Spin-trapping Experiments Research Articles

Inverse opal TiO2-CdS photonic crystal beads with slow light effect for photocatalytic degradation

Photocatalytic oxidation technology using solar energy is an effective strategy to solve environmental pollution and energy shortage. To avoid angle dependence of traditional photonic crystal photocatalysts and address the limitations of high charge recombination rate and low light utilization of TiO2, this study proposed a novel inverse opal TiO2/CdS photonic crystal beads (IO TiO2/CdS PCBs) photocatalyst. By leveraging the synergistic coupling of PCBs’ slow light effect and TiO2/CdS heterojunction, the photocatalytic activity was significantly enhanced. The results revealed that the PCBs matching the blue edge with TiO2′s electronic band gap (IO TiO2-140 PCBs) exhibited the highest apparent rate constant of 0.01901 min−1. By introducing CdS to form a heterojunction with TiO2, the photocatalytic performance was further improved by effectively inhibiting the recombination of photogenerated carriers. The degradation rate of RhB reached 96.6 % in 60 min, outperforming that of IO TiO2 at 65.1 %, with the rate constant increasing by 3.1 times. Electron spin resonance and trapping experiments indicated that h+ was the main active specie, and the possible reaction mechanism path was proposed. The combination of “extrinsic” modifications by doping CdS and “self-structural” modifications by shaping TiO2 into periodic IO PCBs structure provided a systematic insight on the design of novel photocatalysts.

Carbon dot unravels accumulation of triterpenoid in Evolvulus alsinoides hairy roots culture by stimulating growth, redox reactions and ANN machine learning model prediction of metabolic stress response

Evolvulus alsinoides, a therapeutically valuable shrub can provide consistent supply of secondary metabolites (SM) with pharmaceutical significance. Nonetheless, because of its short life cycle, fresh plant material for research and medicinal diagnostics is severely scarce throughout the year. The effects of exogenous carbon quantum dot (CD) application on metabolic profiles, machine learning (ML) prediction of metabolic stress response, and SM yields in hairy root cultures of E. alsinoides were investigated and quantified. The range of the particle size distribution of the CDs was between 3 and 7 nm. The CDs EPR signal and spin trapping experiments demonstrated the formation of O2-•spin-adducts at (g = 2.0023). Carbon dot treatment increased the levels of hydrogen peroxide and malondialdehyde concentrations as well as increased antioxidant enzyme activity. CD treatments (6 μg mL-1) significantly enhanced the accumulation of squalene and stigmasterol (7 and 5-fold respectively). The multilayer perceptron (MLP) algorithm demonstrated remarkable prediction accuracy (MSE value = 1.99E-03 and R2 = 0.99939) in both the training and testing sets for modelling. Based on the prediction, the maximum oxidative stress index and enzymatic activities were highest in the medium supplemented with 10 μg mL-1 CDs. The outcome of this study indicated that, for the first time, using CD could serve as a novel elicitor for the production of valuable SM. MLP may also be used as a forward-thinking tool to optimize and predict SM with high pharmaceutical significance. This study would be a touchstone for understanding the use of ML and luminescent nanomaterials in the production and commercialization of important SM.

A dual-functional α-diketone-based disulfide monomer for visible LED photopolymerization: Mitigating volumetric shrinkage and triggering polymerization

A α-diketone-based disulfide monomer (OHS), which serves the function of both volumetric shrinkage decreases and photopolymerization initiation under the irradiation of 405 light-emitting diode (LED) was designed and synthesized. The photochemical and photoinitiating performances were study by ultraviolet–visible spectrophotometer, electron spin resonance spin trapping (ESR-ST) experiments and real-time infrared spectrometer (FTIR). Despite OHS exhibits weak absorption at approximately 405 nm, OHS can effectively produce aromatic sulfur radicals to induce photopolymerization of itself and the bisphenol A glycerolate dimethacrylate (Bis-GMA)/triethylene glycol dimethacrylate (TEGDMA) photopolymerizable system under 405 nm LED exposure. With increasing OHS addition, the final double bond conversion and maximum polymerization rate of the Bis-GMA/TEGDMA system improved, reaching up to 86.0% and 2.33% s-1, respectively. Importantly, OHS significantly reduces the volumetric shrinkage ratio of the Bis-GMA/TEGDMA photopolymerizable system, with the volumetric shrinkage ratio (5.01%) of the system containing 5% OHS declining by almost 50% compared to that (8.51%) of the control system without OHS. This reduction is attributed to reversible characteristic of the disulphide bonds and intermolecular hydrogen bondings. Furthermore, OHS has little influence on the gelation ratio, thermostability, and frictional resistance of the cured film.

