Search Results (283)

Structure–property relationships in imidazolium-based hybrid Sb(III) chlorides provide critical guidance for designing high-performance materials. Three zero-dimensional metal halides, namely, [C₃mmim]₂SbCl₅ (1, [C₃mmim]⁺ = 1-propyl-2,3-dimethylimidazolium), [C₅mmim]₂SbCl₅ (2, [C₅mmim]⁺ = 1-pentyl-2,3-dimethylimidazolium), and [C₅mim]₂SbCl₅ (3, [C₅mim]⁺ = 1-pentyl-3-methylimidazolium), are synthesized by ionothermal methods. These compounds exhibit markedly distinctly photophysical properties at their optimal excitation wavelengths. Structural analyses reveal that elongated alkyl chains in compounds 2 and 3 increase Sb–Sb distances compared to that in 1, effectively isolating [SbCl₅]²⁻ units, suppressing inter-center energy transfer, and reducing non-radiative transitions, thereby enhancing the photoluminescence quantum yield (PLQY). Furthermore, methyl substitution at the C2-position of the imidazolium ring in compounds 1 and 2 induces asymmetric coordination environments around the [SbCl₅]²⁻ emission centers, leading to pronounced structural distortion. This distortion promotes non-radiative decay pathways and diminishes luminescent efficiency. Furthermore, temperature-dependent spectroscopy analysis and fitting of the Huang–Rhys factor (S) reveal significant electron–phonon coupling in compounds 1–3, which effectively promotes the formation of self-trapped excitons (STEs). However, compound 1 exhibits extremely high S, which significantly enhances phonon-mediated non-radiative decay and ultimately reduces its PLQY. Overall, compound 3 has the highest PLQYs. Full article

In this study, we present a comprehensive theoretical analysis of modifications in the physical and chemical properties of MoSe₂ upon the introduction of substitutional transition metal impurities, specifically, Ti, V, Cr, Fe, Co, Ni, Cu, W, Pd, and Pt. Wet systematically calculated the adsorption enthalpies for various representative analytes, including O₂, H₂, CO, CO₂, H₂O, NO₂, formaldehyde, and ethanol, and further evaluated their free energies across a range of temperatures. By employing the formula for probabilities, we accounted for the competition among molecules for active adsorption sites during simultaneous adsorption events. Our findings underscore the importance of integrating temperature effects and competitive adsorption dynamics to predict the performance of highly selective sensors accurately. Additionally, we investigated the influence of temperature and analyte concentration on sensor performance by analyzing the saturation of active sites for specific scenarios using Langmuir sorption theory. Building on our calculated adsorption energies, we screened the catalytic potential of doped MoSe₂ for CO₂-to-methanol conversion reactions. This paper also examines the correlations between the electronic structure of active sites and their associated sensing and catalytic capabilities, offering insights that can inform the design of advanced materials for sensors and catalytic applications. Full article

Several attempts have been made to replace the critical raw material platinum (Pt) with other metals, mainly focusing on its functional performance, while safety and sustainability criteria are often overlooked. Here, the substitution of Pt by nickel-based coatings is addressed for water electrolysis applications. Risk assessment and life cycle assessment are iteratively performed at the laboratory scale and after upscaling metal coating protocols. The challenges for the transition towards an integrated safe and sustainable by design (SSbD) approach are identified, and strategies are proposed to resolve them. Valuable insights emerge from the individual assessments (e.g., hotspots, trade-offs, and recommendations for sustainability and safety), as well as regarding the transition towards an integrated SSbD (e.g., dealing with data gaps and uncertainties). Full article

Spinel-structured hausmannite (Mn(II)Mn(III)₂O₄) is a vital intermediate in Mn mineralogy and a key player in redox chemistry in the environment. Its transformation into other Mn oxides is a critical factor in controlling its environmental occurrence and reactivity. Yet structural impurities and solution pH, as well as the fate of impurities during transformation, which influence hausmannite transformation processes and products, remain largely unknown. In the present work, we address this knowledge gap by investigating pristine and metal-substituted hausmannite, specifically nickel (Ni) or cobalt (Co), equilibrated at two time periods (8 h and 30 days) and three different pH levels (4, 5, and 7). Solution chemistry data revealed that both the equilibration period and pH had a significant impact on hausmannite dissolution rates and the concomitant repartitioning of Ni or Co. Hausmannite with Ni or Co substitution exhibited lower dissolution rates than pristine mineral under acidic conditions. Mineralogy and crystal chemistry data indicated that hausmannite was the major host phase after 30-day equilibration, followed by minor transformed products, including birnessite and manganite. Although minor, birnessite became more abundant than manganite at low pHs. Analytical high-resolution transmission electron microscopy (HRTEM) analyses revealed a poorly crystalline, nano-scaled MnO₂ formed from hausmannite and the majority of metal impurities remaining in the host hausmannite. Yet Co was associated with both hausmannite and the newly formed birnessite, whereas Ni was only found with hausmannite, indicating the strong sequestration of Co by Mn(II/III) and Mn(IV) mineral phases. This study highlights the significant impacts of metal impurities and pH on the stability of hausmannite and its transformation into birnessite, as well as the control of Mn-oxide minerals on the solubility and sequestration of transition metals in the environment. Full article

