Search Results (414)

A Co interface-doped hierarchical magnesium hydroxide (Co-PMH) heterojunction is fabricated by incorporating Co²⁺ into the L-threonate-directed crystallization of Mg(OH)₂ and its subsequent phosphorization. The interface-doped Co narrows the bandgap of magnesium hydroxide, resulting in enhanced visible light conversion and improved broad-spectrum antimicrobial activity. Under visible light irradiation for 30 min, the Co_0.1-PMH demonstrates an antibacterial efficiency exceeding 97% against Staphylococcus aureus (S. aureus), Escherichia coli (E. coli), and methicillin-resistant S. aureus (MRSA). Mechanism analysis indicates that the stable doped Co-Mg heterojunction interface brings strong redox capabilities via a Z-scheme charge transfer pathway, driving the generation of ROS (primarily ·OH and ·O₂⁻) to eliminate bacteria adsorbed in situ. Even after three cycles, Co_0.1-PMH maintains high bactericidal activity (>95%) and biocompatibility (>93% cell survival). This makes Co-PMH a promising candidate for antimicrobial infection control. Full article

A microscopic model has been elaborated for the description of charge transfer-induced spin transitions in crystals containing tetranuclear Fe₂Co₂ clusters as structural units. The model takes into account the energy spectrum of each Fe₂Co₂ cluster, formed by the states arising from its initial configuration, two low-spin Fe^II and two low-spin Co^III, final configuration two low-spin Fe^III, and two high-spin Co^II, as well as the states that originate from four intermediate configurations of the type of low-spin Fe^II, low-spin Co^III, low-spin Fe^III, and high-spin Co^II. Two different types of cooperative interactions are accounted for in the model, namely, the electron–deformational coupling arising as a result of the observed elongation of the cobalt-nitrogen bonds under the low-spin Co^III$\to$ high-spin Co^II transition and the interaction via the field of phonons that originates from the coupling of the Co-ions with the full symmetric displacements of the nearest ligand surrounding, which are modulated by crystalline vibrations. The role of cooperative interactions is discussed in detail. Different types of spin transitions are predicted, including the gradual and abrupt ones as well as those manifesting hysteretic behavior. Within the framework of the developed approach, a qualitative and quantitative explanation of the experimental data on the {[(Tp*)Fe(CN)₃]₂[Co(bpy^Me)₂]₂}(OTf)₂·2DMF·H₂O compound recently reported oniere is given. Full article

The effect of A-site substitution on the morphological and electrochemical properties of La_1-xSr_xMnO₃ (x = 0, 0.25, 0.50) perovskites was investigated to evaluate their potential as electrode materials for supercapacitors. X-ray diffraction analysis confirmed the formation of the perovskite structure, with minor peak shifts and distortion of crystal structure induced by Sr substitution. Scanning electron microscopy analysis revealed irregularly shaped particulate morphology across all perovskite compositions. The increasing amount of Sr as in La_0.5Sr_0.5MnO₃ (LSM-50) favored the formation of nanosized particles, and energy dispersive X-ray (EDX) analysis confirmed the presence of all constituent elements; EDX elemental mapping also showed a uniform distribution of all elements in the various perovskite compositions. Among all compositions, La_0.75Sr_0.25MnO₃ (LSM-25) possessed the highest specific capacitance (C_sp) of 483 Fg⁻¹ at 1 Ag⁻¹ current density in 3 M KOH electrolyte, as determined by electrochemical analysis. This perovskite material also exhibited a capacitance retention of 87.8% after 5000 charge–discharge cycles. Electrochemical impedance spectroscopy revealed that LSM-25 showed the lowest solution resistance (0.68 Ω*cm²) and charge transfer resistance (1.52 Ω*cm²), indicating strong electrode–electrolyte interaction. Detailed analysis of cyclic voltammetry data revealed that the predominant charge storage mechanism was diffusive in nature, with 88% of the diffusive contribution registered for LSM-25. These findings demonstrate that Sr substitution at the A-site significantly enhances the energy storage performance of LaMnO₃, making it a promising candidate for supercapacitor applications. Full article

