Lead-selective poly(vinyl chloride) membrane electrodes based on acyclic dibenzopolyether diamides

Lipophilic acyclic dibenzopolyether diamides, 12 kinds, have been designed to prepare solvent polymeric membrane ion-selective electrodes (ISEs) for Pb(2+). The ionophores include 1,5-bis[2-(N,N-dialkylcarbamoylmethoxy)phenoxy]-3-oxapentanes1-4, 1,5-bis[2-(N,N-dialkylcarbamoylpentadecyloxy)phenoxy]-3-oxapentanes 5-8, and 1,2-bis[2-(2'-N,N-dialkylcarbamoylpentadecyloxy)phenoxy]ethanes 9-12. Linear response concentration range of the ISE based on 9 is 3 x 10(-2) - 1 x 10(-6) M of Pb(2+) (average slope = 28.5 mV decade(-1)). Potentiometric selectivities of the ISEs based on 1-12 for Pb(2+) over other heavy metal cations, alkali metal cations, and alkaline earth metal cations have been assessed. These ISEs exhibit remarkably high selectivities for Pb(2+) relative to heavy metal cations, such as Cu(2+), Fe(2+), and Ni(2+), the selectivity coefficients (K(Pot)(Pb,Cu)) being 5 x 10(-5) - 6 x 10(-5) for 1-4 and ca. 6 x 10(-4) for 9. For the Pb(2+) selectivities over alkali metal cations, such as Na(+) and K(+), 9 which has an ethylene glycol spacer and a N,N-diethyl group is superior to other dibenzopolyether diamide ionophores 1-8 and 10-12.     

New polymeric membrane cadmium(II)-selective electrodes using tripodal amine based ionophores

Fabrication of PVC membrane electrodes incorporating selective neutral carriers for Cd(2+) was reported. The ionophores were designed to have different topologies, donor atoms and lipophilicity by attaching tripodal amine (TPA) units to the lipophilic anthracene (ionophore I) and p-tert-butylcalix[4]arene (ionophores II, III and IV). The synthesized ionophores were incorporated to the plasticized PVC membranes to prepare Cd(II) ion selective electrodes (ISEs). The membrane electrodes were optimized by changing types and amounts of ionic sites and plasticizers. The selectivity of the membranes fabricated from the synthesized ionophores was evaluated, the relationship between structures of ionophores and membrane characteristics were explored. The ionophore IV which composed of two opposites TPA units on the calix[4]arene compartment showed the best selectivity toward Cd(2+). The best membrane electrode was fabricated from ionophore IV (10.2 mmol kg(-1)) with KTpClPB (50.1 mol% related to the ionophore) as an ion exchanger incorporated in the DOS plasticized PVC membrane (1:2; PVC:DOS). The Cd-ISE fabricated from ionophore IV exhibited good properties with a Nernstian response of 29.4±0.6 mV decade(-1) of activity for Cd(2+) ions and a working concentration range of 1.6×10(-6)-1.0×10(-2)M. The sensor has a fast response time of 10s and can be used for at least 1 week without any divergence in potential. The electrode can be used in the pH range of 6.0-9.0. The proposed electrodes using ionophores III and IV were employed as a probe for determining Cd(2+) from the oxidation of CdS QDs solution and the real treatment waste water sample with excellent results.     

Selective 226Ra2+ ionophores provided by self-assembly of guanosine and isoguanosine derivatives

