Tetraoctylphosphonium Bromide Research Articles

Demulsification of water in crude oil emulsions via phosphonium-based ionic liquids: Statistical modeling and optimization

In the present study, the performance of two ionic liquids namely Tetrabutylphosphonium bromide (TBPB) and Tetraoctylphosphonium bromide (TOPB) as the demulsifying compounds are investigated in the demulsification operation of water in light and medium crude oil emulsions for the first time. The response surface methodology (RSM) is employed to evaluate the impact of temperature, pH, water content, demulsifier concentration, and settling time on the demulsification efficiencies of studied demulsifiers. In order to design the requisite experiments and optimize the effective factors on the water removal efficiency, the central composite design (CCD) is applied. To determine the optimal conditions of input parameters, four exact models are created by utilizing the responses of 184 experiments to predict the demulsification efficiencies of two demulsifiers for two types of crude oils based on statistical tests of different models using the analysis of variance (ANOVA). High R2 coefficient values imply that the developed models could reproduce the experimental results of the studied demulsifiers appropriately. At the optimal conditions, the water in light and medium crude oil emulsions are completely broken in the samples containing TOPB. Moreover, TBPB agent presents high and acceptable demulsification efficiencies for both types of crude oils at the optimal values of process parameters i.e. 98.078% and 96.025% for light and medium crude oil emulsions, respectively. The superior demulsification performance of TOPB with respect to TBPB can be ascribed to the longer alkyl chain length of TOPB.

Recovery of Metals from Electronic Waste-Printed Circuit Boards by Ionic Liquids, DESs and Organophosphorous-Based Acid Extraction.

The extraction of metals from waste printed circuit boards (WPCBs) with ionic liquids (ILs), Deep Eutectic Solvents (DESs) and organophosphorous-based acid (Cyanex 272) has been presented. The study was undertaken to assess the effectiveness of the application of the new leaching liquids, and the new method of extraction of metals from the leachate and the solid phase with or without the leaching process. Solvent extraction from the liquid leachate phase has been studied in detail with popular ILs, such as tetraoctylphosphonium bromide, {[P8,8,8,8][Br] and tributyltetradecylphosphonium chloride, [P4,4,4,14][Cl] using Aqueous Biphasic Systems (ABS) method. Trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl) phosphinate, [P6,6,6,14][Cyanex272], ([P6,6,6,14][BTMPP]), trihexyltetradecylphosphonium thiocyanate, [P6,6,6,14][SCN], methyltrioctylammonium chloride (Aliquat 336), as well as bis(2,4,4-trimethylpentyl)phosphinic acid (Cyanex 272) were also used in the extraction of metals from the leachate. Two DESs (1) {choline chloride + lactic acid, 1:2} and (2) {choline chloride + malonic acid, 1:1} were used in the extraction of metals from the solid phase. The extraction behavior of metals with DESs was compared with that performed with three new bi-functional ILs: didecyldimethylammonium salicylate, [N10,10,1,1][Sal], didecyldimethylammonium bis(2-ethylhexyl) phosphate, [N10,10,1,1][D2EHPA], and didecyldimethylammonium bis(2,4,4-trimethylpentyl) phosphinate, [N10,10,1,1][Cyanex272]. The [P6,6,6,14][Cyanex272]/toluene and (Cyanex 272 + diethyl phosphite ester) mixtures exhibited a high extraction efficiency of about 50–90% for different metal ions from the leachate. High extraction efficiency of about 90–100 wt% with the ABS method using the mixture {[P8,8,8,8][Br], or [P4,4,4,14][Cl] + NaCl + H2O2 + post-leaching liquid phase} was obtained. The DES 2 revealed the efficiency of copper extraction, ECu = 15.8 wt% and silver, EAg = 20.1 wt% at pH = 5 from the solid phase after the thermal pre-treatment and acid leaching. The solid phase extraction efficiency after thermal pre-treatment only was (ECu = 9.6 wt% and EAg = 14.2 wt%). The use of new bi-functional ILs did not improve the efficiency of the extraction of metal ions from the solid phase. Process factors such as solvent concentration, extraction additives, stripping and leaching methods, temperature, pH and liquid/solid as well as organic/water ratios were under control. For all the systems, the selectivity and distribution ratios were described. The proposed extraction processes can represent alternative paths in new technologies for recovering metals from electronic secondary waste.

