Cerium Oxide Nanoparticles Confined in Doped Mesoporous Carbons: A Strategy to Produce Catalysts for Imine Synthesis.

A group of (doped N or P) carbons were synthesized using soluble starch as a carbon precursor. Further, ceria nanoparticles (NPs) were confined into these (doped) carbon materials. The obtained solids were characterized by various techniques such as N2 physisorption, XRD, TEM, SEM, XPS, and XAS. These materials were used as catalysts for the oxidative coupling between benzyl alcohol and aniline as the model reaction. Ceria immobilized on mesoporous-doped carbon shows higher activity than the other materials, benchmark catalysts, and most of the previously reported catalysts. The control of the ceria NP size, the presence of Ce3+ cations, and an increment in the disorder in the ceria NP structure caused by a support-ceria interaction could increase the number of oxygen vacancies and improve its catalytic performance. CN-meso/CeO2 was also used as the catalyst for a rich scope of substrates, such as substituted aromatic alcohols, linear alcohols, and different types of amines. The influence of various reaction parameters (substrate content, reaction temperature, and catalyst content) on the activity of this catalyst was also checked.

On the role of Gd3+ions in enhancement of UV emission from Yb3+-Tm3+up-converting LiYF4nanocrystals.

Materials capable of emitting ultraviolet (UV) radiation are sought for applications ranging from theranostics or photodynamic therapy to specific photocatalysis. The nanometer size of these materials, as well as excitation with near-infrared (NIR) light, is essential for many applications. Tetragonal tetrafluoride LiY(Gd)F4nanocrystalline host for up-converting Tm3+-Yb3+activator-sensitizer pair is a promising candidate to achieve UV-vis up-converted radiation under NIR excitation, important for numerous photo-chemical and bio-medical applications. Here, we provide insights into the structure, morphology, size and optical properties of up-converting LiYF4:25%Yb3+0.5%Tm3+colloidal nanocrystals, where 1, 5, 10, 20, 30 and 40% of Y3+ions were substituted with Gd3+ions. Low gadolinium dopant concentrations modify the size and up-conversion luminescence, while the Gd3+doping that is exceeding the structure resistance limit of the tetragonal LiYF4results in appearance of foreign phase and significant decrease of luminescence intensity. The intensity and kinetic behavior of Gd3+up-converted UV emission are also analyzed for various gadolinium ions concentrations. The obtained results form a background for further optimized materials and applications based on LiYF4nanocrystals.

Thermochromic Luminescent Nanomaterials Based on Mn4+/Tb3+ Codoping for Temperature Imaging with Digital Cameras.

A new thermographic nanocrystalline Sr4Al14O25:Mn4+,Tb3+ phosphor was developed, and the concentrations of both dopants and the synthesis conditions were optimized. The combination of the thermally quenched luminescence from the Mn4+ ions to the almost temperature-independent emission from Tb3+ provides a sensitive luminescent thermometer (SR = 2.8%/°C at 150 °C) with strong emission color variability. In addition, a figure of merit for this luminescence thermochromism was proposed, as the relative sensitivities of the x and y CIE coordinates, which for this phosphor reaches at 150 °C SR(x) = 0.6%/°C and SR(y) = 0.4%/°C, respectively. Noncontact thermal imaging was demonstrated with this phosphor using a single consumer digital camera and exploiting the ratio of red (R) and green (G) channels of the RGB images, thereby confirming the high application potential of Sr4Al14O25:Mn4+,Tb3+ nanocrystals for thermal sensing and mapping.

Implementing Defects for Ratiometric Luminescence Thermometry.

In luminescence thermometry enabling temperature reading at a distance, an important challenge is to propose new solutions that open measuring and material possibilities. Responding to these needs, in the nanocrystalline phosphors of yttrium oxide Y2O3 and lutetium oxide Lu2O3, temperature-dependent emission of trivalent terbium Tb3+ dopant ions was recorded at the excitation wavelength 266 nm. The signal of intensity decreasing with temperature was monitored in the range corresponding to the 5D4 → 7F6 emission band. On the other hand, defect emission intensity obtained upon 543 nm excitation increases significantly at elevated temperatures. The opposite thermal monotonicity of these two signals in the same spectral range enabled development of the single band ratiometric luminescent thermometer of as high a relative sensitivity as 4.92%/°C and 2%/°C for Y2O3:Tb3+ and Lu2O3:Tb3+ nanocrystals, respectively. This study presents the first report on luminescent thermometry using defect emission in inorganic phosphors.

