Atomic imaging of the edge structure and growth of a two-dimensional hexagonal ice.

The formation and growth of water-ice layers on surfaces and of low-dimensional ice under confinement are frequent occurrences1-4. This is exemplified by the extensive reporting of two-dimensional (2D) ice on metals5-11, insulating surfaces12-16, graphite and graphene17,18 and under strong confinement14,19-22. Although structured water adlayers and 2D ice have been imaged, capturing the metastable or intermediate edge structures involved in the 2D ice growth, which could reveal the underlying growth mechanisms, is extremely challenging, owing to the fragility and short lifetime of those edge structures. Here we show that noncontact atomic-force microscopy with a CO-terminated tip (used previously to image interfacial water with minimal perturbation)12, enables real-space imaging of the edge structures of 2D bilayer hexagonal ice grown on a Au(111) surface. We find that armchair-type edges coexist with the zigzag edges usually observed in 2D hexagonal crystals, and freeze these samples during growth to identify the intermediate edge structures. Combined with simulations, these experiments enable us to reconstruct the growth processes that, in the case of the zigzag edge, involve the addition of water molecules to the existing edge and a collective bridging mechanism. Armchair edge growth, by contrast, involves local seeding and edge reconstruction and thus contrasts with conventional views regarding the growth of bilayer hexagonal ices and 2D hexagonal matter in general.

Anomalous water transport in narrow-diameter carbon nanotubes.

Carbon nanotubes (CNTs) mimicking the structure of aquaporins support fast water transport, making them strong candidates for building next-generation high-performance membranes for water treatment. The diffusion and transport behavior of water through CNTs or nanoporous graphene can be fundamentally different from those of bulk water through a macroscopic tube. To date, the nanotube-length-dependent physical transport behavior of water is still largely unexplored. Herein, on the basis of molecular dynamics simulations, we show that the flow rate of water through 0.83-nm-diameter (6,6) and 0.96-nm-diameter (7,7) CNTs exhibits anomalous transport behavior, whereby the flow rate increases markedly first and then either slowly decreases or changes slightly as the CNT length l increases. The critical range of l for the flow-rate transition is 0.37 to 0.5 nm. This anomalous water transport behavior is attributed to the l-dependent mechanical stability of the transient hydrogen-bonding chain that connects water molecules inside and outside the CNTs and bypasses the CNT orifice. The results unveil a microscopic mechanism governing water transport through subnanometer tubes, which has important implications for nanofluidic manipulation.

Mechanistic Insights into Chloric Acid Production by Hydrolysis of Chlorine Trioxide at an Air-Water Interface.

Chlorine oxides play crucial roles in ozone depletion, and the final oxidation steps of chlorine oxide potentially result in the formation of chloric acid (HClO3) or perchloric acid (HClO4). Herein, the solvation and reactive uptake of three stable isomers of chlorine trioxide (Cl2O3), namely, ClOCl(O)O, ClClO3, and ClOOOCl, at the air-water interface were investigated using classical and hybrid quantum mechanics/molecular mechanics (QM/MM) molecular dynamics (MD) coupled with advanced free energy methods. Two distinct mechanisms were revealed for the hydrolysis of ClOCl(O)O and ClClO3: molecular and ionic mechanisms. A comparison of the computed free-energy profiles for the gaseous and air-water interfacial systems indicated that the air-water interface could markedly lower the free-energy barrier for ClO3- or HClO3 formation while stabilizing the product state. In particular, the hydrolysis of ClClO3 at the air-water interface was barrierless. In contrast, our calculations showed that the hydrolysis of ClOOOCl was very slow, indicating that ClOOOCl was inert to water at the air-water interface. This study provides theoretical evidence for the hypothesis that HClO3 is a sink for chlorine oxides and for the widespread distributions of HClO3 recently observed in the Arctic region.

Mechanistic Insights into N2O5-Halide Ions Chemistry at the Air-Water Interface.

