Orientation Of Interfacial Water Research Articles

Orientational dynamics of the water layer adjacent to Au surface accelerated by polarization effect.

The orientation and rearrangement of water on a gold electrode significantly influences its physicochemical heterogeneous performance. Despite numerous experimental and theoretical studies aimed at uncovering the structural characteristics of interfacial water, the orientational behavior resulting from electrode-induced rearrangements remains a subject of ongoing debate. Here, we employed molecular dynamics simulations to investigate the adaptive structure and dynamics properties of interfacial water on Au(111) and Au(100) surfaces by considering a polarizable model for Au atoms in comparison with the non-polarizable model. Compared to the nonpolarizable systems, the polarization effect can enhance the interaction between water molecules and the gold surface. Unexpectedly, the rotational dynamics directly associated with the orientational behavior of water adjacent to the gold surface is accelerated, thereby reducing the hydrogen bond lifetime. The underlying mechanism for this anomalous phenomenon originates from the polarization effect, which induces the attraction of the positive hydrogen atoms to the surface by the negative image charge. This leads to a change in orientation that disrupts the hydrogen bonds in the first water layer and subsequently accelerates reorientation dynamics of water molecules adjacent to the gold surface. These results shed light on the intricate interplay between polarization effects and water molecule dynamics on metal surfaces, establishing the foundation for the rational regulation of the orientation of interfacial water.

Superdiffusive Rotation of Interfacial Water on Noble Metal Surface.

Interfacial water on a metal surface acts as an active layer through the reorientation of water, thereby facilitating the energy transfer and chemical reaction across the metal surface in various physicochemical and industrial processes. However, how this active interfacial water collectively behaves on flat noble metal substrates remains largely unknown due to the experimental limitation in capturing librational vibrational motion of interfacial water and prohibitive computational costs at the first-principles level. Herein, by implementing a machine-learning approach to train neural network potentials, we enable performing advanced molecular dynamics simulations with ab initio accuracy at a nanosecond scale to map the distinct rotational motion of water molecules on a metal surface at room temperature. The vibrational density of states of the interfacial water with two-layer profiles reveals that the rotation and vibration of water within the strong adsorption layer on the metal surface behave as if the water molecules in the bulk ice, wherein the O-H stretching frequency is well consistent with the experimental results. Unexpectedly, the water molecules within the adjacent weak adsorption layer exhibit superdiffusive rotation, contrary to the conventional diffusive rotation of bulk water, while the vibrational motion maintains the characteristic of bulk water. The mechanism underlying this abnormal superdiffusive rotation is attributed to the translation-rotation decoupling of water, in which the translation is restrained by the strong hydrogen bonding within the bilayer interfacial water, whereas the rotation is accelerated freely by the asymmetric water environment. This superdiffusive rotation dynamics may elucidate the experimentally observed large fluctuation of the potential of zero charge on Pt and thereby the conventional Helmholtz layer model revised by including the contribution of interfacial water orientation. The surprising superdiffusive rotation of vicinal water next to noble metals will shed new light on the physicochemical processes and the activity of water molecules near metal electrodes or catalysts.

Platinum Surface Water Orientation Dictates Hydrogen Evolution Reaction Kinetics in Alkaline Media.

The fundamental understanding of sluggish hydrogen evolution reaction (HER) kinetics on a platinum (Pt) surface in alkaline media is a topic of considerable debate. Herein, we combine cyclic voltammetry (CV) and electrical transport spectroscopy (ETS) approaches to probe the Pt surface at different pH values and develop molecular-level insights into the pH-dependent HER kinetics in alkaline media. The change in HER Tafel slope from ∼110 mV/decade in pH 7-10 to ∼53 mV/decade in pH 11-13 suggests considerably enhanced kinetics at higher pH. The ETS studies reveal a similar pH-dependent switch in the ETS conductance signal at around pH 10, suggesting a notable change of surface adsorbates. Fixed-potential calculations and chemical bonding analysis suggest that this switch is attributed to a change in interfacial water orientation, shifting from primarily an O-down configuration below pH 10 to a H-down configuration above pH 10. This reorientation weakens the O-H bond in the interfacial water molecules and modifies the reaction pathway, leading to considerably accelerated HER kinetics at higher pH. Our integrated studies provide an unprecedented molecular-level understanding of the nontrivial pH-dependent HER kinetics in alkaline media.