Efficient recovery of Au(III) through PVDF-based polymer inclusion membranes containing hydrophobic deep eutectic solvent

A novel extractant, hydrophobic deep eutectic solvent (DES) has been synthesized by mixing tetraoctylphosphonium bromide (P8888Br) and di-(2-ethylhexyl) phosphoric acid (P204), and then used as carrier to prepare a homogenous and flexible polyvinylidene fluoride (PVDF)-based polymer inclusion membrane (PIM) for the recovery of Au(III) in hydrochloric acid system. A series of characterizations and conditions optimization experiments have been performed on the elaborated PIMs. It was found that PIM composed of 70 wt% PVDF, 5 wt% NPOE and 25 wt% DES had excellent selectivity and could achieve the quantitative extraction of Au(III) from mixed metals solution. Under the optimal conditions, 99.1% of gold in the feed phase was selectively transported to the receiving phase by the optimized PIM with a high permeability coefficient of 3.52 × 10−5 m s−1, realizing the enrichment and recovery of gold. Besides, the elaborated PIM had high reusability and stability, which still had an extraction efficiency of 92.4% after five consecutive transport experiments. These results all confirm the advantages of the newly developed PIM in the extraction and recovery of gold, and it will be expected to realize a wide range of economic and practical value.

A kaolinite-tetrabutylphosphonium bromide intercalation compound as an effective intermediate for intercalation of bulky organophosphonium salts

A kaolinite-tetrabutylphosphonium bromide (TBPBr) intercalation compound (Kaol-TBPBr) underwent intercalation of dodecyltributylphosphonium bromide (C12TriBPBr), while a kaolinite-dimethyl sulfoxide (DMSO) intercalation compound (Kaol-DMSO) and methoxy-modified kaolinite (MeO-Kaol) showed no such capability. As for the reaction of Kaol-TBPBr and C12TriBPBr, the X-ray diffraction (XRD) patterns revealed expansion of the basal spacing from 1.53 nm of Kaol-TBPBr to 2.10 nm. Fourier transform infrared, solid-state 13C nuclear magnetic resonance (NMR) with cross polarization and magic angle spinning (13C CP/MAS NMR) spectroscopies and the C/P and the Br/P molar ratios indicated intercalation of C12TriBPBr between the layers of kaolinite upon removal of the pre-intercalated TBPBr. As concerns the reactions of Kaol-DMSO and C12TriBPBr, the XRD patterns exhibited no difference as compared to that of Kaol-DMSO or the decrease in basal spacing from the 1.12 nm of Kaol-DMSO to the 0.72 nm of pristine kaolinite. With respect to the reactions of MeO-Kaol with C12TriBPBr, the XRD patterns displayed no expansion of the basal spacing from 0.86 nm of MeO-Kaol. Kaol-TBPBr was also used as an intermediate for successful intercalation of relatively bulk organophosphonium salts, hexadecyltributylphosphonium bromide, tetradecyltrihexylphosphonium chloride and tetraoctylphosphonium bromide. These results clearly reveal the versatility of Kaol-TBPBr as an effective intermediate for use in kaolinite intercalation chemistry.

Use of surfactants to tailor the morphologies and crystalline phases of thin films via aerosol assisted chemical vapor deposition

Morphological control is important for band gap tuning which in turn plays a vital role in device applications. In this article we have reviewed the effect of addition of surfactants (tetraoctylammonium bromide, cetyltrimethylammonium bromide, Triton X-100, span, tetraoctylphosphonium bromide, sodium dodecyl sulfate, tween, oleylamine, acetylacetone and tetrahydrothiophene) during aerosol assisted chemical vapor deposition of iron selenide thin films, gold nanoparticles in vanadium dioxide matrix, zinc oxide thin films, lead sulfide thin films and gold (0) plate growth. We have also discussed the mechanism of thin film formation.