The activation of halogens (X = Cl, Br, I) by N2O5 is linked to NOx sources, ozone concentrations, NO3 reactivity, and the chemistry of halide-containing aerosol particles. However, a detailed chemical mechanism is still lacking. Herein, we explored the chemistry of the N2O5···X- systems at the air-water interface. Two different reaction pathways were identified for the reaction of N2O5 with X- at the air-water interface: the formation of XNO2 or XONO, along with NO3-. In the case of the Cl- system, the ClNO2 generation pathway is more favorable, while for the Br- and I- systems, the formation of BrONO and IONO is barrierless, making them the predominant products. Furthermore, the mechanisms of formation of X2 from XNO2 and XONO were also investigated. The high energy barriers of reactions and the high free energies of the products compared to those of the reactants indicate that ClNO2 is stable at the air-water interface. Contrary to the widely held belief regarding X2 producing from the reaction of XNO2 with X-, our calculations demonstrate that BrONO and IONO initially form stable BrONO···Br- and IONO···I- complexes, which then subsequently react with Br- and I- to form Br3- and I3-, respectively. Finally, Br3- and I3- decompose to form Br2 and I2. These findings have significant implications for experimental interpretation and offer new insights into halogen cycling in the atmosphere.

Formation of a two-dimensional helical square tube ice in hydrophobic nanoslit using the TIP5P water model.

In extreme and nanoconfinement conditions, the tetrahedral arrangement of water molecules is challenged, resulting in a rich and new phase behavior unseen in bulk phases. The unique phase behavior of water confined in hydrophobic nanoslits has been previously observed, such as the formation of a variety of two-dimensional (2D) ices below the freezing temperature. The primary identified 2D ice phase, termed square tube ice (STI), represents a unique arrangement of water molecules in 2D ice, which can be viewed as an array of 1D ice nanotubes stacked in the direction parallel to the confinement plane. In this study, we report the molecular dynamics (MD) simulations evidence of a novel 2D ice phase, namely, helical square tube ice (H-STI). H-STI is characterized by the stacking of helical ice nanotubes in the direction parallel to the confinement plane. Its structural specificity is evident in the presence of helical square ice nanotubes, a configuration unseen in both STI and single-walled ice nanotubes. A detailed analysis of the hydrogen bonding strength showed that H-STI is a 2D ice phase diverging from the Bernal-Fowler-Pauling ice rules by forming only two strong hydrogen bonds between adjacent molecules along its helical ice chain. This arrangement of strong hydrogen bonds along ice nanotube and weak bonds between the ice nanotube shows a similarity to quasi-one-dimensional van der Waals materials. Ab initio molecular dynamics simulations (over a 30 ps) were employed to further verify H-STI's stability at 1 GPa and temperature up to 200 K.

The performance of OPC and OPC3 water models in predictions of 2D structures under nanoconfinement.

Nanoconfined water plays an important role in broad fields of science and engineering. Classical molecular dynamics (MD) simulations have been widely used to investigate water phases under nanoconfinement. The key ingredient of MD is the force field. In this study, we systematically investigated the performance of a recently introduced family of globally optimal water models, OPC and OPC3, and TIP4P/2005 in describing nanoconfined two-dimensional (2D) water ice. Our studies show that the melting points of the monolayer square ice (MSI) of all three water models are higher than the melting points of the corresponding bulk ice Ih. Under the same conditions, the melting points of MSI of OPC and TIP4P/2005 are the same and are ∼90 K lower than that of the OPC3 water model. In addition, we show that OPC and TIP4P/2005 water models are able to form a bilayer AA-stacked structure and a trilayer AAA-stacked structure, which are not the cases for the OPC3 model. Considering the available experimental data and first-principles simulations, we consider the OPC water model as a potential water model for 2D water ice MD studies.

Formation of porous ice frameworks at room temperature.

Bulk crystalline ices with ultralow densities have been demonstrated to be thermodynamically metastable at negative pressures. However, the direct formation of these bulk porous ices from liquid water at negative pressures is extremely challenging. Inspired by approaches toward porous media based on host-guest chemistry, such as metal-organic frameworks and covalent organic frameworks, we herein demonstrate via molecular dynamics simulations that a class of ultralow-density porous ices with upright channels can be formed spontaneously from liquid water at 300 K with the assistance of carbon nanotube arrays. We refer to these porous ice polymorphs as water oxygen-vertex frameworks (WOFs). Notably, our simulations revealed that the liquid-WOF phase transition is first-order and occurs at room temperature. All the WOFs exhibited the unique structural feature that they can be regarded as assemblies of nanoribbons of hexagonal bilayer ice (2D ice I) at their armchair or zigzag edges. Based on density functional theory calculations, a comprehensive phase diagram of the WOFs was constructed considering both the thermodynamic and thermal stabilities of the porous ices at negative pressures. Like other types of porous media, these WOFs may be applicable to gas storage, purification, and separation. Moreover, these biocompatible porous ice networks may be exploited as medical-related carriers.

