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Hierarchical porous TiO2 single crystals templated from partly glassified polystyrene
摘要： Hierarchical macro-mesoporous anatase TiO2 single crystal is one-pot synthesized in an EtOH-H2O system using polystyrene (PS) as the single porogen both for macropore and mesopore and TiF4 as the titanium precursor. The key to the simultaneous growth of single crystal and the introduction of hierarchical pores is the assembly of PS and titania at the glassification temperature of PS (100 °C). During the hydrolytic polymerization of TiF4, PS is encapsulated inside titania and gradually glassified. The interference from elastic PS on the oriental growth of TiO2 crystallite is thus minimized and the final removal of PS through calcination leaves interconnected macropore and mesopore inside the single crystal. According to XPS, EPR and fluorescence analyses, abundant oxygen vacancies are formed on the hierarchical porous single crystal, which presents extraordinary photocatalytic activity and stability in degrading organic pollutants under simulated sunlight irradiation using Rhodamine B as the model. The improved photocatalytic activity is a synergistic effect of improved separation of charge carrier and facilitated interfacial charge transfer benefitting from highly accessible porous single crystal structure.
关键词： Oxygen vacancy,Photocatalysis,Single crystal,Charge transfer,Hierarchical porous TiO2
更新于2025-09-23 15:22:29
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AgCl/Ag/LaFeO3 heterojunction with a prolonged charge lifetime and enhanced visible light catalytic property
摘要： In this study, uniform mesoporous three–dimensional LaFeO3 with diameter of 2–3 μm was prepared by a hydrothermal process and monodispersed AgCl was then decorated on the surface of the LaFeO3 to form AgCl/Ag/LaFeO3 heterojunction via a facile precipitation–deposition process. The e?ects of the proportions employed in the preparation of the heterojunction on the structural, crystallinity, surface areas, and optical properties of AgCl/Ag/LaFeO3 were systematically studied, which showed that the AgCl/Ag/LaFeO3 heterojunction had a strong hybrid–junction structure, suitable absorption edge, and many exposed surface sites. The AgCl/Ag/LaFeO3 heterojunction had a strong catalytic activity during the degradation of methylene blue and phenol under visible light. The results demonstrated that the AgCl/Ag/LaFeO3 heterojunction had a more intense photocurrent response and smaller surface resistance than both AgCl and LaFeO3. The enhanced photocatalytic ability was attributed to the formation of heterojunctions between AgCl and LaFeO3, which suppressed the recombination of photogenerated electron–hole pairs. Our results may facilitate the rational design of highly e?cient heterogeneous heterojunctions for the removal of organic pollution.
关键词： AgCl/Ag/LaFeO3,Hybrid–junction structure,Charge transfer property,Visible light
更新于2025-09-23 15:22:29
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Effect of Planarity of Aromatic Rings Appended to o-Carborane on Photophysical Properties: A Series of o-Carboranyl Compounds Based on 2-Phenylpyridine- and 2-(Benzo[b]thiophen-2-yl)pyridine
摘要： Herein, we investigated the effect of ring planarity by fully characterizing four pyridine-based o-carboranyl compounds. o-Carborane was introduced to the C4 position of the pyridine rings of 2-phenylpyridine and 2-(benzo[b]thiophen-2-yl)pyridine (CB1 and CB2, respectively), and the compounds were subsequently borylated to obtain the corresponding C∧N-chelated compounds CB1B and CB2B. Single-crystal X-ray diffraction analysis of the molecular structures of CB2 and CB2B confirmed that o-carborane is appended to the aryl moiety. In photoluminescence experiments, CB2, but not CB1, showed an intense emission, assignable to intramolecular charge transfer (ICT) transition between the aryl and o-carborane moieties, in both solution and film states. On the other hand, in both solution and film states, CB1B and CB2B demonstrated a strong emission, originating from π-π * transition in the aryl groups, that tailed off to 650 nm owing to the ICT transition. All intramolecular electronic transitions in these o-carboranyl compounds were verified by theoretical calculations. These results distinctly suggest that the planarity of the aryl groups have a decisive effect on the efficiency of the radiative decay due to the ICT transition.
