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.

Elastometry of Complex Fluid Pendant Capsules.

Oil/water interfaces are ubiquitous in nature. Opposing polarities at these interfaces attract surface-active molecules, which can seed complex viscoelastic or even solid interfacial structure. Biorelevant proteins such as hydrophobin, polymers such as PNIPAM, and the asphaltenes in crude oil (CRO) are examples of some systems where such layers can occur. When a pendant drop of CRO is aged in brine, it can form an interfacial elastic membrane of asphaltenes so stiff that it wrinkles and crumples upon retraction. Most of the work studying CRO/brine interfaces focuses on the viscoelastic liquid regime, leaving a wide range of fully solidified, elastic interfaces largely unexplored. In this work, we quantitatively measure elasticity in all phases of drop retraction. In early retraction, the interface shows a fluid viscoelasticity measurable using a Gibbs isotherm or dilatational rheology. Further retraction causes a phase transition to a 2D elastic solid with nonisotropic, nonhomogeneous surface stresses. In this regime, we use new techniques in the elastic membrane theory to fit for the elasticities of these solid capsules. These elastic measurements can help us develop a deeper understanding not only of CRO interfaces but also of the myriad fluid systems with solid interfacial layers.

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.

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.

Ultrasensitive Detection and In Situ Imaging of Analytes on Graphene Oxide Analogues Using Enhanced Raman Spectroscopy.

We demonstrate how algorithm-improved confocal Raman microscopy (ai-CRM), in combination with chemical enhancement by two-dimensional substrates, can be used as an ultrasensitive detection method for rhodamine (R6G) molecules adsorbed from aqueous solutions. After developing a protocol for laser-induced reduction of graphene oxide, followed by noninvasive Raman imaging, a limit of detection (LOD) of 5 × 10-10 M R6G was achieved using ai-CRM. An equivalent subnanomolar LOD was also achieved on another graphene oxide analogue -UV/ozone-oxidized graphene. These record-breaking detection capabilities also enabled us to study the adsorption kinetics and image the spatial distribution of the adsorbed R6G. These findings indicate a strong potential for algorithm-improved graphene-enhanced Raman spectroscopy as a facile method for detecting, imaging, and quantifying trace amounts of adsorbing molecules on a variety of 2D substrates.

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.

Energy Harvesting from Drops Impacting onto Charged Surfaces.

We use a combination of high-speed video imaging and electrical measurements to study the direct conversion of the impact energy of water drops falling onto an electrically precharged solid surface into electrical energy. Systematic experiments at variable impact conditions (initial height; impact location relative to electrodes) and electrical parameters (surface charge density; external circuit resistance; fluid conductivity) allow us to describe the electrical response quantitatively without any fit parameters based on the evolution of the drop-substrate interfacial area. We derive a scaling law for the energy harvested by such "nanogenerators" and find that optimum efficiency is achieved by matching the timescales of the external electrical energy harvesting circuit and the hydrodynamic spreading process.

Characterizing the fluid-matrix affinity in an organogel from the growth dynamics of oil stains on blotting paper.

Grease, as used for lubrication of rolling bearings, is a two-phase organogel that slowly releases oil from its gelator matrix. Because the rate of release determines the operation time of the bearing, we study this release process by measuring the amount of extracted oil as a function of time, while we use absorbing paper to speed up the process. The oil concentration in the resulting stain is determined by measuring the attenuation of light transmitted through the paper, using a modified Lambert-Beer law. For grease, the timescale for paper imbibition is typically 2 orders of magnitude larger than for a bare drop of the same base oil. This difference results from the high affinity, i.e. wetting energy per unit volume, of the oil for the grease matrix. To quantify this affinity, we developed a Washburn-like model describing the oil flow from the porous grease into the paper pores. The stain radius versus time curves for greases at various levels of oil content collapse onto a single master curve, which allows us to extract a characteristic spreading time and the corresponding oil-matrix affinity. Lowering the oil content results in a small increase of the oil-matrix affinity yet also in a significant change in the spreading timescale. Even an affinity increase of a few per mill doubles the timescale.

