A Thermodynamic Discriminator for Carbon Nanomaterials

TL;DR

This study introduces a thermodynamic approach to distinguish carbon nanomaterials based on their unique effects on micellar self-assembly, revealing surface-specific behaviors and potential applications in energy and bioenergetics.

Contribution

It presents a novel thermodynamic discriminator that differentiates carbon nanomaterials by analyzing their influence on micelle formation and stability.

Findings

Graphene uniquely disrupts micelle self-assembly regardless of surfactant charge.

Temperature measurements show a monotonic decrease during micelle formation with graphene.

Enthalpy varies with nanomaterial type, indicating surface-specific thermodynamic signatures.

Abstract

Interaction between carbon nanomaterials and micellar substrates is studied. A notable observation is the dependence of nano-surface topology on thermodynamic signatures of the carbon nanomaterials e.g., single wall carbon nanotube (SWNT), multiwall carbon nanotube (MWNT) and graphene. The disruption of the self assembly process while the micelles were converted to monomer has a unique character in presence of graphene. This unique behavior follows irrespective of whether the micelle forming monomer is anionic (Sodium dodecyl sulfate) or cationic(Cetrimonium bromide). The direct measurement of temperature(T) also indicates that T falls monotonically as the micelles are formed in presence of graphene, this being different in all other cases (SWNT and MWNT). The photon correlation studies indicated formation of smaller and well distributed micelles in contact with graphene,this being not the case with SWNT and MWNT. Importantly the free energy change corresponding to the micelle formation has same order of magnitude (-26 to -25 KJ/Mole), the enthalpy showing a nanosurface specific value that varies between -9 to +7 KJ /mole depending on the nature of the nanomaterial and that of the self assembling micellar monomer. The constancy of the free energy and surface dependent vaiations of enthalpy implies that an entropy enthalpy compensation (free energy being a linear combination of the two) is inevitable in the self assembly process. The micellar cooling induced by graphene further implies a possible potential of the nano-embedded self assembly in fields like energy harnessing and bioenergetic manipulations. .