关键词： radiative decay,structural fluctuation,intramolecular charge transfer,o-carborane
更新于2025-09-23 15:22:29
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Interfacial Charge Transfer in 0D/2D Defect-Rich Heterostructures for Efficient Solar-Driven CO2 Reduction
摘要： Two-dimensional graphitic carbon nitride (g-C3N4) has been widely explored as a promising photocatalyst for solar CO2 conversion. However, rapid charge recombination and low visible-light utilization are severely detrimental to photocatalytic CO2 conversion. Zero-dimensional/two-dimensional (0D/2D) heterostructures are considered the promising materials with size tunability and enhanced charge separation efficiency for photocatalysis. Herein, a 0D/2D heterostructure of oxygen vacancy-rich TiO2 quantum dots confined in g-C3N4 nanosheets (TiO2-x/g-C3N4) was prepared by in-situ pyrolysis of NH2-MIL-125 (Ti) and melamine. Charge dynamics analysis by time-resolved photoluminescence (tr-PL) and femtosecond and nanosecond pump-probed transient absorption (TA) spectra revealed that charges transfer occured from 2D-g-C3N4 to 0D-TiO2 at an ultrafast subpicosecond time scale (<1 ps) through the intimate interface. The overall fast decay of the charge carriers was attributed to interfacial charge transfer, which was accompanied by recombination relaxation mediated by shallow trapped sites. Ultrafast interfacial charge transfer greatly promoted charge separation as well as electrons in shallow trapped sites were easily trapped by CO2. In addition, combing with the synergetic advantage of strong visible light absorption, high CO2 adsorption and large surface area, TiO2-x/g-C3N4 exhibited a superior CO evolution rate of 77.8 μmol g?1 h?1, roughly 5 times that of pristine g-C3N4 (15.1 μmol g?1 h?1). This work provides in-depth insights into optimizing the heterojunction for robust solar CO2 conversion.
关键词： TiO2 quantum dots,solar CO2 reduction,charge transfer,0D/2D heterostructures,oxygen vacancy
更新于2025-09-23 15:22:29
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Synthesis, photophysical properties and DFT studies of the pyridine-imidazole (PyIm) Cu(I) complexes: Impact of the pyridine ring functionalized by different substituents
摘要： A series of the pyridine-imidazole (PyIm) Cu(I) complexes with different substituents (bromide (P1), methyl (P2), and phenyl (P3)) attached on the pyridine ring are synthesized and characterized. All the complexes show the typical metal-to-ligand charge transfer (MLCT) absorption in the visible region. Complex P1 with an electron-withdrawing substituent on the pyridine ring, e.g., a bromine group, shows a red shift of the emission wavelength. Conversely, an electron-donating substituent on the pyridine ring in complex P2, e.g., a methyl group, shifts the emission to longer wavelength. Similarly, complex P3 containing the extended π-conjugation system of the ligand also exhibits a red shift of the emission wavelength. All of the complexes exhibit efficient green-yellow emission in PMMA films at room temperature with emission wavelength of 547–569 nm and quantum yields of 24.8–53.0%. Meanwhile, DFT and TDDFT methods were employed to explain the photophysical properties.
关键词： Pyridine-imidazole,Copper (I) complex,Metal-to-ligand charge transfer,Molar extinction coefficient,Density functional theory
更新于2025-09-23 15:22:29
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Realizing efficient bipolar deep-blue light-emitting poly(2,7-carbazole) derivatives by suppressing intramolecular charge transfer
摘要： Two series of twisted bipolar poly(2,7-carbazole) derivatives, namely PCz-37RSOs and PCz-28SOs, were synthesized by introducing electron-deficient 2,8-dioctyl-dibenzothiophene-S,S-dioxide-3,7-diyl (37RSO) and dibenzothiophene-S,S-dioxide-2,8-diyl (28SO) unit into poly(9-heptadecanyl-2,7-carbazole) (PCz) backbone, respectively. The incorporation of electron-withdrawing 37RSO and 28SO into PCz backbone decreased effective conjugation length, and further restrained charge transfer effect existed in dipolar system, simultaneously, the balanced charge carrier injection/transportation were realized due to the electrophilicity of SO unit. Consequently, the resulting polymers showed hypsochromic shift and narrowed emission spectra regarding to PCz-37SOs that contains linear SO unit in main chain, and exhibited balanced hole/electron fluxes with respect to PCz in the range of 0–10 V. The single-layer devices based on resulting bipolar polymers exhibited excellent electroluminescent spectra stability in the current densities from 100 to 400 mA cm?2, and displayed deep blue electroluminescence spectra with the Commission Internationale de L’ Eclairage (CIE) of (0.16, 0.07) for PCz-37RSO5 and (0.16, 0.09) for PCz-28SO5. The superior device performance was achieved with the maximum luminous efficiency (LEmax) of 2.69 cd A?1 for PCz-28SO20, which obviously outperformed that of 0.24 cd A?1 for PCz. These results indicated that twisted molecular structure design is a promising strategy for efficient deep blue light-emitting polymers.
