H-bonded Water Research Articles

Anionic Surfactant-Tailored Interfacial Microenvironment for Boosting Electrochemical CO2 Reduction.

Both the catalyst and electrolyte deeply impact the performance of the carbon dioxide reduction reaction (CO2RR). It remains a challenge to design the electrolyte compositions for promoting the CO2RR. Here, typical anionic surfactants, dodecylphosphonic acid (DDPA) and its analogues, are employed as electrolyte additives to tune the catalysis interface where the CO2RR occurs. Surprisingly, the anionic surfactant-tailored interfacial microenvironment enables a set of typical commercial catalysts for the CO2RR to deliver a significantly enhanced selectivity of carbon products in both neutral and acidic electrolytes. Mechanistic studies disclose that the DDPA addition restructures the interfacial hydrogen-bond environment via increasing the weak H-bonded water, thus promoting the CO2 protonation to CO. Specifically, in an H-type cell, the Faradaic efficiency of CO increases from 70 to 98% at -1.0 V versus the reversible hydrogen electrode. Furthermore, in a flow cell, the DDPA-containing electrolyte maintains over 90% FECO from 50-400 mA cm-2. Additionally, this electrolyte modulation strategy can be extended to acidic CO2RR with a pH of 1.5-3.5.

Ion-specific ice provides a facile approach for reducing ice friction

HypothesisIce friction plays a crucial role in both basic study and practical use. Various strategies for controlling ice friction have been developed. However, one unsolved puzzle regarding ice friction is the effect of ion–ice interplay on its tribological properties. Experiments and SimulationsHere, we conducted ice friction experiments and summarized the specific effects of hydrated ions on ice friction. By selecting cations and anions, the coefficient of ice friction can be reduced by more than 70 percent. Experimental spectra, low-field nuclear magnetic resonance (LF-NMR), density functional theory (DFT) calculations, and Molecular dynamics (MD) simulations demonstrated that the addition of ions could break the H-bonds in water. FindingsThe link between the charge density of ions and the coefficients of ice friction was revealed. A part of the ice structure was changed from an ice-like to a liquid-like interfacial water structure with the addition of ions. Lower charge density ions led to weaker ionic forces with the water molecules in the immobilized water layer, resulting in free water molecules increasing in the lubricating layer. This study provides guidance for preparing ice-making solutions with low friction coefficients and a fuller understanding of the interfacial water structure at low temperatures.

Nonlinear Effects of Hydrophobic Confinement on the Electronic Structure and Dielectric Response of Water.

Fundamental studies of the dielectrics of confined water are critical to understand the ion transport across biological and synthetic nanochannels. The relevance of these fundamental studies, however, surmounts the difficulty of probing water's dielectric constant as a function of a fine variation in confinement. In this work, we explore the computational efficiency of machine learning potentials to derive the confinement effects on the dielectric constant, polarization, and dipole moment of water. Our simulations predict an enhancement of the axial dielectric constant of water under extreme confinement, arising from either the formation of ferroelectric structures of ordered water or larger dipole fluctuations facilitated by the disruption of water's H-bond network. Our study highlights the impact of hydrophobic nanoconfinement on the dielectric constant and on the ionic and electronic structure of water molecules, pointing to the importance of geometric flexibility and electronic polarizability to properly model confinement effects on water.

Distinction of Plasmonic Intrananoparticle and Internanoparticle Molecular Reaction Rates at the Three-Phase Contact Line of an Evaporating Sessile Droplet.

Molecular reactions on the surface of a plasmonic nanoparticle (intrananoparticle) and between nanoparticles (internanoparticle) may differ in kinetics, dynamics, and product selectivity. We report that the difficulty in distinguishing the kinetics in a dispersion medium could be overcome by probing the reactions at the three-phase contact line (TPCL) of an evaporating sessile droplet using surface-enhanced Raman spectroscopy (SERS). Thus, when an evaporating aqueous droplet on glass containing 4-aminothiophenol-stabilized Ag nanoparticles was monitored by SERS at the TPCL, dimerization into 4,4'-dimercaptoazobenzene followed two steps, each preceded by the loss of H-bonded water accordingly. On the basis of the results, we assigned the first step with a higher relative kinetic rate (∼3 times) to be an intrananoparticle reaction and the second one as an internanoparticle reaction. In D2O medium, the ratio of the rates was ∼1.8. The observed vibrational signatures of the losses of water molecules before reactions and product formations were accounted for by using density functional theoretical calculations.