Cation Modifies Interfacial Water Structures on Platinum during Alkaline Hydrogen Electrocatalysis.

The molecular details of an electrocatalytic interface play an essential role in the production of sustainable fuels and value-added chemicals. Many electrochemical reactions exhibit strong cation-dependent activities, but how cations affect reaction kinetics is still elusive. We report the effect of cations (K+, Li+, and Ba2+) on the interfacial water structure using second-harmonic generation (SHG) and classical molecular dynamics (MD) simulation. The second- (χH2O(2)) and third-order (χH2O(3)) optical susceptibilities of water on Pt are smaller in the presence of Ba2+ compared to those of K+, suggesting that cations can affect the interfacial water orientation. MD simulation reproduces experimental SHG observations and further shows that the competition between cation hydration and interfacial water alignment governs the net water orientation. The impact of cations on interfacial water supports a cation hydration-mediated mechanism for hydrogen electrocatalysis; i.e., the reaction occurs via water dissociation followed by cation-assisted hydroxide/water exchange on Pt. Our study highlights the role of interfacial water in electrocatalysis and how innocent additives (such as cations) can affect the local electrochemical environment.

Computational Investigations of the Water Structure at the α-Al2O3(0001)-Water Interface.

The α-Al2O3(0001)-water interface is investigated using ab initio molecular dynamics (AIMD) simulations. The spectral signatures of the vibrational sum frequency generation (vSFG) spectra of OH stretching mode for water molecules at the interface are related to the interfacial water orientation, hydrogen bond network, and water dissociation process at different water/alumina interfaces. Significant differences are found between alumina surfaces at different hydroxylation levels, namely, Al-terminated and O-terminated α-Al2O3(0001). By calculating the vibrational sum frequency generation spectrum and its imaginary component from AIMD results, the structure of interfacial waters as well as the termination of alumina slab are related to the spectral signatures of vSFG data.

Platinum-Water Interaction Induced Interfacial Water Orientation That Governs the pH-Dependent Hydrogen Oxidation Reaction.

Understanding the electrode-water interface structure in acid and alkali is crucial to unveiling the underlying mechanism of pH-dependent hydrogen oxidation reaction (HOR) kinetics. In this work, we construct the explicit Pt(111)-H2O interface models in both acid and alkali to investigate the relationship between the HOR mechanism and electrode-electrolyte interface structure using ab initio molecular dynamics and density functional theory. We find that the interfacial water orientation in the outer Helmholtz layer (OHP) induced by the Pt-water interaction governs the pH-dependent HOR kinetics on Pt(111). In alkali, the strong Pt-interfacial water electrostatic interaction behaves as a narrow OHP, which increases the proportion of "H-down" interfacial water and leads to less adsorbed water entering the inner Helmholtz plane (IHP), decreasing the work function of Pt(111). Furthermore, the more "H-down" interfacial water stabilizes the Had adsorption, prevents Had desorption, and suppresses the Volmer step of HOR by forming the solvated [Had···H2O···H2O] complex. Our work provided a visualized molecular-level mechanism to understand the nature of pH-dependent HOR kinetics.

Water Orientation at the Anatase TiO2 Nanoparticle Interface: A Probe of Surface pKa Values.

