Nanometer-Resolved Operando Photo-Response of Faceted BiVO4 Semiconductor Nanoparticles.

Photo(electro)catalysis with semiconducting nanoparticles (NPs) is an attractive approach to convert abundant but intermittent renewable electricity into stable chemical fuels. However, our understanding of the microscopic processes governing the performance of the materials has been hampered by the lack of operando characterization techniques with sufficient lateral resolution. Here, we demonstrate that the local surface potentials of NPs of bismuth vanadate (BiVO4) and their response to illumination differ between adjacent facets and depend strongly on the pH of the ambient electrolyte. The isoelectric points of the dominant {010} basal plane and the adjacent {110} side facets differ by 1.5 pH units. Upon illumination, both facets accumulate positive charges and display a maximum surface photoresponse of +55 mV, much stronger than reported in the literature for the surface photo voltage of BiVO4 NPs in air. High resolution images reveal the presence of numerous surface defects ranging from vacancies of a few atoms, to single unit cell steps, to microfacets of variable orientation and degree of disorder. These defects typically carry a highly localized negative surface charge density and display an opposite photoresponse compared to the adjacent facets. Strategies to model and optimize the performance of photocatalyst NPs, therefore, require an understanding of the distribution of surface defects, including the interaction with ambient electrolyte.

Ion adsorption and hydration forces: a comparison of crystalline mica vs. amorphous silica surfaces.

Hydration forces are ubiquitous in nature and technology. Yet, the characterization of interfacial hydration structures and their dependence on the nature of the substrate and the presence of ions have remained challenging and controversial. We present a systematic study using dynamic Atomic Force Microscopy of hydration forces on mica surfaces and amorphous silica surfaces in aqueous electrolytes containing chloride salts of various alkali and earth alkaline cations of variable concentrations at pH values between 3 and 9. Our measurements with ultra-sharp AFM tips demonstrate the presence of both oscillatory and monotonically decaying hydration forces of very similar strength on both atomically smooth mica and amorphous silica surfaces with a roughness comparable to the size of a water molecule. The characteristic range of the forces is approximately 1 nm, independent of the fluid composition. Force oscillations are consistent with the size of water molecules for all conditions investigated. Weakly hydrated Cs+ ions are the only exception: they disrupt the oscillatory hydration structure and induce attractive monotonic hydration forces. On silica, force oscillations are also smeared out if the size of the AFM tip exceeds the characteristic lateral scale of the surface roughness. The observation of attractive monotonic hydration forces for asymmetric systems suggests opportunities to probe water polarization.

Nonequilibrium configurations of swelling polymer brush layers induced by spreading drops of weakly volatile oil.

Polymer brush layers are responsive materials that swell in contact with good solvents and their vapors. We deposit drops of an almost completely wetting volatile oil onto an oleophilic polymer brush layer and follow the response of the system upon simultaneous exposure to both liquid and vapor. Interferometric imaging shows that a halo of partly swollen polymer brush layer forms ahead of the moving contact line. The swelling dynamics of this halo is controlled by a subtle balance of direct imbibition from the drop into the brush layer and vapor phase transport and can lead to very long-lived transient swelling profiles as well as nonequilibrium configurations involving thickness gradients in a stationary state. A gradient dynamics model based on a free energy functional with three coupled fields is developed and numerically solved. It describes experimental observations and reveals how local evaporation and condensation conspire to stabilize the inhomogeneous nonequilibrium stationary swelling profiles. A quantitative comparison of experiments and calculations provides access to the solvent diffusion coefficient within the brush layer. Overall, the results highlight the-presumably generally applicable-crucial role of vapor phase transport in dynamic wetting phenomena involving volatile liquids on swelling functional surfaces.

Absence of anomalous underscreening in highly concentrated aqueous electrolytes confined between smooth silica surfaces.

