Aqueous Electrolyte Solutions Research Articles

Fundamentals and Implication of Point of Zero Charge (PZC) Determination for Activated Carbons in Aqueous Electrolytes.

The point of zero charge (PZC) is a crucial parameter for investigating the charge storage mechanisms in energy storage systems at the molecular level. This paper presents findings from three different electrochemical techniques, compared for the first time: cyclic voltammetry (CV), staircase potentio electrochemical impedance spectroscopy (SPEIS), and step potential electrochemical spectroscopy (SPECS), for two activated carbons (ACs) with 0.1molL-1 aqueous solution of LiNO3, Li2SO4, and KI. The charging process of AC operating in aqueous electrolytes appears as a complex phenomenon - all ionic species take an active part in electric double-layer formation and the ion-mixing zone covers a wide potential region. Therefore, the so-called PZC should not be considered as an absolute one-point potential value, but rather as a range of zero charge (RZC). SPECS technique is found to be a universal and fast method for determining RZC, as applied here together with the EQCM. In most cases, the RZC covers a potential range from ≈100 to ≈200mV and the correlation of the range with the carbon microtexture is clear, highlighting the role of the ion-sieving effect. It is postulated that PZC for porous materials in aqueous electrolytic solutions should be considered instead as RZC.

Sorption-desorption of rare earth metal cations by ferromanganese crusts of Govorov’s guyote of the Magellanic Mountains of the Pacific Ocean

The article presents the results of experimental studies on the sorption and desorption of rare earth metal (REM) cations by cobalt-rich ferromanganese crusts (CMC) of Govorov’s guyot. It has been established that the sorption of REM cations occurs on the ore minerals KMK – Fe-vernadite, vernadite, Mn-feroxygite, goethite. The crusts are characterized by a high exchange capacity – 1.78–3.57 mg-eq/g, which increases in a series: (Dy Gd Lu Sm Nd Y, La Eu) Ce. The sorption of REM cations proceeds by an ion exchange equivalent irreversible mechanism. The exchange complex of ore minerals consists of Na+, K+, Ca2+, Mg2+ cations, which contribute 97‒98% to their total capacity. The crusts are characterized by the group sorption of REM cations from multicomponent aqueous solutions of metal salts. The selectivity of ore manganese and ferruginous minerals of crusts to REM cations is significantly higher than to the main cations of ocean water. From experimental data on the desorption of sorbed REM cations with NaCl solution, their irreversible absorption by ore minerals follows, and the strengthening of the chemical bond of sorbed REM cations with the main structural elements of these minerals over time. An important property of ore minerals, primarily manganese minerals, is their chemical and structural stability in aqueous solutions of electrolytes. This suggests the repeated use of ferromanganese crusts as sorbents of REM cations.

Modified Debye-Hückel-Onsager theory for electrical conductivity in aqueous electrolyte solutions: Account of ionic charge nonlocality.

This paper presents a mean field theory of electrolyte solutions, extending the classical Debye-Hückel-Onsager theory to provide a detailed description of the electrical conductivity in strong electrolyte solutions. The theory systematically incorporates the effects of ion specificity, such as steric interactions, hydration of ions, and their spatial charge distributions, into the mean-field framework. This allows for the calculation of ion mobility and electrical conductivity, while accounting for relaxation and hydrodynamic phenomena. At low concentrations, the model reproduces the well-known Kohlrausch's limiting law. Using the exponential (Slater-type) charge distribution function for solvated ions, we demonstrate that experimental data on the electrical conductivity of aqueous 1:1, 2:1, and 3:1 electrolyte solutions can be approximated over a broad concentration range by adjusting a single free parameter representing the spatial scale of the nonlocal ion charge distribution. Using the fitted value of this parameter at 298.15K, we obtain good agreement with the available experimental data when calculating electrical conductivity across different temperatures. We also analyze the effects of temperature and electrolyte concentration on the relaxation and electrophoretic contributions to total electrical conductivity, explaining the underlying physical mechanisms responsible for the observed behavior.

Ion-Specific Surface Tension of Aqueous Electrolyte Solutions: Analytical Insights from a Restricted Primitive Model.

