Ice-like Structure Research Articles

Electric field-facilitated dehumidification of natural gas through nanochannels

The existence of water in natural gas causes serious congestion and acid corrosion problems during exploitation and transport. Water must be removed. Here, we performed molecular dynamics simulations to investigate the effect of electric fields on natural gas dehydration through nanochannels. When the electric field is applied, only water molecules occupy the nanochannel in place of C1-C3 paraffins, acid gases and N2 molecules. The dominant mechanism is that the electric field and confinement of channels induce the ordered arrangements of water molecules, forming stable ice-like structures and restricting the entry of other components. Once removing the electric field, the water molecules will be released from the channel due to the relatively low water-channel interaction. Importantly, hydrophilic and hydrophobic channels both exhibit effective separation for water. The separation selectivity is not strictly dependent on channel diameters, avoiding the trade-off effect between adsorption capacity and selectivity based on the size sieving mechanism.

Analysis of the Electron Density of a Water Molecule Encapsulated by Two Cholic Acid Residues

Cholic acid is a trihydroxy bile acid with a nice peculiarity: the average distance between the oxygen atoms (O7 and O12) of the hydroxy groups located at C7 and C12 carbon atoms is 4.5 Å, a value which perfectly matches with the O/O tetrahedral edge distance in Ih ice. In the solid phase, they are involved in the formation of hydrogen bonds with other cholic acid units and solvents. This fact was satisfactorily used for designing a cholic dimer which encapsulates one single water molecule between two cholic residues, its oxygen atom (Ow) being exactly located at the centroid of a distorted tetrahedron formed by the four steroid hydroxy groups. The water molecule participates in four hydrogen bonds, with the water simultaneously being an acceptor from the 2 O12 (hydrogen lengths are 2.177 Å and 2.114 Å) and a donor towards the 2 O7 (hydrogen bond lengths are 1.866 Å and 1.920 Å). These facts suggest that this system can be a nice model for the theoretical study of the formation of ice-like structures. These are frequently proposed to describe the water structure found in a plethora of systems (water interfaces, metal complexes, solubilized hydrophobic species, proteins, and confined carbon nanotubes). The above tetrahedral structure is proposed as a reference model for those systems, and the results obtained from the application of the atoms in molecules theory are presented here. Furthermore, the structure of the whole system allows a division into two interesting subsystems in which water is the acceptor of one hydrogen bond and the donor of another. The analysis of the calculated electron density is performed through its gradient vector and the Laplacian. The calculation of the complexation energy used correction of the basis set superposition error (BSSE) with the counterpoise method. As expected, four critical points located in the H…O bond paths were identified. All calculated parameters obey the proposed criteria for hydrogen bonds. The total energy for the interaction in the tetrahedral structure is 54.29 kJ/mol, while the summation obtained of the two independent subsystems and the one between the alkyl rings without water is only 2.5 kJ/mol higher. This concordance, together with the calculated values for the electron density, the Laplacian of the electron density, and the lengths of the oxygen atom and the hydrogen atom (involved in the formation of each hydrogen bond) to the hydrogen bond critical point, suggests that each pair of hydrogen bonds can be considered independent of each other.

CO2 gas hydrate as an innovative leavening agent for baked goods

In the presented research, the use and technical realization of CO2 gas hydrate (GH) as a novel baking agent is investigated. GH are ice-like structures where one mole of hydrate typically consists of about 85% water and 15% gas. Hydrates were formed in a lab-scale 1.1 L stirred tank reactor at 1-2 °C and 3.5 MPa, and transferred into a temperature-controlled, gas-tight measuring cell. The leavening effect of gas hydrates was assessed by measuring the CO2 release rates. Storage stability at -20 to 0 °C and stability above 0 °C were investigated experimentally and a coupled thermodynamic and kinetic decay model implemented. At -10 °C, gas release was highest in the first minutes and stopped completely after 5 days. After 21 days storage at -10 °C, the GH still contained 20 % of the initial gas content. Above 0 °C, dissociation rates were highly temperature dependent, and half value times ranged from 30 min (3 °C) to 4 min (20 - 30 °C). Above 10 °C, ambient temperature had only a minor effect on the dissociation rates. Results from the kinetic decay model, applied for a 21 mm particle, showed similar dissociation behavior as a particle from experiments. Applying the model for a 3 mm particle, showed full dissociation after approximately 15 min. Stability and baking tests showed that CO2 hydrate is in principle suitable as a leavening agent. However, GH production still needs to be optimized and recipes for GH application require further development.

