Enhancement of bubble transport in porous electrodes and catalysts.

We investigate the formation and transport of gas bubbles across a model porous electrode/catalyst using lattice Boltzmann simulations. This approach enables us to systematically examine the influence of a wide range of morphologies, flow velocities, and reaction rates on the efficiency of gas production. By exploring these parameters, we identify critical parameter combinations that significantly contribute to an enhanced yield of gas output. Our simulations reveal the existence of an optimal pore geometry for which the product output is maximized. Intriguingly, we also observe that lower flow velocities improve gas production by leveraging coalescence-induced bubble detachment from the electrode/catalyst.

Local electroneutrality breakdown for electrolytes within varying-section nanopores.

We determine the local charge dynamics of a [Formula: see text] electrolyte embedded in a varying-section channel. By means of an expansion based on the length scale separation between the axial and transverse direction of the channel, we derive closed formulas for the local excess charge for both, dielectric and conducting walls, in 2D (planar geometry) as well as in 3D (cylindrical geometry). Our results show that, even at equilibrium, the local charge electroneutrality is broken whenever the section of the channel is not homogeneous for both dielectric and conducting walls as well as for 2D and 3D channels. Interestingly, even within our expansion, the local excess charge in the fluid can be comparable to the net charge on the walls. We critically discuss the onset of such local electroneutrality breakdown in particular with respect to the correction that it induces on the effective free energy profile experienced by tracer ions.

Entropy by Neighbor Distance as a New Measure for Characterizing Spatiotemporal Orders in Microscopic Collective Systems.

Collective systems self-organize to form globally ordered spatiotemporal patterns. Finding appropriate measures to characterize the order in these patterns will contribute to our understanding of the principles of self-organization in all collective systems. Here we examine a new measure based on the entropy of the neighbor distance distributions in the characterization of collective patterns. We study three types of systems: a simulated self-propelled boid system, two active colloidal systems, and one centimeter-scale robotic swarm system. In all these systems, the new measure proves sensitive in revealing active phase transitions and in distinguishing steady states. We envision that the entropy by neighbor distance could be useful for characterizing biological swarms such as bird flocks and for designing robotic swarms.

Nonmonotonous Translocation Time of Polymers across Pores.

Polymers confined in corrugated channels, i.e., channels of varying amplitude, display multiple local maxima and minima of the diffusion coefficient upon increasing their degree of polymerization N. We propose a theoretical effective free energy for linear polymers based on a Fick-Jacobs approach. We validate the predictions against numerical data, obtaining quantitative agreement for the effective free energy, the diffusion coefficient, and the mean first passage time. Finally, we employ the effective free energy to compute the polymer lengths N_{min} at which the diffusion coefficient presents a minimum: we find a scaling expression that we rationalize with a blob model. Our results could be useful to design porous adsorbers, that separate polymers of different sizes without the action of an external flow.

Diffusion of gold nanoparticles in porous silica monoliths determined by dynamic light scattering.

HYPOTHESIS: The applicability of the dynamic light scattering method for the determination of particle diffusivity under confinement without applying refractive index matching was not adequately explored so far. The confinement effect on particle diffusion in a porous material which is relevant for particle chromatography has also not yet been fully characterized. EXPERIMENTS: Dynamic light scattering experiments were performed for unimodal dispersions of 11-mercaptoundecanoic acid-capped gold nanoparticles. Diffusion coefficients of gold nanoparticles in porous silica monoliths were determined without limiting refractive index matching fluids. Comparative experiments were also performed with the same nanoparticles and porous silica monolith but applying refractive index matching. FINDINGS: Two distinct diffusivities could be determined inside the porous silica monolith, both smaller than that in free media, showing a slowing-down of the diffusion processes of nanoparticles under confinement. While the larger diffusivity can be related to the slightly slowed-down diffusion of particles in the bulk of the pores and in the necks connecting individual pores, the smaller diffusivity might be related to the diffusion of particles near the pore walls. It shows that the dynamic light scattering method with a heterodyne detection scheme can be used as a reliable and competitive tool for determining particle diffusion under confinement.