Recent surface forces apparatus experiments that measured the forces between two mica surfaces and a series of subsequent theoretical studies suggest the occurrence of universal underscreening in highly concentrated electrolyte solutions. We performed a set of systematic Atomic Force Spectroscopy measurements for aqueous salt solutions in a concentration range from 1 mM to 5 M using chloride salts of various alkali metals as well as mixed concentrated salt solutions (involving both mono- and divalent cations and anions), that mimic concentrated brines typically encountered in geological formations. Experiments were carried out using flat substrates and submicrometer-sized colloidal probes made of smooth oxidized silicon immersed in salt solutions at pH values of 6 and 9 and temperatures of 25 °C and 45 °C. While strong repulsive forces were observed for the smallest tip-sample separations, none of the conditions explored displayed any indication of anomalous long range electrostatic forces as reported for mica surfaces. Instead, forces are universally dominated by attractive van der Waals interactions at tip-sample separations of ≈2 nm and beyond for salt concentrations of 1 M and higher. Complementary calculations based on classical density functional theory for the primitive model support these experimental observations and display a consistent decrease in screening length with increasing ion concentration.

Correlation between Electrostatic and Hydration Forces on Silica and Gibbsite Surfaces: An Atomic Force Microscopy Study.

The balance between hydration and Derjaguin-Landau-Verwey-Overbeek (DLVO) forces at solid-liquid interfaces controls many processes, such as colloidal stability, wetting, electrochemistry, biomolecular self-assembly, and ion adsorption. Yet, the origin of molecular scale hydration forces and their relation to the surface charge density that controls the continuum scale electrostatic forces is poorly understood. We argue that these two types of forces are largely independent of each other. To support this hypothesis, we performed atomic force microscopy experiments using intermediate-sized tips that enable the simultaneous detection of DLVO and molecular scale oscillatory hydration forces at the interface between composite gibbsite:silica-aqueous electrolyte interfaces. We extract surface charge densities from forces measured at tip-sample separations of 1.5 nm and beyond using DLVO theory in combination with charge regulation boundary conditions for various pH values and salt concentrations. We simultaneously observe both colloidal scale DLVO forces and oscillatory hydration forces for an individual crystalline gibbsite particle and the underlying amorphous silica substrate for all fluid compositions investigated. While the diffuse layer charge varies with pH as expected, the oscillatory hydration forces are found to be largely independent of pH and salt concentration, supporting our hypothesis that both forces indeed have a very different origin. Oscillatory hydration forces are found to be distinctly more pronounced on gibbsite than on silica. We rationalize this observation based on the distribution of hydroxyl groups available for H bonding on the two distinct surfaces.

Facet-Dependent Surface Charge and Hydration of Semiconducting Nanoparticles at Variable pH.

Understanding structure and function of solid-liquid interfaces is essential for the development of nanomaterials for various applications including heterogeneous catalysis in liquid phase processes and water splitting for storage of renewable electricity. The characteristic anisotropy of crystalline nanoparticles is believed to be essential for their performance but remains poorly understood and difficult to characterize. Dual scale atomic force microscopy is used to measure electrostatic and hydration forces of faceted semiconducting SrTiO3 nanoparticles in aqueous electrolyte at variable pH. The following are demonstrated: the ability to quantify strongly facet-dependent surface charges yielding isoelectric points of the dominant {100} and {110} facets that differ by as much as 2 pH units; facet-dependent accumulation of oppositely charged (SiO2 ) particles; and that atomic scale defects can be resolved but are in fact rare for the samples investigated. Atomically resolved images and facet-dependent oscillatory hydration forces suggest a microscopic charge generation mechanism that explains colloidal scale electrostatic forces.

Electrically Controlled Localized Charge Trapping at Amorphous Fluoropolymer-Electrolyte Interfaces.

