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Adsorption and photocatalytic oxidation of ibuprofen using nanocomposites of TiO2 nanofibers combined with BN nanosheets: Degradation products and mechanisms
摘要： This study investigated the adsorption and photocatalytic activity of TiO2-boron nitride (BN) nanocomposites for the removal of contaminants of emerging concern in water using ibuprofen as a model compound. TiO2 nanofibers wrapped by BN nanosheets were synthesized by electrospinning method. Characterization of the nanocomposite photocatalysts indicated the BN nanosheets improved the light absorbance and reduced the recombination of the photoexcited charge carriers (e- and h+). The photocatalytic oxidation products and mechanisms of ibuprofen by the TiO2-BN catalysts were elucidated using a multiple analysis approach by high performance liquid chromatography, ultraviolet absorbance, dissolved organic carbon, fluorescence excitation-emission matrices, and electrospray ionization–liquid chromatography–tandem mass spectrometry. The experimental results revealed that the photocatalytic oxidation by the TiO2-BN nanocomposites is a multi-step process and the interactions between ibuprofen molecules and the TiO2-BN nanocomposites govern the adsorption process. The increasing BN nanosheet content in the TiO2 nanofibers facilitated the breakdown of ibuprofen degradation intermediates (hydroxyibuprofen, carboxyibuprofen, and oxypropyl ibuprofen). Kinetic modeling indicated both adsorption and photocatalytic oxidation of ibuprofen by the TiO2-BN nanocomposites followed the first-order kinetic model. The photocatalytic oxidation rate increased with the increasing BN content in the nanocomposite catalysts, which was attributed to the enhanced light absorption capacity and the separation efficiency of the photoexcited electron (e-)-hole (h+) pairs. Multiple photocatalytic cycles were conducted to investigate the reusability and regeneration of the nanofibers for ibuprofen degradation.
关键词： adsorption,titanium dioxide boron-nitride nanocomposites,photocatalytic degradation mechanisms,degradation intermediates,photocatalytic oxidation
更新于2025-09-23 15:23:52
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Photocatalytic degradation of Microcystin-LR by visible light active and magnetic, ZnFe2O4-Ag/rGO nanocomposite and toxicity assessment of the intermediates
摘要： In this work, we aimed to study photocatalytic degradation of Microcystin-LR (MC-LR), a cyanotoxin known to cause acute as well as chronic toxicity and even mortality. The nanocomposite (NC) based on zinc ferrite (ZnFe2O4) was modified with graphene oxide (GO) and Ag nanoparticles (NPs) to enhance its photocatalytic properties under visible light. The so-formed ZnFe2O4-Ag/rGO NC exhibited superior performance in visible light allowing complete degradation of MC-LR within 120 mins of treatment with pseudo rate constant, k = 0.0515 min-1, several times greater than other photocatalysts, TiO2 (k = 0.0009 min-1), ZnFe2O4 (k = 0.0021 min-1), ZnFe2O4-Ag (k = 0.0046 min-1) and ZnFe2O4/rGO (k = 0.007 min-1) respectively. The total organic carbon analysis revealed that only 22% of MC-LR was mineralized on 120 mins of treatment time indicating presence of different intermediate by-products. The intermediates formed during photocatalytic treatment were identified using liquid chromatography–mass spectrometry (LCMS) based on which probable degradation pathways were proposed. The attack from ?OH radicals formed during the photocatalytic process resulted to hydroxylation and subsequent cleavage of diene bond. The toxicity assessment with Daphnia magna revealed that the degradation process has alleviated toxicity of the MC-LR and no toxic intermediates were formed during the treatment which is very important from eco-toxicological view point. Therefore, ZnFe2O4-Ag/rGO has a good potential in the field of environmental applications as visible light active and magnetic photocatalyst with enhanced performance.
关键词： Photocatalytic degradation,Toxicity,Daphnia magna,Microcystin,Intermediates
更新于2025-09-23 15:23:52
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Investigation into the Oxygen-Involved Electrochemiluminescence of Porphyrins and Its Regulation by Peripheral Substituents/Central Metals
摘要： We provide evidence of oxygen-involved electrochemiluminescence (ECL) of metal-free porphyrins and metalloporphyrins firstly. O2?? and OH?, that are oxygen intermediates, are indispensable for the formation of excited porphyrins, which has been proven by trapping free radical strategies. The wide differences regarding emission location and mechanism between metal-free porphyrins [including meso-tetra(4-methoxyphenyl)porphine (H2TMPP), meso-tetraphenylporphyrin (H2TPP) and meso-tetra(4-carboxyphenyl)porphine (H2TCPP)] and metalloporphyrins (MTPP) depend on whether protons are present in the center of the porphin ring. Besides, the oxygen-involved ECL of porphyrins can be controlled regularly by peripheral substituents with different polarities. Because of the stretched molecular structure and the decrease in electron density around the protons located at porphin ring; electron-withdrawing groups are more conducive to protons being attacked by O2??, as well as the enhancement of porphyrins ECL. The ECL efficiency [ФECL, which is normalized with respect to Ru(bpy)3(PF6)2 (taking ФECL of Ru(bpy)3(PF6)2 = 1 )] is gradually improved from H2TMPP (ФECL = 0.16), H2TPP (ФECL = 2.20) to H2TCPP (ФECL = 3.83); and the ФECL = 4.21 of Zn(II)TPP is significantly higher than other MTPP [e.g. Co(II)TPP and Cu(II)TPP]. A deeper understanding regarding the improvement of porphyrins ECL efficiency and new application towards porphyrins-related devices can be achieved from this work.
