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Issue 40, 2017
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A Waugh type [CoMo9O32]6− cluster with atomically dispersed CoIV originates from Anderson type [CoMo6O24]3− for photocatalytic oxygen molecule activation

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Abstract

An atomically dispersed Waugh type [CoMo9O32]6− cluster is obtained, employing the most flexible structure unit Anderson type [Co(OH)6Mo6O18]3− as a precursor. The structure of the [CoMo9O32]6− cluster is identified by single crystal X-ray diffraction and also well characterized by FT-IR, ESI-MS, UV-Vis, EA, and TGA spectroscopy. Its 3D framework forms a quasi 2D material and possesses curved edge triangle shape nanopores with a diameter of 8.9 Å. The CoIV and MoVI oxidation states and the related valence band and electronic state of Co are definitely confirmed by X-ray photoelectron spectroscopy (XPS), ultraviolet photoemission spectroscopy (UPS), and bond valence sum (BVS). The [CoMo9O32]6− cluster is a typical n-type inorganic semiconductor with a HOMO–LOMO gap of ca. 1.67 eV and exhibits reversible two-electron redox properties, evidenced by UPS, cyclic voltammetric (CV), and Mott–Schottky plot analyses. Furthermore, [CoMo9O32]6− can effectively generate 1O2 under laser (365 and 532 nm) and sunlight irradiation, detected using a water-soluble DAB probe. Such an n-type multielectron reservoir semiconductor anionic [CoMo9O32]6− cluster with thermal and electrochemical stability as an effective photosensitizer serves as a promising material in solar energy scavenging.

Graphical abstract: A Waugh type [CoMo9O32]6− cluster with atomically dispersed CoIV originates from Anderson type [CoMo6O24]3− for photocatalytic oxygen molecule activation

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Publication details

The article was received on 18 Jun 2017, accepted on 10 Jul 2017 and first published on 12 Jul 2017


Article type: Paper
DOI: 10.1039/C7NR04373B
Citation: Nanoscale, 2017,9, 15332-15339
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    A Waugh type [CoMo9O32]6− cluster with atomically dispersed CoIV originates from Anderson type [CoMo6O24]3− for photocatalytic oxygen molecule activation

    Y. Chen, C. Zhang, C. Yang, J. Zhang, K. Zheng, Q. Fang and G. Li, Nanoscale, 2017, 9, 15332
    DOI: 10.1039/C7NR04373B

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