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Nitrogen doped tin(iv) oxide (SnO2) materials in the form of nanometric powders have been prepared by precipitation with ammonia. Their properties have been compared with those of undoped materials obtained in a similar way using various physical techniques such as photoelectron spectroscopies (XPS and UPS), UV-Vis-NIR spectroscopy and electron paramagnetic resonance (EPR). Nitrogen doping leads to the formation of various nitrogen containing species, the more relevant of which is a nitride-type ionic species, based on the substitution of a lattice oxygen atom with a nitrogen atom. This species exists in two forms, paramagnetic (hole centre, formally N2−) and diamagnetic (N3−). The mutual ratio of the two species varies according to the oxidation state of the material. The doped solid, like most of the semiconducting oxides, tends to lose oxygen forming oxygen vacancies upon annealing under vacuum and leaving an excess of electrons in the solid. The stoichiometry of the solid can thus be markedly changed depending on the external conditions. Excess electrons are present both as itinerant electrons in the conduction band and as Sn(ii) states lying close to the valence band maximum. The presence of nitride-type centres, which are low energy states located below the top of the valence band, decreases the energy cost for the formation of oxygen vacancies by O2 release from the lattice. This particular feature of the doped system represents a severe limit to the preparation of a p-type SnO2via nitrogen doping. [ABSTRACT FROM AUTHOR]

Two novel symmetrical blue squaraine sensitizers were synthesized, which exhibit panchromatic light harvesting and a record efficiency over 6% with Jsc exceeding 14 mA cm−2, and Voc over 620 mV under 1 sun. Their color, low cost, easiness of synthesis, and relatively high photo- and thermal stability open up the way for commercial applications. [ABSTRACT FROM AUTHOR]

In this study, we present for the first time the incorporation of two distinct nonsymmetrical squaraines (SQ) into hierarchically porous Hafnium-based UiO-66 Metal-Organic Frameworks (MOFs), each functionalized with various moieties, for application as photosensitizers in photodynamic therapy. SQs are meticulously designed to feature COOH moieties for interaction with the MOF's metallic cluster and bromine atoms to enhance intersystem crossing and reactive oxygen species (ROS) production. The distinct central functionalizations, one with squaric acid and the other with a dicyanovinyl-substituted squaric acid derivative, result in unique geometric conformations. The latter, as well as the molecular size and density, have been analyzed by computational methods, facilitating the optimal design of MOF cavities for SQ accommodation. Our synthetic methodology involves the production of hierarchically porous Hf-MOFs that integrate both micro- and mesopores. The resultant SQ@MOF systems preserve photosensitizing properties, enhancing solubility and stability without compromising ROS generation or MOF structural integrity. As proof of concept, in vitro evaluations against PANC-1 cells were evaluated, demonstrating the cytocompatibility of SQ@MOFs in the dark up to concentrations of 200 μg mL -1 . Photoactivity is assessed using a statistical multivariate design, enabling identification of the SQ@MOF system with the highest phototoxicity and determination of the variables that significantly influence phototoxicity.

In this contribution, we tackle the replacement of the Hg-based catalyst and fossil-derived isocyanate precursors toward the formulation of a more sustainable polyurethane thermosetting resins (PUs), emulating the performance of a fully fossil-based one employed in industrial encapsulation of optoelectronics. A mixed Bi-Zn catalyst and a 71% bio-based isocyanate are exploited at this aim through multivariate chemometric approaches, namely Design of Experiment (DoE). DoE allows us to investigate the effect of different formulation factors on selected parameters, such as the film flexibility and transparency or the gel time. More in detail, it is found that a low amount of Zn-rich catalytic mixture leads to a ready-to-market polyurethane only when a fossil-based isocyanate is used. Differently, PUs formulated with bio-based isocyanate, albeit showing a higher bio-based content, present an insufficient optical purity, jeopardizing their market acceptability. Nevertheless, adding a negligible amount of a specific long chain fatty acid as reactivity modulator in the formulation leads to a bubbles-free and ready-to-market resin showing an impressive 65% w/w content of circular and bio-based components., (© 2024 Wiley‐VCH GmbH.)

