Boron nitride nanotube precursor formation during high-temperature synthesis: kinetic and thermodynamic modelling.

We performed integrated modelling of the chemical pathways of formation for boron nitride nanotube (BNNT) precursors during high-temperature synthesis in a B/N2mixture. Integrated modelling includes quantum chemistry, Quantum-classical molecular dynamics, thermodynamic modelling, and kinetic approaches. We demonstrate that BN compounds are formed via the interaction of molecular nitrogen with small boron clusters, rather than through interactions with less reactive liquid boron. (This process can also be described as N2molecule fixation.) Liquid boron evaporates to produce these boron clusters (Bmwithm≤ 5), which are subsequently converted into BmNnchains. The production of such chains is crucial to the growth of BNNTs because these chains form the building blocks of bigger and longer BN chains and rings, which are in turn the building blocks of fullborenes and BNNTs. Additionally, kinetic modelling revealed that B4N4and B5N4species in particular play a major role in the N2molecule fixation process. The formation of these species via reactions with B4and B5clusters is not adequately described under the assumption of thermodynamic equilibrium, as is demonstrated in our kinetic modelling. Thus, the accumulation of both B4N4and B5N4depends on the background gas pressure and the gas cooling rate. Long BN chains and rings, which are precursors of the fullborene and BNNT growth, form via self-assembly of components B4N4and B5N4. Our modelling results-particularly the increased densities of B4N4and B5N4species at higher gas pressures-explain the experimentally observed effect of gas pressure on the yield of high-quality BNNTs. The catalytic role of hydrogen was also studied; it is shown that HBNH molecules can be the main precursor of BNNT synthesis in the presence of hydrogen.