The self-assembled guanosine (G 1)-based hexadecamers and isoguanosine (isoG 2)-based decamers are excellent 226Ra2+ selective ionophores even in the presence of excess alkali (Na+, K+, Rb+, and Cs+) and alkaline earth (Mg2+, Ca2+, Sr2+, and Ba2+) cations over the pH range 3-11. G 1 requires additional picrate anions to provide a neutral assembly, whereas the isoG 2 assembly extracts 226Ra2+ cations without any such additives. Both G 1-picrate and isoG 2 assemblies show 226Ra2+ extraction even at a 0.35 x 10(6) fold excess of Na+, K+, Rb+, Cs+, Mg2+, or Ca2+ (10(-2) M) to 226Ra2+ (2.9 x 10(-8) M) and at a 100-fold salt to ionophore excess. In the case of the G 1-picrate assembly, more competition was observed from Sr2+ and Ba2+, as extraction of 226Ra2+ ceased at an M2+/226Ra2+ ratio of 10(6) and 10(4), respectively. With the isoG 2 assembly, 226Ra2+ extraction also occurred at a Sr2+/226Ra2+ ratio of 10(6) but ceased at a 10(6) excess of Ba2+. The results clearly demonstrate the power of molecular self-assembly for the construction of highly selective ionophores.     

Tetrabenzyl pyrophosphate as a new class of neutral carrier responsive to lead ion

Tetrabenzyl pyrophosphate and diphenylphosphinic anhydride, with two phosphoryl groups (PO) as ligating sites, can be used as novel ionophores to make Pb(2+)-selective membrane electrodes. A good result was obtained with tetrabenzyl pyrophosphate, and the electrode based on this ionophore and bis(1-butylpentyl) adipate as a solvent mediator in a poly(vinyl chloride) membrane matrix exhibited a near-Nernstian response to Pb(2+) in the concentration range of 1x10(-5)-1x10(-2) M with a slope of 28.7 mV per concentration decade in a solution containing 0.1 M Mg(NO(3))(2). The limit of detection was 3x10(-6) M. The selectivity of this electrode to other metal cations was comparable to the best case in many Pb(2+)-selective electrodes so far developed. Addition of potassium tetrakis(p-chlorophenyl)borate (40 mol% relative to tetrabenzyl pyrophosphate) caused a drastic change in the response slope (53.3 mV per concentration decade), probably due to the formation of PbA(+), where A stands for anions present in the sample solution, and decreased significantly the electrode selectivity to other metal cations.     

Mercury(II) ion-selective electrodes based on heterocyclic systems

Mercury ion-selective electrodes (ISEs) were prepared with a polymeric membrane based on heterocyclic systems: 2-methylsulfanyl-4-(4-nitro-phenyl)-l-p-tolyl-1H-imidazole (I) and 2,4-diphenyl-l-p-tolyl-1H-imidazole (II) as the ionophores. Several ISEs were conditioned and tested for the selection of common ions. The electrodes based on these ionophores showed a good potentiometric response for Hg2+ ions over a wide concentration range of 5.0 x 10(5-) - 1.0 x 10(-1)M with near-Nernstian slopes. Stable potentiometric signals were obtained within a short time period of 20 s. The detection limits, the working pH range of the electrodes were 1.0 x 10(-5) M and 1.6-4.4 respectively. The electrodes showed better selectivity for Hg2+ ions over many of the alkali, alkaline-earth and heavy metal ions. Also sharp end points were obtained when these sensors were used as indicator electrodes for the potentiometric titration of Hg2+ ions with iodide ions.     

PVC ion-selective electrodes based on calcium bis-[dialkyl- and di-(4-alkylphenyl) phosphates] and mixed solvent mediators

PVC calcium ion-selective electrodes based on either calcium bis-di(n-decyl)phosphate or calcium bis-di[4-(1,1,3,3-tetramethylbutyl)phenyl]phosphate with various solvent mediators (alone or in pairs) have been evaluated with particular respect to interference from Na(+), K(+), Mg(2+), Sr(2+), Ba(2+), Mn(2+), Cu(2+), Ni(2+) and Zn(2+) ions. PVC calcium ion-selective electrodes based on calcium bis-di[4-(n-octyl)phenyl]phosphate with varied amounts of decan-l-ol plus di-n-octyl phenylphosphonate showed a continuous gradation in selectivity coefficients on going from a high fraction of decan-l-ol to a high fraction of the second mediator. Thus, k(pot)(Ca,Mg) changed from 1.6 for an electrode based exclusively on decan-l-ol to 4.9 x 10(-4) for one based completely on di-n-octyl phenylphosphonate. The corresponding k(pot)(Ca,Na) values were 7.0 x 10(-2) and 1.1 x 10(-3).     