Design and wavefront characterization of an electrically tunable aspherical optofluidic lens.

We present a novel design of an exclusively electrically controlled adaptive optofluidic lens that allows for manipulating both focal length and asphericity. The device is totally encapsulated and contains an aqueous lens with a clear aperture of 2mm immersed in ambient oil. The design is based on the combination of an electrowetting-driven pressure regulation to control the average curvature of the lens and a Maxwell stress-based correction of the local curvature to control spherical aberration. The performance of the lens is evaluated by a dedicated setup for the characterization of optical wavefronts using a Shack Hartmann Wavefront Sensor. The focal length of the device can be varied between 10 and 27mm. At the same time, the Zernike coefficient Z40, characterising spherical aberration, can be tuned reversibly between 0.059waves and 0.003waves at a wavelength of λ=532nm. Several possible extensions and applications of the device are discussed.

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.

X-ray Photoelectron Spectroscopy with Electrical Modulation Can Be Used to Probe Electrical Properties of Liquids and Their Interfaces at Different Stages.

Operando X-ray photoelectron spectroscopy (o-XPS) has been used to record the binding energy shifts in the C 1s peak of a pristine poly(ethylene glycol) (PEG) liquid drop in an electrowetting on dielectric (EWOD) geometry and after exposing it to several high-voltage breakdown processes. This was achieved by recording XPS data while the samples were subjected to 10 V dc and ac (square-wave modulation) actuations to extract electrical information related to the liquid and its interface with the dielectric. Through analysis of the XPS data under ac actuation, a critical frequency of 170 Hz is extracted for the pristine PEG, which is translated to a resistance value of 14 MΩ for the liquid and a capacitance value of 60 pF for the dielectric, by the help of simulations using an equivalent circuit model and also by XPS analyses of a mimicking device under similar conditions. The same measurements yield an increased value of 23 MΩ for the resistance of the liquid after the breakdown by assuming that the capacitance of the dielectric stays constant. In addition, an asymmetry in polarity dependence is observed with respect to both the onset of the breakdown voltage and also the leakage behavior of the deteriorated (PEG + dielectric) system such that deviations are more pronounced at positive voltages. Both dc and ac behaviors of the postbreakdown system can also be simulated, but only by introducing an additional element, a diode or a polarity- and magnitude-dependent voltage source (VCVS), which might be attributed to negative charge accumulation at the interface. Measurements for a liquid mixture of PEG with 8% ionic liquid yields an almost 2 orders of magnitude smaller resistance for the drop as a result of the enhanced conductivity by the ions. Coupled with modeling, XPS measurements under dc and ac modulations enable probing unique electrochemical properties of liquid/solid interfaces.

Behaviour of flexible superhydrophobic striped surfaces during (electro-)wetting of a sessile drop.

We study here the microscopic deformations of elastic lamellae constituting a superhydrophobic substrate under different wetting conditions of a sessile droplet using electrowetting. The deformation profiles of the lamellae are experimentally evaluated using confocal microscopy. These experimental results are then explained using a variational principle formalism within the framework of linear elasticity. We show that the local deformation profile of a lamella is mainly controlled by the net horizontal component of the capillary forces acting on its top due to the pinned droplet contact line. We also discuss the indirect role of electrowetting in dictating the deformation characteristics of the elastic lamellae. One important conclusion is that the small deflection assumption, which is frequently used in the literature, fails to provide a quantitative description of the experimental results; a full solution of the non-linear governing equation is necessary to describe the experimentally obtained deflection profiles.

Slippery when wet: mobility regimes of confined drops in electrowetting.