Electrochemical chlorine production is of considerable industrial importance in areas such as water treatment, chemical manufacturing, and disinfection. However, conventional precious metal-based dimensionally stable anodes (DSAs), such as RuO₂- and IrO₂-based systems, are limited by high cost and resource constraints, motivating the development of low-cost alternative catalysts. In this study, Mn₃O₄ electrodes with controllable defect characteristics were fabricated by electrochemical deposition under various processing conditions. The effects of defect modulation and surface modification on the structural, electronic, and electrochemical properties of the electrodes were systematically evaluated. X-ray diffraction analysis confirmed that all deposited films retained a stable tetragonal Mn₃O₄ crystal structure, indicating that the deposition parameters primarily influenced defect states rather than the bulk phase. Mott–Schottky measurements revealed that the Mn₃O₄ electrodes exhibited p-type semiconducting behavior, with charge carrier densities on the order of 10¹⁴ cm⁻³, suggesting that oxygen vacancy-related defect states may contribute to the observed electronic properties of the electrodes. To further enhance anodic performance, Pt was introduced onto the Mn₃O₄ surface via sputtering, resulting in significantly improved charge transfer characteristics. Electrochemical measurements demonstrated that the best performing Pt/Mn₃O₄ electrodes delivered a current density exceeding 100 mA cm⁻² at an applied potential of 1.5 V versus Ag/AgCl. More importantly, defect-enriched Pt/Mn₃O₄ electrodes exhibited markedly enhanced chlorine evolution activity, with the chlorine production rate increasing from approximately 14 µmol cm⁻² to 29 µmol cm⁻², corresponding to an enhancement of about 2.07-fold. Faradaic efficiency analysis further showed that sample (g) and sample (n) achieved chlorine evolution efficiencies of 59.2% and 74.6%, respectively, indicating a higher tendency toward chlorine evolution for the Pt-modified electrodes under the tested conditions. These findings suggest that the synergistic combination of defect engineering and surface modification effectively modulates the electronic structure of Mn₃O₄, providing a viable strategy for improving chlorine evolution performance. Full article

HfO₂ films have become a critical component for advanced electronics and a wide range of applications. However, their implementation requires control of their microstructure and defects, which often act as charge carrier traps, leading to leakage current in devices and hindering their dielectric properties. Here, we deposit HfO₂ thin films by atomic layer deposition (ALD) on sapphire, Ga₂O₃, and InGaO₃ substrates at low temperature and investigate the dependence of their crystal structure on substrate type, annealing, and thickness. X-ray diffraction measurements showed that alloying Ga₂O₃ with a modest amount of Indium transferred HfO₂ films from amorphous to polycrystalline, an important finding that may be applicable to the deposition of other material systems. The study also presents an interesting approach to measuring shallow and deep traps formed in the films and shows how to control their levels and distributions in the band gap. The measurements reveal that the difference in band gap between the substrate and film, as well as the presence of impurities, strongly influences trap densities and depths. Electron paramagnetic resonance (EPR) measurements were performed to probe the electronic structure of specific point defects detectable by EPR and to correlate these results with trap measurements. Full article

The electrochemical CO₂ reduction reaction (CO₂RR) offers a sustainable route for converting greenhouse gases into high-value fuels; however, its efficiency has long been constrained by the thermodynamic stability of CO₂ molecules and the competing hydrogen evolution reaction. Using density functional theory (DFT) calculations, this work systematically investigates the catalytic performance of Ni₅ and alloy Ni₄Cu clusters anchored on divacancy graphene (DVG) for CO₂RR. The results demonstrate that the introduction of Cu atoms significantly enhances the interfacial binding energy between the cluster and the support (shifting from −6.2 eV to −7.5 eV). Charge density difference analysis combined with Bader charge analysis further reveals that interfacial charge transfer and the formation of Ni–C bonds serve as the electronic origin of this improved stability. Free energy calculations show that, compared to Ni₅/DVG, Ni₄Cu/DVG substantially reduces the energy barrier of the rate-determining step for formic acid (HCOOH) formation from 1.18 eV to 0.26 eV, thereby significantly optimizing the reaction kinetics. Crystal orbital Hamilton population (COHP) analysis demonstrates that Cu doping modulates metal–oxygen bond strength in the key *OCHO intermediate (ICOHP: Ni-O bonds at −0.697 eV/−0.976 eV vs. Cu-O bonds at −0.408 eV/−0.492 eV), optimizing the adsorption–desorption balance and steering selectivity toward HCOOH. This work elucidates the atomic-scale electronic and bonding mechanisms underlying Ni–Cu synergistic effects, providing theoretical guidance for designing efficient non-noble metal CO₂RR electrocatalysts. Full article

