Controlling the spacing of the linked graphene oxide system with dithiol linkers under confinement.

2D nanoscale confined systems exhibit behavior that is markedly different from that observed at the macroscale. Confinement can be tuned by controlling the interlayer spacing between confining layers using organic dithiol linkers. Adjusting spacing and selective intercalation have important impacts for catalysis, superconductivity, spin engineering, sodium ion batteries, 2D magnets, optoelectronics, and many other applications. In this study, we report how reaction conditions and organic linkers can be used to create variable, reproducible spacings between graphene oxide to provide confinement systems. We determined the conditions under which the spacing can be variably adjusted by the type of linker used, the concentration of the linker, and the reaction conditions. Employing dithiol linkers of different lengths, such as three (TPDT) and four (QPDT) aromatic rings, we can adjust the spacing between graphene oxide layers under varied reaction conditions. Here, we show that by varying dithiol linker length and using different reaction conditions, we can reproducibly control the spacing between graphene oxide layers from 0.37 nm to over 0.50 nm.

Photocatalytic CO2 Reduction with Dissolved Carbonates and Near-Zero CO2(aq) by Employing Long-Range Proton Transport.

Photocatalytic CO2 reduction (CO2R) in ∼0 mM CO2(aq) concentration is challenging but is relevant for capturing CO2 and achieving a circular carbon economy. Despite recent advances, the interplay between the CO2 catalytic reduction and the oxidative redox processes that are arranged on photocatalyst surfaces with nanometer-scale distances is less studied. Specifically, mechanistic investigation on interdependent processes, including CO2 adsorption, charge separation, long-range chemical transport (∼100 nm distance), and bicarbonate buffer speciation, involved in photocatalysis is urgently needed. Photocatalytic CO2R in ∼0 mM CO2(aq), which has important applications in integrated carbon capture and utilization (CCU), has rarely been studied. Using 0.1 M KHCO3 (aq) of pH 7 but without continuously bubbling CO2, we achieved ∼0.1% solar-to-fuel conversion efficiency for CO production using Ag@CrOx nanoparticles that are supported on a coating-protected GaInP2 photocatalytic panel. CO is produced at ∼100% selectivity with no detectable H2, even with copious protons co-generated nearby. CO2 flux to the Ag@CrOx CO2R sites enhances CO2 adsorption, probed by in situ Raman spectroscopy. CO is produced with local protonation of dissolved inorganic carbon species in a pH as high as 11.5 when using fast electron donors such as ethanol. Isotopic labeling using KH13CO3 was used to confirm the origin of CO from the bicarbonate solution. We then employed COMSOL Multiphysics modeling to simulate the spatial and temporal pH variation and the local concentrations of bicarbonates and CO2(aq). We found that light-driven CO2R and CO2 reactive transport are mutually dependent, which is important for further understanding and manipulating CO2R activity and selectivity. This study enables direct bicarbonate utilization as the source of CO2, thereby achieving CO2 capture and conversion without purifying and feeding gaseous CO2.

Erratum: Obtaining self-similar scalings in focusing flows [Phys. Rev. E 92, 043016 (2015)].

This corrects the article DOI: 10.1103/PhysRevE.92.043016.

Testing constitutive relations by running and walking on cornstarch and water suspensions.

The ability of a person to run on the surface of a suspension of cornstarch and water has fascinated scientists and the public alike. However, the constitutive relation obtained from traditional steady-state rheology of cornstarch and water suspensions has failed to explain this behavior. In another paper we presented an averaged constitutive relation for impact rheology consisting of an effective compressive modulus of a system-spanning dynamically jammed structure [R. Maharjan et al., this issue, Phys. Rev. E 97, 052602 (2018)10.1103/PhysRevE.97.052602]. Here we show that this constitutive model can be used to quantitatively predict, for example, the trajectory and penetration depth of the foot of a person walking or running on cornstarch and water. The ability of the constitutive relation to predict the material behavior in a case with different forcing conditions and flow geometry than it was obtained from suggests that the constitutive relation could be applied more generally. We also present a detailed calculation of the added mass effect to show that while it may be able to explain some cases of people running or walking on the surface of cornstarch and water for pool depths H>1.2 m and foot impact velocities V_{I}>1.7 m/s, it cannot explain observations of people walking or running on the surface of cornstarch and water for smaller H or V_{I}.