Liquid-liquid extraction of cobalt(II) and zinc(II) from aqueous solutions using novel ionic liquids as an extractants

Abstract Extraction efficiencies of Co(II) and Zn(II) from aqueous phase with new ionic liquids (ILs) in comparison with already studied in literature ILs, but without addition of acids and at low temperatures are presented. Thus the new, environmental-friendly method of extraction of metal ions is proposed. A novel ammonium ILs, benzyldimethyloctadecylammonium bis(2,4,4-trimethylpentyl)phosphinate [NBz,1,1,18][BTMPP], didecyldimethylammonium saccharinate, [N10,10,1,1][SACH] and didecyldimethylammonium acesulfamate, [N10,10,1,1][ACE] were synthesized and used between others for this extraction. The solvent extraction behavior was compared to well known in this process ILs: methyltrioctylammonium chloride ([N8,8,8,1][Cl]), Aliquat 336, trihexyltetradecylphosphonium chloride, ([P6,6,6,14][Cl]), Cyphos IL 101 and trihexyltetradecylphosphonium bis(2,4,4-trimethylpentyl)phosphinate, ([P6,6,6,14][BTMPP]). Extraction was provided with pure ILs and with addition of complexion agents, such as: 18-crown-6, 24-crown-8, alkanes C24H50, C27H56, Triton TM X-100 and L-histidine. It was shown that quick and efficient extraction, where >90% of Co(II) and Zn(II) may be obtained using pure IL, or with additives, using synergistic effects of mixture of two ILs, or using ILs in Aqueous Biphasic Systems (ABS) method with NaCl at low temperature T = 303 K. The tributyltetradecylphosphonium chloride, [P4,4,4,14][Cl], tetraoctylphosphonium bromide, [P8,8,8,8][Br], and benzalkonium chloride [NBz,1,1,R][Cl] (R = C12H25–60%; C14H29–40%) were used in ABS experiment. The extraction behavior was carried out also using Deep Eutectic Solvents, DES non miscible with water, which presented lower efficiency. The extraction process confirmed the large efficiency and distribution ratio using [P6,6,6,14][BTMPP] with addition of 18-Crown-6 at pH = 7 for Co(II), as well as using Cyphos IL 101 ([P6,6,6,14][Cl]) with addition of 18-crown-6, or Triton TM X-100, or L-histidine at pH 1 (no addition of acid) for Zn(II). The same results for Zn(II) were obtained with ABS method with {[P4,4,4,14][Cl] + NaCl + Zn (II)}. However, the best results were obtained with trihexyltetradecylphosphonium thiocyanate, [P6,6,6,14][SCN] for both metal ions.

PREPARATION, CHARACTERIZATION AND PERFORMANCE OF POLYVINYLIDENE FLUORIDE/TETRAOCTYL PHOSPHONIUM BROMIDE NANOCOMPOSITE ULTRAFILTRATION MEMBRANE

Ultrafiltration (UF) membrane is widely used in many industrial areas and applications. Polyvinylidene fluoride (PVDF) is one of the commonly used materials for UF membrane fabrication due to its excellent properties. However, its hydrophobic nature causes the decrease of its demands and limits its applications. Hence, tetraoctyl phosphonium bromide (TOPBr) clay was used as a nanofiller material and was added into the PVDF matrix to decrease the hydrophobic surface through the antifouling properties of the PVDF/TOPBr nanocomposite membrane. The phase inversion process was employed for membrane fabrication which characterizes the water content and porosity of the PVDF/TOPBr nanocomposite UF membrane and to determine the performance of membrane in terms of pure water permeation, protein separation and fouling parameters. The results showed the increment of TOPBr dosage increases the water content and porosity, as well as enhances the porosity structure of PVDF/TOPBr nanocomposite membrane compared to the original PVDF membrane. The protein separation performance test revealed that after the addition of TOPBr, the flux increased from 2.06 L/m2.h to 20.22 L/m2.h with a 1.0 wt.% increase in protein separation as a result of the increase in the membrane hydrophilicity and porosity of the nanocomposite membrane. Moreover, PVDF/TOPBr1.0 nanocomposite showed the highest antifouling properties and flux recovery at 93% compared to other PVDF/TOPBr, as well as the native PVDF membrane.

EFFECT OF TETRAOCTYLPHOSPHONIUM BROMIDE (TOPBR) CLAY COMPOSITION ON POLYVINYLIDENE FLUORIDE (PVDF) NANOCOMPOSITE ULTRAFILTRATION MEMBRANE

Nanocomposite membranes containing polyvinylidene fluoride (PVDF) and tetraoctylphosphonium bromide clay (TOPBr) were prepared by phase inversion method. Different TOPBr and PVDF contents were used in order to investigate the effect of TOPBr clay composition on the membrane properties. The morphology of PVDF/TOPBr nanocomposite ultrafiltration (UF) membrane was characterized by scanning electron microscopy (SEM) and hydrophilicity of the nanocomposite membrane was evaluated in terms of water content, porosity and pure water flux (PWF). The results revealed that the increasing of TOPBr clay content produced more porous nanocomposite membrane due to the formation of many finger like pores and microvoids. The hydrophilicity of the membranes was strongly enhanced by increasing the contents of TOPBr clay.

