Monitoring Catalytic 2-Propanol Oxidation over Co3O4 Nanowires via In Situ Photoluminescence Spectroscopy

Spectroscopic methods enabling real-time monitoring of dynamic surface processes are a prerequisite for identifying how a catalyst triggers a chemical reaction. We present an in situ photoluminescence spectroscopy approach for probing the thermo-catalytic 2-propanol oxidation over mesostructured Co3O4 nanowires. Under oxidative conditions, a distinct blue emission at ~420 nm is detected that increases with temperature up to 280 °C, with an intermediate maximum at 150 °C. Catalytic data gained under comparable conditions show that this course of photoluminescence intensity precisely follows the conversion of 2-propanol and the production of acetone. The blue emission is assigned to the radiative recombination of unbound acetone molecules, the n - π* transition of which is selectively excited by a wavelength of 270 nm. These findings open a pathway for studying thermo-catalytic processes via in situ photoluminescence spectroscopy thereby gaining information about the performance of the catalyst and the formation of intermediate products.

Increasing the photoluminescence intensity of silicon nitride by forming K and N radioactive centres

Creating a light emitter to transfer an electrical signal by optical way has a great importance in development of optoelectronics. The silicon nitride films studied by photoluminescence techniques, and determined luminescence is associated with presence of an extended zone of tail states. Defects play the main role in radiative recombination for structures annealed at 600 °C and 1100 °C. Photoluminescence (Pl) intensity of obtained films by plasma enhanced chemical vapor deposition is increased after annealing at 600 °C which are related to increased concentration of defects as a result of broken Si–H and N–H bonds. Due to the formation of N-centers through the breaking of N–H bonds, annealing at 1100 °C led to sharp decrease in the luminescence intensity 5 and 3 times for SiN1.1 and SiN1.5 samples respectively. Replacement of Si-Si bonds by Si-N enhance Eg with increasing stoichiometric parameter, which leads to blue shift edge of photoluminescence maximum. Carbon implantation of silicon nitride films with extra Si obtained by Plasma Enhanced Chemical Vapor deposition at 1x1014 cm‒2, 2x1015 cm‒2, and 1x1016 cm‒2 fluencies, in combination with prolonged annealing at 1100 °C temperature leads to the formation of additional K-centers.

Фотоиндуцированный перенос заряда в слоистых 2D наноструктурах PbSe-MoS-=SUB=-2-=/SUB=-

Semiconductor 2D nanostructures are a new platform for the creation of modern optoelectronic devices. Layered 2D PbSe-MoS2 nanostructures with efficient photoinduced charge transfer from PbSe nanoplatelets (NPLs) to MoS2 were created. When PbSe NPLs with short organic ligands are deposited onto a thin layer of MoS2 NPLs, a decrease in their photoluminescence intensity and a decrease in the average photoluminescence lifetime are observed. When a layered 2D PbSe-MoS2 nanostructure is illuminated with IR radiation, a photocurrent appears, which indicates the contribution of PbSe NPLs to the electrical response of the system. Ultrathin layers of transition metal dichalcogenides sensitized with nanostructures based on lead chalcogenides can be used in photodetectors with a spectral sensitivity region extended to the near-IR range.

Origin of the Bright Photoluminescence of Thiolate-protected Gold Nanoclusters: Confined Structural Water Molecules as Real Emitters

The availability of a range of excited states has enriched zero-, one- and two- dimensional quantum nanomaterials with interesting luminescence properties, in particular for noble metal nanoclusters (NCs) as typical examples. But, the elucidation and origin of optoelectronic properties remains elusive. In this report, using widely used Au(I)-alkanethiolate complex (Au(I)-SRs, R = -(CH2)12H) with AIE characteristics as a model system, by judiciously manipulating the delicate surface ligand interactions at the nanoscale interface, together with a careful spectral investigations and an isotope diagnostic experiment of heavy water (D2O), we evidenced that the structural water molecules (SWs) confined in the nanoscale interface or space are real emitter centers for photoluminescence (PL) of metal NCs and the aggregate of Au(I)-SRs complexes, instead of well-organized metal core dominated by quantum confinement mechanics. Interestingly, the aggregation of Au(I)-SRs generated dual fluorescence-phosphorescence emission and the photoluminescence intensity was independent on the degree of aggregation but showed strong dependency on the content and state of structural water molecules (SWs) confined in the aggregates. SWs are different from traditional hydrogen bonded water molecules, wherein, due to interfacial adsorption or spatial confinement, the p orbitals of two O atoms in SWs can form a weak electron interaction through spatial overlapping, which concomitantly constructs a group of interfacial states with π bond characteristics, consequently providing some alternative channels (or pathways) to the radiation and/or non-radiation relaxation of electrons. Our results provide completely new insights to understand the fascinating properties (including photoluminescence, catalysis and chirality, etc.) of other low-dimension quantum dots and even for aggregation-induced emission luminophores (AIEgens). This also answers the century old debate on whether and how water molecules emit bright color.