The acid-base properties of surfaces significantly influence catalytic and (photo)electrochemical processes. Estimation of acid dissociation constants (pKa values) for colloids is commonly performed through electroanalytical techniques or spectroscopic methods employing label molecules. Here, we show that polarimetric angle-resolved second harmonic scattering (AR-SHS) can be used as an all-optical, label-free probe of colloid surface pKa values. We apply AR-SHS to dispersions of 100 nm anatase TiO2 particles to extract surface potential and surface susceptibility, a measure of interfacial water orientation, as a function of pH. The surface potential follows changes in surface charge density, while the interfacial water orientation inverts at pH ∼4.8, ∼6, and ∼7.6. As the variation in bulk pH modifies the populations of Ti-OH2+, Ti-OH, and Ti-O- interfacial groups, a change in water orientation reports on the ratio of protonated/deprotonated species. Such observation allows for pKa evaluation from plots of surface susceptibility versus pH. A Nerstian trend in the surface potential is additionally demonstrated.

Design of acrylamide-based thermoresponsive copolymer with potential capability for physical network formation in water: a molecular dynamics study

In this work, a new smart copolymer of poly(N-isopropylacrylamide)-b-polyacrylamide-b-poly(N-isopropylacrylamide) (PNIPAm-b-PAM-b-PNIPAm) was designed as an efficient thermo-sensitive polymer with a potential for formation a physical network structure above a certain temperature in water. To design the desired copolymer, molecular behaviors of the copolymer blocks were investigated in water at different blocks fractions and temperatures via atomistic simulation. The blocks were evaluated from the interactional aspects via estimating the electrostatic and van der Waals contributions of their interaction energies with the media to consider the amount of hydrophilicity variation of the blocks with temperature variation. To find the origin of changes in blocks hydrophilicity, the structure and orientation of interfacial water were determined via calculating coordination number and order parameters of the water molecules in the first and second hydration shell of the blocks. In this regard, a novel parameter based on water ordering and hydration level was presented. The PAM block in the copolymer with shorter PNIPAm blocks, particularly 8 mol% (percentage by mole) PNIPAm, enforced the thermoresponsive end blocks to behave like a water-soluble polymer above their lower critical solution temperature. In contrast, increasing the PNIPAm content to 32 mol% caused an interactive competition between the blocks. Finally, the copolymer with the PNIPAm/PAM = 0.19 was found as the most efficient copolymer composition for the mentioned goal via using the analysis of variance (ANOVA) of the calculated responses.

Interaction mechanism of chitosan oligomers in pure water with cell membrane models studied by SFG vibrational spectroscopy

Chitosan is a versatile and biocompatible cationic antimicrobial polymer obtained from sustainable sources that is effective against a wide range of microorganisms. Although it is soluble only at low pH, chitosan oligomers (ChitO) are soluble in pure water and thus more appropriate for antibacterial applications. Although there is a vast literature on chitosan’s antimicrobial activity, the molecular details of its interaction with biomembranes remain unclear. Here we investigate these molecular interactions by resorting to phospholipid Langmuir films (zwitterionic DPPC and anionic DPPG) as simplified membrane models (for mammalian and bacterial membranes, respectively), and using SFG vibrational spectroscopy to probe lipid tail conformation, headgroup dynamics and interfacial water orientation. For comparison, we also investigate the interactions of another simple cationic antimicrobial polyelectrolyte, poly(allylamine) hydrochloride – PAH. By forming the lipid films over the polyelectrolyte solutions, we found that both have only a very small interaction with DPPC, but PAH adsorption is able to invert the interfacial water orientation (membrane potential). This might explain why ChitO is compatible with mammalian cells, while PAH is toxic. In contrast, their interaction with DPPG films is much stronger, even more so for ChitO, with both insertion within the lipid film and interaction with the oppositely charged headgroups. Again, PAH adsorption inverts the membrane potential, while ChitO does not. Finally, ChitO interaction with DPPG is weaker if the antimicrobial is injected underneath a pre-assembled Langmuir film, and its interaction mode depends on the time interval between end of film compression and ChitO injection. These differences between ChitO and PAH effects on the model membranes highlight the importance of molecular structure and intermolecular interactions for their bioactivity, and therefore this study may provide insights for the rational design of more effective antimicrobial molecules.