Electropolymerization of aniline in phosphonium‐based ionic liquids and their application as protective films against corrosion

ABSTRACTConductive polyaniline (PANI) films were deposited on mild steel by an electropolymerization technique in the presence of different types of phosphonium‐based ionic liquids, including tetrabutylphosphonium bromide, tetraoctylphosphonium bromide, and ethyltributylphosphonium diethylphosphate. The formation of the PANI films was followed by repetitive cyclic voltammetry scans and was confirmed with diffuse reflectance infrared Fourier transform spectroscopy. The morphology, surface roughness parameters, and grain sizes of these coatings were evaluated by atomic force microscopy. The corrosion behavior of the bare and PANI‐coated electrodes was investigated by potentiodynamic polarization, open‐circuit potential, and electrochemical impedance spectroscopy techniques in a simulated marine environment in 3.5 wt % aqueous NaCl solutions. The quantum chemical parameters of the PANI composite films were also calculated with parametric method 3, a semi‐empirical quantum mechanical method. The theoretical conclusions were found to be consistent with the reported experimental data. © 2016 Wiley Periodicals, Inc. J. Appl. Polym. Sci. 2016, 133, 43923.

Role of Halides in the Ordered Structure Transitions of Heated Gold Nanocrystal Superlattices.

Dodecanethiol-capped gold (Au) nanocrystal superlattices can undergo a surprisingly diverse series of ordered structure transitions when heated (Goodfellow, B. W.; Rasch, M. R.; Hessel, C. M.; Patel, R. N.; Smilgies, D.-M.; Korgel, B. A. Nano Lett.2013, 13, 5710–5714). These are the result of highly uniform changes in nanocrystal size, which subsequently force a spontaneous rearrangement of superlattice structure. Here, we show that halide-containing surfactants play an essential role in these transitions. In the absence of any halide-containing surfactant, superlattices of dodecanethiol-capped (1.9-nm-diameter) Au nanocrystals do not change size until reaching about 190–205 °C, at which point the gold cores coalesce. In the presence of halide-containing surfactant, such as tetraoctylphosphonium bromide (TOPB) or tetraoctylammounium bromide (TOAB), the nanocrystals ripen at much lower temperature and superlattices undergo various ordered structure transitions upon heating. Chloride- and iodide-containing surfactants induce similar behavior, destabilizing the Au–thiol bond and reducing the thermal stability of the nanocrystals.

Thermophysical properties of phosphonium-based ionic liquids

Experimental data for density, viscosity, refractive index and surface tension of four phosphonium-based ionic liquids were measured in the temperature range between (288.15 and 353.15)K and at atmospheric pressure. The ionic liquids considered include tri(isobutyl) methylphosphonium tosylate, [Pi(444) 1][Tos], tri(butyl) methylphosphonium methylsulfate, [P4441][CH3SO4], tri(butyl) ethylphosphonium diethylphosphate, [P4442][(C2H5O)2PO2], and tetraoctylphosphonium bromide, [P8888][Br]. Additionally, derivative properties, such as the isobaric thermal expansion coefficient, the surface thermodynamic properties and the critical temperatures for the investigated ionic liquids were also estimated and are presented and discussed. Group contribution methods were evaluated and fitted to the density, viscosity and refractive index experimental data.

Dielectric and shear relaxations of ionic liquid composed of symmetric ions.

The frequency-dependent conductivity and shear viscosity of an ionic liquid composed of symmetric ions were determined experimentally in the MHz region. The ionic liquid studied was tetraoctylphosphonium bromide. An isomer with an asymmetric cation, trihexyltetradecylphosphonium bromide, was also investigated to clarify the possible role of the reorientational motion of the cations in the two relaxation spectra. Both the conductivity and the shear viscosity show relaxation in the MHz region, and these relaxation spectra scarcely depend on the asymmetry of the cations. It is, therefore, concluded that the coupling of the reorientational mode of cations with these relaxation spectra is marginal, and that these spectra reflect mainly the frequency-dependent translational motion of ions.

