Proton‐Coupled O<sub>2</sub> Reduction Reaction Catalysed by Cobalt Phthalocyanine at Liquid/Liquid Interfaces

Li, Yan; Wu, Suozhu; Su, Bin

doi:10.1002/chem.201200191

Cited by 32 publications

(31 citation statements)

References 78 publications

(91 reference statements)

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“…Both the current at the positive potential limit and that resulting from Fc + transfer increased with increasing concentration of Fe III TMPyP. The former current signal is assigned to an interfacial ORR (as confirmed by the generation of H 2 O 2 and continuous production of Fc + in the following section), namely a proton‐coupled electron‐transfer (PCET) process, which is akin to that reported previously for similar experimental systems using ferrocene and porphyrins/phthalocyanines as the electron donor and catalysts . The catalytic ability of iron porphyrins towards O 2 reduction is well known in both chemical and biological systems.…”

Section: Resultssupporting

confidence: 70%

Unraveling the Phase‐Transfer Catalysis Mechanism of Oxygen Reduction Catalyzed by Iron(III) meso‐tetra‐(4‐N‐Methyl‐pyridyl) Porphine at the Liquid/Liquid Interface

et al. 2016

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We report an investigation of the oxygen reduction reaction (ORR) catalyzed by FeIII meso‐tetra‐(4‐N‐methyl‐pyridyl) porphine (FeIIITMPyP) at the polarized water/1,2‐dichloroethane (DCE) interface. FeIIITMPyP is a water soluble pentavalent cation, which has a standard Galvani transfer potential of +0.19 V at the water/DCE interface. By four‐electrode cyclic voltammetry and shake‐flask biphasic reactions controlled by chemical polarization at the macroscale water/DCE interface, we demonstrated that FeIIITMPyP can catalyze the reduction of O2 by electron donors (e.g., ferrocene and 1,1′‐dimethylferrocene). Further, based on voltammetry at the free‐standing silica nanochannel membrane (SNM) supported nano‐ITIES (interface between two immiscible electrolyte solutions) array where the transfer of FeIIITMPyP is physically blocked owing to the size‐exclusion effect, we proved that the overall reaction proceeds through a phase‐transfer catalysis (PTC) process, namely the heterogeneous ion transfer of FeIIITMPyP from water to DCE followed by the homogeneous catalyzed ORR in DCE.

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Section: Resultssupporting

confidence: 70%

Unraveling the Phase‐Transfer Catalysis Mechanism of Oxygen Reduction Catalyzed by Iron(III) meso‐tetra‐(4‐N‐Methyl‐pyridyl) Porphine at the Liquid/Liquid Interface

et al. 2016

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“…Previously in the literature, the presence of DiMFc + has been attributed to slow formation in air‐saturated stock solutions of DiMFc . However, no DiMFc + was detected here in the stock solution immediately prior to the voltammetry measurements (see Figure S2 in the Supporting Information).…”

Section: Resultsmentioning

confidence: 68%

Oxygen Reduction at the Liquid–Liquid Interface: Bipolar Electrochemistry through Adsorbed Graphene Layers

Rodgers

Dryfe

2015

ChemElectroChem

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The reduction of oxygen and protons at the interface between two immiscible electrolyte solutions (ITIES) has received a great deal of interest over the last decade, with various materials being used to catalyse these reactions. Probing the mechanisms through which these reactions proceed when using interfacial catalysts is important from both from the perspective of fundamental understanding and for catalyst optimisation. Herein, we have used interfacial‐assembled graphene to probe the importance of simple electron conductivity towards the catalysis of the oxygen reduction reaction (ORR) at the ITIES, and a bipolar setup to probe the homogeneous/heterogeneous nature of the ORR proceeding through interfacial graphene. We found that interfacial graphene provides a catalytic effect towards the reduction of oxygen at the ITIES, proceeding via the heterogeneous mechanism when using a strong reducing agent.

