Charge injection mediated by inverse micelles in nonpolar solvents: A microscopic model.

HYPOTHESIS: Nonpolar solvents with added charge control agents are widely used in various applications, such as E-paper displays. In spite of previous work, the mechanisms governing charge generation in nonpolar liquids, particularly those induced by electrochemical reactions at the liquid-solid interface, are not completely understood. We hypothesize that a physics-based model, according to the modified Butler-Volmer equation, can be used to quantitatively predict the injection of charges and the corresponding currents, in nonpolar solvents with surfactants. SIMULATION AND EXPERIMENTS: We propose a model to describe the migration and charge generation of inverse micelles. In addition to the mechanisms of electromigration, diffusion and charge generation via disproportionation that were introduced in earlier models, we include charge generation via electron injection at the electrodes using a microscopically justified expression as opposed to the previously used semi-empirical approaches. To validate our model, we compare its results to experimental current measurements in a simplified, effectively 1D, geometry. FINDINGS: We find that the incorporation of both bulk and electrochemical reaction mechanisms in the model can effectively explain the experimental steady-state currents in a wide range of concentrations, voltages (0.5 V-5 V), and cell thicknesses. These numerical results of currents at longer time scales show a steady-state current only when both bulk and electrochemical reactions are taken into account. Moreover, we have observed in our simulation that at low applied voltages, the electric field in the bulk is fully shielded, and the steady-state current in this low-voltage regime is governed by the charge injection at the electrodes. Conversely, when the voltage is high enough and the electric field remains partially unscreened, the bulk disproportionation mechanism dominates the current generation. This also explains why we observe a non-Ohmic behavior where the steady-state currents at high voltages are independent of applied voltage. Hence, by elucidating the physical processes underlying the experimental observations, our model offers a more profound comprehension of charge transport in these systems, which could facilitate advancements in the design of enhanced E-ink displays and smart windows.

The Electrode/Electrolyte Interface Study during the Electrochemical CO2 Reduction in Acidic Electrolytes.

Electrochemical CO2 Reduction (CO2R) in acidic electrolytes has gained significant attention owing to higher carbon efficiency and stability than in alkaline counterparts. However, the proton source and the role of alkali cations for CO2R are still under debate. By using rotating ring disk electrode and surface-enhanced infrared absorption spectroscopy, we find that a neutral/alkaline environment at the interface is necessary for CO2R even in acidic electrolytes. We also confirm that water molecules, rather than protons serve as the proton source for CO2R. Alkali cations in the outer Helmholtz plane activate H2O and promote the desorption of adsorbed carbon monoxide. Additionally, the solvated CO2, or CO2(aq), is the actual reactant for CO2R. This study provides a deeper understanding of the electrode/electrolyte interface during CO2R in acidic electrolytes and sheds light on further performance improvement of this system.

Recent Advances in On-Line Mass Spectrometry Toolbox for Mechanistic Studies of Organic Electrochemical Reactions.

Electrochemical reactions are very complex and involve a variety of physicochemical processes. Accurate and systematic monitoring of intermediate process changes during the reaction is essential for understanding the mechanism of electrochemical reactions and is the basis for rational design of new electrochemical reactions. On-line electrochemical analysis based on mass spectrometry (MS) has become an important tool for studying electrochemical reactions. This technique is based on different ionization and sampling means and realizes on-line analysis of electrochemical reactions by establishing electrochemistry-MS (EC-MS) coupling devices. In particular, it provides key evidence for elucidating the reaction mechanism by capturing and identifying the reactive reaction intermediates. This review will categorize various EC-MS devices and the organic electrochemical reaction systems they study, highlighting the latest research progress in recent years. It will also analyze the properties of various devices and look forward to the future development of EC-MS.

Quasi-Solid-State Na-O2 Battery with Composite Polymer Electrolyte.