2+1] Cycloadditions Modulate the Hydrophobicity of Ni-N4 Single-Atom Catalysts for Efficient CO2 Electroreduction.

Microenvironment regulation of M-N4 single-atom catalysts (SACs) is a promising way to tune their catalytic properties toward the electrochemical CO2 reduction reaction. However, strategies that can effectively introduce functional groups around the M-N4 sites through strong covalent bonding and under mild reaction conditions are highly desired. Taking the hydrophilic Ni-N4 SAC as a representative, we report herein a [2+1] cycloaddition reaction between Ni-N4 and in situ generated difluorocarbene (F2C:), and enable the surface fluorocarbonation of Ni-N4, resulting in the formation of a super-hydrophobic Ni-N4-CF2 catalyst. Meanwhile, the mild reaction conditions allow Ni-N4-CF2 to inherit both the electronic and structural configuration of the Ni-N4 sites from Ni-N4. Enhanced electrochemical CO2-to-CO Faradaic efficiency above 98 % is achieved in a wide operating potential window from -0.7 V to -1.3 V over Ni-N4-CF2. In situ spectroelectrochemical studies reveal that a highly hydrophobic microenvironment formed by the -CF2- group repels asymmetric H-bonded water at the electrified interface, inhibiting the hydrogen evolution reaction and promoting CO production. This work highlights the advantages of [2+1] cycloaddition reactions on the covalent modification of N-doped carbon-supported catalysts.

Solvation Properties of Neutral Gold Species in Supercritical Water Studied By THz Spectroscopy.

Supercritical water provides distinctly different solvation properties compared to what is known from liquid water. Despite its prevalence deep in the Earth's crust and its role in chemosynthetic ecosystems in the vicinity of hydrothermal vents, molecular insights into its solvation mechanisms are still very scarce compared to what is known for liquid water. Recently, neutral metal particles have been detected in hydrothermal fluids and proposed to explain the transport of gold species to ore deposits on Earth. Using ab initio molecular dynamics, we elucidate the solvation properties of small gold species at supercritical conditions. The neutral metal clusters themselves contribute enormous THz intensity not because of their intramolecular vibrations, but due to their pronounced electronic polarization coupling to the dynamical supercritical solvent, leading to a continuum absorption up to about 1000 cm-1. On top, long-lived interactions between the gold clusters and solvation water leads at these supercritical conditions to a sharp THz resonance that happens to be close to the one due to H-bonding in liquid water at ambient conditions. The resulting distinct resonances can be used to analyse the solvation properties of neutral metal particles in supercritical aqueous solutions.

Balancing the Binding of Intermediates Enhances Alkaline Hydrogen Oxidation on D-Band Center Modulated Pd Sites.

Exploring efficient alkaline hydrogen oxidation reaction (HOR) electrocatalysts is of great concern for constructing anion exchange membrane fuel cells (AEMFCs). Herein, d-band center modulated PdCo alloys with ultralow Pd content anchored onto the defective carbon support (abbreviated as PdCo/NC hereafter) are proposed as highly efficient HOR catalyst. The as-prepared catalyst exhibits exceptional HOR performance compared to the Pt/C catalyst, achieving thermodynamically spontaneous and kinetically preferential reactions. Specifically, the resultant PdCo/NC demonstrates a marked enhancement in alkaline HOR performance, with the highest mass and specific activities of 1919.6 mA mgPd-1 and 1.9 mA cm-2, 51.1 and 4.2 times higher than those of benchmark of Pt/C, along with an excellent stability in a chronoamperometry test. In the analysis of in situ Raman spectra, it was discovered that tetrahedrally coordinated H-bonded water molecules were formed during the HOR process. This indicates that the promotion of interfacial water molecule formation and enhancement of HOR activities in PdCo/NC are facilitated by defect engineering and the turning of d-band center in PdCo alloy. The essential knowledge obtained in this study could open up a new direction for modifying the electronic structure of cost-effective HOR catalysts through electronic structure engineering.

Revealing the Molecular Origin of Anisotropy around Chloride Ions in Bulk Water.