Advancing photopolymerization and 3D printing: High-Performance NiII complexes bearing N2O2 Schiff-base ligands as photocatalysts

New high-performance photocatalysts based on metal structures are being developed for polymerization. However, using low-cost metals while ensuring effectiveness is challenging. In this study, two NiII complexes NiL1 and NiL2 were synthesized using N2O2 Schiff-base ligands bearing π-extended rings (naphthaldehyde (H2L1) and phenylsalicylaldehyde (H2L2) groups), respectively. These complexes were characterized by FTIR, UV–Vis and 1H NMR spectroscopy, elemental analysis, cyclic voltammetry, and MALDI-TOF mass spectrometry. NiL1 and NiL2 were evaluated in photoinitiating system as new photocatalysts for the Free Radical Photopolymerization of Ethoxylated (3) Trimethylolpropane Triacrylate (TMPETA) for violet and green light. Three-component systems were employed in the presence of Di-tert-butyl-diphenyl iodonium hexafluorophosphate (Iod) and ethyl dimethylaminobenzoate (EDB). The absorption, luminescence, and redox properties of nickel complexes and ligands were explored and compared for a better understanding of their structure/reactivity relationship. The designed nickel complexes showed good photoinitiation abilities. NiL2 exhibited the highest monomer conversion, and it was investigated in the on–off process under green light irradiation, demonstrating the efficiency of the system in reactivating the polymerization process. An oxidative pathway mechanism was proposed based on free energy, steady state photolysis and electron spin resonance spin trapping experiments. The best system was successfully applied in cationic photopolymerization and 3D printing.

Triphenylamine based oxime ester photoinitiator for LED-induced free radical photopolymerization and 3D printing

With the development of light-emitting diode (LED), it is increasingly important to design and prepare photoinitiators that can be used for LED excitation. We designed and synthesized four new LED oxime ester photoinitiators (TOXEs) based on the triphenylamine group. Among them, the maximum absorption wavelengths of TOXE-3 and TOXE-4 are red-shifted to 402 nm and 397 nm, and have high molar absorption coefficients (ε) of 24315 M-1cm−1 and 29915 M-1cm−1, respectively, which are higher than that of ethenone, 1-[9-ethyl-6-(2-methylbenzoyl)-9H-carbazol-3-yl] ethanone 1-(O-acetyloxime) (OXE02, 342 nm, 21836 M-1cm−1), indicating that it can be used in LED polymerization. Investigating the photopolymerization properties of the TOXEs/α, ω-diacryloyl poly(ethylene glycol) (PEGDA) system, under LED@365 nm irradiation, the double bond conversion rate (DC) of TOXE-1 and TOXE-2 were 83 % and 92 %, which were higher than OXE02 (80 %). Under LED@405 nm irradiation, the DC of TOXE-3 and TOXE-4 are 80 % and 78 % respectively, which is higher than that of OXE02 (52 %). To improve the photoinitiation ability of TOXEs, a two-component photoinitiation system using bis(4-tert-butylphenyl) iodonium (Iod) as an additive was tested. The DC of TOXEs has been improved under different light sources. Under LED@480 nm irradiation, the final DC of TOXE-4/Iod/PEGDA is 83 %. In addition, TOXE-3 and TOXE-4 can be applied to the laser cladding deposition (LCD) 3D printers. At the same time, we conduct research and verification on the polymerization mechanism of TOXEs through steady-state photolysis and electron spin resonance spin trapping experiments (ESR-ST). In addition, cytotoxicity assay and thermal stability testing showed that TOXEs exhibited excellent biocompatibility and thermal stability.

