中空结构纳米TiO_2微球的可控制备
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摘要
纳米TiO_2作为一种氧化还原能力强、化学性质稳定、来源广泛和环境友好的多功能材料,被认为是非常有前景的半导体光催化材料之一。在各种形貌的纳米TiO_2中,中空结构TiO_2微球因具有密度低、比表面积大、渗透性好和稳定性高的特点而受到越来越多研究者的青睐。寻求工艺简单、重复性好和产物形貌可控的中空纳米TiO_2微球的制备方法显得尤为重要。中空纳米TiO_2微球的制备方法根据制备原理可分为溶胶-凝胶法、水热法、溶剂热法、喷雾干燥法和层层自组装法等;根据制备过程中是否加入模板剂又可分为硬模板法、软模板法和无模板法。本文针对硬模板法、软模板法和无模板法进行了综述。其中,硬模板是最早应用于中空TiO_2微球制备的方法,最终所得中空TiO_2的形貌、空腔大小和表面所带电荷与所用模板剂种类密切相关。目前常用的模板剂有三大类,包括聚合物、碳球和无机氧化物。而在制备模板剂过程中需要消耗大量的时间和有机溶剂,造成成本升高和环境污染。软模板法是目前最高效的一种制备方法,其制备机理与硬模板法较为相似,主要区别在于模板剂的选择上,前者的模板剂大多为刚性较强的无机粒子,而软模板剂通常为乳液液滴、超分子胶束、聚合物聚集体/囊泡等强度较低的气体或者液体。相比于硬模板法其最明显的优势在于后期对于模板剂的去除较为容易,不需要高温处理,多次洗涤即可除去,因此具有效率高、工艺简单等优势。无模板法是一种最具应用潜力的中空TiO_2微球制备方法。此法大多为一步反应,因此其可控性较差,尚未实现大范围应用与生产。但是,该法具有制备步骤少、成本低和产率高等优势,在后期的批量生产和规模化制备中空TiO_2微球方面具有潜在的优势。目前,对于中空纳米TiO_2微球的研究除了有效且成熟的制备工艺外,其高效的光催化性能也是研究者追求的目标。笔者认为通过以下三方面可以进一步提高中空纳米TiO_2的光催化性能:其一,多种半导体材料的复合可拓宽其在可见光下的响应区域;其二,非金属阴离子(氮、碳)或金属(铁、铜)离子参杂等可提高光诱导二氧化钛电子空穴对的分离效率;其三,金属氧化物的表面修饰或双原位聚合改性等多种手段共同作用可降低电子-空穴对的重组。延长光生载流子的寿命、提高光催化活性将成为今后中空TiO_2微球研究的重点。
As a multifunctional material with strong redox ability,stable chemical properties,wide source and environmental friendliness,nano-TiO_2 is considered as one of the most promising semiconductor photocatalytic materials. Among various morphologies of nano-TiO_2,hollow-structured TiO_2 microspheres have aroused increasing interests owing to their low density,large specific surface area,favorable permeability and high stability.Undoubtedly,it is of great significance to seek an ideal approach with simple process,favorable repeatability and controllable morphology for hollow nano-TiO_2 microsphere preparation. According to the preparation principle,preparation methods of hollow nano-TiO_2 microspheres can be divided into sol-gel method,hydrothermal method,solvothermal method,spray drying method and layer self-assembly method. According to whether the template is added in the preparation process,these methods can also be classified into hard template method,soft template method and template-free method.In this article,preparation approaches of hollow nano-TiO_2 microspheres with and without template are reviewed. Among them,the hard template is regarded as the earliest method applied for the preparation of hollow TiO_2 microspheres. Concerning the hard template method,the morphology,cavity size and surface charge of the obtained hollow nano-TiO_2 are closely related to the types of adopting templates. Currently,there are mainly three kinds of hard template agents commonly used by researchers,including polymers,carbon spheres and inorganic oxides. However,it is time consuming and a waste of organic solvent to prepare template agent,which resulted in an increase in production cost and environmental pollution. The soft template method is considered as one of the most efficient approach to prepare hollow nano-TiO_2,which shares similar preparation principle with hard template method. The major distinction between hard template method and soft template method lies in the selection of template agents. Specifically speaking,the former usually employ rigid inorganic particles as template agents,and the latter commonly adopt low-intensity gas or liquid like emulsion droplets,supramolecular micelles,polymer aggregates or vesicles as template agents. Particularly,soft template method is superior to hard template method because of its convenience for removing the template agent in the later stage( no high temperature treatment is required). Therefore,soft template method features high efficiency and simple process. The template-free method is one of the most promising preparation methods for hollow nano-TiO_2 microspheres. Unfortunately,the one-step reaction of template-free method leads to poor controllability for its products,which blocks the practical application,not to mention mass production. Nevertheless,thanks to the simple preparation steps,low cost and high yield of template-free method,it still exhibits great potential in batch production and large-scale preparation of hollow TiO_2 microspheres.At present,in addition to the effective and mature preparation process,numerous efforts have been made by researchers in pursuit of high-efficiency photocatalytic performance of hollow nano-TiO_2 microspheres. It is believed that the photocatalytic properties of hollow nano-TiO_2 can be further improved through the following three attempts. Firstly,the combination of a plurality of semiconductor materials will contribute to improving the response area under visible light. Secondly,non-metal anions( nitrogen,carbon) or metal( iron,copper) ion doping is beneficial to the sepa-ration efficiency of photoinduced titanium dioxide electron-hole pairs. Thirdly,surface modification of metal oxide and in-situ polymerization modification are conducive to reduce the recombination of electron-hole pairs. It is worth pointing out that prolonging the lifetime of photogenerated carriers and increasing photocatalytic activity will become the research focus of hollow TiO_2 microspheres in the future.
