Ordered structures of defect clusters in gadolinium-doped ceria

The nano-domain, with short-range ordered structure, has been widely observed in rare-earth-doped ceria. Atomistic simulation has been employed to investigate the ordering structure of the nano-domain, as a result of aggregation and segregation of dopant cations and the associated oxygen vacancies in gadolinium-doped ceria. It is found that the binding energy of defect cluster increases as a function of cluster size, which provides the intrinsic driving force for the defect cluster growth. However, the ordered structures of the defect clusters are different from the chain model as previously reported. Adjacent oxygen vacancies prefer to locate along <110>/2 lattice vector, which results in a unique stable structure (isosceles triangle) formation. Such isosceles triangle structure can act as the smallest unit of cluster growth to form a symmetric dumbbell structure. This unique dumbbell structure is hence considered as a building block for the development of larger defect clusters, leading to nano-domain formation in rare-earth-doped ceria.     

Surface characterization of stepwise oxidized spruce thermomechanical pulp samples by different analytical methods

An investigation of the fiber samples with various amounts of lignin, hemicelluloses and cellulose was conducted by means of dye adsorption, spectrometric and chemical analyses. Five fiber samples were prepared by the oxidation of unbleached Norway spruce thermo-mechanical pulp with acidic potassium permanganate solution. Each sample was oxidized with defined amount of KMnO₄ and the degree of oxidation was determined as kappa number. Fibers were additionally characterized by conductometric titration, the determination of hemicelluloses and infrared spectrometry. Sorption of various types of dye, namely Methylene Blue (MB), Crystal Violet (CV) and Astra Blue (AB) on the fiber surface was studied and compared to the kappa number and other fiber characteristics. The adsorption of MB and CV is found to follow the amount of anionic (carboxylic) groups, which at first increase and later decrease toward the final stages of oxidation. The behavior of AB is nearly the opposite, its adsorption increases with the depletion of lignin and carboxylate groups, pointing to a different mechanism of AB binding on fibers.     

Impregnation of gadolinium-doped ceria backbone electrodes modified by addition of pore-formers for SOFC application

Journal of Solid State Electrochemistry - Solid oxide fuel cells (SOFCs) are promising devices for energy conversion applications due to their high electrical efficiency and eco-friendly behavior....     

Microwave-hydrothermal synthesis of gadolinium-doped nanocrystalline ceria in the presence of hexamethylenetetramine

A new method is proposed for producing nanodisperse ceria-based solid solutions, involving microwave-hydrothermal (MW-HT) treatment of aqueous solutions containing salts of cerium and dopant elements and hexamethylenetetramine (HMTA). The specifics of HMTA hydrolysis under hydrothermal conditions are studied. X-ray and electron diffraction, Raman spectroscopy, and transmission electron microscopy are used to analyze the physicochemical characteristics of Ce_{1 ? x} Gd _x O_{2 ? x/2} (x = 0.10, 0.15, 0.20) nanocrystalline solid solutions produced using the new method.     

Cobalt(III) dicarboxylato bis-ethylenediamine nitrates: Preparation and characterization by thermal analysis and other analytical methods

Compounds with the general formulacis ortrans-[Coen ₂ (RCOO)₂]NO₃ were prepared by modifications of known procedures; R was H, CH₃, C₂H₅ or C₃H₇, anden was ethylenediamine. The compounds were characterized by TLC and UV-Vis spectrophotometry, and their thermal behaviour was examined via TG and DTA, and via IR spectra on heated samples.The thermal stabilities are discussed in terms of the strengths of the bonds in the solids [1] and steric hindrance; the thermal decompositions are described with the aid of hypothesized intermediates and IR spectra.Reaction steps are identified and the thermal stability sequence is discussed: thecis compounds are less stable than the correspondingtrans compounds, due to the lower reticulation effect; the sequence of thecis compounds is the reverse of the sequence of carboxylate ion basicity, while the sequence displalyed by thetrans compounds can be interpreted in terms of solid lattice stabilization.

