H<sub>2</sub>O<sub>2</sub> Generation by Decamethylferrocene at a Liquid|Liquid Interface

Su, Bin; Nia, Raheleh Partovi; Li, Fēi; Hojeij, Mohamad; Prudent, Michel; Corminbœuf, Clémence; Samec, Zdeněk; Girault, Hubert H.

doi:10.1002/anie.200801004

Cited by 90 publications

(132 citation statements)

References 28 publications

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“…Triiodide was generated by oxidation of iodide by H 2 O 2 . 7 These results suggest the occurrence of oxygen reduction to H 2 O 2 by DMFc in DCE in the presence of the organic acid:…”

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confidence: 82%

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Oxygen and proton reduction by decamethylferrocene in non-aqueous acidic media

Hatay

et al. 2010

Chem. Commun.

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Experimental studies and density functional theory (DFT) computations suggest that oxygen and proton reduction by decamethylferrocene (DMFc) in 1,2-dichloroethane involves protonated DMFc, DMFcH + , as an active intermediate species, producing hydrogen peroxide and hydrogen in aerobic and anaerobic conditions, respectively.O 2 reduction by ferrocene and its derivatives in organic media in the presence of an acid, such as trichloroacetic and trifluoroacetic acids and perchloric acid, has been known for many years. [1][2][3][4][5] Recently, O 2 reduction has also been studied in biphasic systems composed of an organic solvent containing a ferrocene derivative in contact with an aqueous inorganic acid solution containing a very lipophilic anion. 6-8 At such liquid-liquid interfaces, O 2 reduction takes place by involving the lipophilic electron donors i.e. ferrocene derivatives located in the organic phase and aqueous protons. Moreover, it has been found that in the same biphasic system the electron-rich decamethylferrocene (DMFc) can also reduce aqueous protons under anaerobic conditions, leading to the evolution of hydrogen. 9 In both cases, the reaction has been proposed to proceed in two steps: first a heterogeneous proton transfer facilitated by DMFc from the aqueous to the organic phase as observed by voltammetry experiments at liquid-liquid interfaces, followed by a homogenous proton/oxygen reduction in the organic phase, the mechanism of which being yet unresolved. In this communication, we present experimental results for oxygen/proton reductions by DMFc in bulk 1,2-dichloroethane (DCE) in the presence of organic acids. In the case of oxygen reduction, DFT computations support a reaction pathway involving protonated DMFc, DMFcH + , as an intermediate species, which reacts with oxygen to produce hydrogen peroxide. Fig. 1a illustrates an experiment performed in DCE under aerobic conditions. A dilute solution of DMFc appeared yellow, to which addition of an acid, hydrogen tetrakis(pentafluorophenyl)borate (HTB),y led to an immediate colour change to bright green. In the UV-visible spectrum, the absorption band of DMFc centered at 425 nm is replaced by a strong band of DMFc + at 779 nm. Moreover, by shaking the green organic solution with pure water and then by titrating this aqueous phase with sodium iodide (NaI), triiodide was detected with a spectroscopic signature at 286 nm and 330 nm. Triiodide was generated by oxidation of iodide by H 2 O 2 . 7 These results suggest the occurrence of oxygen reduction to H 2 O 2 by DMFc in DCE in the presence of the organic acid:However, only 0.03 mM of H 2 O 2 was detected, an amount which is about five times less than that of DMFc + produced (1.5 mM). This indicates a much lower yield than the stoichiometric value for H 2 O 2 . One possible reason is the further reduction of H 2 O 2 by DMFc to finally produce water. Indeed, in biphasic systems, the yield of H 2 O 2 can reach 40% as its extraction to water competes with further reduction. 7 Another possible reason for th...

