Mohammed
Bin Jassar
* and
Simone
Pezzotti
*
Laboratoire CPCV, Département de Chimie, École normale supérieure, PSL University, Sorbonne Université, CNRS, Paris, 75005, France. E-mail: mohammed.bin-jassar@ens.psl.eu; simone.pezzotti@ens.psl.eu
First published on 13th June 2025
Recent studies discovered the existence of large hydrophobic solvation driving forces at macroscopically hydrophilic metal/and oxide/aqueous interfaces, which dictate several physical and chemical processes. They arise from the coexistence of local hydrophobic and hydrophilic behaviors. Rationally tuning these newly discovered driving forces by small adjustments of surface (or electrolyte) properties will open exciting perspectives in heterogeneous catalysis, geochemistry, nanofluidics, and electrochemistry. Here, we provide a molecular understanding of the origin of these driving forces, including how they are tuned by surface properties and why they can manifest at very diverse interfaces, from metals to oxides, from conductors to insulators. Our work builds a foundation to control these driving forces for improving existing technologies.
In the last decade, a growing number of studies reported interfaces that do not fit into the established picture: they exhibit an atypical behavior with mixed properties of both hydrophilic and hydrophobic interfaces.8,11,13,34–39 Fascinating wetting and solvation properties are being dug out for many of these interfaces, with promising applications in heterogeneous catalysis, geochemistry, prebiotic chemistry, and electrochemistry, to cite a few.8,11–13,32,34,37,39–41 Intriguingly, these interfaces have apparently little in common with each other – they range from geochemical to electrochemical, from metals to oxides, from conductors to insulators.
The first report was on talc surfaces.34 There, individual water molecules adsorb strongly (hydrophilic behavior) at low relative humidity due to adhesive surface–water interactions; however, at saturation, a droplet of water beads on the surface, as typical for hydrophobic interfaces. Rotenberg et al.34 rationalized this duality in terms of a competition between adhesion and cohesion (water–water interactions). Surprisingly, they noted that a water droplet forms on top of a strongly adsorbed water monolayer (adlayer), even on the most adhesive surfaces. For rutile, molecular dynamic (MD) simulations, contact angle measurements, and sum frequency generation (SFG) spectroscopy by Qu et al.35 proved the surface is strongly wet by a water bilayer. However, the addition of more water results in the formation of a droplet with a finite contact angle on top of it, which led the authors to question whether the interface is hydrophilic or hydrophobic. Experimental measurements of water adsorption enthalpy on alpha-(0001)-quartz surfaces reported strongly exothermic adsorption of a 1st water monolayer, as typical of very hydrophilic surfaces.36 This is due to strong H-bonding between quartz SiOH terminations and water, as confirmed by several MD and SFG studies.2 However, the addition of a 2nd water layer was surprisingly found much less exothermic and to leave the 1st monolayer structure virtually unperturbed.
At Pt/water interfaces, Limmer, Willard et al.8,37 initiated a quest on how hydrophobic properties – such as enhanced density fluctuations – arise despite strong metal–water interactions, due to the ordering of the water adlayer on top of the metal. We could later show11,42 for Au/water interfaces that strong metal–water interactions template a very ordered water adlayer, where intra-layer water–water H-bonds and interactions with the surface are both maximized. This leaves few spots available for H-bonding between the adlayer and the adjacent water layer. Hence, next to the hydrophilic metal–adlayer interface, where density fluctuations are suppressed, a water–water interface with a low H-bond density is formed, where water density fluctuations are enhanced, as typical of hydrophobic interfaces.