Eosin Y derivatives for visible light-mediated free-radical polymerization: Applications in 3D-photoprinting and bacterial photodynamic inactivation

This study reports the design and the subsequent use of mono-allylated (EY-MA) and di-allylated (EY-DA) derivatives of eosin Y (EY) as highly efficient visible light-sensitive photosensitizers (PS) of bio-based H-donor molecules (cysteamine (Cys) or N-acetyl-L-cysteine (NAC)) and an electron donor (N-methyldiethanolamine, MDEA) for free-radical and thiol-acrylate polymerizations of a biobased monomer derived from soybean oil (SOA) upon exposure to visible light. High final acrylate conversions for SOA polymerization (up to 80 %) evidence the efficient photoinitiating properties of the eosin derivatives systems under irradiation with light emitting diodes (LEDs) centred at 405, 455 and 505 nm, and outperform those obtained with EY and other common photosensitizers such as camphorquinone or benzophenone. As described by fluorescence and phosphorescence analyses, laser flash photolysis (LFP) and electron paramagnetic resonance spin-trapping (EPR-ST) experiments, EY-MA and EY-DA can react via a proton/proton-coupled electron transfer reaction with Cys (or NAC) and MDEA respectively. The efficient singlet oxygen generation of the EY-MA-based materials upon exposure to visible light leads to excellent antibacterial properties, against both Gram-positive Staphylococcus aureus (S. aureus) and Gram-negative Escherichia coli (E. coli). A 3-log decrease of E. coli adhesion on the surface of the materials is observed and 100 % adhesion inhibition of S. aureus is also demonstrated. The co-polymerization of the eosin-derived PS with the polymer matrix ensures sustainable antibacterial properties against both bacteria strains upon visible light exposure as it prevents their leakage out of the polymer network. Finally, finely complex 3D structures are successfully obtained by a 3D-photoprinting technology with the investigated EY-MA-based formulation using LED@405 nm.

Aerobic Oxidative Synthesis of Formamides from Amines and Bioderived Formyl Surrogates

AbstractHerein we present a new strategy for the oxidative synthesis of formamides from various types of amines and bioderived formyl sources (DHA, GLA and GLCA) and molecular oxygen (O2) as oxidant on g‐C3N4 supported Cu catalysts. Combined characterization data from EPR, XAFS, XRD and XPS revealed the formation of single CuN4 sites on supported Cuphen/C3N4 catalysts. EPR spin trapping experiments disclosed ⋅OOH radicals as reactive oxygen species and ⋅NR1R2 radicals being responsible for the initial C−C bond cleavage. Control experiments and DFT calculations showed that the successive C−C bond cleavage in DHA proceeds via a reaction mechanism co‐mediated by ⋅NR1R2 and ⋅OOH radicals based on the well‐equilibrated CuII and CuI cycle. Our catalyst has much higher activity (TOF) than those based on noble metals.

Electrochemical selection of ferrous phosphide (FexP) as efficient catalyst for wastewater treatment: Performance and mechanism

Iron phosphide (FexP) has a great potential for electrochemical catalysis attributing to its outstanding electrical conductivity and activity. In the present study, a series of FexP (FeP, Fe2P and Fe3P) were carried out as catalysts for the oxidation of phenol from wastewater by the heterogeneous EF processes. Compared with FeP and Fe2P catalysts, Fe3P has shown significant two-electron oxygen reduction activity and H2O2 selectivity (90–100 %). The degradation efficiencies of phenol in Fe3P/EF (100 %) were higher than those in Fe2P/EF (91 %) and FeP/EF (67 %) upon 60-min electrochemical oxidation under pH 7. The Fe3P-CF/EF system could broaden the range of solution pH, as well the decay kinetics of phenol was enhanced by 1.5–2.4 times and the disposal cost was reduced by 33–41 % compared with FeP/EF and Fe2P/EF. Feɑ+ in Fe3P could promote the generation of •OH via accelerating Fe(II)/Fe(III) cycle and accelerating the transfer rate of electrons between Fe3P and H2O2. It was proved that •OH played a dominant role in removing phenol with the electron spin resonance (ESR) tests and trapping experiments. This work selected the most effective FexP catalyst in heterogeneous EF process and would bring new insights for organics removal from wastewater via H2O2 activation.

