Citation: Wei-Wei Cai, Hui Yang, Xing-Zhong Guo. A facile one-step route to synthesize titania hollow microspheres with incontinuous multicavities[J]. Chinese Chemical Letters, ;2014, 25(3): 441-446. doi: 10.1016/j.cclet.2013.12.002 shu

A facile one-step route to synthesize titania hollow microspheres with incontinuous multicavities

1.
Department of Materials Science and Engineering, Zhejiang University, Hangzhou 310024, China

Corresponding author: Xing-Zhong Guo,
Received Date: 29 July 2013
Available Online: 21 November 2013
Fund Project: This work is supported by the National Natural Science Foundation of China (No. 51372225) (No. 51372225)Zhejiang Provincial Natural Science Foundation of China (No. LY13B010001). (No. LY13B010001)

The titania hollow microspheres with incontinuous multicavities were successfully fabricated via an oil/water (O/W) emulsion process accompanied by sol-gel reaction in the presence of polyvinylpyrrolidone (PVP). In the one-step route, the addition of PVP to the tetrabutyl titanate (TBT) 1-octanol solution as the oil phase of the O/W emulsion clearly expands the size of the cavities inside the microspheres. The npropanol and atoleine alters the polarity of the oil phase to affect the interior structure significantly. The Span 80 is used as a stabilizer to preserve spherical shape. A preliminary mechanism based on phaseseparation for the structural evolution of titania hollow microspheres with multicavities is suggested. Zirconia and alumina hollow microspheres with incontinuous multicavities can also be prepared by this one-step route successfully.
- Hollow microspheres,
- Multicavities,
- Phase separation,
- Titania
1. [1]
  [1] J. Hu, M. Chen, X.S. Fang, L.M. Wu, Fabrication and application of inorganic hollow spheres, Chem. Soc. Rev. 40 (2011) 5472-5491.
2. [2]
  [2] S. Schacht, Q. Huo, I.G. Voigt-Martin, G.D. Stucky, F. Schü th, Oil-water interface templating of mesoporous macroscale structures, Science 273 (1996) 768-771.
3. [3]
  [3] J.H. Park, C. Oh, S. Shin, S.K. Moon, S.G. Oh, Preparation of hollowsilicamicrospheres in w/o emulsions with polymers, J. Colloid Interface Sci. 266 (2003) 107-114.
4. [4]
  [4] T. Nakashima, N. Kimizuka, Interfacial synthesis of hollow TiO₂ microspheres in ionic liquids, J. Am. Chem. Soc. 125 (2003) 6386-6387.
5. [5]
  [5] H.L. Xu, W.Z. Wang, Template synthesis of multishelled Cu₂O hollow spheres with a single-crystalline shell wall, Angew. Chem. Int. Ed. 46 (2007) 1489-1492.
6. [6]
  [6] J.G. Guan, F.Z. Mou, Z.G. Sun, W.D. Shi, Preparation of hollow spheres with controllable interior structures by heterogeneous contraction, Chem. Commun. 46 (2010) 6605-6607.
7. [7]
  [7] Y.B. Kim, K.S. Yoon, A physical method of fabricating hollow polymer spheres directly from oil/water emulsions of solutions of polymers, Macromol. Rapid Commun. 25 (2004) 1643-1649.
8. [8]
  [8] E. Kamio, S. Yonemura, T. Ono, H. Yoshizawa, Microcapsules with macroholes prepared by the competitive adsorption of surfactants on emulsion droplet surfaces, Langmuir 24 (2008) 13287-13298.
9. [9]
  [9] J. Han, P. Fang, J. Dai, R. Guo, One-pot surfactantless route to polyaniline hollow nanospheres with incontinuous multicavities and application for the removal of lead ions from water, Langmuir 28 (2012) 6468-6475.
10. [10]
