Assembly of high-nuclearity Sn26 , Sn34 -oxo clusters: solvent strategies and inorganic Sn incorporation.

Yu Zhu,Jian Zhang,Lei Zhang

doi:10.1039/c9sc02503k

Yu Zhu, Jian Zhang + Show 1 more

Open Access

https://doi.org/10.1039/c9sc02503k

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Abstract

A series of unprecedented high-nuclearity tin-oxo nanoclusters (up to Sn34 ) with structural diversity have been obtained. The characteristics of the applied solvents had great influence on the assembly of these Sn-O clusters. Pure alcohol environments only gave rise to small clusters of Sn6 , whilst the introduction of water significantly increased the nuclearity to Sn26 , which greatly exceeds those of the known tin-oxo clusters (≤14); the use of aprotic CH3CN finally produced the largest Sn34 to date. Apart from the nuclearity breakthrough, the obtained tin-oxo clusters also present new structural types that are not found in previous reports, including a layered nanorod-like structure of Sn26 and the cage-dimer structure of Sn34 . The layered Sn26 clusters represent good molecular models for SnO2 materials. Moreover, an electrode derived from TOC-17 with a {Sn26 } core shows better electrocatalytic CO2 reduction activity than that from TOC-18 with Sn34 . This work not only provides an efficient methodology for the rational assembly of high-nuclearity Sn-O clusters, but also extends their potential applications in energy conversion.

Highlights

Tin oxide (SnO2) has attracted increasing research attention due to its application in a variety of areas, including gas sensors,1 catalysis,2,3 lithium batteries,4,5 solar cells6,7 and transparent electrodes.8 Some important factors, such as the size, composition, and structure, greatly in uence the electronic and physicochemical properties of SnO2.9–11 it is crucial to understand the binding mode and atomic connectivity of tin oxide materials at the molecular level, which will be bene cial for exploring the structure–property relationship and further achieving precise tuning of the physicochemical properties.As molecular models of tin oxide materials, crystalline tinoxo clusters (TOCs) can provide precise atomic structural information by X-ray diffraction analysis
Pure alcohol environments only gave rise to small clusters of Sn6, whilst the introduction of water significantly increased the nuclearity to Sn26, which greatly exceeds those of the known tin-oxo clusters (#14); the use of aprotic CH3CN produced the largest Sn34 to date
Different from the back-to-back linking mode of two O-capped {Sn3O4} units via PP ligands in TOC-13, the Ocapped {Sn3O4} units in TOC-12 are linked by a Na atom in a face-to-face fashion to form a sandwich-like {Sn3NaSn3} architecture

Summary

Introduction

Tin oxide (SnO2) has attracted increasing research attention due to its application in a variety of areas, including gas sensors,[1] catalysis,[2,3] lithium batteries,[4,5] solar cells[6,7] and transparent electrodes.[8] Some important factors, such as the size, composition, and structure, greatly in uence the electronic and physicochemical properties of SnO2.9–11 it is crucial to understand the binding mode and atomic connectivity of tin oxide materials at the molecular level, which will be bene cial for exploring the structure–property relationship and further achieving precise tuning of the physicochemical properties.As molecular models of tin oxide materials, crystalline tinoxo clusters (TOCs) can provide precise atomic structural information by X-ray diffraction analysis. A series of unprecedented high-nuclearity tin-oxo nanoclusters (up to Sn34) with structural diversity have been obtained. Apart from the nuclearity breakthrough, the obtained tin-oxo clusters present new structural types that are not found in previous reports, including a layered nanorod-like structure of Sn26 and the cage-dimer structure of Sn34.

Results

Conclusion