Anion-Binding-Induced Electrochemical Signal Transduction in Ferrocenylimidazolium: Combined Electrochemical Experimental and Theoretical Investigation.

Five ferrocene alkymethylimidazolium cations 1a⁻1d and 2 with different alkyl spacer lengths were reinvestigated using voltammetry and density functional theory (DFT) calculations. The voltammetric responses of ligand 2 toward various anions are described in detail. An interesting and unprecedented finding from both experimental and theoretical studies is that coupled electron and intramolecular anion (F-) transfer may be present in these molecules. In addition, it was also observed that, in these studied molecules, the electrostatic attraction interaction toward F- would effectively vanish beyond 1 nm, which was previously reported only for cations.

Development of the Fray-Farthing-Chen Cambridge Process: Towards the Sustainable Production of Titanium and Its Alloys.

The Kroll process has been employed for titanium extraction since the 1950s. It is a labour and energy intensive multi-step semi-batch process. The post-extraction processes for making the raw titanium into alloys and products are also excessive, including multiple remelting steps. Invented in the late 1990s, the Fray-Farthing-Chen (FFC) Cambridge process extracts titanium from solid oxides at lower energy consumption via electrochemical reduction in molten salts. Its ability to produce alloys and powders, while retaining the cathode shape also promises energy and material efficient manufacturing. Focusing on titanium and its alloys, this article reviews the recent development of the FFC-Cambridge process in two aspects, (1) resource and process sustainability and (2) advanced post-extraction processing.

Magnesia-stabilised zirconia solid electrolyte assisted electrochemical investigation of iron ions in a SiO2-CaO-MgO-Al2O3 molten slag at 1723 K.

Production of metallic iron through molten oxide electrolysis using inert electrodes is an alternative route for fast ironmaking without CO2 emissions. The fact that many inorganic oxides melt at ultrahigh temperatures (>1500 K) challenges conventional electro-analytical techniques used in aqueous, organic and molten salt electrolytes. However, in order to design a feasible and effective electrolytic process, it is necessary to best understand the electrochemical properties of iron ions in molten oxide electrolytes. In this work, a magnesia-stabilised zirconia (MSZ) tube with a closed end was used to construct an integrated three-electrode cell with a "MSZ|Pt|O2 (air)" assembly functioning as the solid electrolyte, the reference electrode and also the counter electrode. Electrochemical reduction of iron ions was systematically investigated on an iridium (Ir) wire working electrode in a SiO2-CaO-MgO-Al2O3 molten slag at 1723 K by cyclic voltammetry (CV), square wave voltammetry (SWV), chronopotentiometry (CP) and potentiostatic electrolysis (PE). The results show that the electroreduction of the Fe2+ ion to Fe on the Ir electrode in the molten slag follows a single two-electron transfer step, and the rate of the process is diffusion controlled. The peak current on the obtained CVs is proportional to the concentration of the Fe2+ ion in the molten slag and the square root of scan rate. The diffusion coefficient of Fe2+ ions in the molten slag containing 5 wt% FeO at 1723 K was derived to be (3.43 ± 0.06) × 10-6 cm2 s-1 from CP analysis. However, a couple of subsequent processes, i.e. alloy formation on the Ir electrode surface and interdiffusion, were found to affect the kinetics of iron deposition. An ECC mechanism is proposed to account for the CV observations. The findings from this work confirm that zirconia-based solid electrolytes can play an important role in electrochemical fundamental research in high temperature molten slag electrolytes.

Correction: Preparation of Mo nanopowders through electroreduction of solid MoS2 in molten KCl-NaCl.

Correction for 'Preparation of Mo nanopowders through electroreduction of solid MoS2 in molten KCl-NaCl' by Haiping Gao et al., Phys. Chem. Chem. Phys., 2014, 16, 19514-19521.

High energy supercapattery with an ionic liquid solution of LiClO4.