To develop high-performance iridium phosphorescent complexes, we designed and synthesized a series of iridium phosphorescent complexes (G-1, G-2, B-1, B-2, R-1, R-2) using 3-hydroxy-2-methyl-4-pyrone (maltol, short for mal) and 3-hydroxy-2-ethyl-4-pyrone (ethyl maltol, short for emal) as auxiliary ligands, in combination with 2-phenylpyridine (ppy), 2-(2,4-difluorophenyl)pyridine (dfppy), and 1-phenylisoquinoline (piq) as cyclometalating ligands. We systematically investigated their crystal structures, photophysical behavior, electrochemical properties, and electroluminescent performance. The results revealed that the combination of a pyranone auxiliary ligand with the highly conjugated piq ligand leads to the formation of R-1 and R-2, which possess high molecular symmetry and display favorable photophysical performance. These complexes exhibit solution-phase phosphorescence quantum yields of 64% and 55%, and electroluminescent devices incorporating them reach a maximum external quantum efficiency of 13.4%, with brightness exceeding 13,000 cd/m² and minimal efficiency roll-off. In contrast, complexes incorporating pyridine-based cyclometalating ligands (ppy, dfppy)—G-1, G-2, B-1, and B-2—display weak emission in solution but show enhanced solid-state emission through π–π stacking, with a maximum quantum yield of 25.8%. Density functional theory calculations and electrochemical analysis indicate that the presence of both the pyranone auxiliary ligand and the piq ligand results in optimized frontier orbital energy alignment, enhanced metal-to-ligand charge transfer, and reduced non-radiative transitions, thereby improving emission efficiency. This study provides a theoretical framework and molecular design strategy for the application of pyranone auxiliary ligands in high-performance iridium phosphorescent materials. Full article

We report a rare family of pyridine-coordinated iodobismuthate(III) salts supported by alkyltriphenylphosphonium and tetraphenylphosphonium cations. Reactions of BiI₃ with Ph₃PR⁺I⁻ (R = Me, Et, ⁿPr, ⁿBu, Ph) in neat pyridine, followed by crystallization, yield structurally tunable bismuth-halide-pyridine anions dictated by reagent stoichiometry. Combination of BiI₃ and Ph₃PR⁺I⁻ in 2:1 ratio produced [Ph₃PR]₂[BiI₅Py], 1 (R = Me, Et, ⁿPr, Ph), while combination in 1:1 ratio resulted in three compounds: [Ph₃PR][cis-BiI₄Py₂], 2 (R = ⁿPr, Ph), [Ph₃PR][trans-BiI₄Py₂], 3 (R = Me, Et, Ph), and [Ph₃PR]₂[transoid-Bi₂I₈Py₂], 4 (R = Me, Et, ⁿPr, ⁿBu, Ph). In many cases, the compounds were isolated as Py or Et₂O solvates, and in some cases, multiple degrees of solvation or polymorphism were encountered. Hirshfeld analysis of 1–4 showed the major anion–cation/anion/solvent interactions to be H⋯I, H⋯H, and C⋯H. Diffuse reflectance measurements of representative compounds, all of which were yellow-orange to red-orange, revealed bandgaps in the range of 1.9–2.2 eV, where density-of-states KS-DFT calculations attribute the absorption to metal-centered charge transfer within the anionic unit. NLMO and QTAIM analyses further indicate predominantly ionic Bi(III)–I/pyridine bonding with robust inner-sphere coordination that is insensitive to anion speciation. Full article

The manipulation of the electrocatalyst nanoarchitecture, particularly transition metal compounds, regarding size, shape, facets, and composition, significantly enhances the electrocatalytic activity in energy transformations. This study introduces a novel methodology for the precipitation of mesoporous nanoparticles of nickel tungstate (meso-NiWO₄) using direct chemical deposition from a template of Brij^®78 surfactant liquid crystal. Physicochemical analyses revealed the formation of amorphous meso-NiWO₄ nanoparticles with dual sizes of 10 ± 3 and 120 ± 8 nm and a specific surface area of 34.2 m²/g, exceeding that of nickel tungstate deposited in the absence of surfactant (bare-NiWO₄, 4.0 m²/g). The meso-NiWO₄ nanoparticles exhibit improved electrocatalytic stability, reduced charge-transfer resistance (R_ct = 1.11 ohm), and a current mass activity of ~365 mA/cm² mg at 1.6 V vs. RHE during the electrolysis of urea in alkaline solution. Furthermore, by employing meso-NiWO₄ in a two-electrode urea electrolyzer, a remarkable 4.8-fold increase in the cathodic hydrogen concurrent production rate was achieved (373.40 µmol/h at a bias potential of 2.0 V), compared to that of the bare-NiWO₄ catalyst. The exceptional urea oxidation electroactivity and the enhanced hydrogen evolution rate arise from substantial specific surface area and mesoporous structure, facilitating effective charge transfer and mass transport through the meso-NiWO₄ catalyst. Using the surfactant liquid crystal template for electrocatalyst synthesis enables a one-pot deposition of diverse nanoarchitectures and compositions with high surface area at ambient conditions for an improved electrocatalytic and hydrogen green production process. Full article

