AN ELECTROCHEMICAL STUDY OF THE REVERSIBLE REDUCTION OF ORGANIC COMPOUNDS<sup>1</sup>

Conant, James Β.; Kahn, H. M.; Fieser, Louis; Kurtz, S. S.

doi:10.1021/ja01427a020

Cited by 42 publications

(28 citation statements)

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“…The entropy contributions to the total free energies of reaction have been neglected because the entropies of reduction of quinones are found to be very similar 22,23 , and the E 0 of the oxidation-reduction system is linearly expressed as (−nF) −1 H f + b, where b is a constant. It was also assumed that the reduction of quinones takes place in a single-step reaction involving a two-electron twoproton process 9,24 . The total free energies of molecules were obtained from first-principles quantum chemical calculations within density functional theory (DFT) at the level of generalized gradient approximation (GGA) using the PBE functional 25 .…”

Section: Theory and Methodsmentioning

confidence: 99%

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A metal-free organic–inorganic aqueous flow battery

Huskinson

Marshak

Suh

et al. 2014

Nature

1,401

1,331

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This paper can be cited as: B. Huskinson, M.P. Marshak, C. Suh, S. Er, M.R. Gerhardt, C.J. Galvin, X. Chen, A. Aspuru-Guzik, R.G. Gordon and M.J. Aziz, "A metal-free organicinorganic aqueous flow battery", Nature 505, 195-198 (2014).The formatted version of this manuscript can be found at the following link: http://www.nature.com/nature/journal/v505/n7482/full/nature12909.html A metal-free organic-inorganic aqueous flow batteryBrian Huskinson 1 *, Michael P. Marshak 1,2 *, Changwon Suh 2 , Süleyman Er 2,3 , Michael R. *These authors contributed equally to this work.As the fraction of electricity generation from intermittent renewable sources-such as solar or wind-grows, the ability to store large amounts of electrical energy is of increasing importance. Solid-electrode batteries maintain discharge at peak power for far too short a time to fully regulate wind or solar power output 1,2 . In contrast, flow batteries can independently scale the power (electrode area) and energy (arbitrarily large storage volume) components of the system by maintaining all of the electro-active species in fluid form 3-5 . Wide-scale utilization of flow batteries is, however, limited by the abundance and cost of these materials, particularly those using redox-active metals and precious metal electrocatalysts 6,7 . Here we describe a class of energy storage materials that exploits the favourable chemical and electrochemical properties of a family of molecules known as quinones. The example we demonstrate is a metal-free flow battery based on the redox chemistry of 9,10-anthraquinone-2,7-disulphonic acid (AQDS). AQDS undergoes extremely rapid and reversible two-electron two-proton reduction on a glassy carbon electrode in sulphuric acid. An aqueous flow battery with inexpensive carbon electrodes, combining the quinone/hydroquinone couple with the Br 2 /Br  redox couple, yields a peak galvanic power density exceeding 0.6 W cm Solutions of AQDS in sulphuric acid (negative side) and Br 2 in HBr (positive side) were pumped through a flow cell as shown schematically in Fig. 1a. The quinone-bromide flow battery (QBFB) was constructed using a Nafion 212 membrane sandwiched between Toray carbon paper electrodes (six stacked on each side) with no catalysts; it is similar to a cell described elsewhere (see figure 2 in ref. 7). We report the potential-current response (Fig. 1b) and the potential-power relationship ( measured with respect to the quinone side of the cell). As the SOC increased from 10% to 90%, the open-circuit potential increased linearly from 0.69 V to 0.92 V. In the galvanic direction, peak power densities were 0.246 W cm 2 and 0.600 W cm 2 at these same SOCs, respectively ( Fig. 1c). In order to avoid significant water splitting in the electrolytic direction, we used a cutoff voltage of 1.5 V, at which point the current densities observed at 10% and 90% SOCs were −2.25 A cm −2 and −0.95 A cm −2 , respectively, with corresponding power densities of −3.342 W cm −2 and −1.414 W cm −2 .In Fig. 2 we report the results of initial cy...

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Section: Theory and Methodsmentioning

confidence: 99%

“…Cyclic voltammetry of a 1 mM solution of AQDS in 1 M sulphuric acid on a glassy carbon disk working electrode shows current peaks corresponding to reduction and oxidation of the anthraquinone species [9][10][11] (Fig. 3d, solid trace).…”

mentioning

confidence: 99%

A metal-free organic–inorganic aqueous flow battery

Huskinson

Marshak

Suh

et al. 2014

Nature

1,401

1,331

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“…(4) in the literature [13]. The acid dissociation of the quinone units is important, from the viewpoint of electroanalytical application of PHQ, since it might lead to instable adsorption of the film; the PHQ molecules with anionic charges are expected to dissociate into the bulk solution phase.…”

Section: Electrochemical Properties Of the Phq-electrodementioning

confidence: 99%

Poly(hydroquinone)-coated electrode for immobilizing of 5′-amine functioned capture probe DNA and electrochemical response to DNA hybridization

Nakano¹,

Hirayama²,

Toguchi³

et al. 2006

Science and Technology of Advanced Materials

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Enzymatically polymerized hydroquinone, PHQ, was applied for polymer-coated electrode whose surface was further modified with 5 0 -amine dodecamer DNAs (capture probe DNA, CP-DNA) by taking advantage of Michael reaction. The film-forming property of PHQ on graphite substrate surfaces was confirmed to be satisfactory by AFM imaging. Cyclic voltammetric (CV) measurements showed that the PHQ-modified graphite electrode gave well-defined redox waves showing characteristics for surface process. The pH dependence of the formal potential, E 1/2 , suggested that the electrode reaction occurred by two-proton and two-electron mechanism (À59 mV per a pH decade). CVs also gave the specific amount of PHQ adsorption of 0.52 or 0.83 nmol cm À2 (monomer unit) for the different electrode preparations. This was indicative of two-or three-monolayer adsorption of PHQ. For applications of gene detection, the immobilization reaction including the CP-DNA hybridization was studied by microgravimetric analysis using a quartz-crystal microbalance (QCM). Summaries for the two different runs were 1.01 and 0.69 nmol cm À2 (monomer unit) for PHQ adsorption on gold surfaces, 0.19 and 0.15 nmol cm À2 for CP-DNA attachment on the PHQ/Au, and 0.14 and 0.11 nmol cm À2 for hybridization with the complementary DNA on the CP-DNA/PHQ/Au, respectively. Importantly, monitoring of the series of the experiments were possible by measuring the voltammetric properties of the electrode; the distinct redox waves due to PHQ-electrode reaction are suppressed upon immobilizing of the CP-DNA, and its hybridization further suppressed the redox activity. Neither treating of the PHQ-electrode with native DNAs nor treating of CP-DNA/PHQ-electrode with non-target DNA gave no noticeable responses. A possible mechanism for the electrode response was discussed briefly based on electrochemical QCM measurements. We think these observations are important as the basis of DNA hybridization sensor that enables totally, label-free electrochemical detection of the target DNA. r

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“…Electrochemical behavior of redox active organic compounds in aqueous solutions has been studied for nearly a century, with research efforts dating back to the 1920s [9,10]. During this long period, the family of organic compounds termed quinones showed good electrochemical reversibility, leading to further investigation [11][12][13].…”

Section: Introductionmentioning

confidence: 99%