光催化活性环境矿物材料的制备及应用研究
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摘要
光催化氧化技术是近几十年来发展起来的一种深度氧化技术(advanced oxidation process,AOP)。它是将特定光源(如紫外光)与催化剂联合作用对有机污染物进行降解处理的过程。利用光催化氧化技术,大多数有机污染物可以被降解为CO_2、H_2O等无污染的小分子。因此,光催化氧化技术应用于环境污染物的治理已成为环境保护领域研究的热点。
利用这一技术的关键在于光催化材料的制备。因此,制备既高效又经济的光催化材料是目前研究者关心和迫切需要研究的问题。TiO_2因其具有效率高、能耗低、操作简便、反应条件温和、适用范围广、可减少二次污染等优点而被认为是诸多光催化材料中最有应用前途的一种材料,因此是目前研究的热点。
本论文介绍了半导体光催化理论、TiO_2光催化基本原理、纳米TiO_2光催化材料的制备、提高TiO_2光催化材料光催化活性的途径、TiO_2光催化材料的应用、TiO_2光催化材料负载技术的研究进展以及目前存在的问题等。
通过粉碎、分级等手段制备了天然金红石光催化材料。用制备的天然金红石光催化材料处理含偶氮染料废水,结果表明其对偶氮染料的作用既有吸附,也有降解,表明天然金红石光催化材料有一定的光催化活性。
选用四种不同结构和性质的矿物,分别是架状结构的辉沸石、石英,层状结构的累托石、高岭土,采用溶胶-凝胶法制备了矿物负载纳米TiO_2光催化材料。用制备的光催化材料处理含偶氮染料废水,结果表明其对偶氮染料废水有较高的脱色率。辉沸石、累托石、高岭土负载纳米TiO_2光催化材料对偶氮染料的作用主要为吸附,石英负载纳米TiO_2光催化材料对偶氮染料的作用主要为降解。
用γ-巯丙基三甲氧基硅烷对石英进行干法改性,用氧化剂将巯基氧化为磺酸基,通过静电自组装TiO_2制备石英表面自组装纳米TiO_2光催化材料。用制备的光催化材料处理含偶氮染料废水,结果表明其对偶氮染料废水有较高的脱色率。其对偶氮染料有一定的吸附作用,但主要为降解作用。
运用XRD、XPS等测试手段对制备的光催化材料进行了表征以研究其组成。运用紫外-可见光扫描分析及红外光谱等测试手段研究了制备的光催化材料的光催化脱色作用机理。
Photocatalysis oxidation process is a kind of advanced oxidation process which has developed for several decades. It is a process of organic pollutant degradation under the action of UV and photocatalyst. Most organic pollutants can be degraded to non-polluting small molecules such as CO_2, H_2O etc. Therefore, Photocatalysis oxidation process applied to environment pollution control has become the hotspot of environmental protection research.The key of using this technology is the preparation of photocatalyst. Therefore, preparing effective and economic photocatalyst is a problem which researchers care of and need to resolve. Because TiO_2 has high photocatalysis activity, low energy consumption, simple operation, gentle reaction condition, extensive application, with reduced secondary pollution etc., it is indeed a photocatalyst which has the best perspective and has become the hotdspot of the research.This paper introduced the theory of photocatalysis of semiconductor, the principle of TiO_2 photocatalysis, preparation of nanometer TiO_2, the approach of improving the photocatalytic activity of TiO_2, the application of TiO_2, and the research of loading techniques of TiO_2.Natural rutile photocatalyst was prepared with the method of grinding and sizing. This photocatalyst was used to treat wastewater containing azo dye. It shows that natural rutile photocatalyst has certain photocatalytic action on azo dye.Minerals of different structures were used to prepare mineral loading photocatalyst and study the effect of minerals and TiO_2. on wastewater treatment. Using these photocatalyst to treat wastewater containing azo dye showed that these photocatalysts have high decoloration effect.. The main action of TiO_2 loaded on stilbite, rectorite, kaolin on azo dye was adsorption . The main action of quartz loading TiO_2 photocatalyst on azo dye was photocatalysis.Surface modification was made on quartz with ( OCH_3 )_3Si(CH_2)_3SH by dry process. The radical of -SH was oxidized to -SO_3~- and electrostatic self -assembled TiO_2 was made on the surface of quartz . By this way the self-assembled TiO_2 photocatalyst on quartz was prepared. Using this photocatalyst to treat wastewater
containing azo dye showed that this photocatalyst has high decoloration effect.. The main action of this photocatalyst on azo dye is photocatalysis.XRD and XPS were used to study the composition of the photocatalyts . U V-vis and FTIR were used to analyse the mechanism of the photocatalytic action of the nano titanium dioxide photocatalyts.