Water Charge Transfer Accelerates Criegee Intermediate Reaction with H2O- Radical Anion at the Aqueous Interface.

Criegee intermediates (CIs) are important carbonyl oxides that may react with atmospheric trace chemicals and impact the global climate. The CI reaction with water has been widely studied and is a main channel for trapping CIs in the troposphere. Previous experimental and computational reports have largely focused on reaction kinetic processes in various CI-water reactions. The molecular-level origin of CI's interfacial reactivity at the water microdroplet surface (e.g., as found in aerosols and clouds) is unclear. In this study, by employing the quantum mechanical/molecular mechanical (QM/MM) Born-Oppenheimer molecular dynamics with the local second-order Møller-Plesset perturbation theory, our computational results reveal a substantial water charge transfer up to ∼20% per water, which creates the surface H2O+/H2O- radical pairs to enhance the CH2OO and anti-CH3CHOO reactivity with water: the resulting strong CI-H2O- electrostatic attraction at the microdroplet surface facilitates the nucleophilic attack to the CI carbonyl by water, which may counteract the apolar hindrance of the substituent to accelerate the CI-water reaction. Our statistical analysis of the molecular dynamics trajectories further resolves a relatively long-lived bound CI(H2O-) intermediate state at the air/water interface, which has not been observed in gaseous CI reactions. This work provides insights into what may alter the oxidizing power of the troposphere by the next larger CIs than simple CH2OO and implicates a new perspective on the role of interfacial water charge transfer in accelerating molecular reactions at aqueous interfaces.

Molecular Insights into the Spontaneous Generation of Cl2O in the Reaction of ClONO2 and HOCl at the Air-Water Interface.

Chemical processes involving chlorine nitrate (ClONO2) at the surface of stratospheric aerosols are crucial to ozone depletion. Herein, we show a reaction route for the formation of Cl2O, which is a source of stratospheric chlorine, in the ClONO2 + HOCl reaction at the air-water interface. Our ab initio molecular dynamics (AIMD) simulations show that the (ClONO2)Cl···O(HOCl) halogen bond plays a key role in the reaction and is the main interaction between ClONO2 and HOCl both at the air-water interface and in the bulk liquid water. Furthermore, metadynamics-based AIMD simulations reveal two pathways: (i) The OCl fragment of HOCl binds to the Cl atom in ClONO2, resulting in the formation of Cl2O and NO3-. Simultaneously, the remaining hydrogen atom is transferred to a water molecule to form H3O+. (ii) HOCl acts as a bridge for Cl atom transfer from ClONO2 to the O atom of a water molecule, and this water molecule transfers one of its H atoms to another water molecule, forming two HOCl molecules, NO3-, and H3O+. Free-energy calculations show that the former is the energetically more favorable process. More importantly, the free-energy barrier for Cl2O formation at the air-water interface is only ∼0.8 kcal/mol, and the reaction is exothermic. These findings provide insights into the importance of fundamental chlorine chemistry and the broader implications of the aerosol air-water interface for atmospheric chemistry.

Mechanistic Insights into the Reactive Uptake of Chlorine Nitrate at the Air-Water Interface.

It is well-known that the aqueous-phase processing of chlorine nitrate (ClONO2) plays a crucial role in ozone depletion. However, many of the physical and chemical properties of ClONO2 at the air-water interface or in bulk water are unknown or not understood on a microscopic scale. Here, the solvation and hydrolysis of ClONO2 at the air-water interface and in bulk water at 300 K were investigated by classical and ab initio molecular dynamics (AIMD) simulations combined with free energy methods. Our results revealed that ClONO2 prefers to accumulate at the air-water interface rather than in the bulk phase. Specifically, halogen bonding interactions (ClONO2)Cl···O(H2O) were found to be the predominant interactions between ClONO2 and H2O. Moreover, metadynamics-biased AIMD simulations revealed that ClONO2 hydrolysis is catalyzed at the air-water interface with an activation barrier of only ∼0.2 kcal/mol; additionally, the difference in free energy between the product and reactant is only ∼0.1 kcal/mol. Surprisingly, the near-barrierless reaction and the comparable free energies of the reactant and product suggested that the ClONO2 hydrolysis at the air-water interface is reversible. When the temperature is lowered from 300 to 200 K, the activation barrier for the ClONO2 hydrolysis at the air-water interface is increased to ∼5.4 kcal/mol. These findings have important implications for the interpretation of experiments.

