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A quarter of Earth's land surface is covered by porous sedimentary silicate rocks, so silica–water interfaces are critical to the fate and transport of chemical species on a global-scale.
Understanding the microscopic driving force of water wetting is challenging and important for design of materials. The relations between structure, dynamics and hydrogen bonds of interfacial water can be investigated using molecular dynamics simulations. Here, contact angles at the alumina (0001) and ($11\bar{2}0$) surfaces are studied using both classical molecular dynamics simulations and experiments. To test the superhydrophilicity, the free energy cost of removing waters near the interfaces are calculated using the density fluctuations method. The strength of hydrogen bonds is determined by their lifetime and geometry. Both surfaces are superhydrophilic and the (0001) surface is more hydrophilic. Interactions between surfaces and interfacial waters promote a templating effect whereby the latter are aligned in a pattern that follows the underlying lattice of the surfaces. Translational and rotational dynamics of interfacial water molecules are slower than in bulk water. Hydrogen bonds between water and both surfaces are asymmetric, water-to-aluminol ones are stronger than aluminol-to-water ones. Molecular dynamics simulations eliminate the impacts of surface contamination when measuring contact angles and the results reveal the microscopic origin of the macroscopic superhydrophilicity of alumina surfaces: strong water-to-aluminol hydrogen bonds.
The role that interfacial water plays in both promoting and inhibiting the electrochemical oxygen reduction reaction (ORR) remains somewhat unclear and controversial. Here, we use electroanalytical chemistry, spectroscopy, and microkinetic modeling to probe the impact of hydrophobic ionic liquid (IL) thin films on interfacial water structure and its role in promoting or inhibiting the ORR. Through the use of in situ ATR-SEIRAS, we find that the IL thin films limit the content of water at the interface and prevent the formation of hydrogen bond stabilized water organization. The impact of this exclusion of water on the promotion of the ORR is through the reduced coverage of OH ad spectator species. The decreased solvation of “active” OH ad species weakens its interaction with the catalyst surface, lowering the barrier to the last step in the ORR mechanism. This “destabilized” OH ad impact on ORR kinetics is confirmed through a microkinetic model. Furthermore, the results presented here highlight the mechanistic pathway through which hydrophobic ILs enhance ORR kinetics and point to pathways to both further improve this performance enhancement and the potential for integration of hydrophobic ILs into other technologically relevant elementary electrochemical reactions.
Abstract Synchrotron X‐ray microtomography (XMT) was used to measure total air‐water interfacial areas (A aw ) as a function of water saturation (S w ) for several soils that comprise a range of physical and geochemical properties. Measurements were also conducted for glass beads and quartz sands for comparison. Apparent near‐linearA aw ‐S w relationships are observed for the three sands and the three sandy soils. In contrast, the measured interfacial areas for two soils that contain greater proportions of silt and clay are strongly nonlinear functions of water saturation. The greater degree of nonlinearity observed for these two soils is due to their much greater particle‐size distributions (i.e., uniformity coefficients) and their concomitant greater range in pore sizes. Interfacial areas determined with the thermodynamic method were used to benchmark the XMT measurements. XMT‐measured interfacial areas compare well to the thermodynamic‐determined values for the sands and sandy soils. In contrast, the XMT‐measured interfacial areas for the two soils with larger particle‐size distributions are not fully congruent with the thermodynamic‐determined values. Both of these soils have large fractions of pore space comprising nominal pore diameters smaller than the resolution of the XMT imaging. These results suggest that air‐water interfacial area may not always be fully characterized by standard XMT for soils with large particle‐size distributions.
