Electrochemistry at YBa2Cu3O7 superconductor electrodes at temperatures above Tc

McDevitt, John T.; Longmire, M. L.; Gollmar, R.; Jernigan, J. C.; Dalton, E. F.; McCarley, Robin L.; Murray, Royce W.; Little, W. A.; Yee, Gordon T.; Holcomb, Matthew J.; Hutchinson, J. E.; Collman, James P.

doi:10.1016/0022-0728(88)80049-4

Cited by 35 publications

(18 citation statements)

References 21 publications

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“…Hitherto solid electrolytes1•2 or frozen aqueous glasses3•4 have been employed, the latter involving irresolvably complex proton re-ductions3 or poorly-resolved FeII/m processes. 4 Electron transfer effected between a superconducting electrode and free electroactive species in a fluid solution offers a wider choice of systems and more intimate electrode/electrolyte contact.5 R. W. Murray et al,4"9 having developed low-temperature electrolytes and oxocuprate microelectrodes (on which low currents i minimize large iR potential drops through high electrolyte resistances R at ~100 K), now employ silver-coated oxocuprate macroelectrodes10 (with proximity-effect Ag superconduction) bearing surface-bound electroactive species.…”

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confidence: 99%

Nanoarchitectures. 3. Aggregation of hexa(phenylacetylene) macrocycles in solution: a model system for studying .pi.-.pi. interactions

1992

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mentioning

confidence: 99%

Nanoarchitectures. 3. Aggregation of hexa(phenylacetylene) macrocycles in solution: a model system for studying .pi.-.pi. interactions

1992

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“…Hitherto solid electrolytes1'2 or frozen aqueous glasses3,4 have been employed, the latter involving irresolvably complex proton re-ductions3 or poorly-resolved FeII/m processes. 4 Electron transfer effected between a superconducting electrode and free electroactive species in a fluid solution offers a wider choice of systems and more intimate electrode/electrolyte contact.5 R. W. Murray et al,4…”

mentioning

confidence: 99%

Direct electron transfer involving free-solute ferrocene in fluid electrolyte on an oxocuprate (Bi(Pb) 2223) electrode in the superconducting state

Green¹,

Rosseinsky²,

Toohey³

1992

J. Am. Chem. Soc.

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rigidly held planar geometry of PAMs promotes cooperative, ?M interactions among several pairs of aromatic rings in neighboring molecules. Consequently, weak interactions between a single pair of aromatic rings that may be difficult to observe in small molecules are amplified by the PAM molecular architecture.I6 Because our synthetic chemistry allows aromatic functionalities to be varied easily, PAMs should provide a unique opportunity to study substituent effects on a-stacking interactions. K , , . was also found to vary significantly with temperature.According to van't Hoff analyses, Lw = -5.0 f 0.2 kcal mol-' and AS = -9.2 f 0.8 cal mol-' IC1. Surprisingly, PAM 2, with alternating alkoxyl and ester groups, was found to have a smaller dimerization constant than 1 at 20 OC (K, = 18 M-I). Further studies give AH = -5.6 f 0.3 kcal mol-' and AS = -13.6 * 1.0 cal mol-] K-' for the self-association of 2. These results suggest that donoracceptor interactions between alkoxyl and ester groups slightly favor *-stacking enthalpically, but disfavor a-stacking entropically relative to 1. Overall, the entropy effect dominates near ambient temperature, resulting in a decrease in K , , for 2.The difference in AS might also indicate that the dimer pair of 2 is more highly ordered than that of 1. For 3, which has segregated alkoxyl and ester groups, it was found that K , , = 26 M-', AH = -5.1 f 0.3 kcal mol-', and AS = -10.8 f 1.0 cal mol-'

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“…These materials may have electronic properties as electrodes unlike any previously investigated. We have already reported some of our work, so far carried out above Tc (32)(33)(34), with electrodes fabricated from the superconductor ceramic materials.…”

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Liquid Phase Electrochemistry at Ultralow Temperatures

Ching

McDevitt

Peck

et al. 1991

J. Electrochem. Soc.

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Fluid electrolyte solutions based on mixtures of butyronitrile (PrCN) and ethyl chloride (EtCl) with Bu4NPF6 or Bu4NClO4 as electrolyte freeze below −180°C and provide excellent media for cryogenic electrochemical experiments. A 1:2 mixture of PrCN and EtCl exhibits the best combination of freezing point and ionic conductivity for ultralow temperature electrochemistry. Diffusion coefficients for bis(pentamethylcyclopentadienyl) iron false(Cp2*normalFefalse) are measurable by potential step chronoamperometry down to −160°C using a conventionally sized electrode, but the resistivity of the solvent mixture is such that potential sweep voltammetry benefits from the use of microdisk (10 and 25 μm diam Pt) or microband (0.2 μm wide Au) electrodes. Voltammetry at a chemically modified electrode down to −170°C is presented for the case of thin films of normalpoly‐false[normalOsfalse(normalbpy)2false(normalvpy)2false]false[PF6]2 .

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Electrochemistry at YBa2Cu3O7 superconductor electrodes at temperatures above Tc

Cited by 35 publications

References 21 publications

Nanoarchitectures. 3. Aggregation of hexa(phenylacetylene) macrocycles in solution: a model system for studying .pi.-.pi. interactions

Nanoarchitectures. 3. Aggregation of hexa(phenylacetylene) macrocycles in solution: a model system for studying .pi.-.pi. interactions

Direct electron transfer involving free-solute ferrocene in fluid electrolyte on an oxocuprate (Bi(Pb) 2223) electrode in the superconducting state

Liquid Phase Electrochemistry at Ultralow Temperatures

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