利用这一技术的关键在于光催化材料的制备。因此,制备既高效又经济的光催化材料是目前研究者关心和迫切需要研究的问题。TiO_2因其具有效率高、能耗低、操作简便、反应条件温和、适用范围广、可减少二次污染等优点而被认为是诸多光催化材料中最有应用前途的一种材料,因此是目前研究的热点。
本论文介绍了半导体光催化理论、TiO_2光催化基本原理、纳米TiO_2光催化材料的制备、提高TiO_2光催化材料光催化活性的途径、TiO_2光催化材料的应用、TiO_2光催化材料负载技术的研究进展以及目前存在的问题等。
通过粉碎、分级等手段制备了天然金红石光催化材料。用制备的天然金红石光催化材料处理含偶氮染料废水,结果表明其对偶氮染料的作用既有吸附,也有降解,表明天然金红石光催化材料有一定的光催化活性。
选用四种不同结构和性质的矿物,分别是架状结构的辉沸石、石英,层状结构的累托石、高岭土,采用溶胶-凝胶法制备了矿物负载纳米TiO_2光催化材料。用制备的光催化材料处理含偶氮染料废水,结果表明其对偶氮染料废水有较高的脱色率。辉沸石、累托石、高岭土负载纳米TiO_2光催化材料对偶氮染料的作用主要为吸附,石英负载纳米TiO_2光催化材料对偶氮染料的作用主要为降解。
用γ-巯丙基三甲氧基硅烷对石英进行干法改性,用氧化剂将巯基氧化为磺酸基,通过静电自组装TiO_2制备石英表面自组装纳米TiO_2光催化材料。用制备的光催化材料处理含偶氮染料废水,结果表明其对偶氮染料废水有较高的脱色率。其对偶氮染料有一定的吸附作用,但主要为降解作用。
运用XRD、XPS等测试手段对制备的光催化材料进行了表征以研究其组成。运用紫外-可见光扫描分析及红外光谱等测试手段研究了制备的光催化材料的光催化脱色作用机理。
Photocatalysis oxidation process is a kind of advanced oxidation process which has developed for several decades. It is a process of organic pollutant degradation under the action of UV and photocatalyst. Most organic pollutants can be degraded to non-polluting small molecules such as CO_2, H_2O etc. Therefore, Photocatalysis oxidation process applied to environment pollution control has become the hotspot of environmental protection research.The key of using this technology is the preparation of photocatalyst. Therefore, preparing effective and economic photocatalyst is a problem which researchers care of and need to resolve. Because TiO_2 has high photocatalysis activity, low energy consumption, simple operation, gentle reaction condition, extensive application, with reduced secondary pollution etc., it is indeed a photocatalyst which has the best perspective and has become the hotdspot of the research.This paper introduced the theory of photocatalysis of semiconductor, the principle of TiO_2 photocatalysis, preparation of nanometer TiO_2, the approach of improving the photocatalytic activity of TiO_2, the application of TiO_2, and the research of loading techniques of TiO_2.Natural rutile photocatalyst was prepared with the method of grinding and sizing. This photocatalyst was used to treat wastewater containing azo dye. It shows that natural rutile photocatalyst has certain photocatalytic action on azo dye.Minerals of different structures were used to prepare mineral loading photocatalyst and study the effect of minerals and TiO_2. on wastewater treatment. Using these photocatalyst to treat wastewater containing azo dye showed that these photocatalysts have high decoloration effect.. The main action of TiO_2 loaded on stilbite, rectorite, kaolin on azo dye was adsorption . The main action of quartz loading TiO_2 photocatalyst on azo dye was photocatalysis.Surface modification was made on quartz with ( OCH_3 )_3Si(CH_2)_3SH by dry process. The radical of -SH was oxidized to -SO_3~- and electrostatic self -assembled TiO_2 was made on the surface of quartz . By this way the self-assembled TiO_2 photocatalyst on quartz was prepared. Using this photocatalyst to treat wastewater
containing azo dye showed that this photocatalyst has high decoloration effect.. The main action of this photocatalyst on azo dye is photocatalysis.XRD and XPS were used to study the composition of the photocatalyts . U V-vis and FTIR were used to analyse the mechanism of the photocatalytic action of the nano titanium dioxide photocatalyts.