The dual local hydrophobic/hydrophilic nature was recognized to dictate many properties of metal/aqueous interfaces. For example, hydrophobic solvation at the water–water side of the interface regulates adsorption and transport of reactive species across the interface, e.g., by promoting the adsorption of hydrophobic and amphiphilic molecules,8,11,42 as well as some ions, influencing the properties of the electric double layer.12,37,43 The local solvation environment in this region was further recognized to modulate acid-base chemistry, providing shifts in pKa values similar to that observed at hydrophobic interfaces.32 The difference in cavitation free energies between the metal–adlayer and water–water interfacial regions was shown to provide large solvation driving forces, up to 0.5 eV, which can modulate the outcome of several chemical reactions in the field of renewable energies.39,40,44
Most recently, Gäding et al.13 discussed how the degree of ordering within the adlayer also dictates friction and osmotic transport at the interface, by determining the corrugation of the free energy landscape of water on the surface. Independently, Li et al.41 proposed that the low H-bond density at the water–water interface close to the metal limits proton transport across the interface and dominates the kinetic pH effect in hydrogen electrocatalysis.41,45
The rising challenge is how these newly identified driving forces can be tuned by adjusting the properties of the metal electrode (or the electrolyte), to improve electrochemical processes. Moreover, the manifestation of apparently similar properties at other aqueous interfaces, including oxides and insulators, suggests that the same driving forces may play key roles in other fields, as, e.g., recently proposed for geochemical and prebiotic processes.13,39 Exploiting these emerging opportunities requires molecular understanding.
Here, we aim to fill this gap of knowledge by means of extended MD simulations. We start from a well-characterized electrified Au/water interface, where surface polarization and applied voltage are explicitly treated with the classical constant-potential method,46 providing a realistic description of the structural, solvation and charging properties.11–13,32,40,47 By taking advantage of the tunability of the theoretical model, we systematically vary the surface properties one-by-one, to explore the effects of surface adhesion, metallicity, applied voltage and topology. This allows us to rationalize why similar mixed hydrophobic/hydrophilic behaviors manifest at very diverse interfaces, as we further confirm with additional DFT-MD simulations of oxide/water interfaces. We hence propose a picture that unites all these diverse interfaces and observations within a single family of systems. We name this family “amphiphilic interfaces”, whose common trait is – in analogy to amphiphilic solutes – to display both a hydrophilic and a hydrophobic side. We identify the molecular origin of amphiphilic behavior, and we rationalize how it is regulated by surface adhesion and topology. These results provide a recipe for fine-tuning hydrophobic solvation driving forces by adjusting surface properties, paving the way toward exploiting them for improving electrochemical and renewable energy processes.
The surface properties suspected to be relevant are: (i) the strength of adhesive surface–water interactions, since amphiphilic behavior was observed for strongly adhesive surfaces; (ii) surface metallicity, as amphiphilicity was intriguingly observed for both insulators and conductors; (iii) applied voltage, as many amphiphilic interfaces are electrified. Adhesive surface–water interactions were tuned by the ε parameter in the Lennard-Jones potential between Au and water (O-atom). Metallicity was tuned by changing the image plane position (which corresponds to changing the width ζ of the Gaussian charge distribution used to represent the atomic charges in Au,47 see Methods). The image plane zim defines the effective location of the induced screening charge in response to an external perturbation, such as applied electric field or surface charge. When the image plane position zim − za is positive, it lies outside the material, indicating that the screening charge is localized near the interface. This behavior is characteristic of good metallic screening. In contrast, a negative image plane position places it inside the material, implying that the screening charge is more delocalized and distributed within the bulk, which is indicative of weaker or non-metallic screening behavior. The applied voltage was varied within the water electrochemical window, from the point of zero charge (PZC = 0 V) to −0.5 V on the negative side and to +0.5 V on the positive side.
