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Fabrication of Perylene Tetracarboxylic Diimide-Graphitic Carbon Nitride Heterojunction Photocatalyst for Efficient Degradation of Aqueous Organic Pollutants
摘要： Metal-free g-C3N4 is the promising candidate for the next generation visible light-responsive photocatalyst, however, high recombination probability of the photogenerated charge carriers on g-C3N4 limits its photocatalytic activity. To further increase the intrinsic photocatalytic activity of g-C3N4, here perylene tetracarboxylic diimide-g-C3N4 heterojunctions (PDI/GCN) are prepared by one-step imidization reaction between perylene tetracarboxylic dianhydride (PTCDA) and g-C3N4 in aqueous solution. By the combination of various testing results it is confirmed that the surface hybridization of PTCDA and g-C3N4 in the PDI/GCN heterojunctions via O=C?N?C=O covalent bonds occurs at lower PTCDA-to-g-C3N4 weight percentage. By selecting p-nitrophenol and levofloxacin as the target organic pollutants, the visible light photocatalytic performance of the PDI/GCN heterojunctions are studied. It shows that the PDI/GCN heterojunction prepared at PTCDA-to-g-C3N4 weight percentage of 1% exhibits remarkably higher visible light photocatalytic degradation and mineralization ability towards aqueous target pollutants as compared with g-C3N4 and Degussa P25 TiO2. On the basis of the experimental results including photoelectrochemistry, indirect chemical probe and electron spin resonance spectroscopy it is verified that the surface hybridization in the heterojunctions is responsible for this enhanced photocatalytic activity via accelerating the migration and separation of the photogenerated charge carriers, causing to produce more active species like ?O2?, hVB+ and ?OH for deep oxidation of PNP or LEV to CO2 and inorganic anions.
关键词： graphitic carbon nitride,heterojunction,perylene tetracarboxylic diimide,visible light photocatalysis,organic pollutant
更新于2025-09-04 15:30:14
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2D organic molecular metallic soft material derived from BEDO-TTF with electrochromic and rectifying properties
摘要： In this article we demonstrate that a migration of iodine species and chemical transformation in a moist environment induced by a voltage-biased Pt electrode is able to alter the color and degree of charge transfer in a layer of the 2D organic molecular metal (BEDO-TTF)2.4I3 [BEDO = bis(ethylenedioxy)tetrathiafulvalene] self-assembled at the surface of a polycarbonate film. These effects produce a reversible electrochromic behavior of the layer with low operating voltages and fast operation times. Adjuvant with electrochromism, this flexible material exhibits rectifying behavior whose I-V curves are dependent on the voltage sweep directions. These results open new possibilities for the design and fabrication of organic flexible materials for soft electrochromic and rectifying components. The easy working principle ensures reliability, low power consumption, and versatility through its implementation into simple devices. Such working principle has been confirmed by temperature dependent resistance measurements, X-Ray, EDX-SEM, and conducting-AFM studies.
关键词： 2D organic molecular metal,flexible electronics,rectifying properties,BEDO-TTF,electrochromic
更新于2025-09-04 15:30:14
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Recent advances in the synthesis of [ <i>a</i> ]-benzo-fused BODIPY fluorophores
摘要： This feature article summarizes the di?erent strategies for the synthesis of [a]-benzo-fused BODIPYs that have been reported in the literature until 2018. These p-extended BODIPYs are promising fluorophores for bio-imaging and organic photovoltaic applications due to both their attractive photophysical properties in the near-infrared area and their higher (photo)chemical stability compared to conventional bis-styryl derivatives. The four main strategies described in this review can be used to access either directly the expected [a]-benzo-fused BODIPYs or through the di-/tetra-hydroisoindole.
关键词： organic photovoltaic,fluorophores,near-infrared,BODIPY,bio-imaging
更新于2025-09-04 15:30:14
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Baking soda: an ultra-cheap and air stable electron injection layer for organic electronic devices
摘要： To realize high performance printed organic optoelectronic devices, the development of air-stable, cheap, and solution-processable electron injection layers (EILs) is urgently required to avoid the use of a low work-function metal electrode with poor air stability. We report sodium bicarbonate (baking soda, NaHCO3) as an efficient, low-cost, air-stable, and environmentally friendly EIL material in various printed organic electronic devices including organic solar cells (OSCs), organic light-emitting diodes (OLEDs), organic photodiodes (OPDs) and n-channel organic thin film transistors (OFETs). UV photoelectron spectroscopy results indicated that the work-function of various common electrodes used for organic devices such as ITO, Au, Al and poly(3,4-ethylenedioxythiophene):poly(styrenesulfonate) decreased significantly by more than 1 eV following deposition of a thin NaHCO3 film. The performance and stability of these organic devices improved by around 15% overall with ultra-cheap, air stable EILs. In particular, high performance OSCs based on PTB7:PC71BM with a power conversion efficiency of 8.40% and solution processed OLEDs based on PVK:PBD:Ir(ppy)3 with light emitting efficiencies of 68.5 cd A?1 and 20 lm A?1 were achieved by applying a NaHCO3 interlayer.
