Search Results (207)

A facile and versatile strategy to obtain NPs@ZnAlO nanocomposite materials, comprising controlled-size nanoparticles (NPs) within a ZnAlO matrix is reported. The mono-(Au, Ni) and bimetallic (Ni-Au) NPs serving as an active phase were prepared by the polyol-alkaline method, while the ZnAlO support was obtained via the thermal decomposition of its corresponding layered double hydroxide (LDH) precursors. X-ray diffraction (XRD) patterns confirmed the successful fabrication of the nanocomposites, including the synthesis of the metallic NPs, the formation of LDH-like structure, and the subsequent transformation to ZnO phase upon LDH calcination. The obtained nanostructures confirmed the nanoplate-like morphology inherited from the original LDH precursors, which tended to aggregate after the addition of gold NPs. According to the UV-Vis spectroscopy, loading NPs onto the ZnAlO support enhanced the light absorption and reduced the band gap energy. ATR-DRIFT spectroscopy, H₂-TPR measurements, and XPS analysis provided information about the functional groups, surface composition, and reducibility of the materials. The catalytic performance of the developed nanostructures was evaluated by the photodegradation of bisphenol A (BPA), under simulated solar irradiation. The conversion of BPA over the bimetallic Ni-Au@ZnAlO reached up to 95% after 180 min of irradiation, exceeding the monometallic Ni@ZnAlO and Au@ZnAlO catalysts. Its enhanced activity was correlated with good dispersion of the bimetals, narrower band gap, and efficient charge carrier separation of the photo-induced e⁻/h⁺ pairs. Full article

M-edge X-ray absorption spectroscopy (XAS), which probes 3p→3d transitions in first-row transition metals, provides detailed insights into oxidation states, spin-states, and local electronic structure with high element and orbital specificity. Operating in the extreme ultraviolet (XUV) region, this technique provides sharp multiplet-resolved features with high sensitivity to ligand field and covalency effects. Compared to K- and L-edge XAS, M-edge spectra exhibit significantly narrower full widths at half maximum (typically 0.3–0.5 eV versus >1 eV at the L-edge and >1.5–2 eV at the K-edge), owing to longer 3p core-hole lifetimes. M-edge measurements are also more surface-sensitive due to the lower photon energy range, making them particularly well-suited for probing thin films, interfaces, and surface-bound species. The advent of tabletop high-harmonic generation (HHG) sources has enabled femtosecond time-resolved M-edge measurements, allowing direct observation of ultrafast photoinduced processes such as charge transfer and spin crossover dynamics. This review presents an overview of the fundamental principles, experimental advances, and current theoretical approaches for interpreting M-edge spectra. We further discuss a range of applications in catalysis, materials science, and coordination chemistry, highlighting the technique’s growing impact and potential for future studies. Full article

Vanillin photoinduced deprotonation was evaluated and analyzed. Vibronic states and transitions were computationally investigated. Optimizations and vertical electron transitions in the gas phase and with the continuum solvation model were computed using the time-dependent density functional theory. Static absorption and emission (photostatic optical) spectra were statistically averaged over the excited instantaneous molecular conformers fluctuating on quantum–classical molecular dynamic trajectories. Photostatic optical spectra were generated using the hybrid quantum–classical molecular dynamics for explicit solvent models. Conical intersection searching and nonadiabatic molecular dynamics simulations defined potential energy surface propagations, intersections, dissipations, and dissociations. The procedure included mixed-reference spin–flip excitations for both procedures and trajectory surface hopping for photodynamics. Insignificant structural deformations vs. hydroxyl bond cleavage followed by deprotonation were demonstrated starting from different initial structural conditions, which included optimized, transition state, and several other important fluctuating configurations in various environments. Vanillin electronic structure changes were illustrated and analyzed at the key points on conical intersection and nonadiabatic molecular dynamics trajectories by investigating molecular orbital symmetry and electron density difference. The hydroxyl group decomposed on transition to a σ-molecular orbital localized on the elongated O–H bond. Full article

In this work, methyl viologen (MV) was adsorbed into the nanopores of Si/Al H-β-zeolite via cation exchange. The resulting MV@β-zeolite possessed absorption/fluorescence dual-mode and photo/chemical synergistic stimuli-responsive chromism. Owing to the acidic surrounding provided by β-zeolite, the chromism of MV required the synergistic stimuli of UV irradiation and a chemical reductant (such as Na₂SO₃). UV irradiation induced single electron transfer from the chemical reductant to MV@β-zeolite, leading to enhanced absorption at 610 nm together with a daylight color change from pale yellow to blue. Meanwhile, the nanopores of β-zeolite inhibited aggregation-caused quenching of MV, enabling MV to emit cyan fluorescence at 500 nm. After the single electron transfer of the chemical reductant under UV irradiation, the cyan fluorescence of MV@β-zeolite was quenched. Additionally, MV@β-zeolite exhibited a short stimulus response time (250 s) and good color change reversibility. These findings in this work provide valuable insights into the design of multi-mode and synergistic stimuli-responsive viologen-based chromic materials, particularly for applications in secure high-throughput information storage, high-level anti-counterfeiting and multi-target multi-mode sensing. Full article