Molecular dynamics simulations are used to study the nonlinear dielectric responses of a confined aqueous film in a planar nanopore under perpendicular electric fields at varied voltages between confining graphene sheets. Dielectric saturation reminiscent of the bulk phase behavior is prevalent at very strong fields, whereas we observe a nonmonotonic permittivity dependence on the electric field at intermediate strengths where field-alignment and spontaneous polarization of interfacial water are of comparable magnitude. The coupling between the two effects results in distinct dielectric responses at opposite confinement walls. The normal component of both the differential dielectric constant and dielectric difference constant tensors averaged over the region closer to the wall under an incoming electric field (field pointing from the liquid to the solid phase) initially increases with the strength of the imposed field. The differential permittivity peaks at a field strength previously shown to offset the surface-induced orientation bias of hydration molecules at this wall. Further strengthening of the field results in a conventional saturation behavior. At the opposite wall (subject to outgoing field) and in the central region of the water slab, the nonlinear dielectric response resembles bulklike saturation. The conditions at the permittivity extremum coincide with the window of accelerated reorientation rates of interfacial water molecules under an incoming field we uncovered in earlier molecular dynamics analyses.
Controlling water structure and dynamics at silica interfaces are central to a wide range of technologies, including protective oxide layers for solar water splitting and nanoporous membranes. In this work, we develop a machine learning interatomic potential, trained via active learning, to achieve ab initio accuracy for water confined between hydroxylated silica surfaces over a range of silanol coverages and slit widths. We find that partially hydroxylated surfaces (50 and 75% OH) support stronger water−surface hydrogen bonding and more extended interfacial density profiles than fully hydroxylated (100% OH) surfaces, indicating that increasing OH coverage does not necessarily strengthen interfacial hydrogenbond networks. Translational diffusion decreases approximately linearly with slit width and OH coverage, whereas rotational dynamics respond nonlinearly. In particular, at the smallest slit width of 5 Å, 75% OH coverage produces an enhanced local tetrahedral ordered interfacial network that strongly suppresses reorientation, while 100% coverage yields a crowded, disordered interfacial layer that also hinders rotation. In contrast, the 50% OH coverage is sufficiently sparse that it does not markedly alter water structure or dynamics under confinement. These results show that coupled control of pore size and surface chemistry enables nonlinear tuning of interfacial water structure and transport, providing a design strategy for optimizing porous silica for either enhanced interfacial stability and controlled reactivity or rapid and selective transport.
Herein we discuss graphene oxide as a promising, emerging separation material, as it is durable, dispersible in water, and has naturally forming functional groups. Bulk studies using graphene oxide flakes have demonstrated impressive metal adsorption. However, little interfacial information about water and metal organization near graphene oxide is available. A mechanistic understanding of water and ions interactions with graphene oxide films is critical toward advanced separations, including improved sorption efficiency and membrane regeneration. We study metal ion and local water organization near graphene oxide thin films formed at the air/water interface. These films are not typical membranes and allow us to determine nanoscale information about the graphene oxide-water interface. We accomplish this with x-ray reflectivity (XR), x-ray fluorescence near total reflection (XFNTR), and vibrational sum frequency generation spectroscopy (SFG). These interface-specific techniques provide the electron density profile normal to the interface, number of adsorbed ions, and information about the orientational ordering and hydrogen-bonding network of interfacial water, respectively. Via XFNTR and SFG, we find that trivalent yttrium ions preferentially adsorb to graphene oxide and affect its structure, compared to divalent strontium and monovalent cesium ions. Two different interfacial water populations can be described, based on their hydrogen bonding strength, and the adsorbed ions affect these populations differently. These results provide fundamental information about ion and water organization at the interface and help address the large computational-experimental agreement gap for graphene oxide systems. Additionally, they are relevant for improved soft-scaffold graphene oxide membranes and downstream applications.