引文
[1] 高濂,郑珊,张青红.纳米氧化钛光催化材料及应用[M].化学工业出版社.2002,12:1.
[2] 鲁安怀.无机界矿物天然自净化功能之矿物光催化作用[J].岩石矿物学杂志.2003,22(4):324～331.
[3] Fujishima A, Honda K. Nature, 1972, 37: 238～245.
[4] CareyJ.H, Lawrencej, Tosinehm. Photodechlorination of PCB's in the presnce of titanium dioxide in aqueous suspension [J]. Bull. Environ. Contain. Toxicol. 1976, 16: 697～701.
[5] Blake D.M. Bibliography of work on the photocatalytic removal of hazaradous compounds from water and air. National renewal Energy Laboratory, 1994.
[6] 刘国光,丁雪军,张学治,郑立庆.光催化氧化技术的研究现状及发展趋势[J].环境污染治理技术与设备.2003,4(8):65～66.
[7] 孙晓君,蔡伟民等.二氧化钛半导体光催化技术研究进展[J].哈尔滨工业大学学报.2001,33(4):534～535.
[8] 唐小红,张云.纳米二氧化钛的光催化性能研究[J].功能材料.2004,35(2):236～238.
[9] 孙静,高濂,张青红.制备具有光催化活性的金红石相纳米氧化钛粉体[J].化学学报.2003,61(1):74～77.
[10] 王正平,叶贤富,安红波.纳米TiO_2的光催化机理、制备方法及应用[J].化学与粘合.2003,1:23～25.
[11] 叶超群,孟中岩.纳米二氧化钛系材料的合成及表征技术[J].陶瓷学报.2002,23(3):205～209.
[12] 陈德明,王亭杰,雨山江,金涌.纳米TiO_2的性能、应用及制备方法[J].材料工程.2002,11:45～46.
[13] 杨华明,史蓉蓉等.纳米二氧化钛光催化剂改性研究进展[J].化工新型材料.2005,33(6):57～59.
[14] 彭峰,任艳群.提高二氧化钛光催化性能的研究进展[J].现代化工.2002,22(10):6～9.
[15] 牛新书,李红花,蒋凯.金属离子掺杂纳米TiO_2光催化研究进展[J].电子元件与材料.2004,23(8):40～42.
[16] 于向阳,梁文,程继健.提高二氧化钛光催化性能的途径[J].硅酸盐通报.2000,1:53～57.
[17] 杜飞鹏,余颖,曾艳.纳米TiO_2光催化氧化技术研究进展[J].环境科学与技术.2004,27(2):94～96.
[18] 胡安正,唐超群.纳米TiO_2光催化材料及其应用于环境保护的研究进展[J].功能材料.2001,32(6):586～589.
[19] 吕妍,仇雁翎,赵建夫.TiO_2半导体光催化氧化技术处理气相污染物研究进展[J].重庆环境科学.2003,25(11):167～169.
[20] 王建营,胡文祥,孙家跃,王卫.纳米二氧化钛光催化氧化在环境治理中的研究[J].化工时刊.2004,18(2):22～24.
[21] 廖振华,陈建军,姚可夫,赵方辉,李荣先.纳米TiO_2光催化剂负载化的研究进展[J].无机材料学报.2004,19(1):17～22.
[22] 贺飞,唐怀军,赵文宽,方佑龄.纳米TiO_2光催化剂负载技术研究环境污染治理技术与设备[J].2001,2(2):49～51.
[23] Kuhn H., Ulman A., Ed.Thin films. New York: Academic press, 1995: 20.
[24] 翟怡,张金利等.自组装单层膜的制备与应用[J].化学进展.2004,16(4):477～454.