Charge trapping is a long-standing problem in electrowetting on dielectric, causing reliability reduction and restricting its practical applications. Although this phenomenon is investigated macroscopically, the microscopic investigations are still lacking. In this work, the trapped charges are proven to be localized at the three-phase contact line (TPCL) region by using three detecting methods-local contact angle measurements, electrowetting (EW) probe, and Kelvin probe force microscopy. Moreover, it is demonstrated that this EW-assisted charge injection (EWCI) process can be utilized as a simple and low-cost method to deposit charges on fluoropolymer surfaces. Charge densities near the TPCL up to 0.46 mC m-2 and line widths of the deposited charge ranging from 20 to 300 µm are achieved by the proposed EWCI method. Particularly, negative charge densities do not degrade even after a "harsh" testing with a water droplet on top of the sample surfaces for 12 h, as well as after being treated by water vapor for 3 h. These findings provide an approach for applications which desire stable and controllable surface charges.

Ion-Specific and pH-Dependent Hydration of Mica-Electrolyte Interfaces.

Hydration forces play a crucial role in a wide range of phenomena in physics, chemistry, and biology. Here, we study the hydration of mica surfaces in contact with various alkali chloride solutions over a wide range of concentrations and pH values. Using atomic force microscopy and molecular dynamics simulations, we demonstrate that hydration forces consist of a superposition of a monotonically decaying and an oscillatory part, each with a unique dependence on the specific type of cation. The monotonic hydration force gradually decreases in strength with decreasing bulk hydration energy, leading to a transition from an overall repulsive (Li+, Na+) to an attractive (Rb+, Cs+) force. The oscillatory part, in contrast, displays a binary character, being hardly affected by the presence of strongly hydrated cations (Li+, Na+), but it becomes completely suppressed in the presence of weakly hydrated cations (Rb+, Cs+), in agreement with a less pronounced water structure in simulations. For both aspects, K+ plays an intermediate role, and decreasing pH follows the trend of increasing Rb+ and Cs+ concentrations.

Spontaneous electrification of fluoropolymer-water interfaces probed by electrowetting.

Fluoropolymers are widely used as coatings for their robustness, water-repellence, and chemical inertness. In contact with water, they are known to assume a negative surface charge, which is commonly attributed to adsorbed hydroxyl ions. Here, we demonstrate that a small fraction of these ions permanently sticks to surfaces of Teflon AF and Cytop, two of the most common fluoropolymer materials, upon prolonged exposure to water. Electrowetting measurements carried out after aging in water are used to quantify the density of 'trapped' charge. Values up to -0.07 and -0.2 mC m-2 are found for Teflon AF and for Cytop, respectively, at elevated pH. A similar charge trapping process is also observed upon aging in various non-aqueous polar liquids and in humid air. A careful analysis highlights the complementary nature of electrowetting and streaming potential measurements in quantifying interfacial energy and charge density. We discuss the possible mechanism of charge trapping and highlight the relevance of molecular scale processes for the long term stability and performance of fluoropolymer materials for applications in electrowetting and elsewhere.

Impact of surface defects on the surface charge of gibbsite nanoparticles.

We use high resolution Atomic Force Microscopy to study the surface charge of the basal plane of gibbsite nanoparticles, with a lateral resolution of approximately 5 nm, in ambient electrolyte of variable pH and salt content. Our measurements reveal surface charge variations on the basal planes that correlate with the presence of topographic defects such as atomic steps. This surface charge heterogeneity, which increases with increasing pH, suggests that for a pH between 6 and 9 the defect sites display a stronger chemical activity than adjacent, apparently atomically smooth regions of the basal plane. Smooth regions display a slight positive surface charge of ≈0.05e per nm2 that hardly varies within this pH range. In contrast, near the topographic defects we observe a much lower charge. Considering the size of the interaction area under the probing tip, this implies that at the defect sites the charge density must be negative, ≈-0.1e per nm2. These measurements demonstrate that surface defects have a large influence on the average surface charge of the gibbsite basal plane. These findings will contribute to understand why surface defects play an important role in various applications, such as fuel cells, chemical synthesis, self-assembly, catalysis and surface treatments.

Atomic structure and surface defects at mineral-water interfaces probed by in situ atomic force microscopy.

