This study aims to assess the reliability of micro-X-ray fluorescence spectroscopy (mu-XRF) as a quantitative, non-invasive tool for the in-situ compositional analysis of ancient glass. mu-XRF is widely employed in archaeological and materials science contexts due to its ability to rapidly detect major, minor, and trace elements without the need for sampling. However, it is often assumed that its limited sensitivity to light elements (Z < 13) in field applications poses challenges for a comprehensive characterisation of glass-making technologies and raw materials. In this study, we evaluate the analytical performance of mu-XRF for glass analysis, going beyond compositional characterisation by systematically comparing it with Laser Ablation Inductively Coupled Plasma Mass Spectrometry (LA-ICP-MS). LA-ICP-MS offers superior detection limits and a broader elemental range, but its use is constrained by the need for sample preparation and its non-portable nature. The precision of mu-XRF was assessed through repeated daily measurements, while accuracy was evaluated using the certified reference glasses Corning A and B. Correction trends were developed by comparing mu-XRF results with both the nominal concentrations of these standards and with corresponding LA-ICP-MS data, in order to mitigate inherent limitations and enhance the method's reliability. The validated protocol was then applied to a set of Roman glass samples of unknown composition. The results confirm that, despite its limitations, mu-XRF can deliver accurate and reproducible data, supporting its use as a rapid and versatile method for in-situ compositional analysis of ancient glass.

This work provides the first experimental evidence of a fully novel and innovative green-synthesis protocol for dendritic mesoporous silica nanoparticles (DMSNs). DMSNs are widely used in various scientific fields, such as drug delivery, catalysis, and environmental remediation; however, their production still presents critical challenges, particularly with respect to sustainability for both operators and the environment. The novel method proposed here is rapid and straightforward, carried out entirely in aqueous solution using a microwave reactor operated in sealed vessels. Owing to the simplicity and strict parameter control of this approach, the roles of temperature and pressure in directing surfactant self-assembly are reported for the first time, resulting in a center-symmetric arrangement of the mesoporous structure. This method eliminates the need for organic solvents, pore modifiers, or cosurfactants, which are typically required to obtain the radial mesostructure. Moreover, the use of microwave-based reactors enables scalability through a modular setup and allows for a significant reduction in reaction time (∼10 min) and energy consumption. A comparative analysis with mesoporous silica nanoparticles (MSNs) featuring longitudinal channel structures reveals that the radial configuration of DMSNs exhibits more efficient mass transport, higher loading capacity for active species, and improved diffusion dynamics, which translate into superior performance across several applications.

The preservation of archaeological and historical glass requires advanced conservation strategies. While some existing methods are effective in some instances, they often have limitations, such as the need for high‐temperature densification treatments or undesirable interactions with the glass substrate. This study investigates the development of sol–gel‐based protective coatings for glass, focusing on both inorganic and hybrid formulations. The main aim is to formulate silica sol–gel solutions catalyzed with low acid concentrations and applied at room temperature, reducing the risks associated with conventional methods while enhancing the long‐term preservation of ancient artifacts. Silica‐based coatings are synthesized using three silica precursors–one fully inorganic and two containing organic alkyl groups of different lengths–along with variations in the molar ratio of precursors, water and ethanol. These formulations are applied to soda‐lime glass substrates via dip coating, forming thin films between 100 and 150 nm. The coated samples undergo multiscale analysis, including accelerated ageing tests to simulate environmental degradation. Results demonstrate that hybrid coatings functionalized with methyl and octyl groups provide superior barriers against the diffusion of alkaline and alkaline‐earth elements, outperforming purely inorganic coatings. This research highlights the potential of hybrid sol–gel coatings as effective and durable protective solutions for glass conservation.

