Fabrication and photoluminescence properties of Ag0 and Ag0–Er3+ containing plasmonic glass nanocomposites in the K2O–ZnO–SiO2 system

Here, we report the preparation of nano silver (Ag) and nano Ag-erbium (Ag–Er) co-embedded potassium–zinc-silicate based monolithic glass nanocomposites by a controlled heat-treatment process of precursor glasses. The nanocomposites were characterized by differential scanning calorimeter, dilatometer, UV–Visible absorption spectrophotometer, X-ray diffractometer and transmission electron microscope and spectroflurimeter. A strong surface plasmon resonance (SPR) band is observed around 430 nm in all the heat-treated glass nanocomposite samples due to the formation of Ag⁰ nanoparticles (NP). The Ag-glass nanocomposite samples display nearly 2-fold enhanced photoluminescence (PL) at 470 nm upon excitation at 290 nm until the size of the NP increases to the value equals to the mean free path of conduction electrons inside the particles. On contrary to this, the photoluminescence spectra of Er³⁺ ions exhibit a gradual decrease of NIR emission at 1540 nm due to ⁴I_13/2 → ⁴I_15/2 transition under excitation at 523 nm in the heat-treated glass nanocomposites which happened due to excitation energy transfer of Er³⁺ ions to the Ag NP, acting as ‘plasmonics diluents’ for Er³⁺ ions. These nanocomposites have huge potential for various nanophotonic applications.     

Chemically dealloyed Pt–Au–Cu ternary electrocatalysts with enhanced stability in electrochemical oxygen reduction

We report simple synthesis of ternary Pt–Au–Cu catalysts consisting of active Pt-rich shell and Pt transition-metal alloy core for use as highly active and durable electrocatalysts in oxygen reduction reactions. The ternary Pt–Au–Cu catalysts were synthesized by chemical coreduction followed by thermal treatment and chemical dealloying. During synthesis, thermal treatment formed metal particles into high-degree alloys, and chemical dealloying led to selective dissolution of soluble Cu species from the outer surface layer of the thermally treated alloy particles, resulting in Pt-based alloys@Pt-rich surface core–shell configuration. Compared with a commercial Pt/C catalyst, our Pt_1?xAu _x Cu₃/C-AT catalysts exhibited approximately 2.4-fold enhanced performance in oxygen reduction reactions. Among the catalysts employed in this work, Pt_0.97Au_0.3Cu₃/C-AT showed the highest performance in terms of mass activity, specific activity, and electrochemically active surface area loss with negligible change during 10,000 potential cycles. The synthesis details, electrochemical characteristics, oxygen reduction reaction performance, and durability of the chemically dealloyed ternary Pt–Au–Cu catalysts are presented and discussed.     

Nd3+:LaCl3中的上转换发光研究

当用582.6 nm的黄色激光激发Nd3+:LaCl3的2G7/2+4G5/2能级时,观察到了4D3/2和2G9/2能级的兰光和紫外发射.研究表明,2D3/2上转换的机理是能量传递和激发态吸收,而2G9/2则是由于4G5/2+4Gs/2→2G9/2+4F7/2交叉驰豫过程.通过对12K下4D3/2→4I11/2荧光衰减曲线的分析,得出能量传递几率为wt1＝1468 s-1.测量和讨论了Nd3+:LaCl3和NdCl3主要发光能级室温和12K下的寿命.     

Long-lived emission from Eu3+:PbF2 nanocrystals distributed into sol–gel silica glass

This paper reports an optical investigation of Eu³⁺:PbF₂ nanocrystals distributed into silica glasses fabricated by sol–gel methods. The sample microstructure was investigated using scanning transmission electron microscopy. The β-cubic PbF₂ crystalline phase was identified using X-ray diffraction analysis. The observed emission bands correspond to ⁵D₀ → ⁷F_J (J = 0–4) transitions of Eu³⁺. The spectroscopic parameters for Eu³⁺ ions were determined based on excitation and emission measurements as well as luminescence decay analysis. Emission originating from ⁵D₀ state of Eu³⁺ ions in sample containing PbF₂ nanocrystals is long-lived in comparison to precursor sol–gel silica glasses.     