A clear picture of the local solvation structure around halide anions in liquid water remains elusive. This discussion has been stimulated by pioneering simulation results that proposed a "hydrophobic cavity" around anions in the bulk, which is analogous to air at the air-water interface. However, there is also sound experimental and theoretical evidence that halide ions are rather symmetrically solvated in the bulk, leading to a different viewpoint. Using extensive ab initio molecular dynamics simulations of an aqueous Cl- solution, we indeed find an anisotropic arrangement of H-bonded versus interstitial water molecules. The latter are not H-bonded to the anions and thus do not couple much electronically to Cl-. The resulting purely electronic anisotropy of the local solvation environment correlates with that structural anisotropy, which however should not be understood as an empty cavity─as it would be at the air-water interface─but rather contains interstitial water molecules.

Probing the Fermi resonance of pyridine surrounded by hydrogen bonding network by density functional theory

The Fermi resonance (FR) occurs between the ring breathing vibrational (ν1) and the triangular stretching (ν12) mode of pyridine in aqueous pyridine solution was studied using Raman spectroscopy combined with density functional theory (DFT) calculations. The effect of H-Bond on the FR in the mixture was performed by MD analysis. Combined with the FR parameters, it was found that due to the H-Bond effect the FR coupling changed significantly when the pyridine mole fractions were near 0.7 and 0.5, respectively. The water H-Bond network structure is most favorable for pyridine molecule bonding at a pyridine mole concentration around 0.5, and water preferentially affinity to the pyridine molecule at x = 0.7. In addition, we analyzed the OH vibrational region at different mole fractions and theoretically calculated Py associated OH in specific molecular bonds.

Coordination-cage binding and catalysed hydrolysis of organophosphorus chemical warfare agent simulants.

The use of organophosphorus chemical warfare agents still remains an ongoing global threat. Here we investigate the binding of small-molecule organic guests including phosphate esters, sulfonate esters, carbonate esters and a sulfite ester - some of which act as simulants for organophosphorus chemical warfare agents - in the cavity of a water-soluble coordination cage. For several of these guest species, binding constants in the range 102 to 103 M-1 were determined in water/DMSO (98 : 2 v/v) solution, through a combination of fluorescence and 1H NMR spectroscopy, and subsequent fitting of titration data to a 1 : 1 binding isotherm model. For three cage/guest complexes crystallographic structure determinations were possible: in two cases (with guests phenyl methanesulfonate and phenyl propyl carbonate) the guest lies inside the cavity, forming a range of CH⋯O hydrogen-bonding interactions with the cage interior surface involving CH groups on the cationic cage surface that act as H-bond donors and O atoms on the guests that act as H-bond acceptors. In a third case, with the guest 4-nitrophenyl-methanesulfonate, the guest lies in the spaces outside a cage cavity between cages and forms weak CH⋯O interactions with the cage exterior surface: the cavity is occupied by a network of H-bonded water molecules, though this guest does show cavity binding in solution. For the isomeric guests 4-nitrophenyl-methanesulfonate and 4-nitrophenyl methyl sulfite, hydrolysis in water/DMSO (98 : 2 v/v) could be monitored colorimetrically via appearance of the 4-nitrophenolate anion; both showed accelerated hydrolysis rates in the presence of the host cage with second-order rate constants for the catalysed reactions in the range 10-3 to 10-2 M-1 s-1 at pH 9. The typical rate dependence on external pH and the increased reaction rates when chloride ions are present (which can bind inside the cavity and displace other cavity-bound guests) imply that the catalysed reaction actually occurs at the external surface of the cage rather than inside the cavity.

Vibrational dynamics and spectroscopy of water at porous g-C3N4 and C2N surfaces.

