Stabilization of Polyoxometalate Charge Carriers via Redox‐Driven Nanoconfinement in Single‐Walled Carbon Nanotubes

Jordan, Jack W.; Cameron, Jamie M.; Lowe, Grace A.; Rance, Graham A.; Fung, Kayleigh L. Y.; Johnson, Lee R.; Walsh, Darren A.; Khlobystov, Andrei N.; Newton, Graham N.

Abstract

We describe the preparation of hybrid redox materials based on polyoxomolybdates encapsulated within single-walled carbon nanotubes (SWNTs). Polyoxomolybdates readily oxidize SWNTs under ambient conditions in solution, and here we study their charge-transfer interactions with SWNTs to provide detailed mechanistic insights into the redox-driven encapsulation of these and similar nanoclusters. We are able to correlate the relative redox potentials of the encapsulated clusters with the level of SWNT oxidation in the resultant hybrid materials and use this to show that precise redox tuning is a necessary requirement for successful encapsulation. The host–guest redox materials described here exhibit exceptional electrochemical stability, retaining up to 86 % of their charge capacity over 1000 oxidation/reduction cycles, despite the typical lability and solution-phase electrochemical instability of the polyoxomolybdates we have explored. Our findings illustrate the broad applicability of the redox-driven encapsulation approach to the design and fabrication of tunable, highly conductive, ultra-stable nanoconfined energy materials.

Citation

Jordan, J. W., Cameron, J. M., Lowe, G. A., Rance, G. A., Fung, K. L. Y., Johnson, L. R., Walsh, D. A., Khlobystov, A. N., & Newton, G. N. (2022). Stabilization of Polyoxometalate Charge Carriers via Redox‐Driven Nanoconfinement in Single‐Walled Carbon Nanotubes. Angewandte Chemie, 134(8), Article e202115619. https://doi.org/10.1002/ange.202115619

• Journal Article Type: Article
• Acceptance Date: Dec 17, 2021
• Online Publication Date: Jan 3, 2022
• Publication Date: Feb 14, 2022
• Deposit Date: May 20, 2022
• Publicly Available Date: May 24, 2022
• Journal: Angewandte Chemie
• Print ISSN: 0044-8249
• Electronic ISSN: 1521-3757
• Publisher: Wiley
• Peer Reviewed: Peer Reviewed
• Volume: 134
• Issue: 8
• Article Number: e202115619
• DOI: https://doi.org/10.1002/ange.202115619
• Public URL: https://nottingham-repository.worktribe.com/output/7511295
• Publisher URL: https://onlinelibrary.wiley.com/doi/10.1002/ange.202115619
• Additional Information: This is the German version of Angewandte Chemie. Note for articles published since 1962: Do not cite this version alone. Take me to the International Edition version with citable page numbers, DOI, and citation export.