A general approach for selective enhancement of green upconversion emissions in Er3+ doped oxides by Yb3+–MoO4 2− dimer sensitizing

In this paper, we report a general approach to enhance the upconversion (UC) luminescence of Er³⁺ doped oxides phosphors by Yb³⁺–MoO₄ ^2? dimer sensitizing, which induced strong green UC emissions under the 976 nm laser diode excitation. By codoping of Yb³⁺ and Mo⁶⁺ in the Er³⁺ doped TiO₂ and ZnO, the green UC emissions intensity can be selectively increased about 10 and 500 times than those of Er³⁺–Yb³⁺ codoped TiO₂ and ZnO, respectively. The high excited state energy transfer between |²F_7/2, ³T₂> state of Yb³⁺–MoO₄ ^2? dimer and ⁴F_7/2 level of Er³⁺ significantly avoids the nonradiative decay processes happened at lower energy levels of Er³⁺, and then increases the green UC emissions efficiently. The proposed Yb³⁺–MoO₄ ^2? dimer sensitizing has been realized as an efficient way to enhance the green UC emissions in other Er³⁺ doped oxides phosphors. It is expected that the selective enhanced green UC emissions sensitized by Yb³⁺–MoO₄ ^2? dimer in Er³⁺ doped oxides phosphors can greatly extend their scope of applications.     

An investigation of enhanced secondary ion emission under Au n + (n=1–7) bombardment

We investigate the mechanism of the nonlinear secondary ion yield enhancement using Au(n)+ (n = 1, 2, 3, 5, 7) primary ions bombarding thin films of Irganox 1010, DL-phenylalanine and polystyrene on Si, Al, and Ag substrates. The largest differences in secondary ion yields are found using Au+, Au2+, and Au3+ primary ion beams. A smaller increase in secondary ion yield is observed using Au5+ and Au7+ primary ions. The yield enhancement is found to be larger on Si than on Al, while the ion yield is smaller using an Au+ beam on Si than on Al. Using Au(n)+ ion structures obtained from Density Functional Theory, we demonstrate that the secondary yield enhancement is not simply due to an increase in energy per area deposited into the surface (energy deposition density). Instead, based on simple mechanical arguments and molecular dynamics results from Medvedeva et al, we suggest a mechanism for nonlinear secondary ion yield enhancement wherein the action of multiple concerted Au impacts leads to efficient energy transfer to substrate atoms in the near surface region and an increase in the number of secondary ions ejected from the surface. Such concerted impacts involve one, two, or three Au atoms, which explains well the large nonlinear yield enhancements observed going from Au+ to Au2+ to Au3+ primary ions. This model is also able to explain the observed substrate effect. For an Au+ ion passing through the more open Si surface, it contacts fewer substrate atoms than in the more dense Al surface. Less energy is deposited in the Si surface region by the Au+ primary ion and the secondary ion yield will be lower for adsorbates on Si than on Al. In the case of Au(n)+ the greater density of Al leads to earlier break-up of the primary ion and a consequent reduction in energy transfer to the near-surface region when compared with Si. This results in higher secondary ion yields and yield enhancements on silicon than aluminum substrates.     

Mesoporous pyrophyllite–titania nanocomposites: synthesis and activity in phenol photocatalytic degradation

Research on Chemical Intermediates - Pyrophyllite–TiO2 nanocomposite PTi750 was successfully synthesized using a sol–gel method at ambient temperature based on exfoliation of the...     