As a multifunctional material with strong redox ability,stable chemical properties,wide source and environmental friendliness,nano-TiO_2 is considered as one of the most promising semiconductor photocatalytic materials. Among various morphologies of nano-TiO_2,hollow-structured TiO_2 microspheres have aroused increasing interests owing to their low density,large specific surface area,favorable permeability and high stability.Undoubtedly,it is of great significance to seek an ideal approach with simple process,favorable repeatability and controllable morphology for hollow nano-TiO_2 microsphere preparation. According to the preparation principle,preparation methods of hollow nano-TiO_2 microspheres can be divided into sol-gel method,hydrothermal method,solvothermal method,spray drying method and layer self-assembly method. According to whether the template is added in the preparation process,these methods can also be classified into hard template method,soft template method and template-free method.In this article,preparation approaches of hollow nano-TiO_2 microspheres with and without template are reviewed. Among them,the hard template is regarded as the earliest method applied for the preparation of hollow TiO_2 microspheres. Concerning the hard template method,the morphology,cavity size and surface charge of the obtained hollow nano-TiO_2 are closely related to the types of adopting templates. Currently,there are mainly three kinds of hard template agents commonly used by researchers,including polymers,carbon spheres and inorganic oxides. However,it is time consuming and a waste of organic solvent to prepare template agent,which resulted in an increase in production cost and environmental pollution. The soft template method is considered as one of the most efficient approach to prepare hollow nano-TiO_2,which shares similar preparation principle with hard template method. The major distinction between hard template method and soft template method lies in the selection of template agents. Specifically speaking,the former usually employ rigid inorganic particles as template agents,and the latter commonly adopt low-intensity gas or liquid like emulsion droplets,supramolecular micelles,polymer aggregates or vesicles as template agents. Particularly,soft template method is superior to hard template method because of its convenience for removing the template agent in the later stage( no high temperature treatment is required). Therefore,soft template method features high efficiency and simple process. The template-free method is one of the most promising preparation methods for hollow nano-TiO_2 microspheres. Unfortunately,the one-step reaction of template-free method leads to poor controllability for its products,which blocks the practical application,not to mention mass production. Nevertheless,thanks to the simple preparation steps,low cost and high yield of template-free method,it still exhibits great potential in batch production and large-scale preparation of hollow TiO_2 microspheres.At present,in addition to the effective and mature preparation process,numerous efforts have been made by researchers in pursuit of high-efficiency photocatalytic performance of hollow nano-TiO_2 microspheres. It is believed that the photocatalytic properties of hollow nano-TiO_2 can be further improved through the following three attempts. Firstly,the combination of a plurality of semiconductor materials will contribute to improving the response area under visible light. Secondly,non-metal anions( nitrogen,carbon) or metal( iron,copper) ion doping is beneficial to the sepa-ration efficiency of photoinduced titanium dioxide electron-hole pairs. Thirdly,surface modification of metal oxide and in-situ polymerization modification are conducive to reduce the recombination of electron-hole pairs. It is worth pointing out that prolonging the lifetime of photogenerated carriers and increasing photocatalytic activity will become the research focus of hollow TiO_2 microspheres in the future.