[25] 蒲利春,崔旭梅.自组装技术及其影响因素分析[J].化工新型材料.2004,32(10):18.
[26] Decher G. Fuzzy. Nanoassemblies: toward layered polymeric multicomoosites [J]. Science. 1997. 277: 1232～1237.
[27] 余海湖.静电自组装纳米复合薄膜研究.博士论文.2001,12:10.
[28] 肖中党,黄丹,顾建华,陆祖宏.自组装成膜技术制备TiO_2薄膜的XPS研究[J].物理化学学报.1998,14(1):57～61.
[29] 余海湖,伍洪标,吴仪温,李小甫.玻璃表面静电自组装TiO_2基薄膜研究[J].硅酸盐通报.2004,3:97～99.
[30] 河北沧州瑞东化工有限公司产品说明书.
[31] 天鹅牌直接紫N产品说明书.天津市绿洲化工有限公司.
[32] 吴瑾光.近代傅里叶变换红外光谱技术及应用[M].科学技术文献出版社.1994,12.
[33] Maria Stylidi, Dimitris I, Kondarides, Xenophon E. Verykios. Visible light induced photocatalytic degradation of Acid Orange 7 in aqueous TiO_2 suspensions. Applied Catalysis B: Environme-ntal, 2004, 47(3): 189～201.
[34] 李巧荣,鲁安怀,李宁等.天然金红石光催化降解藏红T实验研究[J].矿物岩石地球化学通报.2003,22(3):215～223.
[35] 李巧荣,鲁安怀,李宁等.天然含钒金红石降解卤代烃实验研究[J].岩石矿物学杂志.2003,22(4):345～348.
[36] 刘娟,鲁安怀,郭延军等.天然含钒金红石加热、淬火及电子辐射改性实验研究[J].岩石矿物学杂志.2003,22(4):339～344.
[37] 李宁,鲁安怀,秦善等.孕育光催化活性的天然含钒金红石矿物学特征[J].岩石矿物学杂志.2003,22(4):332～338.
[38] 鲁安怀,郭延军,刘娟等.天然含钒金红石:一种用于降解卤代有机污染物的光催化剂[J].科学通报.2004,49(22):2350～2353.
[39] 郑红,汤鸿霄.天然矿物锰矿砂对苯酚的界面吸附与降解研究[J].环境科学学报.1999,19(6):619～624.
[40] 鲁安怀,卢晓英,任子平等.天然铁锰氧化物及氢氧化物环境矿物学研究[J].地学前缘.2000,7(2):473～483.
[41] 阮新潮,杜予民,赵晖,曾庆福.天然锰矿-次氯酸钠光催化氧化处理分散蓝2BLN废水[J].城市环境与城市生态.2003,16(5):65～66.
[42] 李海燕,施银桃,曾庆福.紫外光锰矿协同催化臭氧化水中4-氯苯酚[J].安全与环境学报.2004,4(2):31～33.
[43] 孙振亚,祝春水,龚文琪.铁(氢)氧化物矿物对有机污染物的光催化氧化作用[J].矿物学报.2003,23(4):341～348.
[44] Hofstadler K, Bauer B, Novalic S, Heisler G. Environ Sci.Technol, 1994, 28: 670.
[45] Torimoto T, Ito S, Kuwabata S, Yoneyama H. Eniron Sci.Technol., 1996, 30: 1257.
[46] 宋海燕,江宏富,刘杏芹,孟广耀.非金属矿物用作催化剂载体光降解污水中的有机物[J].中国非金属矿工业导刊.2004,5:26.
[47] 孙振世,陈英旭,柯强,杨晔,袁骏.TiO_2膨润土纳米复合光催化剂降解偶氮染料的研究[J].环境科学学报.2003,23(1):129～133.
[48] Mogyoroso K.Dekany I, Fendler J.H. Preparation and characterization of clay mineral intercalated titanium dioxide nanoparticles[J]. Langmuire, 2003, 19: 2938～2946.
[49] 胡春,王怡中.凹凸棒石负载TiO_2对偶氮染料和纺织废水光催化脱污[J].环境科学学报.2001,21(1):123～125.
[50] 栾亚兰,刘恒等.海泡石/TiO_2的制备及光降解有机物性能研究[J].矿产综合利用.2004,4:7～11.
