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1.
Molecules ; 27(23)2022 Dec 01.
Artículo en Inglés | MEDLINE | ID: mdl-36500481

RESUMEN

A rapid, cheap and feasible new approach was used to synthesize the Mg0.375Fe0.375Al0.25-LDH in the presence of tetramethylammonium hydroxide (TMAH), as a nontraditional hydrolysis agent, applying both mechano-chemical (MC) and co-precipitation methods (CP). For comparison, these catalysts were also synthesized using traditional inorganic alkalis. The mechano-chemical method brings several advantages since the number of steps and the energy involved are smaller than in the co-precipitation method, while the use of organic alkalis eliminates the possibility of contaminating the final solid with alkaline cations. The memory effect was also investigated. XRD studies showed Fe3O4 as stable phase in all solids. Regardless of the alkalis and synthesis methods used, the basicity of catalysts followed the trend: mixed oxides > parent LDH > hydrated LDH. The catalytic activity of the catalysts in the Claisen−Schmidt condensation between benzaldehyde and cyclohexanone showed a linear dependence to the basicity values. After 2 h, the calcined sample cLDH-CO32−/OH−-CP provided a conversion value of 93% with a total selectivity toward 2,6-dibenzylidenecyclohexanone. The presence of these catalysts in the reaction media inhibited the oxidation of benzaldehyde to benzoic acid. Meanwhile, for the self-condensation of cyclohexanone, the conversions to mono- and di-condensed compounds did not exceed 3.8%.


Asunto(s)
Óxidos , Catálisis , Oxidación-Reducción
2.
Inorg Chem ; 60(19): 14820-14830, 2021 Oct 04.
Artículo en Inglés | MEDLINE | ID: mdl-34515470

RESUMEN

A molecular precursor approach to titania (anatase) nanopowders modified with different amounts of rare-earth elements (REEs: Eu, Sm, and Y) was developed using the interaction of REE nitrates with titanium alkoxides by a two-step solvothermal-combustion method. The nature of an emerging intermetallic intermediate was revealed unexpectedly for the applied conditions via a single-crystal study of the isolated bimetallic isopropoxide nitrate complex [Ti2Y(iPrO)9(NO3)2], a nonoxo-substituted compound. Powders of the final reaction products were characterized by powder X-ray diffraction, scanning electron microscopy-energy-dispersive spectroscopy, Fourier transform infrared, X-ray photoelectron spectroscopy, Raman spectroscopy, and photoluminescence (PL). The addition of REEs stabilized the anatase phase up to ca. 700 °C before phase transformation into rutile became evident. The photocatalytic activity of titania modified with Eu3+ and Sm3+ was compared with that of Degussa P25 titania as the control. PL studies indicated the incorporation of Eu and Sm cations into titania (anatase) at lower annealing temperatures (500 °C), but an exclusion to the surface occurred when the annealing temperature was increased to 700 °C. The efficiency of the modified titania was inferior to the control titania while illuminated within narrow wavelength intervals (445-465 and 510-530 nm), but when subjected to a wide range of visible radiation, the Eu3+- and Sm3+-modified titania outperformed the control, which was attributed both to doping of the band structure of TiO2 with additional energy levels and to the surface chemistry of the REE-modified titania.

3.
Soins Pediatr Pueric ; 39(303): 32-37, 2018.
Artículo en Francés | MEDLINE | ID: mdl-30032917

RESUMEN

More and more newborns are being taken to paediatric emergency departments in France. A study was carried out between 2013 and 2015 to identify the reasons for non-emergency consultations, and to analyse the risk factors. The most common diagnoses were: rhinitis, gastro-oesophageal reflux and colic. There were three main predictive factors for consultation: the young age of the mother, primiparity and the short stay in the maternity hospital.


