000200488 001__ 200488
000200488 005__ 20190316235947.0
000200488 0247_ $$2doi$$a10.1016/j.jelechem.2014.07.001
000200488 022__ $$a1572-6657
000200488 02470 $$2ISI$$a000342269300007
000200488 037__ $$aARTICLE
000200488 245__ $$aMechanism of oxygen reduction by metallocenes near liquid|liquid interfaces
000200488 260__ $$bElsevier$$c2014$$aLausanne
000200488 269__ $$a2014
000200488 300__ $$a10
000200488 336__ $$aJournal Articles
000200488 520__ $$aThe mechanism of the oxygen reduction reaction (ORR) at a liquid|liquid interface, employing ferrocene (Fc) derivatives – such as decamethylferrocene (DMFc) – as a lipophilic electron donor along with sulfuric acid as an aqueous proton source, was elucidated through comparison of experimentally obtained cyclic voltammograms (CVs) to simulated CVs generated through COMSOL Multiphysics software which employs the finite element method (FEM). The simulations incorporated a potential dependent proton transfer (i.e . ion transfer, IT) step from the water (w) to organic (o) phases along with two homogeneous reactions (C1C2) occurring in the organic phase – an IT-C1C2 mechanism. The reaction of DMFc with H+(o) to form DMFc-hydride (DMFc-H+) was considered the first step (reaction 1), while reaction of DMFc-H+ with oxygen to form a peroxyl radical species, View the MathML sourceHO2, and DMFc+ was deemed the second step (reaction 2). Subsequent reactions, between View the MathML sourceHO2 and either DMFc or H+, were considered to be fast and irreversible so that 2 was a ‘proton-sink’, such that further reactions were not included; in this way, the simulation was greatly simplified. The rate of 1, kcf, and 2, kchem, were determined to be 5 × 102 and 1 × 104 L mol−1 s−1, respectively, for DMFc as the electron donor. Similarly, the rates of biphasic ORR for 1,1′-dimethylferrocene (DFc) and Fc were considered equivalent in terms of this reaction mechanism; therefore, their rates were determined to be 1 × 102 and 5 × 102 L mol−1 s−1 for 1 and 2, respectively. The reactive and diffusive layer thicknesses are also discussed.
000200488 6531_ $$aOxygen reduction reaction
000200488 6531_ $$aLiquidiliquid interface
000200488 6531_ $$aDecamethy/ferrocene
000200488 6531_ $$aFerrocene
000200488 6531_ $$a1
000200488 6531_ $$a1 '-Dimethylferrocene
000200488 6531_ $$aCOMSOL
000200488 700__ $$0247544$$g208534$$aJane Stockmann, T.
000200488 700__ $$0244421$$g199475$$aDeng, Haiqiang
000200488 700__ $$0247474$$g218461$$aPeljo, Pekka
000200488 700__ $$aKontturi, Kyösti
000200488 700__ $$aOpallo, Marcin
000200488 700__ $$0242739$$g105258$$aGirault, Hubert H.
000200488 773__ $$j729$$tJournal of Electroanalytical Chemistry$$q43-52
000200488 8564_ $$uhttps://infoscience.epfl.ch/record/200488/files/1-s2.0-S1572665714002811-fx1.jpg$$zTOC$$s21166$$yTOC
000200488 8564_ $$uhttps://infoscience.epfl.ch/record/200488/files/1-s2.0-S1572665714002811-main.pdf$$zPublisher's version$$s1851866$$yPublisher's version
000200488 8564_ $$uhttps://infoscience.epfl.ch/record/200488/files/mmc1.pdf$$zSupporting Information$$s828602$$ySupporting Information
000200488 909C0 $$xU10100$$0252090$$pLEPA
000200488 909CO $$ooai:infoscience.tind.io:200488$$qGLOBAL_SET$$pSB$$particle
000200488 917Z8 $$x208650
000200488 917Z8 $$x208650
000200488 937__ $$aEPFL-ARTICLE-200488
000200488 973__ $$rREVIEWED$$sPUBLISHED$$aEPFL
000200488 980__ $$aARTICLE