Electrolysis with electrolyte dropping electrode: II. Basic properties of the system

In a theoretical discussion the conditions have been pointed out where an interface of two immiscible electrolyte solution behaves as an equilibrium system metal ion-metallic electrode, as an ideally polarized electrode and as an electrode under faradaic current flow. The basic equations for current-electrical potential difference across the interface have been deduced for the cases of ion as well as electron transfer.Experimentally, various base electrolyte systems were studied, the most advantageous among these are LiCl in water+tetrabutylammonium tetraphenylborate in nitrobenzene and MgCl₂ in water+tetrabutylammonium dicarbollyl cobaltate in nitrobenzene. S-shaped polarographic curves were observed with the tetramethylammonium ion. The limiting current is directly proportional to concentration. The limiting currents are somewhat higher than those predicted by the Ilkovi? equation which has been ascribed to the tangential movement of the interface.     

Distribution mechanism of protonated l,10-phenanthroline between unbuffered aqueous and 1,2-dichloroethane phases

The faradaic ion transfer of protonated l.iO-phenanthroline [H(Phen)+] across the interface between unbuffered aqueous and 1,2-dichloroethane (DCE) solutions was investigated by means of current scan polarography at ascending aqueous electrolyte electrode, as well as chronopotentiometry. It follows from the splitting of the waves observed at the pH of aqueous phase (sodium sulfate solution) between 2.5–3.8 that neutral reagent (Phen) distributes into the aqueous phase, where it is protonated. The positive wave is associated with the mass transfer controlled by the H+influx, whereas the negative one is by the Phen influx. The reverse chronopotentiometry indicated that all the protonated transfer processes were reversible. A good agreement between experimental results and theoretical treatment was achieved. The aqueous acid dissociation constant of protonated Phen, K₂ can be evaluated from the dependence of the wave heights on the pH in the base of the equilibrium.     

Comparative study of electron transfer reactions at the ionic liquid/water and organic/water interfaces

The rates of electron transfer (ET) reactions at the water/ionic liquid (IL) interface have been measured for the first time using scanning electrochemical microscopy. The standard bimolecular rate constant of the interfacial ET between ferrocene dissolved in 1-octyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide and aqueous ferricyanide (0.4 M-1 cm s-1) was found to be approximately 30 times higher than the corresponding rate constant measured at the water/1,2-dichloroethane interface. The driving force dependence of the ET rate was investigated over a wide range of the interfacial potential drop values (>200 mV). The observed Butler-Volmer-type dependence is discussed in terms of the interfacial model. The ET was also probed at the interface between aqueous solution and the mixture of the IL and 1,2-dichloroethane. The mole fractions in this mixture were varied systematically to investigate the transition from the water/organic to the water/IL interface. The observed decrease in the rate constant with increasing mole fraction of 1,2-dichloroethane is in contrast with the previously reported direct correlation between the electrochemical rate constant and the diffusion coefficient of redox species in solution.     

Quasi-elastic laser light scattering from thermally excited capillary waves on the polarised water/1,2-dichloroethane interface

Quasi-elastic laser light scattering (QELS) from thermally excited capillary waves on the polarised water/1,2-dichloroethane interface was measured using optical heterodyne mixing technique. Interfacial potential difference was controlled by equilibrium partition of tetraethylammonium, tetrapropylammonium, tetrabutylammonium or tetrapentylammonium bromide. Frequency of the capillary wave of a selected wavelength was shown to decrease with the increasing electrolyte concentration. Frequency decrease was related to the decreasing interfacial tension being caused by the increasing relative surface excess of the electrolyte. No significant effect of the electrolyte concentration on the capillary wave damping was observed. Adsorption data obtained from these measurements are consistent with the results of the double layer capacity studies.     

Ion transfer of bromophenol blue across liquid-liquid interfaces

The ion transfer of the acidic dye bromophenol blue (BPB) at the interfaces of water/nitrobenzene (W/NB), water/1,2-dichloroethane (W/1,2-DCE) and water/(nitrobenzene+chlorobenzene) (W/(NB +CB)) was studied in detail by cyclic voltammetry (CV), chronopotentiometry with linear current scanning (CLC), controlled potential electrolysis and UV spectroscopic methods. Using controlled potential electrolysis, we observed successfully the transfer process of BPB across the W/NB interface from the colour changes of BPB in two different phases. The proposed transfer mechanism for BPB is proved to be reasonable using UV spectroscopy of the product of the electrolysis. The standard potential differences Δ^o_w^o and the standard Gibbs energies of the BPB transfer from water to some organic solvents were calculated. The dissociation constants of BPB obtained were quite close to the literature values.     