Alternative methods to sol-gel coatings have gained considerable research attention in recent decades. Among these, plasma-polymerised coatings have proven to be effective in enhancing homogeneity, thinness and adhesion to treated surfaces. Due to these advantages, plasma technologies have also emerged as promising tools in the conservation field, particularly for treating fragile and specialised materials like glass. This study investigates the application of an atmospheric pressure plasma jet for depositing two silica-based coating on glass using two distinct precursors - the inorganic silane TEOS and the organo-silane HMDSO. In this context, plasma polymerisation refers to the plasma-induced fragmentation and recombination of precursor molecules, resulting in the formation of cross-linked inorganic or hybrid films. The relationship between plasma deposition parameters and coating properties was analysed to achieve precise control over film thickness and morphology. The barrier properties and the stability of the coatings were further evaluated under artificial ageing conditions, involving 70 degrees C and cycling relative humidity between 10 % and 90 %. Results revealed that while inorganic plasmapolymerised films provide some degree of protection by preventing precipitate formation on glass surface, their performance is limited by densification process that occurs during ageing. In contrast, hybrid plasmapolymerised coatings exhibited superior protective properties, attributed to the incorporation of organic groups that enhanced barrier performance and effectively prevented calcium leaching.

The sustainable production of renewable fuels and feedstocks is currently constrained by the slow kinetics of anodic oxygen evolution reaction (OER). Precious metal‐based catalysts such as Ir suffer from stability issues as well as high capital cost. To enforce the future of green hydrogen production, this study develops Ru‐integrated W 18 O 49 nanowires (NWs), as an efficient and stable OER electrocatalyst. This study obtains Ru‐W 18 O 49 NWs by a combined physical vapor deposition–chemical vapor deposition approach. It discovers the NWs growth mechanism, characterized by two different growth kinetics. Herein, it finds that the integration of just 3% of Ru in the oxygen‐deficient W 18 O 49 NWs remarkably increases the number of active catalytic sites during OER, showing faster kinetics (60 mV dec −1 ) and a reduced overpotential of 360 mV at 10 mA cm −2 . The electrode's observed catalytic performance and long‐term durability over 36 h (12 h each at 10, 30, and 100 mA cm −2 ) combined with the versatility of the two‐step synthetic route, are a promising research approach for future industrial applications.

Sol‐gel technology has long been recognized as a promising stabilization treatment for glass. However, the acidity of its formulations may pose challenges, particularly due to the potential for corrosive effects, making its application on ancient and artistic glass more complex and requiring a delicate balance between safeguarding its structural integrity and preserving its visual and historical significance. This study investigates the incorporation of silica nanoparticles into silica‐based coatings to reduce the synthesis acidity and enhance anticorrosion protection. The sol‐gel formulations, tailored to minimize their acidity (from ̴pH 1–2 to pH 4) and ensure optimal compatibility with glass surfaces, are combined with 50nm and 200nm silica nanoparticles and applied using dip‐coating. Comprehensive analyses, including optical characterization, water contact angle measurements, and nanoindentation tests, reveals that composite coatings with 50nm nanoparticles, applied through a double‐dipping process, significantly improves resistance to alteration. These coatings demonstrates superior protective performance compare to both pure silica coatings and composite compositions containing 200nm nanoparticles. Surface analyses further highlighted that incorporating nanoparticles allowed for precise control over the formation of alteration structures on glass surfaces. This approach effectively manage the development of alteration patina, offering a promising solution for mitigating ancient glass alteration while maintaining its aesthetic integrity.

Rare earths (REs) incorporated in glasses, mostly in the form of RE3+ ions, have several applications such as lasers and optical amplifiers, spectral conversion layers for solar cells, light emitters and sensors. In this context, both the composition and the structural properties of the glass, as well as the dopant concentration play an important role in determining the optical properties and the efficiency of the system. Usually, the concentration of REs is small, below 1 at

Correction for ‘High performance, binder-free electrodes with single atom catalysts on doped nanocarbons for electrochemical water splitting synthesized using one-step thermally controlled delamination of thin films’ by Efrat Shawat Avraham et al., J. Mater. Chem. A, 2024, https://doi.org/10.1039/D4TA04701J.