This study presents the synthesis and electrochemical characterization of meso-tetracyanobutadiene (TCBD)-functionalized diphenylporphyrin (DPP) complexes incorporating copper (Cu) and nickel (Ni) metals. These push–pull metallo diphenylporphyrin–TCBD complexes were synthesized via a [2 + 2] cycloaddition–retroelectrocyclization reaction between 5-bromo-15-formyl-10,20-diphenylporphyrin metal(II) complexes (M = Cu, Ni) and tributyl(phenylethynyl)stannate, followed by tetracyanoethylene (TCNE) addition. The resulting TCBD-functionalized porphyrins were obtained in moderate yields (70–75%) and thoroughly characterized by ¹H and ¹³C NMR, UV-Vis spectroscopy, MALDI-TOF-MS, and single-crystal XRD. Although the single-crystal X-ray structure of NiDPP was solved, DFT calculations were used to determine the structures of the donor–acceptor MDPP-TCBD systems and to visualize their electronic structures. HOMO on the porphyrin π system and LUMO on the TCBD entity were observed, and energy level diagrams clearly laid out the electron donor and acceptor parts of the molecular systems. As expected, these novel donor–acceptor porphyrinoid assemblies exhibited enhanced push–pull properties in both the ground and excited states. Femtosecond transient absorption studies revealed that both NiDPP-TCBD and CuDPP-TCBD populate the charge-transfer state upon photoexcitation, with lifetimes of 383.1 ps and 484.7 ps, respectively, in benzonitrile. The charge-transfer states populated the triplet or doublet states (in the case of CuDPP) before returning to the ground state. Full article

In this study, a highly crystalline 2H (hexagonal)-phase MoS₂ sensing layer with a precisely controlled crystal structure was realized through a combination of DC sputtering and sulfurization annealing processes, and subsequently integrated with a D-shaped optical fiber to develop a highly sensitive carbon dioxide (CO₂) sensor. Conventionally sputtered MoS₂ thin films often suffer from the presence of unstable metallic 1T (tetragonal) phases and a high density of sulfur vacancies, which significantly degrade sensor reversibility and long-term stability. Here, high-temperature annealing under a sulfur-rich atmosphere was employed to induce a complete phase transition from the metastable 1T phase to the stable semiconducting 2H phase, while simultaneously healing sulfur vacancies. Enhanced crystallinity was confirmed by Raman spectroscopy. The fabricated sensor exhibited excellent linearity (R² > 0.99) and markedly improved repeatability over a CO₂ concentration range of 1000–10,000 ppm. This significant performance enhancement is attributed to reversible charge transfer induced by sulfur vacancy passivation, which modulates the complex refractive index of the MoS₂ layer and optimizes optical interaction with the evanescent field of the D-shaped fiber. The phase engineering and defect-healing strategy presented in this work effectively addresses the drift issues commonly observed in conventional electrical gas sensors and provides a crucial pathway toward the realization of high-performance optical gas sensors. Full article

Phenothiazine is a heteroaromatic molecule capable of various noncovalent interactions, including halogen bonding and π-stacked association. Despite its broad use in functional materials and pharmaceutical ingredients, a systematic comparison of these interaction modes has been lacking. Here, we report a combined experimental and computational study of intermolecular interactions of phenothiazine with a prototypical halogen-bond (HaB) donor (tetrabromomethane), planar π-electron acceptors (tetracyanopyrazine and tetrafluoro-p-benzoquinone), and multifunctional species capable of both interaction types (iodo- and bromo-3,5-dinitrobenzenes). X-ray structural analysis revealed that CBr₄ forms exclusively C–Br···π halogen bonds with the aromatic rings of phenothiazine, whereas all π-acceptors yield alternating donor–acceptor stacks characterized by multiple short contacts indicative of multicenter interactions. Notably, co-crystals of iodo- and bromodinitrobenzenes with phenothiazine display only π-stacked architectures. Density-functional calculations showed that isolated HaB complexes involving N, S, or π sites of phenothiazine possess comparable binding energies (≈−3 kcal mol⁻¹), whereas π-stacked complexes are substantially stronger (≈−9–12 kcal mol⁻¹). QTAIM, NCI, NBO, and energy-decomposition analyses indicated that while amounts of charge transfer in halogen-bonded and π-stacked complexes are comparable, the enhanced stability of the latter originates primarily from a large dispersion contribution. These results rationalize the solid-state preference for π-stacking over halogen bonding in systems where both motifs are accessible and clarify the hierarchy and physical origin of noncovalent interactions involving phenothiazine, providing guidance for the design of supramolecular assemblies and functional materials based on this versatile electron donor. Full article