Spontaneous Oxidation of Thiols and Thioether at the Air-Water Interface of a Sea Spray Microdroplet.

The transport of dissolved organic sulfur, including thiols and thioethers, from the ocean surface to the atmosphere through sea spray aerosol (SSA) is of great importance for the global sulfur cycle. Thiol/thioether in SSA undergoes rapid oxidation that is historically linked to photochemical processes. Here, we report the discovery of a non-photochemical, spontaneous path of thiol/thioether oxidation in SSA. Among 10 investigated naturally abundant thiol/thioether, seven species displayed rapid oxidation in SSA, with disulfide, sulfoxide, and sulfone comprising the major products. We suggest that such spontaneous oxidation of thiol/thioether was mainly fueled by thiol/thioether enrichment at the air-water interface and generation of highly reactive radicals by the loss of an electron from ions (e.g., glutathionyl radical produced from ionization of deprotonated glutathione) at or near the surface of the water microdroplet. Our work sheds light on a ubiquitous but previously overlooked pathway of thiol/thioether oxidation, which could contribute to an accelerated sulfur cycle as well as related metal transformation (e.g., mercury) at ocean-atmosphere interfaces.

Accelerated Photolysis of H2O2 at the Air-Water Interface of a Microdroplet.

Photochemical homolysis of hydrogen peroxide (H2O2) occurs widely in nature and is a key source of hydroxyl radicals (·OH). The kinetics of H2O2 photolysis play a pivotal role in determining the efficiency of ·OH production, which is currently mainly investigated in bulk systems. Here, we report considerably accelerated H2O2 photolysis at the air-water interface of microdroplets, with a rate 1.9 × 103 times faster than that in bulk water. Our simulations show that due to the trans quasiplanar conformational preference of H2O2 at the air-water interface compared to the bulk or gas phase, the absorption peak in the spectrum of H2O2 is significantly redshifted by 45 nm, corresponding to greater absorbance of photons in the sunlight spectrum and faster photolysis of H2O2. This discovery has great potential to solve current problems associated with ·OH-centered heterogeneous photochemical processes in aerosols. For instance, we show that accelerated H2O2 photolysis in microdroplets could lead to markedly enhanced oxidation of SO2 and volatile organic compounds.

Enhanced CO2 Electroreduction Selectivity toward Ethylene on Pyrazolate-Stabilized Asymmetric Ni-Cu Hybrid Sites.

Metal-organic frameworks (MOFs) possess well-defined, designable structures, holding great potential in enhancing product selectivity for electrochemical CO2 reduction (CO2R) through active site engineering. Here, we report a novel MOF catalyst featuring pyrazolate-stabilized asymmetric Ni/Cu sites, which not only maintains structural stability under harsh electrochemical conditions but also exhibits extraordinarily high ethylene (C2H4) selectivity during CO2R. At a cathode potential of -1.3 V versus RHE, our MOF catalyst, denoted as Cu1Ni-BDP, manifests a C2H4 Faradaic efficiency (FE) of 52.7% with an overall current density of 0.53 A cm-2 in 1.0 M KOH electrolyte, surpassing that on prevailing Cu-based catalysts. More remarkably, the Cu1Ni-BDP MOF exhibits a stable performance with only 4.5% reduction in C2H4 FE during 25 h of CO2 electrolysis. A suite of characterization tools─such as high-resolution transmission electron microscopy, X-ray absorption spectroscopy, operando X-ray diffraction, and infrared spectroscopy─and density functional theory calculations collectively reveal that the cubic pyrazolate-metal coordination structure and the asymmetric Ni-Cu sites in the MOF catalyst synergistically facilitate the stable formation of C2H4 from CO2.

Excessive Iodine Enabled Ultrathin Inorganic Perovskite Growth at the Liquid-Air Interface.