Polyvinyl butyral (PVB) is a high-performance thermoplastic polymer, commonly used as an interlayer material in laminated safety glass for the automotive and architectural sectors. Currently, there is no end-of-life cycle program for a substantial amount of PVB film, which mainly ends up in landfills. According to a circular approach, PVB can be revalorized after efficient separation and recovery from glass. Thus, the aim of this work was to develop functional coatings for textile applications using recycled PVB (re-PVB), also in combination with an organic UV absorber, to enable the production of UV-protective final coated fabrics. The re-PVB-coated fabrics were obtained through an industrially scalable spraying process (leading to an average weight increase of 20 ± 3 wt.%), and the effectiveness of the application was evaluated according to different characterization techniques, such as FT-IR (Fourier transform-infrared) spectroscopy, SEM (scanning electron microscope), a washing test, a mechanical test, a thermo-physiological test, and the ultraviolet protection factor (UPF). Based on the results, the re-PVB-coated fabrics appeared stable upon washing (with a negligible weight loss compared to the average amount of coating) and effective in UV protection (with a final UPF being four times higher and a reduced UVA transmittance from 2.0% to 0.6%).

Until recently, recycling thermoset polyurethanes (PUs) was limited to degrading methods. The development of covalent adaptable networks (CANs), to which PUs can be assigned, has opened novel possibilities for actual recycling. Most efforts in this area have been directed toward inventing new materials that can benefit from CAN theory; presently, little or nothing has been applied to industrially producible materials. In this study, both an industrially available polyol (Sovermol780 ® ) and isocyanate (Tolonate X FLO 100 ® ) with percentages of bioderived components were employed, resulting in a potentially scalable and industrially producible material. The resultant network could be reworked up to three times, maintaining the crosslinked structure without significantly changing the thermal properties. Improvements in mechanical parameters were observed when comparing the pristine material to the material exposed to three rework processes, with gains of roughly 50% in elongation at break and 20% in tensile strength despite a 25% decrease in Young's modulus and crosslink density. Thus, it was demonstrated that theory may be profitably applied even to materials that are not designed including additional bonds but instead rely just on the dynamic urethane bond that is naturally present in the network.

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., Competing Interests: There are no conflicts to declare., (This journal is © The Royal Society of Chemistry.)

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., Competing Interests: The authors declare no competing financial interest., (© 2024 The Authors. Published by American Chemical Society.)

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.

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., (Creative Commons Attribution license.)

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.

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., (Creative Commons Attribution license.)

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 m 2 g -1 ) and micropore volume (0.014 cm 3 g -1 with an averaged pore size of 5.6-8 Å). Notwithstanding this, TAPB-QOT COP shows a remarkably high iodine (I 2 ) 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 I 2 . As a result, TAPB-QOT COP shows the highest volumetric I 2 uptake ( i.e. , the amount of I 2 uptaken per volume unit) up to 331 g cm -3 coupled with a remarkably high reversibility (>80% after five cycles).

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 Cu I homoleptic complexes is investigated by means of a multi-technique approach (electronic and vibrational spectroscopies, DFT, electrochemistry). Among the four tested complexes, [Cu I (6,6'-dimethyl-2,2'-bipyridine) 2 ] (PF 6 ) shows a peculiar behavior when oxidized with an organic peroxide ( i.e. tert -butyl hydroperoxide, t BuOOH). 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 [Cu II OH] + species. The latter, being able to oxidize a model molecule ( i.e. cyclohexene) and showing the restoration of the original Cu I complex and the formation of cyclohexanone, confirms the potential of these simple homoleptic Cu I complexes as model catalysts for partial oxygenation reactions.

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.

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., Competing Interests: Declaration of Competing Interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Copyright © 2022 Elsevier B.V. All rights reserved.)

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., (© 2022 The Authors. Advanced Materials published by Wiley-VCH GmbH.)

In the quest for sustainable materials for quasi-solid-state (QS) electrolytes in aqueous dye-sensitized solar cells (DSSCs), novel bioderived polymeric membranes were prepared in this work by reaction of preoxidized kraft lignin with poly(ethylene glycol)diglycidylether (PEGDGE). The effect of the PEGDGE/lignin relative proportions on the characteristics of the obtained membranes was thoroughly investigated, and clear structure-property correlations were highlighted. In particular, the glass transition temperature of the materials was found to decrease by increasing the amount of PEGDGE in the formulation, indicating that polyethylene glycol chains act as flexible segments that increase the molecular mobility of the three-dimensional polymeric network. Concurrently, their swelling ability in liquid electrolyte was found to increase with the concentration of PEGDGE, which was also shown to influence the ionic transport efficiency within the membrane. The incorporation of these lignin-based cross-linked systems as QS electrolyte frameworks in aqueous DSSCs allowed the preparation of devices with excellent long-term stability under UV-vis light, which were found to be superior to benchmark QS-DSSCs incorporating state-of-the-art carboxymethylcellulose membranes. This study provides the first demonstration of lignin-based QS electrolytes for stable aqueous DSSCs, establishing a straightforward strategy to exploit the potential of lignin as a functional polymer precursor for the field of sustainable photovoltaic devices., Competing Interests: The authors declare no competing financial interest., (© 2021 The Authors. Published by American Chemical Society.)