2-Dimensional porphyrin self-assemblies at molecular interfaces

The heterodimer formed by electrostatic association of zinc(II) meso-tetrakis(N-methylpyridyl)porphyrin (ZnTMPyP) and zinc(II) meso-tetrakis(p-sulfonatophenyl)porphyrin (ZnTPPS) exhibits a strong affinity for the interface between water and 1,2-dichloroethane (DCE). Surface tension measurements using the quasi-elastic light scattering (QELS) technique reveal that the heterodimer adsorption can be described in terms of a Langmuir isotherm with standard Gibbs energy of adsorption of -45.5 kJ mol(-1). The orientation of the heterodimer transition dipole moment, as estimated from light polarization modulated reflectance (LPMR), shows a marked dependence on the bulk concentration of heterodimer. On the other hand, changes in the Galvani potential difference between the two phases have little effect on the heterodimer organization at the water/1,2-dichloroethane interface when the surface coverage is close to maximum. This behavior suggests that the ZnTPPS-ZnTMPyP heterodimer forms an adsorbed layer of aggregated molecules which affects the physical properties of the interface. Indeed, capacitance and surface tension measurements reveal that the dielectric properties of the water/DCE interface are significantly altered in the presence of heterodimer species.     

Thermodynamic analysis of the cation binding to a phosphatidylcholine monolayer at a polarised interface between two immiscible electrolyte solutions

Thermodynamic analysis of the polarised interface between two immiscible electrolyte solutions (ITIES) was outlined, which accounts for the adsorption of phosphatidylcholine (PC) both as a zwitterion and a cation formed by the aqueous cation association with the zwitterionic PC form, as well as for the aqueous cation transfer facilitated by PC leading to its depletion from the interface. Electrocapillary equation was derived clarifying the physical significance of the surface charge density; the differential capacity and the PC surface excess concentration. The potential dependence of the interfacial tension calculated using the Damaskin’s adsorption model of a compound adsorbed in two different forms was found to agree well with that measured for the polarised water|1,2-dichloroethane interface in the presence of dl-α-dipalmitoylphosphatidylcholine. Experimentally observed effect of the nature of the aqueous cation on the interfacial tension was ascribed to the difference in the PC association constant.     

TRANSFER MECHANISM OF QUININE DRUG ACROSS THE OIL/WATER (O/W) INTERFACE

The transfer phenomena of quinine drug at the aqueous 1,2- dichloroethane (DCE)interface have been studied by the current- scanning polarography. The relationships be-tween the wave height and pH of aqueous phase, concentration of quinine as well as therate of water drop are discussed. The effect of supporting electrolyte, buffer solution andthe nature of organic solvent on the polarographic wave is studied. The transfer char-acteristics of quinine in aqueous phase and in organic phase are compared, The mono- pro-tonated and diprotonated quinines can both transfer at the interface so as to produce twopolarographic waves. The transfer process of quinine at the interface is simultaneouslycontrolled by diffusion and reestablishment of the disturbed protonated equilibrium ofquinine. A further investigation is made by chronopotentiometry. On the basis of thetheoretical analysis, the formulae of the limiting current are derived and discussed. Thetheoretical results are in agreement with the experimental ones.     

Synergy of Cu/C3N4 Interface and Cu Nanoparticles Dual Catalytic Regions in Electrolysis of CO to Acetic Acid

Electrochemical reduction reaction of carbon monoxide (CORR) offers a promising way to manufacture acetic acid directly from gaseous CO and water at mild condition. Herein, we discovered that the graphitic carbon nitride (g-C₃N₄) supported Cu nanoparticles (Cu−CN) with the appropriate size showed a high acetate faradaic efficiency of 62.8 % with a partial current density of 188 mA cm⁻² in CORR. In situ experimental and density functional theory calculation studies revealed that the Cu/C₃N₄ interface and metallic Cu surface synergistically promoted CORR into acetic acid. The generation of pivotal intermediate −*CHO is advantage around the Cu/C₃N₄ interface and migrated *CHO facilitates acetic acid generation on metallic Cu surface with promoted *CHO coverage. Moreover, continuous production of acetic acid aqueous solution was achieved in a porous solid electrolyte reactor, indicating the great potential of Cu−CN catalyst in the industrial application.     