System-spanning dynamically jammed region in response to impact of cornstarch and water suspensions.

We experimentally characterize the structure of concentrated suspensions of cornstarch and water in response to impact. Using surface imaging and particle tracking at the boundary opposite the impactor, we observed that a visible structure and particle flow at the boundary occur with a delay after impact. We show the delay time is about the same time as the strong stress response, confirming that the strong stress response results from deformation of the dynamically jammed structure once it spans between the impactor and a solid boundary. A characterization of this strong stress response is reported in a companion paper [Maharjan, Mukhopadhyay, Allen, Storz, and Brown, Phys. Rev. E 97, 052602 (2018)10.1103/PhysRevE.97.052602]. We observed particle flow in the outer part of the dynamically jammed region at the bottom boundary, with a net transverse displacement of up to about 5% of the impactor displacement, indicating shear at the boundary. Direct imaging of the surface of the outer part of the dynamically jammed region reveals a change in surface structure that appears the same as the result of dilation in other cornstarch suspensions. Imaging also reveals cracks, like a brittle solid. These observations suggest the dynamically jammed structure can temporarily support stress according to an effective modulus, like a soil or dense granular material, along a network of frictional contacts between the impactor and solid boundary.

Constitutive relation for the system-spanning dynamically jammed region in response to impact of cornstarch and water suspensions.

We experimentally characterize the impact response of concentrated suspensions consisting of cornstarch and water. We observe that the suspensions support a large normal stress-on the order of MPa-with a delay after the impactor hits the suspension surface. We show that neither the delay nor the magnitude of the stress can yet be explained by either standard rheological models of shear thickening in terms of steady-state viscosities, or impact models based on added mass or other inertial effects. The stress increase occurs when a dynamically jammed region of the suspension in front of the impactor propagates to the opposite boundary of the container, which can support large stresses when it spans between solid boundaries. We present a constitutive relation for impact rheology to relate the force on the impactor to its displacement. This can be described in terms of an effective modulus but only after the delay required for the dynamically jammed region to span between solid boundaries. Both the modulus and the delay are reported as a function of impact velocity, fluid height, and weight fraction. We report in a companion paper the structure of the dynamically jammed region when it spans between the impactor and the opposite boundary [Allen et al., Phys. Rev. E 97, 052603 (2018)10.1103/PhysRevE.97.052603]. In a direct follow-up paper, we show that this constitutive model can be used to quantitatively predict, for example, the trajectory and penetration depth of the foot of a person walking or running on cornstarch and water [Mukhopadhyay et al., Phys. Rev. E 97, 052604 (2018)10.1103/PhysRevE.97.052604].

Highly stiff yet elastic microcapsules incorporating cellulose nanofibrils.

Microcapsules with high mechanical stability and elasticity are desirable in a variety of contexts. We report a single-step method to fabricate such microcapsules by microfluidic interfacial complexation between high stiffness cellulose nanofibrils (CNF) and an oil-soluble cationic random copolymer. Single-capsule compression measurements reveal an elastic modulus of 53 MPa for the CNF-based capsule shell with complete recovery of deformation from strains as large as 19%. We demonstrate the ability to manipulate the shell modulus by the use of polyacrylic acid (PAA) as a binder material, and observe a direct relationship between the shell modulus and the PAA concentration, with moduli as large as 0.5 GPa attained. These results demonstrate that CNF incorporation provides a facile route for producing strong yet flexible microcapsule shells.

Obtaining self-similar scalings in focusing flows.

The surface structure of converging thin fluid films displays self-similar behavior, as was shown in the work by Diez et al. [Q. Appl. Math. 210, 155 (1990)]. Extracting the related similarity scaling exponents from either numerical or experimental data is nontrivial. Here we provide two such methods. We apply them to experimental and numerical data on converging fluid films driven by both surface tension and gravitational forcing. In the limit of pure gravitational driving, we recover Diez' semianalytic result, but our methods also allow us to explore the entire regime of mixed capillary and gravitational driving, up to entirely surface-tension-driven flows. We find scaling forms of smoothly varying exponents up to surprisingly small Bond numbers. Our experimental results are in reasonable agreement with our numerical simulations, which confirm theoretically obtained relations between the scaling exponents.