Perovskite solar cells are a hot topic of photovoltaic research, reaching, in few years, an impressive efficiency (25.5%), but their long-term stability still needs to be addressed for industrial production. One of the most sizeable reasons for instability is the doping of the Hole Transporting Material (HTM), being the salt commonly employed as a vector bringing moisture in contact with perovskite film and destroying it. With this respect, the research focused on new and stable "dopant-free" HTMs, which are inherently conductive, being able to effectively work without any addition of dopants. Notwithstanding, they show impressive efficiency and stability results. The dopant-free polymers, often made of alternated donor and acceptor cores, have properties, namely the filming ability, the molecular weight tunability, the stacking and packing peculiarities, and high hole mobility in absence of any dopant, that make them very attractive and a real innovation in the field. In this review, we tried our best to collect all the dopant-free polymeric HTMs known so far in the perovskite solar cells field, providing a brief historical introduction, followed by the classification and analysis of the polymeric structures, based on their building blocks, trying to find structure-activity relationships whenever possible. The research is still increasing and a very simple polymer (PFDT-2F-COOH) approaches PCE = 22% while some more complex ones overcome 22%, up to 22.41% (PPY2).

Most photovoltaic (PV) technologies are opaque to maximize visible light absorption. However, see-through solar cells open additional perspectives for PV integration. Looking beyond maximizing visible light harvesting, this work considers the human eye photopic response to optimize a selective near-infrared sensitizer based on a polymethine cyanine structure (VG20-C x ) to render dye-sensitized solar cells (DSSCs) fully transparent and colorless. This peculiarity was achieved by conferring to the dye the ability to strongly and sharply absorb beyond 800 nm (S 0 -S 1 transition) while rejecting the upper S 0 -S n contributions far in the blue where the human retina is poorly sensitive. When associated with an aggregation-free anatase TiO 2 photoanode, the selective NIR-DSSC can display 3.1% power conversion efficiency, up to 76% average visible transmittance (AVT), a value approaching the 78% AVT value of a standard double glazing window while reaching a color rendering index (CRI) of 92.1%. The ultrafast and fast charge transfer processes are herein discussed, clarifying the different relaxation channels from the dye monomer excited states and highlighting the limiting steps to provide future directions to enhance the performances of this nonintrusive NIR-DSSC technology., Competing Interests: The authors declare no competing financial interest., (© 2021 American Chemical Society.)

A municipal solid waste incinerator (MSWI) was installed in a peripheral area of the city of Turin. In this study, we evaluated the contribution of this plant to the massive concentration of PM 10 , to its chemical composition and to the distribution of the lead isotopes during the start-up phase.We assessed the inorganic composition of PM 10 collected in the vicinity of the Turin incinerator by inductively coupled plasma atomic emission spectroscopy (ICP-AES), magnetic sector inductively coupled plasma mass spectrometer (SF-ICP-MS) and ion chromatography (IC). The lead isotope ratios in PM 10 samples were determined by SF-ICP-MS by a method developed and optimized using experimental design approach. Element trends and data chemometric treatment evidence that the vehicular traffic, increased in this area due to the opening of the MSWI plant, and, to a lesser degree, the direct incinerator emissions influence As, Cd, Cr, Cu, Ba, Mo, Pb, Sn and Zn concentrations. As a whole, however, the element concentrations in PM 10 and the Enrichment Factors (EFs) were comparable with the values reported for other urban sites and target pollutant concentrations of MSWI emissions, namely Cd, Cr, Cu and Pb, were lower than in PM 10 emitted from older MSWIs. This confirms that incinerators of new installation have a lower impact on atmospheric PM 10 composition thanks to stricter current legislation and up-to-date technologies. The lead isotope ratios investigation allowed to distinguish the diverse sources (crustal, vehicular traffic and MSWI) that influence lead concentration in PM 10 collected near incinerator during start-up phase., Competing Interests: Declaration of competing interest The authors declare that they have no known competing financial interests or personal relationships that could have appeared to influence the work reported in this paper., (Published by Elsevier Ltd.)