ZnO tetrapod morphology influence on UV sensing properties.

The aim of this work was to investigate how ZnO tetrapod (ZnO-T) morphology, structure, and surface charge properties (i.e. Debye length) influence their UV sensing properties, shedding light on the underlying photoresponse mechanisms. ZnO-Ts were synthesized and centrifuged to obtain three different fractions with tuned morphology, which were characterized by scanning electron microscopy, transmission electron microscopy, and high-resolution transmission electron microscopy microscopies, x-ray diffraction analysis, Brunauer-Emmett-Teller measurements, FTIR and UV-vis spectroscopies. ZnO-T UV sensors were fabricated and tested comparing among ZnO-T fractions and commercial ZnO nanoparticles. ZnO-T photoresponse was mostly influenced by ZnO-T leg diameter, with the optimal value close to the double Debye length. We also demonstrated how fractionating ZnO-Ts for morphology optimization can increased the responsivity by 2 orders of magnitude. Moreover, ZnO-T showed 3 orders of magnitude higher responsivity compared to commercial ZnO nanopowder. These results are beneficial for the engineering of efficient UV sensors and contribute to a deeper understanding the overall mechanism governing UV photoresponse.

Roadmap on thermoelectricity.

The increasing energy demand and the ever more pressing need for clean technologies of energy conversion pose one of the most urgent and complicated issues of our age. Thermoelectricity, namely the direct conversion of waste heat into electricity, is a promising technique based on a long-standing physical phenomenon, which still has not fully developed its potential, mainly due to the low efficiency of the process. In order to improve the thermoelectric performance, a huge effort is being made by physicists, materials scientists and engineers, with the primary aims of better understanding the fundamental issues ruling the improvement of the thermoelectric figure of merit, and finally building the most efficient thermoelectric devices. In this Roadmap an overview is given about the most recent experimental and computational results obtained within the Italian research community on the optimization of composition and morphology of some thermoelectric materials, as well as on the design of thermoelectric and hybrid thermoelectric/photovoltaic devices.

Imidazo[1,5-a]pyridine-Based Fluorescent Probes: A Photophysical Investigation in Liposome Models.

Imidazo[1,5-a]pyridine is a stable scaffold, widely used for the development of emissive compounds in many application fields (e.g., optoelectronics, coordination chemistry, sensors, chemical biology). Their compact shape along with remarkable photophysical properties make them suitable candidates as cell membrane probes. The study of the membrane dynamics, hydration, and fluidity is of importance to monitor the cellular health and to explore crucial biochemical pathways. In this context, five imidazo[1,5-a]pyridine-based fluorophores were synthesized according to a one-pot cyclization between an aromatic ketone and benzaldehyde in the presence of ammonium acetate and acetic acid. The photophysical features of prepared compounds were investigated in several organic solvents and probes 2-4 exhibited the greatest solvatochromic behavior, resulting in a higher suitability as membrane probes. Their interaction with liposomes as artificial membrane model was tested showing a successful intercalation of the probes in the lipid bilayer. Kinetic experiments were carried out and the lipidic phase influence on the photophysical features was evaluated through temperature-dependent experiments. The results herein reported encourage further investigations on the use of imidazo[1,5-a]pyridine scaffold as fluorescent membrane probes.

Novel Ligand and Device Designs for Stable Light-Emitting Electrochemical Cells Based on Heteroleptic Copper(I) Complexes.

This work reports on the positive impact of (i) attaching methoxy groups at the ortho position of the bipyridine ligand (6,6'-dimethoxy-2,2'-bipyridine) in heteroleptic copper(I) complexes belonging to the [Cu(bpy)(POP)]+ family, and (ii) a new device design comprising a multilayered architecture to decouple hole/electron injection and transport processes on the performance of light-emitting electrochemical cells (LECs). In short, the substituted complex showed enhanced thermal- and photostability, photoluminescence, and ionic conductivity features in thin films compared to those of the archetypal complex without substitution. These beneficial features led to LECs outperforming reference devices in terms of luminance, stability, and efficacy. Furthermore, a new device design resulted in a 10-fold enhancement of the stability without negatively affecting the other figures of merit. Here, hole/electron injection and transport processes are performed at two different layers, while electron injection and electron-hole recombination occur at the copper(I) complex layer. As such, this work provides further insights into a smart design of N^N ligands for copper(I) complexes, opening the path to a simple device architecture toward an enhanced electroluminescence response.