关键词： Poly(2,7-carbazole),Bipolar,Twisted structure,Blue light-emitting polymers,Charge transfer effect
更新于2025-09-23 15:22:29
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Charge transfer processes and carrier dynamics at the pentacene - C60 interface
摘要： Heterostructures of pentacene (PEN) and Buckminsterfullerene (C60) are frequently attracting scientific interest as a well-defined small-molecule model-system for the study of internal interfaces between two organic semiconductors. They are prototypical representatives forming a donor-acceptor combination for studies of fundamental optoelectronic processes in organic photovoltaics. Despite their importance in exciton dissociation, the energetics of their interfacial charge-transfer (CT) states and their microscopic excitation dynamics are not yet clarified and still being discussed. Here, we present steady-state and time-resolved photoluminescence measurements on stacked heterostructures between these two materials. All experiments are performed in the visible and near-infrared spectral regions as CT states are expected at energies below the fundamental electronic transitions of the respective bulk materials. A characteristic, interface specific emission at around 1.13-1.17 eV is found, which we attribute to an interfacial CT state. Its excitation-energy dependence reveals the intricate relaxation dynamics of excitons formed in both constituent materials. Moreover, the analysis of the dynamics of the C60 excitons shows that the lifetime of this state is reduced in the presence of an interface with PEN. This quenching is attributed to a long-range interaction, i.e., the relaxation of excitations into the interfacial CT state.
关键词： organic heterostructures,charge-transfer exciton,light harvesting,donor-acceptor pair,Organic thin films,pentacene,fullerene
更新于2025-09-23 15:22:29
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Nature of the excited states of layered systems and molecular excimers: Exciplex states and their dependence on structure
摘要： Weakly bound systems, like noble-gas dimers or two-dimensional layered materials (graphite, hexagonal boron nitride, or transition-metal dichalcogenides), exhibit excited electronic states of a particular nature. These so-called exciplex states combine on-site (or intralayer) and charge-transfer (or interlayer) configurations in a well-balanced way. We show by ab initio many-body perturbation theory that the energy and composition of the exciplex states depend sensitively on the bond length or interlayer distance of the material. When the constituents approach each other, the charge-transfer contribution increases and the excitation is redshifted to lower energy. If the system is excited into the exciplex state, then a covalent-like bond results. In consequence, noble-gas dimers form excimer complexes, while layered materials exhibit interlayer contraction.
关键词： charge-transfer excitations,many-body perturbation theory,interlayer contraction,exciplex states,layered systems
更新于2025-09-23 15:22:29
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In-situ ion exchange synthesis of Ag2S/AgVO3 graphene aerogels for enhancing photocatalytic antifouling efficiency
摘要： Efficient charge separation and cycle stability are critical for water purification by semiconductor photocatalyst. Herein, novel Ag2S/AgVO3 graphene aerogels (Ag2S/AgVO3@GAs) were synthesized via an in-situ ion exchange method. The series of characterization results verified that the Ag2S/AgVO3@GAs synergistically integrate the excellent properties of the Ag2S and AgVO3 into the macroscopic porous graphene aerogel. Furthermore, owing to the chelation of chitosan (CS) for AgVO3 and the ion exchange between well-dispersed AgVO3 and Na2S, the Ag2S can in situ grow on AgVO3, which prevents Ag2S and AgVO3 agglomeration/shedding in the photocatalytic reaction and contributes to the enhanced photocatalytic activity and cyclic stability. Benefiting from the unique structure, the Ag2S/AgVO3@GAs with excellent stability displayed the outstanding photodegradation efficiency for methyl orange (97% removal rate in 40 min) and disinfection activity for Escherichia coli (100% antibacterial efficiency in 36 min).
关键词： Photodegradation,Disinfection,Charge transfer,Three-dimensional graphene aerogel,Heterojunction
更新于2025-09-23 15:22:29
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Enhanced Charge Transport and Increased Active Sites on α-Fe <sub/>2</sub> O <sub/>3</sub> (110) Nanorod Surface Containing Oxygen Vacancies for Improved Solar Water Oxidation Performance
摘要： The e?ect of oxygen vacancies (VO) on α-Fe2O3 (110) facet on the performance of photoelectrochemical (PEC) water splitting is researched by both experiments and density functional theory (DFT) calculations. The experimental results manifest that the enhancement in photocurrent density by the presence of VO is related with increased charge separation and charge-transfer e?ciencies. The electrochemical analysis reveals that the sample with VO demonstrates an enhanced carrier density and reduced charge-transfer resistance. The results of DFT calculation indicate that the better charge separation is also contributed by the decrease of potential on the VO surface, which improves the hole transport from the bulk to the surface. The reduced charge-transfer resistance is owing to the greatly increased number of active sites. The current study provides important insight into the roles of VO on α-Fe2O3 photoanode, especially on its surface catalysis. The generated lesson is also helpful for the improvement of other PEC photoanode materials.
关键词： oxygen vacancies,α-Fe2O3,photoelectrochemical water splitting,charge-transfer efficiencies,density functional theory,charge separation
更新于2025-09-23 15:21:21