Asunto(s)
Servicio de Urgencia en Hospital/estadística & datos numéricos , Enfermedades del Recién Nacido/diagnóstico , Derivación y Consulta/estadística & datos numéricos , Adulto , Femenino , Francia , Humanos , Recién Nacido , Persona de Mediana Edad , Madres , Pediatría , Estudios Retrospectivos , Adulto Joven
4.
Clin Infect Dis ; 65(9): 1469-1476, 2017 Oct 16.
Artículo en Inglés | MEDLINE | ID: mdl-29048511

RESUMEN

BACKGROUND: Many antibiotics are prescribed inappropriately in pediatric emergency departments (PEDs), but little data are available in these settings about effective interventions based on guidelines that follow the antimicrobial stewardship principle. Our aim was to assess the impact of implementing the 2011 national guidelines on antibiotic prescriptions for acute respiratory tract infection (ARTI) in PEDs. METHOD: We conducted a multicentric, quasiexperimental, interrupted time series analysis of prospectively collected electronic data from 7 French PEDs. We included all pediatric patients who visited a participating PED during the study period from November 2009 to October 2014 and were diagnosed with an ARTI. The intervention consisted of local protocol implementation, education sessions, and feedback. The main outcome was the antibiotic prescription rate of discharge prescriptions for ARTI per 1000 PED visits before and after implementation, analyzed using the segmented regression model. RESULTS: We included 242534 patients with an ARTI. The intervention was associated with a significant change in slope for the antibiotic prescription rate per 1000 PED visits (-0.4% per 15-day period, P = .04), and the cumulative effect at the end of the study was estimated to be -30.9%, (95% CI [-45.2 to -20.1]), representing 13136 avoided antibiotic prescriptions. The broad-spectrum antibiotic prescription relative percentage decreased dramatically (-62.7%, 95% CI [-92.8; -32.7]) and was replaced by amoxicillin. CONCLUSION: Implementation of the 2011 national French guidelines led to a significant decrease in the antibiotic prescription rate for ARTI and a dramatic drop in broad-spectrum antibiotic prescriptions, in favor of amoxicillin.


Asunto(s)
Antibacterianos/uso terapéutico , Programas de Optimización del Uso de los Antimicrobianos , Prescripciones de Medicamentos/estadística & datos numéricos , Infecciones del Sistema Respiratorio/epidemiología , Adolescente , Niño , Preescolar , Servicio de Urgencia en Hospital , Humanos , Lactante , Recién Nacido , Análisis de Series de Tiempo Interrumpido , Guías de Práctica Clínica como Asunto , Estudios Prospectivos , Infecciones del Sistema Respiratorio/tratamiento farmacológico , Resultado del Tratamiento
5.
Phys Chem Chem Phys ; 18(27): 18268-77, 2016 Jul 21.
Artículo en Inglés | MEDLINE | ID: mdl-27333335

RESUMEN

We investigate the effects of heterovalent co-dopants on the structural and emission properties of 1% Er-CeO2 nanoparticles. The CeO2 oxide host was selected on the basis of its fairly well-understood defect chemistry in either a pure or doped state. As a luminescent activator, Er is acknowledged as an interesting element due to its rich luminescence and excitation properties spanning the visible to near-infrared range. The optically inactive trivalent La and monovalent Li metal ions with a concentration of up to 20% were chosen to presumably generate a variable amount of defects in the Er-CeO2 lattice. It was found that La and Li co-dopants induced distinct changes related to the size, lattice constant, bandgap energy, lattice and surface defects of Er-CeO2. As a result of these changes, a strong modulation of the luminescence intensity and shape was measured using a suite of excitation conditions (charge-transfer absorption band of CeO2, direct/up-conversion into Er absorptions and X-ray excitation modes). The use of Eu as a luminescent probe offered additional information concerning the effects of La/Li co-doping on the local structure surrounding the luminescent activator. Remarkably high percentages of 90 and 98% of the total emission of Er measured between 500 and 1100 nm are measured in the near-infrared region at 980 nm under X-ray and up-conversion excitation at ∼1500 nm, respectively. The optical properties suggest that Li, Er co-doped CeO2 has good potential for therapy and biological imaging.

6.
Soins Pediatr Pueric ; 37(291): 39-41, 2016.
Artículo en Francés | MEDLINE | ID: mdl-27444537

RESUMEN

The treatment of pain, particularly in infants, is today a public health priority. The mix of nitrous oxide and oxygen, colloquially known as 'gas and air' is an important analgesia for infants for short, painful procedures. Its fast action and almost immediate reversibility when the child stops inhaling facilitates its use and its tolerance. Subject to a medical prescription, it must be administered by a specially trained member of nursing staff.