The ion-specific surface tension of aqueous electrolyte solutions is of fundamental importance in physical chemistry, solution chemistry, electrochemistry, and biochemistry, yet it remains a challenge to be qualitatively predicted. In this work, an analytical theory of ion-specific surface tension is developed. By modeling the solution to a restricted primitive model (RPM), the surface tension increment of the electrolyte solution reduces to the surface tension of the RPM, which is further determined analytically by using the integral equation theory and the morphological thermodynamics theory. According to our formula, the surface tension increment of the electrolyte solution consists of a dominant and positive hard sphere contribution, which depends on the salt concentration, and a secondary electrostatic contribution, which depends on the inverse Debye length and the salt concentration. Our theory is applied to 1:1, 2:2, 1:2, 2:1, 3:1, and 3:2 electrolyte solutions with typical salt concentrations up to several mol/L and compared with experimental data. Without introducing any adjustable parameters, our theory leads to a good prediction of the surface tension increment of more than 50 kinds of aqueous solutions. Such a good agreement demonstrates the great potential of our theory for a fundamental understanding of specific ion effects in a variety of electrolyte solutions.

Derivation of the General Equation of State for a Doped Semiconductor. The Equation is Solved Concerning the Electron Concentration in the Conduction Band for Different Concentrations and Properties of Doping Substances

The paper examines the state of a system consisting of a crystalline semiconductor doped with donor and acceptor impurities. The General Equation of State of the system is derived. Methods are proposed to solve the general equation for the concentration of electrons or holes in a semiconductor. The identity of the General Equations of State of semiconductors and aqueous solutions of electrolytes is discussed. An assumption is made about the practical application of the found relationships.

Work function and electrochemistry of ZnO (wurtzite) single crystals (F-1:L07)

The work functions of two polar surfaces of ZnO (wurtzite), i.e., O-(000–1) and Zn-(0001) are determined by photoelectron spectroscopy in ultrahigh vacuum or in the presence of oxygen or water vapor at near-ambient pressures, and by Kelvin probe in air. The work functions were also determined by Mott-Schottky analysis in aqueous or aprotic (acetonitrile) electrolyte solutions. The values obtained by different techniques and in different environments are much less scattered compared to the fluctuations, reported for TiO2 (anatase or rutile). The Zn-(0001) surface has a smaller work function for all the solid/vacuum and solid/gas interfaces, and also in the acetonitrile electrolyte solution. Solely at the aqueous electrochemical interface, the difference is small or even opposite. We propose a hypothesis that the dissociative water adsorption on the O-(000–1) is responsible for this irregular downshift of the work function in aqueous medium.

Evaluation of sensitivity in a vertically misaligned double-gate electrolyte-insulator-semiconductor extended source tunnel FET as pH sensor

In this research, the primary objective is to investigate the impact of vertical gate misalignment on the source and drain regions of 30 nm. The double-gate Electrolyte-Insulated-Semiconductor extended-source Tunnel Field-Effect Transistor (ES-VTFET) is proposed for its potential application as a pH sensor. The gate electrode cannot be perfectly aligned with the channel due to fabrication tolerances, particularly in very short-channel structures. This study aims to introduce a vertical electrolyte Bio-TFET-based pH sensor capable of detecting pH changes in aqueous (electrolyte) solutions. The effect of variation in pH values on the electrical characteristics of the device such as drain current (IDS), transconductance (gm), voltage sensitivity (SV) and current sensitivity (SI) have been examined. It has been assumed that the electrolyte section is an intrinsic semiconductor material where electrons and holes signify mobile ions in aqueous solutions. The electrolyte region has an electrolyte dielectric constant of 78, an energy bandgap of 1.12 eV, and an electron affinity of 1.32 eV. Finally, the gate misalignment aspect of the proposed bio TFET-based pH sensor is emphasized by comparing sensitivity parameters. Hence, the proposed pH sensor can be used as a potential candidate for the futuristic application of biosensors.

