Solids

The generation of solvated electrons (SEs) from solid-state sources represents a transformative approach to driving challenging reduction reactions under ambient conditions. Diamond, with its almost unique negative electron affinity (NEA) and tunable electronic properties, is emerging as a promising candidate for SE generation in aqueous media. This perspective article reviews the current state of diamond-based SE generators and discusses their potential to catalyze sustainable nitrogen reduction (NRR) to ammonia, carbon dioxide reduction (CO₂RR), and the degradation of persistent environmental pollutants. Emphasis is placed on the fundamental processes enabling SE photoinjection from diamond to water, recent experimental breakthroughs, and the prospects for scalable, green applications. Full article

The search for effective and reliable methods of photosensitization of oxide-based semiconductor materials is of great significance for their use in photocatalytic reactions of hydrogen production and environmental remediation under natural sunlight. The present study is focused on partial substitution of titanium with manganese in the structure of layered perovskite-like titanate Na₂La₂Ti₃O₁₀, which was employed to yield a series of photocatalytically active materials, Na₂La₂Mn_xTi_3−xO₁₀ (x = 0.002–1.0), as well as their protonated forms H₂La₂Mn_xTi_3−xO₁₀ and nanosheets. It was established that the manganese cations Mn⁴⁺ are embedded in the middle sublayer of oxygen octahedra in the perovskite slabs La₂Mn_xTi_3−xO₁₀²⁻ and that the maximum achievable manganese content x in the products is ≈0.9. The partial cationic substitution in the perovskite sublattice led to a pronounced contraction of the optical band gap from 3.20 to 1.35 eV (depending on x) and, therefore, allowed the corresponding photocatalysts to utilize not only ultraviolet, but also visible and near-infrared light with wavelengths up to ≈920 nm. The materials obtained were tested as photocatalysts of hydrogen evolution from aqueous methanol, and the greatest activity in this reaction was demonstrated by the samples with low manganese contents (x = 0.002–0.01). However, the materials with greater substitution degrees may be of high interest for use in other photocatalytic processes and, especially, in thermophotocatalysis due to their improved ability to absorb the near-infrared part of solar radiation. Full article

This article discusses the superionic glassy GeS₂-Sb₂S₃-AgI system with mobile silver ions as a material for creating new energy-efficient solid-state ion emitters. The effect of replacing silver iodide with germanium sulfide on the structure of the electrolyte, activation energy of diffusion, and specific ionic conductivity was studied. Electrolytes (2.5 + x)GeS₂-27.5Sb₂S₃-(70 − x)AgI, x = 0, 5, 10, 15 were synthesized using the melt-quenching technique in evacuated quartz ampoules. The temperature dependence of conductivity and glass stability parameters (Hruby’s, Weinberg’s and Lu–Liu’s) were determined for them, and the mechanism for increasing glass-forming ability was clarified. It was shown that the presence of iodine in a germanium structural unit is more preferable than in an antimony structural unit; germanium structural units compete for iodine, reducing the number of SbI₃ crystallization centers and chain terminations, resulting in additional structural connectivity and stability. It was shown that when silver iodide was replaced by germanium sulfide, the decrease in conductivity due to the reduction in charge carriers was less than expected due to the expansion of the conduction channels. Full article

Rare earth-doped phosphate glasses have found widespread application in the field of solid-state and fiber laser technologies. Nevertheless, the fabrication of high-quality rare earth-doped phosphate glasses with minimal residual hydroxyl groups remains a significant challenge. To address this, a two-step melting process was utilized in this work to synthesize Er³⁺-Yb³⁺ co-doped phosphate glasses with low residual hydroxyl group content and improved optical quality. When re-melted under a N₂ atmosphere at 900 °C for 12 to 16 h, the hydroxyl absorption coefficient (α_-OH) decreased to ~1 cm⁻¹. The structural and compositional characteristics of the glass remained essentially unchanged throughout the re-melting process. The weak broadband absorption in the visible range and the red-shift of the ultraviolet absorption edge were attributed to the reduction in residual hydroxyl group content rather than carbon contamination. The dehydroxylation mechanism was governed by the physical diffusion of hydroxyl groups within the glass matrix. Full article

