Hydrophobic Hydration of Xenon and Tetrahydrofuran in Amorphous Solid Water

Abstract

On the basis of temperature-programmed desorption (TPD), interactions of water with polar (tetrahydrofuran (THF)) and nonpolar (Xe) additives were investigated on the surfaces of bare, oxygenated, and CO-chemisorbed Pt(111) substrates, together with amorphous solid water (ASW) and crystalline ice films. The influences of these additives on the crystallization kinetics of water were discussed based on reflection high-energy electron diffraction. The Xe adspecies is hydrated by a water monolayer on the clean and CO-adsorbed Pt(111) substrates, resulting in a sharp Xe TPD peak during ice nucleation, whereas the Xe adspecies capped with the water monolayer is detached gradually from the oxygenated Pt(111), crystalline ice, and ASW surfaces. Results indicate that the hydration of Xe tends to be disturbed when hydrogen bonds are formed with the surface during water deposition. Moreover, when Xe is hydrated on Pt(111), the crystallization is delayed relative to the free water species. This behavior is observed more remarkably using THF adspecies; they tend to quench the spontaneous nucleation of multilayer ASW films because hydrogen bonds are formed with the O moiety. The THF adspecies on the ASW film surface is incorporated in the interior, suggesting that hydration is induced by hydrogen bonds between water and the O moiety of THF.

A temperature programmed desorption study of interactions between water and hydrophobes at cryogenic temperatures

“…It might be presumed that the sharp peaks A and B are indicative of the formation of crystalline CHs. However, no long-range ordering is identified in electron diffraction patterns during the heating process of the composite films till ice Ic is formed at T c = 160 K. 54 The results for crystallization kinetics are fundamentally identical to those using pure ASW films. This is reasonable because most of the nonpolar additives are released in the liquidlike phase prior to crystallization as demonstrated here.…”

Nonaqueous Solvent Adsorption on Transition Metal Surfaces with Density Functional Theory: Interaction of N,N-Dimethylformamide (DMF), Tetrahydrofuran (THF), and Dimethyl Sulfoxide (DMSO) with Ag, Cu, Pt, Rh, and Re Surfaces

“…For example, some experiments have investigated the behavior of DMSO in situ /operando for battery applications. , Some of the fundamental experiments on interactions of solvent molecules with transition metal surfaces have also been carried out as part of studies of metal-catalyzed reactions; for example, spectroscopic observations of THF on Pt(111) were made as part of a study on furan hydrogenation, finding evidence for the upright structure of THF on Pt. A recent study reported experiments on the interactions between THF and water on Pt(111), though this work focused primarily on hydration interactions rather than specific THF-metal interactions. THF adsorption has also been studied on Cu(111), finding evidence that THF adsorbs significantly more strongly on Cu than does its aromatic counterpart, furan.…”