Photocatalytic Activity of TiO2-Doped Fe, Ag and Ni with N under Visible Light Irradiation

Doping with noble metal ions or doping with nitrogen has been attempted to prepare TiO2 that reacts even in visible light. In this study, TiO2 was doped with nitrogen and various metal ions instead of noble metals. The TiO2 photocatalysts doped with metal ions (Fe, Ag, Ni) and nitrogen were prepared by a sol-gel method. Their physicochemical properties were characterized and their photocatalytic activities were investigated under visible light irradiation. In TiO2 doped with metal ions and nitrogen, the light absorption region was extended to visible light. The photoluminescence intensity was much greater in N/Ni/TiO2 than in N/Ag/TiO2 and N/Fe/TiO2. The photolysis activities of N/Ni/TiO2 were the highest in formaldehyde decomposition and methylene blue decomposition. The sterilization efficiency of N/Ni/TiO2 was the highest in the evaluation test for the inhibition of the proliferation of Pseudomonas aeruginosa. The bandgap of N/Ni/TiO2 was 2.4 eV, which was significantly lower than that of anatase TiO2 (3.2 eV). The N/Ni/TiO2 had a much higher optical intensity than other metal ion-doped TiO2, so it was highly active under visible light irradiation.

LUMINESCENCE OF YAG:Ce DOPED WITH SILVER NANOPARTICLES

В работе впервые было исследовано влияние наночастиц серебра на люминесценцию иттрий-алюминиевого граната, легированного церием. С помощью метода химического восстановления был синтезирован золь с размером наночастиц серебра ≈100 нм. Керамический порошок люминофора иттрий-алюминиевого граната, легированного церием, был получен методом двухстадийного осаждения в уротропин. Золь наночастиц серебра в концентрациях от 0,125 до 0,1 мл вводили в порошок-прекурсор перед прокаливанием. Было показано, что при данном способе введения наночастиц серебра интенсивность фотолюминесценции возрастала по сравнению с эталоном. Оптимальной концентрацией в рамках исследования являлась концентрация 0,25 мл. При данной концентрации увеличение интенсивности фотолюминесценции на длине волны 540 нм составило порядка 10%. Проведенные исследования показали, что наночастицы серебра могут с успехом применяться для увеличения яркости люминофора иттрий-алюминиевого граната, легированного церием, без искажения и ухудшения спектральных характеристик. This work was the first to study the effect of silver nanoparticles on the luminescence of cerium doped yttrium-aluminum garnet. A sol with the size of silver nanoparticles of ≈100 nm was synthesized using the method of chemical reduction. Phosphor ceramic powder of the yttrium-aluminum garnet doped with cerium was obtained by the two-stage precipitation method. The silver nanoparticles sol was introduced into the precursor powder before calcination in concentrations from 0,125 to 0,1 ml. It was shown that the photoluminescence intensity increased in comparison with the reference when we used this method of introducing silver nanoparticles. The optimal concentration within the study was 0,25 ml. At this concentration, the increase in the photoluminescence intensity at a wavelength of 540 nm was about 10 %. Studies have shown that silver nanoparticles can be successfully used to increase the brightness of the phosphor of the yttrium-aluminum garnet doped with cerium without distortion and deterioration of spectral characteristics.