The influence of these surface properties is evaluated by analysis of water density fluctuations (as quantified by cavitation free energies), which provide a well-established measure of local hydrophobicity:4,5,8,11,21,48,49 the free energy cost to spontaneously form a small cavity in the liquid is reduced compared to bulk water at hydrophobic interfaces (δμcavity < 0) due to enhanced fluctuations of the water density, while δμcavity ≥ 0 at hydrophilic interfaces. δμcavity(z) profiles along the z distance from the surface (where δ identifies a difference between the z-position at the interface and the bulk) were computed from the MD simulations (see Methods). Corresponding contact angle values were deduced with the approach of ref. 5 and are shown in the ESI.†
Fig. 1A and B compare the effect of adhesive interactions vs. metallicity and applied voltage, respectively. Strikingly, adhesion emerges as the dominant parameter, while comparably smaller modulations of δμcavity(z) arise from the surface being insulator/conductor or neutral/charged. The adhesive forces were controlled by tuning the interaction strength between the Au electrode and the oxygen atom of water, i.e., the εAu–O parameter in the adopted Lennard-Jones potential. Three values of εAu–O were chosen to represent different surface interaction regimes: (i) the original Au electrode value from ref. 50, εAu−O = 3.79 kJ mol−1 (see Methods for more details about this choice); (ii) a weak interaction case, εAu−O = 0.12 kJ mol−1, simulating a hydrophobic surface; (iii) a stronger interaction case, εAu−O= 5.36 kJ mol−1. At low interaction strength (εAu−O = 0.12 kJ mol−1), we systematically recover the typical δμcavity(z) profile of a hydrophobic interface: δμcavity(z) monotonically decreases when approaching the surface.21,48 Instead, for interaction strength equal (εAu−O = 3.79 kJ mol−1) or higher (εAu−O = 5.36 kJ mol−1) than for the original Au(100) surface, the amphiphilic behavior arises, independently of metallicity and applied voltage. As illustrated in Fig. 1C, this is characterized by exceptionally high δμcavity(z) at the hydrophilic interface formed between the surface and the water adlayer (z < 3.5 Å), where there is a high density of water–surface interactions and intra-adlayer water–water H-bonds.42 Instead, δμcavity(z) becomes negative (i.e., hydrophobic-like) at the adjacent water–water interface, where the density of inter-layer H-bonds between the adlayer and the adjacent water layer is low. Such exceptionally large structure and cavitation free energy variations within a few angstroms from the surface are at the origin of the many hydrophobic solvation driving forces discovered in recent studies at amphiphilic interfaces.8,11–13,32,34,37,39–41,44,45 From the results of Fig. 1, we can already rationalize why these driving forces were observed for both insulators and conductors, electrified and neutral surfaces: they can manifest with sufficiently strong surface–water interactions, independently of the nature of the surface.
This may appear surprising at first glance, since both metallicity and applied voltage influence the way water molecules interact with the surface and with themselves.11,47,51 To understand this, we characterize the effect of applied voltage on the interfacial water H-bond network in Fig. 2. Tuning the voltage across the PZC does not substantially influence the water oxygen density profile (Fig. 2A), in particular the height and position of the first density peak corresponding to the water adlayer. However, it strongly alters the orientation of water molecules within the adlayer (Fig. 2B): water molecules are mostly oriented with their dipole parallel to the surface at PZC = 0 V (probability maximum for cosθ ≃ 0), but reorient pointing their dipole toward the negative surface (cos
θ < 0 for −0.5 V) and away from the positive surface (cos
θ > 0 for +0.5 V). As shown in Fig. 2C, the reorientation alters inter-layer H-bonding at the water–water interface: adlayer water mostly accepts H-bonds from water in the subsequent layer at negative voltage, while it mostly donates at positive voltage. However, the total density of H-bonds remains constant. Since what matters for density fluctuations is the density of H-bonds that has to be perturbed to create a cavity, δμcavity(z) is not very sensitive to applied voltage variations. A similar molecular rationalization applies for the effect of metallicity, too (Fig. S1 in the ESI†).