  [10] J.X. Xu, G.J. Chen, R. Yan, et al., One-stage synthesis of cagelike porous polymeric microspheres and application as catalyst scaffold of Pd nanoparticles, Macromolecules 44 (2011) 3730-3738.
11. [11]
  [11] H. Zhang, A.I. Cooper, Synthesis of monodisperse emulsion-templated polymer beads by oil-in-water-in-oil (O/W/O) sedimentation polymerization, Chem. Mater. 14 (2002) 4017-4020.
12. [12]
  [12] H. Wang, M.Z. Wang, X.W. Ge, One-step fabrication of multihollow polystyrene particles from miniemulsion system with nonionic surfactant, Polymer 49 (2008) 4974-4980.
13. [13]
  [13] G.H. Zhang, R.X. Hou, D.X. Zhan, et al., Fabrication of hollow porous PLGA microspheres for controlled protein release and promotion of cell compatibility, Chin. Chem. Lett. 24 (2013) 710-714.
14. [14]
  [14] L. Li, E.S.G. Choo, X.S. Tang, J. Ding, J.M. Xue, A facile one-step route to synthesize cage-like silica hollow spheres loaded with superparamagnetic iron oxide nanoparticles in their shells, Chem. Commun. 45 (2009) 938-940.
15. [15]
  [15] F. Iskandar, K. Okuyama, Controllability of pore size and porosity on self-organized porous silica particles, Nano Lett. 2 (2002) 389-392.
16. [16]
  [16] X. Du, J.H. He, Fine-tuning of silica nanosphere structure by simple regulation of the volume ratio of cosolvents, Langmuir 26 (2010) 10057-10062.
17. [17]
  [17] D. Grosso, G.J. de A.A. Soler-Illia, E.L. Crepaldi, B. Charleux, C. Sanchez, Nanocrystalline transition-metal oxide spheres with controlled multi-scale porosity, Adv. Funct. Mater. 13 (2003) 37-42.
18. [18]
  [18] K. Nakanishi, Pore structure control of silica gels based on phase separation, J. Porous Mater. 4 (1994) 67-112.
19. [19]
  [19] Q.L. Zhang, F. Wu, H. Yang, D. Zou, Preparation and dielectric properties of (Ca0.61,Nd0.26)TiO₃ nanoparticles by a sol-gel method, J. Mater. Chem. 18 (2008) 5339-5343.
20. [20]
  [20] T. Sato, A. Sato, T. Arai, Adsorption of polyvinylpyrrolidone on titanium dioxide from binary solvents (methanol/water) and its effect on dispersion stability, Colloids Surf. A 142 (1998) 117-120.
21. [21]
  [21] M.P. Zheng, M.Y. Gu, Y.P. Jin, G.L. Jin, Preparation, structure and properties of TiO₂-PVP hybrid films, Mater. Sci. Eng. B 77 (2000) 55-59.
22. [22]
  [22] Y. Frere, P. Gramain, Reaction kinetics of polymer substituents: macromolecular steric hindrance effect in quaternization of poly(vinylpyridines), Macromolecules 25 (1992) 3184-3189.
23. [23]
  [23] K. Nakanishi, N. Tanaka, Sol-gel with phase separation. Hierarchically porous materials optimized for high-performance liquid chromatography separations, Acc. Chem. Res. 40 (2007) 863-873.
24. [24]
  [24] F. Gao, Z.G. Su, P. Wang, G.H. Ma, Double emulsion templated microcapsules with single hollow cavities and thickness-controllable shells, Langmuir 25 (2009) 3832-3838.
25. [25]
  [25] A.Y. Khan, S. Talegaonkar, Z. Iqbal, J.F. Ahmed, R.K. Khar, Multiple emulsions: an overview, Curr. Drug Deliv. 3 (2006) 429-443.
26. [26]
  [26] Y. Tokudome, K. Fujita, K. Nakanishi, K. Miura, K. Hirao, Synthesis of monolithic Al₂O₃ with well-defined macropores and mesostructured skeletons via the sol-gel process accompanied by phase separation, Chem. Mater. 19 (2007) 3393-3398.
27. [27]
  [27] F.Q. Lin, W.S. Dong, C.L. Liu, Z.T. Liu, M.Y. Li, In situ source-template-interface reaction route to hollow ZrO₂ microspheres with mesoporous shells, J. Colloid Interface Sci. 323 (2008) 365-371.