"On-water" catalysis, the unusual activity of water molecules at the organic solvent-water interface, has been demonstrated in many organic reactions. However, the catalytic mechanism has remained unclear, largely because of the irreproducibility of the organic-water interface under the common stirring condition. In this work, the interfacial area was controlled by employing adsorbed water on mesoporous silica nanoparticles as the catalyst. Reliable kinetics of the cycloaddition reaction of quadricyclane and diethyl azodicarboxylate (DEAD) at the toluene-water interface within the nanoparticle pores were measured. Data reveal an Eley-Rideal mechanism, wherein DEAD adsorbs at the toluene-water interface via hydrogen bonds formed with interfacial water, which lower the activation energy of the cycloaddition reaction. The mechanistic insights gained and preparation of surface water in silica pores described herein may facilitate the future design of improved "on-water" catalysts.
Electrochemical reduction of CO 2 to CO is a key step in carbon utilization technologies, yet maintaining high CO selectivity under elevated temperatures relevant to industrial membrane-electrode-assembly (MEA) electrolyzers remains challenging due to the competing hydrogen evolution reaction (HER). Additionally, the temperature dependence of CO selectivity on Cu-based catalysts has remained largely unexplored. Here, we demonstrate that incorporating atomic In or Sn into Cu fundamentally reshapes the selectivity of Cu catalysts at elevated temperatures. Dilute alloy catalysts, In 1 Cu and Sn 1 Cu, achieve >95% FE of CO over a broad current-density window (0.1−1.1 A cm −2 ) at 60 °C in MEA electrolyzers, far exceeding their performance at ambient temperature. In situ attenuated total reflection surface-enhanced infrared absorption spectroscopy suggests that elevating temperature depletes interfacial water activity, which favors a shift in CO 2 activation from a proton-coupled *COOH pathway toward an electron-driven *COO − -associated pathway, while also suppressing HER and CO hydrogenation. In contrast, benchmark CO-selective catalysts such as Ag exhibit minimal temperature-induced changes in CO production at 20−60 °C. These findings identify temperature as an unavoidable yet previously underutilized operating parameter in MEA electrolyzers for high-rate, selective CO production on Cubased catalysts.
Controlling electrochemical reactivity requires a detailed understanding of the charging behavior and thermodynamics of the electrochemical interface. Experiments can independently probe the overall charge response of the electrochemical double layer by capacitance measurements and the thermodynamics of the inner layer with potential of maximum entropy measurements. Relating these properties by computational modeling of the electrochemical interface has so far been challenging due to the low accuracy of classical molecular dynamics (MD) for capacitance and the limited time and length scales of ab initio MD. Here, we combine large ensembles of long-time-scale classical MD simulations with charge response from electronic density functional theory to predict the potential-dependent capacitance of a family of ideal aqueous electrochemical interfaces with different peak capacitances. We show that while the potential of maximum capacitance varies, this entire family exhibits an electrode charge of maximum capacitance (CMC) between -2.9 and -2.2 μC/cm 2 , regardless of the details in the electronic response. Simulated heating of the same interfaces reveals that the entropy peaks at a charge of maximum entropy (CME) of -5.1 ± 0.6 μC/cm 2 , in agreement with experimental findings for metallic electrodes. The CME and CMC both indicate asymmetric response of interfacial water that is stronger for negatively charged electrodes, while the difference between CME and CMC illustrates the richness in behavior of even the ideal electrochemical interface.
Vibrational spectroscopy is a powerful tool for probing water at oxide–electrolyte interfaces, but its molecular interpretation can be challenging. Here, we employ deep potential long-range molecular dynamics simulations with layer-resolved spectral analysis to investigate the microscopic origins of the infrared (IR) response of water at the interface with anatase TiO 2 (101), a prototypical oxide surface. The calculated interfacial spectra exhibit characteristic modifications compared to bulk water IR spectra, including enhanced intensities, a red shifted and broadened stretching band, and a higher-frequency shoulder, in qualitative agreement with experiments. Spectral decomposition shows that these signatures originate mainly from the first interfacial water layer, dominated by surface-bound H 2 O at Ti 5C sites, with secondary contributions from the second layer. A moderate salt concentration (0.4 M NaCl) leaves both the interfacial structure and the spectra essentially unchanged, while tuning the pH strongly modulates the spectral intensity. We establish a scaling relation linking the spectral intensity to the surface water dissociation fraction and the dipole moment, both governed by interfacial electric fields. These findings provide a microscopic framework for interpreting IR spectra of oxide–electrolyte interfaces.