New cesium ion-selective electrodes based on anilino-(1,3-dioxo-2-indanylidene) acetonitrile derivatives

Cesium ion-selective PVC membrane electrodes based on anilino-(1,3-dioxo-2-indanylidene) acetonitrile derivatives as a novel class of neutral ionophores were examined. The ionophores were p-methoxyanilino-(1,3-dioxo-2-indanylidene) acetonitrile, p-methylanilino-(1,3-dioxo-2-indanylidene) acetonitrile and p-N,N-dimethylanilino-(1,3-dioxo-2-indanylidene) acetonitrile. The anilino-(1,3-dioxo-2-indanylidene) acetonitrile proved to work well with cesium, the corresponding electrodes display a response to this ion. The most favourable ionophore was p-methoxyanilino-(1,3-dioxo-2-indanylidene) acetonitrile, especially when the secondary ion exchanger potassium tetrakis (4-chlorophenyl) borate was incorporated in 2-nitrophenyl octyl ether for ion-selective electrode membrane construction. The response function was linear within the concentration range 10(-1)-2.5x10(-5) mol l(-1) and the slope was 52 mV decade(-1). The detection limit remained at 6.3x10(-6) mol(-1). The selectivity and response time of the electrode was studied and it was found that the electrode exhibited good selectivity for cesium over alkali, alkaline earth and some transition metal ions. The electrode response was stable over a wide pH range. The lifetime of the electrode was about 1 month.     

Potentiometric determination of silver(I) by selective membrane electrode based on derivative of porphyrin.

The performance of silver metal complexes with meso-tetraphenylporphyrin ([H2T(4-CH3)]PP) as ionophores for ion-selective electrodes was studied. The electrode exhibited linear response with Nernstian slope of 59.2 +/- 1.0 mV per decade within the concentration range of 1.0 x 10(-7)-1.0 x 10(-1) M silver ions. The limit of detection as determined from the intersection of the extrapolated linear segments of the calibration plot, was 1.0 x 10(-7) M. The response time of the electrode was < 10 s over the entire concentration range. The silver-selective electrode exhibited good selectivity for Ag(I) with respect to alkali, alkaline earth and heavy metal ions. The electrodes could be used at least three months without a considerable divergence in their potential. The electrodes are suitable for use in aqueous solutions in a wide pH range of 3.0-9.0. They were used as indicator electrodes in titration of Ag(I) with sodium iodide solution and were successfully applied to direct determination of silver in real samples.     

Uranyl-selective PVC membrane electrodes based on some recently synthesized benzo-substituted macrocyclic diamides

Four different recently synthesized macrocyclic diamides were studied to characterize their abilities as uranyl ion carriers in PVC membrane electrodes. The electrodes based on macrocycle 1,18-diaza-3,4;15,16-dibenzo-5,8,11,14,21,24-hexaoxacyclohexaeicosane-2,17-dione resulted in a Nernstian response for UO(2)(2+) ion over wide concentration ranges. The linear concentration range for the polymeric membrane electrode (PME) is 3.0x10(-6)-8.2x10(-3) M with a detection limit of 2.2x10(-6) and that for the coated graphite electrode (CGE) is 5.0x10(-7)-1.5x10(-3) M with a detection limit of 3.5x10(-7) M. The electrodes manifest advantages of low resistance, very fast response and, most importantly, good selectivities relative to a wide variety of other cations.     

Triethylene glycol ether end-grafted carbosilane dendrimer: a potential ionophore for potassium ion recognition.