Atomic scale details of surface structure play a crucial role for solid-liquid interfaces. While macroscopic characterization techniques provide averaged information about bulk and interfaces, high resolution real space imaging reveals unique insights into the role of defects that are believed to dominate many aspects of surface chemistry and physics. Here, we use high resolution dynamic Atomic Force Microscopy (AFM) to visualize and characterize in ambient water the morphology and atomic scale structure of a variety of nanoparticles of common clay minerals adsorbed to flat solid surfaces. Atomically resolved images of the (001) basal planes are obtained on all materials investigated, namely gibbsite, kaolinite, illite, and Na-montmorillonite of both natural and synthetic origin. Next to regions of perfect crystallinity, we routinely observe extended regions of various types of defects on the surfaces, including vacancies of one or few atoms, vacancy islands, atomic steps, apparently disordered regions, as well as strongly adsorbed seemingly organic and inorganic species. While their exact nature is frequently difficult to identify, our observations clearly highlight the ubiquity of such defects and their relevance for the overall physical and chemical properties of clay nanoparticle-water interfaces.

Extracting local surface charges and charge regulation behavior from atomic force microscopy measurements at heterogeneous solid-electrolyte interfaces.

We present a method to determine the local surface charge of solid-liquid interfaces from Atomic Force Microscopy (AFM) measurements that takes into account shifts of the adsorption/desorption equilibria of protons and ions as the cantilever tip approaches the sample. We recorded AFM force distance curves in dynamic mode with sharp tips on heterogeneous silica surfaces partially covered by gibbsite nano-particles immersed in an aqueous electrolyte with variable concentrations of dissolved NaCl and KCl at pH 5.8. Forces are analyzed in the framework of Derjaguin-Landau-Verwey-Overbeek (DLVO) theory in combination with a charge regulation boundary that describes adsorption and desorption reactions of protons and ions. A systematic method to extract the equilibrium constants of these reactions by simultaneous least-squared fitting to experimental data for various salt concentrations is developed and is shown to yield highly consistent results for silica-electrolyte interfaces. For gibbsite-electrolyte interfaces, the surface charge can be determined, yet, an unambiguous identification of the relevant surface speciation reactions is not possible, presumably due to a combination of intrinsic chemical complexity and heterogeneity of the nano-particle surfaces.

Stretching of collapsed polymers causes an enhanced dissipative response of PNIPAM brushes near their LCST.

Poly(N-isopropyl acrylamide) (PNIPAM) is a stimulus-responsive polymer that can switch in water from an expanded state below the lower critical solution temperature (LCST) of 32 °C to a globular state above the LCST. It was recently shown that, as a consequence of this conformational transition, the interfacial and (tribo-)mechanical properties of polymeric systems composed of PNIPAM can be switched between two states. Here we show that the tribo-mechanical properties of a particular type of PNIPAM system, which is the PNIPAM brush, do not just change between two states, but instead evolve continuously and non-monotonically upon increasing/decreasing temperature. To do so, we present atomic force microscopy experiments in which we measure the adhesion hysteresis and the friction upon bringing a gold colloid in relative motion with PNIPAM brushes at temperatures around the LCST. Both the friction and the adhesion hysteresis display a pronounced maximum exactly at the LCST. The force vs. distance data captured at these temperatures show a long-ranged adhesive interaction upon moving the colloid away from the original point of contact, which indicates that during this retraction the partly collapsed polymers in the brush become strongly stretched.

Ion adsorption-induced wetting transition in oil-water-mineral systems.

The relative wettability of oil and water on solid surfaces is generally governed by a complex competition of molecular interaction forces acting in such three-phase systems. Herein, we experimentally demonstrate how the adsorption of in nature abundant divalent Ca(2+) cations to solid-liquid interfaces induces a macroscopic wetting transition from finite contact angles (≈ 10°) with to near-zero contact angles without divalent cations. We developed a quantitative model based on DLVO theory to demonstrate that this transition, which is observed on model clay surfaces, mica, but not on silica surfaces nor for monovalent K(+) and Na(+) cations is driven by charge reversal of the solid-liquid interface. Small amounts of a polar hydrocarbon, stearic acid, added to the ambient decane synergistically enhance the effect and lead to water contact angles up to 70° in the presence of Ca(2+). Our results imply that it is the removal of divalent cations that makes reservoir rocks more hydrophilic, suggesting a generalizable strategy to control wettability and an explanation for the success of so-called low salinity water flooding, a recent enhanced oil recovery technology.