Thermodynamic Model for the Solubility of NdF3(cr) in the Na+–NH 4 + –Nd3+–F−–H2O System at 25 °C

The major objective of this study, based on critical review and experimental studies, was to develop a reliable thermodynamic model for the Nd–F system at 25 °C. The SIT model was used to convert concentration constants reported in the literature to constants at zero ionic strengths for cross comparison and selection of reliable values. The critically evaluated thermodynamic constants for the formation of NdF²⁺ and NdF ₂ ⁺ were then used to interpret the extensive NdF₃(cr) solubility data in NaF and NH₄F solutions, ranging in concentrations from extremely low values to as high as 1.0 mol·kg^?1, equilibrated for different periods ranging up to as long as 72 days. These efforts have resulted in $ \log_{10} \beta_{n}^{0} $ log 10 β n 0 for the reaction [Nd³⁺ + nF^? ? NdF _n ^3?n ] of (3.81 ± 0.10), (5.89 ± 0.77), and <12.48 for n values of 1–3, respectively. The $ \log_{10} K_{\text{sp}}^{0} $ log 10 K sp 0 for the solubility of NdF₃(cr) (NdF₃(cr) ? Nd³⁺ + 3F^?) was determined to be (?20.49 ± 0.37). Because (1) Nd is an excellent analog for trivalent actinides—An(III) (i.e., Pu(III), Am(III), and Cm(III)), and (2) the available data for the An(III)–F system, especially the solubility products of AnF₃(cr), are of extremely poor quality, the critical literature review in combination with the experimental Nd–F system data have been used to assign thermodynamic constants for the An(III)–F reactions until good quality specific data for them becomes available.     

Luminescent core–shell Fe3O4@Gd2O3:Er3+, Li+ composite particles with enhanced optical properties

Bifunctional magneto-optical nanocomposites with Fe₃O₄ nanoparticles as a core and erbium and lithium codoped gadolinium (Gd₂O₃:Er³⁺, Li⁺) as the shell were synthesized successfully using a simple urea homogeneous precipitation method. The fabricated Fe₃O₄@Gd₂O₃:Er³⁺, Li⁺ particles were characterized by X-ray diffraction, field emission scanning electron microscopy, transmission electron microscopy, photoluminescence spectroscopy and quantum design vibrating sample magnetometry. The upconversion emission intensity was enhanced significantly comparing to that without Li⁺ ions. These bifunctional composites are expected to be potentially applied for drug delivery, cell separation and bioimaging.     

Effect of fluorine ions on 2.7 μm emission in Er3+/Nd(3+)-codoped fluorotellurite glass

The 2.7 μm emission properties of Er(3+)/Nd(3+)-codoped fluorotellurite glasses were investigated in the present work. The thermal stability, refractive index, absorption and transmission spectra, and emission spectra were measured and investigated. The 2.7 μm emission in Er(3+)/Nd(3+)-codoped fluorotellurite glasses was enhanced with the increase of fluorine ions. The Judd-Ofelt analysis based on absorption spectra was performed in order to determine the Judd-Ofelt intensity parameters Ωt (t = 2, 4, 6), spontaneous emission probability, radiative lifetime and branching ratios of Er(3+):(4)I(11/2) → (4)I(13/2) transition. It is found that the Er(3+)/Nd(3+)-codoped fluorotellurite glass possesses a lower spontaneous transition probability A (58.95 s(-1)) but a higher branching ratio β (15.72%) corresponding to the stimulated emission of Er(3+):(4)I(11/2) → (4)I(13/2) transition. Additionally, the transmittance was also tested and reached a maximum when the molar concentration of ZnF(2) is 15%. The presence of fluorine ions greatly decreases the population of OH(-) groups, which affects the 2.7 μm emission effectively by means of decreasing the rate of energy transfer to impurities (e.g., OH(-) groups).     

Photoacoustic Spectrometry Investigation and Determination of Rare Earth Ions Ho3+ and Nd3+ in a Solution

A home-made high sensitive photoacoustic transducer was used to determine the photoacoustic signal in a solution. The photoacoustic spectra of Ho in different solvents were measured and comparedwith its absorption spectrum. The affection factors of photoacousticsensitivity are discussed. The trivalent rare earth ions Ho3+ and Nd3+in an aqueous acetonitrile solution were determined. The detection limit is 5×10-8 mol/L for Ho3+ and 1.0 ×10-7 mol/L for Nd3+, and corresponds to the absorbance of 1.5×10 and 6.3×10-7.respectively.     