[51] 蒋引珊,金为群,张军,方送生.TiO_2/沸石复合物结构与光催化性能[J].无机材料学报.2002,17(6):1302～1305.
[52] 鲍长利,周波,刘淑霞,蒋引姗,方送生.沸石负载TiO_2的制备及其对农药敌敌畏的光降解性能[J].应用化学.2003,20(12):1222～1224.
[53] Tsanjuan Ana, Aguirre Guillermo, Alvaro Mercedes. 2, 4, 6-Triphenyl pyrylium ion encapsulated in Y zeolite as photocatalyst. A co-operative contribution of the zeolite host to the photodegradation of 4-chloro phenoxyacetic acid using solar ligh[J]. Applied Catalysis B: Environmental. 1998, (15): 247～257.
[54] 梁金生,冯艳文,梁广川,丁燕,王静,冀志江,金宗哲.电气石/TiO_2复合薄膜的显微结构及光催化活性研究[J].硅酸盐学报.2004,32(5):652～655.
[55] Nonami T, Hase H, Funakoshi K. Apatite-coated titanaium dioxide photocatalyst [J]. Materials Scicence Forum, 2003, 439: 337～343.
[56] Nonami T, Hase H, Funakoshi K. Apatite-coated titanaium dioxide photocatalyst for air purification Source: Catalysis Today, 2004, 96(3): 113～118.
[57] 郑水林,袁继祖.非金属加工技术及应用手册[M].冶金工业出版社.2005,5:143～509.
[58] 杨南如.无机非金属材料图谱手册[M].武汉工业大学出版社.2000.
[59] 朱永法,曹立礼.Ti/SiO_2界面反应的研究[J].真空科学与技术.1994,14(6):390～396.
[60] 颜秀茹,郭伟巍.新型光催化剂TiO_2/SiO_2的制备和催化性能研究[J].化学工业与工程.2000,17(6):330～335.
[61] 唐芳琼,侯莉萍,郭广生.单分散纳米二氧化钛的研制[J].无机材料学报.2001,16(4):615～619.
[62] Newman A C D. Chemistry of Clays and Clay Minerals [M]. London: Longman Group UK Limited, 1987: 208.
[63] 管俊芳,陈林丽等.珍珠岩微粉表面改性及应用研究[J].非金属矿.2002,25(4):8～10.
[64] 杭晓敏.环氧油一步合成的反应机理和动力学研究[J].化学反应工程与工艺.1996,12(1):1～8.
[2] 鲁安怀.无机界矿物天然自净化功能之矿物光催化作用[J].岩石矿物学杂志.2003,22(4):324～331.
[3] Fujishima A, Honda K. Nature, 1972, 37: 238～245.
[4] CareyJ.H, Lawrencej, Tosinehm. Photodechlorination of PCB's in the presnce of titanium dioxide in aqueous suspension [J]. Bull. Environ. Contain. Toxicol. 1976, 16: 697～701.
[5] Blake D.M. Bibliography of work on the photocatalytic removal of hazaradous compounds from water and air. National renewal Energy Laboratory, 1994.
[6] 刘国光,丁雪军,张学治,郑立庆.光催化氧化技术的研究现状及发展趋势[J].环境污染治理技术与设备.2003,4(8):65～66.
[7] 孙晓君,蔡伟民等.二氧化钛半导体光催化技术研究进展[J].哈尔滨工业大学学报.2001,33(4):534～535.
[8] 唐小红,张云.纳米二氧化钛的光催化性能研究[J].功能材料.2004,35(2):236～238.
[9] 孙静,高濂,张青红.制备具有光催化活性的金红石相纳米氧化钛粉体[J].化学学报.2003,61(1):74～77.
[10] 王正平,叶贤富,安红波.纳米TiO_2的光催化机理、制备方法及应用[J].化学与粘合.2003,1:23～25.
[11] 叶超群,孟中岩.纳米二氧化钛系材料的合成及表征技术[J].陶瓷学报.2002,23(3):205～209.
[12] 陈德明,王亭杰,雨山江,金涌.纳米TiO_2的性能、应用及制备方法[J].材料工程.2002,11:45～46.
[13] 杨华明,史蓉蓉等.纳米二氧化钛光催化剂改性研究进展[J].化工新型材料.2005,33(6):57～59.