Asunto(s)
Analgésicos no Narcóticos/uso terapéutico , Óxido Nitroso/uso terapéutico , Oxígeno/uso terapéutico , Manejo del Dolor/métodos , Preescolar , Servicio de Urgencia en Hospital , Humanos , Lactante
7.
Phys Chem Chem Phys ; 17(46): 30988-92, 2015 Dec 14.
Artículo en Inglés | MEDLINE | ID: mdl-26411533

RESUMEN

Herein, we report on the pure and almost pure near-infrared (NIR) emission at around 807 nm observed for Tm(Yb) (co)-doped CeO2 nanoparticles (NPs) under UV, X-ray and NIR up-conversion excitation. The optical responses are attributed to the low-lying charge-transfer of CeO2 that acts as a selective antenna sensitizer of the Tm (3)H4 emission and Yb doping that lowers the local symmetry at Tm sites and introduces additional phonon modes. Selective antenna sensitization is also observed for Er/Ho (Yb) (co)-doped CeO2 NPs. To the best of our knowledge, this is a first study which correlates the down- and up-conversion emission properties of lanthanide(s)-(co) dopants with the CeO2 structure highlighting also the outstanding potential of these NPs in high-penetration tissue imaging and therapy.


Asunto(s)
Cerio/química , Nanopartículas del Metal/química , Tulio/química , Iterbio/química , Espectrofotometría Infrarroja , Espectrofotometría Ultravioleta , Rayos X
8.
Phys Chem Chem Phys ; 16(12): 5793-802, 2014 Mar 28.
Artículo en Inglés | MEDLINE | ID: mdl-24535212

RESUMEN

We report on structure-property relationships in Pr-doped CeO2 and ZrO2 using X-ray diffraction (XRD), Raman, UV to Vis Diffuse Reflectance (DR-UV/Vis), X-ray Photoelectron (XPS), and luminescence (PL) spectroscopies. Both 3+ and 4+ valence states of Pr are evidenced, irrespective of the host and calcination temperature, T (T = 500 and 1000 °C) with consequences on absorption, surface, vibrational and luminescence properties. Only zirconia represents a suitable host for Pr(3+) luminescence. The distinct trivalent Pr centers and their excitation mechanism are identified in relation to the tetragonal and monoclinic phases of ZrO2. A near-infrared to visible up-conversion (UPC) emission of Pr(3+) is observed upon excitation at 959 nm which occurs, most probably, via a two-photon excited state process. By using a multi-wavelength, time-gated excitation, the UPC process is established as phase selective, i.e. only Pr(3+) located in the monoclinic sites of the mixed phase, monoclinic and tetragonal ZrO2 (T = 1000 °C) contribute to the UPC emission. We believe that, besides the local symmetry, a key role in phase selective UPC is played by the presence of Pr(3+) low-lying 4f 5d levels. To the best of our knowledge, this is the first report of phase selective up-conversion emission in a lanthanide doped multi-phase host.

9.
Phys Chem Chem Phys ; 16(2): 703-10, 2014 Jan 14.
Artículo en Inglés | MEDLINE | ID: mdl-24263248

RESUMEN

Although homogeneity at the atomic level of CeO2-ZrO2 with a Ce/Zr atomic ratio close to unity is considered to be one of the main causes for the increased total oxygen storage capacity (OSC), the characterization approaches of homogeneity remain a major challenge. We propose a simple, yet effective method, to assess both structural and compositional homogeneity of CeO2-ZrO2 by using Eu(3+) luminescence measured with time and dual spectral resolution (emission and excitation). For Eu(3+)-CeO2-ZrO2 calcined at 750 °C, the X-ray diffraction, Raman and High-Resolution Transmission Electron Microscopy data converge to a single pseudo-cubic phase. However, the evolution of Eu(3+)-delayed luminescence from cubic ceria-like to tetragonal zirconia-like emission reveals the formation of CeO2- and ZrO2-rich nanodomains and provides evidence for early phase separation. For Eu(3+)-CeO2-ZrO2 calcined at 1000 °C, the emission of Eu(3+) reveals both structural and compositional inhomogeneity. Our study identifies the differences between the local structure properties of CeO2 and ZrO2 parent oxides and CeO2-ZrO2 mixed oxide, also confirming the special chemical environment of the oxygen atoms in the mixed oxide as reported earlier by Extended X-ray Absorption Fine Structure investigations.