关键词： electrochemiluminescence,oxygen intermediates,central metals,porphyrins,peripheral substituents
更新于2025-09-23 15:22:29
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Enhanced triplet state generation through radical pair intermediates in BODIPY-quantum dot complexes
摘要： Generation of triplet excited states through radical pair intermediates has been extensively studied in molecular complexes. Similar schemes remain rare in hybrid structures of quantum dot-organic molecules, despite intense recent interest of quantum dot sensitized triplet excited state generation. Herein, we demonstrate that the efficiency of the intersystem crossing from the singlet to the triplet state in boron dipyrromethene (BODIPY) can be enhanced in CdSe quantum dot-BODIPY complexes through a radical pair intermediate state consisting of an unpaired electron in the quantum dot conduction band and that in oxidized BODIPY. By transient absorption spectroscopy, we show that the excitation of BODIPY with 650 nm light leads to the formation of a charge separated state by electron transfer from BODIPY to CdSe (with a time constant of 6.33 ± 1.13 ns), competing with internal conversion to the ground state within BODIPY, and the radical pair state decays subsequently by back charge recombination to generate a triplet excited state (with a time constant of 158 ± 28 ns) or the ground state of BODIPY. The overall quantum efficiency of BODIPY triplet excited state generation was determined to be (27.2 ± 3.0)%. The findings of efficient triplet state formation and intermediate radical pair states in this hybrid system suggest that quantum dot-molecule complexes may be a promising platform for spintronics applications.
关键词： CdSe quantum dot,radical pair intermediates,transient absorption spectroscopy,intersystem crossing,spintronics,triplet excited states,BODIPY,quantum dot-organic molecules
更新于2025-09-12 10:27:22
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Well-grown low-defect MAPbI3–xClx films for perovskite solar cells with over 20% efficiency fabricated under controlled ambient humidity conditions
摘要： The conventional MAI [(CH3NH3I (MAI)):PbI2:PbCl2= 3 : 0 : 1 [abbreviated as (3:0:1)]] precursor solution is known to result in CH3NH3PbI3–xClx films with large grain sizes when processed in an inert atmosphere, but it gives non-uniform perovskite films containing lots of voids and cracks when processed in ambient air. Furthermore, a dramatically longer annealing time (usually 100 min) is required for these films (3:0:1) due to the slow formation of the MAPbI3 phase via MACl loss, which is not conducive to perovskite film formation under ambient conditions due to perovskite degradation upon long exposure to moisture. Pure MAPbI3 films can be formed very rapidly from (1:1:0) (MAI:PbI2:PbCl2= 1 : 1 : 0) solution within a short annealing time, but they show small grain sizes and poor film quality. This work demonstrated that a fractional substitution of PbI2 with PbCl2 in the ([MAI]:[PbI2]= 1 : 1) precursor solution has a significant influence on film morphology and quality in terms of crystallization rate, grain size, crystallinity, and trap density of the formed perovskite film. Perovskite films can be formed with 5-min annealing at 100 °C from the precursor (MAI: PbI2:PbCl2= 1: 0.8 : 0.2) processed in ambient air (humidity, 20% RH), exhibiting more uniform, increased grain size and higher film quality with reduced trap densities compared to film (1:1:0), thus leading to significantly improved power conversion efficiency (PCE), from 16.7% for perovskite solar cells (PrSCs) based on film (1:1:0) to 20.04% for the cell based on film (1:0.8:0.2). Further, the effects of R (R= [MAI]/[PbI2+PbCl2]) on morphology, hole mobility, carrier lifetime and efficiency of PrSCs were systematically and thoroughly investigated. This study found that MAPbI3–xClx at R=1 can enable the highest hole mobility and longest carrier lifetime, thus giving the best performance at R=1.
关键词： mixed halide perovskite solar cells,lead chloride,grain size,trap density,crystal growth intermediates
更新于2025-09-12 10:27:22
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TEM Sample Preparation of Patterned Quantum Dots
摘要： Electrochemistry and heterogeneous catalysis continue to attract enormous interest. In situ surface analysis is a dynamic research field capable of elucidating the catalytic mechanisms of reaction processes. Shell-isolated nanoparticle-enhanced Raman spectroscopy (SHINERS) is a non-destructive technique that has been cumulatively used to probe and analyze catalytic-reaction processes, providing important spectral evidence about reaction intermediates produced on catalyst surfaces. In this perspective, we review recent electrochemical- and heterogeneous-catalysis studies using SHINERS, highlight its advantages, summarize the flaws and prospects for improving the SHINERS technique, and give insight into its future research directions.