Transition metal (II) complexes stabilized by 2,6-di(pyrazol-3-yl)pyridine as a novel coplanar tridentate nitrogen-donor ligand have been reported for their unusual structures and photoluminescent properties. In this work, the ligand 2,6-bis(5-isopropyl-1H-pyrazole-3-yl)pyridine (denoted as L) and its transition metal (II) halogenido complexes viz [ZnCl₂(L)] (1), [ZnBr₂(L)] (2), [CuCl₂(L)] (3), and [CuCl(L)(thf)](PF₆) (4) were synthesized and characterized by single crystal X-ray crystal analysis. Its structures contained N–H groups in its pyrazole rings and hydrogen bonds between these N–H donors and the coordinated halogenide ions and lattice solvent molecules. Tautomers between 3-pyridyl and 5-pyridyl substitutes were also observed. In L, the N–H group at the pyrazole nitrogen was located adjacent to the pyridine ring to form hydrogen bonds with adjacent pyrazoles. However, on complexation, the H atoms at the pyrazole nitrogens are shifted remotely to the pyridine. The zinc (II) complexes [ZnCl₂(L)] (1) and [ZnBr₂(L)] (2) possessed distorted trigonal pyramidal structures in the solid state. By comparison, the copper (II) complexes [CuCl₂(L)] (3) and [CuCl(L)(thf)](PF₆) (4) adopted square pyramidal geometry with a Jahn–Teller distortion resulting from their d⁹ electron configurations. Full article

Metal halide perovskite (MHP) nanocrystals (NCs) offer great potential for high-efficiency optoelectronic devices; however, they suffer from structural softness and chemical instability. Doping MHP NCs can overcome this issue. In this work, we synthesize Mn-doped methylammonium lead bromide (MAPbBr₃) NCs using the ligand-assisted reprecipitation method and investigate their structural and optical stability. X-ray diffraction confirms Mn²⁺ substitution at Pb²⁺ sites and lattice contraction. Photoluminescence (PL) measurements show a blue shift, significant PL quantum yield enhancement, reaching 72% at 17% Mn²⁺ doping, and a 34% increase compared to undoped samples, attributed to effective defect passivation and reduced non-radiative recombination, supported by time-resolved PL data. Mn²⁺ doping also improves long-term stability under ambient conditions. Low-temperature PL reveals the crystal-phase transitions of perovskite NCs and Mn-doped NCs to be somewhat different than those of pure MAPbBr₃. Mn²⁺ incorporation into perovskite promotes self-assembly into superlattices with larger crystal sizes, better structural order, and stronger inter-NC coupling. These results demonstrate that Mn²⁺ doping enhances both optical performance and structural robustness, advancing the potential of MAPbBr₃ NCs for stable optoelectronic applications. Full article

Atmospheric aqueous-phase reactions have been recognized as an important source of secondary organic aerosols (SOAs). However, the unclear reaction kinetics and mechanics hinder the in-depth understanding of the SOA sources and formation processes. This study selected ten different substituted phenolic compounds (termed as PhCs) emitted from biomass burning as precursors, to investigate the kinetics using OH oxidation reactions under simulated sunlight. The factors influencing reaction rates were examined, and the contribution of reactive oxygen species (ROS) was evaluated through quenching and kinetic analysis experiments. The results showed that the pseudo-first-order rate constants (k_obs) for the OH oxidation of phenolic compounds ranged from 1.03 × 10⁻⁴ to 7.85 × 10⁻⁴ s⁻¹ under simulated sunlight irradiation with an initial H₂O₂ concentration of 3 mM. Precursors with electron-donating groups (-OH, -OCH₃, -CH₃, etc.) exhibited higher electrophilic radical reactivity due to the enhanced electron density of the benzene ring, leading to higher reaction rates than those with electron-withdrawing groups (-NO₂, -CHO, -COOH). At pH 2, the second-order reaction rate (k_{PhCs, OH}) was lower than at pH 5. However, the k_obs did not show dependence on pH. The presence of O₂ facilitated substituted phenols’ photodecay. Inorganic salts and transition metal ions exhibited varying effects on reaction rates. Specifically, NO₃⁻ and Cu²⁺ promoted k_{PhCs, OH}, Cl⁻ significantly enhanced the reaction at pH 2, while SO₄²⁻ inhibited the reaction. The k_{PhCs, OH} were determined to be in the range of 10⁹~10¹⁰ L mol⁻¹ s⁻¹ via the bimolecular rate method, and a modest relationship with their oxidation potential was found. Additionally, multiple substituents can suppress the reactivity of phenolic compounds toward •OH based on Hammett plots. Quenching experiments revealed that •OH played a dominant role in phenolic compound degradation (exceeding 65%). Electron paramagnetic resonance confirmed the generation of singlet oxygen (¹O₂) in the system, and probe-based quantification further explored the concentrations of •OH and ¹O₂ in the system. Based on reaction rates and concentrations, the atmospheric aqueous-phase lifetimes of phenolic compounds were estimated, providing valuable insights for expanding atmospheric kinetic databases and understanding the chemical transformation and persistence of phenolic substances in the atmosphere. Full article