引文
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2 Zhang R Y, Tu B, Zhao D Y. Chemistry-A European Journal,2010,16(33),9977.
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18 Ao Y H, Xu J J, Fu D G, et al. Journal of Hazardous Materials,2009,167(1-3),413.
19 Cui Y, Liu L, Li B, et al. Journal of Physical Chemistry C,2010,114(6),2434.
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23 Xiong X, Yu Z, Lin M, et al. Reactive & Functional Polymers,2012,72(6),365.
24 Bao Y, Yang Y Q, Jianzhong M A. Journal of Inorganic Materials,2013,28(5),459.
25 Caruso F, Shi X Y, Caruso R A, et al. Advanced Materials,2001,13,740.
26 Petkovich N D, Stein A. Chemical Society Reviews,2013,42(9),3721.
27 Lu Y, Mclellan J, Xia Y. Langmuir,2004,20(8),3464.
28 Zhuang Y, Sun J, Guan M. Journal of Alloys & Compounds,2016,662,84.
29 Zhang K, Zhang X, Chen H, et al. Langmuir,2004,20(26),11312.
30 Song X S, Gao L. Journal of Physical Chemistry C,2007,111(23),8180.
31 Bao Y, Kang Q L. Journal of Inorganic Materials,2017,32(6),581(in Chinese).鲍艳,康巧玲.无机材料学报,2017,32(6),581.
32 Xiong X, Lin M, Duan J, et al. Reactive & Functional Polymers,2012,72(6),365.
33 Perlich J, Memesa M, Diethert A, et al. Physica Status Solidi-Rapid Research Letters,2009,3(4),118.
34 Kim T H, Lee K H, Kwon Y K. Journal of Colloid & Interface Science,2006,304(2),370.
35 Strohm H, L?bmann P. Journal of Materials Chemistry,2004,14(2),138.
36 Strohm H. Journal of Materials Chemistry,2004,14(17),2667.
37 Imhof A. Langmuir,2001,17(12),3579.
38 Kang Q L, Bao Y, Li M, et al. Progress in Organic Coatings,2017,112,153.
39 Wang D, Song C, Lin Y, et al. Materials Letters,2006,60(1),77.
40 Li H, Ha C S, Kim I. Langmuir,2008,24(19),10552.
41 Sun X, Liu J, Li Y. Chemistry-A European Journal,2006,12(7),2039.
42 Ren W, Ai Z, Jia F, et al. Applied Catalysis B Environmental,2007,69(3),138.
43 Réti B, Kiss G I, Gyulavári T, et al. Catalysis Today,2016,284,160.
44 Wang C, Ao Y, Wang P, et al. Journal of Hazardous Materials,2010,178(1),517.
45 Zhao D, Peng T, Xiao J, et al. Materials Letters,2007,61(1),105.
46 Parida K M, Sahu N. Journal of Molecular Catalysis A Chemical,2008,287(1),151.
47 Zhao D, Peng T, Liu M, et al. Microporous & Mesoporous Materials,2008,114(1),166.
48 Peng T, Zhao D, Song H, et al. Journal of Molecular Catalysis A Chemical,2005,238(1),119.
49 Ao Y H, Xu J J, Fu D G, et al. Journal of Hazardous Materials,2009,167(1),413.
50 Liu J, Qin W, Zuo S, et al. Journal of Hazardous Materials,2009,163(1),273.
51 Wong M S, Hsu S W, Rao K K, et al. Journal of Molecular Catalysis A Chemical,2008,279(1),20.
52 Wang S H, Chen T K, Rao K K, et al. Applied Catalysis B Environmental,2007,76(3),328.
53 Wang C, Ao Y, Wang P, et al. Powder Technology,2011,210(3),203.
54 Wang C, Ao Y, Wang P, et al. Applied Surface Science,2010,257(1),227.
55 Yu J, Wang G. Journal of Physics & Chemistry of Solids,2008,69(5),1147.
56 Li G, Liu F, Zhang Z. Journal of Alloys & Compounds,2010,493(1-2),L1.
57 Ji B J, Qiao Z, Lee I, et al. Advanced Functional Materials,2012,22(1),166.
58 Bala H, Yu Y, Zhang Y. Materials Letters,2008,62(14),2070.
59 Wang Y, Zhou A, Yang Z. Materials Letters,2008,62(12-13),1930.
60 Nakashima T, Kimizuka N. Journal of the American Chemical Society,2003,125(21),6386.
61 Nagamine S, Sugioka A, Iwamoto H, et al. Powder Technology,2008,186(2),168.
62 Li B, Wang J H, Guo Y Z, et al. Materials Review,2006,20(7),36(in Chinese).李斌,王剑华,郭玉忠,等.材料导报,2006,20(7),36.
63 Castillo S I R, Krans N A, Pompe C E, et al. Colloids & Surfaces A Physicochemical & Engineering Aspects,2016,504,228.
64 Lu L Y, Xu L, Yin T T, et al. Advanced Materials Research,2013,634-638(1),2189.
65 Bao Y, Guo J, Ma J, et al. Journal of Industrial & Engineering Chemistry,2017,53,51.
66 Deng F P, Li Y, Qi X H, et al. Journal of Inorganic Materials,2009,24(1),39(in Chinese).邓凤萍,李岳,岂兴红,等.无机材料学报,2009,24(1),39.