The performance of a newly synthesized carbosilane dendrimer bearing four triethylene glycol ether (TEG) units, Si(CH2CH2CH2Si(Me)2CH2CH2CH2(OCH2CH2)3Me)4 (1), as ionophores in ion-selective electrodes has been investigated. Optimization of the plasticized polyvinyl chloride membrane composition has produced electrodes that exhibit a Nernstian response for potassium ions. The best general characteristics exhibited by the electrodes were found when the membrane composition ratio of DPE:1:NaTPB:PVC 60:3:2:35 (wt%) was used. The response of the electrode was linear with a Nernstian slope of 58.3 mV/decade over the K+ ion concentration range of 1.9x10(-7) to 1.0x10(-1) M with a detection limit of 3.1x10(-7) M. The response time to achieve a 95% steady potential for the K+ concentration ranging from 1.0x10(-1) to 1.0x10(-8) M was less than 10 s, and it was found that the electrode is suitable for use within a pH range of 5.5-8.5. The selectivity coefficients (log KPotK+,Mn+)), which were determined by the fixed interference method, showed good selectivity for K+ against most of the interfering cations. The influence of this selective ion-binding behavior using electrospray ionization time-of-flight (ESI-TOF) mass spectrometric studies is discussed.     

Sr2GaScO5, Sr10Ga6Sc4O25, and SrGa0.75Sc0.25O2.5: a play in the octahedra to tetrahedra ratio in oxygen-deficient perovskites

Three different perovskite-related phases were isolated in the SrGa(1-x)Sc(x)O(2.5) system: Sr(2)GaScO(5), Sr(10)Ga(6)Sc(4)O(25), and SrGa(0.75)Sc(0.25)O(2.5). Sr(2)GaScO(5) (x = 0.5) crystallizes in a brownmillerite-type structure [space group (S.G.) Icmm, a = 5.91048(5) ?, b = 15.1594(1) ?, and c = 5.70926(4) ?] with complete ordering of Sc(3+) and Ga(3+) over octahedral and tetrahedral positions, respectively. The crystal structure of Sr(10)Ga(6)Sc(4)O(25) (x = 0.4) was determined by the Monte Carlo method and refined using a combination of X-ray, neutron, and electron diffraction data [S.G. I4(1)/a, a = 17.517(1) ?, c = 32.830(3) ?]. It represents a novel type of ordering of the B cations and oxygen vacancies in perovskites. The crystal structure of Sr(10)Ga(6)Sc(4)O(25) can be described as a stacking of eight perovskite layers along the c axis ...[-(Sc/Ga)O(1.6)-SrO(0.8)-(Sc/Ga)O(1.8)-SrO(0.8)-](2).... Similar to Sr(2)GaScO(5), this structure features a complete ordering of the Sc(3+) and Ga(3+) cations over octahedral and tetrahedral positions, respectively, within each layer. A specific feature of the crystal structure of Sr(10)Ga(6)Sc(4)O(25) is that one-third of the tetrahedra have one vertex not connected with other Sc/Ga cations. Further partial replacement of Sc(3+) by Ga(3+) leads to the formation of the cubic perovskite phase SrGa(0.75)Sc(0.25)O(2.5) (x = 0.25) with a = 3.9817(4) ?. This compound incorporates water molecules in the structure forming SrGa(0.75)Sc(0.25)O(2.5)·xH(2)O hydrate, which exhibits a proton conductivity of ～2.0 × 10(-6) S/cm at 673 K.     

Acyclic neutral carrier-based polymer membrane electrode for a stimulant, phentermine.

Groups of dioxadicarboxylic diamides, which were developed as potential ionophores for inorganic cations, were found to act as ionophores for a stimulant, phentermine. Especially, N,N-dioctadecyl-N',N'-dipropyl-3,6-dioxaoctanediamide, which was originally developed as a lead ionophore and is commercially available from Fluka as lead ionophore I, was suitable for making a phentermine-selective electrode. The electrode constructed using this ionophore and bis(2-ethylhexyl) sebacate as a solvent mediator in a poly(vinyl chloride) membrane matrix discriminated between phentermine and analogous compounds more effectively than an electrode based on dibenzo-18-crown-6, a representative ionophore for organic ammonium ions. Moreover, the present electrode showed remarkably little interference by inorganic cations, such as Na+ and K+, as well as lipophilic quaternary ammonium ions including (C2H5)4N+ and (C3H7)4N+. The electrode exhibited a near-Nernstian response to phentermine in the concentration range of 2 x 10(-6) to 1 x 10(-2) M with a slope of 54.8 mV per concentration decade in 0.1 M MgCl2. The lower limit of detection was 7 x 10(-7) M. This electrode was applied to determine phentermine in a cationic-exchange resin complex of this stimulant, which is the general dosage form in medical use.     