The influence of the quantity of silanol in an active silicic acid solution (ASAS) on the growth rate of colloidal silica particles was investigated. The quantity of silanol in the ASAS was controlled by varying the acid concentration as a hydrolysis catalyst for tetramethoxysilane (TMOS). As expected, the particle growth rate was confirmed to be a function of the acid concentration in the water used to prepare the ASAS. In addition, when the entire process was conducted under basic conditions to obtain spherical particles, the initial basicity had a secondary influence on the particle growth rate. When a partial process was conducted under acidic conditions to obtain morphologically modified particles, the low acidity was found to have a secondary influence on the particle growth rate. Furthermore, it was clarified that the relative silica deposition rate based on acid-free ASAS could be predicted by assuming the seed particle size at the time it was determined. Thus, a production control system was established for highly purified colloidal silica using ASAS derived from TMOS. Full article

The development of innovative proton-conducting materials for low-temperature fuel cells (FCs) is, today, a central topic among the scientific community. Polyantimonic acid (PAA) is characterized by high conductivity and sufficient thermal stability; however, PAA-based solid membrane fabrication with high proton conductivity remains challenging. Additionally, PAA cannot be compacted into solid shaped electrolytes without a binder. In a previous work, using a fluoroplastic binder, the authors fabricated and investigated proton conductivity of bulk PAA-based membranes in the temperature range 25–250 °C. In the present research, the authors opted to use another binder, poly(vinyl alcohol), PVA (which already allowed to obtain PAA sensors with higher sensitivity to moisture, low hysteresis, and similar aging than the produced previously with the fluoroplastic binder), for fabricating new solid membranes. The sample’s structure and morphology were studied using diverse experimental techniques (Thermogravimetric analysis, X-ray diffraction analysis, etc.). Electrical Impedance spectroscopy, EIS, was used to assess the electrical response and respective time stability of the membranes; it also allowed the development of an equivalent model circuit to better interpret the samples’ electrical behavior and respective contributions. The samples with 20 wt% PVA content showed improved protonic conductivity and chemical stability up to 100 °C, when compared to previous prepared and reported ones using the fluoroplastic binder. Full article

Fly ash, a byproduct of coal burning and gasification, is a significant source of global pollution and is classified as hazardous waste. However, physicochemical treatments can improve their adsorption capacity by increasing their surface area. This research aimed to enhance the adsorption capacity of fly ash from the brick manufacturing industry to remove Cd(II) ions by optimizing its surface area. The treatment process was designed with two factors: sodium hydroxide concentration and stirring time, each evaluated at three levels. The modification was confirmed through X-ray diffraction analysis of its mineralogical composition. Using the BET method, the initial fly ash exhibited a surface area of 8.59 m²/g, which increased to a maximum of 33.99 m²/g after treatment. The proposed modification method successfully quadrupled the surface area under optimal conditions: 2.0 M NaOH concentration and 60 min of stirring. The 3² factorial design shows that the highest degree of Cd(II) removal is 99.75%, which is achieved using the modified fly ash with a surface area of 33.99 m²/g under favorable operating conditions of 30 min and 600 rpm stirring speed. Full article

The microstructural, mechanical and corrosion properties of low-alloyed Mg-Zn-Ca alloys with different Zn/Ca atomic ratios were investigated. The results show that the microstructure of the extruded Mg-1Zn-0.3Ca (ZX1.0) alloy mainly consists of α-Mg and Ca₂Mg₆Zn₃ phases and a small amount of Mg₂Ca phase. In contrast, the Mg₂Ca phase disappears in the alloys Mg-1.4Zn-0.3Ca (ZX1.4), Mg-1.8Zn-0.3Ca (ZX1.8) and Mg-2.3Zn-0.5Ca (ZX2.3). The Ca₂Mg₆Zn₃ phases are mainly distributed along the extrusion direction, showing irregular particle shapes and banded particles. Meanwhile, the grain size of the extruded Mg-Zn-Ca alloy is reduced gradually with the increase of the Zn and Ca contents, decreasing from 1.87 μm in ZX1.0 to 1.28 μm in ZX2.3 alloy. Fine grain strengthening and second-phase strengthening increase the yield strength and ultimate tensile strength of the alloy. In addition, when the Zn/Ca ratio is the same, the total elemental content dominates the effect on alloy properties. When increasing the Zn/Ca ratio, the potential difference between Ca₂Mg₆Zn₃ and the Mg matrix increased, resulting in an increase in galvanic corrosion. The negative effect of the volume fraction of the second phase and the positive effect of the fine grain size determine the corrosion performance together. Therefore, ZX1.8 exhibits the best corrosion resistance, of 0.14 mm/y. Full article