Surface viscosity in simple liquids.

The response of Newtonian liquids to small perturbations is usually considered to be fully described by homogeneous transport coefficients like shear and dilatational viscosity. However, the presence of strong density gradients at the liquid/vapor boundary of fluids hints at the possible existence of an inhomogeneous viscosity. Here, we show that a surface viscosity emerges from the collective dynamics of interfacial layers in molecular simulations of simple liquids. We estimate the surface viscosity to be 8-16 times smaller than that of the bulk fluid at the thermodynamic point considered. This result can have important implications for reactions at liquid surfaces in atmospheric chemistry and catalysis.

Closed Formula for Transport across Constrictions.

In the last decade, the Fick-Jacobs approximation has been exploited to capture transport across constrictions. Here, we review the derivation of the Fick-Jacobs equation with particular emphasis on its linear response regime. We show that, for fore-aft symmetric channels, the flux of noninteracting systems is fully captured by its linear response regime. For this case, we derive a very simple formula that captures the correct trends and can be exploited as a simple tool to design experiments or simulations. Lastly, we show that higher-order corrections in the flux may appear for nonsymmetric channels.

Szilard Engines and Information-Based Work Extraction for Active Systems.

The out of equilibrium nature of active systems can be exploited for the design of information-based engines. We design two types of an active Szilard engine that use a Maxwell demon to extract work from an active bath composed of noninteracting active Brownian particles. The two engines exploit either the quasistatic active pressure of active Brownian particles or the long correlation time of their velocities. For both engines the active bath allows us to overcome the Landauer principle and to extract larger work compared to conventional Szilard engines operating in quasithermal equilibrium. For both of our engines, we identify the optimal regimes at which the work extracted and the efficiency are maximized. Finally, we discuss them in the context of synthetic and biological active systems.

Nucleation as a rate-determining step in catalytic gas generation reactions from liquid phase systems.

The observable reaction rate of heterogeneously catalyzed reactions is known to be limited either by the intrinsic kinetics of the catalytic transformation or by the rate of pore and/or film diffusion. Here, we show that in gas generation reactions from liquid reactants, the nucleation of gas bubbles in the catalyst pore structure represents an additional important rate-limiting step. This is highlighted for the example of catalytic hydrogen release from the liquid organic hydrogen carrier compound perhydro-dibenzyltoluene. A nucleation-inhibited catalytic system produces only dissolved hydrogen with fast saturation of the fluid phase around the active site, while bubble formation enhances mass transfer by more than a factor of 50 in an oscillating reaction regime. Nucleation can be efficiently triggered not only by temperature changes and catalyst surface modification but also by a mechanical stimulus. Our work sheds new light on performance-limiting factors in reactions that are of highest relevance for the future green hydrogen economy.

Rolling microswarms along acoustic virtual walls.

Rolling is a ubiquitous transport mode utilized by living organisms and engineered systems. However, rolling at the microscale has been constrained by the requirement of a physical boundary to break the spatial homogeneity of surrounding mediums, which limits its prospects for navigation to locations with no boundaries. Here, in the absence of real boundaries, we show that microswarms can execute rolling along virtual walls in liquids, impelled by a combination of magnetic and acoustic fields. A rotational magnetic field causes individual particles to self-assemble and rotate, while the pressure nodes of an acoustic standing wave field serve as virtual walls. The acoustic radiation force pushes the microswarms towards a virtual wall and provides the reaction force needed to break their fore-aft motion symmetry and induce rolling along arbitrary trajectories. The concept of reconfigurable virtual walls overcomes the fundamental limitation of a physical boundary being required for universal rolling movements.

Hydrodynamic simulations of sedimenting dilute particle suspensions under repulsive DLVO interactions.