Photocatalytic Degradation of Single and Binary Mixture of Brilliant Green and Rhodamine B Dyes by Zinc Sulfide Quantum Dots

We present the preparation of octadecylamine-capped ZnS quantum dots from bis(morpholinyldithiocarbamato)Zn(II) complex. The complex was thermolyzed at 130 °C in octadecylamine at different times, to study the effect of reaction time on the morphological and photocatalytic properties of the ZnS quantum dots. Powder X-ray diffraction patterns confirmed a hexagonal wurtzite crystalline phase of ZnS, while HRTEM images showed particle sizes of about 1–3 nm, and energy band gaps of 3.68 eV (ZnS–1), 3.87 eV (ZnS–2), and 4.16 eV (ZnS–3) were obtained from the Tauc plot for the ZnS nanoparticles. The as-prepared ZnS were used as photocatalysts for the degradation of brilliant green, rhodamine B, and binary dye consisting of a mixture of brilliant green-rhodamine B. The highest photocatalytic degradation efficiency of 94% was obtained from ZnS–3 with low photoluminescence intensity. The effect of catalytic dosage and pH of the dyes solution on the photocatalytic process shows that pH 8 is optimal for the degradation of brilliant green, while pH 6.5 is the best for photocatalytic degradation of rhodamine B. The degradation of the binary dyes followed the same trends. The effect of catalytic dosage shows that 1 mg mL−1 of the ZnS nano-photocatalyst is the optimum dosage for the degradation of organic dyes. Reusability studies show that the ZnS quantum dots can be reused five times without a significant reduction in degradation efficiency.

A simple and green photoreduction approach for synthesis of Au/g-C3N4 hybrid nanocomposites with high solar light photocatalytic activity

In this study, we developed a green and easy to scale up approach for producing Au/g-C3N4 (Au/GCN) hybrid plasmonic photocatalyst without using the chemical reducing agents via the growing of Au nanoparticles (Au NPs) on the surface of g-C3N4 nanosheets under the photo-reduction of UV-radiation. Different characterization techniques were conducted for investigating the structure, morphology, surface chemistry and optical properties of the as-prepared catalysts. The SEM image shows that the homogeneous Au NPs anchored on the surface of the g-C3N4 nanosheet increased with the UV illumination time. The XPS results prove the coexistence of g-C3N4 nanosheets with heptazine heterocyclic ring (C6N7) units and Au nanoparticles in the Au/GCN. The photoluminescence intensity (PL) decreased sharply with the time of UV irradiation, indicating that the recombination rate of photogenerated electron-hole recombination decreased. The photocatalytic activity of the hybrid catalysts was evaluated by degrading rhodamine B under simulated sunlight irradiation. The results show that the Au/GCN photocatalyst exhibits superior sunlight photocatalytic activity than that of bare g-C3N4. The 6h-irradiated fabricating sample exhibited the strongest photocatalytic activity, completely decomposing the 10 ppm RhB in 30 minutes of irradiation. This report can provide the design of a simple and green synthesis method for the highly active Au/g-C3N4 photocatalyst.

Polyaniline Synthesized by Different Dopants for Fluorene Detection via Photoluminescence Spectroscopy

The effects of different dopants on the synthesis, optical, electrical and thermal features of polyaniline were investigated. Polyaniline (PANI) doped with p-toluene sulfonic acid (PANI-PTSA), camphor sulphonic acid (PANI-CSA), acetic acid (PANI-acetic acid) and hydrochloric acid (PANI-HCl) was synthesized through the oxidative chemical polymerization of aniline under acidic conditions at ambient temperature. Fourier transform infrared light, X-ray diffraction, UV-visible spectroscopy, field emission scanning electron microscopy, photoluminescence spectroscopy and electrical analysis were used to define physical and structural features, bandgap values, electrical conductivity and type and degree of doping, respectively. Tauc calculation reveals the optical band gaps of PANI-PTSA, PANI-CSA, PANI-acetic acid and PANI-HCl at 3.1, 3.5, 3.6 and 3.9 eV, respectively. With the increase in dopant size, crystallinity is reduced, and interchain separations and d-spacing are strengthened. The estimated conductivity values of PANI-PTSA, PANI-CSA, PANI-acetic acid and PANI-HCl are 3.84 × 101, 2.92 × 101, 2.50 × 10−2, and 2.44 × 10−2 S·cm−1, respectively. Particularly, PANI-PTSA shows high PL intensity because of its orderly arranged benzenoid and quinoid units. Owing to its excellent synthesis, low bandgap, high photoluminescence intensity and high electrical features, PANI-PTSA is a suitable candidate to improve PANI properties and electron provider for fluorene-detecting sensors with a linear range of 0.001–10 μM and detection limit of 0.26 nM.