The liquid-air interface offers a platform for the in-plane growth of free-standing materials. However, it is rarely used for inorganic perovskites and ultrathin non-layered perovskites. Herein the liquid-air interfacial synthesis of inorganic perovskite nanosheets (Cs3 Bi2 I9 , Cs3 Sb2 I9 ) is achieved simply by drop-casting the precursor solution with only the addition of iodine. The products are inaccessible without iodine addition. The thickness and lateral size of these nanosheets can be adjusted through the iodine concentration. The high volatility of the iodine spontaneously drives precursors that normally stay in the liquid to the liquid-air interface. The iodine also repairs in situ iodine vacancies during perovskite growth, giving enhanced optical and optoelectronic properties. The liquid-air interfacial growth of ultrathin perovskites provides multi-degree-of-freedom for constructing perovskite-based heterostructures and devices at atomic scale.

Role of an Ice Surface in the Photoreaction of Coumarins.

Ice affects many chemical reactions in nature, which greatly influences the atmosphere, climate, and life. However, the exact mechanism of ice in these chemical reactions remains elusive. For example, it is still an open question as to whether ice can act as a catalyst to greatly enhance the reactivity and selectivity, which is essential for the production of some natural compounds in our planet. Here, we discover that ice can lead to high efficiency and stereoselectivity of the [2 + 2] photodimerization of coumarin and its derivatives. The conversion of the [2 + 2] photodimerization of coumarins enhanced by ice is dozens of times higher than that in the unfrozen saturated solution, and the reaction displays a high syn-head-head stereoselectivity (>95%) in comparison with those in the absence of the ice. Note that almost no reaction occurs in the crystal powder and melt of the coumarins, indicating that the role of ice in the photodimerization reaction is not simply due to the usual mechanisms found in the freezing concentration. We further reveal that the reaction rate is found to be proportional to the total area of the ice surface and follows Michaelis-Menten-like kinetics, indicating that the ice surface catalyzes the reaction. Molecular dynamics simulations demonstrate that ice surfaces can induce reactants to form a two-dimensional liquid-crystal-ordered layer with a suitable intermolecular distance and unique side-by-side packing, facilitating stereoselective photodimerization for syn-head-head dimers. These findings give evidence that ice-surface-induced molecular assembly may play an important role in atmospheric heterogeneous photoreaction processes.

Efficient exploration of complex free energy landscapes by stepwise multi-subphase space metadynamics.

We present an efficient method based on an extension of metadynamics for exploring complex free energy landscapes (FELs). The method employs two-step metadynamics simulations. In the first step, rapid metadynamics simulations using broad and tall Gaussians are performed to identify a free energy pathway (FEP) connecting the two states of interest. The FEP is then divided into a series of independent subphase spaces that comprise selected discrete images of the system. Using appropriate collective variables (CVs) chosen according to the FEP, the accurate FEL of each subphase space is separately calculated in subsequent divide-and-conquer metadynamics simulations with narrow and low Gaussians. Finally, all FELs calculated in each subphase space are merged to obtain the full FEL. We show that the method greatly improves the performance of the metadynamics approach. In particular, we are able to efficiently model chemical systems with complex FELs, such as chemical reactions at the air/water interface. We demonstrate the performance of this method on two model reactions: the hydrolysis of formaldehyde in the gas phase and at the air/water interface.

An ultralow-density porous ice with the largest internal cavity identified in the water phase diagram.

The recent back-to-back findings of low-density porous ice XVI and XVII have rekindled the century-old field of the solid-state physics and chemistry of water. Experimentally, both ice XVI and XVII crystals can be produced by extracting guest atoms or molecules enclosed in the cavities of preformed ice clathrate hydrates. Herein, we examine more than 200 hypothetical low-density porous ices whose structures were generated according to a database of zeolite structures. Hitherto unreported porous EMT ice, named according to zeolite nomenclature, is identified to have an extremely low density of 0.5 g/cm3 and the largest internal cavity (7.88 Å in average radius). The EMT ice can be viewed as dumbbell-shaped motifs in a hexagonal close-packed structure. Our first-principles computations and molecular dynamics simulations confirm that the EMT ice is stable under negative pressures and exhibits higher thermal stability than other ultralow-density ices. If all cavities are fully occupied by hydrogen molecules, the EMT ice hydrate can easily outperform the record hydrogen storage capacity of 5.3 wt % achieved with sII hydrogen hydrate. Most importantly, in the reconstructed temperature-pressure (T-P) phase diagram of water, the EMT ice is located at deeply negative pressure regions below ice XVI and at higher temperature regions next to FAU. Last, the phonon spectra of empty-sII, FAU, EMT, and other zeolite-like ice structures are computed by using the dispersion corrected vdW-DF2 functional. Compared with those of ice XI (0.93 g/cm3), both the bending and stretching vibrational modes of the EMT ice are blue-shifted due to their weaker hydrogen bonds.