Relationship among EPR oxidative stability and spectrophotometric parameters connected to antioxidant activity in beer samples

A relationship between EPR and spectrophotometric parameters related to beer staling and antioxidant activity, was identified. AUC (area under the curve), intensity at 150 min (T150), radical scavenging activity (RSA), total phenolic compounds (TPC), hydroxyl radical scavenging capacity (HRSC) and one parameter linked to staling degree of beers (thiobarbituric index, TBI) were related. Temperature was modified to find the proper working conditions for EPR spin-trapping experiments and it was found that it affected the kinetic of PBN adduct evolution. For the samples reaching a maximum intensity signal, the higher the heating temperature, the shorter the time interval needed to reach it. No linear relationship was detected among parameters obtained with EPR spin trapping experiments and RSA, TPC, TPI, and HRSC when correlating one parameter with another. On the contrary, a good linear relationship was found among AUC or T150 and a combination of RSA, TPC, TPI, and HRSC (R2 = 0.9562 and 0.9694, respectively). The goodness of fit increased to R2 = 1 when a combination of AUC and T150 was related to a combination of RSA, TPC, and TPI, and HRSC.

Visible-Light Activation of Diorganyl Bis(pyridylimino) Isoindolide Aluminum(III) Complexes and Their Organometallic Radical Reactivity.

We report on the synthesis and characterization of a series of (mostly) air-stable diorganyl bis(pyridylimino) isoindolide (BPI) aluminum complexes and their chemistry upon visible-light excitation. The redox non-innocent BPI pincer ligand allows for efficient charge transfer homolytic processes of the title compounds. This makes them a universal platform for the generation of carbon-centered radicals. The photo-induced homolytic cleavage of the Al-C bonds was investigated by means of stationary and transient UV/Vis spectroscopy, spin trapping experiments, as well as EPR and NMR spectroscopy. The experimental findings were supported by quantum chemical calculations. Reactivity studies enabled the utilization of the aluminum complexes as reactants in tin-free Giese-type reactions and carbonyl alkylations under ambient conditions, which both indicated radical-polar crossover behavior. A deeper understanding of the physical fundamentals and photochemical process was provided, furnishing in turn a new strategy to control the reactivity of bench-stable aluminum organometallics.

Aktivierung von Diorganyl‐bis(pyridylimino)isoindolid‐Aluminiumkomplexen mit sichtbarem Licht und deren organometallische Radikalreaktivität

AbstractWir berichten über die Synthese und Charakterisierung einer Reihe von weitgehend luftstabilen Diorganyl‐bis(pyridylimino)isoindolid(BPI)−Aluminiumkomplexen und deren Reaktivität durch elektronische Anregung mittels sichtbarem Licht. Der redox‐aktive, “nicht‐unschuldige” BPI‐Pinzettenligand ermöglicht eine effiziente Charge‐Transfer‐Homolyse der Al−C‐Bindung. Dadurch dienen die vorgestellten Verbindungen als Ausgangsmaterialien für die Generierung von kohlenstoffzentrierten Radikalen. Die photo‐induzierte homolytische Spaltung der Al−C‐Bindung wurde mittels stationärer und transienter UV/Vis‐Spektroskopie, Abfangexperimenten der entsprechenden Radikale, sowie EPR‐ und NMR‐Spektroskopie analysiert und zudem mithilfe von quantenchemischen Rechnungen untersucht. Studien zur Reaktivität der entsprechenden Aluminiumkomplexe ermöglichten deren Nutzung als Reagenzien in Giese‐artigen Reaktionen und der Alkylierung von organischen Carbonylverbindungen, wobei Hinweise auf einen Wechsel von radikalischen zu polaren Mechanismen (radical‐polar‐crossover) gefunden wurden. Durch diese Arbeit wurde ein vertieftes Verständnis der physikalischen Hintergründe und der ablaufenden photochemischen Prozesse generiert, wodurch eine neue Strategie der Reaktionskontrolle von luftstabilen Organometallverbindungen des Aluminiums etabliert wurde.

Ultrafast Sunlight-Induced Polymerization: Unveiling 2-Phenylnaphtho[2,3-d]Thiazole-4,9-dione as a Unique Scaffold for High-Speed and Precision 3D Printing.