Visualizing Molecular-Scale Adsorption Structures of Anti-freezing Surfactants on Sapphire (0001) Surfaces at Different Concentrations by 3D Scanning Force Microscopy.

Anti-freezing surfactants form an adsorption layer at the solid-water interface to inhibit the nucleation and growth of ice. However, this mechanism has not been elucidated at the molecular scale because of the difficulties in visualizing such adsorption structures. In this study, we overcome this limitation by directly visualizing the three-dimensional (3D) adsorption structures of anti-freezing surfactants, hexadecyltrimethylammonium bromide (C16TABs), on sapphire (0001) surfaces through 3D scanning force microscopy. We present molecularly resolved two-dimensional/3D images of the adsorption structures in solutions of 1, 10, and 100 ppm. At 1 ppm, the molecules form a monolayer with a flat-lying configuration. At 10 ppm, the molecular orientation is closer to the upright configuration, with a relatively large tilt angle. At 100 ppm, the molecules form a bilayer with almost upright configurations, providing excellent screening of the sapphire surface from water. Owing to the steric and electrostatic repulsion between adjacent molecular head groups, the surface of the bilayer exhibits relatively large fluctuations, inhibiting the formation of stable ice-like structures. The understanding of molecular-level mechanisms provides important guidelines for improving the design of anti-freezing surfactants for practical applications such as car coolants.

Hydrogen bonding network dynamics of 1,2-propanediol-water binary solutions by Raman spectroscopy and stimulated Raman scattering

Raman spectroscopy and stimulated Raman scattering (SRS) were used to investigate the hydrogen bonding (HB) network in 1,2-propanediol (1,2-PD)-water binary solutions. Abnormal changes in hydrogen bonds (HBs) were detected when V1,2-PD (volume fraction of the1,2-PD) was 0.4. In the case of Raman spectroscopy, the HB strength of water is weakened and then strengthened with the increase of 1,2-PD volume fraction. In the case of SRS, two new peaks at 3283 cm−1 and 3319 cm−1 were appeared, which demonstrated the appearance of ice-like structures near the methyl group and the weakening of HBs. Based on these phenomena, the HB structure of this binary system underwent a transition from H2O-H2O to H2O-1,2-PD when the V1,2-PD was 0.4 as V1,2-PD increased. This work serves as a reference value for the study of HB networks in alcohol-water binary solutions.

"Nanoreactors" for Boosting Gas Hydrate Formation toward Energy Storage Applications.

Hydrogen and methane can be molecularly incorporated in ice-like water structures up to mass fractions of 4.3% and 13.3%, respectively. The resulting solid structures, called gas hydrates, offer great potential for the efficient storage of hydrogen and natural gas. However, slow gas encapsulation by bulk water hinders this application. Porous structures have been shown to effectively promote gas hydrate formation and are a potential enabler for the development of hydrate-based gas storage technologies. Here, we offer an insightful perspective on using porous structures as nanoreactors for achieving fast gas hydrate formation for gas storage applications. We critically discuss and elucidate the working mechanisms of nanoreactors and identify the criteria for efficient nanoreactors. Based on the concepts founded, we propose a theoretical framework for designing next-generation porous materials for delivering better promoting effects on gas hydrate formation.

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

Local Ice-like Structure at the Liquid Water Surface.