Can solid surface energy be a predictor of ice nucleation ability?

Surface energy is one of the most important properties of materials that dictate many behaviors such as the spreading of water and ice nucleation. It is commonly thought that low surface energy leads to hydrophobicity and delays ice formation. Conventional studies mainly focus on rough surfaces where surface energy is amplified/reduced accordingly and it remains elusive to clearly decouple the effect of surface energy on ice nucleation. Here we experimentally construct the atomically smooth surfaces of halogen chemistry by varying silane self-assembled monolayers with exactly the same aliphatic chain but varied end groups of F, Cl, Br and I. By analyzing ice nucleation rate and free energy barrier based on the measured freezing temperature/delay time and the classical nucleation theory, we demonstrate that the ice nucleation efficiencies of various halogen chemistry surfaces increase in the order of Br, F, I and Cl, which is inconsistent with the surface energy sequence. The results indicate that solid surface energy is not a secure predictor of ice nucleation ability. By further analyzing the surface potentials of different halogen chemistry surfaces, we find that surface polarity plays a key role in ice nucleation maybe through impacting the orientation of interfacial water.

Insight into the boosted activity of TiO2–CoP composites for hydrogen evolution reaction: Accelerated mass transfer, optimized interfacial water, and promoted intrinsic activity

The use of abundant elements in the earth as electrocatalytic hydrogen production catalysts is of great significance for hydrogen energy cycling. Herein, we report amorphous TiO2-decorated CoP/NF (TiO2–CoP/NF) as an excellent electrocatalyst for alkaline hydrogen evolution reaction (HER). The well-dispersed amorphous TiO2 on nanoneedle-like CoP arrays preserves the crystal structure of CoP and changes its electronic structure by interfacial charge transfer. Compared to CoP/NF catalyst, the TiO2–CoP/NF composite catalyst exhibits high HER activity with an overpotential of 61 mV at 10 mA cm−2 and high stability. Importantly, it almost maintains the Volmer step as a rate-determining step (RDS) and the Tafel slope at a wide cathodic potential range showing the fast kinetics under large polarization regions. Theoretical simulations reveal that the combination of TiO2 and CoP selectively accelerates the hydrated K+ diffusion, regulates the interfacial water orientation to adapt to the subsequent smooth water dissociation, and optimizes *H adsorption/H2 desorption. The strengthened coupling of HER multi-scale-processes on transition metal compound composites catalysts is the underlying mechanism for improving HER activity.

Tuning Ice Nucleation by Mussel-Adhesive Inspired Polyelectrolytes: The Role of Hydrogen Bonding

Tuning Ice Nucleation by Mussel-Adhesive Inspired Polyelectrolytes: The Role of Hydrogen Bonding

Interfacial dynamics in inverted-headgroup lipid membranes.

Inverted-headgroup (choline-phosphate) lipids are synthetic lipids that are not found in nature and are used as model systems to understand the role of headgroup dipole orientation. Recently, studies revealed that the net orientation of interfacial water strongly depends on the headgroup electrostatics, i.e., the charges and dipole generated by the phosphate and the choline groups. In order to characterize interfacial H-bond dynamics, we measured two-dimensional infrared spectra of the ester carbonyl band and performed molecular dynamics simulations in fully hydrated 1,2-dioleoyl-sn-glycero-3-phosphocholine and 2-((2,3-bis(oleoyloxy)propyl)-dimethyl-ammonio)ethyl ethyl phosphate (DOCPe) lipid bilayers. The experiments and simulations suggest that the reverse dipole generated by the inverted-headgroup in DOCPe does not affect the carbonyl H-bond populations or the interfacial water H-bond dynamics. However, while phosphate-associated waters in both lipids appear to show a similar H-bond structure, carbonyl-associated waters are characterized by a slightly disrupted H-bond structure in the DOCPe bilayer, especially within the second hydration shell. Our findings show that changes in net water orientation perturb the water H-bonds at the linker region between the headgroup and the lipid tail, although this perturbation is weak.