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Fig. 3 The hydrophobic-hydrophilic-amphiphilic crossover with increasing surface–water interactions, εAu−O. (A) Lennard-Jones potential V(rAu−O) for each εAu−O. (B) Water oxygen density profiles, showing the progressive appearence of an ordered water adlayer (1st density peak). (Inset) accompanying changes in the number of water–water H-bonds (HBs/w) formed within the adlayer (red) and between the adlayer and the adjacent water layer (blue). (C) Water chemical potential δμwater across the interface, as computed from the density profiles. (D) δμcavity(z) (in units of β = 1/kBT) profiles (see Fig. S2 in ESI† for the corresponding changes in contact angle, which varies from 90° to full wetting with increasing εAu−O). (E) δμcavity(z) changes are quantified by plotting the values at z = 1.8 Å (inner) and 4.5 Å (outer) as a function of εAu−O. The color gradient highlights the progressive crossover: δμcavity(z) inner <outer at a hydrophobic interface (blue), inner ≃ outer at a hydrophilic interface (orange), and inner >outer at an amphiphilic interface (brown). (F) The hydrophilic-amphiphilic crossover is also observed for silica–water interfaces, where the adhesive force is increased by increasing surface hydroxylation rate (SiOH/nm2) instead of εAu−O, showing the generality of our findings. |
Strikingly, they are accompanied by a continuous crossover from δμcavity(z) profiles typical of hydrophobic interfaces (blue in Fig. 3D) to δμcavity(z) profiles typical of an amphiphilic interface (red/brown). As soon as adhesive interactions start to increase, spatial fluctuations, within ∼8 Å from the surface, become progressively evident in the free energy profiles. This is a well-know consequence of the layering of water close to a hydrophilic surface, as observed in the density profiles. However, from orange to brown curves in Fig. 3D, the magnitude of the δμcavity spatial fluctuations grows suddenly, beyond the standard layering effect. The metal- and oxide-water interfaces with atypical wetting properties, where a water droplet beads with a finite contact angle on top of a strongly bound water adlayer, systematically exhibit this kind of δμcavity profiles.8,11,34,39 Once again, it is the large magnitude of the spatial fluctuation of δμcavity (and of H-bonding properties, Fig. 3B) that gives rise to the hydrophobic solvation driving forces at these interfaces that we aim to rationalize and tune.
The transition toward the amphiphilic behavior is marked by the progressive appearance of a δμcavity maximum at z < 3.5 Å (where the cavity is formed inner-sphere, i.e., in direct contact with the surface and within the adlayer) and a minimum at ∼4.5 Å (where the cavity is formed outer-sphere, i.e., at the adjacent water–water interface where it is separated from the surface by the adlayer). These changes are quantified in Fig. 3E by plotting the δμcavity values at ∼1.8 Å (red, inner-sphere) and at ∼4.5 Å (blue, outer-sphere) as a function of εAu−O. At low εAu−O, inner-sphere is more favorable than outer-sphere cavity formation, and both are favored with respect to bulk (δμcavity < 0). This indicates hydrophobic behavior, as δμcavity monotonically decreases when approaching a hydrophobic surface.21,48 With increasing εAu−O, the δμcavity value for inner-sphere increases, approaches zero, and becomes positive, while crossing with the decreasing value for outer-sphere (at around εAu−O = 2 kJ mol−1 in our model). In this range, δμcavity for inner-sphere, outer-sphere and bulk are most similar to each other, which is typical of hydrophilic interfaces.21,39,48 This is the canonical hydrophobic–hydrophilic transition. However, when further increasing surface–water interactions, inner- and outer-sphere δμcavity diverge, and the interface progressively partition into a hydrophilic side (the surface–adlayer interface) and a hydrophobic side (the subsequent water–water interface), giving rise to the amphiphilic behavior.