Experiments and computer simulations have established that liquid water's surfaces can deviate in important ways from familiar bulk behavior. Even in the simplest case of an air-water interface, distinctive layering, orientational biases, and hydrogen bond arrangements have been reported, but an overarching picture of their origins and relationships has been incomplete. Here we show that a broad set of such observations can be understood through an analogy with the basal face of crystalline ice. Using simulations, we demonstrate a number of structural similarities between water and ice surfaces, suggesting the presence of domains at the air-water interface with ice-like features that persist over 2-3 molecular diameters. Most prominent is a shared characteristic layering of molecular density and orientation perpendicular to the interface. Lateral correlations of hydrogen bond network geometry point to structural similarities in the parallel direction as well. Our results bolster and significantly extend previous conceptions of ice-like structure at the liquid's boundary and suggest that the much-discussed quasi-liquid layer on ice evolves subtly above the melting point into a quasi-ice layer at the surface of liquid water.

Ice-like Structure of Water Confined in Hydrophobic Sub-nanometer Spaces at Room Temperature

Abstract Properties of water confined in nanoporous carbon are significantly different from those of bulk water. In this study, we investigate the micro- and mesoscopic structure of the confined water using in-situ X-ray scattering measurements. In hydrophobic sub-nanometer spaces, the water density is almost constant from 20 to 298 K, and hydrogen bonding networks are highly developed at room temperature, suggesting that the ice-like structure is maintained in sub-nanometer carbon slit pores even at room temperature.

Investigated hydrogen-bond network kinetics of acetone-water solutions by spontaneous and stimulated Raman spectroscopy.

The hydrogen bond (HB) network structure and kinetics of the acetone-water mixed solutions were investigated by the spontaneous Raman and stimulated Raman scattering (SRS) spectra. The HB network of water molecules was enhanced when the volume fraction of acetone ranged from 0 to 0.25. Two new SRS peaks of water at 3272 and 3380 cm-1 were obtained, resulting from the cooperation of the polar carbonyl (C = O)-enhanced HB and the ice-like structure formed around the methyl groups. However, when the volume fraction went beyond 0.25, the spontaneous Raman main peak at 3445 cm-1 showed a significant blue-shift, and the corresponding SRS signal disappeared, indicating that the HB of water was weakened, which originated from the self-association of acetone. In the meantime, the fully tetrahedral HB structure among water molecules was destroyed at the higher volume fraction (≥ 0.8). Hopefully, our study here would advance the study of HB network structures and kinetics in other aqueous solutions.

Density functional theory of waterwith the machine-learned DM21 functional.

The delicate interplay between functional-driven and density-driven errors in density functional theory (DFT) has hindered traditional density functional approximations (DFAs) from providing an accurate description of water for over 30 years. Recently, the deep-learned DeepMind 21 (DM21) functional has been shown to overcome the limitations of traditional DFAs as it is free of delocalization error. To determine if DM21 can enable a molecular-level description of the physical properties of aqueous systems within Kohn-Sham DFT, we assess the accuracy of the DM21 functional for neutral, protonated, and deprotonated water clusters. We find that the ability of DM21 to accurately predict the energetics of aqueous clusters varies significantly with cluster size. Additionally, we introduce the many-body MB-DM21 potential derived from DM21 data within the many-body expansion of the energy and use it in simulations of liquid water as a function of temperature at ambient pressure. We find that size-dependent functional-driven errors identified in the analysis of the energetics of small clusters calculated with the DM21 functional result in the MB-DM21 potential systematically overestimating the hydrogen-bond strength and, consequently, predicting a more ice-like local structure of water at room temperature.

Polymorphism, Structure, and Nucleation of Cholesterol·H2O at Aqueous Interfaces and in Pathological Media: Revisited from a Computational Perspective.