A series of 15 dyes based on the 2-phenylnaphtho[2,3-d]thiazole-4,9-dione scaffold and 1 compound based on the 2,3-diphenyl-1,2,3,4-tetrahydrobenzo[g]quinoxaline-5,10-dione scaffold are studied as photoinitiators. These compounds are used in two- and three-component high-performance photoinitiating systems for the free radical polymerization of trimethylolpropane triacrylate (TMPTA) and polyethylene glycol diacrylate (PEGDA) under sunlight. Remarkably, the conversion of TMPTA can reach ≈60% within 20s, while PEGDA attains a 96% conversion within 90s. To delve into the intricate chemical mechanisms governing the polymerization, an array of analytical techniques is employed. Specifically, UV-vis absorption and fluorescence spectroscopy, steady-state photolysis, stability experiments, fluorescence quenching experiments, cyclic voltammetry, and electron spin resonance spin trapping (ESR-ST) experiments, collectively contribute to a comprehensive understanding of the photochemical mechanisms. Photoinitiation capacities of these systems are determined using real-time Fourier transformed infrared spectroscopy (RT-FTIR). Of particular interest is the revelation that, owing to the superior initiation ability of these dyes, high-resolution 3D patterns can be manufactured by direct laser write (DLW) technology and 3D printing. This underscores the efficient initiation of free radical polymerization processes by the newly developed dyes under both artificial and natural light sources, presenting an avenue for energy-saving, and environmentally friendly polymerization conditions.

DFT Studies of Dimethylaminophenyl-Substituted Phthalocyanine and Its Silver Complexes.

The dimethylaminophenyl-substituted silver phthalocyanine [dmaphPcAg] can be used as a UV-vis photoinitiator for in situ preparation of a silver/polymer nanocomposite. To verify early steps of the supposed mechanism of radical polymerization, we performed quantum chemical calculations of m[dmaphPcAg]q complexes with charges q = +1 to -2 in the two lowest spin states m, of a free ligand and its dehydrogenated/deprotonated products m[dmaphPcHn]q, n = 2 to 0, q = 0, -1 or -2, in the lowest spin states m. The calculated electronic structures and electron transitions of all the optimized structures in CHCl3 solutions are compared with experimental EPR and UV-vis spectra, respectively. The unstable 3[dmaphPcAg]+ species deduced only from previous EPR spin trap experiments was identified. In addition to 2[dmaphPcAg]0, our results suggest the coexistence of both reaction intermediates 1[dmaphPcAg]- and 3[dmaphPcAg]- in reaction solutions. Silver nanoparticle formation is a weak point of the supposed reaction mechanism from the energetic, stereochemistry, and electronic structure points of view.

Synthesis And In-Silico Anti-Cancer Potential of N-Aryl-Keto-Nitrone As A Spin Adducts

Introduction: This study explores N-Aryl-Keto-Nitrone synthesis and its impact on spin-trapping chemistry, revealing crucial insights into free radicals' roles in diseases. While aldo-nitrones are well-studied, keto-nitrones, especially linear ones, are underexplored as spin traps. Seven novel keto-nitrones are introduced, and their efficacy in capturing carbon-centered radicals is assessed. Methods: Synthesis involves dissolving N-aryl-nitroso compounds in THF, adding NaOH, and introducing dimethyl or diethyl bromo malonate. Thin-layer chromatography monitors the reaction, yielding crude keto-nitrones purified through extraction, drying, and recrystallization. Spin trapping experiments use various radical sources, analyzed by EPR at room temperature. In silico predictions assess ADME properties, P-glycoprotein substrate potential, and molecular docking explores binding orientations with VEGFR2 and EGFR. Results: Diverse N-aryl-keto-nitrones with unique structures and reactivity towards carbon-centered radicals are successfully synthesized. Enhanced interpretability is observed in penta-deuterated compounds N6 and N7. The compounds exhibit varying lipophilicity and resistance to oxidative or reducing agents, broadening their potential applications. In silico predictions show favorable properties, and the compounds demonstrate potential as VEGFR1 downregulators, suggesting applications in disrupting angiogenic signals in cancers. Conclusion: This research advances spin-trapping chemistry by introducing linear keto-nitrones as effective agents. The synthesized compounds demonstrate versatility and impact, with ongoing research focusing on additional applications and refinement for practical use.