Iron selenide films by aerosol assisted chemical vapor deposition from single source organometallic precursor in the presence of surfactants

This article presents the synthesis and characterization (multinuclear nuclear magnetic resonance, Fourier transform infrared spectroscopy, carbon–hydrogen–nitrogen–sulfur analyzer, atomic absorption spectrometry and thermogravimetric analysis) of a single source organometallic precursor namely 1-acetyl-3-(4-ferrocenylphenyl)selenourea for the fabrication of iron selenide (FeSe) films on glass substrates using aerosol assisted chemical vapor deposition (AACVD). The changes in the morphologies of the films have been monitored by the use of two different surfactants i.e. triton X-100 and tetraoctylphosphonium bromide during AACVD. The role of surfactant has been evaluated by examining the interaction of the surfactants with the precursor by using UV–vis spectroscopy and cyclic voltammetry. The fabricated FeSe films have been characterized with powder X-ray diffraction, scanning electron microscopy and energy dispersive spectroscopy.

Huge Seebeck coefficients in nonaqueous electrolytes

The Seebeck coefficients of the nonaqueous electrolytes tetrabutylammonium nitrate, tetraoctylphosphonium bromide, and tetradodecylammonium nitrate in 1-octanol, 1-dodecanol, and ethylene-glycol are measured in a temperature range from T = 30 °C to T = 45 °C. The Seebeck coefficient is generally of the order of a few hundreds of microvolts per Kelvin for aqueous solution of inorganic ions. Here we report huge values of 7 mV/K at 0.1 M concentration for tetrabutylammonium nitrate in 1-dodecanol. These striking results open the question of unexpectedly large kosmotrope or "structure making" effects of tetraalkylammonium ions on the structure of alcohols.

Thin-Film Voltammetry of a Lutetium Bisphthalocyanine at Ionic Liquid|Water Interface

At room temperature, tetraoctylphosphonium bromide is a viscous ionic liquid, this gel-like organic phase can be cast over a basal-plane graphite electrode (BPGE). Cyclic voltammetry at such a modified electrode, in contact with an aqueous solution have revealed one reversible oxidation and five reversible reduction steps for a LuIII bisphthalocyanine dissolved in the ionic liquid film, a proof that the highly reactive reduced species were protected from interaction with water in this highly lipophilic phase. It has also been shown that the redox properties are influenced by the ions in the aqueous phase, a property which has been attributed to ion-pairing effects; obviously, the ion transfers at the organic|aqueous interface has been ignored. Electrochemistry of Lu(III)[(tBu)4Pc]2 (cyclic voltammetry and square wave voltammetry) under similar conditions shows that the nature and concentration of the anion in the aqueous solution in contact with the ionic liquid film influences the potential of the electrode reaction. This can be attributed to variations of the interfacial potential and also because the organic phase is an anion exchanger. Moreover, SWV experiments suggest that the rate of the overall reaction varies with the nature and concentration of the anion of the aqueous electrolyte, which implies that the ion transfer through the organic|aqueous interface is slower than the electron exchange rate of the molecule at the surface of graphite.

Tailoring the local structure and electronic property of AuPd nanoparticles by selecting capping molecules

Nine AuPd nanoparticle samples selectively capped with tetraoctylphosphonium bromide, primary amine and tertiary amine molecules were studied with the Au L3-edge x-ray absorption spectroscopy (XAS). The AuPd mixing patterns were analyzed by comparing the XAS results with the theoretical coordination numbers of 24 AuPd model clusters of varied size, Au concentration, and bimetal mixing pattern. It was found that the use of amines, particularly tertiary amine, produced a more homogeneous AuPd mixing pattern and the Au d-electron density was fine-tunable by tailoring the density of Au–Pd bonds. Mechanisms for the tailored structural and electronic properties of these nanoparticles were proposed.

Phosphonium salt intercalated montmorillonites

Tri-phenyl vinylbenzyl phosphonium chloride and tetraoctyl phosphonium bromide salts have been used as intercalant agents for Na-montmorillonite. Fourier Transform Infrared spectroscopy (FTIR) and Thermogravimetric Analysis coupled with Mass-spectrometry (TG/DTG-MS) were used to characterize the modified montmorillonites and the thermal decomposition products. X-ray Diffraction (XRD) and Transmission Electron Microscopy (TEM) techniques were used to evaluate the increase of the basal spacing. An easier and more effective intercalation takes place with the tetraoctyl phosphonium salt giving rise to a higher concentration of intercalant with a sensible increase in the interlayer spacing. This phosphonium salt modified montmorillonite is thermally more stable and easier to exfoliate during the compounding process.