Na-O2 batteries have emerged as promising candidates due to their high theoretical energy density (1,601 Wh kg-1), the potential for high energy storage efficiency, and the abundance of sodium in the earth's crust. Considering the safety issue, quasi-solid-state composite polymer electrolytes are among the promising solid-state electrolyte candidates. Their higher mechanical toughness provides superior resistance to dendritic penetration compared with traditional liquid electrolytes. The flexibility of the composite polymer electrolyte matrix allows it to conform to various battery configurations and considerably reduces safety concerns related to the combustion risks associated with conventional liquid electrolytes. In this study, we employed poly(ethylene oxide) (PEO) and sodium bis(trifluoromethanesulfonyl)imide (NaTFSI) as the polymer matrix and sodium ion-conducting agent, respectively. We incorporated nanosized NZSP (25 wt %) to create the composite polymer electrolyte membrane. This CPE design facilitates ion conduction pathways through both sodium salt and NZSP. By utilizing a liquid electrolyte infiltration method, we successfully enhanced its ionic conductivity, achieving an ionic conductivity of 10-4 S cm-1 at room temperature.

Enhanced ammonia oxidation by a photoelectrocatalysis­chlorine system: The role of ClO• and free chlorine.

The decomposition of ammonia-N to environmental-friendly N2 remains a fundamental problem for water treatment. We proposed a way to selectively and efficiently oxidize ammonia to N2 through an integrated photoeletrocatalysis­chlorine reactions (PECCl) system based on a bifunctional TiO2 nanotube photoanode. The ·OH and HClO can be simultaneously generated on the TiO2 nanotube photoanode in this system, which can in situ form ClO· for efficient ammonia removal. Compared with electrochemical­chlorine (EC-Cl), photocatalysis­chlorine (PC-Cl) and photoelectrocatalysis (PEC) systems, the PEC-Cl system exhibited much higher electrocatalytic activity due to the synergetic effect of photoelectrocatalyst and electrocatalyst in bifunctional TiO2 nanotube electrode. The removal efficiency of ammonia-N and total-N reached 100.0 % and 93.3 % at 0.3 V (vs Ag/AgCl) in the PEC-Cl system. Moreover, the system was efficient under various pH conditions. The reactions between ClO-/ClO· and the N-containing intermediates contributed to the high performance of the system, which expanded the reactions from the electrode surface to the electrolyte. Furthermore, radical scavenging and free chlorine determination experiments confirmed that ClO· and free chlorine were the main active species that enabled the ammonia oxidation. This study presents new understanding on the role of active species for ammonia removal in wastewater.

High-Performance and Stable Perovskite X-ray Detection and Imaging Based on a Ti Cathode.

High-energy radiation detectors with a good imaging resolution, fast response, and high sensitivity are desired to operate at a high electric field. However, strong ion migration triggered by electrochemical reactions at the interface between a high-potential electrode and an organic-inorganic hybrid perovskite limits the stability of radiation detectors under a high electric field. Herein, we demonstrate that such ion migration could be effectively suppressed in devices with a Ti cathode, even at a high electric field of 50 V mm-1, through time-of-flight secondary-ion mass spectrometry. X-ray photoelectron spectroscopy illustrates that Ti-N bonds formed at the interface of MAPbBr3 perovskite single crystals/Ti electrode effectively inhibit the electrochemical reaction in organic-inorganic hybrid perovskite devices and ultimately improve the operating stability under a high electric field. The device with a Ti electrode reaches a high sensitivity of 96 ± 1 mC Gyair-1 cm-2 and a low detection limit of 2.8 ± 0.3 nGy s-1 under hard X-ray energy.

Molecular Connectors Boosting the Performance of MoS2 Cathodes in Zinc-Ion Batteries.

Zinc-ion batteries (ZIBs) are promising energy storage systems due to high energy density, low-cost, and abundant availability of zinc as a raw material. However, the greatest challenge in ZIBs research is lack of suitable cathode materials that can reversibly intercalate Zn2+ ions. 2D layered materials, especially MoS2-based, attract tremendous interest due to large surface area and ability to intercalate/deintercalate ions. Unfortunately, pristine MoS2 obtained by traditional protocols such as chemical exfoliation or hydrothermal/solvothermal methods exhibits limited electronic conductivity and poor chemical stability upon charge/discharge cycling. Here, a novel molecular strategy to boost the electrochemical performance of MoS2 cathode materials for aqueous ZIBs is reported. The use of dithiolated conjugated molecular pillars, that is, 4,4'-biphenyldithiols, enables to heal defects and crosslink the MoS2 nanosheets, yielding covalently bridged networks (MoS2-SH2) with improved ionic and electronic conductivity and electrochemical performance. In particular, MoS2-SH2 electrodes display high specific capacity of 271.3 mAh g-1 at 0.1 A g-1, high energy density of 279 Wh kg-1, and high power density of 12.3 kW kg-1. With its outstanding rate capability (capacity of 148.1 mAh g-1 at 10 A g-1) and stability (capacity of 179 mAh g-1 after 1000 cycles), MoS2-SH2 electrodes outperform other MoS2-based electrodes in ZIBs.