Synergistic advancements in battery-grade energy storage: Nb2C/MoTe2(PANI) hybrid electrode material as a enhanced electrocatalyst for hydrogen reduction reaction

The inherent stratified arrangement, narrow energy band gap, and similar electrical conductivity of two-dimensional (2D) molybdenum ditelluride (MoTe2) have attracted considerable interest for their use in supercapacitors. Integrating Niobium Carbide (Nb2C) into the MXene framework significantly improves self-aggregation and electrochemical activity. The current work, Nb2C/MoTe2 was synthesized via a cost-effective and simple hydrothermal technique. However, the Nb2C/MoTe2 nanocomposite shows pronounced self-stacking problems during electrode fabrication, which can significantly restrict the capacity for storing charge. PANI was incorporated as a dopant to address these challenges and enhance electrochemical activity, such as Nb2C/MoTe2(PANI). The performance of supercapacitors was assessed by electrochemical measurement in an aqueous electrolytic solution with a concentration of 2 M potassium hydroxide (KOH). Based on the GCD profile, the Nb2C/MoTe2(PANI) material demonstrates a notable specific capacity (Qs) of 270 C/g, energy density of 72.2 Wh/kg, and power density of 935 W/kg at a current density of 2 A g-1. In contrast, the composite material demonstrates a specific capacity of 185 C/g, as proven by CV conducted at 5 mV/s. In addition, the nanohybrid has a high level of capacitance retention of 87.6 % after undergoing 8500 consecutive cycles. The exceptional efficiency of supercapacitor applications can be ascribed to the enhanced mechanical flexibility, active cooperation, and synergistic impacts of Nb2C/MoTe2 and PANI. The Nb2C/MoTe2(PANI) nanocomposite possesses significant potential for eco-friendly energy generation and allows for a simple single-step fabrication procedure. Consequently, it can serve as an electrode for highly efficient supercapacitors.

The influence of salt concentration on the dissolution of microbubbles in bulk aqueous electrolyte solutions.

We study microbubbles (MBs) in aqueous electrolyte solutions and show that increasing the salt concentration slows down the kinetics of MB dissolution. We modified the Epstein-Plesset theory and experimented with NaCl aqueous solutions to estimate the MB effective surface charge and to compare it with predictions from the modified Poisson-Boltzmann theory. Our results reveal a mechanism responsible for the change in the dissolution of MBs in aqueous electrolyte solutions, with implications for emerging fields ranging from physics of solutions to soft and biological matter.

Effect of Aqueous Electrolyte Composition on Efficiency of Electrochemical Post-Processing of Additive Manufacturing Products from Ti-6Al-4V Alloy Obtained by Selective Electron Beam Melting

The influence of the anionic composition of an aqueous electrolyte on the efficiency of the electrochemical leveling of the initial microgeometry of samples obtained by the selective electron beam melting (SEBM) at the following mode parameters was studied: current density – 20 A/cm2, initial interelectrode gap – 0.3 mm, average speed of electrolyte pumping – 12 m/c. Aqueous solutions of sodium chloride, nitrate, perchlorate and bisalt electrolytes based on them were studied. It was that aqueous solutions of sodium perchlorate have the best microleveling properties among the studied working media, which provides the ability to reduce the parameters Ra and Rz from values of 35 and 180 μm, respectively, to values of 3.2 and 20 μm during electrolysis of 30 s in a direct-flow electrolyzer. It was established that the microgeometry leveling corresponds to the model of the secondary distribution of dissolution rates; two main factors were identified that significantly influenced on the result: polarization of the electrodes and a decrease in the oxidation state of metal ions passing into the solution during electrochemical machining in the vicinity of the depression in relation to the protrusion due to changes in the local conditions of electrolysis. Microetching along grain boundaries in the studied electrolytes was not detected at the accepted parameters of the electrolysis mode.

PEDOT:PSS Wire: A Two-Terminal Synaptic Device for Operation in Electrolyte and Saline Solutions.

Synaptic devices, which are designed to emulate the synaptic functions of neurons, have recently gained attention as key elements in the development of neuromorphic hardware. To date, most synaptic devices utilizing conductive polymer materials, particularly poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) (PEDOT:PSS), have been designed as three-terminal devices. Nevertheless, a recent study revealed that a single PEDOT:PSS wire can function as a two-terminal synaptic device through additional polymerization, which creates asymmetry in the wire diameter between the anode and cathode. Owing to its high biocompatibility, PEDOT is considered a promising candidate for use in clinical information-processing devices. However, previous studies examined the synaptic function of PEDOT:PSS only in PSS solutions. Therefore, the performance of PEDOT:PSS wires in other solutions, such as physiological saline solutions, remains unknown. Herein, we investigated the effects of operating environmental conditions (including phosphate-buffered saline (PBS)) on the synaptic functions of the asymmetric PEDOT:PSS wire. Our results indicate that the synaptic conductance change in the PEDOT:PSS wire occurred in all investigated aqueous electrolyte solutions. Moreover, we revealed the relationship between the synaptic conductance change behavior and the molecular properties of the electrolyte ions. Furthermore, the waveform of the conductance change can be controlled by adjusting the conditions for wire asymmetrization. These results demonstrate that the PEDOT:PSS wire exhibits a synaptic conductance change, yielding a waveform suitable for machine learning, even under wet conditions (i.e., in any electrolyte solution, including PBS). Therefore, PEDOT:PSS wire is a promising material for two-terminal synaptic devices applicable in clinical studies.