We revisit the important issues of polymorphism, structure, and nucleation of cholesterol·H2O using first-principles calculations based on dispersion-augmented density functional theory. For the lesser known monoclinic polymorph, we obtain a fully extended H-bonded network in a structure akin to that of hexagonal ice. We show that the energy of the monoclinic and triclinic polymorphs is similar, strongly suggesting that kinetic and environmental effects play a significant role in determining polymorph nucleation. Furthermore, we find evidence in support of various O–H···O bonding motifs in both polymorphs that may result in hydroxyl disorder. We have been able to explain, via computation, why a single cholesterol bilayer in hydrated membranes always crystallizes in the monoclinic polymorph. We rationalize what we believe is a single-crystal to single-crystal transformation of the monoclinic form on increased interlayer growth beyond that of a single cholesterol bilayer, interleaved by a water bilayer. We show that the ice-like structure is also relevant to the related cholestanol·2H2O and stigmasterol·H2O crystals. The structure of stigmasterol hydrate both as a trilayer film at the air–water interface and as a macroscopic crystal further assists us in understanding the polymorphic and thermal behavior of cholesterol·H2O. Finally, we posit a possible role for one of the sterol esters in the crystallization of cholesterol·H2O in pathological environments, based on a composite of a crystalline bilayer of cholesteryl palmitate bound epitaxially as a nucleating agent to the monoclinic cholesterol·H2O form.

Static and dynamic water structures at interfaces: A case study with focus on Pt(111).

An accurate atomistic treatment of aqueous solid-liquid interfaces necessitates the explicit description of interfacial water ideally via ab initio molecular dynamics simulations. Many applications, however, still rely on static interfacial water models, e.g., for the computation of (electro)chemical reaction barriers and focus on a single, prototypical structure. In this work, we systematically study the relation between density functional theory-derived static and dynamic interfacial water models with specific focus on the water-Pt(111) interface. We first introduce a general construction protocol for static 2D water layers on any substrate, which we apply to the low indexsurfaces of Pt. Subsequently, we compare these with structures from a broad selection of reference works based on the Smooth Overlap of Atomic Positions descriptor. The analysis reveals some structural overlap between static and dynamic water ensembles; however, static structures tend to overemphasize the in-plane hydrogen bonding network. This feature is especially pronounced for the widely used low-temperature hexagonal ice-like structure. In addition, a complex relation between structure, work function, and adsorption energy is observed, which suggests that the concentration on single, static water models might introduce systematic biases that are likely reduced by averaging over consistently created structural ensembles, as introduced here.

Electrocatalysis of CO2 and CH4 Hydrates at Subzero Temperatures

So far electrocatalytic process in aqueous solution have been extensively studied as a function of the temperature in the range 0 and 99 °C but very little is known about electrocatalytic processes at temperatures below the freezing point. In electrochemistry at low temperatures, the reactions associated with water splitting might be suppressed due to the formation of ice-like structure at the interface, while the stabilization of other reaction species can be stabilized resulting in changes to the kinetics of the reactions studied.1-3 In addition, decreasing the temperature of water to subfreezing temperatures would significantly increase the solubility of some gases in water thus affecting the reaction rate and reaction mechanism of the electrochemical reactions. By taking advantage of the high solubility of the carbon monoxide and methane at low temperature, achievable in brines, we report the electrochemical conversion of these gases in aqueous media down to −40 °C. We will report the electrochemical conversion of CO2 at low temperatures and demonstrate, unexpectedly, that its reduction in these conditions follows an anti-Arrhenius kinetics electrochemical environment. We will also show that electrochemical oxidation of CH4 is feasible at subzero temperatures due to the 5-fold increase in the concentration of CH4 and the formation of in gas hydrate slurries. These findings open windows of investigation into electrocatalysis in brines below the freezing point of water.Gas hydrates or clathrates are a crystalline solid formed of water and gas. Clathrates looks and acts much like ice, but it contains large amounts of gas trapped within a crystal structure of water. Gas hydrates such as hydrates of hydrocarbons, sulfur dioxide (SO2) and carbon dioxide (CO2) have been reported but they are only used for academic purposes with just a very few examples which have reached technical application. However, gas hydrates might have play an important role in the origin of life, and the chemistry on gas hydrates is relevant in energy applications in particular for space exploration.We will show the electrochemical behavior of hydrogen and oxygen adsorption and desorption processes on different metal electrodes in aqueous brines at subfreezing temperatures. Finally, we will report the first electrochemical results of the CO2RR and the oxidation of CH4 in aqueous brines at subfreezing temperatures down to -40°C.4 Our results will be explained on the basis of the presence of ice-structure clathrates,5,6 solubility of the gases as a function of temperature, kinematic viscosity, mass transport and the changes in the pH of the solution.7,8 The understanding of the electrochemistry of gas hydrates at low temperature is paramount for the development of sustainable energy cycle based on CH4 and CO2 reversible fuel cells under severe environmental conditions. This will be critical to ensure the availability of key in situ resources sustaining future human exploration and colonization of other planets.

