Alberto Savoini

Photoanodes Based on Nanostructured WO3 for Water Splitting

Anodically grown WO(3) photoelectrodes prepared in an N-methylformamide (NMF) electrolyte have been investigated with the aim of exploring the effects induced by anodization time and water concentration in the electrochemical bath on the properties of the resulting photoanodes. An n-type WO(3) semiconductor is one of the most promising photoanodes for hydrogen production from water splitting and the electrochemical anodization of tungsten allows very good photoelectrodes, which are characterized by a low charge-transfer resistance and an increased spectral response in the visible region, to be obtained. These photoanodes were investigated by a combination of steady state and transient photoelectrochemical techniques and a correlation between photocurrent produced, morphology, and charge transport has been evaluated.

Hybrid organic–inorganic H2-evolving photocathodes: understanding the route towards high performance organic photoelectrochemical water splitting

A promising, yet challenging, route towards renewable production of hydrogen is the direct conversion of solar energy at a simple and low cost semiconductor/water junction. Despite the theoretical simplicity of such a photoelectrochemical device, different limitations among candidate semiconductor materials have hindered its development. After many decades of research on inorganic semiconductors, a conclusive solution still appears out of reach. Here, we report an efficient hybrid organic–inorganic H2 evolving photocathode, consisting of a donor/acceptor blend sandwiched between charge-selective layers and a thin electrocatalyst layer. The role and stability of the different interfaces are investigated, and the conductive polymer is proven to be an efficient material for a semiconductor/liquid PEC junction. The best performing electrodes show high performances with a photocurrent of 3 mA cm−2 at 0 V vs. RHE, optimal process stability with 100% faradaic efficiency during electrodes lifetime, excellent energetics with +0.67 V vs. RHE onset potential, promising operational activity of several hours and by-design compatibility for implementation in a tandem architecture. This work demonstrates organic semiconductors as a radically new option for efficient direct conversion of solar energy into fuels, and points out the route towards high performance organic photoelectrochemical water splitting.

Neat C70-Based Bulk-Heterojunction Polymer Solar Cells with Excellent Acceptor Dispersion

The replacement of common fullerene derivatives with neat-C70 could be an effective approach to restrain the costs of organic photovoltaics and increase their sustainability. In this study, bulk-heterojunction solar cells made of neat-C70 and low energy-gap conjugated polymers, PTB7 and PCDTBT, are thoroughly investigated and compared. Upon replacing PC70BM with C70, the mobility of positive carriers in the donor phase is roughly reduced by 1 order of magnitude, while that of electrons is only slightly modified. It is shown that the main loss mechanism of the investigated neat-C70 solar cells is a low mobility-lifetime product. Nevertheless, PCDTBT:C70 devices undergo a limited loss of 7.5%, compared to the reference PCDTBT:PC70BM cells, reaching a record efficiency (4.44%) for polymer solar cells with unfunctionalized fullerenes. The moderate efficiency loss of PCDTBT:C70 devices, due to an unexpected excellent miscibility of PCDTBT:C70 blends, demonstrates that efficient solar cells made of neat-fullerene are possible. The efficient dispersion of C70 in the PCDTBT matrix is attributed to an interaction between fullerene and the carbazole unit of the polymer.

Reactivity of decafluorobenzophenone and decafluoroazobenzene towards aromatic diamines: a practical entry to donor–acceptor systems

A series of Donor–Acceptor–Donor (D–A–D) and Acceptor–Donor–Acceptor (A–D–A) compounds have been prepared exploiting the relative ability of polyfluorinated azobenzenes and benzophenone to undergo aromatic nucleophilic substitution reactions with aromatic amines. A high para-regioselectivity is obtained when fluorene and carbazole-based diamines have been used in a high Donor Number solvent environment such as DMSO. The prepared triads have been employed in the synthesis of oligomers with the aim of evaluating them as photovoltaic material additives in optoelectronic applications.

Hyperspectral imaging of polymer/fullerene blends

Abstract The effectiveness of a hyperspectral imaging system integrated on an enhanced dark-field microscope for probing the microscale morphology of model poly(3- hexylthiopene): [6,6]-phenyl-C61- butyric acid methyl ester (P3HT:PCBM) blends is demonstrated. This non-contact technique provides both spectral and spatial information in one measurement, providing an effective mapping of the presence and location of the component materials in the investigated P3HT:PCBM blends spincoated over different substrates (zinc oxide, poly(3,4- ethylenedioxythiophene):poly(styrenesulfonate). The hyperspectral analysis accounts for the micro-scale morphology of P3HT:PCBM blends, even in case of high film roughness, and the quantitative determination of blend components reveals a preferential accumulation of the lowenergy material (P3HT) at the interface with air, confirming the findings reported with other mapping techniques