We present guidelines to estimate the effect of electrostatic repulsion in sedimenting dilute particle suspensions. Our results are based on combined Langevin dynamics and lattice Boltzmann simulations for a range of particle radii, Debye lengths and particle concentrations. They show a simple relationship between the slope K of the concentration-dependent sedimentation velocity and the range χ of the electrostatic repulsion normalized by the average particle-particle distance. When χ → 0, the particles are too far away from each other to interact electrostatically and K = 6.55 as predicted by the theory of Batchelor. As χ increases, K likewise increases as if the particle radius increased in proportion to χ up to a maximum around χ = 0.4. Over the range χ = 0.4-1, K relaxes exponentially to a concentration-dependent constant consistent with known results for ordered particle distributions. Meanwhile the radial distribution function transitions from a disordered gas-like to a liquid-like form. Power law fits to the concentration-dependent sedimentation velocity similarly yield a simple master curve for the exponent as a function of χ, with a step-like transition from 1 to 1/3 centered around χ = 0.6.

Microscopic Swarms: From Active Matter Physics to Biomedical and Environmental Applications.

Microscopic swarms consisting of, e.g., active colloidal particles or microorganisms, display emergent behaviors not seen in equilibrium systems. They represent an emerging field of research that generates both fundamental scientific interest and practical technological value. This review seeks to unite the perspective of fundamental active matter physics and the perspective of practical applications of microscopic swarms. We first summarize experimental and theoretical results related to a few key aspects unique to active matter systems: the existence of long-range order, the prediction and observation of giant number fluctuations and motility-induced phase separation, and the exploration of the relations between information and order in the self-organizing patterns. Then we discuss microscopic swarms, particularly microrobotic swarms, from the perspective of applications. We introduce common methods to control and manipulate microrobotic swarms and summarize their potential applications in fields such as targeted delivery, in vivo imaging, biofilm removal, and wastewater treatment. We aim at bridging the gap between the community of active matter physics and the community of micromachines or microrobotics, and in doing so, we seek to inspire fruitful collaborations between the two communities.

Order and information in the patterns of spinning magnetic micro-disks at the air-water interface.

The application of the Shannon entropy to study the relationship between information and structures has yielded insights into molecular and material systems. However, the difficulty in directly observing and manipulating atoms and molecules hampers the ability of these systems to serve as model systems for further exploring the links between information and structures. Here, we use, as a model experimental system, hundreds of spinning magnetic micro-disks self-organizing at the air-water interface to generate various spatiotemporal patterns with varying degrees of order. Using the neighbor distance as the information-bearing variable, we demonstrate the links among information, structure, and interactions. We establish a direct link between information and structure without using explicit knowledge of interactions. Last, we show that the Shannon entropy by neighbor distances is a powerful observable in characterizing structural changes. Our findings are relevant for analyzing natural self-organizing systems and for designing collective robots.

Active microrheology in corrugated channels: Comparison of thermal and colloidal baths.

HYPOTHESIS: The dynamics of colloidal suspension confined within porous materials strongly differs from that in the bulk. In particular, within porous materials, the presence of boundaries with complex shapes entangles the longitudinal and transverse degrees of freedom inducing a coupling between the transport of the suspension and the density inhomogeneities induced by the walls. METHOD: Colloidal suspension confined within model porous media are characterized by means of active microrheology where a net force is applied on a single colloid (tracer particle) whose transport properties are then studied. The trajectories provided by active microrheology are exploited to determine the local transport coefficients. In order to asses the role of the colloid-colloid interactions we compare the case of a tracer embedded in a colloidal suspension to the case of a tracer suspended in an ideal bath. FINDING: Our results show that the friction coefficient increases and the passage time distribution widens upon increasing the corrugation of the channel. These features are obtained for a tracer suspended in a (thermalized) colloidal bath as well as for the case of an ideal thermal bath. These results highlight the relevance of the confinement on the transport and show a mild dependence on the colloidal/thermal bath. Finally, we rationalize our numerical results with a semi-analytical model. Interestingly, the predictions of the model are quantitatively reliable for mild external forces, hence providing a reliable tool for predicting the transport across porous materials.

Reconfiguring confined magnetic colloids with tunable fluid transport behavior.