Two-layered structures consisting of piezopolymer and magnetic elastomer were investigated as magnetoelectric material. Three types of magnetic elastomer based on cobalt ferrite (CoFe₂O₄) and Ni- or Zn-substituted CoFe₂O₄ nanoparticles were used as magnetically sensitive layers. Cobalt ferrite nanoparticles are considered one of the most promising metal-oxide nanomaterials because of their favorable magnetic properties, such as high saturation magnetization and magnetic anisotropy. The substitution of Co²⁺ in cobalt ferrite with other transition metals allows for additional tailoring of these properties. The modified magnetic behavior of the substituted CoFe₂O₄ nanoparticles directly influenced the magnetic properties of magnetic elastomers and, consequently, the magnetoelectric response of composite structures. In this case, the resonant frequency of the magnetoelectric effect remained largely independent of the type of magnetic nanoparticles in the magnetic elastomer layer but its magnitude increased upon Zn substitution up to ~107 mV·cm⁻¹·Oe⁻¹. These findings highlight the potential of chemically engineered magnetic properties of CoFe₂O₄ nanoparticles for manufacturing magnetoelectric composites to expand their applications in energy harvesting and sensors. Full article

Using density functional theory (DFT) and scanning tunneling microscopy (STM), the intrinsic point defects, formation energy, and electronic structure of 1T-TiS₂ were investigated. Defect systems include single-atom vacancies, interstitial and adatom additions, and direct atomic substitution. Using a collective approach for analyzing realistic systems for point defect investigation, we provide a more straightforward comparison to the experimental measurements, reproducing more realistic environmental conditions related to thin film growth. STM images are compared to computationally simulated electron density images to identify specific geometries that result from favorable point defects. DFT suggests that titanium interstitials are the most energetically favorable intrinsic defect, and sulfur vacancies are more likely to form than titanium vacancies within this realistic analysis, which is in agreement with STM data. A pristine, stoichiometric monolayer system is calculated to have a direct band gap of 0.422 eV, which varies based on local point defects. Local semiconducting-to-metallic electronic transitions are predicted to occur based on the presence of Ti interstitials. Full article

Fe₂P (iron phosphide) alloys have garnered significant interest in recent years due to their potential applications in permanent magnet materials, particularly in the context of energy-efficient and environmentally friendly technologies. We have sought to tailor the magnetic properties, such as magnetization, coercivity, and Curie temperature, to meet the specific requirements of rare-earth-free permanent magnets for various industrial sectors. In this work, we review recent advancements in the exploration of substitutions (Si, Co, Mn, and Ni) within $\mathrm{F}{\mathrm{e}}_2\mathrm{P}$ alloys aimed at enhancing their magnetic performance as candidates for permanent magnets. The X-ray patterns of (Fe,Co)₂P show great crystallinity with a pure Fe₂P phase even with Mn and Ni substitutions. The Fe₂P structure crystallizes in the P-62m space group. It has been confirmed that the transition metals substitute the 3g Fe-site, sometimes with adverse effects regarding magnetic properties with Co vs. Ni substitution, and that Si substitutes the 2c P-site. The saturation magnetization increases ($M_S=87\mathrm{A}{\mathrm{m}}^2/\mathrm{k}\mathrm{g}$) with Mn substitution, while the Curie temperature decreases with these substitutions. The impact of various substitutional elements on the magnetic properties of $\mathrm{F}{\mathrm{e}}_2\mathrm{P}$ alloys is highlighted, and challenges encountered in this field are reported. Full article

