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A zeolitic vanadotungstate family with structural diversity and ultrahigh porosity for catalysis.

ABSTRACT: Design of the structure and composition of crystalline microporous inorganic oxides is of great importance in catalysis. Developing new zeolites is one approach towards this design because of the tunable pore system and high thermal stability. Zeolites are limited to main group elements, which limits their applications in redox catalysis. Another promising choice is zeolitic transition metal oxides providing both porosity and redox activity, thereby further expanding the diversity of porous materials. However, the examples of zeolitic transition metal oxides are rare. Here, we report a new class of zeolitic vanadotungstates with tunable frameworks exhibiting a large porosity and redox activity. The assembly of [W₄O₁₆]^8- units with VO²⁺ forms two isomeric porous frameworks. Owing to the complex redox properties and open porosity, the vanadotungstates efficiently catalyse the selective reduction of NO by NH₃. This finding provides an opportunity for design and synthesis of inorganic multifunctional materials for future catalytic applications.

SUBMITTER: Zhang Z

PROVIDER: S-EPMC6141569 | biostudies-literature | 2018 Sep

REPOSITORIES: biostudies-literature

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A zeolitic vanadotungstate family with structural diversity and ultrahigh porosity for catalysis.

Zhang Zhenxin Z Zhu Qianqian Q Sadakane Masahiro M Murayama Toru T Hiyoshi Norihito N Yamamoto Akira A Hata Shinichi S Yoshida Hisao H Ishikawa Satoshi S Hara Michikazu M Ueda Wataru W

Nature communications 20180917 1

Design of the structure and composition of crystalline microporous inorganic oxides is of great importance in catalysis. Developing new zeolites is one approach towards this design because of the tunable pore system and high thermal stability. Zeolites are limited to main group elements, which limits their applications in redox catalysis. Another promising choice is zeolitic transition metal oxides providing both porosity and redox activity, thereby further expanding the diversity of porous mate ...[more]

PMID: 30224654

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Project description:We describe why the cyclic heteropolyanion [P8W48O184]40- (abbreviated as {P8W48}) is an ideal building block for the construction of intrinsically porous framework materials by classifying and analyzing >30 coordination polymers incorporating this polyoxometalate (POM) ligand. This analysis shows that the exocyclic coordination of first-row transition metals (TMs) to {P8W48} typically yields frameworks which extend through {W-O-TM-O-W} bridges in one, two, or three dimensions. However, despite the rich structural diversity of such compounds, the coordination of TMs to the {P8W48} ring is poorly understood, and therefore largely unpredictable, and had not until now been present with any structural classification that could allow rational design. Herein, not only do we present a new approach to understand and classify this new class of materials, we also present three {P8W48}-based frameworks which complement those frameworks which have previously been described. These new compounds help us postulate a new taxonomy of these materials. This is possible because the TM coordination sites of the {P8W48} ring are found, once fully mapped, to lead to well-defined classes of connectivity. Together, analysis provides insight into the nature of the building block connectivity within each framework, to facilitate comparisons between related structures, and to fundamentally unite this family of compounds. Hence we have tentatively named these compounds as "POMzites" to reflect the POM-based composition and zeolitic nature of each family member, although crucially, POMzites differ from zeolites in the modular manner of their preparation. As the synthesis of further POMzites is anticipated, the classification system and terminology introduced here will allow new compounds to be categorized and understood in the context of the established materials. A better understanding of TM coordination to the {P8W48} ring may allow the targeted synthesis of new frameworks rather than the reliance on serendipity apparent in current methods.

Dataset Information

A zeolitic vanadotungstate family with structural diversity and ultrahigh porosity for catalysis.

Publications

A zeolitic vanadotungstate family with structural diversity and ultrahigh porosity for catalysis.

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