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Zusammenfassung Unter Durchführung einiger Abänderungen des bekannten Verfahrens wurden Verbindungen der allgemeinen Formel conf-Co[en₂(RCOO)₂]NO₃ hergestellt. Der AlkylrestR war H, CH₃, C₂H₅, C₃H₇ unden war Ethylendiamin. Die Verbidungen mitconf=cis odertrans wurden mittels TLC und UV-Spektrophotometrie charakterisiert. Ihr thermisches Verhalten wurdeanhand von TG, DTA und IR-Spektren von erhitzten Proben untersucht. Die thermische Stabilität wurde untersucht und in Abhängigkeit von Bindungsstärke und sterischer Behinderung diskutirt; weiterhin wurden die thermischen Zersetzungen mit Hilfe angenommener Intermediäre und deren IR-Spektren beschrieben. Die Reaktionsschritte wurden identifiziert und eine Stabilitätsreihe aufgestellt und diskutiert: cis-Verbindungen erwiesen sich als instabiler als die entsprechenden trans-Verbindungen, was einem geringeren Vernetzungseffekt zuzuschreiben ist; Die Reihenfolge folgt im Falle voncis dem Reziproken der Carboxylationenbasizität, während die Reihenfolge im Falle vontrans mittels der Gitterstabilisierung erklärt werden kann.

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, -[Coen₂(RCOO)₂]NO₃, R=H, CH₃, C₂H₅, C₃H₇, aen= . - - - . , . . , . : - , , . - -, - .

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This work was carried out with the financial support of the Consiglio Nazionale delle Ricerche (C.N.R.), which also gave a grant to one of us (A.M.G.).     

Formation and characterization of different ceria/silica composite materials via dispersion of ceria gel or soluble ceria precursors in silica sols

Composite ceria/silica materials of 10 and 20% (w/w) were prepared by calcination, at 650 degrees C for 3 h, of the xerogels obtained by mixing the corresponding amount of a ceria precursor with freshly prepared sols of spherical silica particles (Stober particles) in their mother liquors. Two different ceria precursors were examined in this investigation. The first was a gel produced by the prehydrolysis of cerium(IV) isopropoxide in isopropanol medium, and the second was an aqueous solution of cerium(IV) ammonium nitrate. Different textural and morphological characteristics that developed by calcination were investigated by TGA, FTIR, XRD, SEM, and analyses of N2 adsorption isotherms. The results indicated that ceria dispersion and formation of mesoporous textural composite materials produced by the second precursor, cerium(IV) ammonium nitrate, are better than those produced by the first precursor, prehydrolyzed cerium(IV) isopropoxide. The results are discussed in terms of the effect of precursors and mixing media on nucleation and growth of ceria particles and their protection from sintering on calcination at the test temperature.     

Critical review on analytical methods for biodiesel characterization

Biodiesel is an alternative fuel composed of mono-alkyl esters and obtained mainly from the base-catalyzed transesterification reaction of oils or fats. Its use (pure or blended) does not demand any modification in the diesel engine and in the existing fuel distribution and storage infrastructure. Moreover, biodiesel has a high energetic yield, fixes the solar energy and contains insignificant amounts of sulphur. Therefore, biodiesel is currently the best substitute for fossil diesel fuel.Besides mono-alkyl esters, glycerol (main co-product), alcohol, catalyst, free fatty acids, tri-, di- and monoglycerides compose the final mixture of biodiesel production process. These and other kinds of contaminants can lead to severe operational and environmental problems. Therefore, the quality control of biodiesel is greatly significant to the success of its commercialization and market acceptance. Some important issues on the biodiesel quality control involve the monitoring of transesterification reaction, the quantification of mono-alkyl esters and free- and bonded glycerol as well as determination of residual catalysts and alcohol. Moreover, the determination of blend levels is another key aspect of biodiesel analyses. Chromatography and spectroscopy are the analytical methods most used for the biodiesel characterization, but procedures based on physical properties are also available.Previously, a review on analytical methods used to evaluate biodiesel quality was written by Knothe. Due to the importance of this field, we made an update of Knothes’ review. Therefore, in this paper, we will describe new developments in biodiesel analyses and some references showed in Knothes’ paper. Specially, we will describe analytical methods used for quantification of glycerol, mono-, di-, triglycerides, methanol, water, Na, K, P, and steroids in biodiesel or along the transesterification reaction. Also, the determination of biodiesel content in blends and some physicochemical parameters are discussed. At the end, we will assess the available techniques and point out some improvements on analytical methods for biodiesel characterization.     