Revealing the Subzero-Temperature Electrochemical Kinetics Behaviors in Ni-Rich Cathode.

The sluggish kinetics in Ni-rich cathodes at subzero temperatures causes decreased specific capacity and poor rate capability, resulting in slow and unstable charge storage. So far, the driving force of this phenomenon remains a mystery. Herein, with the help of in-situ X-ray diffraction and time of flight secondary ion mass spectrometry techniques, the continuous accumulation of both the cathode electrolyte interphase (CEI) film formation and the incomplete structure evolution during cycling under subzero temperature are proposed. It is presented that excessively uniform and thick CEI film generated at subzero temperatures would block the diffusion of Li+ -ions, resulting in incomplete phase evolution and clear charge potential delay. The incomplete phase evolution throughout the Li+ -ion intercalation/de-intercalation processes would further cause low depth of discharge and poor electrochemical reversibility with low initial Coulombic efficiency, as well. In addition, the formation of the thick and uniform CEI film would also consume Li+ -ions during the charging process. This discovery highlights the effects of the CEI film formation behavior and incomplete phase evolution in restricting electrochemical kinetics under subzero temperatures, which the authors believe would promote the further application of the Ni-rich cathodes.

Ultrasensitive and Robust CsPbBr3 Single-Crystal X-ray Detectors Based on Interface Engineering.

Halide lead perovskites have shown great development in recent years for ionizing radiation detection. However, the bias-induced interfacial electrochemical reaction between the perovskite and electrode severely deteriorates detector performance. We report that BCP strongly interacts with Al and constructs a stable Al-BCP chelating interface, resulting in the suppression of a detrimental electrochemical reaction. The fabricated Au/Al/BCP/C60/CsPbBr3/Au detector shows a low dark current of 3 nA with a stable baseline at an extremely high bias of 100 V (∼100 V mm-1). The superior high-bias stability enables a high sensitivity of 7.3 × 104 µC Gyair-1 cm-2 at 100 V. Meanwhile, a low detection limit of 15 nGyair s-1 at 40 V is achieved due to the reduced noise. The outstanding performance of our device exceeds that of most advanced detectors based on CsPbBr3 single crystals. Besides, X-ray imaging with 1 mm spatial resolution is well demonstrated at a low dose rate of 200 nGyair s-1. The interfacial chelating strategy overcomes the technical limitation of bias-induced instability of perovskite radiation detectors and can be anticipated to operate under an extremely high electrical field.

Characterization of Information-Transmitting Materials Produced in Ionic Liquid-based Neuromorphic Electrochemical Devices for Physical Reservoir Computing.

Device implementation of reservoir computing, which is expected to enable high-performance data processing in simple neural networks at a low computational cost, is an important technology to accelerate the use of artificial intelligence in the real-world edge computing domain. Here, we propose an ionic liquid-based physical reservoir device (IL-PRD), in which copper cations dissolved in an IL induce diverse electrochemical current responses. The origin of the electrochemical current from the IL-PRD was investigated spectroscopically in detail. After operating the device under various operating conditions, X-ray photoelectron spectroscopy of the IL-PRD revealed that electrochemical reactions involving Cu, Cu2O, Cu(OH)2, CuSx, and H2O occur at the Pt electrode/IL interface. These products are considered information transmission materials in IL-PRD similar to neurotransmitters in biological neurons. By introducing the Faradaic current components due to the electrochemical reactions of these materials into the output signal of IL-PRD, we succeeded in improving the time-series data processing performance of the nonlinear autoregressive moving average task. In addition, the information processing efficiency in machine learning to classify electrocardiogram signal waveforms was successfully improved by using the output current from IL-PRD. Optimizing the electrochemical reaction products of IL-PRD is expected to advance data processing technology in society.