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“…The IT step can be catalysed by the presence of various aniline derivatives [9,30] and free-base-or metalloporphyrins [44,45], porphines [42] or phthalocyanines [31] in the organic phase and the desired reduction product (H 2 O versus H 2 O 2 ) can be favoured by interfacial assemblies of cobalt porphyrins [12,32,33] or choice of electron donor [10]. Recently, biphasic O 2 reduction has been achieved under neutral and alkaline conditions [17].…”

Section: Biphasic O 2 Reduction By the Ion Transfer -Electron Transfementioning

confidence: 99%

“…Whereas several reports have highlighted the catalysis of biphasic reactions by (i) facilitating the transfer of protons [12,30,31], or other ions [17], across the soft interface and (ii) the use of interfacial species, either molecular [12,32,33] or solid particulates [22,26], to coordinate reactants to enable electrocatalysis, far less common is (iii) the use of NPs as bipolar electrodes to facilitate catalysis via direct interfacial electron transfer (IET) between a lipophilic electron donor and a hydrophilic electron acceptor or vice versa [8]. Such a process is termed interfacial redox catalysis.…”

Section: Introductionmentioning

confidence: 99%

Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

Smirnov

Peljo

Scanlon

et al. 2016

Electrochimica Acta

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A B S T R A C TFunctionalization of a soft or liquid-liquid interface by a one gold nanoparticle thick "nanofilm" provides a conductive pathway to facilitate interfacial electron transfer from a lipophilic electron donor to a hydrophilic electron acceptor in a process known as interfacial redox catalysis. The gold nanoparticles in the nanofilm are charged by Fermi level equilibration with the lipophilic electron donor and act as an interfacial reservoir of electrons. Additional thermodynamic driving force can be provided by electrochemically polarising the interface. Using these principles, the biphasic reduction of oxygen by a lipophilic electron donor, decamethylferrocene, dissolved in a,a,a-trifluorotoluene was catalysed at a gold nanoparticle nanofilm modified water-oil interface. A recently developed microinjection technique was utilised to modify the interface reproducibly with the mirror-like gold nanoparticle nanofilm, while the oxidised electron donor species and the reduction product, hydrogen peroxide, were detected by ion transfer voltammetry and UV/vis spectroscopy, respectively. Metallization of the soft interface allowed the biphasic oxygen reduction reaction to proceed via an alternative mechanism with enhanced kinetics and at a significantly lower overpotential in comparison to a bare soft interface. Weaker lipophilic reductants, such as ferrocene, were capable of charging the interfacial gold nanoparticle nanofilm but did not have sufficient thermodynamic driving force to significantly elicit biphasic oxygen reduction.

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Proton‐Coupled O₂ Reduction Reaction Catalysed by Cobalt Phthalocyanine at Liquid/Liquid Interfaces

Cited by 32 publications

References 78 publications

Unraveling the Phase‐Transfer Catalysis Mechanism of Oxygen Reduction Catalyzed by Iron(III) meso‐tetra‐(4‐N‐Methyl‐pyridyl) Porphine at the Liquid/Liquid Interface

Unraveling the Phase‐Transfer Catalysis Mechanism of Oxygen Reduction Catalyzed by Iron(III) meso‐tetra‐(4‐N‐Methyl‐pyridyl) Porphine at the Liquid/Liquid Interface

Oxygen Reduction at the Liquid–Liquid Interface: Bipolar Electrochemistry through Adsorbed Graphene Layers

Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

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Proton‐Coupled O2 Reduction Reaction Catalysed by Cobalt Phthalocyanine at Liquid/Liquid Interfaces

Cited by 32 publications

References 78 publications

Unraveling the Phase‐Transfer Catalysis Mechanism of Oxygen Reduction Catalyzed by Iron(III) meso‐tetra‐(4‐N‐Methyl‐pyridyl) Porphine at the Liquid/Liquid Interface

Unraveling the Phase‐Transfer Catalysis Mechanism of Oxygen Reduction Catalyzed by Iron(III) meso‐tetra‐(4‐N‐Methyl‐pyridyl) Porphine at the Liquid/Liquid Interface

Oxygen Reduction at the Liquid–Liquid Interface: Bipolar Electrochemistry through Adsorbed Graphene Layers

Gold Nanofilm Redox Catalysis for Oxygen Reduction at Soft Interfaces

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Proton‐Coupled O₂ Reduction Reaction Catalysed by Cobalt Phthalocyanine at Liquid/Liquid Interfaces