A progressive hydrophilic–amphiphilic crossover hence takes place when maximizing surface adhesion by increasing the attractive interaction between surface site and water molecule. This is typically the way surface adhesion varies across metal surfaces, e.g., from Au to Cu to Pt.50,52 However, this does not apply to oxides, for which amphiphilic behaviors have been reported, too.34–36,39 There, the adhesive interactions are primarily modulated by the amount of surface (–OH) terminations that interact strongly with water. A typical example are silica/water interfaces, where surface adhesion increases monotonically with the degree of hydroxilation, i.e., the density of surface SiOH termination that form strong H-bonds with water (which is tuned by changing the way the surface is heat-treated).28,53 To explore the generality of our findings, we also performed our analysis on three well-characterized silica surfaces with increasing hydroxylation rate of 3.5 SiOH per nm2, 4.5 SiOH per nm2 and 9.6 SiOH per nm2 (from previously performed DFT-MD simulations39). These model systems were shown to reproduce well the properties of heat treated amorphous silica, amorphous silica and α-(0001)-quartz surfaces in contact with liquid water, respectively.28,39,53 The corresponding δμcavity(z) profiles (Fig. 3F) show again a smooth, continuous crossover from a canonical hydrophilic behavior (3.5 SiOH per nm2), with similar δμcavity(z) values in inner-, outer-sphere and bulk, to the amphiphilic quartz/water interface (9.6 SiOH per nm2), where the hydrophilic and hydrophobic sides (with suppressed and enhanced density fluctuations, respectively) emerge.39 We show in Table S1 of the ESI† that the hydrophilic–amphiphilic transition is, also in this case, accompanied by an increasing connectivity within the adlayer and decreasing H-bonding between the adlayer and the second water layer. The hydrophilic–amphiphilic crossover is accessible independently of the way surface adhesion is increased.
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Fig. 4 Molecular understanding of the crossover. (A) δμcavity(z) changes vs. εAu−O at the hydrophobic water–water side of the interface (from Fig. 3E, outer at z ≈ 4.5 Å) are dictated by changes in the number of inter-layer H-bonds (HBs/w, Fig. 3B). The inset highlights the linear correlation between the two. (B) δμcavity(z) changes at the hydrophilic side (inner at z ≈ 1.8 Å) are dictated by the free energy cost to displace a water molecule from the adlayer (δμadlayer), which depends on both water–surface and water–water interactions. The inset correlates δμcavity (inner) with δμadlayer. (C) and (D) Effect of surface topology at different sides of the crossover, evaluated by comparing δμcavity(z) profiles at Au(100) and Au(111) derived surfaces with same εAu−O, zim = 1.0 Å, and ΔV = 0 V, for εAu−O = 0.12 kJ mol−1 (C, hydrophobic), and εAu−O = 5.36 kJ mol−1 (D, amphiphilic). (E) Updated understanding of aqueous interfaces, combining our results with recent literature. The arrows follow the crossover with increasing surface adhesion. The sketches illustrate the accompanying changes in surface-water (red lines), intra-adlayer (blue) and inter-layer (cyan) H-bonds. For increasingly adhesive surfaces, the newly discovered amphiphilic behavior can be reached, beyond the canonical hydrophobic–hydrophilic crossover, if the surface topology matches that of the water adlayer. |
At the surface-adlayer interface (Fig. 4B), cavity formation requires displacing water molecules from the ordered adlayer structure, which involves perturbing both surface–water and intra-adlayer water–water HBs. Here, δμcavity is dictated by surface desolvation, i.e. by the free energy cost to remove water molecules from the adlayer (δμadlayer).38,40,42,54 At low εAu−O, in the hydrophobic domain, water–surface interactions are weaker than water–water H-bonds and the adlayer structure is only little sensitive to the εAu−O increase. Thus, both δμadlayer and local δμcavity are almost insensitive to changes in surface adhesion, until surface–water overcomes water–water interactions (at εAu−O ≃ 1.5 kJ mol−1 in our model). After that, both the strength of water–surface interactions and the number of intra-adlayer HBs/w monotonically increase with εAu−O, causing δμadlayer and δμcavity to increase. Upon entering the amphiphilic domain, the number of intra-adlayer HBs/w saturates, but δμadlayer and δμcavity keep increasing due to the continuous increase in surface adhesion. Therefore, the mechanism of the crossover is the following. For hydrophobic interfaces, water–water interactions dominate and increasing surface adhesion has little effect on wetting properties until surface–water overcomes water–water interactions. In the hydrophilic domain, the more adhesive the surface, the more ordered the water adlayer, the lower the inter-layer H-bond density in the adjacent water–water region. These structural changes progressively cause density fluctuations in the two regions to diverge, with formation of a locally super-hydrophilic surface-adlayer interface followed by a locally hydrophobic water–water interface.