67 Kresge C T, Leonowicz M E, Roth W J, et al. Nature,1992,359(6397),710.
68 Li X, Xiong Y, Li Z, et al. Inorganic Chemistry,2006,45(9),3493.
69 Tian Q, Song J, Zhang Z, et al. Materials Chemistry & Physics,2015,151(154),66.
70 Wang L, Bao J, Wang L, et al. Chemistry-A European Journal,2006,12(24),6341.
71 Wei W, Xiao X, Zhang S, et al. Nanoscale Research Letters,2009,4(8),926.
72 Zhu G N, Wang Y G, Xia Y Y. Energy & Environmental Science,2012,5(5),6652.
73 Etacheri V, Marom R, Ran E, et al. Energy & Environmental Science,2011,4(9),3243.
74 Yang H G, Zeng H C. Journal of Physical Chemistry B,2004,108(11),3492.
75 Bao Y, Kang Q L, Ma J Z. Colloids & Surfaces A Physicochemical & Engineering Aspects,2018,537,69.
76 Wang Q, Qin Z, Chen J, et al. Applied Surface Science,2016,364(427),1.
77 Bao Y, Kang Q L, Ma J Z, et al. Ceramics International,2017,43,8596.
78 Nguyen D T, Kim K S. Chemical Engineering Journal,2016,286,266.
79 Li J, Zeng H C. Journal of the American Chemical Society,2007,129(51),15839.
80 Bordes M C, Vicent M, Moreno A, et al. Surface & Coatings Technology,2013,220(15),179.
81 Lakhotiya H, Singh R, Bahadur J, et al. Journal of Alloys & Compounds,2014,584(1),101.
82 Fang X, Zhao X, Fang W, et al. Nanoscale,2013,5(6),2205.
2 Zhang R Y, Tu B, Zhao D Y. Chemistry-A European Journal,2010,16(33),9977.
3 Diaz-Real J A, Dubed-Bandomo G C, Galindo-de-la-Rosa J, et al. Applied Catalysis B Environmental,2018,222,18.
4 Seadira T W P, Sadanandam G, Ntho T, et al. Applied Catalysis B Environmental,2017,222,133.
5 Dong W, Yao Y, Li L, et al. Applied Catalysis B Environmental,2017,217,293.
6 Nguyen C C, Vu N N, Do T O. Journal of Materials Chemistry A,2015,3(36),18345.
7 Valtchev V, Tosheva L. Chemical Reviews,2013,113(8),6734.
8 Fujishima A, Honda K. Nature,1972,238(5358),37.
9 Fujishima A, Rao T N, Tryk D A. Journal of Photochemistry & Photobio-logy C Photochemistry Reviews,2000,1(1),1.
10 Chen R, Wang J, Wang H, et al. Solid State Sciences,2011,13(3),630.
11 Wanag A, Rokicka P, Kusiaknejman E, et al. Ecotoxicology & Environmental Safety,2018,147,788.
12 Ma Q, Wang H, Zhang H, et al. Separation & Purification Technology,2017,189,193.
13 Zhang W, Xi Z, Li G, et al. Small,2009,5(15),1742.
14 Yu X, Yu J, Cheng B, et al. Journal of Physical Chemistry C,2009,113(40),17527.
15 Cong H, Yu S. Advanced Functional Materials,2010,17(11),1814.
16 Fang X, Zhao X, Fang W, et al. Nanoscale,2013,5(6),2205.
17 Liu B, Zeng H. Small,2005,1(5),566.
18 Ao Y H, Xu J J, Fu D G, et al. Journal of Hazardous Materials,2009,167(1-3),413.
19 Cui Y, Liu L, Li B, et al. Journal of Physical Chemistry C,2010,114(6),2434.
20 Lv Y J, Shi K Y, Guo X Z, et al. Chemical Journal of Chinese Universities,2006,27(2),346(in Chinese).吕幼军,石可瑜,郭先芝,等.高等学校化学学报,2006,27(2),346.
21 Song X Q, Yang X H, Chen R F, et al. Acta Chimica Sinica,2006,64(3),198(in Chinese).宋秀芹,杨晓辉,陈汝芬,等.化学学报,2006,64(3),198.
