A series of electron donor−acceptor (DA) dyads, composed of a porphyrin donor and a fullerene acceptor
covalently linked with two molecular chains, were used to fabricate solid molecular films with the Langmuir−Blodgett (LB) technique. By means of the LB technique, the DA molecules can be oriented perpendicular
to the plane of the substrate. In DHD6ee and its zinc derivative hydrophilic groups are attached to the
phenyl moieties in the porphyrin end of the molecule; while in the other three dyads, TBD6a, TBD6hp,
and TBD4hp, the hydrophilic groups are in the fullerene end of the molecule. This makes it possible to
alternate the orientation of the molecules in two opposite directions with respect to the air−water interface
and to fabricate molecular assemblies in which the direction of the primary photoinduced vectorial electron
transfer can be controlled both by the deposition direction of the LB monolayer and by the selection of the
used DA molecule. This was proved by the time-resolved Maxwell displacement charge measurements.
The spectroscopic properties of the DA films were studied with the steady-state absorption and fluorescence
methods. In addition, the time correlated single photon counting technique was used to determine the
fluorescence properties of the dyad films.
Harnessing solar energy for the production of clean hydrogen by photoelectrochemical water splitting represents a very attractive, but challenging approach for sustainable energy generation. In this regard, the fabrication of Fe2O3–TiO2 photoanodes is reported, showing attractive performances [≈2.0 mA cm−2 at 1.23 V vs. the reversible hydrogen electrode in 1 M NaOH] under simulated one‐sun illumination. This goal, corresponding to a tenfold photoactivity enhancement with respect to bare Fe2O3, is achieved by atomic layer deposition of TiO2 over hematite (α‐Fe2O3) nanostructures fabricated by plasma enhanced‐chemical vapor deposition and final annealing at 650 °C. The adopted approach enables an intimate Fe2O3–TiO2 coupling, resulting in an electronic interplay at the Fe2O3/TiO2 interface. The reasons for the photocurrent enhancement determined by TiO2 overlayers with increasing thickness are unraveled by a detailed chemico‐physical investigation, as well as by the study of photogenerated charge carrier dynamics. Transient absorption spectroscopy shows that the increased photoelectrochemical response of heterostructured photoanodes compared to bare hematite is due to an enhanced separation of photogenerated charge carriers and more favorable hole dynamics for water oxidation. The stable responses obtained even in simulated seawater provides a feasible route in view of the eventual large‐scale generation of renewable energy.
Harvesting radiant energy to trigger water photoelectrolysis and produce clean hydrogen is receiving increasing attention in the search of alternative energy resources. In this regard, hematite (α-Fe2O3) nanostructures with controlled nano-organization have been fabricated and investigated for use as anodes in photoelectrochemical (PEC) cells. The target systems have been grown on conductive substrates by plasma enhanced-chemical vapor deposition (PE-CVD) and subjected to eventual ex situ annealing in air to further tailor their structure and properties. A detailed multitechnique approach has enabled to elucidate the interrelations between system characteristics and the generated photocurrent. The present α-Fe2O3 systems are characterized by a high purity and hierarchical morphologies consisting of nanopyramids/organized dendrites, offering a high contact area with the electrolyte. PEC data reveal a dramatic response enhancement upon thermal treatment, related to a more efficient electron transfer. The reasons underlying such a phenomenon are elucidated and discussed by transient absorption spectroscopy (TAS) studies of photogenerated charge carrier kinetics, investigated on different time scales for the first time on PE-CVD Fe2O3 nanostructures.
The long term stability of air processed inkjet infiltrated carbon based perovskite solar cells (CPSCs) is investigated under intense ultra-violet light soaking equivalent to 1.5 Sun UV light illumination.
Nanocomposite Fe2O3Co3O4 photoanodes for photoelectrochemical H2O splitting were prepared by a plasma‐assisted route. Specifically, Fe2O3 nanostructures were grown by plasma enhanced‐chemical vapor deposition, followed by cobalt sputtering for different process durations. The systems were annealed in air after, or both prior and after, sputtering of Co, to analyze the treatment influence on functional performances. The interplay between processing conditions and chemico‐physical features was investigated by a multi‐technique characterization. Photocurrent density measurements in sunlight‐assisted H2O splitting revealed a performance improvement upon Co3O4 loading. A cathodic shift of the onset potential was also observed, highlighting Co3O4 activity as catalyst for the oxygen evolution reaction.
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