Enhancing the Photocatalytic Activity and Luminescent Properties of Rare-Earth-Doped CeO2 Nanoparticles

Our study is focused on the structural and morphological characteristics, optical behaviour and photocatalytic properties of undoped and 5 at% Eu3+-, Gd3+- and Y3+-doped CeO2 nanoparticles prepared by a green hybrid sol-gel combustion method. Several techniques such as X-ray diffraction powder (XRD), Transmission Electron Microscopy (TEM), UV-Vis spectroscopy, Photoluminescence spectroscopy (PL) and Electron Paramagnetic Resonance (EPR) have been used to investigate the obtained samples. Moreover, the correlation between the characteristics and properties has been studied. The nanoparticles observed by TEM exhibit a pseudo-spherical shape, except for Y3+-doped CeO2, which presents an acicular shape. The average size of undoped and rare-earth-doped CeO2 nanoparticles is below 10 nm, in good agreement with the calculations performed based on XRD analyses. From UV-Vis analyses it has been deduced that with doping the band gap energy decreases, which shows that additional levels are introduced by doping into the CeO2 band gap. The EPR spectra evidence similar behaviour for all doped samples. The photocatalytic activity was evaluated by the degradation of rhodamine B (RhB) under UV light irradiation. The photodegradation mechanism has been studied in depth based on the formation of electron-hole pairs, and to evidence the reactive oxygen species, ESR coupled with spin-trapping experiments was performed. In the case of Y-doped CeO2 nanoparticles, the generation of both •OOH and •O2− radicals involved in RhB photodegradation was highlighted.

Thioxanthone-Based Siloxane Photosensitizer for Cationic/Radical Photopolymerization and Photoinduced Sol-Gel Reactions.

In this investigation, a multifunctional visible-light TX-based photosensitizer containing a siloxane moiety (TXS) was designed with a good overall yield of 54%. The addition of a siloxane moiety enabled the incorporation of a TX photosensitizer into a siloxane network by photoinduced sol-gel chemistry, thus avoiding its release. Both liquid 1H and solid-state 29Si NMR measurements undeniably confirmed the formation of photoacids resulting from the photolysis of the TXS/electron acceptor molecule (Iodonium salt), which promoted the photoinduced hydrolysis/condensation of the trimethoxysilane groups of TXS, with a high degree of condensation of its inorganic network. Notably, the laser flash photolysis, fluorescence, and electron paramagnetic resonance spin-trapping (EPR ST) experiments demonstrated that TXS could react with Iod through an electron transfer reaction through its excited states, leading to the formation of radical initiating species. Interestingly, the TXS/Iod was demonstrated to be an efficient photoinitiating system for free-radical (FRP) and cationic (CP) polymerization under LEDs@385, 405, and 455 nm. In particular, whatever the epoxy monomer mixtures used, remarkable final epoxy conversions were achieved up to 100% under air. In this latter case, we demonstrated that both the photoinduced sol-gel process (hydrolysis of trimethoxysilane groups) and the cationic photopolymerization occurred simultaneously.

Visible light photocatalytic NOx removal with suppressed poisonous NO2 byproduct generation over simply synthesized triangular silver nanoparticles coupled with tin dioxide.

The treatment or conversion of air pollutants with a low generation of secondary toxic substances has become a hot topic in indoor air pollution abatement. Herein, we used triangle-shaped Ag nanoparticles coupled with SnO2 for efficient photocatalytic NO removal. Ag triangular nanoparticles (TNPs) were synthesized by the photoreduction method and SnO2 was coupled by a simple chemical impregnation process. The photocatalytic NO removal activity results show that the modification with Ag TNPs significantly boosted the removal performance up to 3.4 times higher than pristine SnO2. The underlying roles of Ag TNPs in NO removal activity improvement are due to some advantages of Ag TNPs. Moreover, the Ag TNPs contributed photogenerated holes as the main active species toward enhancing the NO oxidation reaction. In particular, the selectivity toward green products significantly improved from 52.78% (SnO2) to 86.99% (Ag TNPs/SnO2). The formation of reactive radicals under light irradiation was also verified by DMPO spin-trapping experiments. This work provides a potential candidate for visible-light photocatalytic NO removal with low toxic byproduct generation.