DNA-Induced Reorganization of Water at Model Membrane Interfaces Investigated by Heterodyne-Detected Vibrational Sum Frequency Generation Spectroscopy.

Lipid-DNA complexes are important nonviral vectors to be used in gene therapy, which is one of the promising strategies for the cure of many diseases. Although interfacial water is expected to play a significant role in lipid-DNA complexation, a molecular-level understanding about the role of interfacial water in the DNA-lipid complexation is still sparse. In this study, the structure and orientation of water at cationic and zwitterionic lipid monolayer/water interfaces in the presence of DNA are studied by the use of interface-selective heterodyne-detected vibrational sum frequency generation (HD-VSFG) spectroscopy. It is found that the adsorption of DNA at a cationic lipid interface drastically decreases the orientation of interfacial water reflecting the neutralization of the positively charged interface, whereas the adsorption of DNA at a zwitterionic lipid interface makes interfacial water become more "H-up", indicating that the originally zwitterionic interface becomes negatively charged due to the DNA adsorption. Furthermore, interfacial water having relatively strong hydrogen bonds is observed at both the cationic and zwitterionic lipid interfaces in the presence of DNA.

Second Harmonic Scattering Reveals Ion-Specific Effects at the SiO2 and TiO2 Nanoparticle/Aqueous Interface

Ion-specific effects play a crucial role in controlling the stability of colloidal systems and regulating interfacial processes. Although mechanistic pictures have been developed to explain the electrostatic structure of solid/water colloidal interfaces, ion-specific effects remain poorly understood. Here we quantify the average interfacial water orientation and the electrostatic surface potential around 100 nm SiO2 and TiO2 colloidal particles in the presence of NaCl, RbCl, and CaCl2 using polarimetric angle-resolved second harmonic scattering. We show that these two parameters can be used to establish the ion adsorption mechanism in a low ionic strength regime (<1 mM added salt). The relative differences between salts as a function of the ionic strength demonstrate cation- and surface-specific preferences for inner- vs outer-sphere adsorption. Compared to monovalent Rb+ and Na+, Ca2+ is found to be preferentially adsorbed as outer-sphere on SiO2 surfaces, while a dominant inner-sphere adsorption is observed for Ca2+ on TiO2. Molecular dynamics simulations performed on crystalline SiO2 and TiO2 surfaces support the experimental conclusions. This work contributes to the understanding of the electrostatic environment around colloidal nanoparticles on a molecular level by providing insight into ion-specific effects with micromolar sensitivity.

Interfacial Water Structure as a Descriptor for Its Electro-Reduction on Ni(OH)2-Modified Cu(111).

The hydrogen evolution reaction (HER) has been crucial for the development of fundamental knowledge on electrocatalysis and electrochemistry, in general. In alkaline media, many key questions concerning pH-dependent structure–activity relations and the underlying activity descriptors remain unclear. While the presence of Ni(OH)2 deposited on Pt(111) has been shown to highly improve the rate of the HER through the electrode’s bifunctionality, no studies exist on how low coverages of Ni(OH)2 influence the electrocatalytic behavior of Cu surfaces, which is a low-cost alternative to Pt. Here, we demonstrate that Cu(111) modified with 0.1 and 0.2 monolayers (ML) of Ni(OH)2 exhibits an unusual non-linear activity trend with increasing coverage. By combining in situ structural investigations with studies on the interfacial water orientation using electrochemical scanning tunneling microscopy and laser-induced temperature jump experiments, we find a correlation between a particular threshold of surface roughness and the decrease in the ordering of the water network at the interface. The highly disordered water ad-layer close to the onset of the HER, which is only present for 0.2 ML of Ni(OH)2, facilitates the reorganization of the interfacial water molecules to accommodate for charge transfer, thus enhancing the rate of the reaction. These findings strongly suggest a general validity of the interfacial water reorganization as an activity descriptor for the HER in alkaline media.

