- Award ID(s):
- 2125806
- NSF-PAR ID:
- 10479213
- Publisher / Repository:
- APS
- Date Published:
- Journal Name:
- Physical Review E
- Volume:
- 107
- Issue:
- 5
- ISSN:
- 2470-0045
- Page Range / eLocation ID:
- 054608
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
More Like this
-
null (Ed.)We derive a perturbation solution to the one-dimensional Poisson–Nernst–Planck (PNP) equations between parallel electrodes under oscillatory polarization for arbitrary ionic mobilities and valences. Treating the applied potential as the perturbation parameter, we show that the second-order solution yields a nonzero time-average electric field at large distances from the electrodes, corroborating the recent discovery of Asymmetric Rectified Electric Fields (AREFs) via numerical solution to the full nonlinear PNP equations [Hashemi Amrei et al. , Phys. Rev. Lett. , 2018, 121 , 185504]. Importantly, the first-order solution is analytic, while the second-order AREF is semi-analytic and obtained by numerically solving a single linear ordinary differential equation, obviating the need for full numerical solutions to the PNP equations. We demonstrate that at sufficiently high frequencies and electrode spacings the semi-analytical AREF accurately captures both the complicated shape and the magnitude of the AREF, even at large applied potentials.more » « less
-
It is well established that application of an oscillatory excitation with zero time-average but temporal asymmetry can yield net drift. To date this temporal symmetry breaking and net drift has been explored primarily in the context of point particles, nonlinear optics, and quantum systems. Here, we present two new experimental systems where the impact of temporally asymmetric force excitations can be readily observed with mechanical motion of macroscopic objects: (1) solid centimeter-scale objects placed on a uniform flat surface made to vibrate laterally, and (2) charged colloidal particles in water placed between parallel electrodes with an applied oscillatory electric potential. In both cases, net motion is observed both experimentally and numerically with nonantiperiodic, two-mode, sinusoids where the frequency modes are the ratio of odd and even numbers (e.g., 2Hz and 3Hz). The observed direction of motion is always the same for the same applied waveform, and is readily reversed by changing the sign of the applied waveform, for example, by swapping which electrode is powered and grounded. We extend these results to other nonlinear mechanical systems, and we discuss the implications for facile control of object motion using tunable periodic driving forces.more » « less
-
Recent experimental studies have utilized AC electric fields and electrochemical reactions in multicomponent electrolyte solutions to control colloidal assembly. However, theoretical investigations have thus far been limited to binary electrolytes and have overlooked the impact of electrochemical reactions. In this study, we address these limitations by analyzing a system with multicomponent electrolytes, while also relaxing the assumption of ideally blocking electrodes to capture the effect of surface electrochemical reactions. Through a regular perturbation analysis in the low-applied-potential regime, we solve the Poisson–Nernst–Planck equations and obtain effective equations for electrical potential and ion concentrations. By employing a combination of numerical and analytical calculations, our analysis reveals a significant finding: electrochemical reactions alone can generate asymmetric rectified electric fields (AREFs), i.e., time-averaged, long-range electric fields, even when the diffusivities of the ionic species are equal. This finding expands our understanding beyond the conventional notion that AREFs arise solely from diffusivity contrast. Furthermore, we demonstrate that AREFs induced by electrochemical reactions can be stronger than those resulting from asymmetric diffusivities. Additionally, we report the emergence of asymmetric rectified concentration fields (ARCFs), i.e., time-averaged, long-range concentration fields, which supports the electrodiffusiophoresis mechanism of colloidal assembly observed in experiments. We also derive analytical expressions for AREFs and ARCFs, emphasizing the role of imbalances in ionic strength and charge density, respectively, as the driving forces behind their formation. The results presented in this article advance the field of colloidal assembly and also have implications for improved understanding of electrolyte transport in electrochemical devices.
-
Contact charge electrophoresis (CCEP) uses steady electric fields to drive the continuous, oscillatory motion of conductive particles and droplets between two or more electrodes. These rapid oscillations can be rectified to direct the motion of objects within microfluidic environments using low-power, dc voltage. Here, we compare high precision experimental measurements of CCEP within a microfluidic system to equally detailed theoretical predictions on the motion of a conductive particle between parallel electrodes. We use a simple, capillary microfluidic platform that combines high-speed imaging with precision electrical measurements to enable the synchronized acquisition of both the particle location and the electric current due to particle motion. The experimental results are compared to those of a theoretical model, which relies on a Stokesian dynamics approach to accurately describe both the electrostatic and hydrodynamic problems governing particle motion. We find remarkable agreement between theory and experiment, suggesting that particle motion can be accurately captured by a combination of classical electrostatics and low-Reynolds number hydrodynamics. Building on this agreement, we offer new insight into the charge transfer process that occurs when the particle nears contact with an electrode surface. In particular, we find that the particle does not make mechanical contact with the electrode but rather that charge transfer occurs at finite surface separations of >0.1 μm by means of an electric discharge through a thin lubricating film. We discuss the implications of these findings on the charging of the particle and its subsequent dynamics.more » « less
-
Interfacial microenvironments critically define reaction pathways for electrocatalytic processes through a combination of electric field gradients and proton activity. Non-aqueous ionic liquid electrolytes have been shown to sustain enhanced interfacial electric field gradients at intermediate ion concentration regimes of around 1 M, creating local environments that promote CO2 electroreduction. Notably, water at low concentrations absorbed by non-aqueous electrolytes is usually assumed to be the proton donor for CO2 reduction. Consumption of protons causes proton donors to become more negative by one unit charge, which significantly modifies the local concentration of charged species and hence should strongly impact local electric fields. Yet, how the coupling between proton donation and changing interfacial electric fields influences electrocatalytic processes in non-aqueous electrolytes remains largely unexplored. In this work, we show that the high activity of 1,3-dialkylimidazolium ionic liquids for CO2 reduction in acetonitrilebased electrolytes stems from the ability to act as cationic proton donors that release neutral conjugate bases. Using in situ electrochemical surface-enhanced Raman spectroscopy, we find that the formation of neutral conjugate bases from imidazolium cations preserves local electric field strengths at electrode-electrolyte interfaces, providing a powerful strategy to maintain an active local microenvironment for CO2 reduction. In contrast, conditions where water behaves as the primary proton donor generates [OH]- anions as negative “co-ions” in the electric double layer, which weakens the interfacial electric field and significantly compromises the steady-state CO2 reduction activity. Our study highlights that electrochemical driving forces are highly sensitive to the charge state of both reactant and product species and highlights the fact that the generation of interfacial co-ions plays a key role in determining electrochemical driving forces.more » « less