Sorption-determined deposition of platinum on well-defined platelike WO3.

The photodeposition of Pt nanoparticles from [PtCl6 ](2-) on platelike WO3 crystals occurs preferentially on the small, subordinate facets. Rather than the often-used explanation of preferred light-induced charge migration, we propose that this phenomenon is due to differences in the intrinsic surface charges of WO3 facets exposed to water; thus, the dark sorption of [PtCl6 ](2-) on positively charged facets/edges is preferred. This conclusion is based on 1) (dark) impregnation studies, which showed Pt deposition to also be facet-specific, and 2) aqueous-phase AFM studies, which suggest intrinsic surface charges to be in agreement with sorption-based Pt distributions.

Direct observation of ionic structure at solid-liquid interfaces: a deep look into the Stern Layer.

The distribution of ions and charge at solid-water interfaces plays an essential role in a wide range of processes in biology, geology and technology. While theoretical models of the solid-electrolyte interface date back to the early 20th century, a detailed picture of the structure of the electric double layer has remained elusive, largely because of experimental techniques have not allowed direct observation of the behaviour of ions, i.e. with subnanometer resolution. We have made use of recent advances in high-resolution Atomic Force Microscopy to reveal, with atomic level precision, the ordered adsorption of the mono- and divalent ions that are common in natural environments to heterogeneous gibbsite/silica surfaces in contact with aqueous electrolytes. Complemented by density functional theory, our experiments produce a detailed picture of the formation of surface phases by templated adsorption of cations, anions and water, stabilized by hydrogen bonding.

Ions-induced nanostructuration: effect of specific ionic adsorption on hydrophobic polymer surfaces.

The effect of surface charges on the ionic distribution in close proximity to an interface has been extensively studied. On the contrary, the influence of ions (from dissolved salts) on deformable interfaces has been barely investigated. Ions can adsorb from aqueous solutions on hydrophobic surfaces, generating forces that can induce long-lasting deformation of glassy polymer films, a process called ion-induced polymer nanostructuration, IPN. We have found that this process is ion-specific; larger surface modifications are observed in the presence of water ions and hydrophobic and amphiphilic ions. Surface structuration is also observed in the presence of certain salts of lithium. We have used streaming potential and atomic force microscopy to study the effect of dissolved ions on the surface properties of polystyrene films, finding a good correlation between ionic adsorption and IPN. Our results also suggest that the presence of strongly hydrated lithium promotes the interaction of anions with polystyrene surfaces and more generally with hydrophobic polymer surfaces, triggering then the IPN process.

Salt dependent stability of stearic acid Langmuir-Blodgett films exposed to aqueous electrolytes.

We use contact angle goniometry, imaging ellipsometry, and atomic force microscopy to study the stability and wettability of Langmuir-Blodgett (LB) monolayers of stearic acid on silica substrates, upon drying and exposure to aqueous solutions of varying salinity. The influences of Ca(2+) and Na(+) ions are compared by varying their concentrations, both in the subphase before the LB transfer, and in the droplets to which the dried LB layers are exposed. Ca(2+) ions in the subphase are found to enhance the stability, leading to contact angles up to 100°, as compared to less than 5° for Na(+). Consistent with the macroscopic wettability, AFM images show almost intact films with few holes exposing bare substrate when prepared in the presence of Ca(2+), while subphases containing Na(+) result in large areas of bare substrate after exposure to aqueous drops. The observations on varying the composition of the droplets corroborate the stabilizing effect of Ca(2+). We attribute these findings to the cation-bridging ability of Ca(2+) ions, which can bind the negatively charged stearate groups to the negatively charged substrates. We discuss the relevance of our findings in the context of enhanced oil recovery.