Nd3+-Sensitized Upconversion Metal–Organic Frameworks for Mitochondria-Targeted Amplified Photodynamic Therapy

Herein, we report the design and synthesis of a mitochondria-specific, 808 nm NIR light-activated photodynamic therapy (PDT) system based on the combination of metal–organic frameworks (MOFs) and upconversion photochemistry with an organelle-targeting strategy. The system was synthesized through the growth of a porphyrinic MOF on Nd³⁺-sensitized upconversion nanoparticles to achieve Janus nanostructures with further asymmetric functionalization of the surface of the MOF domain. The PDT nanoplatform allows for photosensitizing with 808 nm NIR light, which could effectively avoid the laser-irradiation-induced overheating effect. Furthermore, mitochondria-targeting could amplify PDT efficacy through the depolarization of the mitochondrial membrane and the initiation of intrinsic apoptotic pathway. This work sheds light on the hybrid engineering of MOFs to combat their current limitations for PDT.     

Synthesis of mixed ionic–electronic Li+–NASICON glass-ceramic nanocomposites for cathode applications

Journal of Solid State Electrochemistry - A novel route for preparation of mixed ionic–electronic (MIE) glass-ceramics is proposed. Glass-ceramic nanocomposites are prepared by externally...     

Preparation of ZnO–B2O3–SiO2:Mn2+ optical-storage glass–ceramics with different ZnF2 dopant by sol–gel method

Journal of Sol-Gel Science and Technology - ZnO–B2O3–SiO2:Mn2+ (ZBSM) optical-storage glass–ceramics doped with ZnF2 were successfully prepared via sol–gel method. The...     

Shape-memory poly(p-dioxanone)–poly(ε-caprolactone)/sepiolite nanocomposites with enhanced recovery stress

Shape-memory poly(p-dioxanone)–poly(e-caprolactone)/sepiolite(PPDO–PCL/OSEP) nanocomposites with different OSEP nanofiber loading were fabricated by chain-extending the PPDO-diol and PCL/OSEP precursors. The precursors and the composites were characterized by1 H NMR, FT-IR, GPC, SEM and TEM.The results demonstrate that a part of PCL segments grafted on the surface of OSEP and composites display a fine dispersion of OSEP fiber in nanoscale with low OSEP content. The shape memory effect(SME) was evaluated by DMA, the results reveal that the PPDO–PCL/OSEP nanocomposites exhibit desirable shape-memory performance. The reinforcement of composites by incorporation of trace OSEP nanofiber evokes an effective improvement in shape-memory recovery stress.     

Thermally stimulated discharge current (TSDC) characteristics in β-phase PVDF–BaTiO3 nanocomposites

β-phase polyvinylidene fluoride (PVDF)–BaTiO₃ nanocomposite samples have been prepared by solution mixing method. XRD data represent that the crystallinity of PVDF decreases with increase in loading level of BaTiO₃ nanoparticles. DSC curve represents that the melting point of PVDF is lightly affected by loading concentration of BaTiO₃. The morphology and microstructure of PVDF and PVDF embedded by BaTiO₃ nanofillers were investigated by using inverted contrast microscopy (ICM) and scanning electron microscopy (SEM). FTIR interferrometry is proven that PVDF and BaTiO₃ are not chemically interacting; therefore, interaction of BaTiO₃ is van der Waals type of interaction. The thermally stimulated discharge current (TSDC) of PVDF and PVDF–BaTiO₃ nanocomposites sample was characterized by single peak. The observed TSDC peak is discussed on the basis of dipolar and interfacial polarization.     

