Toby Sainsbury

Oxygen Radical Functionalization of Boron Nitride Nanosheets

The covalent chemical functionalization of exfoliated hexagonal boron-nitride nanosheets (BNNSs) is achieved by the solution-phase oxygen radical functionalization of boron atoms in the h-BN lattice. This involves a two-step procedure to initially covalently graft alkoxy groups to boron atoms and the subsequent hydrolytic defunctionalization of the groups to yield hydroxyl-functionalized BNNSs (OH-BNNSs). Characterization of the functionalized-BNNSs using HR-TEM, Raman, UV-vis, FTIR, NMR, and TGA was performed to investigate both the structure of the BNNSs and the covalent functionalization methodology. OH-BNNSs were used to prepare polymer nanocomposites and their mechanical properties analyzed. The influence of the functional groups grafted to the surface of the BNNSs is investigated by demonstrating the impact on mechanical properties of both noncovalent and covalent bonding at the interface between the nanofiller and polymer matrixes.

Covalently Functionalized Hexagonal Boron Nitride Nanosheets by Nitrene Addition

The covalent functionalization of exfoliated hexagonal boron nitride (h-BN) nanosheets by nitrene addition is described. Integration of functionalized h-BN nanosheets within a polycarbonate matrix is demonstrated and was found to afford significant increases in mechanical properties. This integration methodology was further extended by the covalent modification of the h-BN nanosheets with polymer chains of a polycarbonate analogue, and the integration of the polymer modified h-BN within the polymer matrix.

Covalent Carbene Functionalization of Graphene: Toward Chemical Band-Gap Manipulation.

In this work, we employ dibromocarbene (DBC) radicals to covalently functionalize solution exfoliated graphene via the formation of dibromocyclopropyl adducts. This is achieved using a basic aqueous/organic biphasic reaction mixture to decompose the DBC precursor, bromoform, in conjunction with a phase-transfer catalyst to facilitate ylide formation and carbene migration to graphene substrates. DBC-functionalized graphene (DBC-graphene) was characterized using a range of spectroscopic and analytical techniques to confirm the covalent nature of functionalization. Modified optical and electronic properties of DBC-graphene were investigated using UV-vis spectroscopy, analysis of electrical I-V transport properties, and noncontact terahertz time-domain spectroscopy. The implications of carbene functionalization of graphene are considered in the context of scalable radical functionalization methodologies for bulk-scale graphene processing and controlled band-gap manipulation of graphene.

Excitons at the B K edge of boron nitride nanotubes probed by x-ray absorption spectroscopy

We have performed a near-edge x-ray absorption fine-structure (NEXAFS) investigation of multi-walled boron nitride nanotubes (BNNTs). We show that the one-dimensionality of BNNTs is clearly evident in the B K edge spectrum, while the N K edge spectrum is similar to that of layered hexagonal BN (h-BN). We observe a sharp feature at the σ* onset of the B K edge, which we ascribe to a core exciton state. We also report a comparison with spectra taken after an ammonia plasma treatment, showing that the B K edge becomes indistinguishable from that of h-BN, due to the breaking of the tubular order and the formation of small h-BN clusters.

Terahertz time-domain spectroscopy as a novel metrology tool for liquid-phase exfoliated few-layer graphene

Few-layer graphene (FLG) platelets exfoliated directly from graphite are finding a wide range of potential applications, including composites and printed electronics. However, characterisation of the FLG material following incorporation into polymers, including the quality of the dispersion, remains a challenge. Here, we present the use of terahertz time-domain spectroscopy as a potential solution to this challenge which could form the basis of a rapid characterisation tool. The THz refractive index was found to be highly sensitive to the loading of FLG, opening the route to mapping local FLG concentration within a polymer composite sample. By fitting the measured permittivity of the flakes to the Drude-Smith model of conductivity, we also show that the carrier concentrations of these materials are comparable to un-doped chemical vapour deposition produced materials. The ability to measure electronic properties of FLG following processing is important to ensure that defects have not been introduced or chemical functionalisation removed during processing.