Atropine-selective membrane electrodes and relative selectivity concept

TFPB was introduced as a charged ionophore for atropine selective electrodes. Typical Nernstian responses were found (57.78, 58.95 and 58.41 mV/decade) for PVC-membrane electrodes incorporating NPOE, DOS, and DDP as plasticizers. They exhibited practical linear ranges of 9.1 x 10(-3) - 10(-6), 9.1 x 10(-3) - 10(-6) and 9.1 x 10(-3) - 10(-7) M, respectively. It works in the sub-micro scale of atropine concentrations. The optimum pH-range was 3.18 - 8.97. The selectivity coefficient values were estimated for different organic and inorganic cations. They were interpreted by using the "Relative Selectivity Concept", which was introduced for the first time. The new concept was applied for comparing the selectivity properties of previously reported electrodes. The effect of the presence of ephedrine, caffeine, glucose, Na(+), Ca(2+), and Mg(2+) on the calibration graphs of the electrodes was studied.     

Promising oxonitridosilicate phosphor host Sr3Si2O4N2: synthesis, structure, and luminescence properties activated by Eu2+ and Ce3+/Li+ for pc-LEDs

A novel oxonitridosilicate phosphor host Sr(3)Si(2)O(4)N(2) was synthesized in N(2)/H(2) (6%) atmosphere by solid state reaction at high temperature using SrCO(3), SiO(2), and Si(3)N(4) as starting materials. The crystal structure was determined by a Rietveld analysis on powder X-ray and neutron diffraction data. Sr(3)Si(2)O(4)N(2) crystallizes in cubic symmetry with space group Pa ?3, Z = 24, and cell parameter a = 15.6593(1) ?. The structure of Sr(3)Si(2)O(4)N(2) is constructed by isolated and highly corrugated 12 rings which are composed of 12 vertex-sharing [SiO(2)N(2)] tetrahedra with bridging N and terminal O to form three-dimensional tunnels to accommodate the Sr(2+) ions. The calculated band structure shows that Sr(3)Si(2)O(4)N(2) is an indirect semiconductor with a band gap ≈ 2.84 eV, which is close to the experimental value ≈ 2.71 eV from linear extrapolation of the diffuse reflection spectrum. Sr(3-x)Si(2)O(4)N(2):xEu(2+) shows a typical emission band peaking at ~600 nm under 460 nm excitation, which perfectly matches the emission of blue InGaN light-emitting diodes. For Ce(3+)/Li(+)-codoped Sr(3)Si(2)O(4)N(2), one excitation band is in the UV range (280-350 nm) and the other in the UV blue range (380-420 nm), which matches emission of near-UV light-emitting diodes. Emission of Sr(3-2x)Si(2)O(4)N(2):xCe(3+),xLi(+) shows a asymmetric broad band peaking at ~520 nm. The long-wavelength excitation and emission of Eu(2+) and Ce(3+)/Li(+)-doped Sr(3)Si(2)O(4)N(2) make them attractive for applications in phosphor-converted white light-emitting diodes.     

Silver(I) ion selective PVC membrane based on bis-pyridine tetramide macrocycle

A PVC membrane based on bis-pyridine tetramide macrocycle exhibits a good response for silver ion over a wide concentration range (1.0x10(-1)-4.0x10(-5) mol l(-1)). The electrode has a relatively fast response time and can be used for more than 5 months without observing any divergence. High selectivity for Ag(+) ions over that of Na(+), K(+), Ca(2+), Sr(2+), Pb(2+) and Hg(2+) have been observed.     