Developing high performance catalysts for electrochemical water splitting is critical for an efficient and sustainable route to hydrogen production. For this, single-atom catalysts (SACs) are the best candidates, as they offer the highest atom efficiency. However, current methods to produce SACs involve a complex synthesis, often requiring multiple lengthy and expensive steps and yielding an insufficient density of single atoms. Here, we report a one-step chemical vapor deposition (CVD) synthesis to produce free-standing (FS) electrodes with Ni SACs on a matrix of sulfur-doped carbon nanofibers (CNFs), referred to as SACs@nanocarbon. The mechanism is based on a temperature-controlled delamination of thin films, with Au in contact with a SiO2 substrate, leading to the nucleation and growth of SACs@nanocarbon. Advanced characterization methods indicate the presence of Ni and Au single atoms and larger gold aggregates on the CNF matrix surface. These non-platinum group metal (non-PGM) electrodes showed exceptional performance for the oxygen evolution reaction (OER) and hydrogen evolution reaction (HER). They performed for over 20 000 cycles with negligible change in overpotential at higher currents, with low onset overpotentials of 305 mV at 10 mA cm-2 for the OER and 40 mV at 17 mA cm-2 for the HER. The overpotential decreased to 195 mV at a current density of 100 mA cm-2. Remarkably, the electrode performance improved over cycling, while gold was dissolving in the electrolyte. This novel synthesis yielding SACs@nanocarbon could pave the way for the development of non-PGM, high performance electrodes for many other electrocatalytic applications. Additionally, the new paradigm of temperature-controlled delamination of thin films could be used to synthesize new materials. Developing high performance catalysts for electrochemical water splitting is critical for an efficient and sustainable route to hydrogen production.

The role of the material structure in the energy transfer between Ag and Tb3+/Yb3+ ions is studied in silica-sodazirconia sol-gel glasses and glass-ceramics. The preparation of Tb3+ and Yb3+ doped silica-soda-zirconia layers was carried out by sol-gel and dip-coating, followed by thermal annealing. The precipitation of zirconia nano crystals was obtained by controlling the annealing temperature: from a full amorphous glass at 700 degrees C into a glass-ceramic at 1000 degrees C. A different crystalline structure of zirconia nanocrystals, tetragonal or cubic, was controlled by the rare-earth doping and investigated in relation to the Tb3+/Yb3+ optical properties. Moreover, Ag codoping was introduced by ion-exchange, obtaining a significant photoluminescence enhancement, both in the intensity and in the broadness of the excitation band, covering the whole UV region and part of the violet blue region. Ag-sensitized Tb3+/Yb3+ doped silica-soda-zirconia glass-ceramics were attested to be potential candidates for energy-related applications, such as spectral conversion layers for solar cells, lasers and light emitting devices (LEDs) in the visible and NIR spectral regions.

This study reports important analytical evidence of an unusual non-uniform element distribution in the super-ficial layers of glass matrices (from few nm up to 1 mu m). The unforeseen observation was made on silica-soda-lime glass mock-ups before and after their artificial ageing, using secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS) surface analysis techniques. The analyses showed a marked non-homogeneous element distribution at the glass surface. The results indicated a very low concentration of Na at the surface up to a depth of around 500 nm below the surface, where its concentration increases reaching a plateau. In addition, the profile distribution of H in the first 200 nm of the pristine glass surface indicated a diffusion of hydrogen from the surrounding environment to the glass network. Additional modifications during the glass ageing process related to external factors (such as temperature and humidity) were also identified in relation to sodium atoms, with atoms on the glass surface showing a different chemical state from those in the bulk. This study confirms that glass composition as well as glass alteration are non-homogeneous locally sup-porting the importance of studying glass surface as region of interaction with surrounding environment.

