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NANOMOL Report Summary

Project ID: 277784
Funded under: FP7-IDEAS-ERC
Country: United Kingdom

Final Report Summary - NANOMOL (From Nano Test Tube to Nano Reactor: Visualisation, Manipulation and Synthesis of Molecules at Nanoscale)

Everything around us is made of molecules - tiny particles of matter - composition, size and shape of which fully determine the properties of everything, from construction materials to medicines. ERC-funded NANOMOL project was set to revolutionise the way we make and study molecules by bridging the molecular world with the macro world via one-dimensional nanostructures, such as nanotubes and nanofibres.

The first step in this ambitious quest requires the molecules being securely connected with the 1D nanostructures. In this project we determined that the ubiquitous van der Waals forces play a critical role in attachment or encapsulation of the guest-molecules to/in nanotubes. In the case of nanoparticles, their surface charge contributes an additional parameter which can be utilised to control interactions and bonding with 1D nanostructures. Determination of these driving forces enabled efficient assembly of super-structures where molecules or nanoparticles are precisely positioned on or in nanotube or nanofibre. Furthermore, this knowledge provided a powerful tool to control the assembly using external stimuli (temperature, concentration, type of solvent, pH or ionic strength).

1D nanostructures, especially the atomically thin yet extremely robust single-walled carbon nanotubes, represent an excellent platform for high-resolution transmission electron microscopy imaging of individual molecules with atomic resolution thus offering precise structural analysis at the single-molecule level. Within NANOMOL project we developed the first mathematically rigorous and physically complete framework describing interactions of the e-beam with atoms of different molecules, which recently enabled a rational design of the experimental conditions in the electron microscope for damage-free imaging of complex molecules. In addition, our newly acquired knowledge established a basis for the dual use of the e-beam: an imaging tool and a source of energy to promote controlled chemical transformations in molecules while they are imaged in real time with atomic resolution (ChemTEM). This revolutionary concept has provided first ‘movies’ of chemical reactions taking place at the single-molecule level, shedding light on reaction mechanisms, structure and stability of reactive intermediates, the number and the order of reaction steps. NANOMOL gave rise to ChemTEM methodology that is able to discover new, previously unforeseen reactions and to deliver unique products with superior electronic, catalytic, optical and electrochemical properties, as demonstrated in this project.

In order to harness the wealth of fundamental discoveries made at the nanoscale for molecules confined in nanotubes, NANOMOL has established strong links between the chemical processes observed in the microscope with the preparative scale synthesis inside nano-reactors. We have proven a powerful influence of the nanotube diameter and morphology of its channel (e.g. the presence of step-edges) on the pathways of catalytic and non-catalytic reactions, activated by heat, electron beam, light or electrochemical potential. Nanotube diameter is a key factor dictating steric requirements for structures of reaction products (e.g. graphene nanoribbon vs. graphene sheet; para-isomer vs. ortho-isomer of bis-substituted benzene) and in controlling the size, shape and stability of catalytic centres, all of which have enormous potentials for the large scale synthesis of valuable products inaccessible by any other means. Exceptional stability, durability and recyclability of metal catalysts inside nanoreactors demonstrated in NANOMOL opens a door for sustainable use of rare transition metals in preparative catalysis, including industrially highly relevant catalytic hydrogenation and electrocatalytic oxygen reduction reactions, both of which demonstrated outstanding performance in nanoreactors developed in NANOMOL.

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United Kingdom
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