[14] 彭峰,任艳群.提高二氧化钛光催化性能的研究进展[J].现代化工.2002,22(10):6～9.
[15] 牛新书,李红花,蒋凯.金属离子掺杂纳米TiO_2光催化研究进展[J].电子元件与材料.2004,23(8):40～42.
[16] 于向阳,梁文,程继健.提高二氧化钛光催化性能的途径[J].硅酸盐通报.2000,1:53～57.
[17] 杜飞鹏,余颖,曾艳.纳米TiO_2光催化氧化技术研究进展[J].环境科学与技术.2004,27(2):94～96.
[18] 胡安正,唐超群.纳米TiO_2光催化材料及其应用于环境保护的研究进展[J].功能材料.2001,32(6):586～589.
[19] 吕妍,仇雁翎,赵建夫.TiO_2半导体光催化氧化技术处理气相污染物研究进展[J].重庆环境科学.2003,25(11):167～169.
[20] 王建营,胡文祥,孙家跃,王卫.纳米二氧化钛光催化氧化在环境治理中的研究[J].化工时刊.2004,18(2):22～24.
[21] 廖振华,陈建军,姚可夫,赵方辉,李荣先.纳米TiO_2光催化剂负载化的研究进展[J].无机材料学报.2004,19(1):17～22.
[22] 贺飞,唐怀军,赵文宽,方佑龄.纳米TiO_2光催化剂负载技术研究环境污染治理技术与设备[J].2001,2(2):49～51.
[23] Kuhn H., Ulman A., Ed.Thin films. New York: Academic press, 1995: 20.
[24] 翟怡,张金利等.自组装单层膜的制备与应用[J].化学进展.2004,16(4):477～454.
[25] 蒲利春,崔旭梅.自组装技术及其影响因素分析[J].化工新型材料.2004,32(10):18.
[26] Decher G. Fuzzy. Nanoassemblies: toward layered polymeric multicomoosites [J]. Science. 1997. 277: 1232～1237.
[27] 余海湖.静电自组装纳米复合薄膜研究.博士论文.2001,12:10.
[28] 肖中党,黄丹,顾建华,陆祖宏.自组装成膜技术制备TiO_2薄膜的XPS研究[J].物理化学学报.1998,14(1):57～61.
[29] 余海湖,伍洪标,吴仪温,李小甫.玻璃表面静电自组装TiO_2基薄膜研究[J].硅酸盐通报.2004,3:97～99.
[30] 河北沧州瑞东化工有限公司产品说明书.
[31] 天鹅牌直接紫N产品说明书.天津市绿洲化工有限公司.
[32] 吴瑾光.近代傅里叶变换红外光谱技术及应用[M].科学技术文献出版社.1994,12.
[33] Maria Stylidi, Dimitris I, Kondarides, Xenophon E. Verykios. Visible light induced photocatalytic degradation of Acid Orange 7 in aqueous TiO_2 suspensions. Applied Catalysis B: Environme-ntal, 2004, 47(3): 189～201.
[34] 李巧荣,鲁安怀,李宁等.天然金红石光催化降解藏红T实验研究[J].矿物岩石地球化学通报.2003,22(3):215～223.
[35] 李巧荣,鲁安怀,李宁等.天然含钒金红石降解卤代烃实验研究[J].岩石矿物学杂志.2003,22(4):345～348.
[36] 刘娟,鲁安怀,郭延军等.天然含钒金红石加热、淬火及电子辐射改性实验研究[J].岩石矿物学杂志.2003,22(4):339～344.
[37] 李宁,鲁安怀,秦善等.孕育光催化活性的天然含钒金红石矿物学特征[J].岩石矿物学杂志.2003,22(4):332～338.
[38] 鲁安怀,郭延军,刘娟等.天然含钒金红石:一种用于降解卤代有机污染物的光催化剂[J].科学通报.2004,49(22):2350～2353.
[39] 郑红,汤鸿霄.天然矿物锰矿砂对苯酚的界面吸附与降解研究[J].环境科学学报.1999,19(6):619～624.
[40] 鲁安怀,卢晓英,任子平等.天然铁锰氧化物及氢氧化物环境矿物学研究[J].地学前缘.2000,7(2):473～483.