Understanding electron density migration along excited-state pathways in photochemical systems is critical for optimizing solar energy conversion processes. In this study, we investigate photoinduced electron transfer (PET) in a covalently linked donor–bridge–acceptor (D-B-A) system, where [Cu(I)-bis(1,10-phenanthroline)]⁺ acts as an electron donor, and anthraquinone, tethered to one of the phenanthroline ligands via a vibrationally active ethyne bridge, behaves as an electron acceptor. Visible transient absorption spectroscopy revealed the dynamic processes occurring in the excited state, including PET to the acceptor species. This was indicated by the spectral features of the anthraquinone radical anion that appeared on a timescale of 30 ps in polar solvents. Time-resolved infrared (TRIR) spectroscopy of the alkyne vibration (CC stretch) of the ethyne bridge provided insight into electronic structural changes in the metal-to-ligand charge transfer (MLCT) state and along the PET reaction coordinate. The observed spectral shift and enhanced transition dipole moment of the CC stretch demonstrated that there was already partial delocalization to the anthraquinone acceptor following MLCT excitation, verified by DFT calculations. An additional excited-state TRIR signal unrelated to the vibrational mode highlighted delocalization between the phenanthroline ligands in the MLCT state. This signal decayed and the CC stretch narrowed and shifted towards the ground-state frequency following PET, indicating a degree of localization onto the acceptor species. This study experimentally elucidates charge redistribution during PET in a Cu(I) diimine D-B-A system, yielding important information on the ligand design for optimizing PET reactions. Full article

This study presents the first comprehensive theoretical investigation of the antioxidant mechanisms of trans-isoferulic acid against hydroperoxyl (HOO^•) radicals in aqueous solution, using the DFT/M062X/6-311+G(d,p)/PCM method. Thermodynamic and kinetic parameters, including reaction energy barriers and bimolecular rate constants, were determined for the three major pathways: hydrogen transfer (HT), radical adduct formation (RAF), and single electron transfer (SET). The results indicate that, at physiological pH, the RAF mechanism is both more exergonic and approximately eight-times faster than HT. At a higher pH, where the phenolate anion dominates, antioxidant activity is enhanced by an additional fast, diffusion-limited SET pathway. Isoferulic acid was also found to effectively chelate Fe²⁺ ions at pH 7.4 and above, forming stable complexes that could inhibit Fenton-type hydroxyl radical generation. Moreover, its strong UV absorption suggests a role in limiting photo-induced free radical formation. These findings not only clarify the antioxidant behavior of isoferulic acid but also provide novel theoretical insights applicable to related phenolic compounds. The compound’s multi-target antioxidant profile highlights its potential as a photoprotective agent in sunscreen formulations. Full article

A new type of CeO₂-modified AgCl catalyst (CeO₂/AgCl) was prepared by a one-step method, which efficiently inhibits the recombination of photogenerated carriers. During the visible-light degradation process, this catalyst exhibited excellent and stable performance. It could not only effectively degrade rhodamine B (RhB), methyl orange (MO) and crystal violet (CV) but also maintain excellent activity under different environmental conditions. In the RhB degradation experiment in particular, the CeO₂/AgCl-30 composite with the optimal proportion had a degradation rate 5.43 times that of pure AgCl in the seawater system and 9.17 times that of pure AgCl in the deionized water condition, while also showing excellent stability. Through characterization tests such as XRD, XPS and ESR, its crystal structure, elemental composition and so on were analyzed. Based on the characterization results, the CeO₂/AgCl composite showed a relatively wide light absorption range and a relatively high photo-induced charge separation efficiency. Meanwhile, it was inferred that the main active species in the reaction process were ·O₂⁻ and ·OH. Finally, based on its electronic band structure, an S-scheme heterojunction structure was proposed. Full article