LiAl5O8:Fe3+ and LiAl5O8:Fe3+, Nd3+ as a New Luminescent Nanothermometer Operating in 1st Biological Optical Window.

New types of contactless luminescence nanothermometers, namely, LiAl5O8:Fe3+ and LiAl5O8:Fe3+, Nd3+ are presented for the first time, revealing the potential for applications in biological systems. The temperature-sensing capability of the nanocrystals was analyzed in wide range of temperature (-150 to 300 °C). The emission intensity of the Fe3+ ions is affected by the change in temperature, which induces quenching of the 4T1 (4G) → 6A1 (6S) Fe3+ transition situated in the 1st biological window. The highest relative sensitivity in the temperature range (0 to 50 °C) was found to be 0.82% °C (at 26 °C) for LiAl5O8: 0.05% Fe3+ nanoparticles that are characterized by long luminescent lifetime of 5.64 ms. In the range of low and high temperatures the Smax was calculated for LiAl5O8:0.5% Fe3+ to be 0.92% °C at -100 °C and for LiAl5O8:0.01% Fe3+ to be 0.79% °C at 150 °C. The cytotoxicity assessment carried out on the LiAl5O8:Fe3+ nanocrystals, demonstrated that they are biocompatible and may be utilized for in vivo temperature sensing. The ratiometric luminescent nanothermometer, LiAl5O8:Fe3+, Nd3+, which was used as a reference, possesses an Smax = 0.56%/°C at -80 °C, upon separate excitation of Fe3+ and Nd3+ ions using 266 nm and 808 nm light, respectively.

Structural modification of nanohydroxyapatite Ca10(PO4)6(OH)2 related to Eu3+ and Sr2+ ions doping and its spectroscopic and antimicrobial properties.

The Eu3+ and Sr2+ ions co-doped hydroxyapatite nanopowders (Ca10(PO4)6(OH)2) were synthesized via a precipitation method and post heat-treated at 500 °C. The concentration of Eu3+ ions was established in the range of 0.5-5 mol% to investigate the site occupancy preference. The concentration of Sr2+ ions was set at 5 mol%. The structural and morphological properties of the obtained materials were studied by an X-ray powder diffraction, a transmission electron microscopy techniques and infrared spectroscopy. As synthesized nanoparticles were in the range of 11-17 nm and annealed particles were in the range of 20-26 nm. The luminescence properties in dependence of the dopant concentration and applied temperature were investigated. The 5D0 → 7F0 transition shown the abnormally strong intensity for annealed materials connected with the increase of covalency character of Eu3+-O2- bond, which arise as an effect of charge compensation mechanism. The Eu3+ ions occupied three possible crystallographic sites in these materials revealed in emission spectra: one Ca(1) site with C3 symmetry and two Ca(2) sites with Cs symmetry arranged as cis and trans symmetry. The antibacterial properties of Eu3+ and Sr2+ ions doped and co-doped hydroxyapatite nanopowders were also determined against Gram-negative pathogens such as Pseudomonas aeruginosa, Klebsiella pneumoniae and Escherichia coli. Obtained results suggest that both europium and strontium ions may implement antibacterial properties for hydroxyapatites. In the most cases, better antibacterial effect we noticed for dopants at 5 mol% ratio. However, the effect is strongly species- and strain-dependent feature.

Enhancing the Relative Sensitivity of V5+, V4+ and V3+ Based Luminescent Thermometer by the Optimization of the Stoichiometry of Y3Al5-xGaxO12 Nanocrystals.

In this work the influence of the Ga3+ concentration on the luminescent properties and the abilities of the Y3Al5-xGaxO12: V nanocrystals to noncontact temperature sensing were investigated. It was shown that the increase of the Ga3+ amount enables enhancement of V4+ emission intensity in respect to the V3+ and V5+ and thus modify the color of emission. The introduction of Ga3+ ions provides the appearance of the crystallographic sites, suitable for V4+ occupation. Consequently, the increase of V4+ amount facilitates V5+ → V4+ interionic energy transfer throughout the shortening of the distance between interacting ions. The opposite thermal dependence of V4+ and V5+ emission intensities enables to create the bandshape luminescent thermometr of the highest relative sensitivity of V-based luminescent thermometers reported up to date (Smax, 2.64%/°C, for Y3Al2Ga3O12 at 0 °C). An approach of tuning the performance of Y3Al5-xGaxO12: V nanocrystals to luminescent temperature sensing, including the spectral response, maximal relative sensitivity and usable temperature range, by the Ga3+ doping was presented and discussed.