28. [28]
  [28] J. Konishi, K. Fujita, S. Oiwa, K. Nakanishi, K. Hirao, Crystalline ZrO₂ monoliths with well-defined macropores and mesostructured skeletons prepared by combining the alkoxy-derived sol-gel process accompanied by phase separation and the solvothermal process, Chem. Mater. 20 (2008) 2165-2173.
1. [1]
  Ruotong Wei , Aokun Liu , Jian Kuang , Zhiwen Wang , Lu Yu , Changlin Tian . Probing the dynamic properties in the LLPS process via site-directed spin labeling-electron paramagnetic resonance (SDSL-EPR) spectroscopy. Chinese Chemical Letters, 2025, 36(4): 110029-. doi: 10.1016/j.cclet.2024.110029
2. [2]
  Zhefei Hu , Jingwen Liao , Jiawen Zhou , Lulu Zhao , Yanjuan Liu , Yuefei Zhang , Wei Chen , Sheng Tang . A new green approach to synthesizing MIP-202@porous silica microspheres for positional isomer/enantiomer/hydrophilic separation. Chinese Chemical Letters, 2025, 36(1): 109985-. doi: 10.1016/j.cclet.2024.109985
3. [3]
  Ning Zhang , Mengjie Qin , Jiawen Zhu , Xuejing Lou , Xiao Tian , Wende Ma , Youmei Wang , Minghua Lu , Zongwei Cai . Thickness-controllable synthesis of metal-organic framework based hollow nanoflowers with magnetic core via liquid phase epitaxy for phosphopeptides enrichment. Chinese Chemical Letters, 2025, 36(4): 110177-. doi: 10.1016/j.cclet.2024.110177
4. [4]
  Yu ZHANG , Fangfang ZHAO , Cong PAN , Peng WANG , Liangming WEI . Application of double-side modified separator with hollow carbon material in high-performance Li-S battery. Chinese Journal of Inorganic Chemistry, 2024, 40(6): 1218-1232. doi: 10.11862/CJIC.20230412
5. [5]
  Sifan Du , Yuan Wang , Fulin Wang , Tianyu Wang , Li Zhang , Minghua Liu . Evolution of hollow nanosphere to microtube in the self-assembly of chiral dansyl derivatives and inversed circularly polarized luminescence. Chinese Chemical Letters, 2024, 35(7): 109256-. doi: 10.1016/j.cclet.2023.109256
6. [6]
  Jiaxu Wang , Jinxie Zhang , Xiuping Wang , Jingying Wang , Lina Chen , Jiahui Cao , Wei Cao , Siyu Liang , Ping Luan , Ke Zheng , Xiao-Kun Ouyang , Li Gao , Xiaowen Ou , Fan Zhang , Meitong Ou , Lin Mei . CaCO₃-coated hollow mesoporous silica nanoparticles for pH-responsive fungicides release. Chinese Chemical Letters, 2024, 35(12): 109697-. doi: 10.1016/j.cclet.2024.109697
7. [7]
  Xueyan Zhang , Jicong Chen , Songren Han , Shiyan Dong , Huan Zhang , Yuhong Man , Jie Yang , Ye Bi , Lesheng Teng . The size-switchable microspheres co-loaded with RANK siRNA and salmon calcitonin for osteoporosis therapy. Chinese Chemical Letters, 2024, 35(12): 109668-. doi: 10.1016/j.cclet.2024.109668
8. [8]
  Rui Li , Ruijie Lu , Libin Yang , Jianwen Li , Zige Guo , Qiquan Yan , Mengjun Li , Yazhuo Ni , Keying Chen , Yaoyang Li , Bo Xu , Mengzhen Cui , Zhan Li , Zhiying Zhao . Immobilization of chitosan nano-hydroxyapatite alendronate composite microspheres on polyetheretherketone surface to enhance osseointegration by inhibiting osteoclastogenesis and promoting osteogenesis. Chinese Chemical Letters, 2025, 36(4): 110242-. doi: 10.1016/j.cclet.2024.110242
9. [9]
  Pengcheng Su , Shizheng Chen , Zhihong Yang , Ningning Zhong , Chenzi Jiang , Wanbin Li . Vapor-phase postsynthetic amination of hypercrosslinked polymers for efficient iodine capture. Chinese Chemical Letters, 2024, 35(9): 109357-. doi: 10.1016/j.cclet.2023.109357
10. [10]