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“…Triiodide was generated by oxidation of iodide by H 2 O 2 . 7 These results suggest the occurrence of oxygen reduction to H 2 O 2 by DMFc in DCE in the presence of the organic acid:…”

mentioning

confidence: 82%

“…Indeed, in biphasic systems, the yield of H 2 O 2 can reach 40% as its extraction to water competes with further reduction. 7 Another possible reason for this low yield is the competing proton reduction. The latter hypothesis was investigated by performing the same experiment under anaerobic conditions.…”

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confidence: 99%

Oxygen and proton reduction by decamethylferrocene in non-aqueous acidic media

Hatay

et al. 2010

Chem. Commun.

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“…Furthermore, by controlling the polarization of the interface, it is possible to control the rate of either proton or electron transfer across the interface. Recently, we have investigated oxygen reduction by lipophilic donors in 1,2-dichloroethane (DCE) in contact with aqueous acid solutions and shown that the final product of this biphasic reaction was hydrogen peroxide (H 2 O 2 ) in water [4].…”

Section: Introductionmentioning

confidence: 99%

Detection of hydrogen peroxide produced at a liquid/liquid interface using scanning electrochemical microscopy

Salazar

et al. 2009

Electrochemistry Communications

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a b s t r a c tScanning electrochemical microscopy (SECM) was used to monitor in situ hydrogen peroxide (H 2 O 2 ) produced at a polarized water/1,2-dichloroethane (DCE) interface. The water/DCE interface was formed between a DCE droplet containing decamethylferrocene (DMFc) supported on a solid electrode and an acidic aqueous solution. H 2 O 2 was generated by reducing oxygen with DMFc at the water/DCE interface, and was detected with a SECM tip positioned in the vicinity of the interface using a substrate generation/ tip collection mode. This work shows unambiguously how the H 2 O 2 generation depends on the polarization of the liquid/liquid interface, and how proton-coupled electron transfer reactions can be controlled at liquid/liquid interfaces.

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“…10,11 This control of the polarization can be used to drive or monitor adsorption or desorption processes 8,9,12 as well as to conduct and investigate ion 7,13 and/or electron transfer reactions across the interface. 14 Assisted ion transfer reactions are an important class of charge transfer reactions where ligands or ionophores in the organic phase can interfacially complex aqueous ions to extract them to the organic phase. 5,6,15,16 The electrochemical methodology can be used to determine the stoichiometry of the organic complexes, as well as their lipophilicity.…”

Section: Introductionmentioning

confidence: 99%

Biphasic Electrospray Ionization for the Study of Interfacial Complexes

Prudent

Méndez

2008

ANAL. SCI.

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Biphasic electrospray ionization (BESI) mass spectrometry is achieved by using a dual-channel microsprayer, where channels filled with different immiscible phases meet at the Taylor cone. Two types of interfacial complexation reactions have been studied: the interfacial complexation of aqueous lead ions by thioether crown molecules, and the interfacial complexation of an aqueous dipeptide by dibenzo-18-crown-6 as ionophore. The mass spectra also give valuable information on the stoichiometry of the complexation reaction.

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H₂O₂ Generation by Decamethylferrocene at a Liquid|Liquid Interface

Cited by 90 publications

References 28 publications

Oxygen and proton reduction by decamethylferrocene in non-aqueous acidic media

Oxygen and proton reduction by decamethylferrocene in non-aqueous acidic media

Detection of hydrogen peroxide produced at a liquid/liquid interface using scanning electrochemical microscopy

Biphasic Electrospray Ionization for the Study of Interfacial Complexes

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H2O2 Generation by Decamethylferrocene at a Liquid|Liquid Interface

Cited by 90 publications

References 28 publications

Oxygen and proton reduction by decamethylferrocene in non-aqueous acidic media

Oxygen and proton reduction by decamethylferrocene in non-aqueous acidic media

Detection of hydrogen peroxide produced at a liquid/liquid interface using scanning electrochemical microscopy

Biphasic Electrospray Ionization for the Study of Interfacial Complexes

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Product

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H₂O₂ Generation by Decamethylferrocene at a Liquid|Liquid Interface