اشترك بالحزمة الذهبية واحصل على وصول غير محدود شمرا أكاديميا
تسجيل مستخدم جديدTheory of linear sweep voltammetry with diffuse charge: unsupported electrolytes, thin films, and leaky membranes
143
0
0.0
(
0
)
اسأل ChatGPT حول البحث
ﻻ يوجد ملخص باللغة العربية
Linear sweep and cyclic voltammetry techniques are important tools for electrochemists and have a variety of applications in engineering. Voltammetry has classically been treated with the Randles-Sevcik equation, which assumes an electroneutral supported electrolyte. In this paper, we provide a comprehensive mathematical theory of voltammetry in electrochemical cells with unsupported electrolytes and for other situations where diffuse charge effects play a role, and present analytical and simulated solutions of the time-dependent Poisson-Nernst-Planck (PNP) equations with generalized Frumkin-Butler-Volmer (FBV) boundary conditions for a 1:1 electrolyte and a simple reaction. Using these solutions, we construct theoretical and simulated currentvoltage curves for liquid and solid thin films, membranes with fixed background charge, and cells with blocking electrodes. The full range of dimensionless parameters is considered, including the dimensionless Debye screening length (scaled to the electrode separation), Damkohler number (ratio of characteristic diffusion and reaction times) and dimensionless sweep rate (scaled to the thermal voltage per diffusion time). The analysis focuses on the coupling of Faradaic reactions and diffuse charge dynamics, although capacitive charging of the electrical double layers (EDL) is also studied, for early time transients at reactive electrodes and for non-reactive blocking electrodes. Our work highlights cases where diffuse charge effects are important in the context of voltammetry, and illustrates which regimes can be approximated using simple analytical expressions and which require more careful consideration.
قيم البحث
اقرأ أيضاً
We present a new computational approach to simulate linear sweep and cyclic voltammetry experiments that does not require a discretized grid in space to quantify diffusion. By using a Greens function solution coupled to a standard implicit ordinary d
ifferential equation solver, we are able to simulate current and redox species concentrations using only a small grid in time. As a result, where benchmarking is possible, we find that the current method is faster (and quantitatively identical) to established techniques. The present algorithm should help open the door to studying adsorption effects in inner sphere electrochemistry.
Zinc oxide (ZnO) epitaxial thin films grown on c-sapphire substrates by pulsed laser deposition were investigated using angle and polarization-resolved photoluminescence spectroscopy. Side-emission spectra differed significantly from surface-emission
spectra in exhibiting dominant, narrow, polarization-resolved peaks. These spectral features were attributed to leaky substrate modes in the layers. Observations were first verified using transmission calculations with non-adjustable parameters, which took into account the dispersion, the anisotropy of the ZnO refractive index and the dependence on film thickness. Results were consistent with Fabry-Perot-like interference being the origin of the distinctive ZnO luminescence observed at grazing incidence angles. A second analysis, based on the source terms method, was used in order to retrieve the bulk emission properties, including the wavelength-dependent quantum yield and the emission anisotropy. While ZnO thin films were considered here, this analysis method can be extended to any luminescent thin film of similar geometry, demonstrating the potential of leaky mode analysis for probing passive and active material properties.
This paper presents a combined theoretical and experimental investigation of aqueous near-neutral electrolytes based on chloride salts for rechargeable zinc-air batteries (ZABs). The resilience of near-neutral chloride electrolytes in air could exten
d ZAB lifetime, but theory-based simulations predict that such electrolytes are vulnerable to other challenges including pH instability and the unwanted precipitation of mixed zinc hydroxide chloride products. In this work, we combine theory-based simulations with experimental methods such as full cell cycling, operando pH measurements, ex-situ XRD, SEM, and EDS characterization to investigate the performance of ZABs with aqueous chloride electrolytes. The experimental characterization of near-neutral ZAB cells observes the predicted pH instability and confirms the composition of the final discharge products. Steps to promote greater pH stability and control the precipitation of discharge products are proposed.
The performance of gold nanoparticles (NPs) in applications depends critically on the structure of the NP-solvent interface, at which the electrostatic surface polarization is one of the key characteristics that affects hydration, ionic adsorption, a
nd electrochemical reactions. Here, we demonstrate significant effects of explicit metal polarizability on the solvation and electrostatic properties of bare gold NPs in aqueous electrolyte solutions of sodium salts of various anions (Cl$^-$, BF$_4$$^-$, PF$_6$$^-$, Nip$^-$(nitrophenolate), and 3- and 4-valent hexacyanoferrate (HCF)), using classical molecular dynamics simulations with a polarizable core-shell model of the gold atoms. We find considerable spatial heterogeneity of the polarization and electrostatic potentials on the NP surface, mediated by a highly facet-dependent structuring of the interfacial water molecules. Moreover, ion-specific, facet-dependent ion adsorption leads to large alterations of the interfacial polarization. Compared to non-polarizable NPs, polarizability modifies water local dipole densities only slightly, but has substantial effects on the electrostatic surface potentials, and leads to significant lateral redistributions of ions on the NP surface. Besides, interfacial polarization effects on the individual monovalent ions cancel out in the far field, and effective Debye-Huckel surface potentials remain essentially unaffected, as anticipated from continuum `image-charge concepts. Hence, the explicit charge response of metal NPs is crucial for the accurate description and interpretation of interfacial electrostatics (as, e.g., for charge transfer and interface polarization in catalysis and electrochemistry).
The increasing availability of a variety of two-dimensional materials has generated enormous growth in the field of nanoengineering and nanomechanics. Recent developments in thin film synthesis have enabled the fabrication of freestanding functional
oxide membranes that can be readily incorporated in nanomechanical devices. While many oxides are extremely brittle in bulk, recent studies have shown that, in thin membrane form, they can be much more robust to fracture as compared to their bulk counterparts. Here, we investigate the ultimate tensile strength of SrTiO$_3$ membranes by probing freestanding SrTiO$_3$ drumheads using an atomic force microscope. We demonstrate that SrTiO$_3$ membranes can withstand an elastic deformation with an average strain of ~6% in the sub-20 nm thickness regime, which is more than an order of magnitude beyond the bulk limit. We also show that these membranes are highly resilient upon a high cycle fatigue test, surviving up to a billion cycles of force modulation at 85% of their fracture strain, demonstrating their high potential for use in nanomechanical applications.
سجل دخول لتتمكن من نشر تعليقات
التعليقات
جاري جلب التعليقات
سجل دخول لتتمكن من متابعة معايير البحث التي قمت باختيارها