Direct observation of 2-dimensional ices on different surfaces near room temperature without confinement.

Water-solid interfaces play important roles in a wide range of fields, including atmospheric science, geochemistry, electrochemistry, and food science. Herein, we report simulation evidence of 2-dimensional (2D) ice formation on various surfaces and the dependence of the 2D crystalline structure on the hydrophobicity and morphology of the underlying surface. Contrary to the prevailing view that nanoscale confinement is necessary for the 2D liquid-to-bilayer ice transition, we find that the liquid-to-bilayer hexagonal ice (BHI) transition can occur either on a model smooth surface or on model fcc-crystal surfaces with indices of (100), (110), and (111) near room temperature. We identify a critical parameter that characterizes the water-surface interaction, above which the BHI can form on the surface. This critical parameter increases as the temperature increases. Even at temperatures above the freezing temperature of bulk ice (Ih ), we find that BHI can also form on a superhydrophilic surface due to the strong water-surface interaction. The tendency toward the formation of BHI without confinement reflects a proper water-surface interaction that can compensate for the entropy loss during the freezing transition. Furthermore, phase diagrams of 2D ice formation are described on the plane of the adsorption energy versus the fcc lattice constant (Eads-afcc), where 4 monolayer square-like ices are also identified on the fcc model surfaces with distinct water-surface interactions.

Mechanistic Insights into Fast Charging and Discharging of the Sodium Metal Battery Anode: A Comparison with Lithium.

Na metal anode receives increasing attention as a low-cost alternative to Li metal anode for the application in high energy batteries. Despite extensive research efforts to improve the reversibility and cycle life of Na metal electrodes, their rate performance, i.e. electrochemical plating and stripping of Na metal at high current, is underexplored. Herein, we report that Na metal electrodes, unlike the more widely studied Li metal electrodes which survive high current density up to 20 mA/cm2, cannot be fast charged or discharged in common ether electrolyte. The fast charging, namely metal plating, is comprised by severe side reactions that decompose electrolyte into electrochemically inactive Na(I) solid species. The fast discharging, namely metal stripping, is disabled by local Na removal that deteriorates the electrical contact with the current collector. While the fast charging failure is permanent, the capacity loss from fast discharging can be recovered through a restructuring process at a low discharging current which rebuilds the electrical connection. We further reveal that the unsatisfactory rate performance of Na metal electrodes is associated with intrinsic physicochemical properties of Na. This study delineates the mechanistic origins of Na's limitation in fast plating and stripping, and demonstrates the necessity of improving the charging and discharging rate performance of Na metal electrodes.

First-Principles Molecular Dynamics Simulations of the Spontaneous Freezing Transition of 2D Water in a Nanoslit.

As with bulk ices, two-dimensional (2D) ices exhibit diverse crystalline structures, and the majority of these 2D structures have been predicted based on classical molecular dynamics (MD) simulations. Here, the spontaneous freezing transition of 2D liquid water within hydrophobic nanoslits is demonstrated for the first time using first-principles MD simulations. Various 2D ices are observed under different lateral pressure and temperature conditions. Notably, the liquid water confined to a 6.0 Å-wide nanoslit can spontaneously freeze into a monolayer ice consisting of an array of zigzag water chains at 2.5 GPa and 250 K. Moreover, within an 8.0 Å-wide nanoslit and at 4.0 GPa and 300 K, a previously unreported bilayer ice forms spontaneously that has a structure resembling that of the double surface layers of bulk ice-VII. Both 2D crystalline ices do not obey the ice rule, suggesting first-principles simulation can access a certain phase space that is not easily approached using classical simulations.