Tuning Electrochemical Stability of 5,10-Ditolylphenazine-Based Antiaromatic Materials for Unipolar Memristor toward Artificial Synapses Application.

Three organic conjugated small molecules, DTA-DTPZ, Cz-DTPZ, and DTA-me-DTPZ comprising an antiaromatic 5,10-ditolylphenazine (DTPZ) core and electron-donating peripheral substituents with high HOMOs (-4.2 to -4.7 eV) and multiple reversible oxidative potentials are reported. The corresponding films sandwiched between two electrodes show unipolar and switchable hysteresis current-voltage (I-V) characteristics upon voltage sweeping, revealing the prominent features of nonvolatile memristor behaviors. The numerical simulation of the I-V curves suggests that the carriers generated by the oxidized molecules lead to the increment of conductance. However, the accumulated carriers tend to deteriorate the device endurance. The electroactive sites are fully blocked in the dimethylated molecule DTA-me-DTPZ, preventing the irreversible electrochemical reaction, thereby boosting the endurance of the memristor device over 300 cycles. Despite the considerable improvement in endurance, the decrement of on/off ratio from 105 to 101 after 250 cycles suggests that the excessive charge carriers (radical cations) remains a problem. Thus, a new strategy of doping an electron-deficient material, CN-T2T, into the unipolar active layer was introduced to further improve the device stability. The device containing DTA-me-DTPZ:CNT2T (1:1) blend as the active layer retained the endurance and on/off ratio (∼104) upon sweeping 300 cycles. The molecular designs and doping strategy demonstrate effective approaches toward more stable metal-free organic conjugated small-molecule memristors.

Electrocatalytic Reactions for Converting CO2 to Value-Added Products: Recent Progress and Emerging Trends.

Carbon dioxide (CO2) emissions are an important environmental issue that causes greenhouse and climate change effects on the earth. Nowadays, CO2 has various conversion methods to be a potential carbon resource, such as photocatalytic, electrocatalytic, and photo-electrocatalytic. CO2 conversion into value-added products has many advantages, including facile control of the reaction rate by adjusting the applied voltage and minimal environmental pollution. The development of efficient electrocatalysts and improving their viability with appropriate reactor designs is essential for the commercialization of this environmentally friendly method. In addition, microbial electrosynthesis which utilizes an electroactive bio-film electrode as a catalyst can be considered as another option to reduce CO2. This review highlights the methods which can contribute to the increase in efficiency of carbon dioxide reduction (CO2R) processes through electrode structure with the introduction of various electrolytes such as ionic liquid, sulfate, and bicarbonate electrolytes, with the control of pH and with the control of the operating pressure and temperature of the electrolyzer. It also presents the research status, a fundamental understanding of carbon dioxide reduction reaction (CO2RR) mechanisms, the development of electrochemical CO2R technologies, and challenges and opportunities for future research.

Theoretical Study on B-doped FeN4 Catalyst for Potential-Dependent Oxygen Reduction Reaction.

Electrochemical reactions mostly take place at a constant potential, but traditional DFT calculations operate at a neutral charge state. In order to really model experimental conditions, we developed a fixed-potential simulation framework via the iterated optimization and self-consistence of the required Fermi level. The B-doped graphene-based FeN4 sites for oxygen reduction reaction were chosen as the model to evaluate the accuracy of the fixed-potential simulation. The results demonstrate that *OH hydrogenation gets facile while O2 adsorption or hydrogenation becomes thermodynamically unfavorable due to the lower d-band center of Fe atoms in the constant potential state than the neutral charge state. The onset potential of ORR over B-doped FeN4 by performing potential-dependent simulations agree well with experimental findings. This work indicates that the fixed-potential simulation can provide a reasonable and accurate description on electrochemical reactions.

Novel electrochemical method to activate biochar derived from spent coffee grounds for enhanced adsorption of lead (Pb).