Layered Ruddlesden–Popper titanates HLnTiO₄ and H₂Ln₂Ti₃O₁₀ (Ln = La, Nd) have been exfoliated into nanosheets in aqueous tetrabutylammonium hydroxide and systematically investigated as hydrogen evolution photocatalysts. The nanosheets were tested both in as-prepared pristine form and after reassembly by two methods (simple filtration and precipitation by hydrochloric acid). The nanosheet-based samples demonstrated by up to 88 times greater photocatalytic performance in comparison with the bulk precursors and, after modification with a Pt cocatalyst, provided apparent quantum efficiency of hydrogen generation up to 14.2% in 1 mol.% aqueous methanol and 3.15% in pure water. It was established that the form in which the nanosheets are used strongly affects the hydrogen production efficiency: the latter typically decreases when moving from the pristine nanosheets to filtered ones and then to those restacked by hydrochloric acid, which is determined by the difference in their physical–chemical characteristics being influenced by the reassembly approach. Full article

In this study, nanostructured copper oxide-based films with crystallite size below 10 nm were electrochemically synthesized on copper foil and foam electrodes and investigated for their supercapacitive behaviour. The synthesis was carried out via cyclic voltammetry (CV) for up to 1000 cycles in an alkaline electrolyte. By tuning the upper vertex potential (−0.3 V to 0.65 V vs. Ag/AgCl), both phase composition (Cu₂O, Cu(OH)₂, CuO) and morphology (grains, nanoneedles, nanoplatelets) were precisely controlled, demonstrating the versatility of this approach. The kinetics of oxide/hydroxide film formation on foil and foam electrodes were analysed based on EIS data that were interpreted in the frame of equivalent electric circuits and their changes with potential. The capacitive properties of the synthesized films were evaluated using CV in the potential range of 0 V–0.65 V, and the optimized CuO film synthesized on Cu foam exhibited a high specific capacitance of 1380 mF cm⁻². An energy density of 0.061 mWh cm⁻² and power density of 1.28 mW cm⁻² were obtained at 10 mA cm⁻² discharge current. Charge–discharge cycling at 100 mV s⁻¹ for 1000 cycles indicated an initial capacitance increase followed by stable retention, highlighting the structural integrity and electrochemical stability of the films obtained on 3D foam. These findings provide valuable insights into the controlled electrochemical synthesis of copper oxide nanostructures and their potential for high-performance capacitor applications. Full article

Carbonized polymer dots (CPDs) have emerged as a fascinating class of functional nanomaterials with unique physicochemical properties. However, the mechanisms governing their formation and photoluminescence remain a subject of intense debate. In this study, we conducted a systematic comparison of the structural, morphological, and optical properties of CPDs synthesized using various methods, revealing the self-assembly characteristics of low-molecular-weight CPDs with relatively complex structures. Through comprehensive structural, morphological, and optical analyses, we found that CPDs with fewer endogenous derivatives exhibited pronounced concentration-dependent self-assembly, leading to larger particle sizes and enhanced fluorescence emission at higher concentrations. In contrast, CPDs with higher proportions of endogenous derivatives showed limited self-assembly due to complex supramolecular interactions between the derivatives and polymer chains. Remarkably, the removal of endogenous derivatives using a ternary solvent extraction method significantly enhanced the self-assembly and fluorescence of the CPDs. These findings highlight the critical role of endogenous derivatives in modulating the self-assembly and photophysical properties of CPDs, paving the way for future advancements in this field. Full article

Large organic molecules and metal complexes are promising candidates for organic electronics, optoelectronics, and spintronics, with interfaces to metals being critical. Clean preparation in ultra-high vacuum (UHV) is ideal, but many systems are fragile and cannot be thermally sublimed. This study details the preparation of thin films of the metallacrown Cu(II)[12-MC_Cu(II)N(Shi)-4] (short: CuCu4) from the liquid phase using electrospray injection (ESI) and, in particular, liquid injection (LI). Both methods produce films with intact CuCu4 complexes, but they differ in the amount of co-adsorbed solvent molecules. Enhancements using an argon stream perpendicular to the molecular beam significantly reduce these contaminants. An additional effect occurs due to the counterions (HNEt₃)₂ of CuCu4. They are co-deposited by LI, but not by ESI. The advantages and limitations of the LI method are discussed in detail. The CuCu4 films prepared by different methods were analyzed with infrared (IR) spectroscopy, ultraviolet and X-ray photoelectron spectroscopy (UPS, XPS), and scanning tunneling microscopy (STM). For thicker films, ex situ and in situ prepared CuCu4 films to exhibit similar properties, but for studying interface effects or ultrathin films, in situ preparation is necessary. Full article