The effective removal of organic pollutants and bacteria are of great significance considering the hazards to the environment and human health. The two-dimensional AgBiO₃/Bi₂MoO₆ heterojunction with rich oxygen vacancies was successfully fabricated via a hydrothermal method and systematically characterized by various analytical techniques. The photocatalytic experimental results revealed that the addition of AgBiO₃ improved the photocatalytic performance of Bi₂MoO₆, and the AgBiO₃/Bi₂MoO₆-10 heterojunction possessed the best degradation effect toward RhB (72%) within 100 min, with 1.38 and 1.44 times higher activity than pure Bi₂MoO₆ and AgBiO₃, respectively. The bacteria were completely inactivated within 90 min by AgBiO₃/Bi₂MoO₆-10 heterojunction. The reason for the enhancement of photocatalytic activity was the synergistic effect between AgBiO₃ and Bi₂MoO₆. The constructed Z-scheme heterojunction with oxygen vacancies improved the separation efficiency of photo-induced electrons and holes and broadened the range of visible-light absorption. The trapping experiments and ESR indicated that superoxide radical and holes were the main reactive species. Full article

Conical intersections (CIs) are the most efficient channels of photodeactivation and energy transfer, while femtosecond spectroscopy is the main experimental tool delivering information on molecular CI-driven photoinduced processes. In this work, we undertake a comprehensive ab initio investigation of the CI-mediated internal conversion in fulvene by simulating evolutions of electronic populations, bond lengths and angles, and time-resolved transient absorption (TA) pump-probe (PP) spectra. TA PP spectra are evaluated on the fly by combining the symmetrical quasiclassical/Meyer–Miller–Stock–Thoss (SQC/MMST) dynamics and the doorway-window representation of spectroscopic signals. We show that the simulated time-resolved TA PP spectra reveal not only the population dynamics but also the key nuclear motions as well as mode–mode couplings. We also demonstrate that TA PP signals are not only experimental observables: They can also be considered as information-rich purely theoretical observables, which deliver more information on the CI-driven dynamics than conventional electronic populations. This information can be extracted by the appropriate theoretical analyses of time-resolved TA PP signals. Full article

Z-scheme Zn₃In₂S₆/NiFe₂O₄ nanocomposites were prepared by electrospinning and hydrothermal methods, and their photocathodic protection performance was studied on 304 SS and Q235 CS in NaCl solution (3.5 wt.%). The two-dimensional Zn₃In₂S₆ loaded on the one-dimensional NiFe₂O₄ resulted in faster electron migration and enhanced light absorption capability. Moreover, it had been observed through electrochemical testing that the assembly of Zn₃In₂S₆/NiFe₂O₄ heterojunctions improves the efficacy of photocathodic protection. Following illumination, the self-corrosion potentials of 304 SS and Q235 CS coupled with Zn₃In₂S₆/NiFe₂O₄ nanocomposites decreased by 1040 mV and 560 mV, and the photoinduced current densities were 1.2 times and 3.9 times greater than the value of Zn₃In₂S₆. Furthermore, the mechanism of enhanced photocathodic protection performance for Zn₃In₂S₆/NiFe₂O₄ heterojunctions was systematically discussed. XPS and ESR analysis indicated that Zn₃In₂S₆/NiFe₂O₄ composites follow the Z-scheme electron migration path and retain the stronger reduction and oxidation capacity of Zn₃In₂S₆/NiFe₂O₄. Therefore, the Z-scheme heterostructures are responsible for the realization of cathodic protection for carbon steel. Full article

TiO₂ is still a prototype material in photocatalytic studies. The defects, including the intrinsic and foreign defects, are reported to be important in determining the TiO₂ photocatalytic properties. In the current research, amorphous TiO₂- and Nb-doped TiO₂ (NTO) films were firstly prepared through magnetron sputtering, which were then heated under vacuum. The as-deposited TiO₂ and NTO films were amorphous, and transferred to anatase after heating. The vacuum heating at a higher temperature caused an obvious reduction in TiO₂ films, and the NTO film was more prone to be reduced as Nb dopants decreased the thermal stability of the TiO₂ lattice. The structure change induced by vacuum annealing had a great effect on electric and optical properties. The conductivity of the NTO films was 10,000 times and 100 times higher than that of the undoped TiO₂ films after post-vacuum heating at 450 °C and 650 °C, respectively. In addition to an increase in the band tail absorption, the NTO films presented strong free-electron absorption after vacuum heating; this means that the NTO films presented a clear Bornstein moss shift after vacuum heating because of the high conduction electron density. The change in the photoinduced absorption spectra revealed a possible result that photo-induced electrons can be also trapped at Nb sites, indicating that the Nb-related defect forms deep gap states; this greatly limits the photo-induced electron interfacial transfer. The results showed that the photocatalytic degradation of methylene blue decreased after vacuum heating. Full article

