Temperature effects on the electrohydrodynamic and electrokinetic behaviour of ion-selective nanochannels

A non-isothermal formulation of the Poisson–Nernst–Planck with Navier–Stokes equations is used to study the influence of heating effects in the form of Joule heating and viscous dissipation and imposed temperature gradients on a microchannel/nanochannel system. The system is solved numerically under various cases in order to determine the influence of temperature-related effects on ion-selectivity, flux and fluid flow profiles, as well as coupling between these phenomena. It is demonstrated that for a larger reservoir system, the effects of Joule heating and viscous dissipation only become relevant for higher salt concentrations and electric field strengths than are compatible with ion-selectivity due to Debye layer overlap. More interestingly, it is shown that using different temperature reservoirs can have a strong influence on ion-selectivity, as well as the induced electrohydrodynamic flows

Diffusiophoretic Behavior of Polyelectrolyte-Coated Particles

Diffusiophoresis, the movement of particles under a solute concentration gradient, has practical implications in a number of applications, such as particle sorting, focusing, and sensing. For diffusiophoresis in an electrolyte solution, the particle velocity is described by the electrolyte relative concentration gradient and the diffusiophoretic mobility of the particle. The electrolyte concentration, which typically varies throughout the system in space and time, can also influence the zeta potential of particles in space and time. This variation affects the diffusiophoretic behavior, especially when the zeta potential is highly dependent on the electrolyte concentration. In this work, we show that adsorbing a single bilayer (or 4 bilayers) of a polyelectrolyte pair (PDADMAC/PSS) on the surface of microparticles resulted in effectively constant zeta potential values with respect to salt concentration throughout the experimental range of salt concentrations. This allowed a constant potential model for diffusiophoretic transport to describe the experimental observations, which was not the case for uncoated particles in the same electrolyte system. This work highlights the use of simple polyelectrolyte pairs to tune the zeta potential and maintain constant values for precise control of diffusiophoretic transport

Mass Transport Limitations in Microbial Fuel Cells:Impact of Flow Configurations

The performance of microbial fuel cells (MFCs) is limited by a number of factors, including metabolic activity of electroactive microorganisms and electrochemical systematic constraints, such as overpotentials at the electrodes or IR losses. Heterogeneities of substrate distribution (availability) can also strongly limit current in MFCs. In this work we investigate how mass transport can be enhanced by changing the flow configurations in MFCs, e.g. by directing the flow through a porous anode or by applying inserts and channels to anodes. Experimental results using a perpendicular flow through the anode were compared to a parallel flow setup, showing increased current output. Finite element method (FEM) simulations were used to simulate the flow profiles and substrate distribution in each setup. The simulations revealed higher average substrate concentrations for the perpendicular flow through a porous carbon fabric anode vs. a parallel flow in the bulk phase of the MFC, related to the enhancement of transport via convection in perpendicular flow. The simulated substrate distributions found for the different inlet setups could be correlated to the experimentally obtained current flow, power output and biofilm distribution. It can be concluded that the increased current output can be explained by the flow profile in the system resulting in an increased substrate distribution in the biofilm on the electrode and a hindered oxygen transport from the cathode

Oxidative protein refolding on size exclusion chromatography:From batch single-column to multi-column counter-current continuous processing

Recently protein refolding on size exclusion chromatography (SEC) operated in multi-column continuous simulated moving bed (SMB) configurations (hereinafter SMB-SEC) has been investigated for future industrial applications. This is due to several advantages offered by SMB configurations particularly when process parameters are thoroughly screened and optimized. A robust mathematical model is essential for high-throughput process screening and optimization. In this work, a previously investigated single-column mathematical model was modified to extend its applicability for protein oxidative refolding/aggregation predictions in SMB-SEC. The model considers a wide loading concentration range of the model protein (lysozyme) on SEC. The potential influences of high concentrations of chaotropic reagents on kinetic and thermodynamic model parameters have been discussed based on previous experimental results and their predicted local concentrations through the SMB-SEC columns and at the product stream. It was observed that aggregation occurs when local protein concentration exceeds a critical concentration. No urea recovery at the product stream indicated that the refolding reaction will continue off-column to recover the native-protein product. Therefore, it is suggested that the developed model is tested against experimental results for total soluble protein (early intermediates and native conformations) in the presence of L{small}-arginine additive and process performance indicators are defined based on this criterion

Influence of temperature gradients on mono- and divalent ion transport in electrodialysis at limiting currents