Although interfacial solution structure impacts environmental, biological, and technological phenomena, including colloidal stability, protein assembly, heterogeneous nucleation, and water desalination, its molecular details remain poorly understood. Here, we visualize the three-dimensional (3D) hydration structure at the boehmite(010)-water interface using fast force mapping (FFM). Using a self-consistent scheme to decouple long-range tip-sample interactions from short-range solvation forces, we obtain the solution structure with lattice resolution. The results are benchmarked against molecular dynamics simulations that explicitly include the effects of the tip with different levels of approximation and systematically account for tip size, chemistry, and confinement effects. We find four laterally structured water layers within 1 nm of the surface, with the highest water densities at sites adjacent to hydroxyl groups. The key features beyond the first two layers can only be predicted using a full-scale simulation of the boehmite-water-silica system. Our findings further reveal a complex relationship between site-specific chemistry, water density, and long-range particle interactions; and present important advances toward quantitative data interpretation in 3D FFM.
The structure and ultrafast dynamics of the electric double layer (EDL) are central to chemical reactivity and physical properties at solid/aqueous interfaces. While the Gouy–Chapman–Stern model is widely used to describe EDLs, it is solely based on the macroscopic electrostatic attraction of electrolytes for the charged surfaces. Structure and dynamics in the Stern layer are, however, more complex because of competing effects due to the localized surface charge distribution, surface–solvent–ion correlations, and the interfacial hydrogen bonding environment. Here, we report combined time-resolved vibrational sum frequency generation (TR-vSFG) spectroscopy with ab initio DFT-based molecular dynamics simulations (AIMD/DFT-MD) to get direct access to the molecular-level understanding of how ions change the structure and dynamics of the EDL. We show that innersphere adsorbed ions tune the hydrophobicity of the silica–aqueous interface by shifting the structural makeup in the Stern layer from dominant water–surface interactions to water–water interactions. This drives an initially inhomogeneous interfacial water coordination landscape observed at the neat interface toward a homogeneous, highly interconnected in-plane 2D hydrogen bonding (2D-HB) network at the ionic interface, reminiscent of the canonical, hydrophobic air–water interface. This ion-induced transformation results in a characteristic decrease of the vibrational lifetime (T 1 ) of excited interfacial O–H stretching modes from T 1 ~ 600 fs to T 1 ~ 250 fs. Hence, we propose that the T 1 determined by TR-vSFG in combination with DFT-MD simulations can be widely used for a quantitative spectroscopic probe of the ion kosmotropic/chaotropic effect at aqueous interfaces as well as of the ion-induced surface hydrophobicity.
Oriented attachment (OA) of nanoparticles is an important and common crystallization pathway. Efforts to isolate and quantify the interparticle forces that underlie OA have only recently been initiated and the role played by the interfacial solvent structure in the confined region between nanocrystal surfaces in enabling and controlling OA remains an open question. In this work, classical molecular dynamics (MD) simulations were performed to compute the free energy landscape of nanoparticles approaching mineral substrates in both vacuum and pure water. Periclase (MgO), muscovite (KAl 3 Si 3 O 10 (OH) 2 ), and pyrophyllite (Al 2 Si 4 O 10 (OH) 2 ) nanoparticles exposing the (100), (001), and (001) surfaces, respectively, were brought to contact with substrates exposing the same surfaces. These mineral surfaces were selected to investigate a range of hydrophilicities (periclase > muscovite > pyrophyllite). The MD simulations revealed that the interfacial water structure created free energy minima for nanoparticle approach that corresponded to integer numbers of intervening water layers. The depth of the free energy minima and the free energy barriers between minima correlated positively with the hydrophilicity of the mineral surface. While the range of solvent-mediated interactions was predicted to be short (a few intervening water layers at most for MgO), the free energy barriers were calculated to be large (fraction of an eV per nm 2 ) and the effect of misalignment diminished rapidly with the number of intervening water layers. The results help explain the formation of mesocrystals and the observed ability of nanoparticles to rotate before attachment while in a long-lived solvent-separated state.