Biochar (BC) has received much attention as a promising adsorbent that can be exploited to remove heavy metals in domestic and wastewater. The adsorption capacity of BC is, however, relatively low compared to that of conventional adsorbents, and its performance is inversely proportional to its stability. Various chemical and physical methods have been tried to address these limitations, but BC activation still generates too much acidic or alkaline wastewater. Here we propose a novel electrochemical method and compare its lead (Pb) adsorption capacity to that of acid- and alkaline-based approaches. We found that electrochemical activation significantly increased the number of hydroxyl and carboxylic groups on the BC surface, which led to an increase in Pb absorption from 27 % (pristine BC) to 100 % because the oxygenated-functional groups contributed to the adsorption of Pb. Pb capacity was 1.36, 2.64, 3.31, and 5.00 mg g-1, corresponding to pristine, acidic, alkaline, and electrochemical activation, respectively. The Pb absorption capacity of electrochemically activated BC was also higher than that of acid- and alkali-activated BC, which we attribute to the observed increases in oxygen ratio and surface area. Moreover, the adsorption rate of BC after electrochemical activation was 190 times faster and its capacity was 2.4 times higher than that of pristine BC. These findings show that the electrochemical activation of BC results in greater adsorption capacity than conventional methods.

Bipolar Electrospray from Electrodeless Emitters for ESI without Electrochemical Reactions in the Sprayer.

A bipolar ESI source is developed to generate a simultaneous emission of charged liquid jets of opposite polarity from an electrodeless sprayer. The sprayer consists of two emitters, and the electrosprays are initiated by applying a high potential difference (HV) across the counter electrodes facing each emitter. The sprayer and the liquid delivery system are made of all insulators without metal components, thus enabling the total elimination of electrochemical reactions taking place at the liquid-electrode interface in the typical electrosprayer. The bipolar electrospray has been implemented using an online configuration that uses a syringe pump for flow rate regulation and an offline configuration that relies on HV for adjusting the flow rate. The voltage-current and flow rate-current relationships of bipolar electrospray were found to be similar to the standard electrospray. The application of bipolar ESI to the mass spectrometry of protein, peptide, and metallocene without electrochemically induced oxidation/reduction is demonstrated.

Parametric Study and Electrocatalyst of Polymer Electrolyte Membrane (PEM) Electrolysis Performance.

An investigation was conducted to determine the effects of operating parameters for various electrode types on hydrogen gas production through electrolysis, as well as to evaluate the efficiency of the polymer electrolyte membrane (PEM) electrolyzer. Deionized (DI) water was fed to a single-cell PEM electrolyzer with an active area of 36 cm2. Parameters such as power supply (50-500 mA/cm2), feed water flow rate (0.5-5 mL/min), water temperature (25-80 °C), and type of anode electrocatalyst (0.5 mg/cm2 PtC [60%], 1.5 mg/cm2 IrRuOx with 1.5 mg/cm2 PtB, 3.0 mg/cm2 IrRuOx, and 3.0 mg/cm2 PtB) were varied. The effects of these parameter changes were then analyzed in terms of the polarization curve, hydrogen flowrate, power consumption, voltaic efficiency, and energy efficiency. The best electrolysis performance was observed at a DI water feed flowrate of 2 mL/min and a cell temperature of 70 °C, using a membrane electrode assembly that has a 3.0 mg/cm2 IrRuOx catalyst at the anode side. This improved performance of the PEM electrolyzer is due to the reduction in activation as well as ohmic losses. Furthermore, the energy consumption was optimal when the current density was about 200 mA/cm2, with voltaic and energy efficiencies of 85% and 67.5%, respectively. This result indicates low electrical energy consumption, which can lower the operating cost and increase the performance of PEM electrolyzers. Therefore, the optimal operating parameters are crucial to ensure the ideal performance and durability of the PEM electrolyzer as well as lower its operating costs.

Study on electrochemical reduction mechanisms of iron oxides in pipe scale in drinking water distribution system.

Iron release from pipe scale is an important reason for water quality deterioration in drinking water distribution systems (DWDS) globally. Disruption of pipe scale, release and transformation of iron compounds are hot topics in the field of water supply. The aim of this study is to determine whether and how ferric components in pipe scale be reduced under anoxic condition. In this study, new investigation approaches were applied, which include simplifying the complex scale into electrode pairs, developing novel simulating reactors and conducting tailored electrochemical assays. A galvanic cell reactor with anode of metallic iron (Fe0) and various cathode made of certain iron oxide (FeOx) was firstly developed to simulate the complex niche and components of pipe scale. Electrochemical methods were used to study the reduction characteristics of scale. The results proved that reduction of iron oxide scale did occur under anoxic condition. Electromotive forces between various electrodes match the Nernst Equation quite well. As main components in pipe scale, lepidocrocite (γ-FeOOH) was found to be the most reducible iron oxide but at low rate, while goethite (α-FeOOH) has weak reducibility but can be quickly reduced. As a result of electrochemical reactions, goethite in pipe scale was transformed into magnetite (Fe3O4). By these means, electrochemical reaction mechanisms of pipe scale disruption were revealed, which is helpful to restrain pipe corrosion and water deterioration in DWDS.