A supercapattery combining an ideally polarized capacitor-like electrode and a battery-like electrode is demonstrated theoretically and practically using an ionic liquid electrolyte containing 1-butyl-1-methylpyrrolidinium tri(pentafluoroethyl)trifluorophosphate (BMPyrrFAP), gamma-butyrolactone (γ-GBL) and LiClO4. The electrochemical deposition and dissolution of lithium metal on a platinum and glass carbon electrode were investigated in this ionic liquid solution. The CVs showed that the fresh electrochemically deposited lithium metal was stable in the electrolyte, which encouraged the investigation of this ionic liquid solution in a supercapattery with a lithium battery negative electrode. The active material counted specific energy of the supercapattery based on a lithium negative electrode and an activated carbon (Act-C) positive electrode could reach 230 W h kg(-1) under a galvanostatic charge-discharge current density of 1 mA cm(-2). The positive electrode material (Act-C) was also investigated by CV, AC impedance, SEM and BET. The non-uniform particle size and micropores dominated porous structure of the Act-C enabled its electric double layer capacitor (EDLC) behavior in the ionic liquid solution. The measured specific capacitance of the Act-C in this ionic liquid solution is higher than the same Act-C in aqueous solution, which indicates the Act-C can also perform well in the ionic liquid electrolyte.

Electrolysis of metal oxides in MgCl2 based molten salts with an inert graphite anode.

Electrolysis of solid metal oxides has been demonstrated in MgCl2-NaCl-KCl melt at 700 °C taking the electrolysis of Ta2O5 as an example. Both the cathodic and anodic processes have been investigated using cyclic voltammetry, and potentiostatic and constant voltage electrolysis, with the cathodic products analysed by XRD and SEM and the anodic products by GC. Fast electrolysis of Ta2O5 against a graphite anode has been realized at a cell voltage of 2 V, or a total overpotential of about 400 mV. The energy consumption was about 1 kW h kgTa(-1) with a nearly 100% Ta recovery. The cathodic product was nanometer Ta powder with sizes of about 50 nm. The main anodic product was Cl2 gas, together with about 1 mol% O2 gas and trace amounts of CO. The graphite anode was found to be an excellent inert anode. These results promise an environmentally-friendly and energy efficient method for metal extraction by electrolysis of metal oxides in MgCl2 based molten salts.

Developing energy efficient lignin biomass processing - towards understanding mediator behaviour in ionic liquids.

Environmental concerns have brought attention to the requirement for more efficient and renewable processes for chemicals production. Lignin is the second most abundant natural polymer, and might serve as a sustainable resource for manufacturing fuels and aromatic derivatives for the chemicals industry after being depolymerised. In this work, the mediator 2,2'-azino-bis(3-ethylbenthiazoline-6-sulfonic acid) diammonium salt (ABTS), commonly used with enzyme degradation systems, has been evaluated by means of cyclic voltammetry (CV) for enhancing the oxidation of the non-phenolic lignin model compound veratryl alcohol and three types of lignin (organosolv, Kraft and lignosulfonate) in the ionic liquid 1-ethyl-3-methylimidazolium ethyl sulfate, ([C2mim][C2SO4]). The presence of either veratryl alcohol or organosolv lignin increased the second oxidation peak of ABTS under select conditions, indicating the ABTS-mediated oxidation of these molecules at high potentials in [C2mim][C2SO4]. Furthermore, CV was applied as a quick and efficient way to explore the impact of water in the ABTS-mediated oxidation of both organosolv and lignosulfonate lignin. Higher catalytic efficiencies of ABTS were observed for lignosulfonate solutions either in sodium acetate buffer or when [C2mim][C2SO4] (15 v/v%) was present in the buffer solution, whilst there was no change found in the catalytic efficiency of ABTS in [C2mim][C2SO4]-lignosulfonate mixtures relative to ABTS alone. In contrast, organosolv showed an initial increase in oxidation, followed by a significant decrease on increasing the water content of a [C2mim][C2SO4] solution.

Preparation of Mo nanopowders through electroreduction of solid MoS2 in molten KCl-NaCl.

