta Phys. -Chim. Sin., 2014,30(4): 662-668
103. ZHANG Chen, ZHAO Jing-Mao.Synergistic Inhibition Effect of Imidazoline Ammonium Salt and Sodium Dodecyl Sulfate in CO2 System[J]. Acta Phys. -Chim. Sin., 2014,30(4): 677-685
104. ZHAO Hai-Na, CHENG Xin-Hao, ZHAO Ou-Di, HUANG Jian-Bin, LIU Chen-Jiang, ZHAO Bo.Mixed Cationic and Anionic Surfactant Systems Achieve Ultra-Low Interfacial Tension in the Karamay Oil Field[J]. Acta Phys. -Chim. Sin., 2014,30(4): 693-698
105.