10.
Nanomaterials (Basel) ; 14(3)2024 Jan 29.
Artículo en Inglés | MEDLINE | ID: mdl-38334548

RESUMEN

The primary objective of this research was to develop efficient solid catalysts that can directly convert the lactic acid (LA) obtained from lignocellulosic biomass into alanine (AL) through a reductive amination process. To achieve this, various catalysts based on ruthenium were synthesized using different carriers such as multi-walled carbon nanotubes (MWCNTs), beta-zeolite, and magnetic nanoparticles (MNPs). Among these catalysts, Ru/MNP demonstrated a remarkable yield of 74.0% for alanine at a temperature of 200 °C. This yield was found to be superior not only to the Ru/CNT (55.7%) and Ru/BEA (6.6%) catalysts but also to most of the previously reported catalysts. The characterization of the catalysts and their catalytic results revealed that metallic ruthenium nanoparticles, which were highly dispersed on the external surface of the magnetic carrier, significantly enhanced the catalyst's ability for dehydrogenation. Additionally, the -NH2 basic sites on the catalyst further facilitated the formation of alanine by promoting the adsorption of acidic reactants. Furthermore, the catalyst could be easily separated using an external magnetic field and exhibited the potential for multiple reuses without any significant loss in its catalytic performance. These practical advantages further enhance its appeal for applications in the reductive amination of lactic acid to alanine.

11.
Phys Chem Chem Phys ; 14(37): 12970-81, 2012 Oct 05.
Artículo en Inglés | MEDLINE | ID: mdl-22903237

RESUMEN

Pure and europium (Eu(3+)) doped ZrO(2) synthesized by an oil-in-water microemulsion reaction method were investigated by in situ and ex situ X-ray diffraction (XRD), ex situ Raman spectroscopy, high-resolution transmission electron microscopy (HRTEM), steady state and time-resolved photoluminescence (PL) spectroscopies. Based on the Raman spectra excited at three different wavelengths i.e. 488, 514 and 633 nm and measured in the spectral range of 150-4000 cm(-1) the correlation between the phonon spectra of ZrO(2) and luminescence of europium is clearly evidenced. The PL investigations span a variety of steady-state and time resolved measurements recorded either after direct excitation of the Eu(3+) f-f transitions or indirect excitation into UV charge-transfer bands. After annealing at 500 °C, the overall Eu(3+) emission is dominated by Eu(3+) located in tetragonal symmetry lattice sites with a crystal-field splitting of the (5)D(0)-(7)F(1) emission of 20 cm(-1). Annealing of ZrO(2) at 1000 °C leads to a superposition of Eu(3+) emissions from tetragonal and monoclinic lattice sites with monoclinic crystal-field splitting of 200 cm(-1) for the (5)D(0)-(7)F(1) transition. At all temperatures, a non-negligible amorphous/disordered content is also measured and determined to be of monoclinic nature. It was found that the evolutions with calcination temperature of the average PL lifetimes corresponding to europium emission in the tetragonal and monoclinic sites and the monoclinic phase content of the Eu(3+) doped ZrO(2) samples follow a similar trend. By use of specific excitation conditions, the distribution of europium on the amorphous/disordered surface or ordered/crystalline sites can be identified and related to the phase content of zirconia. The role of zirconia host as a sensitizer for the europium PL is also discussed in both tetragonal and monoclinic phases.


Asunto(s)
Circonio/química , Europio/química , Mediciones Luminiscentes , Nanotecnología , Espectrometría Raman , Temperatura
12.
ACS Appl Mater Interfaces ; 14(8): 10428-10437, 2022 Mar 02.
Artículo en Inglés | MEDLINE | ID: mdl-35171567

RESUMEN

Palladium nanoparticles entrapped in porous aromatic frameworks (PAFs) or covalent organic frameworks may promote heterogeneous catalytic reactions. However, preparing such materials as active nanocatalysts usually requires additional steps for palladium entrapment and reduction. This paper reports as a new approach, a simple procedure leading to the self-entrapment of Pd nanoparticles within the PAF structure. Thus, the selected Sonogashira synthesis affords PAF-entrapped Pd nanoparticles that can catalyze the C-C Suzuki-Miyaura cross-coupling reactions. Following this new concept, PAFs were synthesized via Sonogashira cross-coupling of the tetraiodurated derivative of tetraphenyladamantane or spiro-9,9'-bifluorene with 1,6-diethynylpyrene, then characterized them using powder X-ray diffraction, diffuse reflectance infrared Fourier transform spectroscopy, X-ray photoelectron spectroscopy, high-resolution scanning transmission electron microscopy, and textural properties (i.e., adsorption-desorption isotherms). The PAF-entrapped Pd nanocatalysts showed high catalytic activity in Suzuki-Miyaura coupling reactions (demonstrated by preserving the turnover frequency values) and stability (demonstrated by palladium leaching and recycling experiments). This new approach presents a new class of PAFs with unique structural, topological, and compositional complexities as entrapped metal nanocatalysts or for other diverse applications.