Local Proton Source in Electrocatalytic CO2 Reduction with [Mn(bpy-R)(CO)3 Br] Complexes.

The electrochemical behavior of fac-[Mn(pdbpy)(CO)3 Br] (pdbpy=4-phenyl-6-(phenyl-2,6-diol)-2,2'-bipyridine) (1) in acetonitrile under Ar, and its catalytic performances for CO2 reduction with added water, 2,2,2-trifluoroethanol (TFE), and phenol are discussed in detail. Preparative-scale electrolysis experiments, carried out at -1.5 V versus the standard calomel electrode (SCE) in CO2 -saturated acetonitrile, reveal that the process selectivity is extremely sensitive to the acid strength, producing CO and formate in different faradaic yields. A detailed spectroelectrochemical (IR and UV/Vis) study under Ar and CO2 atmospheres shows that 1 undergoes fast solvolysis; however, dimer formation in acetonitrile is suppressed, resulting in an atypical reduction mechanism in comparison with other reported MnI catalysts. Spectroscopic evidence of Mn hydride formation supports the existence of different electrocatalytic CO2 reduction pathways. Furthermore, a comparative investigation performed on the new fac-[Mn(ptbpy)(CO)3 Br] (ptbpy=4-phenyl-6-(phenyl-3,4,5-triol)-2,2'-bipyridine) catalyst (2), bearing a bipyridyl derivative with OH groups in different positions to those in 1, provides complementary information about the role that the local proton source plays during the electrochemical reduction of CO2 .

Electrolyte containing lithium cation in squaraine-sensitized solar cells: interactions and consequences for performance and charge transfer dynamics.

By optimizing the lithium concentration in an electrolyte to 50 mmol L-1 and the dye-to-chenodeoxycholic acid ratio in a VG1-based dye solution, we achieved 4.7% power conversion efficiency under standard AM 1.5G conditions. In addition to this performance, we herein discuss the role played by lithium in the electrolyte and its interplay in the charge transfer processes from ms to fs dynamics. Based on electrochemical impedance spectroscopy, photoluminescence and pump-probe transient absorption spectroscopy, we conclude that although lithium increases the electron diffusion length, this has no satisfactory impact on electron injection and even slows dye regeneration. This study provides evidence that lithium is not only specifically adsorbed on the surface of TiO2 but prompts a molecular reorganization of the self-assembled dye monolayer, forming harmful H-aggregates.

Aqueous dye-sensitized solar cells.

Nowadays, dye-sensitized solar cells (DSSCs) are the most extensively investigated systems for the conversion of solar energy into electricity, particularly for implementation in devices where low cost and good performance are required. Nevertheless, a key aspect is still to be addressed, being considered strongly harmful for a long time, which is the presence of water in the cell, either in the electrolyte or at the electrode/electrolyte interface. Here comes the present review, in the course of which we try our best to address the highly topical role of water in DSSCs, trying to figure out if it is a poisoner or the keyword to success, by means of a thoroughly detailed analysis of all the established phenomena in an aqueous environment. Actually, in the last few years the scientific community has suddenly turned its efforts in the direction of using water as a solvent, as demonstrated by the amount of research articles being published in the literature. Indeed, by means of DSSCs fabricated with water-based electrolytes, reduced costs, non-flammability, reduced volatility and improved environmental compatibility could be easily achieved. As a result, an increasing number of novel electrodes, dyes and electrolyte components are continuously proposed, being highly challenging from the materials science viewpoint and with the golden thread of producing truly water-based DSSCs. If the initial purpose of DSSCs was the construction of an artificial photosynthetic system able to convert solar light into electricity, the use of water as the key component may represent a great step forward towards their widespread diffusion in the market.

Combining label-free and fluorescence operation of Bloch surface wave optical sensors.

We report on the design, fabrication, and characterization of optical sensors based on Bloch surface waves propagating at the truncation edge of one-dimensional photonic crystals. The sensors can be simultaneously operated in both a label-free mode, where small refractive index changes at the surface are detected, and a fluorescence mode, where the fluorescence from a novel heptamethyne dye label in the proximity of the surface is collected. The two modes operate in the near-infrared spectral range with the same configuration of the optical reading apparatus. The limit of detection is shown to be smaller than that of equivalent surface plasmon sensors and the fluorescence collection efficiency is such that it can be efficiently analyzed by the same camera sensor used for label-free operation.