Structural Study of Aqueous Electrolyte Solution by MeV Liquid Electron Scattering.

The impact of ions on water has long been a subject of great interest, as it is closely tied to the hydration structure, dynamics, and properties of electrolyte solutions. Over centuries of investigation, the influence of ions on water's structure remains highly debated. Prevailing techniques, such as neutron and X-ray scattering, primarily focus on the microscopic structure of salt solutions at very high concentrations, mostly above 1 mol/L. In this study, we measured the structure of aqueous potassium iodide (KI) and potassium chloride (KCl) solutions using MeV liquid electron scattering (MeV-LES) across a concentration range of 0.10 to 0.75 mol/L. The obtained results provide detailed insights into the variations in ion-oxygen and oxygen-oxygen correlations as a function of concentration. The observed structural differences between KI and KCl solutions are in line with the structure maker/breaker theory, which suggests that iodide ions exert a more pronounced effect than chloride ions on disrupting the water shell. This work demonstrates the potency of MeV-LES for investigating the atomic structure in liquids, augmenting the modern analytical toolbox.

X-ray Induced Cycling of Rare-Earth Elements between Bulk and Interfacial Liquid.

Reversible cycling of rare-earth elements between an aqueous electrolyte solution and its free surface is achieved by X-ray exposure. This exposure alters the competitive equilibrium between lanthanide ions bound to a chelating ligand, diethylenetriamine pentaacetic acid (DTPA), in the bulk solution and to insoluble monolayers of extractant di-hexadecyl phosphoric acid (DHDP) at its surface. Evidence for the exposure-induced temporal variations in the lanthanide surface density is provided by X-ray fluorescence near total reflection measurements. Comparison of results when X-rays are confined to the aqueous surface region to results when X-rays transmit into the bulk solution suggests the importance of aqueous radiolysis in the adsorption cycle. Amine binding sites in DTPA are identified as a likely target of radiolysis products. The molecules DTPA and DHDP are like those used in the separation of lanthanides from ores and in the reprocessing of nuclear fuel. These results suggest that an external source of X-rays can be used to drive rare-earth element separations. More generally, use of X-rays to controllably dose a liquid interface with lanthanides could trigger a range of interfacial processes, including enhanced metal ion extraction, catalysis, and materials synthesis.

Fabrication of NiO/TiO2/rGO nanocomposites as a quasi-solid-state asymmetric supercapacitor: Paving the way for PhotoSupercapacitor application

In this present communication, a novel ternary nanocomposite, NiO/TiO2/rGO (NTG), was synthesised via a simple hydrothermal technique for photosupercapacitor application. The XRD pattern confirmed the crystalline nature and phase structure of the as-synthesised material. FE-SEM and HR-TEM analyses demonstrated the embellishment of NiO/TiO2 nanoparticles on the rGO sheets, which facilitates more voids and shorter diffusion paths. The electrochemical investigation of the prepared samples was assessed using 1 M Na2SO4 and Na2CO3 aqueous electrolyte solutions. Among the synthesised samples, NTG-2 carried out under 1 M Na2SO4 electrolyte exhibited a maximum specific capacitance of 1285 Fg-1 at 1 Ag-1, maintaining a capacitance retention of 94 % after 5000 cycles. The NTG-2 electrode was additionally utilised in the construction of an asymmetric supercapacitor that has an impressive specific capacitance of 478 Fg-1 at 1 Ag-1. This displays an intriguing performance in terms of energy and power density of 42.2 Wh Kg−1 at 0.5 kW kg−1. In PSC, the as-fabricated TiO2/N719/I−/I3−/Pt@NTG-2//AC architecture possessed a specific capacitance of 567.5 Fg-1 at 1 Ag-1, with an energy density of 50.4 Wh Kg−1 and a power density of 0.4 kW kg−1. As a result, it has been concluded that the novel NTG-2 device opens new opportunities to develop new architectures for efficient energy storage applications.