13.
Phys Chem Chem Phys ; 13(38): 17135-45, 2011 Oct 14.
Artículo en Inglés | MEDLINE | ID: mdl-21869965

RESUMEN

Pure and europium (Eu(3+)) doped cerium dioxide (CeO(2)) nanocrystals have been synthesized by a novel oil-in-water microemulsion reaction method under soft conditions. In-situ X-ray diffraction and RAMAN spectroscopy, high-resolution transmission electron microscopy, UV/Vis diffuse-reflectance and Fourier transform infrared spectroscopy as well as time-resolved photoluminescence spectroscopy were used to characterize the nanaocrystals. The as-synthesized powders are nanocrystalline and have a narrow size distribution centered on 3 nm and high surface area of ~250 m(2) g(-1). Only a small fraction of the europium ions substitutes for the bulk, cubic Ce(4+) sites in the europium-doped ceria nanocrystals. Upon calcination up to 1000 °C, a remarkable high surface area of ~120 m(2) g(-1) is preserved whereas an enrichment of the surface Ce(4+) relative to Ce(3+) ions and relative strong europium emission with a lifetime of ~1.8 ms and FWHM as narrow as 10 cm(-1) are measured. Under excitation into the UV and visible spectral range, the europium doped ceria nanocrystals display a variable emission spanning the orange-red wavelengths. The tunable emission is explained by the heterogeneous distribution of the europium dopants within the ceria nanocrystals coupled with the progressive diffusion of the europium ions from the surface to the inner ceria sites and the selective participation of the ceria host to the emission sensitization. Effects of the bulk-doping and impregnation with europium on the ceria host structure and optical properties are also discussed.


Asunto(s)
Cerio/química , Emulsiones/química , Europio/química , Sustancias Luminiscentes/química , Nanopartículas/química , Sustancias Luminiscentes/síntesis química , Nanopartículas/ultraestructura , Nanotecnología/métodos , Aceites/química , Espectrometría Raman , Agua/química , Difracción de Rayos X
14.
Eur J Pediatr ; 170(9): 1151-7, 2011 Sep.
Artículo en Inglés | MEDLINE | ID: mdl-21340485

RESUMEN

We tested the hypothesis that application of the principles learned from the European Paediatric Life Support (EPLS) course improves child health assessment and care. In a retrospective study, residents from five paediatric emergency departments were included. For each of them, we analysed five medical records of infants and children suffering from diarrhoea; three were in ambulatory care and two were in-hospital care with IV hydration. Two independent observers analysed the records using a standardized checklist of 14 clinical points, as well as three items to evaluate the adequacy of treatment according to hydration status. Agreement between readers was evaluated the kappa coefficient of concordance. Statistical associations between each item and the EPLS course status was assessed by logistic regression taking into account the clustered data structure. Fifty residents and 240 medical records were included. Twenty-six residents were EPLS trained (intervention group) and 24 residents were not (control group). The results of the analyses of the medical records by the observers were concordant (kappa >0.91). Medical records in the intervention group contained more clinical information on circulatory status (P < 0.0001). Residents in the intervention group prescribed goal-directed therapy more often (P = 0.006). For children with shock, they administered volume resuscitation (P = 0.01) with goal-directed therapy more often (P = 0.003). This is the first evaluation of an educational program focusing on the actions of "learners" in the clinical environment. Our findings highlight that the EPLS course is associated with a better clinical analysis of hydration and circulation status as well as with goal-directed therapy.