Isomerization reaction dynamics and equilibrium at the liquid-vapor interface of water. A molecular-dynamics study

The gauche-trans isomerization reaction of 1,2-dichloroethane at the liquid-vapor interface of water is studied using molecular-dynamics computer simulations. The solvent bulk and surface effects on the torsional potential of mean force and on barrier recrossing dynamics are computed. The isomerization reaction involves a large change in the electric dipole moment, and as a result the trans/gauche ratio is considerably affected by the transition from the bulk solvent to the surface. Reactive flux correlation function calculations of the reaction rate reveal that deviation from the transition-state theory due to barrier recrossing is greater at the surface than in the bulk water. This suggests that the system exhibits non-Rice-Ramsperger-Kassel-Marcus behavior due to the weak solvent-solute coupling at the water liquid-vapor interface.     

端烯基液晶冠醚推动钠离子在微液/液界面的转移

用循环伏安法研究新型载体端烯基液晶冠醚推动钠离子的转移,结果表明,钠离子的转移由扩散控制.探讨了影响钠离子转移的因素,如端烯基液晶冠醚和钠离子的浓度等.求算出端烯基液晶冠醚在1,2-二氯乙烷中的扩散系数为(2.61±0.12)×10^-6cm²/s,端烯基液晶冠醚和钠离子在1,2-二氯乙烷中所形成的配合物稳定常数lgβ_o=5.7.     

Unlocking Reversible Silicon Redox for High-Performing Chlorine Batteries

Chlorine (Cl)-based batteries such as Li/Cl₂ batteries are recognized as promising candidates for energy storage with low cost and high performance. However, the current use of Li metal anodes in Cl-based batteries has raised serious concerns regarding safety, cost, and production complexity. More importantly, the well-documented parasitic reactions between Li metal and Cl-based electrolytes require a large excess of Li metal, which inevitably sacrifices the electrochemical performance of the full cell. Therefore, it is crucial but challenging to establish new anode chemistry, particularly with electrochemical reversibility, for Cl-based batteries. Here we show, for the first time, reversible Si redox in Cl-based batteries through efficient electrolyte dilution and anode/electrolyte interface passivation using 1,2-dichloroethane and cyclized polyacrylonitrile as key mediators. Our Si anode chemistry enables significantly increased cycling stability and shelf lives compared with conventional Li metal anodes. It also avoids the use of a large excess of anode materials, thus enabling the first rechargeable Cl₂ full battery with remarkable energy and power densities of 809 Wh kg⁻¹ and 4,277 W kg⁻¹, respectively. The Si anode chemistry affords fast kinetics with remarkable rate capability and low-temperature electrochemical performance, indicating its great potential in practical applications.     

Voltammetric characterisation of polyelectrolyte adsorption/transfer at the water∣1,2-DCE interface

The voltammetric characterisation of aqueous soluble polyelectrolytes at the water∣1,2-dichloroethane interface was investigated. The polyelectrolytes studied included poly (diallyldimethylammonium chloride) (PDADMACl) and polyethylenimine (PEI). The adsorption process followed by the transfer of these polyelectrolytes across the interface was characterised. The observable transfer of the monomer cation of the PDADMA⁺, namely diallyldimethylammonium (DADMA⁺) ion, was compared to that of the polyelectrolyte transfer process. Physical data including the diffusion coefficient and the Gibbs energy of transfer across the water∣1,2-dichlorethane interface was evaluated for both the polycation and monocation.     

Electrochemistry of dopamine at the polarised liquid|liquid interface facilitated by an homo-oxo-calix[3]arene ionophore

The homo-oxo-calix[3]arene-facilitated electrochemistry of dopamine at the polarised liquid|liquid interface is presented. Cyclic voltammetry indicated that the dopamine: homo-oxo-calix[3]arene complex formed at the interface between water and 1,2-dichloroethane had a 1:2 stoichiometry, which was confirmed by ¹H NMR titration. The electrochemically-determined association constants for the homo-oxo-calix[3]arene complexes with dopamine (log β 8.3), Na⁺ (8.0) and K⁺ (7.5) showed that the ionophore was more selective for dopamine over the two alkali metal cations than the dibenzo-18-crown-6 ionophore. Square wave voltammetry was employed for assessment of low concentration measurements, with a limit of detection of 3.8 μM dopamine achieved. These results show that oxo-calixarene-based ionophores are useful reagents for the detection of dopamine at the interface between two immiscible electrolyte solutions.     