Collective dynamics of confined colloids are crucial in diverse scenarios such as self-assembly and phase behavior in materials science, microrobot swarms for drug delivery and microfluidic control. Yet, fine-tuning the dynamics of colloids in microscale confined spaces is still a formidable task due to the complexity of the dynamics of colloidal suspension and to the lack of methodology to probe colloids in confinement. Here, we show that the collective dynamics of confined magnetic colloids can be finely tuned by external magnetic fields. In particular, the mechanical properties of the confined colloidal suspension can be probed in real time and this strategy can be also used to tune microscale fluid transport. Our experimental and theoretical investigations reveal that the collective configuration characterized by the colloidal entropy is controlled by the colloidal concentration, confining ratio and external field strength and direction. Indeed, our results show that mechanical properties of the colloidal suspension as well as the transport of the solvent in microfluidic devices can be controlled upon tuning the entropy of the colloidal suspension. Our approach opens new avenues for the design and application of drug delivery, microfluidic logic, dynamic fluid control, chemical reaction and beyond.

Antiresonant driven systems for particle manipulation.

We report on the onset of antiresonant behavior of mass transport systems driven by time-dependent forces. Antiresonances arise from the coupling of a sufficiently high number of space-time modes of the force. The presence of forces having a wide space-time spectrum, a necessary condition for the formation of an antiresonance, is typical of confined systems with uneven and deformable walls that induce entropic forces dependent on space and time. We have analyzed, in particular, the case of polymer chains confined in a flexible channel and shown how they can be sorted and trapped. The presence of resonance-antiresonance pairs found can be exploited to design protocols able to engineer optimal transport processes and to manipulate the dynamics of nano-objects.

Activity-Induced Collapse and Arrest of Active Polymer Rings.

We investigate, using numerical simulations, the conformations of isolated active ring polymers. We find that their behavior depends crucially on their size: Short rings (N≲100) swell, whereas longer rings (N≳200) collapse, at sufficiently high activity. By investigating the nonequilibrium process leading to the steady state, we find a universal route driving both outcomes; we highlight the central role of steric interactions, at variance with linear chains, and of topology conservation. We further show that the collapsed rings are arrested by looking at different observables, all underlining the presence of an extremely long timescales at the steady state, associated with the internal dynamics of the collapsed section. Finally, we found that in some circumstances the collapsed state spins about its axis.

Transport of neutral and charged nanorods across varying-section channels.

We study the dynamics of neutral and charged rods embedded in varying-section channels. By means of systematic approximations, we derive the dependence of the local diffusion coefficient on both the geometry and charge of the rods. This microscopic insight allows us to provide predictions for the permeability of varying-section channels to rods with diverse lengths, aspect ratios and charge. Our analysis shows that the dynamics of charged rods is sensitive to the geometry of the channel and that their transport can be controlled by tuning both the shape of the confining walls and the charge of the rod. Interestingly, we find that the channel permeability does not depend monotonically on the charge of the rod. This opens the possibility of a novel mechanism to separate charged rods.

Inhomogeneous surface tension of chemically active fluid interfaces.

We study the dependence of the surface tension of a fluid interface on the density profile of a third suspended phase. By means of an approximated model for the binary mixture and of a perturbative approach, we derive closed-form expressions for the free energy of the system and for the surface tension of the interface. Our results show a remarkable non-monotonous dependence of the surface tension on the spatial separation between the peaks of the density of the suspended phase. Our results also predict the local value of the surface tension in the case in which the density of the suspended phase is not homogeneous along the interface.

Driving an electrolyte through a corrugated nanopore.

We characterize the dynamics of a z - z electrolyte embedded in a varying-section channel. In the linear response regime, by means of suitable approximations, we derive the Onsager matrix associated with externally enforced gradients in electrostatic potential, chemical potential, and pressure, for both dielectric and conducting channel walls. We show here that the linear transport coefficients are particularly sensitive to the geometry and the conductive properties of the channel walls when the Debye length is comparable to the channel width. In this regime, we found that one pair of off-diagonal Onsager matrix elements increases with the corrugation of the channel transport, in contrast to all other elements which are either unaffected by or decrease with increasing corrugation. Our results have a possible impact on the design of blue-energy devices as well as on the understanding of biological ion channels through membranes.