Hierarchical In₂MnS₄ microflowers were synthesized via a hydrothermal approach and evaluated as multifunctional photo-/electrocatalysts for crystal violet (CV) dye degradation and methanol oxidation. The synthesis strategy produced three-dimensional flower-like architectures composed of nanoscale subunits with high crystallinity and uniform elemental distribution. Optical characterization revealed strong visible-light absorption with a bandgap of approximately 1.74 eV, indicating suitability for solar-driven photocatalysis. In₂MnS₄ microflowers achieved 96.6% degradation of CV dye within 100 min, whereas negligible activity was observed without the catalyst. Kinetic analysis followed a pseudo-first-order model with an apparent rate constant of 0.029 min⁻¹. The catalyst maintained stable performance over four consecutive cycles, confirming good recyclability. Photoelectrochemical measurements showed a stable photocurrent response and reduced charge-transfer resistance, indicating efficient separation and transport of photogenerated charge carriers. Furthermore, electrochemical measurements revealed increased anodic responses and sustained current behavior in the presence of methanol, suggesting an electrochemical response upon methanol addition. These results highlight In₂MnS₄ microflowers as promising visible-light-responsive materials for environmental remediation and energy-related catalytic applications. Full article

Co/Fe layered double hydroxides (LDHs) are among the most promising materials for advanced industrial and energy applications. Controlling the synthesis conditions of LDH materials is thus crucial to precisely tailoring cation composition and distribution, thereby regulating surface charge, ion sorption, and electron transfer required for optimal chemical and electrochemical performance. Therefore, characterizing Co/Fe precipitates (chemical composition, purity, morphology, and crystallinity) is also required to further exploit their controlled properties. Thus, solids with Co/Fe cation ratios between 2/2 and 10/2 were synthesized under an air atmosphere, at pH 8 or 11.5. For the first time, multiscale physicochemical techniques (FTIR, TEM-EELS, SEM, AAS, TGA, CHN elemental analysis, and XRD complemented by Rietveld refinement) were used to provide a fully documented characterization of the structure, texture, purity, chemical composition, and thermal properties of Co/Fe LDH-based materials. The combined interpretation of data from these complementary techniques enabled the precise identification and chemical characterization of the mineralogical phases formed. Both acid–base and redox reactions govern the overall Co^II/Fe^III LDH formation process. Well-crystallized LDHs were synthesized, except for the 2/2 ratio at pH 11.5, which led to the formation of α-Co(OH)₂, γ-Fe₂O₃, and Co₃O₄ byproducts. A pH value of 8.0 provides valuable LDH materials made of quasi-hexagonal particles with diagonal lengths between 200 and 500 nm. Rietveld refining showed the presence of LDH phases in the range of 95–98%. Multiple local chemical analyses using EDX on chosen particles demonstrated pure 4/2 and 6/2 LDHs. For the 2/2 ratio, the cumulative mass fraction of two LDH-type products consistently reached 97%, distributed between Co/Fe 1.5/2 (71%) and Co/Fe 4/2 (29%). For the 10/2 ratio, only partial Co precipitation was observed, forming 95% Co/Fe LDH phases distributed between Co/Fe 10/2 (72%) and 7/2 (28%). Full article

Organic luminescent radicals with through-space charge-transfer (TSCT) excited states are attractive for optoelectronic applications, yet donor-dependent structure–property relationships remain underexplored. Here we report a new spirofluorene-bridged TSCT radical, PID-FR-TTM, employing 1-phenyl-1H-indole (PID) as the donor. Single-crystal X-ray diffraction confirms a carbon-centered TTM radical and a less bulky, more planar five-membered N-heterocycle in the donor region. PID-FR-TTM shows TSCT-type absorption and an emission at 609 nm with a photoluminescence quantum yield (PLQY) of 23.1% and a 90.1 ns emission lifetime in cyclohexane. Calculations indicate a TSCT-dominated excited state and a pronounced singly occupied molecular orbital–highest occupied molecular orbital (SOMO–HOMO) inversion. Notably, PID-FR-TTM exhibits markedly improved stability, including high decomposition temperatures (≈340 °C), excellent electrochemical stability, and enhanced photostability. These results provide donor-structure insights for designing high-performance TSCT radical emitters. Full article