Influence of protic ionic liquids on hydration of glycine based peptides

The structure of water, especially around the solute is thought to play an important role in many biological and chemical processes. Water-peptide and cosolvent-peptide interactions are crucial in determining the structure and function of protein molecules. In this work, we present the H-bonding analysis for model peptides like glycyl-glycine (gly-gly), glycine-ւ-valine (gly-val), glycyl-ւ-leucine (gly-leu) and triglycine (trigly) and triethylammonium based carboxylate protic ionic liquids (PILs) in aqueous solutions as well as for peptides in ∼0.2 mol·L−1 of aqueous PIL solutions in the spectral range of 7800–5500 cm−1 using Fourier transform near-infrared (FT-NIR) spectroscopy at 298.15 K. The hydration numbers for peptides and PILs were obtained using NIR method of simultaneous estimation of hydration spectrum and hydration number of a solute dissolved in water. The H-bond of water molecules around peptides and PILs are found to be stronger and shorter than those in pure liquid water. We observe that the hydration shell around zwitterions is a clathrate-like cluster of water in which ions entrap. Watery network analysis confirms that singly H-bonded species or NHBs changes to partial or distorted ice-like structures of water in the hydration shell of PILs. The overall water H-bonding in the hydration sphere of PILs increases in the order TEAF < TEAA < TEAG < TEAPy ≈ TEAP < TEAB. The influence of PILs on hydration behavior of peptides is explored in terms of H-bonding, cooperativity, hydrophobicity, water structural changes, ionic interactions etc.

Structure of the Water Molecule Layer between Ice and Amorphous/Crystalline Surfaces Based on Molecular Dynamics Simulations.

The structure of the water layer between the ice interface and the hydroxylated amorphous/crystalline silica surfaces was investigated using molecular dynamics simulations. The results indicate that the density profile in the direction perpendicular to the surface has two density peaks in the water layer at the ice-silica interface, which are affected by the silanol group density on the wall and the degree of supercooling in the system. In the two density peaks, the one facing the ice interface side has the same structure as the ice crystal, while the other density peak facing the silica surface has an icelike structure. In the solidification process, the ice and icelike structures in the layer progress more on the amorphous silica surface where the density of the silanol groups is low. The relationship between the ice crystallization and the thickness of the layer has been studied in detail; the lower the temperature, the more the ice crystallization progresses and the thinner the layer becomes.

Assessing the Accuracy of the SCAN Functional for Water through a Many-Body Analysis of the Adiabatic Connection Formula.

