The self-assembly of the oppositely charged water-soluble porphyrins, cobalt tetramethylpyridinium porphyrin (CoTMPyP(4+)) and tetrasulphonatophenyl (CoTPPS(4-)), at interface with an organic solvent to form molecular "rafts", provides excellent catalyst perform interfacial four-electron reduction oxygen by lipophilic electron donors such as tetrathiafulvalene (TTF). catalytic activity selectivity self-assembled toward pathway was found be good that Pacman type cofacial porphyrins. assembly...

The fundamental aspects of electrochemistry at liquid-liquid interfaces are introduced to present the concept molecular electrocatalysis. Here, a catalyst is adsorbed interface promote proton coupled electron transfer reaction such as hydrogen evolution or oxygen reduction using lipophilic donors.

Redox electrocatalysis (catalysis of electron-transfer reactions by floating conductive particles) is discussed from the point-of-view Fermi level equilibration, and an overall theoretical framework given. Examples redox in solution, bipolar configuration, at liquid-liquid interfaces are provided, highlighting that interfacial systems allow study electrocatalytic properties particles without effects support, but only measurement current directly. Additionally, photoinduced will be interest,...

The four-electron reduction of oxygen by tetrathiafulvalene (TTF) in acidified 1,2-dichloroethane and at the water/1,2-dichloroethane interface has been observed. Spectroscopy ion transfer voltammetry results suggest that reaction proceeds fast protonation TTF followed 4-electron to form water. Electronic structure computations give evidence formation a helical tetramer assembly ([TTF4H2]2+) two protonated neutral molecules. is potentially able deliver four electrons needed for reduction....

The discrete nature of the charge carriers at polarised soft interfaces yields sharp potential profiles as well concentration and independent capacitances.

The photochemical reactivity of osmocene in a biphasic water-organic solvent system has been investigated to probe its water splitting properties. photoreduction aqueous protons hydrogen under anaerobic conditions induced by dissolved 1,2-dichloroethane and the subsequent osmocenium metal-metal dimer formed during H 2 production were studied electrochemical methods, UV-visible spectrometry, gas chromatography, nuclear magnetic resonance spectroscopy. Density functional theory computations...

Abstract Excitation of the weak electron donor decamethylosmocene on illumination with white light produces an excited‐state species capable reducing organically solubilized protons under biphasic conditions. Insight into mechanism and kinetics light‐driven hydrogen evolution are obtained by analysis gas chromatography, cyclic voltammetry, UV/Vis 1 H NMR spectroscopy. Formation decamethylosmocenium hydride, which occurs prior to evolution, is a rapid step relative release takes place...

Photoexcited protonated tetrathiafulvalene (HTTF+) was found to act as a photosensitizer, injecting electrons into Pt microparticles (floating electrocatalysts) produce H2 and TTF•+ in acidic acetonitrile. In addition, electrochemically reduced back TTF on carbon electrode, be further continuously photochemically. The onset potential for the electrochemical recycling of set at 500 mV more positive than required direct reduction protons. HTTF+ showed no signs decomposition after 51 h...

We report the in situ self-assembly of TTF, TTF•+, and BF4- or PF6- into p-type semiconductors on surface Pt microparticles dispersed water/acetonitrile mixtures. The visible light photoactivation these self-assemblies leads to water oxidation forming O2 H+, with an efficiency 100% respect initial concentration TTF•+. TTF•+ is then completely reduced TTF upon photoreduction water. act as floating microelectrodes whose Fermi level imposed by different redox species solution; here...

Meet at the border: Assembly of water-soluble cobalt tetrakis(N-methylpyridinium-4-yl)porphyrin [CoTMPyP](4+) soft interfaces is enhanced and stabilized by its interfacial interaction with lipophilic anion (C(6)F(5))(4)B(-). The supramolecular structure thus formed provides excellent catalytic activity in four-electron reduction oxygen.

Photoionic cells are a simple and scalable concept for direct solar energy storage, where the redox fuels produced by photoreaction separated in different phases to prevent recombination. The presence of chaotropic agents such as urea, that break structure water, was found drastically enhance quantum yield; 10-fold increase yield over 13% achieved addition chaotropes into system based on reductive quenching Azure B Co(II)EDTA water extraction leuco dye 1,2-dichloroethane.

Abstract Herein is reported the determination of Gibbs energy dioxouranium (UO 2 2+ ) transfer across an interface between two immiscible electrolytic solutions (ITIES), water and 1,2‐dichloroethane, that was supported at a 25 µm diameter microhole, by means linear sweep voltammetry. Through use minimal to no supporting electrolyte, this technique able observe ion (IT) extremely hydrophilic ions voltammetrically. As applied potential in aqueous phase became increasingly positive UO were...

The concept of artificial photosynthesis at a polarised liquid membrane is presented. It includes two photosystems, one each interface for the hydrogen and oxygen evolution respectively. Both reactions involve proton coupled electron transfer reactions, some ultrafast steps photosensitization stage.

The visible light driven water oxidation reaction (WOR) by the organic electron acceptor 2,3,5,6-tetrafluoro-7,7,8,8-tetracyano-quinodimethane (TCNQF4) was studied at water|butyronitrile interface. WOR performed neutral pH, and without any metal or organometallic catalysts. oxygen generated measured GC-MS cyclic voltammetry, protons produced were monitored measuring aqueous pH. This work opens novel perspectives for photo-oxidation in liquids artificial photosynthesis.

The electrochemical oxidation and reduction of decamethylferrocene is demonstrated in supercritical carbon dioxide at a macro gold disc electrode 100 bar 313 K. Fast mass transport effects were exhibited the corresponding steady-state voltammetry was observed high scan rates. A highly lipophilic room temperature ionic liquid that readily dissolved CO2 with acetonitrile as co-solvent used an electrolyte, allowing for conducting single phase. Experimental observations along simulation results...

We present for the first time experimental measurements on ultrafast population dynamics of model surface-active dye methyl orange (MO) during its ion transfer across water|1,2-dichloroethane interface by using time-resolved surface second harmonic generation (TR-SSHG). The interfacial reveals that MO relaxes to ground state within 160 fs without any significant contribution molecular reorientation. It is concluded considerably affects at but has no effect molecule itself.

We show with time-resolved second harmonic generation and molecular mechanics simulations that the kinetics of a two-dimensional triplet–triplet annihilation reaction at liquid–liquid interface is affected by crowding.

Sustainable water oxidation requires low-cost, stable, and efficient redox couples, photosensitizers, catalysts. Here, we introduce the in situ self-assembly of metal-atom-free organic-based semiconductive structures on surface carbon supports. The resulting TTF/TTF•+@carbon junction (TTF = tetrathiafulvalene) acts as an all-in-one highly stable redox-shuttle/photosensitizer/molecular-catalyst triad for visible-light-driven reaction (WOR) at neutral pH, eliminating need metallic or...

Katalytischer Grenzgänger: Die Anordnung von wasserlöslichem Cobalt-tetrakis(N-methylpyridinium-4-yl)porphyrin [CoTMPyP]4+ an „weichen“ Grenzflächen wird durch seine Grenzflächenwechselwirkung mit dem lipophilen Anion (C6F5)4B− stabilisiert (siehe Bild). resultierende supramolekulare Struktur ist hoch aktiv in der katalytischen Vier-Elektronen-Reduktion Sauerstoff.