22 Iida M, Sasaki T, Watanabe M. Chemistry of Materials,1998,10(12),3780.
23 Xiong X, Yu Z, Lin M, et al. Reactive & Functional Polymers,2012,72(6),365.
24 Bao Y, Yang Y Q, Jianzhong M A. Journal of Inorganic Materials,2013,28(5),459.
25 Caruso F, Shi X Y, Caruso R A, et al. Advanced Materials,2001,13,740.
26 Petkovich N D, Stein A. Chemical Society Reviews,2013,42(9),3721.
27 Lu Y, Mclellan J, Xia Y. Langmuir,2004,20(8),3464.
28 Zhuang Y, Sun J, Guan M. Journal of Alloys & Compounds,2016,662,84.
29 Zhang K, Zhang X, Chen H, et al. Langmuir,2004,20(26),11312.
30 Song X S, Gao L. Journal of Physical Chemistry C,2007,111(23),8180.
31 Bao Y, Kang Q L. Journal of Inorganic Materials,2017,32(6),581(in Chinese).鲍艳,康巧玲.无机材料学报,2017,32(6),581.
32 Xiong X, Lin M, Duan J, et al. Reactive & Functional Polymers,2012,72(6),365.
33 Perlich J, Memesa M, Diethert A, et al. Physica Status Solidi-Rapid Research Letters,2009,3(4),118.
34 Kim T H, Lee K H, Kwon Y K. Journal of Colloid & Interface Science,2006,304(2),370.
35 Strohm H, L?bmann P. Journal of Materials Chemistry,2004,14(2),138.
36 Strohm H. Journal of Materials Chemistry,2004,14(17),2667.
37 Imhof A. Langmuir,2001,17(12),3579.
38 Kang Q L, Bao Y, Li M, et al. Progress in Organic Coatings,2017,112,153.
39 Wang D, Song C, Lin Y, et al. Materials Letters,2006,60(1),77.
40 Li H, Ha C S, Kim I. Langmuir,2008,24(19),10552.
41 Sun X, Liu J, Li Y. Chemistry-A European Journal,2006,12(7),2039.
42 Ren W, Ai Z, Jia F, et al. Applied Catalysis B Environmental,2007,69(3),138.
43 Réti B, Kiss G I, Gyulavári T, et al. Catalysis Today,2016,284,160.
44 Wang C, Ao Y, Wang P, et al. Journal of Hazardous Materials,2010,178(1),517.
45 Zhao D, Peng T, Xiao J, et al. Materials Letters,2007,61(1),105.
46 Parida K M, Sahu N. Journal of Molecular Catalysis A Chemical,2008,287(1),151.
47 Zhao D, Peng T, Liu M, et al. Microporous & Mesoporous Materials,2008,114(1),166.
48 Peng T, Zhao D, Song H, et al. Journal of Molecular Catalysis A Chemical,2005,238(1),119.
49 Ao Y H, Xu J J, Fu D G, et al. Journal of Hazardous Materials,2009,167(1),413.
50 Liu J, Qin W, Zuo S, et al. Journal of Hazardous Materials,2009,163(1),273.
51 Wong M S, Hsu S W, Rao K K, et al. Journal of Molecular Catalysis A Chemical,2008,279(1),20.
52 Wang S H, Chen T K, Rao K K, et al. Applied Catalysis B Environmental,2007,76(3),328.
53 Wang C, Ao Y, Wang P, et al. Powder Technology,2011,210(3),203.