Polarised liquid/liquid micro-interfaces move during charge transfer

The externally polarised micro-interface between two immiscible electrolyte solutions (ITIES) has been visualised during ion transfer using confocal laser scanning microscopy (CLSM). A water|1,2-dichloroethane (DCE) micro-interface was formed at the tip of a glass micropipette. The DCE phase contained Nile Red, a fluorophore, which was used to visualise movements in the interface with CLSM. During voltammetric transfer of tetraethylammonium cation from the aqueous phase to DCE (in the micropipette), the interface – with and without adsorbed lipid – was found to undergo significant expansion. The movement of the interface was found to be completely reversible and rapid, as evident from potential step measurements. The studies reported herein have implications for studies of charge transfer at micro-ITIES which generally assume a static interface.     

An Efficient Strategy for Boosting Photogenerated Charge Separation by Using Porphyrins as Interfacial Charge Mediators

Surface recombination at the photoanode/electrolyte junction seriously impedes photoelectrochemical (PEC) performance. Through coating of photoanodes with oxygen evolution catalysts, the photocurrent can be enhanced; however, current systems for water splitting still suffer from high recombination. We describe herein a novel charge transfer system designed with BiVO₄ as a prototype. In this system, porphyrins act as an interfacial‐charge‐transfer mediator, like a volleyball setter, to efficiently suppress surface recombination through higher hole‐transfer kinetics rather than as a traditional photosensitizer. Furthermore, we found that the introduction of a “setter” can ensure a long lifetime of charge carriers at the photoanode/electrolyte interface. This simple interface charge‐modulation system exhibits increased photocurrent density from 0.68 to 4.75 mA cm^?2 and provides a promising design strategy for efficient photogenerated charge separation to improve PEC performance.     

Inhibited and enhanced nucleation of gold nanoparticles at the water|1,2-dichloroethane interface

The deposition of gold at the interface between immiscible electrolyte solutions has been investigated using reduction of tetrachloroaurate or tetrabromoaurate in 1,2-dichloroethane, with aqueous phase hexacyanoferrate as reducing agent. In a clean environment without defects present at the interface, the Au(III) complex was reduced to the Au(I) complex, but no solid phase formation could be observed. A deposition process could only be observed through the addition of artificial nucleation sites in the form of palladium nanoparticles at the interface. This process could be associated with the reduction of the Au(I) halide complex to metallic gold, by determining the gold reduction potentials in 1,2-dichloroethane. XANES measurements indicate that tetrachloroaurate ion transfers intact into the organic phase, with the central Au atom retaining its oxidation state of +3 and the overall anion remaining charged at -1.     

Hydrodynamic voltammetry at the liquid|liquid interface: facilitated ion transfer and the rotating diffusion cell

A new approach to the voltammetric investigation of facilitated ion transfer processes is reported. The technique uses a rotating diffusion cell approach to induce laminar flow in the organic phase of a liquid|liquid electrochemical cell. The interface between two immiscible electrolyte solutions (ITIES) was stabilised against rotation with either γ-alumina or a track-etched polyester membrane. The resultant voltammetry is shown to be consistent with the Koutecký–Levich equation enabling kinetic parameters associated with facilitated transfer of sodium by dibenzo-18-crown-6 across the water|1,2-dichloroethane interface to be evaluated. In particular, the use of the more hydrophilic alumina membrane permits the uncertainties regarding the use of the membrane-stabilised ITIES, namely the interfacial position, to be eliminated.     

Evidence of tetraphenylporphyrin monoacids by ion-transfer voltammetry at polarized liquid|liquid interfaces

We present a simple methodology to illustrate the existence of tetraphenylporphyrin monoacid based on ion-transfer voltammetry at a polarized water|1,2-dichloroethane interface and organic pK values are also estimated.     

Interfacial transfer of Cd2+ assisted by 4′ — morpholino-acetophenone-4-phenyl-3-thiosemicarbazone across the water/1,2-dichloroethane interface

The assisted transfer of heavy metal ions by interfacial complexation with 4′-morpholinoacetophenone-4-phenyl-3-thiosemicarbazone (MAPPT) at the interface between two immiscible electrolyte solutions (ITIES) was studied by cyclic voltammetry. The voltammograms obtained across the water/1,2-dichloroethane interface using the MAPPT ligand in the organic phase shows that the assisted metal ion transfers have different nature for different ions. The quasi-reversible voltammetric peak of the Cd²⁺ ion was obtained and is discussed in detail. The dependence of the half-wave transfer potential on MAPPT concentration showed that the equilibrium is effectively displaced towards a 1:3 (metal:ligand) stoichiometry with an association constant of log β ^o =15.46 (±0.11) for the Cd²⁺ ion, corresponding to the TIC/TID mechanism.