TiO2 thin films are known to promote photodegradation of dyes and pollutants in water solution via heteroge-neous photocatalysis. This ability is guided by the photoexcitation through photons having energies above the band gap. To improve photocatalytic activity, nanostructures with high surface area can be applied, which can ease molecular adsorption/desorption mechanisms, enhance electronic transfer properties and lower excitation energy. For this purpose, square cross-section TiO2 vertically aligned nanorod (TNR) array configuration has been chosen as a semiconductor substrate. On top of it, a thin layer of sub-stoichiometric TiO2_x has been deposited, aiming at inducing a vacancy doped homojunction between two different oxygen rich/deficient TiO2 layers, possibly leading to lower band gap and enhanced photochemical activity. In principle, promotion of electron and holes separation and suppression of charge recombination could occur. Vertically aligned TNRs have been deposited through a hydrothermal growth in acidic conditions on a pre-seeded glass conducting substrate, optimizing the seeding process through spin coating. Sub-stoichiometric TiO2_x layer (50 nm nominal thickness) has been deposited on top of TNRs via radiofrequency magnetron sputtering at three different stoi-chiometries, tuning the oxygen partial pressure in sputtering argon atmosphere at 10 %, 15 % and 20 %, respectively. Photocatalytic activity has been investigated in the photodegradation of an aqueous solution of methylene blue, both under UV and simulated solar light irradiation at room temperature and atmospheric pressure, resulting in the degradation of methylene blue target molecule up to 99 % under UV and 85 % under simulated solar irradiation after 6 h. These promising achievements unlock new environmental applications for enhanced dye degradation industrial processes.

During the forming process of a vial by tubing glass, temperatures of up to 1200 degrees C are applied to adjust the glass viscosity. This process causes the release of volatile components such as alkali borates. Consequently, the percentage of sodium and boron measured on the inner surface of the vial can be higher than that measured on the corresponding glass tube. This study aimed to characterize the inner surface of two different borosilicate glass tubes of type I before and after the vial forming process at the nanoscale level. Quantitative elemental analysis of the surface along the vertical axis of glass tubes and vials was performed by X-ray photoelectron spectroscopy, whereas the topographical investigation was carried out by scanning electron microscopy (SEM). In the near-bottom region of a vial, which is usually the area most prone to corrosion, the SEM micrographs showed the appearance of bulges on the surface. The latter were then analyzed by time-of-flight secondary ion mass spectrometry to characterize their molecular composition. The purpose of this work is to identify possible new strategies for faster identification of factors that eventually influence chemical resistance of pharmaceutical glasses and to provide useful information needed to improve industrial processes.

Zinc oxide (ZnO) is an attractive semiconductor material for photocatalytic applications, owing to its opto-electronic properties. Its performances are, however, strongly affected by the surface and opto-electronic properties (i.e., surface composition, facets and defects), in turn related to the synthesis conditions. The knowledge on how these properties can be tuned and how they are reflected on the photocatalytic performances (activity and stability) is thus essential to achieve an active and stable material. In this work, we studied how the annealing temperature (400 °C vs. 600 °C) and the addition of a promoter (titanium dioxide, TiO2) can affect the physico-chemical properties of ZnO materials, in particular surface and opto-electronic ones, prepared through a wet-chemistry method. Then, we explored the application of ZnO as a photocatalyst in CO2 photoreduction, an appealing light-to-fuel conversion process, with the aim to understand how the above-mentioned properties can affect the photocatalytic activity and selectivity. We eventually assessed the capability of ZnO to act as both photocatalyst and CO2 adsorber, thus allowing the exploitation of diluted CO2 sources as a carbon source.

Consolidation and coating treatments are two types of interventions that form part of the active conservation actions developed for historical and archaeological glass over the years. While thermoplastic and thermosetting resins are widely adopted by conservators worldwide, issues related to the toxicity and the material compatibility of these products remains unsolved. To address these issues, effort s have been made to develop new formulations that can functionally replace or exhibit performance advantages with respect to these canonical polymeric materials. In this review, we discuss the main classes of materials applied thus far for protection and consolidation aims in the cultural heritage glass field, starting from the beginning of the 19th century and continuing until present days. We also assess the potential of hybrid organic-inorganic materials and full inorganic materials as alternative solutions to the limitations of organic materials in application. Finally, we provide our perspectives on future directions for the development of consolidation products that meet the specific requirements of the cultural heritage field. (c) 2023 The Author(s). Published by Elsevier Masson SAS on behalf of Consiglio Nazionale delle Ricerche (CNR). This is an open access article under the CC BY-NC-ND license ( http://creativecommons.org/licenses/by-nc-nd/4.0/ )