Asunto(s)
Deshidratación/terapia , Medicina de Emergencia/educación , Servicio de Urgencia en Hospital , Fluidoterapia , Internado y Residencia , Cuidados para Prolongación de la Vida/normas , Mejoramiento de la Calidad , Preescolar , Deshidratación/diagnóstico , Deshidratación/etiología , Diarrea/complicaciones , Europa (Continente) , Objetivos , Humanos , Lactante , Paris , Estudios Retrospectivos
15.
Nanomaterials (Basel) ; 11(10)2021 Sep 30.
Artículo en Inglés | MEDLINE | ID: mdl-34685015

RESUMEN

ZnO nanoparticle-based multifunctional coatings were prepared by a simple, time-saving microwave method. Arginine and ammonia were used as precipitation agents, and zinc acetate dehydrate was used as a zinc precursor. Under the optimized conditions, flower-like morphologies of ZnO aggregates were obtained. The prepared nanopowders were characterized using X-ray powder diffraction (XRD), scanning electron microscopy (SEM), and UV/Visible spectroscopy. The developed in situ synthesis with microwave irradiation enabled significant ZnO nanoparticle deposition on cotton fabrics, without additional steps. The functionalized textiles were tested as a photocatalyst in methylene blue (MB) photodegradation and showed good self-cleaning and UV-blocking properties. The coated cotton fabrics exhibited good antibacterial properties against common microbial trains (Staphylococcus aureus, Escherichia coli, and Candida albicans), together with self-cleaning and photocatalytic efficiency in organic dye degradation. The proposed microwave-assisted in situ synthesis of ZnO nanocoatings on textiles shows high potential as a rapid, efficient, environmentally friendly, and scalable method to fabricate functional fabrics.

16.
Materials (Basel) ; 14(18)2021 Sep 14.
Artículo en Inglés | MEDLINE | ID: mdl-34576531

RESUMEN

Preventing and controlling the spread of multidrug-resistant (MDR) bacteria implicated in healthcare-associated infections is the greatest challenge of the health systems. In recent decades, research has shown the need for passive antibacterial protection of surfaces in order to reduce the microbial load and microbial biofilm development, frequently associated with transmission of infections. The aim of the present study is to analyze the efficiency of photocatalytic antimicrobial protection methods of surfaces using the new photocatalytic paint activated by light in the visible spectrum. The new composition is characterized by a wide range of analytical methods, such as UV-VIS spectroscopy, electron microscopy (SEM), X-ray powder diffraction (PXRD) or X-ray photoelectron spectroscopy (XPS). The photocatalytic activity in the UV-A was compared with the one in the visible light spectrum using an internal method developed on the basis of DIN 52980: 2008-10 standard and ISO 10678-2010 standard. Migration of metal ions in the composition was tested based on SR EN1186-3: 2003 standard. The new photocatalytic antimicrobial method uses a type of photocatalytic paint that is active in the visible spectral range and generates reactive oxygen species with inhibitory effect against all tested microbial strains.

17.
Phys Chem Chem Phys ; 12(12): 3031-7, 2010 Mar 28.
Artículo en Inglés | MEDLINE | ID: mdl-20449395

RESUMEN

Zeolites NaY and ZSM-5 were used as hosts for styrene polymerization after ion-exchange with europium ions. The parent and hybrid, polystyrene coated Eu-NaY (Eu-NaY/PS) and Eu-ZSM-5 (Eu-ZSM-5/PS) zeolites were investigated by using thermal analysis, SEM, PXRD, FT-IR, DR-UV/Vis, steady state and time-resolved photoluminescence spectroscopy. FT-IR spectra evidenced for the interaction between the zeolitic hosts and polystyrene while the PXRD spectra supported for the presence of the polymer inside the channels/pores of Eu-NaY/PS and Eu-ZSM-5/PS materials. The optical properties of Eu-NaY/PS and Eu-ZSM-5/PS were significantly changed relative to those of the parent zeolites, giving further evidence for the presence of polymer inside zeolites. An interesting case is presented by NaY zeolite: following styrene polymerization, the polymer interacted selectively with one of the two main species co-existing inside zeolite while for ZSM-5 a similar effect was not observed.