Phosphorated calix[6]arene derivatives as an ionophore for atropine-selective membrane electrodes

37,40-bis-[(diethoxy-thiophosphoryl)oxy]-5,11,17, 23,29,35-hexakis(1,1 -dimethyl-ethyl)-calix[6]arene-8,39,41,42-tetrol; 37,38,39,40,41-pentakis-(di-ethoxythiophosphoryl)-oxy]-5,11,17,23,29,35-hexakis (1,1-dimethylethyl)-calix[6]-arene-42-ol; and 37-[(diethoxythiophosphoryl)oxy]-5,11,17,23,29,35-hexakis-(1,1dimethylethyl)-calix[6]arene-38,39,40, 41,42-pentol were introduced as neutral ionophores for atropine-selective electrodes. Practical Nernstian responses were found (54.3, 49.1, and 50.8 mV/decade) for polyvinyl chloride membrane electrodes incorporating these compounds. They exhibited practical linear ranges of 1.9 x 10(-6)-7.9 x 10(-3), 7.9 x 10(-6)-7.9 x 10(-3), and 6.3 x 10(-6)-7.9 x 10(-3) M, respectively. The optimum pH range was 2.5-8.5. The selectivity coefficient values were estimated and interpreted. The electrode performance was correlated to the calixarene structure. Then, the electrode was applied to an actual analysis of pharmaceutical atropine preparations. The recovery values of 18.7 microg/mL-5.5193 mg/mL atropine sulfate were 97.5-99.1%. The corresponding relative standard deviation values ranged between 0.39-0.72% for 5 determinations. The first electrode was applied successfully for analyzing atropine sulfate in injection solution and eye drops.     

MTi(0.7)Mo(0.3)Mo(5)O(10) (M = SR, Eu), first evidence of mono- and bicapped bioctahedral Mo(11) and Mo(12) clusters: synthesis, crystal structures, and physical properties

The novel quaternary reduced molybdenum oxides MTi(0.7)Mo(0.3)Mo(5)O(10) (M = Sr, Eu) have been synthesized by solid-state reaction at 1400 degrees C for 48 h in sealed molybdenum crucibles. Their crystal structures were determined on single crystals by X-ray diffraction. Both compounds crystallize in the orthorhombic space group Pbca with 8 formula units per cell and the following lattice parameters: a(Sr) = 9.1085 (7), b(Sr) = 11.418 (1), and c(Sr) = 15.092 (3) A; a(Eu) = 9.1069 (7), b(Eu) = 11.421 (2), and c(Eu) = 15.075 (1) A. The Mo network is dominated by bioctahedral Mo(10) clusters, which coexist randomly with Mo(11) and Mo(12) clusters (monocapped and bicapped Mo(10) clusters). The Mo-Mo distances within the clusters range from 2.62 to 2.92 A and the Mo-O distances from 1.99 to 2.17 A as usually observed in the reduced molybdenum oxides. The Sr(2+) and Eu(2+) ions occupy large cavities, which result from the fusion of two cubooctahedra and thus are surrounded by 11 oxygen atoms. The M-O distances range from 2.50 to 3.23 A for the Sr compound and from 2.49 to 3.24 A for the Eu analogue. Single-crystal resistivity measurements indicate that both materials are poor metals with transitions to semiconducting states below 50 and 40 K and room temperature resistivity values of 9 x 10(-3) and 5 x 10(-3) Omega.cm for the Sr and Eu compounds, respectively. The magnetic susceptibility data indicate paramagnetic behavior due to the Eu(2+) moment at high temperatures for the Eu compound and do not reveal the existence of localized moments on the Mo and Ti sublattice in the Sr compound. An XPS study clearly suggests that the isolated Ti ions are tetravalent. Theoretical considerations preclude the existence of heterometallic Mo-Ti clusters.     

