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Mesoporous TiO(2) Mesocrystals: Remarkable Defects-Induced Crystallite-Interface Reactivity and Their in Situ Conversion to Single Crystals
[Image: see text] Oriented self-assembly between inorganic nanocrystals and surfactants is emerging as a route for obtaining new mesocrystalline semiconductors. However, the actual synthesis of mesoporous semiconductor mesocrystals with abundant surface sites is extremely difficult, and the correspo...
Autores principales: | , , , , , , , , , , , , , , , , , , , , , , , |
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Formato: | Online Artículo Texto |
Lenguaje: | English |
Publicado: |
American
Chemical Society
2015
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Acceso en línea: | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4827529/ https://www.ncbi.nlm.nih.gov/pubmed/27162998 http://dx.doi.org/10.1021/acscentsci.5b00256 |
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author | Liu, Yong Luo, Yongfeng Elzatahry, Ahmed A. Luo, Wei Che, Renchao Fan, Jianwei Lan, Kun Al-Enizi, Abdullah M. Sun, Zhenkun Li, Bin Liu, Zhengwang Shen, Dengke Ling, Yun Wang, Chun Wang, Jingxiu Gao, Wenjun Yao, Chi Yuan, Kaiping Peng, Huisheng Tang, Yun Deng, Yonghui Zheng, Gengfeng Zhou, Gang Zhao, Dongyuan |
author_facet | Liu, Yong Luo, Yongfeng Elzatahry, Ahmed A. Luo, Wei Che, Renchao Fan, Jianwei Lan, Kun Al-Enizi, Abdullah M. Sun, Zhenkun Li, Bin Liu, Zhengwang Shen, Dengke Ling, Yun Wang, Chun Wang, Jingxiu Gao, Wenjun Yao, Chi Yuan, Kaiping Peng, Huisheng Tang, Yun Deng, Yonghui Zheng, Gengfeng Zhou, Gang Zhao, Dongyuan |
author_sort | Liu, Yong |
collection | PubMed |
description | [Image: see text] Oriented self-assembly between inorganic nanocrystals and surfactants is emerging as a route for obtaining new mesocrystalline semiconductors. However, the actual synthesis of mesoporous semiconductor mesocrystals with abundant surface sites is extremely difficult, and the corresponding new physical and chemical properties arising from such an intrinsic porous mesocrystalline nature, which is of fundamental importance for designing high-efficiency nanostructured devices, have been rarely explored and poorly understood. Herein, we report a simple evaporation-driven oriented assembly method to grow unprecedented olive-shaped mesoporous TiO(2) mesocrystals (FDU-19) self-organized by ultrathin flake-like anatase nanocrystals (∼8 nm in thickness). The mesoporous mesocrystals FDU-19 exhibit an ultrahigh surface area (∼189 m(2)/g), large internal pore volume (0.56 cm(3)/g), and abundant defects (oxygen vacancies or unsaturated Ti(3+) sites), inducing remarkable crystallite-interface reactivity. It is found that the mesocrystals FDU-19 can be easily fused in situ into mesoporous anatase single crystals (SC-FDU-19) by annealing in air. More significantly, by annealing in a vacuum (∼4.0 × 10(–5) Pa), the mesocrystals experience an abrupt three-dimensional to two-dimensional structural transformation to form ultrathin anatase single-crystal nanosheets (NS-FDU-19, ∼8 nm in thickness) dominated by nearly 90% exposed reactive (001) facets. The balance between attraction and electrostatic repulsion is proposed to determine the resulting geometry and dimensionality. Dye-sensitized solar cells based on FDU-19 and SC-FDU-19 samples show ultrahigh photoconversion efficiencies of up to 11.6% and 11.3%, respectively, which are largely attributed to their intrinsic single-crystal nature as well as high porosity. This work gives new understanding of physical and chemical properties of mesoporous semiconductor mesocrystals and opens up a new pathway for designing various single-crystal semiconductors with desired mesostructures for applications in catalysis, sensors, drug delivery, optical devices, etc. |
format | Online Article Text |
id | pubmed-4827529 |
institution | National Center for Biotechnology Information |
language | English |
publishDate | 2015 |
publisher | American
Chemical Society |
record_format | MEDLINE/PubMed |