[41] 阮新潮,杜予民,赵晖,曾庆福.天然锰矿-次氯酸钠光催化氧化处理分散蓝2BLN废水[J].城市环境与城市生态.2003,16(5):65～66.
[42] 李海燕,施银桃,曾庆福.紫外光锰矿协同催化臭氧化水中4-氯苯酚[J].安全与环境学报.2004,4(2):31～33.
[43] 孙振亚,祝春水,龚文琪.铁(氢)氧化物矿物对有机污染物的光催化氧化作用[J].矿物学报.2003,23(4):341～348.
[44] Hofstadler K, Bauer B, Novalic S, Heisler G. Environ Sci.Technol, 1994, 28: 670.
[45] Torimoto T, Ito S, Kuwabata S, Yoneyama H. Eniron Sci.Technol., 1996, 30: 1257.
[46] 宋海燕,江宏富,刘杏芹,孟广耀.非金属矿物用作催化剂载体光降解污水中的有机物[J].中国非金属矿工业导刊.2004,5:26.
[47] 孙振世,陈英旭,柯强,杨晔,袁骏.TiO_2膨润土纳米复合光催化剂降解偶氮染料的研究[J].环境科学学报.2003,23(1):129～133.
[48] Mogyoroso K.Dekany I, Fendler J.H. Preparation and characterization of clay mineral intercalated titanium dioxide nanoparticles[J]. Langmuire, 2003, 19: 2938～2946.
[49] 胡春,王怡中.凹凸棒石负载TiO_2对偶氮染料和纺织废水光催化脱污[J].环境科学学报.2001,21(1):123～125.
[50] 栾亚兰,刘恒等.海泡石/TiO_2的制备及光降解有机物性能研究[J].矿产综合利用.2004,4:7～11.
[51] 蒋引珊,金为群,张军,方送生.TiO_2/沸石复合物结构与光催化性能[J].无机材料学报.2002,17(6):1302～1305.
[52] 鲍长利,周波,刘淑霞,蒋引姗,方送生.沸石负载TiO_2的制备及其对农药敌敌畏的光降解性能[J].应用化学.2003,20(12):1222～1224.
[53] Tsanjuan Ana, Aguirre Guillermo, Alvaro Mercedes. 2, 4, 6-Triphenyl pyrylium ion encapsulated in Y zeolite as photocatalyst. A co-operative contribution of the zeolite host to the photodegradation of 4-chloro phenoxyacetic acid using solar ligh[J]. Applied Catalysis B: Environmental. 1998, (15): 247～257.
[54] 梁金生,冯艳文,梁广川,丁燕,王静,冀志江,金宗哲.电气石/TiO_2复合薄膜的显微结构及光催化活性研究[J].硅酸盐学报.2004,32(5):652～655.
[55] Nonami T, Hase H, Funakoshi K. Apatite-coated titanaium dioxide photocatalyst [J]. Materials Scicence Forum, 2003, 439: 337～343.
[56] Nonami T, Hase H, Funakoshi K. Apatite-coated titanaium dioxide photocatalyst for air purification Source: Catalysis Today, 2004, 96(3): 113～118.
[57] 郑水林,袁继祖.非金属加工技术及应用手册[M].冶金工业出版社.2005,5:143～509.
[58] 杨南如.无机非金属材料图谱手册[M].武汉工业大学出版社.2000.
[59] 朱永法,曹立礼.Ti/SiO_2界面反应的研究[J].真空科学与技术.1994,14(6):390～396.
[60] 颜秀茹,郭伟巍.新型光催化剂TiO_2/SiO_2的制备和催化性能研究[J].化学工业与工程.2000,17(6):330～335.
[61] 唐芳琼,侯莉萍,郭广生.单分散纳米二氧化钛的研制[J].无机材料学报.2001,16(4):615～619.
[62] Newman A C D. Chemistry of Clays and Clay Minerals [M]. London: Longman Group UK Limited, 1987: 208.
[63] 管俊芳,陈林丽等.珍珠岩微粉表面改性及应用研究[J].非金属矿.2002,25(4):8～10.
[64] 杭晓敏.环氧油一步合成的反应机理和动力学研究[J].化学反应工程与工艺.1996,12(1):1～8.