Simulating the Competitive Ion Pairing of Hydrated Electrons with Chaotropic Cations.

Experiments show that the absorption spectrum of the hydrated electron (ehyd-) blue-shifts in electrolyte solutions compared with what is seen in pure water. This shift has been assigned to the ehyd-'s competitive ion-pairing interactions with the salt cation relative to the salt anion based on the ions' positions on the Hofmeister series. Remarkably, little work has been done investigating the ehyd-'s behavior when the salts have chaotropic cations, which should greatly change the ion-pairing interactions given that the ehyd- is a champion chaotrope. In this work, we remedy this by using mixed quantum/classical simulations to analyze the behavior of two different models of the ehyd- in aqueous RbF and RbI electrolyte solutions as a function of salt concentration. We find that the magnitude of the salt-induced spectral blue-shift is determined by a combination of the number of chaotropic Rb+ cations near the ehyd- and the number of salt anions near those cations so that the spectrum of the ehyd- directly reflects its local environment. We also find that the use of a soft-cavity ehyd- model predicts stronger competitive interactions with Rb+ relative to I- than a more traditional hard cavity model, leading to different predicted spectral shifts that should provide a way to distinguish between the two models experimentally. Our simulations predict that at the same concentration, salts with chaotropic cations should produce larger spectral blue-shifts than salts with kosmotropic cations. We also found that at high salt concentrations with chaotropic cations, the predicted blue-shift is greater when the salt anion is kosmotropic instead of chaotropic. Our goal is for this work to inspire experimentalists to make such measurements, which will help provide a spectroscopic means to distinguish between simulations models that predict different hydration structures for the ehyd-.

A flexible solid-state asymmetric supercapacitor device comprising cobalt hydroxide and biomass-derived porous carbon.

Development in the field of alternative and renewable energy sources is becoming necessary considering the current energy demands of the growing technologies. The main challenge associated with the produced energy is to store it for future use, such that it can be used when needed. Supercapacitors are among the electrochemical energy storage systems that provides higher power density, faster charging-discharging, high specific capacitance (C S), and long cycling life. Herein, the fabrication of a flexible solid-state asymmetric supercapacitor (ASC) device is reported, where Co(OH)2 hollow spheres and biomass-derived porous carbon (PC) are the cathode and anode, respectively. Co(OH)2 is a highly redox active material, whereas PC is an electric double-layer capacitive (EDLC) material. In this device, aqueous KOH solution (electrolyte) encapsulated in PVA gel (separator) was used to bind the electrodes. This Co(OH)2//PC ASC device exhibited a high C S of 260 F g-1 (at 2 A g-1). It retained ∼91% of the initial C S value (at 6 A g-1) till ∼5000 cycles. Electrochemical impedance spectroscopy (EIS) study confirmed low internal resistance (0.95 Ω) and charge transfer resistance (1.41 Ω) values of Co(OH)2//PC. These results indicate that the high electron transfer process in the electrode-electrolyte interface during the electrochemical reaction, which is responsible for the excellent performance of this ASC device. The high-performance Co(OH)2//PC ASC device exhibited an energy density of 76.7 W h kg-1 at a power density of 1416.9 W kg-1. To demonstrate its practical use, LED lights were illuminated using this Co(OH)2//PC ASC device.

New Mn Electrochemistry for Rechargeable Aqueous Batteries: Promising Directions Based on Preliminary Results

Aqueous batteries with metal anodes exhibit robust anodic capacities, but their energy densities are low because of the limited potential stabilities of aqueous electrolyte solutions. Current metal options, such as Zn and Al, pose a dilemma: Zn lacks a sufficiently low redox potential, whereas Al tends to be strongly oxidized in aqueous environments. Our investigation introduces a novel rechargeable aqueous battery system based on Mn as the anode. We examine the effects of anions, electrolyte concentration, and diverse cathode chemistries. Notably, the ClO4‐based electrolyte solution exhibits improved deposition and dissolution efficiencies. Although stainless steel (SS 316 L) and Ni are stable current collectors for cathodes, they display limitations as anodes. However, using Ti as the anode resulted in increased Mn deposition and dissolution efficiencies. Moreover, we evaluate this system using various cathode materials, including Mn‐intercalation‐based inorganic (Ag0.33V2O5) and organic (perylenetetracarboxylic dianhydride) cathodes and an anion‐intercalation‐chemistry (coronene)‐based cathode. These configurations yield markedly higher output potentials compared to those of Zn metal batteries, highlighting the potential for an augmented energy density when using an Mn anode. This study outlines a systematic approach for use in optimizing metal anodes in Mn metal batteries, unlocking novel prospects for Mn‐based batteries with diverse cathode chemistries.