We report the topochemical solid-state polymerization of different series of symmetrical diacetylenes (DAs) and asymmetrical chlorodiacetylenes (ClDAs), whose members differ in their alkyl spacing lengths of one to four methylene units (n = 1, 2, 3, 4) between the diyne and carbamate functionalities. Structure determination by single-crystal X-Ray diffraction (SCXRD) confirms that in each of these series, at least 50% of the analyses show monomers with a particular stacking pattern presenting two potential directions of polymerization simultaneously. An organization of a crystalline polydiacetylene (PDA) with an oblique chain orientation with respect to the network of cooperatives hydrogen bonds is rather rare in the literature (only two cases), and here we have obtained two more examples of this type of structural motif (supported by SCXRD analysis of the polymer). Orientation control is essential to optimize the performance of conjugated polymers, and a spacer length modification strategy presents a potential way to achieve this in the case of PDA. Full article

Magnesium and its rare-earth alloys are extensively studied for their lightweight properties and high specific strength, making them attractive for aerospace, automotive, and biomedical applications. However, their hexagonal close-packed structure leads to a strong basal texture, limiting plasticity and formability at room temperature. Considerable research has been devoted to texture control strategies, including alloying, thermomechanical processing, and recrystallization mechanisms, yet a comprehensive understanding of their effects remains an ongoing research focus. This review summarizes recent advances in texture regulation of rare-earth magnesium alloys, focusing on the role of RE elements (Gd, Y, Nd, Ce) and non-RE elements (Zn, Ca) in modifying basal texture and enhancing mechanical properties. The influence of key processing techniques, such as extrusion, rolling, equal channel angular pressing, and rotary shear extrusion, is discussed in relation to their effects on recrystallization behavior. Additionally, the mechanisms governing texture evolution, including continuous dynamic recrystallization, discontinuous dynamic recrystallization (DDRX), and particle-stimulated nucleation, are critically examined. By integrating recent findings, this review provides a systematic perspective on alloying strategies, processing conditions, and recrystallization pathways, offering valuable insights for the development of high-performance magnesium alloys with improved formability and mechanical properties. Full article

With the rapid increase in polyethylene terephthalate (PET) usage in recent years, recycling has become indispensable in mitigating environmental damage and safeguarding natural resources. In this context, this study presents a methodology for valorizing PET waste through phase transfer catalytic hydrolysis conducted at a low temperature (80 °C) and atmospheric pressure, with the goal of recovering the terephthalic acid (TPA) monomer. The recovered TPA monomer was subsequently utilized as a precursor for the synthesis of metal–organic frameworks (MOFs). Tributylhexadecyl phosphonium bromide (3Bu6DPB) was selected as the phase transfer catalyst due to its efficiency and sustainability. The process parameters, including the concentration of NaOH, the wt.% of catalyst to PET, and the concentration of PET in the solution, were varied to optimize the hydrolysis reaction. The Taguchi design methodology with an L9 (3^3) orthogonal array was employed to analyze the influence of these factors on the depolymerization time. The analysis of variance (ANOVA) results revealed that the concentration of NaOH was the most significant factor, contributing to 93.3% of the process efficiency, followed by the wt.% of the catalyst to PET (6.5%). The findings also demonstrated that the concentration of NaOH had the greatest impact (Δ = 4.27, rank = 1), while the concentration of PET had the smallest effect (Δ = 0.16, rank = 3). The optimal conditions for PET depolymerization were achieved in 75 min with 20 g/100 mL of NaOH, 12 wt.% of catalyst to PET, and 5 g/100 mL of PET. The recovered TPA monomer was further employed as an organic ligand to synthesize Fe(III)-TPA MOFs under mild conditions (80 °C for 24 h). The X-ray diffraction (XRD) analysis revealed the simultaneous formation of MOF-235(Fe) and MIL-101(Fe), two multifunctional materials with diverse properties and applications. This study highlights an efficient approach for producing low-cost MOFs while promoting urban waste recycling, contributing to an integrated strategy for PET recycling and resource valorization. Full article