Porous graphitic materials containing nitrogen are promising catalysts for photo(electro)chemical reactions, notably water splitting, but can also serve as "molecular sieves". Nitrogen increases the hydrophilicity of the graphite parent material, among other effects. A deeper understanding of how water interacts with C- and N-containing layered materials, if and which differences exist between materials with different N content and pore size, and what the role of water dynamics is - a prerequsite for catalysis and sieving - is largely absent, however. Vibrational spectroscopy can answer some of these questions. In this work, the vibrational dynamics and spectroscopy of deuterated water molecules (D2O) mimicking dense water layers at room temperature on the surfaces of two different C/N-based materials with different N content and pore size, namely graphitic C3N4 (g-C3N4) and C2N, are studied using ab initio molecular dynamics (AIMD). In particular, time-dependent vibrational sum frequency generation (TD-vSFG) spectra of the OD modes and also time-averaged vSFG spectra and OD frequency distributions are computed. This allows us to distinguish "free" (dangling) OD bonds from OD bonds that are bound in a H-bonded water network or at the surface - with subtle differences between the two surfaces and also to a pure water/air interface. It is found that the temporal decay of OD modes is very similar on both surfaces with a correlation time near 4 ps. In contrast, TD-vSFG spectra reveal that the interconversion time from "bonded" to "free" OD bonds is about 8 ps for water on C2N and thus twice as long as for g-C3N4, demonstrating a propensity of the former material to stabilize bonded OD bonds.

Pre-resonance effects in deep UV Raman spectra of normal and deuterated water.

We have investigated the shape of the OH/OD stretching Raman band of water as a function of the excitation wavelength in the deep UV region (200-266 nm). By analyzing the spectral profiles, we highlighted selective pre-resonance effects in the high wavenumber component of the OH/OD stretching band, associated to distorted H-bonded water configurations. A van't Hoff treatment of the temperature-dependent Raman spectra provides an estimate of the thermal energy associated to the change from ordered (ice-like) to disordered configurations that agrees with values obtained by related methods based on a two-state model of water. These results open the possibility of exploiting the observed pre-resonance deep-UV signal enhancement to investigate H-bonding properties in aqueous media.

Hydration lubrication modulated by water structure at TiO2-aqueous interfaces

The nature of solid–liquid interfaces is of great significance in lubrication. Remarkable advances have been made in lubrication based on hydration effects. However, a detailed molecular-level understanding is still lacking. Here, we investigated water molecule behaviors at the TiO2–aqueous interfaces by the sum-frequency generation vibrational spectroscopy (SFG-VS) and atomic force microscope (AFM) to elucidate the fundamental role of solid–liquid interfaces in lubrication. Combined contributions of water structures and hydration effects were revealed, where water structures played the dominant role in lubrication for TiO2 surfaces of varying hydrophilicity, while hydration effects dominated with the increasing of ion concentrations. Superior lubrication is observed on the initial TiO2 surfaces with strongly H-bonded water molecules compared to the hydrophilic TiO2 surfaces with more disordered water. The stable ordered water arrangement with strong hydrogen bonds and the shear plane occurring between the ordered water layer and subsequent water layer may play a significant role in achieving lower friction. More adsorbed hydrated molecules with the increasing ionic concentration perturb ordered water but lead to the enhancement of hydration effects, which is the main reason for the improved lubrication for both TiO2. This work provides more insights into the detailed molecular-level understanding of the mechanism of hydration lubrication.

Femtosecond Electron-Transfer Dynamics across the D2O/Cs+/Cu(111) Interface: The Impact of Hydrogen Bonding.

Hydrogen bonding is essential in electron-transfer processes at water-electrode interfaces. We study the impact of the H-bonding of water as a solvent molecule on real-time electron-transfer dynamics across a Cs+-Cu(111) ion-metal interface using femtosecond time-resolved two-photon photoelectron spectroscopy. We distinguish in the formed water-alkali aggregates two regimes below and above two water molecules per ion. Upon crossing the boundary of these regimes, the lifetime of the excess electron localized transiently at the Cs+ ion increases from 40 to 60 fs, which indicates a reduced alkali-metal interaction. Furthermore, the energy transferred to a dynamic structural rearrangement due to hydration is reduced from 0.3 to 0.2 eV concomitantly. These effects are a consequence of H-bonding in the water-water interaction and the beginning formation of a nanoscale water network. This finding is supported by real-space imaging of the solvatomers and vibrational frequency shifts of the OH stretching and bending modes calculated for these specific interfaces.

Comparison of classical and abinitio simulations of hydronium and aqueous proton transfer.

