Artificial Photosynthesis at Soft Interfaces

Schaming, Delphine; Hatay, İmren; Cortez, Fernando; Olaya, Astrid J.; Méendez, Manuel A; Ge, Pei Yu; Deng, Haiqiang; Voyame, Patrick; Nazemi, Zahra

doi:10.2533/chimia.2011.356

Cited by 10 publications

(13 citation statements)

References 18 publications

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“…17,91,246 Insights from such studies may potentially find applications in future artificial photosynthesis systems. 247,248 The underlying fundamental reasons for any enhanced photocurrents are as yet unresolved, with electrocatalytic and/or plasmonic factors needing to be considered. Nagatani et al 246 and Schaming et al 91 observed increased photocurrents that may be attributed to increased absorption due to surface plasmons and light-trapping effects, improved charge separation due to a localized intense electromagnetic field, or perhaps electron-storage effects that alter the Fermi level of the interfacial gold nanofilm.…”

Section: Plasmonic Photocatalysismentioning

confidence: 99%

Gold Nanofilms at Liquid–Liquid Interfaces: An Emerging Platform for Redox Electrocatalysis, Nanoplasmonic Sensors, and Electrovariable Optics

et al. 2018

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The functionality of liquid-liquid interfaces formed between two immiscible electrolyte solutions (ITIES) can be markedly enhanced by modification with supramolecular assemblies or solid nanomaterials. The focus of this Review is recent progress involving ITIES modified with floating assemblies of gold nanoparticles or "nanofilms". Experimental methods to controllably modify liquid-liquid interfaces with gold nanofilms are detailed. Also, we outline an array of techniques to characterize these gold nanofilms in terms of their physiochemical properties (such as reflectivity, conductivity, catalytic activity, or plasmonic properties) and physical interfacial properties (for example, interparticle spacing and immersion depth at the interface). The ability of floating gold nanofilms to impact a diverse range of fields is demonstrated: in particular, redox electrocatalysis, surface-enhanced Raman spectroscopy (SERS) or surface plasmon resonance (SPR) based sensors, and electrovariable optical devices. Finally, perspectives on applications beyond the state-of-the-art are provided.

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Section: Plasmonic Photocatalysismentioning

confidence: 99%

Gold Nanofilms at Liquid–Liquid Interfaces: An Emerging Platform for Redox Electrocatalysis, Nanoplasmonic Sensors, and Electrovariable Optics

et al. 2018

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“…S5 showed the intensity of the signal at 5.60 ppm for the watersandwich dimer declining and new signals appearing with time. Analysis of these data shows that the photolysis of the watersandwich dimer followed [8] and [9] rather than [10][11][12] as demonstrated below by computations to form a hydroxo complex, i.e., ½Cp 2 Os IV ðOH − Þ þ (δ ¼ 6.14 ppm) and a hydride complex. The hydroxo species reacts further to a peroxo complex, i.e., Cp 2 Os IV -ðO 2 Þ (δ ¼ 6.02 and 5.56 ppm).…”

Section: H Nmr Analysismentioning

confidence: 97%

“…More generally, we have shown that voltammetry at the interface between two immiscible electrolyte solutions (ITIES) is a very useful tool to study proton coupled electron transfer reactions involving aqueous protons and organic electron donors (8)(9)(10). This methodology has been also applied to molecular electrocatalysis where an amphiphilic catalyst is used to complex oxygen to facilitate its reduction as recently reviewed (10)(11)(12)(13).…”

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confidence: 99%

Biphasic water splitting by osmocene

Todorova

Patır

et al. 2012

Proc. Natl. Acad. Sci. U.S.A.

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The photochemical reactivity of osmocene in a biphasic waterorganic solvent system has been investigated to probe its water splitting properties. The photoreduction of aqueous protons to hydrogen under anaerobic conditions induced by osmocene dissolved in 1,2-dichloroethane and the subsequent water splitting by the osmocenium metal-metal dimer formed during H 2 production were studied by electrochemical methods, UV-visible spectrometry, gas chromatography, and nuclear magnetic resonance spectroscopy. Density functional theory computations were used to validate the reaction pathways.S olar water splitting is undoubtedly a key challenge (1-3), and in the quest for solar fuels, hydrogen is definitely a major target with many industrial applications ranging from transportation to carbon dioxide mitigation (4).Interestingly, some transition metal complexes like metallocenes have been reported to reduce protons to hydrogen. In 1988, cobaltocene was found to produce hydrogen in strong acidic solutions. The mechanism was investigated by pulse radiolysis, and it was found that the reaction kinetics was first order with respect to cobaltocene and the protons pointing to a protonation of the metal as the primary step (5). In 2009, Kunkely and Vogler reported that osmocene dissolved in strong acidic solutions could photogenerate hydrogen and that ½Cp 2 Os IV ðOH − Þ þ could photogenerate oxygen (6). Proton reduction was shown to proceed also by the formation of a hydride followed under UV light by the formation of H 2 and the dimer ½Cp 2 Os III -Os III Cp 2 2þ .One of the major difficulties in studying water splitting by metallocenes is their very poor solubility in aqueous or even acidic solutions. When investigating the reduction of protons in organic phases where metallocenes are soluble, the other major drawback is the low solubility and dissociation of acids in organic solvents. One way to circumvent these issues is to carry out these reactions in biphasic systems.In 2008, we studied the reduction of aqueous protons by decamethylferrocene (DMFc) in 1,2-dichloroethane (1,2-DCE), and, here again the data suggested that the first step is the protonation of the metal (7). In particular, we have shown that hydrogen bubbles can form at the interface and that hydrogen production is associated to the oxidation of the electron donor DMFc. More generally, we have shown that voltammetry at the interface between two immiscible electrolyte solutions (ITIES) is a very useful tool to study proton coupled electron transfer reactions involving aqueous protons and organic electron donors (8-10). This methodology has been also applied to molecular electrocatalysis where an amphiphilic catalyst is used to complex oxygen to facilitate its reduction as recently reviewed (10-13).In this study, the photochemical reactivity of osmocene with water in biphasic systems has been investigated by electrochemical methods on solid electrodes and soft liquid-liquid interfaces to unravel the multistep reaction mechanisms. Density functional theory (DFT)...

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“…Liquid-liquid interfaces, or interfaces between two immiscible electrolyte solutions (ITIES), possess features suitable to engineer innovative artificial photosynthetic Z-schemes capable of driving energetically uphill chemical reactions. 4 Waterorganic interfaces can be ''dye-sensitised'' with molecular photosensitisers, 5 or trap semiconductor nanomaterials through interfacial surface tension. 6 A hydrophobicity gradient across the ITIES facilitates spatial separation of charge carriers on either side of the interface.…”

Section: Introductionmentioning

confidence: 99%