Electrolysis of MoS2 to produce Mo nanopowders and elemental sulfur has been studied in an equimolar mixture of NaCl and KCl at 700 °C. The reduction mechanism was investigated by cyclic voltammetry (CV), potentiostatic and constant voltage electrolysis together with spectroscopic and scanning electron microscopic analyses. The reduction pathway was identified to be MoS2 → LxMoS2 (x ≤ 1, L = Na or K) → L3Mo6S8 and LMo3S3 → Mo, and the last step to format metallic Mo was found to be relatively slow in kinetics. Electrolysis at a cell voltage of 2.7 V has led to a rapid reduction of MoS2 to nodular Mo nanoparticles (50-100 nm), with the current efficiency and energy consumption being about 92% and 2.07 kW h kg(-1)-Mo, respectively.

Electrochemistry of Titanium Carbide MXenes in Supercapacitor.

Novel electrode materials are always explored to achieve better performance of supercapacitors. Titanium carbide MXenes, Ti3 C2 Tx , are one of the very promising candidates for electrode materials in supercapacitors due to their unique structural and ion storage properties as 2D materials. Their large specific surface area, adjustable functionalized surface terminals, high electrical conductivities, hydrophilicity, and high Faradaic capacitance, also known widely but confusingly as pseudocapacitance, are highly desirable for making high-performance electrodes with increased dis-/charging rates and capacities. Herein, some selective electrochemical considerations of Ti3 C2 Tx MXenes for uses in supercapacitors are critically reviewed and assessed, aiming at a better fundamental understanding of the electrochemical basics and processes in Ti3 C2 Tx MXene-based electrode materials for supercapacitor applications.

LiAlO2-Modified Li Negative Electrode with Li10GeP2S12 Electrolytes for Stable All-Solid-State Lithium Batteries.

Lithium (Li) metal has an ultrahigh specific capacity in theory with an extremely negative potential (versus hydrogen), receiving extensive attention as a negative electrode material in batteries. However, the formation of Li dendrites and unstable interfaces due to the direct Li metal reaction with solid sulfide-based electrolytes hinders the application of lithium metal in all-solid-state batteries. In this work, we report the successful fabrication of a LiAlO2 interfacial layer on a Li/Li10GeP2S12 interface through magnetic sputtering. As LiAlO2 can be a good Li+ ion conductor but an electronic insulator, the LiAlO2 interface layer can effectively suppress Li dendrite growth and the severe interface reaction between Li and Li10GeP2S12. The Li@LiAlO2 200 nm/Li10GeP2S12/Li@LiAlO2 200 nm symmetric cell can remain stable for 3000 h at 0.1 mA cm-2 under 0.1 mAh cm-2. Moreover, unlike the rapid capacity decay of a cell with a pristine lithium negative electrode, the Li@LiAlO2 200 nm/Li10GeP2S12/LiCoO2@LiNbO3 cell delivers a reversible capacity of 118 mAh g-1 and a high energy efficiency of 96.6% after 50 cycles. Even at 1.0 C, the cell with the Li@LiAlO2 200 nm electrode can retain 95% of its initial capacity after 800 cycles.

Ionic Liquid-Based Electrolytes for Supercapacitor and Supercapattery.

There is a strong desire to replace or complement aqueous and organic electrolytes by ionic liquids (ILs) in electrochemical energy storage (EES) devices to achieve high operating voltages and hence high energy capacity. ILs are regarded as the inherent and competitive electrolytes since they were introduced to the electrochemical research community because they can overcome many disadvantages of the conventional aqueous and organic electrolytes, such as narrow potential windows, volatility, and flammability. This paper reviews critically the recent literatures of IL-based electrolytes used in supercapacitor, supercapattery, and micro-supercapacitor. Supercapattery is a generic term for various hybrid devices combining the merits of rechargeable battery and supercapacitor and often shows capacitive behavior. Fundamentals of supercapattery are briefly explained with typical examples. Micro-supercapacitor falls in the same scope of supercapacitor and supercapattery and shares the same fundamental concerns besides topology or structure. The future of IL-based electrolytes for the capacitive EES devices are also prospected.

Internally referenced analysis of charge-transfer reactions in a new ferrocenyl bithiophenic conducting polymer through cyclic voltammetry.