Boosted photocatalytic H2 production over p-n S-scheme heterojunction of 0D Ni3V2O8 quantum dots decorated on ultra-thin 2D g-C3N4 nanosheets

Novel 0D Ni3V2O8 quantum dots (QDs) were decorated on the ultra-thin 2D g-C3N4 nanosheet (UCN) using a hydrothermal approach. The embedded Ni3V2O8 QDs play a dual role by trapping charge carriers, promoting electron-hole separation, and forming a p-n S-scheme heterojunction, improving the redox potential of the electrons and holes for surface reactions. HR-TEM analysis confirmed that Ni3V2O8 QDs with a size varying between 3 to 5 nm have intimate contact with the UCN surface. XPS and ESR spin-trapping agents experiment confirmed the formation of S-scheme heterojunctions between Ni3V2O8 QDs and UCN. Photocurrent and PL spectra indicated the synthesized heterostructures have high charge carrier transportation and lower recombination rates. The optimum Ni3V2O8 QDs/UCN heterostructure showed the highest photocatalytic hydrogen evolution activity, about 14 times higher than that of pristine UCN. This remarkable improvement in activity can be ascribed to the synergy effect of the S-scheme charge pathway mechanism and the improved light absorption facilitated by the Ni3V2O8 quantum dots. As a result, these factors effectively accelerate the migration and transportation of photoinduced charge carriers, offering increased active sites for the H2 generation process. This study emphasizes the importance of a well-designed interfacial heterojunction to achieve enhanced photocatalytic performance.

Study on the photoinitiation mechanism of carbazole-based oxime esters (OXEs) as novel photoinitiators for free radical photopolymerization under near UV/visible-light irradiation exposure and the application of 3D printing

In this work, twenty-two oxime esters bearing different functional groups and based on carbazole as the chromophore were designed and synthesized as Type I photoinitiators. Interestingly, all structures mentioned in this work have never been reported before (even for their synthesis). These oxime esters were found to have good light absorption properties in the UV–visible range, and especially at 405 nm which is a reference wavelength in photopolymerization. Noticeably, several structures showed better photoinitiation abilities than the benchmark photoinitiator i.e. diphenyl(2,4,6-trimethylbenzoyl)phosphine oxide (TPO), evidencing the interest of these structures. In order to investigate the photoinitiation mechanism of the two series of oxime esters differing by the position of the photocleavable groups, electronic absorption spectra were determined by molecular modeling and density functional theory calculations. Photopolymerization abilities of the different oxime esters and release of CO2 during the polymerization experiments were determined by Real-Time Fourier Transformed Infrared (RT-FTIR). Active free radicals were characterized by mean of Electron Spin Resonance Spin Trapping (ESR-ST) experiments. On the basis of these different complementary experiments, chemical mechanisms occurring during photopolymerization could be proposed. Experimental results showed that the decarboxylation reaction occurring subsequent to the photocleavage of oxime esters had a beneficial effect on the photoinitiation ability. Finally, 3D printed objects were successfully obtained by using oxime esters exhibiting the best photoinitiating abilities.

Cu-coated graphitic carbon nitride (Cu/CN) with ideal photocatalytic and antibacterial properties

An improved photocatalytic activity of Graphitic carbon nitride (CN) photocatalyst was achieved by incorporating Cu2+ into CN in the presence of hyperbranched polyethylene amine (HPEI) as a capping agent. The addition of Cu to CN (CNHPEI+Cu) increased the photocatalytic degradation efficiency of wastewater dye pollutant methylene blue (MB) from 42 % to 95 %. E. coli and MS2 performed best in terms of inactivation to CNHPEI+Cu, achieving 5.5 ± 0.3 and 5.3 ± 0.1 log inactivation after 60 min of exposure, respectively. Excellent catalyst reusability and photocatalytic activity for MB in various types were obtained. To investigate the photocatalyst structure, morphology, optical, and photoelectric properties, we used X-ray diffraction (XRD), UV–Vis diffuse reflectance spectroscopy (DRS), scanning electron microscopy (SEM), high-resolution transmission electron microscopy (HR-TEM), X-ray photoelectron spectroscopy (XPS), and photocatalytic activity. It was found through XRD and XPS that the prepared photocatalysts were made up of Cu-doped CN and that the valence state of Cu was Cu0. Under the visible part of the solar spectrum (>400 nm), the N2 adsorption-desorption isotherms of pure CN, CNHPEI, and CNHPEI+Cu showed that copper did not alter the microstructure of pure CN. The photocatalytic activity of CNHPEI+Cu was improved by incorporating Cu0 into CN, as this reduces the rate of electron-hole recombination in pure CN and accelerates the separation of electron-hole pairs. Electron spin resonance (ESR) spin trap experiments on the production of reactive oxygen species (ROS) from CNHPEI+Cu under visible light indicate that the presence of superoxide radicals (O2•−), hydroxyl radicals (•OH) and holes could enhance the photocatalytic activity of the material.