Theoretical and experimental determination of the absorption and emission spectra of a prototypical indolenine-based squaraine dye.

The spectroscopy of a prototypical indolenine-based squaraine dye is analysed theoretically using state-of-the-art methodologies for the simulation of spectral lineshapes, and experimentally using optical absorption and emission spectroscopies. Density functional theory and its time-dependent extension are used to determine the stability of several conformers, to compute their excitation energies, equilibrium geometries and vibrational frequencies, both in the ground and in their first excited singlet state. Finally the generating function approach is used to simulate the vibronic lineshape of the low energy valence ππ* excitation and emission spectra. Solvent effects are also computed and discussed by using the polarizable continuum model. The developed model correctly reproduces the main spectral features of the squaraine, and allows us to identify the vibrational motions that mainly contribute to the observed lineshape.

Modulation of [CuOH/O]+ Properties in [2,2'-Bipyridine]2 Homoleptic Complexes through Substitution at the 6,6' Position by Methyl Groups.

In this paper, data from a DFT-based computational study on the reactivity of [Cu(2,2'-S-bpy)2]+PF6- (S indicating substitution by methyl groups at the 6 and/or 6' position and ranging from 0 to 100% through 50%) homoleptic complexes based toward tButOOH were presented. Computational results, supported by cyclic voltammetry analysis, prove the feasibility of finely tuning the chemical properties of the complexes and their reactivity by means of insertion of methyl moieties in selected positions within the bipyridine scaffold.

Exploring zinc oxide morphologies for aqueous solar cells by a photoelectrochemical, computational, and multivariate approach.

Dye-sensitized solar cells assembled with aqueous electrolytes are emerging as a sustainable photovoltaic technology suitable for safe indoor and portable electronics use. While the scientific community is exploring unconventional materials for preparing electrodes and electrolytes, this work presents the first study on zinc oxide as a semiconductor material to fabricate photoanodes for aqueous solar cells. Different morphologies (i.e., nanoparticles, multipods, and desert roses) are synthesized, characterized, and tested in laboratory-scale prototypes. This exploratory work, also integrated by a computational study and a multivariate investigation on the factors that influence electrode sensitization, confirms the possibility of using zinc oxide in the field of aqueous photovoltaics and opens the way to new morphologies and processes of functionalization or surface activation to boost the overall cell efficiency.

A UV-crosslinked polymer electrolyte membrane for quasi-solid dye-sensitized solar cells with excellent efficiency and durability.

Here we report on a novel polymer electrolyte membrane for quasi-solid dye-sensitized solar cells (DSSCs) with excellent efficiency and extended durability. The electrolyte is prepared by an elegant, rapid and cheap UV-induced polymerization method and the chemometric approach is used for the first time, to the best of our knowledge, for the optimization and the fine tuning of the experimental conditions.

Combined experimental and theoretical investigation of the hemi-squaraine/TiO2 interface for dye sensitized solar cells.

A simple hemi-squaraine dye (CT1) has been studied as a TiO2 sensitizer for application in dye sensitized solar cells (DSCs) by means of a combined experimental and theoretical investigation. This molecule is a prototype dye presenting an innovative anchoring group: the squaric acid moiety. Ab initio calculations based on Density Functional Theory (DFT) predict that this acid spontaneously deprotonates at the anatase (101) surface forming chemical bonds that are stronger than the ones formed by other linkers (e.g. cathecol and isonicotinic acid). Moreover an analysis of the electronic structure of the hybrid interface reveals the formation of a type II heterostructure ensuring adiabatic electron transfer from the molecule to the oxide. DSCs containing hemi-squaraine dyes were assembled, characterized and their performances compared to state of the art cells. Experimental results (large incident photon-to-electron conversion efficiency and an efficiency of 3.54%) confirmed the theoretical prediction that even a simple hemi-squaraine is an effective sensitizer for TiO2. Our study paves the way to the design of more efficient sensitizers based on a squaric acid linker and specifically engineered to absorb light in a larger part of the visible range.

Near-infrared sensitization in dye-sensitized solar cells.