spelling | pubmed-48275292016-05-09 Mesoporous TiO(2) Mesocrystals: Remarkable Defects-Induced Crystallite-Interface Reactivity and Their in Situ Conversion to Single Crystals Liu, Yong Luo, Yongfeng Elzatahry, Ahmed A. Luo, Wei Che, Renchao Fan, Jianwei Lan, Kun Al-Enizi, Abdullah M. Sun, Zhenkun Li, Bin Liu, Zhengwang Shen, Dengke Ling, Yun Wang, Chun Wang, Jingxiu Gao, Wenjun Yao, Chi Yuan, Kaiping Peng, Huisheng Tang, Yun Deng, Yonghui Zheng, Gengfeng Zhou, Gang Zhao, Dongyuan ACS Cent Sci [Image: see text] Oriented self-assembly between inorganic nanocrystals and surfactants is emerging as a route for obtaining new mesocrystalline semiconductors. However, the actual synthesis of mesoporous semiconductor mesocrystals with abundant surface sites is extremely difficult, and the corresponding new physical and chemical properties arising from such an intrinsic porous mesocrystalline nature, which is of fundamental importance for designing high-efficiency nanostructured devices, have been rarely explored and poorly understood. Herein, we report a simple evaporation-driven oriented assembly method to grow unprecedented olive-shaped mesoporous TiO(2) mesocrystals (FDU-19) self-organized by ultrathin flake-like anatase nanocrystals (∼8 nm in thickness). The mesoporous mesocrystals FDU-19 exhibit an ultrahigh surface area (∼189 m(2)/g), large internal pore volume (0.56 cm(3)/g), and abundant defects (oxygen vacancies or unsaturated Ti(3+) sites), inducing remarkable crystallite-interface reactivity. It is found that the mesocrystals FDU-19 can be easily fused in situ into mesoporous anatase single crystals (SC-FDU-19) by annealing in air. More significantly, by annealing in a vacuum (∼4.0 × 10(–5) Pa), the mesocrystals experience an abrupt three-dimensional to two-dimensional structural transformation to form ultrathin anatase single-crystal nanosheets (NS-FDU-19, ∼8 nm in thickness) dominated by nearly 90% exposed reactive (001) facets. The balance between attraction and electrostatic repulsion is proposed to determine the resulting geometry and dimensionality. Dye-sensitized solar cells based on FDU-19 and SC-FDU-19 samples show ultrahigh photoconversion efficiencies of up to 11.6% and 11.3%, respectively, which are largely attributed to their intrinsic single-crystal nature as well as high porosity. This work gives new understanding of physical and chemical properties of mesoporous semiconductor mesocrystals and opens up a new pathway for designing various single-crystal semiconductors with desired mesostructures for applications in catalysis, sensors, drug delivery, optical devices, etc. American Chemical Society 2015-09-09 2015-10-28 /pmc/articles/PMC4827529/ /pubmed/27162998 http://dx.doi.org/10.1021/acscentsci.5b00256 Text en Copyright © 2015 American Chemical Society This is an open access article published under an ACS AuthorChoice License (http://pubs.acs.org/page/policy/authorchoice_termsofuse.html) , which permits copying and redistribution of the article or any adaptations for non-commercial purposes. |
spellingShingle | Liu, Yong Luo, Yongfeng Elzatahry, Ahmed A. Luo, Wei Che, Renchao Fan, Jianwei Lan, Kun Al-Enizi, Abdullah M. Sun, Zhenkun Li, Bin Liu, Zhengwang Shen, Dengke Ling, Yun Wang, Chun Wang, Jingxiu Gao, Wenjun Yao, Chi Yuan, Kaiping Peng, Huisheng Tang, Yun Deng, Yonghui Zheng, Gengfeng Zhou, Gang Zhao, Dongyuan Mesoporous TiO(2) Mesocrystals: Remarkable Defects-Induced Crystallite-Interface Reactivity and Their in Situ Conversion to Single Crystals |
title | Mesoporous TiO(2) Mesocrystals: Remarkable
Defects-Induced
Crystallite-Interface Reactivity and Their in Situ Conversion to Single
Crystals |
title_full | Mesoporous TiO(2) Mesocrystals: Remarkable
Defects-Induced
Crystallite-Interface Reactivity and Their in Situ Conversion to Single
Crystals |
title_fullStr | Mesoporous TiO(2) Mesocrystals: Remarkable
Defects-Induced
Crystallite-Interface Reactivity and Their in Situ Conversion to Single
Crystals |
title_full_unstemmed | Mesoporous TiO(2) Mesocrystals: Remarkable
Defects-Induced
Crystallite-Interface Reactivity and Their in Situ Conversion to Single
Crystals |
title_short | Mesoporous TiO(2) Mesocrystals: Remarkable
Defects-Induced
Crystallite-Interface Reactivity and Their in Situ Conversion to Single
Crystals |
title_sort | mesoporous tio(2) mesocrystals: remarkable
defects-induced
crystallite-interface reactivity and their in situ conversion to single
crystals |
url | https://www.ncbi.nlm.nih.gov/pmc/articles/PMC4827529/ https://www.ncbi.nlm.nih.gov/pubmed/27162998 http://dx.doi.org/10.1021/acscentsci.5b00256 |
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