关键词： Catalytic mechanisms,In situ surface analysis,SHINERS,Heterogeneous catalysis,Reaction intermediates,Electrochemistry,Shell-isolated nanoparticle-enhanced Raman spectroscopy
更新于2025-09-11 14:15:04
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Intermolecular Singlet Fission in Unsymmetrical Derivatives of Pentacene in Solution
摘要： Intermolecular singlet fission (SF) is an electronically coupled process between two chromophores, where distance dependences are decisive in terms of rates and yields. In the current work, a family of pentacene derivatives featuring different functional groups have been designed, synthesized, and probed with respect to intermolecular SF in the low, medium, and high concentration regimes rather than in the solid state. By means of advanced photophysical techniques, global analysis modeling, and ab initio calculations, a model for intermolecular SF is postulated. The model is based on an early key intermediate, which involves the diffusional encounter between one pentacene in its singlet excited-state with another one in its ground state and which features excimer characteristics. This is followed by a transformation into a coupled triplet excited-state. The role of the functional group appended to pentacene is analyzed with respect to steric shielding of the pentacene core as a means to prevent photophysical degradation, as well as control diffusional encounter and, subsequently, SF. The findings demonstrate the potential of new molecular materials for SF, especially in solution studies, as well as the challenges of implementing them in energy conversion schemes due to the appearance of photodegradation processes that compete with SF.
关键词： triplet diffusion,excitonic intermediates,singlet fission,unsymmetrical pentacene
更新于2025-09-10 09:29:36
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Insights on the photocatalytic degradation processes supported by TiO2/WO3 systems. The case of ethanol and tetracycline
摘要： TiO2/WO3 composites are widely in the literature as engineered systems for photocatalytic and (photo)electrochemical applications, since the presence of WO3 can promote both visible light absorption and electron transfer phenomena of TiO2. The preparation of these system, depending on the preparation method, can also affect the surface feature with respect to TiO2, modifying adsorption and performance, as well as the reaction mechanisms. Here, TiO2/WO3 composites were prepared by precipitation of WO3 onto the TiO2 surface and characterized in terms of their structural, morphological, optical and surface properties. Raman and IR spectroscopy as well as a marked shift in the isoelectric point support the preferential surface location of WO3. Samples were photocatalytically tested towards the degradation of ethanol and of tetracycline and the adsorption and degradation behaviour were studied, suggesting, in both cases, significant variations of the reaction paths by the addition of WO3.
关键词： Surface properties,Photocatalytic oxidation,Tungsten oxide,Intermediates,Reaction mechanism
更新于2025-09-10 09:29:36
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Segmental <sup>13</sup> C-Labeling and Raman Microspectroscopy of α-Synuclein Amyloid Formation
摘要： Mapping conformational changes of a-synuclein (a-syn) from soluble, unstructured monomers to b-sheet-rich aggregates is crucial towards understanding amyloid formation. Raman microspectroscopy is now used to spatially resolve conformational heterogeneity of amyloid aggregates and monitor amyloid formation of segmentally 13C-labeled a-syn in real-time. As the 13C-isotope shifts the amide-I stretching frequency to lower energy, the ligated construct, 12CS87C–140-a-syn, exhibits two distinct bands allowing for simultaneous detection of secondary structural changes in N-terminal 1–86 and C-terminal 87–140 residues. The disordered-to-b-sheet conformational change is first observed for the N-terminal followed by the C-terminal region. Finally, Raman spectroscopic changes occurred prior to Thioflavin T fluorescence enhancement, indicating that the amide-I band is a superior probe of amyloid formation.
关键词： chemical ligation,aggregation,b-sheets,transmission electron microscopy,kinetic intermediates
更新于2025-09-09 09:28:46
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Mechanistic insights into light-activated catalysis for water oxidation
摘要： The development of catalysts for water oxidation to oxygen has been the subject of intense investigation in the last decade. In parallel to the search for high catalytic performance, many works have focused on the mechanistic analysis of the process. In this perspective, the oxidation of water through light-assisted cycles composed of an electron acceptor (EA), a photosensitizer (PS), and a water oxidation catalyst (WOC) can provide insightful and complementary information with respect to the use of chemical oxidants or to electrochemical techniques. In this microreview, we discuss the mechanistic aspects of the EA/PS/WOC photoactivated cycles, and in particular: (i) the general elementary steps; (ii) the required features and the nature of the PS employed; (iii) the electron transfer processes and kinetics from the WOC to PS+ (hole scavenging); (iv) the detrimental quenching of the PS by the WOC and the alternative mechanistic routes; (v) the identification of WOC intermediates and, finally, (vi) the transposition of the above processes into a dye-sensitized photoanode embedding a WOC.
关键词： reaction mechanisms,intermediates,water oxidation,Electron transfer,photocatalysis
更新于2025-09-04 15:30:14