This study explores the potential of utilizing circulating fluidized bed boiler fly ash (CFBFA) in the production of composite gravels, with the aim of achieving performance comparable to natural gravel while promoting sustainability. CFBFA, activated by hydrated lime and gypsum, was investigated for its pozzolanic reaction and carbonation curing under simulated coal-fired power plant flue gas conditions (80 °C, 0.4 MPa, 15% CO₂, 85% N₂). The study focused on optimizing the ratios of gypsum and hydrated lime in CFBFA-based cementitious materials, with the goal of enhancing their mechanical properties and understanding the underlying hydration and carbonation mechanisms. X-ray diffraction (XRD) and scanning electron microscopy (SEM) were used to analyze the mineral composition and microstructure of the composite gravels. The results revealed that the optimal gypsum-to-hydrated lime ratio for CFBFA composite gravels is 2:1, achieving a compressive strength of 9.01 MPa after 28 days of carbonation curing. Carbonation curing accelerated hydration, improving the material’s strength, stability, and microstructure. Additionally, the production of CFBFA composite gravels demonstrated significant environmental benefits, reducing Cumulative Energy Demand (CED) by 86.52% and Global Warming Potential (GWP) by 87.81% compared to cement road base materials. This research underscores the potential of CFBFA as a sustainable construction material, with insights into improving its mechanical performance and expanding its large-scale use through carbonation curing with flue gas. Full article

Titanium nitride (TiN) is an advantageous material for plasmonic applications and is suitable for extreme conditions in which conventional plasmonic materials such as gold (Au) cannot be utilized. In this study, TiN and Au nanodisk arrays with different lattice spacing (Λ) were fabricated using the electron beam lithography (EBL) method to increase the quality factor of TiN. At a period of 550 nm, the TiN nanodisk arrays demonstrate a higher sensitivity, 412.79 nm·RIU⁻¹, with the plasmonic resonance wavelength shifting from 883 nm (n = 1.3335) to 915 nm (n = 1.4069) in the NIR region. The surface lattice resonance (SLR) properties of the produced TiN nanodisk arrays were investigated in detail with Au nanodisk arrays. The TiN nanodisk arrays caused sharp plasmon resonances by creating a localized plasmon vibration mode coupled with the diffractive grazing wave excited by the incident light. The transmission dips obtained at narrower full width at half maximum (FWHM) values caused at least an almost 10-fold improvement in the quality factor compared to localized surface plasmon resonance (LSPR) dips. This study is significant for assessing the surface plasmon resonance characteristics of TiN and Au nanodisk arrays across various periods and indices. Full article

Austenitic stainless steel SS316LN is used as the material of construction of the vessel and core components of fast breeder reactors, which operate at an elevated temperature of 550 °C. For design and integrity analysis using the finite element method, material models, such as Johnson–Cook and Ramberg–Osgood, are widely used. However, the temperature- and strain-rate-dependent plasticity and damage parameters of these models for this material are not available in the literature. Moreover, the method of evaluation of temperature and strain-rate-dependent plasticity parameters, in literature, has some major shortcomings, which have been addressed in this work. In addition, a new optimization-based procedure has been developed to evaluate all nine plasticity and damage parameters, which uses results of combined finite element analysis and experimental data. The procedure has been validated extensively by testing tensile specimens at different temperatures, by testing notched tensile specimens of different notch radii, and by carrying out high strain-rate tests using a split Hopkinson pressure bar test setup. The parameters of the Johnson–Cook material model, evaluated in this work, have been used in finite element analysis to simulate load-displacement behavior and fracture strains of various types of specimens, and the results have been compared with experimental data in order to check the accuracy of the parameters. The procedure developed in this work shall help the researchers to adopt such a technique for accurate estimation of both plasticity and damage parameters of different types of material models. Full article

This review provides an analysis of non-perovskite hybrid halides of coinage metals templated by metal–organic cations (CCDC November 2023). These materials display remarkable structural diversity, from zero-dimensional molecular complexes to intricate three-dimensional frameworks, allowing fine-tuning of their properties. A total of 208 crystal structures, comprising haloargentates, mixed-metal haloargentates, and halocuprates, are categorized and examined. Their potential in photocatalysis is discussed. Special attention is given to the structural adaptability of these materials for the generation of functional interfaces. This review highlights key compounds and aims to inspire further research into optimizing hybrid halides for advanced technological applications. Full article