Temperature gradients in electrodialysis (ED) stacks can potentially enhance the efficiency of charge separation and the selective transport of ions. We have previously investigated temperature gradients in the Ohmic regime but not in the limiting current regime, where diffusion of ions towards the membrane determines the transport rate and temperature gradients potentially have the largest influence. In this research, commercial ion exchange membranes (FAS and FKS, FUMATECH, Germany) are used for the investigation of temperature gradients in the limiting current regime. In contrast to the Ohmic regime, we find that heating the diluted stream increases the current obtained (at a constant applied potential) when compared to heating the concentrate stream in systems containing monovalent KCl and NaCl solutions. For mixtures of mono- and divalent ions, the temperature gradient has a larger influence on the selectivity of the separation. If the desalinated stream is heated, divalent Mg2+ ions show a higher transport than the monovalent K+ and Na+ ions. This is due to the enhanced competitive transport of the mono- and divalent ions under the application of a temperature gradient. These results show the potential application and relevance of temperature gradients to enhance the selective separation of mono- and divalent ions

Influence of temperature gradients on charge transport in asymmetric nanochannels

Charge selective asymmetric nanochannels are used for a variety of applications, such as nanofluidic sensing devices and energy conversion applications. In this paper, we numerically investigate the influence of an applied temperature difference over tapered nanochannels on the resulting charge transport and flow behavior. Using a temperature-dependent formulation of the coupled Poisson-Nernst-Planck and Navier-Stokes equations, various nanochannel geometries are investigated. Temperature has a large influence on the total ion transport, as the diffusivity of ions and viscosity of the solution are strongly affected by temperature. We find that the selectivity of the nanochannels is enhanced with increasing asymmetry ratios, while the total current is reduced at higher asymmetry cases. Most interestingly, we find that applying a temperature gradient along the electric field and along the asymmetry direction of the nanochannel enhances the selectivity of the tapered channels even further, while a temperature gradient countering the electric field reduces the selectivity of the nanochannel. Current rectification is enhanced in asymmetric nanochannels if a temperature gradient is applied, independent of the direction of the temperature difference. However, the degree of rectification is dependent on the direction of the temperature gradient with respect to the channel geometry and the electric field direction. The enhanced selectivity of nanochannels due to applied temperature gradients could result in more efficient operation in energy harvesting or desalination applications, motivating experimental investigations

Liquid-liquid displacement in slippery liquid-infused membranes (SLIMs)

Liquid-infused membranes inspired by slippery liquid-infused porous surfaces (SLIPS) have been recently introduced to membrane technology. The gating mechanism of these membranes is expected to give rise to anti-fouling properties and multi-phase transport capabilities. However, the long-term retention of the infusion liquid has not yet been explored. To address this issue, we investigate the retention of the infusion liquid in slippery liquid-infused membranes (SLIMs) via liquid-liquid displacement porometry (LLDP) experiments combined with microscopic observations of the displacement mechanism. Our results reveal that pores will be opened corresponding to the capillary pressure, leading to preferential flow pathways for water transport. The LLDP results further suggest the presence of liquid-lined pores in SLIM. This hypothesis is analyzed theoretically using an interfacial pore flow model. We find that the displacement patterns correspond to capillary fingering in immiscible displacement in porous media. The related physics regarding two-phase flow in porous media is used to confirm the permeation mechanism appearing in SLIMs. In order to experimentally observe liquid-liquid displacement, a microfluidic chip mimicking a porous medium is designed and a highly ramified structure with trapped infusion liquid is observed. The remaining infusion liquid is retained as pools, bridges and thin films around pillar structures in the chip, which further confirms liquid-lining. Fractal dimension analysis, along with evaluation of the fluid (non-wetting phase) saturation, further confirms that the fractal patterns correspond to capillary fingering, which is consistent with an invasion percolation with trapping (IPT) model

Performance Enhancement of Electrocatalytic Hydrogen Evolution through Coalescence-Induced Bubble Dynamics

The evolution of electrogenerated gas bubbles during water electrolysis can significantly hamper the overall process efficiency. Promoting the departure of electrochemically generated bubbles during (water) electrolysis is therefore beneficial. For a single bubble, a departure from the electrode surface occurs when buoyancy wins over the downward-acting forces (e.g., contact, Marangoni, and electric forces). In this work, the dynamics of a pair of H2 bubbles produced during the hydrogen evolution reaction in 0.5 M H2SO4 using a dual platinum microelectrode system is systematically studied by varying the electrode distance and the cathodic potential. By combining high-speed imaging and electrochemical analysis, we demonstrate the importance of bubble-bubble interactions in the departure process. We show that bubble coalescence may lead to substantially earlier bubble departure as compared to buoyancy effects alone, resulting in considerably higher reaction rates at a constant potential. However, due to continued mass input and conservation of momentum, repeated coalescence events with bubbles close to the electrode may drive departed bubbles back to the surface beyond a critical current, which increases with the electrode spacing. The latter leads to the resumption of bubble growth near the electrode surface, followed by buoyancy-driven departure. While less favorable at small electrode spacing, this configuration proves to be very beneficial at larger separations, increasing the mean current up to 2.4 times compared to a single electrode under the conditions explored in this study.</p