The motion of confined droplets in immiscible liquid-liquid systems strongly depends on the intrinsic relative wettability of the liquids on the confining solid material and on the typical speed, which can induce the formation of a lubricating layer of the continuous phase. In electrowetting, which routinely makes use of aqueous drops in ambient non-polar fluids that wet the wall material, electric stresses enter the force balance in addition to capillary and viscous forces and confinement effects. Here, we study the mobility of droplets upon electrowetting actuation in a wedge-shaped channel, and the subsequent relaxation when the electrowetting actuation is removed. We find that the droplets display two different mobility regimes: a fast regime, corresponding to gliding on a thin film of the ambient fluid, and a slow regime, where the film is replaced by direct contact between the droplet and the channel walls. Using a combination of experiments and numerical simulations, we show that the cross-over between these regimes arises from the interplay between the small-scale dynamics of the thin film of ambient fluid and the large-scale motion of the droplet. Our results shed light on the complex dynamics of droplets in non-uniform channels driven by electric actuation, and can thus help the rational design of devices based on electrowetting-driven droplet transport.

Soft electrowetting.

Electrowetting is a commonly used tool to manipulate sessile drops on hydrophobic surfaces. By applying an external voltage over a liquid and a dielectric-coated surface, one achieves a reduction of the macroscopic contact angles for increasing voltage. The electrostatic forces all play out near the contact line, on a scale of the order of the thickness of the solid dielectric layer. Here we explore the case where the dielectric is a soft elastic layer, which deforms elastically under the effect of electrostatic and capillary forces. The wetting behaviour is quantified by measurements of the static and dynamic contact angles, complemented by confocal microscopy to reveal the elastic deformations. Even though the mechanics near the contact line is highly intricate, the macroscopic contact angles can be understood from global conservation laws in the spirit of Young-Lippmann. The key finding is that, while elasticity has no effect on the static electrowetting angle, the substrate's viscoelasticity completely dictates the spreading dynamics of electrowetting.

Breath Figures under Electrowetting: Electrically Controlled Evolution of Drop Condensation Patterns.

We show that electrowetting (EW) with structured electrodes significantly modifies the distribution of drops condensing onto flat hydrophobic surfaces by aligning the drops and by enhancing coalescence. Numerical calculations demonstrate that drop alignment and coalescence are governed by the drop-size-dependent electrostatic energy landscape that is imposed by the electrode pattern and the applied voltage. Such EW-controlled migration and coalescence of condensate drops significantly alter the statistical characteristics of the ensemble of droplets. The evolution of the drop size distribution displays self-similar characteristics that significantly deviate from classical breath figures on homogeneous surfaces once the electrically induced coalescence cascades set in beyond a certain critical drop size. The resulting reduced surface coverage, coupled with earlier drop shedding under EW, enhances the net heat transfer.

Mechanical History Dependence in Carbon Black Suspensions for Flow Batteries: A Rheo-Impedance Study.

We studied the effects of shear and its history on suspensions of carbon black (CB) in lithium ion battery electrolyte via simultaneous rheometry and electrical impedance spectroscopy. Ketjen black (KB) suspensions showed shear thinning and rheopexy and exhibited a yield stress. Shear step experiments revealed a two time scale response. The immediate effect of decreasing the shear rate is an increase in both viscosity and electronic conductivity. In a much slower secondary response, both quantities change in the opposite direction, leading to a reversal of the initial change in the conductivity. Stepwise increases in the shear rate lead to similar responses in the opposite direction. This remarkable behavior is consistent with a picture in which agglomerating KB particles can stick directly on contact, forming open structures, and then slowly interpenetrate and densify. The fact that spherical CB particles show the opposite slow response suggests that the fractal structure of the KB primary units plays an important role. A theoretical scheme was used to analyze the shear and time-dependent viscosity and conductivity. Describing the agglomerates as effective hard spheres with a fractal architecture and using an effective medium approximation for the conductivity, we found the changes in the derived suspension structure to be in agreement with our qualitative mechanistic picture. This behavior of KB in flow has consequences for the properties of the gel network that is formed immediately after the cessation of shear: both the yield stress and the electronic conductivity increase with the previously applied shear rate. Our findings thus have clear implications for the operation and filling strategies of semisolid flow batteries.