Decoding the structural information contained in the interfacial vibrational spectrum of water requires understanding how the spectral signatures of individual water molecules respond to their local hydrogen bonding environments. In this study, we isolated the contributions for the five classes of sites that differ according to the number of donor (D) and acceptor (A) hydrogen bonds that characterize each site. These patterns were measured by exploiting the unique properties of the water cluster cage structures formed in the gas phase upon hydration of a series of cations M+·(H2O)n (M = Li, Na, Cs, NH4, CH3NH3, H3O, and n = 5, 20-22). This selection of ions was chosen to systematically express the A, AD, AAD, ADD, and AADD hydrogen bonding motifs. The spectral signatures of each site were measured using two-color, IR-IR isotopomer-selective photofragmentation vibrational spectroscopy of the cryogenically cooled, mass selected cluster ions in which a single intact H2O is introduced without isotopic scrambling, an important advantage afforded by the cluster regime. The resulting patterns provide an unprecedented picture of the intrinsic line shapes and spectral complexities associated with excitation of the individual OH groups, as well as the correlation between the frequencies of the two OH groups on the same water molecule, as a function of network site. The properties of the surrounding water network that govern this frequency map are evaluated by dissecting electronic structure calculations that explore how changes in the nearby network structures, both within and beyond the first hydration shell, affect the local frequency of an OH oscillator. The qualitative trends are recovered with a simple model that correlates the OH frequency with the network-modulated local electron density in the center of the OH bond.
Formation of aqueous secondary organic aerosol (aqSOA) at the air – liquid interface recently has attracted a lot of attention in atmospheric chemistry. The discrepancies in mass distributions, aerosol oxidative capacity, liquid water content, hygroscopic growth of aerosols, and formation of clouds and fogs suggest that interfacial chemistry play a more important role than previously deemed. However, detailed mechanisms at the air–water interface remain unclear owing to the lack of comprehensive understanding that underpins complicated interfacial phenomena, which are not easily measurable from field campaigns, laboratory measurements, or computational simulations. Here, this review highlights relevant and recent technical advancement employed to study aqSOA encompassing spectroscopy and mass spectrometry. The current knowledge on the aqSOA processes is digested with an emphasis on recent research of interfacial aqSOA formation including laboratory studies and model simulations. Finally, future directions of the interfacial chemistry are recommended for field and laboratory studies as well as theoretical efforts to resolve interfacial challenges in atmospheric chemistry.
Abstract Based on the coincident onsets of oxygen evolution reaction (OER) and metal dissolution for many metal‐oxide catalysts it was suggested that OER triggers dissolution. It is believed that both processes share common intermediates, yet exact mechanistic details remain largely unknown. For example, there is still no clear understanding as to why rutile IrO 2 exhibits such an exquisite stability among water‐splitting electrocatalysts. Here, we employ density functional theory calculations to analyze interactions between water and the (110) surface of rutile RuO 2 and IrO 2 as a response to oxygen evolution involving lattice oxygen species. We observe that these oxides display qualitatively different interfacial behavior that should have important implications for their electrochemical stability. Specifically, it is found that IrO 2 (110) becomes further stabilized under OER conditions due to the tendency to form highly stable low oxidation state Ir(III) species. In contrast, Ru species at RuO 2 (110) are prone to facile reoxidation by solution water. This should facilitate the formation of high Ru oxidation state intermediates (>IV) accelerating surface restructuring and metal dissolution.