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Waugh type [CoMo9O32]6- cluster with atomically dispersed Co3+ derives from Anderson type [CoMo6O24]3- for photocatalytic oxygen molecule activation

Abstract

Atomically dispersed Waugh type [CoMo9O32]6- cluster is obtained, employing the most flexible structure unit Anderson type [Co(OH)6Mo6O18]3- as precursor. The structure of [CoMo9O32]6- cluster is identified by the single crystal X-ray diffraction and also well characterized by FT-IR, ESI-MS, UV-Vis, EA, and TGA spectroscopy. Its 3D framework forms quasi 2D material and possesses curved edge triangle shape nanoporous with diameter of 8.9 Å. The CoIII and MoV oxidation state and the related valence band and electronic state of CoIII 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 HOMO-LOMO gap of ca. 1.67 eV and exhibits reversible two-electron redox property, evidenced by UPS, cyclic voltammetric (CV), and Mott-schottky plot analyses. Furthermore, the [CoMo9O32]6- can effectively generate 1O2 under laser (365 and 532 nm) and sunlight irradiation, detected by water-soluble DAB probe. Such n-type multielectron reservoir semiconductor anionic cluster [CoMo9O32]6- with thermal and electrochemical stability as effective photosensitizer served as promising material in solar energy scavenging.

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Supplementary files

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, Accepted Manuscript
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    Waugh type [CoMo9O32]6- cluster with atomically dispersed Co3+ derives from Anderson type [CoMo6O24]3- for photocatalytic oxygen molecule activation

    Y. Chen, C. Zhang, Y. Caoping, J. Zhang, K. zheng, Q. Fang and G. Li, Nanoscale, 2017, Accepted Manuscript , DOI: 10.1039/C7NR04373B

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