A Simple Approach to the Visible-Light Photoactivation of Molecular Metal Oxides

Fujimoto, Satomi; Cameron, Jamie M.; Wei, Rong Jia; Kastner, Katharina; Robinson, David; Sans, Victor; Newton, Graham N.; Oshio, Hiroki

Abstract

© 2017 American Chemical Society. This study explores a new method to maximize the visible-light-driven photocatalytic performance of organic-inorganic hybrid polyoxometalates (POMs). Experimental and theoretical investigations of a family of phosphonate-substituted POMs show that modification of grafted organic moieties can be used to tune the electronic structure and photoactivity of the metal oxide component. Unlike fully inorganic polyoxotungstates, these organic-inorganic hybrid species are responsive to visible light and function as photocatalysts (λ > 420 nm) in the decomposition of a model environmental pollutant. The degree of photoactivation is shown to be dependent on the nature of the inductive effect exerted by the covalently grafted substituent groups. This study emphasizes the untapped potential that lies in an orbital engineering approach to hybrid-POM design and helps to underpin the next generation of bespoke, robust, and cost-effective molecular metal oxide photoactive materials and catalysts.

Citation

Fujimoto, S., Cameron, J. M., Wei, R. J., Kastner, K., Robinson, D., Sans, V., Newton, G. N., & Oshio, H. (2017). A Simple Approach to the Visible-Light Photoactivation of Molecular Metal Oxides. Inorganic Chemistry, 56(20), 12169-12177. https://doi.org/10.1021/acs.inorgchem.7b01499

• Journal Article Type: Article
• Acceptance Date: Aug 7, 2017
• Online Publication Date: Aug 18, 2017
• Publication Date: Aug 18, 2017
• Deposit Date: Sep 8, 2017
• Publicly Available Date: Aug 19, 2018
• Journal: Inorganic Chemistry
• Print ISSN: 0020-1669
• Electronic ISSN: 1520-510X
• Publisher: American Chemical Society
• Peer Reviewed: Peer Reviewed
• Volume: 56
• Issue: 20
• Pages: 12169-12177
• DOI: https://doi.org/10.1021/acs.inorgchem.7b01499
• Keywords: Polyoxometalates, Photocatalysis, Visible Light, Photochemistry, Electrochemistry, Hybrid materials, Redox Chemistry, Density Functional Theory.
• Public URL: https://nottingham-repository.worktribe.com/output/878135
• Publisher URL: http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b01499
• Additional Information: This document is the Accepted Manuscript version of a Published Work that appeared in final form in Inorganic Chemistry, copyright © American Chemical Society after peer review and technical editing by the publisher.; To access the final edited and published work see http://pubs.acs.org/doi/abs/10.1021/acs.inorgchem.7b01499
• Contract Date: Sep 8, 2017