Asunto(s)
Europio/química , Luz , Polímeros/química , Poliestirenos/química , Zeolitas/química , Luminiscencia , Microquímica , Porosidad , Espectroscopía Infrarroja por Transformada de Fourier
18.
ACS Omega ; 4(5): 8881-8891, 2019 May 31.
Artículo en Inglés | MEDLINE | ID: mdl-31459976

RESUMEN

Technologically relevant tetragonal/cubic phases of HfO2 can be stabilized at room temperature by doping with trivalent rare earths using various approaches denoted generically as bulk coprecipitation. Using in situ/ex situ X-ray diffraction (XRD), Raman spectroscopy, high-resolution transmission electron microscopy, and in situ/ex situ site-selective, time-gated luminescence spectroscopy, we show that wet impregnation of hafnia nanoparticles with 10% Eu oxide followed by mild calcination in air at 500 °C produces an efficient stabilization of the cubic phase, comparable to that obtained by bulk precipitation. The physical reasons behind the apparently conflictual data concerning the actual crystallographic phase and the local symmetry around the Eu stabilizer and how these can be mediated by luminescence analysis are also discussed. Apparently, the cubic crystal structure symmetry determined by XRD results in a pseudocubic/tetragonal local structure around Eu determined by luminescence. Considering the recent findings on wet impregnated CeO2 and ZrO2, it is concluded that CeO2, ZrO2, and HfO2 represent a unique case of a family of oxides that is extremely tolerant to heavy doping by wet impregnation. In this way, the same batch of preformed nanoparticles can be doped with different lanthanide concentrations or with various lanthanides at a fixed concentration, allowing a systematic and reliable investigation of the effect of doping, lanthanide type, and lanthanide concentration on the various functionalities of these technologically relevant oxides.

19.
Nanoscale ; 10(37): 18043-18054, 2018 Sep 27.
Artículo en Inglés | MEDLINE | ID: mdl-30229790

RESUMEN

To avoid the deleterious effects of dopant segregation, synthesis methods that facilitate a homogenous dopant distribution in the ceria lattice were employed. Though doping ceria by wet impregnation was also credited to induce a homogeneous solid solution even in the heavy regime (concentration ≥20%, A. Corma, P. Atienzar, H. Garcia and J. Chane-Ching, Nat. Mater., 2004, 3, 394-397), no follow up investigation has been reported. Herein, we investigated ceria nanoparticles (1%Tm-CeO2 and 1%Eu-CeO2) wet-impregnated with trivalent rare-earth (Yb, 20%), bivalent (Ca, 20%) and isovalent (Zr, 30%) metals, followed by annealing in air. Homogeneity of the solid solutions of Yb-impregnated ceria was confirmed by a two-feature characterization toolbox that included X-ray diffraction, Raman spectroscopy, transmission electron microscopy, as well as up-conversion emission as a probe tool. Since the up-conversion emission of Tm was not detectable in the absence of Yb while its efficiency depends on the average distance between Yb and Tm ions, the Yb incorporation and its migration from the surface to the lattice bulk sites in wet-impregnated ceria can be "visualized" and compared with that of the Yb bulk-doped counterpart. The use of Eu luminescence as a local probe confirmed the homogeneity of solid solutions of Ca and Zr-impregnated ceria and also sustained the opposite roles of Ca and Zr as the repeller and the scavenger of oxygen vacancies, respectively. All these results suggested that heavy doping of ceria by wet impregnation with metals with +2, +3 and +4 valencies represent a facile alternative to conventional doping approaches. Therefore, the effects of the amount and the type of metal dopant on the structural properties of CeO2 could be investigated in a more systematic and probably a more reproducible manner, which would significantly increase the potential of ceria in catalysis and other applications.

20.
Nanomaterials (Basel) ; 8(12)2018 Nov 28.
Artículo en Inglés | MEDLINE | ID: mdl-30487442

RESUMEN

Here, we show that wet impregnation of ZrO2 nanoparticles with 10% and 20% Eu oxide followed by thermal anneal in air above 500 °C produces full stabilization of the tetragonal phase of ZrO2 without evidencing any phase separation. The bare ZrO2 nanoparticles were obtained using three synthetic methods: oil in water microemulsion, rapid hydrothermal, and citrate complexation methods. The homogeneity of the solid solutions was assessed using X-ray diffraction, Raman spectroscopy, high resolution transmission electron microscopy, and advanced luminescence spectroscopy. Our findings show that wet impregnation, which is a recognized method for obtaining surface doped oxides, can be successfully used for obtaining doped oxides in the bulk with good homogeneity at the atomic scale. The limits of characterization technique in detecting minor phases and the roles of dopant concentration and host structure in formation of phase stabilized solid solutions are also analyzed and discussed.

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