Dye-sensitized solar cells (DSCs) are a low cost and colorful promising alternative to standard silicon photovoltaic cells. Though many of the highest efficiencies have been associated with sensitizers absorbing only in the visible portion of the solar radiation, there is a growing interest for NIR sensitization. This paper reviews the efforts made so far to find sensitizers able to absorb efficiently in the far-red NIR region of solar light. Panchromatic sensitizers as well as dyes absorbing mainly in the 650-920 nm region have been considered.

Improving Sustainability through Covalent Adaptable Networks in the Recycling of Polyurethane Plastics.

The global plastic waste problem has created an urgent need for the development of more sustainable materials and recycling processes. Polyurethane (PU) plastics, which represent 5.5% of globally produced plastics, are particularly challenging to recycle owing to their crosslinked structure. Covalent adaptable networks (CANs) based on dynamic covalent bonds have emerged as a promising solution for recycling PU waste. CANs enable the production of thermoset polymers that can be recycled using methods that are traditionally reserved for thermoplastic polymers. Reprocessing using hot-pressing techniques, in particular, proved to be more suited for the class of polyurethanes, allowing for the efficient recycling of PU materials. This Review paper explores the potential of CANs for improving the sustainability of PU recycling processes by examining different types of PU-CANs, bond types, and fillers that can be used to optimise the recycling efficiency. The paper concludes that further research is needed to develop more cost-effective and industrial-friendly techniques for recycling PU-CANs, as they can significantly contribute to sustainable development by creating recyclable thermoset polymers.

Quinoid-Thiophene-Based Covalent Organic Polymers for High Iodine Uptake: When Rational Chemical Design Counterbalances the Low Surface Area and Pore Volume.

A novel 2D covalent organic polymer (COP), based on conjugated quinoid-oligothiophene (QOT) and tris(aminophenyl) benzene (TAPB) moieties, is designed and synthesized (TAPB-QOT COP). Some DFT calculations are made to clarify the equilibrium between different QOT isomers and how they could affect the COP formation. Once synthetized, the polymer has been thoroughly characterized by spectroscopic (i.e., Raman, UV-vis), SSNMR and surface (e.g., SEM, BET) techniques, showing a modest surface area (113 m2 g-1) and micropore volume (0.014 cm3 g-1 with an averaged pore size of 5.6-8 Å). Notwithstanding this, TAPB-QOT COP shows a remarkably high iodine (I2) uptake capacity (464 %wt) comparable to or even higher than state-of-the-art porous organic polymers (POPs). These auspicious values are due to the thoughtful design of the polymer with embedded sulfur sites and a conjugated scaffold with the ability to counterbalance the relatively low pore volumes. Indeed, both morphological and Raman data, supported by computational analyses, prove the very high affinity between the S atom in our COP and the I2. As a result, TAPB-QOT COP shows the highest volumetric I2 uptake (i.e., the amount of I2 uptaken per volume unit) up to 331 g cm-3 coupled with a remarkably high reversibility (>80% after five cycles).

An Integrated Characterization Strategy on Board for Recycling of poly(vinyl butyral) (PVB) from Laminated Glass Wastes.

Polyvinyl butyral (PVB) is widely used as an interlayer material in laminated glass applications, mainly in the automotive industry, but also for construction and photovoltaic applications. Post-consumed laminated glass is a waste that is mainly landfilled; nevertheless, it can be revalorized upon efficient separation and removal of adhered glass. PVB interlayers in laminated glass are always plasticized with a significant fraction in the 20-40% w/w range of plasticizer, and they are protected from the environment by two sheets of glass. In this work, the aim is to develop a thorough characterization strategy for PVB films. Neat reference PVB grades intended for interlayer use are compared with properly processed (delaminated) post-consumed PVB grades from the automotive and construction sectors. Methods are developed to open opportunities for recycling and reuse of the latter. The plasticizer content and chemical nature are determined by applying well-known analytical techniques, namely, FT-IR, TGA, NMR. The issue of potential aging during the life cycle of the original laminated material is also addressed through NMR. Based on the findings, a sensor capable of directly sorting PVB post-consumer materials will be developed and calibrated at a later stage.

A multi-technique approach to unveil the redox behaviour and potentiality of homoleptic CuI complexes based on substituted bipyridine ligands in oxygenation reactions.