A3B Zn(II)-Porphyrin-Coated Carbon Electrodes Obtained Using Different Procedures and Tested for Water Electrolysis

In the context of water electrolysis being highlighted as a promising technology for the large-scale sustainable production of hydrogen, the water-splitting electrocatalytic properties of an asymmetrically functionalized A3B zinc metalated porphyrin, namely, Zn(II) 5-(4-pyridyl)-10,15,20-tris(4-phenoxyphenyl)-porphyrin, were evaluated in a wide pH range. Two different electrode manufacturing procedures were employed to outline the porphyrin’s applicative potential for the O2 and H2 evolution reactions (OER and HER). The electrode, manufactured by coating the catalyst on a graphite support from a dimethylsulfoxide solution, displayed electrocatalytic activity for the OER in an acidic electrolyte. An overpotential value of 0.44 V (at i = 10 mA/cm2) and a Tafel slope of 0.135 V/dec were obtained. The modified electrode that resulted from applying a Zn(II)-porphyrin-containing catalyst ink onto the same substrate type was identified as a bifunctional water-splitting catalyst in a neutral medium. OER and HER overpotentials of 0.78 and 1.02 V and Tafel slopes of 0.39 and 0.249 V/dec were determined. This is the first Zn(II)-porphyrin to be reported as a heterogenous bifunctional water-splitting electrocatalyst in neutral aqueous electrolyte solution and is one of very few porphyrins behaving as such. The TEM analysis of the porphyrin’s self-assembly behavior revealed a wide variety of architectures.

Understanding the Electric Double Layer at the Electrode-Electrolyte Interface: Part I - No Ion Specific Adsorption.

In this work, we present a mean-field model that takes into account the key components of electrical double layer theory at the interface between an electrode and an electrolyte solution. The model considers short-range specific interactions between different species, including electrode-ion repulsion, the hydration of ions, dielectric saturation of solvent (water), and excluded volume (steric) interactions between species. By solving a modified Poisson-Boltzmann equation, which is derived from the grand thermodynamic potential of an inhomogeneous electrolyte solution, and using the appropriate results of quantum chemistry calculations on the hydration of ions, we can accurately approximate the differential capacitance profiles of aqueous electrolyte solutions at the boundary with a silver electrode. The specific interactions between the ions and the electrodes in the systems under consideration (aqueous solutions of NaClO4 and KPF6) are assumed to be significantly weaker than their Coulomb interactions. A novel aspect of our research is the investigation of the impact of short-range ion-water interactions on the differential capacitance, which provides new insights into the behavior of the electrical double layer. This model has the potential to be useful for electrochemical engineers working on the development of supercapacitors and related electrochemical energy storage devices. It serves as a basis for future modeling of electrolyte systems on real electrodes, especially in scenarios where chemical ion-electrode interactions are significant.

Peculiar photoelectrochemical activity of zinc oxide and tin dioxide

Zinc oxide thin films made by pulsed reactive magnetron sputtering combined with RF ECWR plasma on FTO or ITO substrates exhibit high photoelectrochemical activity for water splitting under UV light, but are unstable against photocorrosion. It can be suppressed by a protective layer of SnO2 made by atomic layer deposition. The SnO2 layer is quasi-amorphous in the as-received state, but the thermal treatment causes partial crystallization to cassiterite, without significant change of the optical band gap. Ferrocene in acetonitrile electrolyte solution is a useful redox probe for the blocking-quality tests of thin films of n-semiconductors. Both ZnO and SnO2 are sensitive to irreversible electrochemical doping at potentials negative to the flatband potential. The flipping of electrochemical work functions of the Zn-terminated (0001) and O-terminated (000–1) faces of ZnO (wurtzite) takes place in acetonitrile vs. aqueous electrolyte solutions. The potentials for photocurrent onset are near the flatband potentials in an aqueous electrolyte solution for both ZnO and SnO2.