Proton transport in aqueous systems occurs by making and breaking covalent bonds, a process that classical force fields cannot reproduce. Various attempts have been made to remedy this deficiency, by valence bond theory or instantaneous proton transfers, but the ability of such methods to provide a realistic picture of this fundamental process has not been fully evaluated. Here we compare an abinitio molecular dynamics (AIMD) simulation of an excess proton in water to a simulation of a classical H3O+ in TIP3P water. The energy gap upon instantaneous proton transfer from H3O+ to an acceptor water molecule is much higher in the classical simulation than in the AIMD configurations evaluated with the same classical potential. The origins of this discrepancy are identified by comparing the solvent structures around the excess proton in the two systems. One major structural difference is in the tilt angle of the water molecules that accept an hydrogen bond from H3O+. The lack of lone pairs in TIP3P produces a tilt angle that is too large and generates an unfavorable geometry after instantaneous proton transfer. This problem can be alleviated by the use of TIP5P, which gives a tilt angle much closer to the AIMD result. Another important factor that raises the energy gap is the different optimal distance in water-water vs H3O+-water H-bonds. In AIMD the acceptor is gradually polarized and takes a hydronium-like configuration even before proton transfer actually happens. Ways to remedy some of these problems in classical simulations are discussed.

Scott Blair Fractional-Type Viscoelastic Behavior of Thermoplastic Polyurethane.

In this paper, the experimental characterization of the viscoelastic properties of thermoplastic polyurethane (TPU) samples through creep experiments is presented. Experiments were conducted at different constant temperature levels (15, 25, and 35 ∘C), for three different tensile stress levels (0.3, 0.5, and 0.7 MPa), and at different physisorbed water contents, providing access to: (i) the temperature dependency of creep parameters and (ii) the assessment, if behavior is indeed viscoelastic. The physisorbed water content was achieved by exposing virgin samples to environments with relative humidity ranging from 0 to 80 percent until mass stability was reached. Creep tests were conducted immediately afterwards with this particular humidity level. The main results of this study are as follows. The temperature dependency of the obtained creep parameters is well described in Arrhenius plots. With regard to water content, two prototype material responses were observed in the experimental program and accurately modeled using the following fractional-type models: (i) Scott Blair-type (i.e., power-law-type) only behavior, pronounced for the combination of low water content/low temperature; (ii) combined Scott Blair plus Lomnitz (i.e., log-type) behavior for high water content/high temperature. This change in behavior associated with certain thresholds for the specified environmental conditions (temperature and relative humidity) may indicate the initiation of hydrogen bond breakage and rearrangement (carbamate H-bonds and physisorbed water H-bonds). Regarding the short-term or quasi-instantaneous behavior, the Scott Blair element seems highly appropriate and may be better suited than the standard elastic model: the Hookean spring. We associated Scott Blair behavior with the load-induced, quasi-instantaneous re-arrangement of polymer network chains. The secondary viscoelastic mechanism associated with the Lomnitz element, hydrogen bond breakage and rearrangement, comes into play for higher temperatures and/or higher physisorbed water contents. In this case, the contribution of the two constitutive elements is well separated due to the large number of the characteristic time of the Lomnitz element, much larger than the respective value for the Scott Blair element.

Hydrogen-bonding and vibrational coupling of water in a hydrophobic hydration shell: Significance of alkyl chain configuration and charge on the hydrophobe

The interaction between a molecular hydrophobe and water is crucial for their mutual structure and reactivity. Here, we have investigated the hydrogen-bonding (H-bonding) structure and intermolecular vibrational coupling i.e., the collective nature of water, in the hydration shell (HS) of charged and uncharged molecular hydrophobes, using polarization-resolved Raman difference spectroscopy with simultaneous curve fitting (Raman-DS-SCF) and isotopic dilution spectroscopy. Raman-DS-SCF provides the vibrational spectrum of water pertaining to the HS of the hydrophobes. The HS-spectra reveal that the positive charge on the hydrophobe (e.g., deuterated tetramethylammonium cation, d-TMA+) as well as the branching of the alkyl chain (n-butyl alcohol (BA) vs. tert-butyl alcohol (TBA)) reinforces the intermolecular vibrational coupling of water in the HS. The water-water H-bonding in the HS of d-TMA+ and d-TBA are similar to each other, but stronger than that of the bulk water. Apart from the strongly H-bonded water, the hydrophobic hydration shells exhibit weakly interacting dangling OH (ν¯max≈3670) which is intramolecularly coupled with the H-bonded OH of the same water molecule. The prevalence of the dangling-OH decreases with chain-branching and net positive charge on the hydrophobe: BA > d-TBA > d-TMA+. Altogether, the collective nature of water and its propensity for dangling-OH in a hydrophobic hydration shell strongly depend on the net charge and alkyl chain configuration of the hydrophobe.