Packings of deformable spheres.

We present an experimental study of disordered packings of deformable spheres. Fluorescent hydrogel spheres immersed in water together with a tomography technique enabled the imaging of the three-dimensional arrangement. The mechanical behavior of single spheres subjected to compression is first examined. Then the properties of packings of a randomized collection of deformable spheres in a box with a moving lid are tested. The transition to a state where the packing withstands finite stresses before yielding is observed. Starting from random packed states, the power law dependence of the normal force versus packing fraction or strain at different velocities is quantified. Furthermore, a compression-decompression sequence at low velocities resulted in rearrangements of the spheres. At larger packing fractions, a saturation of the mean coordination number took place, indicating the deformation and faceting of the spheres.

Evolution of droplets of perfectly wetting liquid under the influence of thermocapillary forces.

We consider the evolution of sessile droplets of a nonvolatile perfectly wetting liquid on differentially radially heated solid substrates. The heating induces thermocapillary Marangoni forces that affect the contact line dynamics. Our experiments involving a particular heating pattern reveal that the Marangoni effect suppresses the spreading of a drop, typical for perfectly wetting liquids. The result is a rather slow receding motion and a distinctive thinning of the liquid layer in the region close to the contact line. Our theoretical model, based on the lubrication approximation and incorporating the Marangoni effect, recovers the main features observed in the experiments, and in addition predicts novel features that are still to be observed.

Wetting dynamics of thin liquid films and drops under Marangoni and centrifugal forces.

This paper presents an experimental study on thin liquid drops and films under the combined action of centrifugal forces due to rotation and radial Marangoni forces due to a corresponding temperature gradient. We shall examine thinning of a given liquid layer both with and without rotation and also consider the onset of the fingering instability in a completely wetting liquid drop. In many of the experiments described here, we use an interferometric technique which provides key information on height profiles. For thick rotating films in the absence of a temperature gradient, when an initially thick layer of fluid is spun to angular velocities where the classical Newtonian solution is negative, the fluid never dewets for the case of a completely wetting fluid, but leaves a microscopic uniform wet layer in the center. Similar experiments with a radially inward temperature gradient reveal the evolution of a radial height profile given by h(r) = A(t)r(α), where A(t) decays logarithmically with time, and [Formula: see text]. In the case where there is no rotation, small centrally placed drops show novel retraction behavior under a sufficiently strong temperature gradient. Using the same interferometric arrangement, we observed the onset of the fingering instability of small drops placed at the center of the rotating substrate in the absence of a temperature gradient. At the onset of the instability, the height profile for small drops is more complex than previously assumed.

Dynamics of perfectly wetting drops under gravity.

We study the dynamics of small droplets of polydimethylsiloxane silicone oil on a vertical, perfectly wetting, silicon wafer. Interference videomicroscopy allows us to capture the dynamics of these droplets. We use droplets with a volumes typically ranging from 100 t o500nl (viscosities from 10 to 1000 cSt) to understand long time derivations from classical solutions. Past researchers used one dimensional theory to understand the typical t(1/3) scaling for the position of the tip of the droplet in time t . We observe this regime in experiment for intermediate times and discover a two-dimensional similarity solution of the shape of the droplet. However, at long times our droplets start to move more slowly down the plane than the t(1/3) scaling suggests and we observe deviations in droplet shape from the similarity solution. We match experimental data with simulations to show these deviations are consistent with retarded van der Waals forcing which should become significant at the small heights observed.

Instabilities in droplets spreading on gels.

We report a novel surface-tension driven instability observed for droplets spreading on a compliant substrate. When a droplet is released on the surface of an agar gel, it forms arms or cracks when the ratio of surface-tension gradient to gel strength is sufficiently large. We explore a range of gel strengths and droplet surface tensions and find that the onset of the instability and the number of arms depend on the ratio of surface tension to gel strength. However, the arm length grows with an apparently universal law L proportional t(3/4).