Epoxidation of long-chain α-olefins (LAOs) is a process of paramount importance, particularly in the preparation of epoxides. Traditional epoxidation methods, such as the chlorohydrin method and peracid method, suffer from issues such as poor selectivity, by-product formation, and environmental pollution. Mukaiyama epoxidation, with its mild reaction conditions and exceptional selectivity, has attracted widespread attention and considerable research. Transition metal oxide catalysts show potential in the reaction; however, the catalytic efficiency still require substantial improvement due to dilemma of substance activation. In this study, a synergistic enhancement method was employed, achieved through the creation of oxygen vacancies and the electron-rich nature of Cu. The substitution of Cu with Sn in CuO facilitates the creation of oxygen vacancy (Vo), thereby enhancing absorption and activation of O₂. The conversion for O₂ activation paves the way for the formation of benzoyl peroxy radicals. Moreover, the interaction between Sn and Cu promotes charge transfer from Sn to Cu, resulting in an electron-rich Cu surface that significantly accelerates the dehydrogenation of benzaldehyde. The synergistic enhancement protocol exhibits near-quantitative performance, delivering an oxide yield of 92.9%. This study introduces an innovative dual-promotion catalytic strategy for Mukaiyama epoxidation utilizing readily available O₂, providing profound insights into the optimization design of transition metal oxide catalysts and beyond. Full article

This review explores the recent advancements in catalyst technology for hydrogen production, emphasizing the role of catalysts in efficient and sustainable hydrogen generation. This involves a comprehensive analysis of various catalyst materials, including noble metals, transition metals, carbon-based nanomaterials, and metal–organic frameworks, along with their mechanisms and performance outcomes. Major findings reveal that while noble metal catalysts, such as platinum and iridium, exhibit exceptional activity, their high cost and scarcity necessitate the exploration of alternative materials. Transition metal catalysts and single-atom catalysts have emerged as promising substitutes, demonstrating their potential for enhancing catalytic efficiency and stability. These findings underscore the importance of interdisciplinary approaches to catalyst design, which can lead to scalable and economically viable hydrogen production systems. The review concludes that ongoing research should focus on addressing challenges related to catalyst stability, scalability, and the integration of renewable energy sources, paving the way for a sustainable hydrogen economy. By fostering innovation in catalyst development, this work aims to contribute to the transition towards cleaner energy solutions and a more resilient energy future. Full article

To design bioactive glass compositions with optimal thermal, mechanical, and bioactive properties as coatings on Ti6Al4V metallic implants, we investigated phosphosilicate bioactive glasses based on the 6P55 composition. SiO₂ was substituted with B₂O₃ to improve adhesion to the metallic implants and physical properties. This substitution significantly altered the glass structure and is hypothesized to improve adhesion. Computational and experimental methods revealed that boron substitution introduced BO₃ and BO₄ units, disrupted the Si-O network, and formed non-bridging oxygens (NBOs), resulting in a decrease in density and glass transition temperature (T_g). These changes were attributed to boron’s dual role as a network former and modifier, influencing coordination environments and connectivity. Thermal and structural analyses showed that optimal boron levels improved thermal expansion and network flexibility, which are critical for coating applications. By integrating molecular dynamics simulations and experimental techniques, this study provides valuable insights into tailoring glass compositions for enhanced performance on metallic substrates. Full article

In this study, we present the HOAc-catalyzed selective cleavage of the C=C double bond of enaminones, enabling the formation of a new C–N bond and a new C=N bond for the one-pot synthesis of 2-substituted 3,4-dihydroquinazolines directly from ynones and 2-(aminomethyl)anilines. This method operates in ethanol under transition-metal-free and oxidant-free conditions, offering a sustainable and efficient approach for the synthesis of 3,4-dihydroquinazolines with broad functional group tolerance. Full article

Metal–organic framework (MOF)-derived transition metal compounds and their composites have attracted great interest for applications in energy conversion and storage. In this work, hexagonal micro-prisms of Ni-doped CoTiO₃ composited with amorphous carbon (Ni_xCTO/C) were synthesized using Ti-Co-based MOFs as precursors. The experimental results indicate the substitutional doping of Ni²⁺ for Co²⁺ in CoTiO₃ (CTO), leading to improved conductivity, as further confirmed by density functional theory calculations. Thus, the carbon-free sample of Ni-doped CTO exhibits improved lithium storage properties compared to the pristine one. Furthermore, when coupled with in situ-formed carbon, the dually modified Ni_0.05CTO/C micro-prisms demonstrated a significantly increased reversible capacity of 584.8 mA h g⁻¹, excellent rate capability, and superior cycling stability at a high current density of 500 mA g⁻¹. This enhanced electrochemical performance can be attributed to the synergistic effect of Ni doping and carbon coating. Full article