A new ferrocenyl bithiophenic polymer has enabled the first demonstration of internally referenced quantitative analysis of charge-transfer reactions, which may enable better understanding and applications of conducting polymers in e.g. supercapacitors.

Controllable synthesis of (NH4)Fe2(PO4)2(OH)·2H2O using two-step route: Ultrasonic-intensified impinging stream pre-treatment followed by hydrothermal treatment.

(NH4)Fe2(PO4)2(OH)·2H2O samples with different morphology are successfully synthesized via two-step synthesis route - ultrasonic-intensified impinging stream pre-treatment followed by hydrothermal treatment (UIHT) method. The effects of the adoption of ultrasonic-intensified impinging stream pre-treatment, reagent concentration (C), pH value of solution and hydrothermal reaction time (T) on the physical and chemical properties of the synthesised (NH4)Fe2(PO4)2(OH)·2H2O composites and FePO4 particles were systematically investigated. Nano-seeds were firstly synthesized using the ultrasonic-intensified T-mixer and these nano-seeds were then transferred into a hydrothermal reactor, heated at 170 °C for 4 h. The obtained samples were characterized by utilising XRD, BET, TG-DTA, SEM, TEM, Mastersizer 3000 and FTIR, respectively. The experimental results have indicated that the particle size and morphology of the obtained samples are remarkably affected by the use of ultrasonic-intensified impinging stream pre-treatment, hydrothermal reaction time, reagent concentration, and pH value of solution. When such (NH4)Fe2(PO4)2(OH)·2H2O precursor samples were transformed to FePO4 products after sintering at 650 °C for 10 h, the SEM images have clearly shown that both the precursor and the final product still retain their monodispersed spherical microstructures with similar particle size of about 3 µm when the samples are synthesised at the optimised condition.

More affordable electrolytic LaNi5-type hydrogen storage powders.

Compounding between NiO and La(2)O(3) protects the latter from water and molten salt attack, and ensures successful direct electrolytic conversion of the oxide precursors, in the solid state, to more affordable LaNi(5)-type hydrogen storage materials.

Faradaic processes beyond Nernst's law: density functional theory assisted modelling of partial electron delocalisation and pseudocapacitance in graphene oxides.

The study of electron delocalisation in oxygen atom segregated zones in graphene, aided by the first-principles density functional theory, has revealed extra energy bands of ≥2 eV wide around the Fermi level, predicting Faradaic charge storage occurring in a wide range of potentials, which disagrees with Nernst's law but accounts well for the so called pseudocapacitance of heteroatom-modified graphene based electrode materials in supercapacitors.

Highly Efficient Sulfonic/Carboxylic Dual-Acid Synergistic Catalysis for Esterification Enabled by Sulfur-Rich Graphene Oxide.

A new sulfonic/carboxylic dual-acid catalyst based on sulfur-rich graphene oxide (GO-S) was readily prepared and used as a highly efficient and reusable solid acid catalyst toward the esterification of oleic acid with methanol for biodiesel production. Higher yields of methyl oleate (98 %) and over 3 times higher turnover frequencies (TOFs) were observed for the GO-S dual-acid catalyst, compared to liquid sulfuric acid or other carbon-based solid acid catalysts. The "acidity" of sulfonic acid groups was enhanced by the addition of carboxylic acid groups as the combination of the two acids enhances their inherent activity by associative interaction.

Fluorinated Electrolytes for Li-Ion Batteries: The Lithium Difluoro(oxalato)borate Additive for Stabilizing the Solid Electrolyte Interphase.