Transformation of proton-conducting Perovskite-type into fluorite-type fast oxide ion electrolytes using a CO2 capture technique and their electrical properties

Fast oxide ion conducting Ce 1- x M x O 2-delta (M = In, Sm; x = 0.1, 0.2) and Ce 0.8Sm 0.05Ca 0.15O 1.825 were prepared from the corresponding perovskite-like structured materials with nominal chemical composition of BaCe 1- x M x O 3-delta and BaCe 0.8Sm 0.05Ca 0.15O 2.825, respectively, by reacting with CO 2 at 800 degrees C for 12 h. Powder X-ray diffraction (PXRD) analysis showed the formation of fluorite-type CeO 2 and BaCO 3 just after reaction with CO 2. The amount of CO 2 gained per ceramic gram was found to be consistent with the Ba content. The CO 2 reacted samples were washed with dilute HCl and water, and the resultant solid product was characterized structurally and electrically employing various solid-state characterization methods, including PXRD, and alternating current (ac) impedance spectroscopy. The lattice constant of presently prepared Ce 1- x M x O 2-delta and Ce 0.8Sm 0.05Ca 0. 15O 1.825 by a CO 2 capture technique follows the expected ionic radii trend. For example, In-doped Ce 0.9In 0.1O 1.95 (In (3+) (VIII) = 0.92 A) sample showed a fluorite-type cell constant of 5.398(1) A, which is lower than the parent CeO 2 (5.411 A, Ce (4+) (VIII) = 0.97 A). Our attempt to prepare single-phase In-doped CeO 2 samples at 800, 1000, and 1500 degrees C using the ceramic method was unsuccessful. However, we were able to prepare single-phase Ce 0.9In 0.1O 1.95 and Ce 0.8In 0.2O 1.9 by the CO 2 capture method from the corresponding barium perovskites. The PXRD studies showed that the In-doped samples are thermodynamically unstable above 800 degrees C. The ac electrical conductivity studies using Pt electrodes showed the presence of bulk, grain-boundary, and electrode contributions over the investigated temperature range in the frequency range of 10 (-2)-10 (7) Hz. The bulk ionic conductivity and activation energy for the electrical conductivity of presently prepared Sm- and (Sm + Ca)-doped CeO 2 samples shows conductivities similar to those of materials prepared by the ceramic method reported in the literature. For instance, the conductivity of Ce 0.8Sm 0.2O 1.9 using the CO 2 capture technique was determined to be 4.1 x 10 (-3) S/cm, and the conductivity of the same sample prepared using the ceramic method was 3.9 x 10 (-3) S/cm at 500 degrees C. The apparent activation energy of the area-specific polarization resistance for the symmetric cell (Sm,Sr)CoO 3- x |Ce 0.8Sm 0.2O 1.9|(Sm,Sr)CoO 3- x was determined to be 1 eV in air.     

La1-xSrxCoC3钙钛矿在碱性溶液中的析氧电催化

 稳态极化研究结果表明, La1-xSrxCoO3电极的析氧Tafel斜率为2303RT/F, OH-的反应级数近似为1, 在阳极析氧反应中, OH-的电化学脱附为速度控制步骤. 随着La1-xSrxCoO3中Sr含量的增加,氧化物表面的粗糙度提高,当x=02时,析氧反应的活化能最低,即La0.8Sr0.2CoO3表现有最高的析氧电催化活性.     

Poly(vinyl chloride) membrane cesium ion-selective electrodes based on lipophilic calix[6]arene tetraester derivatives

New lipophilic tetraesters of calix[6]arene and calix[6]diquinone are investigated as cesium ion-selective ionophores in poly(vinyl chloride) membrane electrodes. For an ion-selective electrode based on calix[6]arene tetraester I, the linear response is 1x10(-6)-1x10(-1) M of Cs(+) concentrations. The selectivity coefficients for cesium ion over alkali, alkaline earth and ammonium ions are determined. The detection limit (log a (Cs (+))=-6.31) and the selectivity coefficient (log k (Cs (+),Rb (+))(pot )=-1.88) are obtained for polymeric membrane electrode containing calix[6]arene tetraester I.