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Nano Research 2014, 7(2): 246-262 https://doi.org/10.1007/s12274-013-0392-9
Research Article | Issue | Published: 03 January 2014

A versatile cooperative template-directed coating method to synthesize hollow and yolk–shell mesoporous zirconium titanium oxide nanospheres as catalytic reactors

Show Author's Information Buyuan Guan,  Tao Wang,  Shangjing Zeng,  Xue Wang,  Dong An,  Dongmei Wang,  Yu Cao,  Dingxuan Ma,  Yunling Liu,  Qisheng Huo( )
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of Chemistry, Jilin UniversityChangchun China
Keywords:
self-assembly, hollow structure, yolk–shell structure, mesoporous zirconium titanium oxide, multiple catalyst
Cite this article:
Guan B, Wang T, Zeng S, et al. A versatile cooperative template-directed coating method to synthesize hollow and yolk–shell mesoporous zirconium titanium oxide nanospheres as catalytic reactors. Nano Research, 2014, 7(2): 246-262. https://doi.org/10.1007/s12274-013-0392-9
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Abstract Full text Electronic supplementary material About this article

The design of hollow mesoporous nanostructures for cascade catalytic reactions can inject new vitality into the development of nanostructures. In this study, we report a versatile cooperative template-directed coating method for the synthesis of hollow and yolk–shell mesoporous zirconium titanium oxide nanospheres with varying compositions (ZrO2 content from 0 to 100%), high surface areas (465 m2·g–1) and uniform mesopores. In particular, the hexadecylamine (HDA) used in the coating procedure serves as a soft template for silica@mesostructured metal oxide core–shell nanosphere formation. By a facile solvothermal treatment route with an ammonia solution and calcination in air, the silica@mesostructured zirconium titanium oxide spheres can be converted into highly uniform hollow zirconium titanium oxide spheres. By simply replacing hard template silica nanospheres with core–shell silica nanocomposites, the synthesis approach can be further used to prepare yolk–shell mesoporous structures through the coating and etching process. The approach is similar to the preparation of mesoporous silica nanocomposites from the self-assembly of the core, the soft template cetyltrimethylammonium bromide (CTAB) and a silica precursor and can be extended as a general method to coat mesoporous zirconium titanium oxide on other commonly used hard templates (e.g., mesoporous silica spheres, mesoporous organosilica ellipsoids, polymer spheres, and carbon nanospheres). The presence of highly permeable mesoporous channels in the zirconium titanium oxide shells has been demonstrated by the reduction of 4-nitrophenol with yolk–shell Au@mesoporous zirconium titanium oxide as the catalyst. Moreover, a cascade catalytic reaction including an acid catalyzed step and a catalytic hydrogenation to afford benzimidazole derivatives can be carried out very effectively by using the accessible acidity of the yolk–shell structured mesoporous zirconium titanium oxide spheres containing a Pd core as a bifunctional catalyst, which makes the hollow zirconium titanium oxide spheres a practicable candidate for advanced catalytic systems.


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Electronic supplementary material
About this article

A versatile cooperative template-directed coating method to synthesize hollow and yolk–shell mesoporous zirconium titanium oxide nanospheres as catalytic reactors

Show Author's information Buyuan Guan, Tao Wang, Shangjing Zeng, Xue Wang, Dong An, Dongmei Wang, Yu Cao, Dingxuan Ma, Yunling Liu, Qisheng Huo( )
State Key Laboratory of Inorganic Synthesis and Preparative Chemistry College of Chemistry, Jilin UniversityChangchun China

Abstract

The design of hollow mesoporous nanostructures for cascade catalytic reactions can inject new vitality into the development of nanostructures. In this study, we report a versatile cooperative template-directed coating method for the synthesis of hollow and yolk–shell mesoporous zirconium titanium oxide nanospheres with varying compositions (ZrO2 content from 0 to 100%), high surface areas (465 m2·g–1) and uniform mesopores. In particular, the hexadecylamine (HDA) used in the coating procedure serves as a soft template for silica@mesostructured metal oxide core–shell nanosphere formation. By a facile solvothermal treatment route with an ammonia solution and calcination in air, the silica@mesostructured zirconium titanium oxide spheres can be converted into highly uniform hollow zirconium titanium oxide spheres. By simply replacing hard template silica nanospheres with core–shell silica nanocomposites, the synthesis approach can be further used to prepare yolk–shell mesoporous structures through the coating and etching process. The approach is similar to the preparation of mesoporous silica nanocomposites from the self-assembly of the core, the soft template cetyltrimethylammonium bromide (CTAB) and a silica precursor and can be extended as a general method to coat mesoporous zirconium titanium oxide on other commonly used hard templates (e.g., mesoporous silica spheres, mesoporous organosilica ellipsoids, polymer spheres, and carbon nanospheres). The presence of highly permeable mesoporous channels in the zirconium titanium oxide shells has been demonstrated by the reduction of 4-nitrophenol with yolk–shell Au@mesoporous zirconium titanium oxide as the catalyst. Moreover, a cascade catalytic reaction including an acid catalyzed step and a catalytic hydrogenation to afford benzimidazole derivatives can be carried out very effectively by using the accessible acidity of the yolk–shell structured mesoporous zirconium titanium oxide spheres containing a Pd core as a bifunctional catalyst, which makes the hollow zirconium titanium oxide spheres a practicable candidate for advanced catalytic systems.

Keywords: self-assembly, hollow structure, yolk–shell structure, mesoporous zirconium titanium oxide, multiple catalyst

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Publication history
Copyright
Acknowledgements

Publication history

Received: 10 October 2013
Revised: 20 November 2013
Accepted: 21 November 2013
Published: 03 January 2014
Issue date: February 2014

Copyright

© Tsinghua University Press and Springer-Verlag Berlin Heidelberg 2013

Acknowledgements

Acknowledgements

This work was supported by the National Natural Science Foundation of China (Grant Nos. 21171064 and 21071059).

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