Ultrasonic-assisted synthesis of porous S-doped carbon nitride ribbons for photocatalytic reduction of CO2.

A series of porous S-doped carbon nitride ribbons (PSCN) were prepared by one-pot hydrothermal and sonochemical synthesis techniques. The morphologies and nanostructures of the catalysts were characterized by SEM, XRD and IR, which confirmed the pristine graphitic structures of carbon nitrides retained in the products. Due to sonication treatment, PSCN has porous structures in the thin ribbon and larger specific surface areas (PSCN 43.5 m2/g, SCN 26.6 m2/g and GCN 6.5 m2/g). XPS and elemental mappings verified that sulfur atoms were successfully introduced into the carbon nitride framework. Diffuse reflectance spectroscopy (DRS) results showed S-doping in the carbon nitride reduced the bandgap energy and enhanced their capability of the utilization of visible light, which contributed to higher photo-generated current. Photoluminescence (PL) analysis indicates the recombination of photogenerated carriers was suppressed in PSCN. Moreover, the photocatalytic performance showed that S-doping and porous and thin ribbon nanostructures may effectively boost the CO2 reduction rate (to as much as 5.8 times of GCN) when illuminated byvisible light (>420 nm) without the need of sacrificial materials. The preliminary mechanisms of the formation of PSCN and its applications in photocatalytic CO2 reduction are proposed. It highlights the potential of the current technique to produce effective, nonmetal-doped carbon nitride photocatalysts.

Confine, Defect, and Interface Manipulation of Fe3 Se4 /3D Graphene Targeting Fast and Stable Potassium-Ion Storage.

The fast electrochemical kinetics behavior and long cycling life have been the goals in developing anode materials for potassium ion batteries (PIBs). On account of high electron conductivity and theoretical capacity, transition metal selenides have been deemed as one of the promising anode materials for PIBs. Herein, a systematic structural manipulation strategy, pertaining to the confine of Fe3 Se4 particles by 3D graphene and the dual phosphorus (P) doping to the Fe3 Se4 /3DG (DP-Fe3 Se4 /3DG), has been proposed to fulfill the efficient potassium-ion (K-ion) evolution kinetics and thus boost the K-ion storage performance. The theoretical calculation results demonstrate that the well-designed dual P doping interface can effectively promote K-ion adsorption behavior and provide a low energy barrier for K-ion diffusion. The insertion-conversion and adsorption mechanism for multi potassium storage behavior in DP-Fe3 Se4 /3DG composite has been also deciphered by combining the in situ/ex situ X-ray diffraction and operando Raman spectra evidences. As expected, the DP-Fe3 Se4 /3DG anode exhibits superior rate capability (120.2 mA h g-1 at 10 A g-1 ) and outstanding cycling performance (157.9 mA h g-1 after 1000 cycles at 5 A g-1 ).

Electrochemical reactions of highly active nitroxyl radicals with thiol compounds.

Nitroxyl radicals are known to electrochemically oxidize thiols as well as alcohols and amines. In this study, a preliminary investigation of the electrochemical reaction of thiols with 9-azabicyclo[3.3.1]nonane N-oxyl (ABNO), 2-azaadamantane N-oxyl (AZADO), and nortropine N-oxyl (NNO), which are highly active due to their bicyclo structures, for use in electrochemical analysis was performed and the results were compared with those for a typical nitroxyl radical compound, 2,2,6,6-tetramethylpiperidine N-oxyl (TEMPO). Mercaptopropane sulfonic acid (MPS) was used as a model compound to investigate the electrochemical response in aqueous solution. In addition, electrochemical detection of glutathione, a biological thiol molecule, was performed.