Formation of Nickel Clusters Wrapped in Carbon Cages: Toward New Endohedral Metallofullerene Synthesis.

Despite the high potential of endohedral metallofullerenes (EMFs) for application in biology, medicine and molecular electronics, and recent efforts in EMF synthesis, the variety of EMFs accessible by conventional synthetic methods remains limited and does not include, for example, EMFs of late transition metals. We propose a method in which EMF formation is initiated by electron irradiation in aberration-corrected high-resolution transmission electron spectroscopy (AC-HRTEM) of a metal cluster surrounded by amorphous carbon inside a carbon nanotube serving as a nanoreactor and apply this method for synthesis of nickel EMFs. The use of AC-HRTEM makes it possible not only to synthesize new, previously unattainable nanoobjects but also to study in situ the mechanism of structural transformations. Molecular dynamics simulations using the state-of-the-art approach for modeling the effect of electron irradiation are performed to rationalize the experimental observations and to link the observed processes with conditions of bulk EMF synthesis.

Direct Measurement of Electron Transfer in Nanoscale Host-Guest Systems: Metallocenes in Carbon Nanotubes.

Electron-transfer processes play a significant role in host-guest interactions and determine physicochemical phenomena emerging at the nanoscale that can be harnessed in electronic or optical devices, as well as biochemical and catalytic systems. A novel method for qualifying and quantifying the electronic doping of single walled carbon nanotubes (SWNTs) using electrochemistry has been developed that establishes a direct link between these experimental measurements and ab initio DFT calculations. Metallocenes such as cobaltocene and methylated ferrocene derivatives were encapsulated inside SWNTs (1.4 nm diameter) and cyclic voltammetry (CV) was performed on the resultant host-guest systems. The electron transfer between the guest molecules and the host SWNTs is measured as a function of shift in the redox potential (E1/2 ) of Co(II) /Co(I) , Co(III) /Co(II) and Fe(III) /Fe(II) . Furthermore, the shift in E1/2 is inversely proportional to the nanotube diameter. To quantify the amount of electron transfer from the guest molecules to the SWNTs, a novel method using coulometry was developed, allowing the mapping of the density of states and the Fermi level of the SWNTs. Correlated with theoretical calculations, coulometry provides an accurate indication of n/p-doping of the SWNTs.

Atomic mechanism of metal crystal nucleus formation in a single-walled carbon nanotube.

Knowing how crystals nucleate at the atomic scale is crucial for understanding, and in turn controlling, the structure and properties of a wide variety of materials. However, because of the scale and highly dynamic nature of nuclei, the formation and early growth of nuclei are very difficult to observe. Here, we have employed single-walled carbon nanotubes as test tubes, and an 'atomic injector' coupled with aberration-corrected transmission electron microscopy, to enable in situ imaging of the initial steps of nucleation at the atomic scale. With three different metals we observed three main processes prior to heterogeneous nucleation: formation of crystal nuclei directly from an atomic seed (Fe), from a pre-existing amorphous nanocluster (Au) or by coalescence of two separate amorphous sub-nanometre clusters (Re). We demonstrate the roles of the amorphous precursors and the existence of an energy barrier before nuclei formation. In all three cases, crystal nucleus formation occurred through a two-step nucleation mechanism.

Host-Guest Hybrid Redox Materials Self-Assembled from Polyoxometalates and Single-Walled Carbon Nanotubes.

The development of next-generation molecular-electronic, electrocatalytic, and energy-storage systems depends on the availability of robust materials in which molecular charge-storage sites and conductive hosts are in intimate contact. It is shown here that electron transfer from single-walled carbon nanotubes (SWNTs) to polyoxometalate (POM) clusters results in the spontaneous formation of host-guest POM@SWNT redox-active hybrid materials. The SWNTs can conduct charge to and from the encapsulated guest molecules, allowing electrical access to >90% of the encapsulated redox species. Furthermore, the SWNT hosts provide a physical barrier, protecting the POMs from chemical degradation during charging/discharging and facilitating efficient electron transfer throughout the composite, even in electrolytes that usually destroy POMs.

Comparison of atomic scale dynamics for the middle and late transition metal nanocatalysts.

Catalysis of chemical reactions by nanosized clusters of transition metals holds the key to the provision of sustainable energy and materials. However, the atomistic behaviour of nanocatalysts still remains largely unknown due to uncertainties associated with the highly labile metal nanoclusters changing their structure during the reaction. In this study, we reveal and explore reactions of nm-sized clusters of 14 technologically important metals in carbon nano test tubes using time-series imaging by atomically-resolved transmission electron microscopy (TEM), employing the electron beam simultaneously as an imaging tool and stimulus of the reactions. Defect formation in nanotubes and growth of new structures promoted by metal nanoclusters enable the ranking of the different metals both in order of their bonding with carbon and their catalytic activity, showing significant variation across the Periodic Table of Elements. Metal nanoclusters exhibit complex dynamics shedding light on atomistic workings of nanocatalysts, with key features mirroring heterogeneous catalysis.

Single-walled carbon nanotubes as nano-electrode and nano-reactor to control the pathways of a redox reaction.

Single-walled carbon nanotubes have been demonstrated as effective nanoscale containers for a redox active organometallic complex Cp(Me)Mn(CO)3, acting simultaneously as nano-electrode and nano-reactor. Extreme spatial confinement of the redox reaction within the nanotubes changes its pathway compared to bulk solution due to stabilisation of a reactive intermediate.