Confined hydration in nanometer-graded plasma polymer films: Insights from surface-enhanced infrared absorption spectroscopy

To shed light on recently explored long-range surface forces generated by subsurface-confined water, the structural characteristics of water molecules penetrating into nanoporous homogeneous and nanograded siloxane plasma polymer films (PPFs) over the time scale of 24 hours are studied by surface-enhanced IR spectroscopy (SEIRAS). Chemically graded PPFs, with embedded hydrophobic-to-hydrophilic gradient, are found to significantly change the average interfacial water orientation due to a unique nanoporous morphology and silanol group coordination. Diffusion of water through the hydrophobic SiO:CH matrix creates an evolution of the coordination of matrix silanol groups, which are eventually deprotonated as soon as the hydration network connects to the aqueous environment. This occurs after ~6 hours of water immersion and coincides with the change of average interfacial water orientation. Both effects are present on hydrophobic samples, but are significantly amplified by the presence of the subsurface vertical amphiphilic gradient (Vgrad), whereas enhanced water uptake in oxygen-plasma modified graded PPFs is covering such effects.

Silica surface states and their wetting characteristics

The wetting characteristics of silica (SiO2) surfaces can be described by molecular dynamics (MD) and ab initio simulations, including comparison of silica surfaces (talc (001), siloxanated quartz, tridymite (001) and quartz (001)), some of which have not been considered previously in the literature. Classic MD and ab initio simulation methods have been used to determine the contact angle, interfacial water structure, hydroxylation reaction and hydration energy, the results of which are compared with experimental results reported in the literature. Wetting of silica surfaces depends on surface polarity and extent of hydroxylation. The non-polar siloxane surfaces are characterized by a contact angle of about 80°, an MD ‘water exclusion zone’ of about 3 Å, a relaxed interfacial water orientation, inertness to hydroxylation and minimal hydration energy. The polar silica surfaces can be wetted by water and have a more ordered interfacial water structure. Silanol groups form at the polar silica surface during hydroxylation reactions, and the calculated hydration energy of −1·2 and −1·6 eV matches the experimental heat of immersion measurements reported in the literature, which correspond to hydrogen (H) bonding with interfacial water. Fundamental understanding of silica surfaces is important for understanding flotation phenomena and fluid flow in silica nanopores.

Surface Potential and Interfacial Water Order at the Amorphous TiO2 Nanoparticle/Aqueous Interface.

Colloidal nanoparticles exhibit unique size-dependent properties differing from their bulk counterpart, which can be particularly relevant for catalytic applications. To optimize surface-mediated chemical reactions, the understanding of the microscopic structure of the nanoparticle–liquid interface is of paramount importance. Here we use polarimetric angle-resolved second harmonic scattering (AR-SHS) to determine surface potential values as well as interfacial water orientation of ∼100 nm diameter amorphous TiO2 nanoparticles dispersed in aqueous solutions, without any initial assumption on the distribution of interfacial charges. We find three regions of different behavior with increasing NaCl concentration. At very low ionic strengths (0–10 μM), the Na+ ions are preferentially adsorbed at the TiO2 surface as inner-sphere complexes. At low ionic strengths (10–100 μM), a distribution of counterions equivalent to a diffuse layer is observed, while at higher ionic strengths (>100 μM), an additional layer of hydrated condensed ions is formed. We find a similar behavior for TiO2 nanoparticles in solutions of different basic pH. Compared to identically sized SiO2 nanoparticles, the TiO2 interface has a higher affinity for Na+ ions, which we further confirm with molecular dynamics simulations. With its ability to monitor ion adsorption at the surface with micromolar sensitivity and changes in the surface potential, AR-SHS is a powerful tool to investigate interfacial properties in a variety of catalytic and photocatalytic applications.

Decoding Interfacial Water Orientation to Predict Surface Charge Density on a Model Sheet Using a Deep Learning Algorithm

The anomalous behavior of water at the aqueous interface of a surface has been thoroughly investigated over the past decades. However, indirect surface characterization based on the properties of i...