关键词： air-stable,sodium bicarbonate,organic electronic devices,electron injection layers,baking soda,low-cost,solution-processable
更新于2025-09-04 15:30:14
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Continuous multi-channel sensing of volatile acid and organic amine gases using a fluorescent self-assembly system
摘要： A new gelator (1) was designed and synthesized through a Knoevenagel condensation reaction between 4-dimethylaminocinnamaldehyde and a gallic acid derivative containing a carbanion. This gelator could form stable organogels in hexane, petroleum ether, DMSO and acetonitrile. The self-assembly processes of 1 in four solvents were carefully investigated via UV-vis absorption, fluorescence, FTIR, XRD, water-contact angles and field emission scanning electron microscopy (FESEM). Nanofibre and microsphere structures were observed in their self-assembly systems. The xerogel 1 film surfaces exhibited different hydrophobicities with water contact angles of 113.5–1551. The J-type aggregation mode was employed in the self-assembly process, and hydrogen bonding and p–p stacking were the main driving forces for organogel formation. Fluorescence emission of organogel 1 from acetonitrile was shifted from 558 nm of its corresponding diluted acetonitrile solution to 601 nm with a red-shift of 43 nm. Interestingly, compound 1 could sensitively respond to volatile acid, and further to organic amine gases along with obvious color changes. The detection limit for trifluoroacetic acid (TFA) by solution 1 in acetonitrile was 1.03 × 10?8 M with a corresponding association constant (K) of 6.85 × 104 M?1. The detection limit for triethylamine (TEA) by solution 1 in acetonitrile with 1.8 eq. of TFA was 1.27 × 10?8 M with a corresponding association constant (K) of 4.027 × 104 M?1. The yellow color of solution 1 could be reversibly changed to colorless in the titration process. At the same time, xerogel 1 exhibited sensitive response abilities for volatile acids and organic amines. The fluorescence of xerogel 1 could be quenched when in contact with a volatile acid within 7 s and recovered under further contact with a volatile amine within 15 s. The detection limit of xerogel film 1 towards trifluoroacetic acid (TFA) gases was 3.2 ppb. Organogel 1 exhibited sensitive response abilities towards TFA and TEA, and then rapidly expressed fluorescence, a gel state and a color change. This research would provide a new window into fast and sensitive detection of volatile acids and organic amines.
关键词： organic amine gases,sensing,volatile acid,fluorescent self-assembly system,gelator
更新于2025-09-04 15:30:14
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Lateral ordering of PTCDA on the clean and the oxygen pre-covered Cu(100) surface investigated by scanning tunneling microscopy and low energy electron diffraction
摘要： We have investigated the adsorption of perylene-3,4,9,10-tetracarboxylic acid dianhydride (PTCDA) on the clean and on the oxygen pre-covered Cu(100) surface [referred to as (√2 × 2√2)R45° – 2O/Cu(100)] by scanning tunneling microscopy (STM) and low energy electron diffraction (LEED). Our results confirm the (4√2 × 5√2)R45° superstructure of PTCDA/Cu(100) reported by A. Schmidt et al. [J. Phys. Chem. 1995, 99,11770–11779]. However, contrary to Schmidt et al., we have no indication for a dissociation of the PTCDA upon adsorption, and we propose a detailed structure model with two intact PTCDA molecules within the unit cell. Domains of high lateral order are obtained, if the deposition is performed at 400 K. For deposition at room temperature, a significant density of nucleation defects is found pointing to a strong interaction of PTCDA with Cu(100). Quite differently, after preadsorption of oxygen and formation of the (√2 × 2√2)R45° – 2O/Cu(100) superstructure on Cu(100), PTCDA forms an incommensurate monolayer with a structure that corresponds well to that of PTCDA bulk lattice planes.
关键词： PTCDA,STM,template,thin organic films,LEED,Cu(100)
更新于2025-09-04 15:30:14
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De novo design of organic photocatalysts: bithiophene derivatives for the visible-light induced C-H functionalization of heteroarenes
摘要： Herein, we report the de novo synthesis and characterization of a series of substituted bithiophene derivatives as novel inexpensive organic photocatalysts. DFT calculations were used to predict a priori their absorption spectra and redox potentials, which were then confirmed with empirical data. The photocatalytic activity of this novel class of organic photoredox catalyst was demonstrated in two visible-light mediated strategies for the C-H functionalization of heteroarenes. The implementation of these strategies in a continuous-flow photo-microreactor afforded moderate to excellent yields within few minutes of reaction time. Due to their straightforward synthesis, low cost and good photocatalytic properties we believe that the proposed bithiophene derivatives could be employed as a new class of organic photoredox catalysts.
