Both Inter- and Intramolecular Coupling of O-H Groups Determine the Vibrational Response of the Water/Air Interface

Vibrational coupling is relevant not only for dissipation of excess energy after chemical reactions but also for elucidating molecular structure and dynamics. It is particularly important for OH stretch vibrational spectra of water, for which it is known that in bulk both intra- and intermolecular coupling alter the intensity and line shape of the spectra. In contrast with bulk, the unified picture of the inter/intra-molecular coupling of OH groups at the water-air interface has been lacking. Here, combining sum-frequency generation experiments and simulation for isotopically diluted water and alcohols, we unveil effects of inter- and intramolecular coupling on the vibrational spectra of interfacial water. Our results show that both inter- and intramolecular coupling contribute to the OH stretch vibrational response of the neat H2O surface, with intramolecular coupling generating a double-peak feature, while the intermolecular coupling induces a significant red shift in the OH stretch response

Surface-charge-induced orientation of interfacial water suppresses heterogeneous ice nucleation on α-alumina (0001)

Surface charge is one of the surface properties of atmospheric aerosols, which has been linked to heterogeneous ice nucleation and hence cloud formation, microphysics, and optical properties. Despite the importance of surface charge for ice nucleation, many questions remain on the molecular-level mechanisms at work. Here, we combine droplet-freezing assay studies with vibrational sum frequency generation (SFG) spectroscopy to correlate interfacial water structure to surface nucleation strength. We study immersion freezing of aqueous solutions of various pHs on the atmospherically relevant aluminum oxide α-Al2O3 (0001) surface using an isolated droplet on the surface. The high-pH solutions freeze at temperatures higher than that of the low-pH solution, while the neutral pH has the highest freezing temperature. On the molecular level, the SFG spectrum of the interfacial water changes substantially upon freezing. At all pHs, crystallization leads to a reduction of intensity of the 3400 cm−1 water resonance, while the 3200 cm−1 intensity drops for low pH but increases for neutral and high pHs. We find that charge-induced surface templating suppresses nucleation, irrespective of the sign of the surface charge. Heterogeneous nucleation is most efficient for the nominally neutral surface

Probing the Charge Separation Process on In2S3/Pt-TiO2 Nanocomposites for Boosted Visible-light Photocatalytic Hydrogen Production

A simple refluxing wet-chemical approach is employed for fabricating In2S3/Pt-TiO2 heterogeneous catalysts for hydrogen generation under visible light irradiation. When the mass ratio between Pt-TiO2 and cubic-phased In2S3 (denoted as In2S3/Pt-TiO2) is two, the composite catalyst shows the highest hydrogen production, which exhibits an 82-fold enhancement over in-situ deposited Pt-In2S3. UV-vis diffuse reflectance and valence band X-ray photoelectron spectra elucidate that the conduction band of In2S3 is 0.3 eV more negative compared to that of TiO2, favoring charge separation in the nanocomposites. Photoelectrochemical transient photo-current measurements and optical pump - terahertz probe spectroscopic studies further corroborate the charge separation in In2S3/Pt-TiO2. The migration of photo-induced electrons from the In2S3 conduction band to the TiO2 conduction band and subsequently into the Pt nanoparticles is found to occur within 5 picoseconds. Based on the experimental evidence, a charge separation process is proposed which accounts for the enhanced activity exhibited by the In2S3/Pt-TiO2 composite catalysts

Multiscale Effects of Interfacial Polymer Confinement in Silica Nanocomposites

Dispersing hydrophilic nanofillers in highly hydrophobic polymer matrices is widely used to tune the mechanical properties of composite material systems. The ability to control the dispersion of fillers is closely related to the mechanical tunability of such composites. In this work, we investigate the physical–chemical underpinnings of how simple end-group modification to one end of a styrene–butadiene chain modifies the dispersion of silica fillers in a polymer matrix. Using surface-sensitive spectroscopies, we directly show that polymer molecular orientation at the silica surface is strongly constrained for silanol functionalized polymers compared to nonfunctionalized polymers because of covalent interaction of silanol with silica. Silanol functionalization leads to reduced filler aggregation in composites. The results from this study demonstrate how minimal chemical modifications of polymer end groups are effective in modifying microstructural properties of composites by inducing molecular ordering of polymers at the surface of fillers

Experimental and theoretical evidence for bilayer-by-bilayer surface melting of crystalline ice

On the surface of water ice, a quasi-liquid layer (QLL) has been extensively reported at temperatures below its bulk melting point at 273 K. Approaching the bulk melting temperature from below, the thickness of the QLL is known to increase. To elucidate the precise temperature variation of the QLL, and its nature, we investigate the surface melting of hexagonal ice by combining noncontact, surface-specific vibrational sum frequency generation (SFG) spectroscopy and spectra calculated from molecular dynamics simulations. Using SFG, we probe the outermost water layers of distinct single crystalline ice faces at different temperatures. For the basal face, a stepwise, sudden weakening of the hydrogen-bonded structure of the outermost water layers occurs at 257 K. The spectral calculations from the molecular dynamics simulations reproduce the experimental findings; this allows us to interpret our experimental findings in terms of a stepwise change from one to two molten bilayers at the transition temperature