Vibrational Coupling and Hydrogen-Bond Structure of Water in the Extended Hydration Shell of Metal Ions.

Intra- and intermolecular vibrational coupling (VC) and hydrogen bonding (H-bonding) of water are sparsely understood in the hydration shell (HS) of a metal ion, though the corresponding knowledge for an anion is quite extensive. This is primarily due to the overwhelming effect of anions on water, which masks the subtle perturbing influence of most of the cations. Using Raman difference spectroscopy with simultaneous curve fitting (Raman-DS-SCF) in combination with isotopic dilution and polarized Raman spectroscopy, we have elucidated the VC and H-bonding of water in the HS of bi- and trivalent metal ions─Mg2+, Ca2+, La3+, Gd3+, Dy3+. Polarized Raman measurement of the HS water with VC "turned on" and "turned off" (using isotopically diluted water, HOD) reveals that water retains the intra- and intermolecular vibrational coupling in the HS of high-charge-density metal ions, which is in stark contrast to that of an anion. Hydration shell spectroscopy in HOD unambiguously shows that the average H-bonding of water becomes stronger in the HS than that of bulk water. The first HS water strongly donates two H-bonds to the second HS water (ν̅max ≈ 3200 cm-1) but weakly accepts a H-bond from the second HS water (ν̅max ≈ 3590 cm-1), which makes the HS water heterogeneous in terms of its H-bond structure. The weakly interacting OH (ν̅max 3585 cm-1 in HOD) red-shifts by ∼ 15 cm-1 while the VC is "turned on" (ν̅max ≈ 3600 cm-1 in H2O), revealing the intramolecular coupling of water in the HS of metal ions.

3D Ag(I) coordination polymer sandwiched by water-muconate anionic layers: Synthesis, structure, Hirshfeld surface analysis, binding with BSA, and photocatalytic activity

The sonochemical reaction between silver salt, 1,3-bis(4-pyridylpropane (bpp) and trans,trans-muconic acid (H2muc) formed an Ag(I) coordination polymer with a 3D supramolecular sandwich architecture, {[Ag8(bpp)8(H2O)3].(muc)4.29(H2O)}n, (1) consisting of the silver-bpp cationic host that alternates with 2D water–muc guest anionic layers. The latter is formed by H-bonded water molecules-anions comprising hexagonal (H2O)6 clusters. The Hirshfeld surface and fingerprint plots have been used to quantify the weak intermolecular interactions in the crystal packing arrangement. The study showed that intermolecular hydrogen bonds are the most critical in constructing the titled supramolecular complex, accounting for 51.2% of the total Hirshfeld surface. Several spectrofluorimetric methods have been employed to investigate the binding interaction between Bovine Serum Albumin (BSA) and the titled complex. The complex induced significant fluorescence quenching of BSA, indicating a strong binding affinity for the protein. Static or ground state complex formation was envisaged as the primary quenching mechanism when the complex interacts with BSA. In addition, the Ag compound also offers photocatalytic properties by degrading the toxic organic methylene blue dye.

Evolution of the hydrogen-bonded network in methanol-water mixtures upon cooling

The hydrogen-bonded structure of methanol – water mixtures is investigated over the entire alcohol concentration range (from xMethanol = 0.1 to 1.0) at several temperatures, from 300 K down to the freezing point of the given mixture. Classical molecular dynamics simulations have been carried out, using the all-atom OPLS-AA force field for methanol and the TIP4P/2005 model for water molecules. Simulation trajectories (‘particle configurations’) obtained have been analyzed, in order to characterize the hydrogen-bonded network in the mixtures. The temperature and concentration dependence of the average hydrogen bond (H-bond) numbers between different types of molecules, the donor/acceptor roles of water and methanol molecules, and hydrogen bond number distributions have been revealed. The topology of the total system, as well as that of the water and methanol subsystems, has been investigated by calculating the cluster size distributions, the number of primitive rings, and ring size and ring type distributions. It has been found that upon cooling, the average number of H-bonded water molecules increases at every concentration and temperature investigated. As far as the connectivity of the hydrogen-bonded network is concerned, the percolation threshold has been shown to be above xM = 0.9 already at room temperature.