Flexoelectricity and the Formation of Carbon Nanoparticles in Flames

The formation of carbon nanoparticles in flames involves a nucleation step that remains poorly understood. Experimentally, carbon nuclei formation is known to depend strongly on the electrical aspects of combustion but modes of interaction between charged species in the flame and carbon precursors have yet to be found. We present evidence for flexoelectrically polarised aromatics contributing to carbon nanoparticulate nucleation. We imaged the nascent nanoparticles using high resolution transmission electron microscopy, which revealed that the majority of aromatics in the early carbon nanoparticles are fullerene-like and curved. The curvature induces a significant molecular flexoelectric dipole moment in the polyaromatic hydrocarbons. This electric polarization allows these molecules to strongly interact with chemi-ions produced during combustion, which we demonstrate using electronic structure calculations. The results indicate that the physical interaction between fullerene-like polar aromatics and chemi-ions is critically assisting the nucleation, and opens a new route to reduce pollution and improve flame-produced nanomaterials

Polar curved polycyclic aromatic hydrocarbons in soot formation

© 2018 The Combustion Institute. In this paper, we consider the impact of polar curved polycyclic aromatic hydrocarbons (cPAH) on the process of soot formation by employing electronic structure calculations to determine the earliest onset of curvature integration and the binding energy of curved homodimers. The earliest (smallest size) onset of curvature integration was found to be a six ring PAH with at least one pentagonal ring. The σ bonding in the presence of pentagons led to curvature, however, the π bonding strongly favored a planar geometry delaying the onset of curvature and therefore the induction of a flexoelectric dipole moment. The binding energies of cPAH dimers were found to be of similar magnitude to flat PAH containing one or two pentagons, with an alignment of the dipole moments vectors. For the more curved structures, steric effects reduced the dispersion interactions to significantly reduce the interaction energy compared with flat PAH. Homogeneous nucleation of cPAH at flame temperatures then appears unlikely, however, significant interactions are expected between chemi-ions and polar cPAH molecules suggesting heterogeneous nucleation should be explored.This project is supported by the National Research Foundation (NRF), Prime Minister’s Office, Singapore under its Campus for Research Excellence and Technological Enterprise (CREATE) programme

Protein-Mimetic, Molecularly Imprinted Nanoparticles for Selective Binding of Bile Salt Derivatives in Water

A tripropargylammonium surfactant with a methacrylate-terminated hydrophobic tail was combined with a bile salt derivative, divinyl benzene (DVB), and a photo-cross-linker above its critical micelle concentration (CMC). Surface-cross-linking with a diazide, surface-functionalization with an azido sugar derivative, and free-radical-core-cross-linking under UV irradiation yielded molecularly imprinted nanoparticles (MINPs) with template-specific binding pockets. The MINPs resemble protein receptors in size, complete water-solubility, and tailored binding sites in their hydrophobic cores. Strong and selective binding of bile salt derivatives was obtained, depending on the cross-linking density of the system