Elsevier

Materials Letters

Volume 264, 1 April 2020, 127320
Materials Letters

Porous SnO2 triple-shelled hollow nanoboxes for high sensitive toluene detection

https://doi.org/10.1016/j.matlet.2020.127320Get rights and content

Highlights

  • Novel SnO2 triple-shelled hollow nanoboxes were prepared.

  • Easily permeable configuration of primary nanoparticle-assembled multiple layers.

  • Multiplicate activated and porous shells efficiently improved sensing characteristics.

Abstract

A unique triple-shelled architecture with nonspherical shape has been successfully synthesized via a controllable multistep approach in case of polycrystalline SnO2 nanoboxes. The morphological characterizations demonstrate that SnO2 triple-shelled hollow boxes (THBs) are hierarchically constructed by numerous SnO2 primary nanoparticles. The formation mechanism of these SnO2 THBs is discussed based on a localized inside-out Ostwald ripening process. When SnO2 THBs are used as sensing material for toluene detection, the improved sensing performance can be attributed to the rational microstructures for fast transfer of gas molecules.

Introduction

Hollow nanostructures, as one type of less agglomerated configuration, have attracted a great deal of attention because of the structural merits including low density, high surface area, and potential for loading capacity [1], [2], [3]. From a performance perspective, rational design of desired candidates with less-agglomerated micro/nanostructures can endow great performance advantages on account of the fact that their behaviors are easily tunable by the size, morphology, and microstructure [4]. To meet the growing requirement, various hollowing routes and strategies are successfully developed for different hollow micro/nanostructures. Among of them, template-engaged method is probably the most versatile and effective route due to the straightforward mechanism and good reliability for the direct inheritance of hollow structures from templates [5], [6], [7]. However, one still encounters some problems in heterogeneous deposition of candidates on templates, the increased cost and operating steps. In addition, the obtained nanostructures are mostly built up by single-shelled structure, thus it cannot be readily applied because of the breakable shells, the great waste of interior cavity or single functionality.

The disadvantages of single-shelled structures can be overcome using the higher-level hollow organization, including multilayered or core@void@shell (yolk-shell-structured) structures. Recently, the preparation of multilayered nanostructures has been developed through some novel template-free or self-template routes based on several principles [8], [9], [10], [11], [12], [13], [14], [15]. Although a great effort having been devoted to building up the envisaged multilayers, the actual assembly of multilayered nanostructures still suffers from the significantly increased thermodynamic complexity including homogenous growth habit of candidates, shape, and interior complexity without the structural degradation of multilayered configuration. Thus, the intended assembly of desirable multi-shelled nanostructures is of great scientific and practical value remains a great challenge.

In this work, we report a low-cost multistep route for SnO2 THBs via deposition of polycrystalline SnO2 on hybrid SnO2/Zn2SnO4 double-shelled templates followed by removal of Zn2SnO4. The evolution of multilayered structures is detailedly investigated and the formation mechanism of SnO2 THBs is discussed. Benefitting from the improved surface area, the improved gas-sensing performances of SnO2 THBs can be anticipated.

Section snippets

Experimental

All the chemical reagents are of analytical grade (Sinopharm Chemical Reagent Co. Ltd, China) and used without further purification. The route for SnO2 THBs is according to our previous report with some modifications [12]. Briefly, 40 mL of aqueous solution including ZnCl2 (0.025 M), SnCl4·5H2O (0.025 M), and NaOH (11 mmol) was firstly prepared under vigorous stirring and aged for 2 h. Subsequently, additional NaOH (2 M) was added dropwise into the above solution under stirring, and the

Results and discussion

The synthesis strategy is schematically illustrated in Fig. 1a and SnO2 THBs are finally synthesized according to our previous “anneal-etching” procedure with some modification [12]. Firstly, the co-precipitation synthesis of monodisperse zinc hydroxystannate (ZnSn(OH)6, ZHS) solid cubes and subsequent ZHS single-shelled hollow boxes (SHBs) through self-template hollowing evolution. Then, the formation of hybrid Zn2SnO4/SnO2 double-shelled hollow boxes (DHBs) via a simple but crucial

Conclusion

In summary, triple-shelled SnO2 nanoboxes have been prepared by our “anneal-etching” route for deposition of additional SnO2 shell on Zn2SnO4/SnO2 double-shelled templates followed by removal of Zn2SnO4. Detailed characterization confirms that SnO2 THBs are assembled by inner cavities and multiple porous shells, which are hierarchically composed of primary SnO2 nanoparticle subunits. Besides benefiting from general structural advantages of hollow interiors and porous shells, the promotion of

CRediT authorship contribution statement

Tianyi Wang: Writing - original draft. Haoyan Xu: Data curation. Yanzhe Wang: Data curation, Writing - review & editing. Yi Zeng: Supervision, Conceptualization. Bingbing Liu: Supervision, Methodology.

Declaration of Competing Interest

The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper.

Acknowledgements

This research work was financially supported by the National Key R&D Program of China (Grant No. 2018YFA0305900), Science and Technology Development Project, Jilin Province (No. 20170101168JC), and the “Talents Cultivation Program” of Jilin University 2017.

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