Entrapment, Manipulation and Reactions of Molecules at the Nanoscale

Lead Research Organisation: University of Nottingham
Department Name: Sch of Chemistry


This project addresses one of the most fundamental challenges of science related to control of positions, orientations and kinetic energy of molecules at the nanoscale. Innovative methodologies for confinement of molecules in 1D (nanotube) and 2D (graphene) nanomaterials will be developed in this project in order to study their behaviour and to harness their functional properties.
Single-walled carbon nanotubes (internal diameter 1-2 nm) are the world's tiniest test tubes which allow effective entrapment of molecules in cylindrical cavities, where degrees of freedom are significantly limited. Fullerenes, for example, employed as a model molecules in previous studies have clearly demonstrated that positions, orientations, translational and rotational motions of the molecules - all are significantly influenced by the host nanotube [Acc. Chem. Res., 2005, 38, 901]. In this project, we shall expand this concept and introduce active control of the molecular behaviour, using the nanotube as a nanoscale conduit of electrons or phonons, or a nano-antenna harvesting electromagnetic radiation and transferring the energy to entrapped molecules. One of the objectives is to trigger and control reactions of the molecules, and to steer their transformations to desired products at the single-molecule level [ACS Nano, 2017, in press, http://pubs.acs.org/doi/abs/10.1021/acsnano.6b08228 ], which can potentially revolutionise the way we study chemical reactions and make materials.
The approaches developed for nanotubes in this project will be transferred to molecules entrapped on graphene monolayer or within graphene bi-layer, where the principles of 1D confinement in nanotubes will be expanded and explored in 2D. In particular, intermolecular reactions leading to chain-like or ribbon-like products in 1D [Nature Mater., 2011, 10, 687] will be harnessed for molecules on graphene to construct covalent organic framework (COF) materials with bespoke structure and composition, and tuneable electronic and optical properties, thus addressing one of the most critical challenges of the graphene technology.


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Studentship Projects

Project Reference Relationship Related To Start End Student Name
EP/N50970X/1 01/10/2016 30/09/2021
1938907 Studentship EP/N50970X/1 01/10/2017 30/06/2021 Luke Norman
Description It has been discovered that when some crystal systems (e.g. OsS2) are confined and grow along only a single dimension, this can dramatically change the stoichiometry (elemental composition) of the resulting material compared to the same material growing in three dimensions. The calculation of the stoichiometry was achieved via a simple calculation and was tested experimentally using energy-dispersive x-ray analysis and x-ray photoelectron spectroscopy.
Exploitation Route Others, in the future, may want to test other systems that are more complex and perform the same analysis to test if the stoichiometry is affected by growth restrictions.
Sectors Chemicals

Description Collaboration with Ulm University 
Organisation University of Ulm
Country Germany 
Sector Academic/University 
PI Contribution I produced materials that are encapsulated inside carbon nanotubes using a wide variety of techniques.
Collaborator Contribution The team at SALVE (sub-angstrom low voltage electron microscopy) imaged the samples using aberration-corrected transmission electron microscopy.
Impact Production of a 1st year PhD report and 2nd year paper draft that is due to be submitted soon.
Start Year 2017
Description Collaboration with University of Valencia 
Organisation University of Valencia
Country Spain 
Sector Academic/University 
PI Contribution I encapsulated metal sulfide clusters into carbon nanotubes and performed a holistic analytical approach on the material. This approach consisted of: transmission electron microscopy (to image the material and check if the encapsulation was successful), energy-dispersive x-ray analysis (elemental composition) and Raman spectroscopy (to understand electronic communication between the host and guest).
Collaborator Contribution The team at the University of Valencia synthesised the metal sulfide clusters and characterised them.
Impact Production of 1st year PhD report. Beginning to write paper on findings. This collaboration is not multi-disciplinary,
Start Year 2017