Iridium Nanocrystal Synthesis and Surface Coating-Dependent Catalytic Activity

Iridium (Ir) nanocrystals were synthesized by reducing (methylcyclopentadienyl)(1,5-cyclooctadiene)lr with hexadecanediol in the presence of four different capping ligand combinations: oleic acid and oleylamine, trioctylphosphine (TOP), tetraoctylammonium bromide (TOAB), and tetraoctylphosphonium bromide (TOPB). The oleic acid/oleylamine-capped nanocrystals were of the highest quality, with the narrowest size and shape distribution. The Ir nanocrystals were tested for their ability to catalyze the hydrogenation of 1-decene as a model reaction. The oleic acid/oleylamine and TOP-capped nanocrystals were both catalytically dead. TOAB and TOPB-coated nanocrystals both catalyzed 1-decene hydrogenation, with the TOPB-coated nanocrystals exhibiting the highest turnover frequencies. Recycling through several catalytic reactions increased the catalytic activity, presumably as a result of ligand desorption and increased exposure of the metal surface, with ligand desorption eventually leading to precipitation and significantly decreased activity.

Electrochemical and spectroscopic investigation of neutral, oxidized and reduced double-decker lutetium(III) phthalocyanines

The double-decker lutetium(III) phthalocyanine [( C 6 H 13 S )8 Pc ]2 Lu was investigated by electrochemical and spectroelectrochemical methods and comparisons made to previously investigated [( C 12 H 25 S )4 Pc ]2 Lu and ( Pc )2 Lu under the some experimental conditions. All three compounds undergo a single reversible one-electron oxidation and up to four reversible one-electron reductions in CH 2 Cl 2 containing 0.1 M tetra-n-butylammonium perchlorate (TBAP). The octa- and tetra substituted phthalocyanine derivatives exhibit one oxidation and three or four reductions in solution while five reductions can be detected for the two compounds in a gel-like cast film membrane of tetraoctylphosphonium bromide (4 C 8 P + Br −) at a basal plane pyrolytic graphite electrode which was immersed in aqueous 0.5 M KCl . The half-wave potentials of these SR substituted complexes in CH 2 Cl 2 are negatively shifted by 210-490 mV from E1/2 values for the same compounds in the aqueous 4 C 8P+ Br − matrix and five reductions of these compounds are observed under the latter experimental conditions. The UV-visible spectra of the compounds were measured in five different oxidation states and ESR spectra were also characterized for the neutral and doubly reduced complexes. As was expected, [( Pc )2 Lu ]−,{[( C 6 H 13 S )8 Pc ]2 Lu }− and {[( C 12 H 25 S )4 Pc ]2 Lu }− are ESR silent while electrogenerated [( Pc )2 Lu ]2−, {[( C 6 H 13 S )8 Pc ]2 Lu }2− and {[( C 12 H 25 S )4 Pc ]2 Lu }2− show broad strong signals at g = 2.0046, 2.0041 and 2.0034 with linewidths of 13.9, 16.1 and 12.9, respectively. These signals are indicative of organic free radicals where the unpaired electrons of the dianion are delocalized over two macrocycles.

Electrochemistry of a Double-Decker Lutetium(III) Phthalocyanine in Aqueous Media. The First Evidence for Five Reductions

The double-decker lutetium(III) phthalocyanine, Lu[(RS)4Pc]2, where R = C12H25, was synthesized and electrochemically characterized under several solution conditions. The neutral complex undergoes a single reversible one-electron oxidation and up to four reversible one-electron reductions in nonaqueous solutions of CH2Cl2 or benzonitrile containing 0.1 M tetra-n-butylammonium perchlorate (TBAP), while one oxidation and five reductions are seen in aqueous 0.5 M KCl for a gel-like cast film membrane of Lu[(RS)4Pc]2 in a tetraoctylphosphonium bromide (4C8P+Br-) matrix at a basal plane pyrolytic graphite electrode. The half-wave potentials for reduction of Lu[(RS)4Pc]2 in CH2Cl2, 0.1 M TBAP are located at E1/2 = 0.04, −1.03, −1.36 and −1.73 V, while the single oxidation is located at E1/2 = 0.43 V vs SCE. These potentials, when measured vs Fc/Fc+, are negatively shifted by 0.20−0.46 V from the E1/2 values obtained in the 0.5 M KCl solution where the electrogenerated anions of the double-decker complex are sta...