Electrochemistry of redox-active molecules confined within narrow carbon nanotubes
Confinement of molecules within nanocontainers can be a powerful tool for controlling the states of guest-molecules, tuning properties of host-nanocontainers and triggering the emergence of synergistic properties within the host-guest systems. Among nanocontainers, single-walled carbon nanotubes - a...
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| Published in | Chemical Society reviews Vol. 5; no. 19; pp. 1895 - 1916 |
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| Main Authors | , , , , , |
| Format | Journal Article |
| Language | English |
| Published |
London
Royal Society of Chemistry
04.10.2021
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| Subjects | |
| Online Access | Get full text |
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| Summary: | Confinement of molecules within nanocontainers can be a powerful tool for controlling the states of guest-molecules, tuning properties of host-nanocontainers and triggering the emergence of synergistic properties within the host-guest systems. Among nanocontainers, single-walled carbon nanotubes - atomically thin cylinders of carbon, with typical diameters below 2 nm and lengths reaching macroscopic dimensions - are ideal hosts for a variety of materials, including inorganic crystals, and organic, inorganic and organometallic molecules. The extremely high aspect ratio of carbon nanotubes is complemented by their functional properties, such as exceptionally high electrical conductivity and thermal, chemical and electrochemical stability, making carbon nanotubes ideal connectors between guest-molecules and macroscopic electrodes. The idea of harnessing nanotubes both as nanocontainers and nanoelectrodes has led to the incorporation of redox-active species entrapped within nanotube cavities where the host-nanotubes may serve as conduits of electrons to/from the guest-molecules, whilst restricting the molecular positions, orientations, and local environment around the redox centres. This review gives a contemporary overview of the status of molecular redox chemistry within ultra-narrow carbon nanotubes (nanotubes with diameters approaching molecular dimensions) highlighting the opportunities, pitfalls, and gaps in understanding of electrochemistry in confinement, including the role of nanotube diameter, size and shape of guest-molecules, type of electrolyte, solvent and other experimental conditions.
Entrapment of molecules within carbon nanotubes allows investigation of their redox properties in confinement, leading to materials with high electrochemical activity and durability, and with their electrochemical properties at nanoscale still to be fully understood. |
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| Bibliography: | a cross-faculty research facility developing correlative imaging techniques and analysis methods for nanomaterials. Jack W. Jordan is a research associate at the University of Nottingham, UK. He received his MSci in Chemistry from Nottingham in 2016 and carried out his PhD in the Chemistry department under the supervision of Prof. Andrei Khlobystov and Dr. Graham Newton, investigating the properties of polyoxometalates encapsulated within nanotubes, graduating in 2021. He was awarded the EPSRC Postdoctoral prize in his final year, allowing him to further his PhD research into the applications of encapsulated polyoxometalates in the Nottingham Applied Materials & Interfaces group (NAMI Andrei N. Khlobystov is a Professor of Nanomaterials at the University of Nottingham. His research is focused on the chemistry at the nanoscale, particularly reactions confined in nanocontainers. He applied nanotube-based nanoreactors to drive thermally, photo- and electrochemically activated reactions at the macroscale, as well as at the single-molecule level. More recently, in collaboration with the NAMI group, he has been developing carbon nanotubes as electrochemically active nanocontainers, with the potential for energy storage and electrocatalysis. Between 2012 and 2019 he was director of the Nanoscale and Microscale Research Centre Graham N. Newton obtained his PhD from the University of Glasgow (UK) in 2009. After carrying out a JSPS postdoctoral research fellowship he was appointed Assistant Professor at the University of Tsukuba, Japan, in 2011 before moving to the University of Nottingham, UK, in 2015. His research interests include the synthesis and characterisation of redox-active materials, from molecular species through to complex nanomaterials. He has a particular interest in the development of organic-inorganic hybrid molecular metal oxides for applications in energy storage and photocatalysis. www.thenamilab.com Lee R. Johnson received his undergraduate degree from Newcastle University and his PhD from the University of Nottingham (2011). He then joined the research group of Prof. P. G. Bruce FRS at the University of Oxford, where he studied the elementary processes taking place within the lithiumoxygen battery. In 2017, he moved to the University of Nottingham where he was awarded a Nottingham Research Fellowship, followed by an EPSRC Fellowship in 2018. He is currently an Associate Professor in the School of Chemistry. His current research interests focus on understanding interfacial reactions, degradation, and charge transfer, in electrochemical energy devices. Darren A. Walsh obtained his PhD from Dublin City University (Ireland) in 2002. After carrying out postdoctoral research at the University of Texas at Austin, he was appointed Lecturer in Physical Chemistry at Newcastle University. He subsequently moved to the University of Nottingham, where he is currently Associate Professor of Physical Chemistry. His research interests include the development and applications of electrochemical methods, with particular emphasis on the development of electrocatalysts and electrolytes for electrochemical energy conversion and storage. www.nottingham.ac.uk/nmrc William J. V. Townsend completed his MSci in Chemistry at the University of Nottingham in 2018. He continued at the University of Nottingham where he is currently a PhD researcher (Low-Dimensional Materials & Interfaces EPSRC doctoral training programme) under the supervision of Prof. Khlobystov, Dr. Newton and Dr. Johnson. His current research interests include the investigation of redox active species encapsulated in carbon nanotubes for energy materials. . ObjectType-Article-2 SourceType-Scholarly Journals-1 ObjectType-Feature-3 content type line 23 ObjectType-Review-1 |
| ISSN: | 0306-0012 1460-4744 |
| DOI: | 10.1039/d1cs00478f |