Probing the energetics of organic-nanoparticle interactions of ethanol on calcite

Abstract

Knowing the nature of interactions between small organic molecules and surfaces of nanoparticles (NP) is crucial for fundamental understanding of natural phenomena and engineering processes. Herein, we report direct adsorption enthalpy measurement of ethanol on a series of calcite nanocrystals, with the aim of mimicking organic-NP interactions in various environments. The energetics suggests a spectrum of adsorption events as a function of coverage: strongest initial chemisorption on active sites on fresh calcite surfaces, followed by major chemical binding to form an ethanol monolayer and, subsequently, very weak, near-zero energy, physisorption. These thermochemical observations directly support a structure where the ethanol monolayer is bonded to the calcite surface through its polar hydroxyl group, leaving the hydrophobic ends of the ethanol molecules to interact only weakly with the next layer of adsorbing ethanol and resulting in a spatial gap with low ethanol density between the monolayer and subsequent added ethanol molecules, as predicted by molecular dynamics and density functional calculations. Such an ordered assembly of ethanol on calcite NP is analogous to, although less strongly bonded than, a capping layer of organics intentionally introduced during NP synthesis, and suggests a continuous variation of surface structure depending on molecular chemistry, ranging from largely disordered surface layers to ordered layers that nevertheless are mobile and can rearrange or be displaced by other molecules to strongly bonded immobile organic capping layers. These differences in surface structure will affect chemical reactions, including the further nucleation and growth of nanocrystals on organic ligand-capped surfaces.

Keywords: adsorption calorimetry; biomineralization; carbonate formation; ligand-capped nanocrystal; thermodynamics.

Fig. 1.

(A) Ethanol adsorption isotherms, (B) corresponding differential, and (C) integral enthalpies of ethanol adsorption for nanophase calcite samples at 25 °C.

Fig. 2.

(A) Water and ethanol adsorption isotherms, (B) corresponding differential, and (C) integral enthalpies of adsorption for the nanophase calcite NMT-2, at 25 °C. The water adsorption calorimetry data for NMT-2 are reproduced from ref. .

Fig. 3.

(A) Free energies and (B) differential entropies of water (blue) and ethanol (red) adsorption at 25 °C on NMT-2.