  Ce Liang , Qiuhui Sun , Adel Al-Salihy , Mengxin Chen , Ping Xu . Recent advances in crystal phase induced surface-enhanced Raman scattering. Chinese Chemical Letters, 2024, 35(9): 109306-. doi: 10.1016/j.cclet.2023.109306
11. [11]
  Mengjia Luo , Yi Qiu , Zhengyang Zhou . Exploring temperature-driven phase dynamics of phosphate: The periodic to incommensurately modulated long-range ordered phase transition in CsCdPO4. Chinese Journal of Structural Chemistry, 2025, 44(1): 100446-100446. doi: 10.1016/j.cjsc.2024.100446
12. [12]
  Lishan Xiong , Xinyuan Li , Xiaojie Lu , Zhendong Zhang , Yan Zhang , Wen Wu , Chenhui Wang . Inhaled multilevel size-tunable, charge-reversible and mucus-traversing composite microspheres as trojan horse: Enhancing lung deposition and tumor penetration. Chinese Chemical Letters, 2024, 35(9): 109384-. doi: 10.1016/j.cclet.2023.109384
13. [13]
  Lingling Su , Qunyan Wu , Congzhi Wang , Jianhui Lan , Weiqun Shi . Theoretical design of polyazole based ligands for the separation of Am(Ⅲ)/Eu(Ⅲ). Chinese Chemical Letters, 2024, 35(8): 109402-. doi: 10.1016/j.cclet.2023.109402
14. [14]
  Jingwen Zhao , Jianpu Tang , Zhen Cui , Limin Liu , Dayong Yang , Chi Yao . A DNA micro-complex containing polyaptamer for exosome separation and wound healing. Chinese Chemical Letters, 2024, 35(9): 109303-. doi: 10.1016/j.cclet.2023.109303
15. [15]
  Huangjie Lu , Yingzhe Du , Peng Lin , Jian Lin . Separation of americium from lanthanides based on oxidation state control. Chinese Journal of Structural Chemistry, 2024, 43(10): 100344-100344. doi: 10.1016/j.cjsc.2024.100344
16. [16]
  Hao-Cong Li , Ming Zhang , Qiyan Lv , Kai Sun , Xiao-Lan Chen , Lingbo Qu , Bing Yu . Homogeneous catalysis and heterogeneous separation: Ionic liquids as recyclable photocatalysts for hydroacylation of olefins. Chinese Chemical Letters, 2025, 36(2): 110579-. doi: 10.1016/j.cclet.2024.110579
17. [17]
  Ping Lu , Baoyin Du , Ke Liu , Ze Luo , Abiduweili Sikandaier , Lipeng Diao , Jin Sun , Luhua Jiang , Yukun Zhu . Heterostructured In2O3/In2S3 hollow fibers enable efficient visible-light driven photocatalytic hydrogen production and 5-hydroxymethylfurfural oxidation. Chinese Journal of Structural Chemistry, 2024, 43(8): 100361-100361. doi: 10.1016/j.cjsc.2024.100361
18. [18]
  Zhuangzhuang Zhang , Yaru Qiao , Jun Zhao , Dai-Huo Liu , Mengmin Jia , Hongwei Tang , Liang Wang , Dongmei Dai , Bao Li . Fluorine-doped K_0.39Mn_0.77Ni_0.23O_1.9F_0.1 microspheres with highly reversible oxygen redox reaction for potassium-ion battery cathode. Chinese Chemical Letters, 2025, 36(3): 109907-. doi: 10.1016/j.cclet.2024.109907
19. [19]
  Shengyu Zhao , Qinhao Shi , Wuliang Feng , Yang Liu , Xinxin Yang , Xingli Zou , Xionggang Lu , Yufeng Zhao . Suppression of multistep phase transitions of O3-type cathode for sodium-ion batteries. Chinese Chemical Letters, 2024, 35(5): 108606-. doi: 10.1016/j.cclet.2023.108606
20. [20]
  Xue Xin , Qiming Qu , Islam E. Khalil , Yuting Huang , Mo Wei , Jie Chen , Weina Zhang , Fengwei Huo , Wenjing Liu . Hetero-phase zirconia encapsulated with Au nanoparticles for boosting electrocatalytic nitrogen reduction. Chinese Chemical Letters, 2024, 35(5): 108654-. doi: 10.1016/j.cclet.2023.108654

Get Citation

PDF

XML

Metrics

PDF Downloads(0)
Abstract views(625)
HTML views(1)

通讯作者: 陈斌, bchen63@163.com

1.
沈阳化工大学材料科学与工程学院沈阳 110142