The topology effect is remarkable in the amphiphilic domain, instead. The value of δμcavity at the hydrophilic surface–adlayer interface (z < 4 Å) changes by a factor of two between Au(100) and Au(111). This large topology effect is in line with previous studies comparing the wetting of different facets of the same metal.8,13,38 As shown by water density and δμwater profiles in Fig. S3 of the ESI,† we find that surface topology dictates the degree of ordering within the adlayer, and as a consequence δμadlayer. This, in turn, dictates the extent to which amphiphilic behaviors manifest. The effect of surface topology varies depending on where an interface is placed along the hydrophobic–hydrophilic–amphiphilic crossover.
The concept of amphiphilic interfaces changes the way we understand hydrophilicity at solid/liquid interfaces in a similar way as the concept of amphiphilic molecules shaped our understanding of hydrophilicity for molecules. At the macroscopic scale, a molecule's hydrophilicity is determined by its solubility. However, at the molecular level, many water-soluble molecules, such as alcohols or amino acids, are composed of a hydrophilic and a hydrophobic side, which confers them their unique chemical and physical properties. In the same way, interfaces classified as macroscopically hydrophilic by contact angle measurements can exhibit, at the molecular level, both a hydrophobic and a hydrophilic side, which leads to the large hydrophobic solvation driving forces that keep being dug out in recent years.8,11–13,32,34,37,39–41,44,45 These include the low H-bond density at the hydrophobic side of metal/water interfaces, which is suspected to determine the free energy barrier for proton transport and hydrogen evolution reaction in electrochemistry,41 the degree of ordering within the adlayer, which shapes the surface free energy landscape of water that regulates friction and osmotic flow in nanofluidics,13 the difference in solvation free energies between hydrophobic and hydrophilic sides that modulate reaction free energies for heterogeneous catalysis (e.g., for CO2 reduction for renewable energies) and prebiotic chemistry,32,39,40 and many more. The present work provides a unified ground to rationalize all these driving forces and predict how they can be controlled by adjusting the interface composition. This may open exciting perspectives in interface science. For instance, in future studies, the approach outlined here can be expanded to study reactive, functionalized, or defective surfaces, by evaluating water density fluctuations (or corresponding structural-based descriptors for higher spatial/temporal resolution29) before and after the surface modification. This will help understanding how the uncovered solvation driving forces can be controlled in practical applications by playing with the composition of the surface.
We adopted the approach of ref. 47 to tune surface metallicity by the width of the atom-centered Gaussian charge distributions (ζ) on the topmost electrode atoms as a function of the position r:
![]() | (1) |
![]() | (2) |
Cavitation free energy profiles were obtained by computing the probability Pv,s(0,z) of finding zero water oxygen atoms within a defined probing volume v (with shape s) at varying distances z from the surface. The probability Pv,s(0,z) is obtained from MD simulations by analyzing the statistics of fluctuations in waterdensity. It is quantitatively related to the free energy cost of cavity formation (Δμv,s) by:8,11
Pv,s(0,z) = e−βΔμv,s(z) | (3) |
δμcavity(z) = Δμintv,s(z) − Δμbulkv,s | (4) |
Footnote |
† Electronic supplementary information (ESI) available: Additional methodological details regarding the simulations performed for systems containing Au(111) and the three types of silica are provided. Additional analytical details are also included, examining the effects of metallicity and surface topology on the systems studied. See DOI: https://doi.org/10.1039/d5sc03005f |
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