54 Wang C, Ao Y, Wang P, et al. Applied Surface Science,2010,257(1),227.
55 Yu J, Wang G. Journal of Physics & Chemistry of Solids,2008,69(5),1147.
56 Li G, Liu F, Zhang Z. Journal of Alloys & Compounds,2010,493(1-2),L1.
57 Ji B J, Qiao Z, Lee I, et al. Advanced Functional Materials,2012,22(1),166.
58 Bala H, Yu Y, Zhang Y. Materials Letters,2008,62(14),2070.
59 Wang Y, Zhou A, Yang Z. Materials Letters,2008,62(12-13),1930.
60 Nakashima T, Kimizuka N. Journal of the American Chemical Society,2003,125(21),6386.
61 Nagamine S, Sugioka A, Iwamoto H, et al. Powder Technology,2008,186(2),168.
62 Li B, Wang J H, Guo Y Z, et al. Materials Review,2006,20(7),36(in Chinese).李斌,王剑华,郭玉忠,等.材料导报,2006,20(7),36.
63 Castillo S I R, Krans N A, Pompe C E, et al. Colloids & Surfaces A Physicochemical & Engineering Aspects,2016,504,228.
64 Lu L Y, Xu L, Yin T T, et al. Advanced Materials Research,2013,634-638(1),2189.
65 Bao Y, Guo J, Ma J, et al. Journal of Industrial & Engineering Chemistry,2017,53,51.
66 Deng F P, Li Y, Qi X H, et al. Journal of Inorganic Materials,2009,24(1),39(in Chinese).邓凤萍,李岳,岂兴红,等.无机材料学报,2009,24(1),39.
67 Kresge C T, Leonowicz M E, Roth W J, et al. Nature,1992,359(6397),710.
68 Li X, Xiong Y, Li Z, et al. Inorganic Chemistry,2006,45(9),3493.
69 Tian Q, Song J, Zhang Z, et al. Materials Chemistry & Physics,2015,151(154),66.
70 Wang L, Bao J, Wang L, et al. Chemistry-A European Journal,2006,12(24),6341.
71 Wei W, Xiao X, Zhang S, et al. Nanoscale Research Letters,2009,4(8),926.
72 Zhu G N, Wang Y G, Xia Y Y. Energy & Environmental Science,2012,5(5),6652.
73 Etacheri V, Marom R, Ran E, et al. Energy & Environmental Science,2011,4(9),3243.
74 Yang H G, Zeng H C. Journal of Physical Chemistry B,2004,108(11),3492.
75 Bao Y, Kang Q L, Ma J Z. Colloids & Surfaces A Physicochemical & Engineering Aspects,2018,537,69.
76 Wang Q, Qin Z, Chen J, et al. Applied Surface Science,2016,364(427),1.
77 Bao Y, Kang Q L, Ma J Z, et al. Ceramics International,2017,43,8596.
78 Nguyen D T, Kim K S. Chemical Engineering Journal,2016,286,266.
79 Li J, Zeng H C. Journal of the American Chemical Society,2007,129(51),15839.
80 Bordes M C, Vicent M, Moreno A, et al. Surface & Coatings Technology,2013,220(15),179.
81 Lakhotiya H, Singh R, Bahadur J, et al. Journal of Alloys & Compounds,2014,584(1),101.
82 Fang X, Zhao X, Fang W, et al. Nanoscale,2013,5(6),2205.