Three cationic Ir(III) complexes, 1, 2, and 3, were successfully synthesized and characterized by tuning the position of a phenyl group at the pyridyl moiety in 2-phenylpyridine. All three complexes exhibited typical aggregation-induced phosphorescence emission (AIPE) properties in CH₃CN/H₂O. The AIPE property was further utilized to achieve the highly sensitive detection of 2,4,6-trinitrophenol (TNP) in aqueous media with low limit of detection (LOD) values of 164, 176, and 331 nM, respectively. This suggests that the different positions of the phenyl group influence the effectiveness of 1, 2, and 3 in the detection of TNP. In addition, 1, 2, and 3 showed superior selectivity and anti-interference properties for the detection of TNP and were observed to have the potential to be used to detect TNP in practical applications. The changes in the luminescence lifetime and UV-Vis absorption spectra of 1, 2, and 3 before and after the addition of TNP indicate that the corresponding quenching process is a combination of static and dynamic quenching. Additionally, the proton nuclear magnetic resonance spectra and results of spectral studies show that the detection mechanism is photo-induced electron transfer (PET). Full article

A cationic Ru(II) complex Ru1 with 5-phenyl-2,2′-bipyridine as ligand was synthesized and fully characterized. Ru1 exhibits significant aggregation-induced phosphorescent emission (AIPE) activity in THF/H₂O. The AIPE property of Ru1 has been successfully used to detect picric acid (PA) in aqueous media. Ru1 exhibits a sensitive luminescence quenching response to PA, with a high quenching constant (K_SV = 2.5 × 10⁴ M⁻¹) and a low limit of detection (LOD = 91 nM). In addition, Ru1 demonstrates high sensitivity and selectivity for detecting PA in different common water samples. The UV-vis absorption spectra and luminescence lifetime of Ru1 show an obvious change after the addition of PA into the Ru1 samples, indicating that the quenching process is a combination of dynamic and static quenching. The density functional theory calculations indicate that the mechanism for the detection of PA is photo-induced electron transfer. Full article

As a key means to solve energy and environmental problems, photocatalytic technology has made remarkable progress in recent years. Organic semiconductor materials offer structural diversity and tunable energy levels and thus attracted great attention. Among them, porphyrin and its derivatives show great potential in photocatalytic reactions and light therapy due to their unique large-π conjugation structure, high apparent quantum efficiency, tailorable functionality, and excellent biocompatibility. Compared to unassembled porphyrin molecules, supramolecular porphyrin assemblies facilitate the solar light absorption and improve the charge transfer and thus exhibit enhanced photocatalytic performance. Herein, the research progress of porphyrin-based supramolecular assemblies, including the construction, the regulation of charge separation and transfer, stability, and application in photocatalysis, was systematically reviewed. The construction strategy of porphyrin supramolecules, the mechanism of charge separation, and the intrinsic relationship of assembling structure-charge transfer-photocatalytic performance received special attention. Surfactants, peptide molecules, polymers, and metal ions were introduced to improve the stability of the porphyrin assemblies. Donor-acceptor structure and co-catalysts were incorporated to inhibit the recombination of the photoinduced charges. These increase the understanding of the porphyrin supramolecules and provide ideas for the design of high-performance porphyrin-based photocatalysts. Full article

Excessive copper (Cu) has become a common physiological disorder restricting the sustainable production of citrus. Coumarin (COU) is a hydroxycinnamic acid that can protect plants from heavy metal toxicity. No data to date are available on the ameliorative effect of COU on plant Cu toxicity. ‘Xuegan’ (Citrus sinensis (L.) Osbeck) seedlings were treated for 24 weeks with nutrient solution containing two Cu levels (0.5 (Cu0.5) and 400 (Cu400) μM CuCl₂) × four COU levels (0 (COU0), 10 (COU10), 50 (COU50), and 100 (COU100) μM COU). There were eight treatments in total. COU supply alleviated Cu400-induced increase in Cu absorption and oxidative injury in roots and leaves, decrease in growth, nutrient uptake, and leaf pigment concentrations and CO₂ assimilation (A_CO2), and photo-inhibitory impairment to the whole photosynthetic electron transport chain (PETC) in leaves, as revealed by chlorophyll a fluorescence (OJIP) transient. Further analysis suggested that the COU-mediated improvement of nutrient status (decreased competition of Cu²⁺ with Mg²⁺ and Fe²⁺, increased uptake of nutrients, and elevated ability to maintain nutrient balance) and mitigation of oxidative damage (decreased formation of reactive oxygen species and efficient detoxification system in leaves and roots) might lower the damage of Cu400 to roots and leaves (chloroplast ultrastructure and PETC), thereby improving the leaf pigment levels, A_CO2, and growth of Cu400-treated seedlings. Full article