We present a systematic analysis of the accuracy of a series of SCANα functionals for water, with varying fractions (α) of exact exchange, which are constructed through the adiabatic connection formula. Our results indicate that all SCANα functionals exhibit substantial errors in the representation of the water 2-body energies. Importantly, the inclusion of exact exchange is found to have opposite effects on the ability of the SCANα functionals to describe the interaction energies of water clusters with 2-dimensional and 3-dimensional hydrogen-bonding arrangements. These errors are found to directly affect the ability of the SCANα functionals to describe the structure of liquid water at ambient conditions, which is investigated using explicit many-body models (MB-SCANα) derived from the corresponding SCANα data. In particular, it is found that all MB-SCANα models predict a more compact first hydration shell, which results in a denser liquid with a more ice-like structure. These apparent opposite trends can be explained by the inability of the SCANα functionals to provide a balanced description of the water 2B and 3B energies at the fundamental level. The analyses presented in this study provide new insights that can guide future developments of improved exchange-correlation functionals for aqueous systems.

Ammonium fluoride's analogy to ice: Possibilities and limitations.

Ammonium fluoride, NH4F, is often seen as an analog to ice, with several of its solid phases closely resembling known ice phases. While its ionic and hydrogen-ordered nature puts topological constraints on the ice-like network structures it can form, it is not clear what consequences these constraints have for NH4F compound formation and evolution. Here, we explore computationally the reach and eventual limits of the ice analogy for ammonium fluoride. By combining data mining of known and hypothetical ice networks with crystal structure prediction and density functional calculations, we explore the high-pressure phase diagram of NH4F and host-guest compounds of its hydrides. Pure NH4F departs from ice-like behavior above 80GPa with the emergence of close-packed ionic structures. The predicted stability of NH4F hydrides shows that NH4F can act as a host to small guest species, albeit in a topologically severely constraint configuration space. Finally, we explore the binary NH3-HF chemical space, where we find candidate structures for several unsolved polyfluoride phases; among them is the chemical analog to H2O2 dihydrate.

Thermodynamic properties of cotton dyeing with indigo dyes in non-aqueous media of liquid paraffin and D5

On the basis of investigation into the dyeing equilibrium of cotton fibers with indigo dyes in decamethylcyclopentasiloxane (D5), liquid paraffin and water, the thermodynamic properties of cotton dyeing with indigo dyes in non-aqueous medium systems were studied in comparison with aqueous dyeing. The main works involved are as follows: firstly, the adsorption isotherms were created; then, the three theoretical adsorption models of Nernst, Langmuir and Freundlich were used to fit the adsorption isotherms created; finally, the thermodynamic parameters were calculated. The results showed that the adsorption isotherms were all in line with the Freundlich model. The order of dyeing affinity was in the sequence: liquid paraffin &gt; D5 &gt; water. The dyeing entropy in the three media showed positive values, which is mainly attributed to the adsorption of both indigo-leuco and water onto cotton fibers, thus reducing the ice-like structure formed among the water molecules in the dyeing system and the hydrophobic bonding structure formed among the non-aqueous medium molecules, then leading to an increase in the system disorder. The dyeing heat in the three media also showed positive values, due mainly to the absorption of thermal energy to “melt” the ice-like structure and to “break” the hydrophobic bonding structure. These dyeing thermodynamic properties are conducive to understanding and interpreting the dyeing performance and behavior of indigo dyes in non-aqueous dyeing systems.

Liquid Water and Interfacial, Cubic, and Hexagonal Ice Classification through Eclipsed and Staggered Conformation Template Matching.

We propose a novel method based on template matching for the recognition of liquid water, cubic ice (ice Ic), hexagonal ice (ice Ih), clathrate hydrates, and different interfacial structures in atomistic and coarse-grained simulations of water and ice. The two template matrices represent staggered and eclipsed conformations, which are the building blocks of hexagonal and cubic ice and clathrate crystals. The algorithm is rotationally invariant and highly robust against imperfections in the ice structure, and its sensitivity for recognizing ice-like structures can be tuned for different applications. Unlike most other algorithms, it can discriminate between cubic, hexagonal, clathrate, mixed, and other interfacial ice types and is therefore well suited to study complex systems and heterogeneous ice nucleation.