Strong upconversion–downshifting green emission from Tb<Superscript>3+</Superscript> ions in core/shell/shell-structured nanophosphors

Efficient upconversion (UC)–downshifting (DS), dual-mode-emitting NaGdF₄:Yb,Tm/NaGdF₄:Tb/NaYF₄ core/shell/shell (C/S/S) nanophosphors (NPs) were synthesized. The UC luminescence color changed from blue to sky blue after doping Tb³⁺ into NaGdF₄ shell because Tb³⁺ emission peaks via ⁵D₄ → ⁷F_J transition were observed with Tm³⁺ emission peaks via ¹D₂ → ³F₄ and ¹G₄ → ³H₆ transitions through the energy migration UC process of Yb³⁺ → Tm³⁺ → Gd³⁺ → Tb³⁺. Upon increasing the Tb³⁺ concentration in the NaGdF₄ shell from 5 to 15%, the Commission Internationale de l’Éclairage (CIE) color coordinates changed from (0.2188, 0.2390) to (0.2616, 0.3654). When NaGdF₄:Yb(49%),Tm(1%)/NaGdF₄:Tb(15%)/NaYF₄ NPs were excited using 273 nm ultraviolet light, the C/S/S NPs exhibited bright green light with CIE color coordinates of (0.3354, 0.5090) as a result of energy transfer from Gd³⁺ to Tb³⁺. These bright UC–DS, dual-mode-emitting C/S/S NPs could be applied in various applications, including multiplexed imaging and anticounterfeiting.     

Synthesis and phosphorescence properties of Dy3+ and (Pr3+–Dy3+) in MgTiO3

Using tetra-n-butyl titanate and magnesium nitrate as raw materials, Dy³⁺ and Pr³⁺ ions in the matrix of magnesium titanate (MgTiO₃) was successfully synthesized by a modified solid-state reaction. The mixtures to achieve a solid-state reaction were heated in porcelain crucibles at 600?°C for 2?h, 900?°C for 6?h, and 1000.0?°C for 2?h. The reaction products obtained in an air atmosphere were characterized by X-ray powder diffractions. The optimization of reaction conditions were carried out by thermal gravimetry and differential thermal analysis methods. Surface and elemental analyses were performed by using on SEM instrument. The excitation and emission spectra were recorded by photoluminescence spectrophotometer.     

Well-dispersed polyimide/TiO2 nanocomposites: in situ sol–gel fabrication and morphological study

In the presented study, 3,5-diamino-N-(4-methyl-1-oxo-1-(phenylamino)pentan-2-yl)benzamide (V) as a new diamine monomer is synthesized and fully characterized by means of FT-IR, ¹H-NMR, ¹³C-NMR, and elemental analysis techniques. The stated diamine is used for the sol–gel fabrication of a series of polyimide (PI)/titania nanohybrid films with various titania percentages. The special design of diamine monomer containing bulky pendant group increased the flexibility of resulted PI matrixes. On the other hand, the ability to construct strong organic/inorganic H-bond lattice has led to the effective surrounding of nanoparticles by PI grounds and thus the well-dispersed quite spherical nanoparticles were created via a sol–gel procedure. The obtained nanocomposites showed high thermal stability and UV–vis absorption efficiency. The X-ray diffraction experiments confirmed the titania nanoparticles to be amorphous.     

Radioluminescence of Europium(III) in POCl3–SnCl4–235UO2+ 2–Eu3+, and D2O–235UO2+ 2–Eu3+ Solutions

Results of studying the spectral and luminescent properties of Eu³⁺ ions upon homogeneous excitation of POCl₃–SnCl₄–^-UO²⁺ ₂–Eu³⁺ and D₂O–²³⁵UO²⁺ ₂–Eu³⁺ solutions by -particles are presented. It was found that the radioluminescence intensity of Eu³⁺ ions in both solvents increases proportionally to the energy input by -particles. The yield of radioluminescence photons from europium ions in the POCl₃–SnCl₄–UO²⁺ ₂–Eu³⁺ solutions is more than nine times as high as that in D₂O–UO²⁺ ₂–Eu³⁺. The radiation-chemical yields of excited ⁵ D ₀ states of Eu³⁺ ions are 0.74 ± 0.07 and 0.18 ± 0.02 ions/100 eV in POCl₃–SnCl₄–UO²⁺ ₂–Eu³⁺ and D₂O–UO²⁺ ₂–Eu³⁺ solutions, respectively.