关键词： Organic photocatalysts,C-H functionalization,Photoredox catalysis,DFT calculations,Continuous flow catalysis
更新于2025-09-04 15:30:14
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Hybrid Nanomedicine Fabricated from Photosensitizer-Terminated Metal-Organic Framework Nanoparticles for Photodynamic Therapy and Hypoxia-Activated Cascade Chemotherapy
摘要： During photodynamic therapy (PDT), severe hypoxia often occurs as an undesirable limitation of PDT owing to the O2-consuming photodynamic process, compromising the effectiveness of PDT. To overcome this problem, several strategies aiming to improve tumor oxygenation are developed. Unlike these traditional approaches, an opposite method combining hypoxia-activated prodrug and PDT may provide a promising strategy for cancer synergistic therapy. In light of this, azido-/photosensitizer-terminated UiO-66 nanoscale metal–organic frameworks (UiO-66-H/N3 NMOFs) which serve as nanocarriers for the bioreductive prodrug banoxantrone (AQ4N) are engineered. Owing to the effective shielding of the nanoparticles, the stability of AQ4N is well preserved, highlighting the vital function of the nano-carriers. By virtue of strain-promoted azide–alkyne cycloaddition, the nanocarriers are further decorated with a dense PEG layer to enhance their dispersion in the physiological environment and improve their therapeutic performance. Both in vitro and in vivo studies reveal that the O2-depleting PDT process indeed aggravates intracellular/tumor hypoxia that activates the cytotoxicity of AQ4N through a cascade process, consequently achieving PDT-induced and hypoxia-activated synergistic therapy. Benefiting from the localized therapeutic effect of PDT and hypoxia-activated cytotoxicity of AQ4N, this hybrid nanomedicine exhibits enhanced therapeutic efficacy with negligible systemic toxicity, making it a promising candidate for cancer therapy.
关键词： hypoxia-activated prodrugs,cascade therapy,nanoscale metal–organic frameworks,banoxantrone,photodynamic therapy
更新于2025-09-04 15:30:14
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Organic-Inorganic Hybrid Nanoflowers as Potent Materials for Biosensing and Biocatalytic Applications
摘要： Flower-shaped organic-inorganic hybrid nanostructures, termed nanoflowers, have received considerable recent attention as they possess greatly enhanced activity, stability, durability, and even selectivity of entrapped organic biomolecules, which are much better than those from the conventional methods. They can be synthesized simply via co-incubation of organic and inorganic components in aqueous buffer at room temperature and yield hierarchical nanostructures with large surface-to-volume ratios, allowing for low-cost production by easy scale-up, as well as the high loading capacity of biomolecules without severe mass transfer limitations. Since a pioneering study reported on hybrid nanoflowers prepared with protein and copper sulfate, many other organic and inorganic components, which endow nanoflowers with diverse functionalities, have been employed. Thanks to these features, they have been applied in a diverse range of areas, including biosensors and biocatalysis. To highlight the progress of research on organic-inorganic hybrid nanoflowers, this review discusses their synthetic methods and mechanisms, structural and biological characteristics, as well as recent representative applications. Current challenges and future directions toward the design and development of multi-functional nanoflowers for their widespread utilization in biotechnology are also discussed.
关键词： Organic-inorganic hybrid nanoflowers,Coordination interaction,Biosensor,Enzyme immobilization,Biocatalysis
更新于2025-09-04 15:30:14
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Reversible Optical Writing and Data Storage in an Anthracene‐Loaded Metal‐Organic Framework
摘要： Metal-organic frameworks (MOFs) enable the design of host-guest systems with specific properties. In this work, we show how confinement of anthracene in a well-chosen MOF host leads to reversible yellow-to-purple photoswitching of fluorescence emission. This behavior has not been observed before for anthracene, either in pure form or adsorbed in other porous hosts. The photoresponse of the host-guest system is caused by the photodimerization of anthracene, which is greatly facilitated by the pore geometry, connectivity and volume as well as the structural flexibility of the MOF host. The photoswitching behavior is used to fabricate photopatternable and erasable surfaces that, in combination with data encryption and decryption, hold promise in product authentication and secure communication applications.
关键词： product authentication,photoswitching,anthracene,metal-organic frameworks,host-guest system
更新于2025-09-04 15:30:14