The effect of differently substituted 2,2'-bipyridine ligands (i.e. 6,6'-dimethyl-2,2'-bipyridine, 5,5'-dimethyl-2,2'-bipyridine, 6,6'-dimethoxy-2,2'-bipyridine and 2,2'-bipyridine) on the reversible oxidation of the resulting CuI homoleptic complexes is investigated by means of a multi-technique approach (electronic and vibrational spectroscopies, DFT, electrochemistry). Among the four tested complexes, [CuI(6,6'-dimethyl-2,2'-bipyridine)2] (PF6) shows a peculiar behavior when oxidized with an organic peroxide (i.e. tert-butyl hydroperoxide, tBuOOH). The simultaneous use of UV-Vis-NIR and Raman spectroscopy methods and cyclovoltammetry, supported by DFT based calculations, allowed identifying (i) the change in the oxidation state of the copper ion and (ii) some peculiar modification in the local structure of the metal leading to the formation of a [CuIIOH]+ species. The latter, being able to oxidize a model molecule (i.e. cyclohexene) and showing the restoration of the original CuI complex and the formation of cyclohexanone, confirms the potential of these simple homoleptic CuI complexes as model catalysts for partial oxygenation reactions.

Multivariate Analysis Identifying [Cu(N

White light-emitting electrochemical cells (LECs) comprising only [Cu(N^N)(P^P)]+ have not been reported yet, as all the attempts toward blue-emitting complexes failed. Multivariate analysis, based on prior-art [Cu(N^N)(P^P)]+ -based thin-film lighting (>90 papers) and refined with computational calculations, identifies the best blue-emitting [Cu(N^N)(P^P)]+ design for LECs, that is, N^N: 2-(4-(tert-butyl)phenyl)-6-(3,5-dimethyl-1H-pyrazol-1-yl)pyridine and P^P: 4,5-bis(diphenylphosphino)-9,9-dimethylxanthene, to achieve predicted thin-film emission at 490 nm and device performance of 3.8 cd A-1 @170 cd m-2 . Validation comes from synthesis, X-ray structure, thin-film spectroscopic/microscopy/electrochemical characterization, and device optimization, realizing the first [Cu(N^N)(P^P)]+ -based blue-LEC with 3.6 cd A-1 @180 cd m-2 . This represents a record performance compared to the state-of-the-art tricoordinate Cu(I)-complexes blue-LECs (0.17 cd A-1 @20 cd m-2 ). Versatility is confirmed with the synthesis of the analogous complex with 2-(4-(tert-butyl)phenyl)-6-(3,5-dimethyl-1H-pyrazol-1-yl)pyrazine (N^N), showing a close prediction/experiment match: λ = 590/580 nm; efficiency = 0.55/0.60 cd A-1 @30 cd m-2 . Finally, experimental design is applied to fabricate the best white multicomponent host:guest LEC, reducing the number of trial-error attempts toward the first white all-[Cu(N^N)(P^P)]+ -LECs with 0.6 cd A-1 @30 cd m-2 . This corresponds to approximately ten-fold enhancement compared to previous LECs (<0.05 cd A-1 @<12 cd m-2 ). Hence, this work sets in the first multivariate approach to design emitters/active layers, accomplishing first-class [Cu(N^N)(P^P)]+ -based blue/white LECs that were previously elusive.

Polymethine dyes-loaded solid lipid nanoparticles (SLN) as promising photosensitizers for biomedical applications.

Polymethine dyes (PMD) have proved to be excellent candidates in the biomedical field for potential applications in both diagnostic and therapeutic. However, PMD application in biomedicine is hindered by their poor solubility and stability in physiological conditions. Therefore, the incorporation of these dyes in nanosystems could be important to prevent the formation of dye aggregates in aqueous environment and to protect their photophysical characteristics. In the present work, two PMD based on the benzoindolenine ring (bromine benzo-cyanine-C4 and bromine benzo-squaraine-C4) were incorporated into Solid Lipid Nanoparticles (SLN) to solubilize and stabilize them in aqueous solutions. Obtained SLN showed a high incorporation efficiency for both PMD (≈90%) and not only preserved their spectroscopic properties in the NIR region even under physiological conditions but also improved them. Viability assays showed good biocompatibility of both empty and loaded nanocarriers while the cellular uptake and intracellular localization showed the effective internalization in MCF-7 cells, with a partial mitochondrial localization for CY-SLN. Moreover, in vitro phototoxicity assay showed that cyanine loaded-SLN (CY-SLN) is more photoactive than the free dye.