Fluorinated electrolytes based on fluoroethylene carbonate (FEC) have been considered as promising alternative electrolytes for high-voltage and high-energy capacity lithium-ion batteries (LIBs). However, the compatibility of the fluorinated electrolytes with graphite negative electrodes is unclear. In this paper, we have systematically investigated, for the first time, the stability of fluorinated electrolytes with graphite negative electrodes, and the result shows that unlike the ethylene carbonate (EC)-based electrolyte, the FEC-based electrolyte (EC was totally replaced by FEC) is incapable of forming a protective and effective solid electrolyte interphase (SEI) that protects the electrolyte from runaway reduction on the graphite surface. The reason is that the lowest unoccupied molecular orbital energy levels are also lowered by the introduction of fluorine into the solvent, and the FEC solvent has poorer resistance against reduction, leading to instability on the graphite negative electrode. To tackle this problem, two lithium salts of lithium bis(oxalato)borate and lithium difluoro(oxalato)borate (LiDFOB) have been investigated as negative-electrode film-forming additives. Incorporation of only 0.5 wt % LiDFOB to a FEC-based electrolyte [1.0 M LiPF6 in 3:7 (FEC-ethyl methyl carbonate)] results in excellent cycling performance of the graphite negative electrode. This improved property originates from the generation of a thinner and better quality SEI film with little LiF by the sacrificial reduction of the LiDFOB additive on the graphite negative electrode surface. On the other hand, this additive can stabilize the electrolyte by scavenging HF. Meanwhile, the incorporated LiDFOB additive has positive influence on the interphase layer on the positive electrode surface and significantly decreases the amount of HF formation, finally leading to improved cycling stability and rate capability of LiNi0.5Mn1.5O4 electrodes at a high cutoff voltage of 5 V. The data demonstrate that the LiDFOB additive not only exhibits a superior compatibility with graphite but also improves the electrochemical properties of high-voltage spinel LiNi0.5Mn1.5O4 positive electrodes considerably, confirming its potential as a prospective, multifunctional additive for 5 V fluorinated electrolytes in high-energy capacity lithium-ion batteries (LIBs).

Carbon nanotube stabilised emulsions for electrochemical synthesis of porous nanocomposite coatings of poly[3,4-ethylene-dioxythiophene].

The amphiphobic nature of carbon nanotubes allows them to stabilise droplets of water-insoluble monomers dispersed in the aqueous nanotube suspension, leading to a flexible route to electrochemical synthesis of useful nanoporous composites of nanotube doped conducting polymers, and potentially to other chemistry involving reactants incompatible in the same medium.

Voltammetric studies of through-space and through-bond electrostatic interactions in alkyl linked ferrocene and benzoaza-15-crown-5 receptor molecules in acetonitrile.

Six new ferrocene alkyl-benzoaza-15-crown-5 molecules with different alkyl spacer lengths were synthesized and investigated by voltammetry in acetonitrile. Their mean potentials (E(o)') were more negative than that of ferrocene. The changes were greater for the bis-substituted ligands than for the monosubstituted ones. Increasing the alkyl spacer length shifted E(o)' negatively from -CH2- to -(CH2)2- but positively from -(CH2)2- to -(CH2)4-. This unusual variation is attributed to the combined electron donating and withdrawing influences and also the steric effect from the substituents on the ferrocene moiety. Analyses of the potentials of the molecules and their fully protonated forms suggested intramolecular electrostatic signaling through not only the space but also the alkyl chain which is usually considered to be an insulator for through-bond communication. Diffusion coefficients with insignificant differences between the receptors and their fully protonated forms were derived from cyclic voltammograms, suggesting insignificant further conformational variation upon protonation.

Electrochemistry at conductor/insulator/electrolyte three-phase interlines: A thin layer model.

A thin layer model is proposed to assist in the understanding of the electrochemical conversion of insulator to conductor at the conductor/insulator/electrolyte three-phase interline (3PI) when the influence of mass diffusion in the electrolyte phase is negligible. The model predicts, under potentiostatic conditions, a linear variation of the current or the length of the 3PI with time. When polarization is sufficiently large, the logarithm of the current/time ratio or the 3PI-length/time ratio, according to the model, increases linearly with the applied potential. These predictions were tested against and agreed very well with two practical systems: the electroreduction of solid AgCl to Ag in aqueous KCl and of solid SiO2 to Si in molten CaCl2. Kinetic parameters were derived from experimental data using the model. Particularly, the electron transfer coefficient, alpha, was found to be about 0.29 for the reduction of AgCl to Ag in the aqueous KCl solution at room temperature but about 10(-2) for the reduction of SiO2 to Si in molten CaCl2 at 850 degrees C.