Glass has been used in widespread applications within several sectors since ancient times and it has been systematically studied under different perspectives. However, its thermodynamic properties and the variety of its compositions, several aspects related to its durability and its alteration mechanisms remain still open to debate. This literature review presents an overview of the most relevant studies on glass corrosion and the interaction between glass and the environment. The review aims to achieve two objectives. On one hand, it aims to highlight how far research on glass corrosion has come by studying model systems created in the laboratory to simulate different alteration conditions and glass compositions. On the other, it seeks to point out what are the critical aspects that still need to be investigated and how the study of ancient, altered glass can add to the results obtained in laboratory models. The review intends also to demonstrate how advanced analytical techniques commonly used to study modern and technical glass can be applied to investigate corrosion marks on ancient samples.

Optimizing the LA-ICP-MS procedure to obtain 2D and 3D high-resolution multi-elemental imaging of heavily degraded Roman glass for studying glass weathering mechanisms by monitoring the lateral and in-depth distribution of elements.

Chiral semiconductor quantum dots have recently received broad attention due to their promising application in several fields such as sensing and photonics. The extensive work in the last few years was focused on the observation of the chiroptical properties in binary Cd based systems. Herein, we report on the first evidence of ligand-induced chirality in silver indium sulfide semiconductor quantum dots. Ternary disulfide quantum dots are of great interest due to their remarkable optical properties and low toxicity. Non-stoichiometric silver indium sulfide quantum dots were produced via a room temperature coprecipitation in water, in the presence of cysteine as a capping agent. The obtained nanocrystals show a notable photoluminescence quantum yield of 0.24 in water dispersions. Several critical aspects of the nanocrystal growth and chemico-physical characterization, and the optimisation of the surface passivation by the chiral ligand in order to optimize the nanoparticle chirality are thoroughly investigated. Optical spectroscopy methods such as circular dichroism and luminescence as well as nuclear magnetic resonance techniques are exploited to analyze the coordination processes leading to the formation of the ligand-nanocrystal chiral interface. This study highlights the dynamic nature of the interaction between the nanocrystal surface and the chiral ligand and clarifies some fundamental aspects for the transfer and optimization of the chiroptical properties.

This study reports the first analytical evidence of an unexpected non-uniform element distribution in the superficial layers of glass matrices (from few nm up to 1 micron), hitherto unknown. The unforeseen observation was made while analysing silica-soda-lime glass mock-ups before and after their artificial ageing, using secondary ion mass spectrometry (SIMS) and X-ray photoelectron spectroscopy (XPS) surface analysis techniques. The analyses showed a marked, non-homogeneous element distribution at the glass surface and bulk. The results have indicated a very low concentration of Na at the surface up to a depth of around 500 nm in the glass, where its concentration increases, reaching a plateau. In addition, the profile distribution of H in the first 200 nm of the pristine glass surface indicated a diffusion of hydrogen from the surrounding environment to the glass network. Additional modifications during the glass ageing process related to external factors (such as temperature and humidity) have also been identified in relation to sodium atoms, with atoms on the glass surface observed being chemically different from those in the bulk.

This work proposes a microwave-based synthetic route for the preparation of tin nanospheres with a diamond-like α-phase structure on silicon. The main characteristics of the synthesized material are an extraordinarily narrow (around 50 meV) direct bandgap and an improved thermal stability (up to 200° C). Structural and compositional characterizations showed a core–shell structure comprised of an outer amorphous oxide shell and inner core containing α-phase tin domains. Microwaves turned out to be instrumental in achieving the specific nanostructures reported, due to their peculiar heating characteristics. Low pressure, low temperature and compatibility with integrated circuits manufacturing represent the most innovative features of the present synthetic process.