Raman spectroscopy as a probe of temperature and oxidation state for gadolinium-doped ceria used in solid oxide fuel cells

Raman spectroscopy is a noninvasive and highly sensitive analytical technique capable of identifying chemical compounds in environments that can mimic SOFC operating conditions. Here we demonstrate the use of Raman spectroscopy to perform local thermal and temporal measurements, both of which are essential if phase formation diagrams are to be mapped out and compared to thermodynamic phase stability predictions. We find that the time resolution of the Raman technique is more than sufficient to capture essential dynamic effects associated with a change of chemical composition.     

A critical review on analytical methods and characterization of butyl and bromobutyl rubber

The molecular structure characterization of butyl and bromobutyl rubber (BIIR) requires the definition of three main parameters: (I) the unsaturation degree of the rubbers, (II) the total bromine content of the BIIRs, and (III) the functional bromine content of the BIIRs. The analytical methods for the determination of the previously mentioned parameters have been described and critically examined in this review.     

Preparation, characterization and analytical application of a hybrid organic-inorganic silica-based monolith

In the present study, a mercapto groups-incorporated hybrid silica-based monolith, which consists of a continuous porous silica backbone, was successfully synthesized by sol-gel technology. The hybrid silica monolith was characterized by various techniques, such as elemental analysis, scanning electron microscopy, diffused infrared spectroscopy and low temperature nitrogen desorption/adsorption measurements. The results showed that the monolith contains high sulfur content (up to 3.05%) with a hierarchical porous structure (throughpores and mesopores) and large specific surface area (467 m(2)/g). Due to the favorable chemical reactivity of mercapto pendant moieties, the hybrid monolith can be facilely derivatized to yield various functional groups. In this study, they were oxidized by hydrogen peroxide (30%, w/w) to produce sulfonic acid groups, which exhibited excellent cation-exchange capability. The application of this material is demonstrated by in-tube microextraction of anaesthetics followed by capillary electrophoretic separation. The monolith can be effectively applied to purify and enrich the target analytes in human urine.     

Comparison of different types of filters for atmospheric trace element analysis by three analytical methods

Different atmospheric aerosol samples were collected on three types of filters. From both of the loaded and clean areas of each kind of filter, different disks were cut and investigated by XRF, PIXE and scanning electron microscopy (SEM). The blank concentration values of the elements Al, Si, P, S, Cl, K, Ca, Sc, Ti, V, Cr, Mn, Fe, Co, Ni, Cu, Zn, As, Br and Pb in the three types of filter are discussed. It is found that for trace elemental analysis, the Nuclepore membrane filters are the most suitable for sampling. These filters have much lower blank element concentrations than the glass fiber and ash free filters. It was found also that PIXE is a more reliable analytical technique for atmospheric aerosol particles than the other methods used.     

Determination of elements by nuclear analytical methods

The working principle of nuclear analytical methods (NAMs) is not influenced by the chemical bond. Consequently, they are independent counterparts to the well-known chemical procedures. NAMs obey fundamental laws or can be described and understood thoroughly. This qualifies them as candidates for reference methods. Although following similar nuclear reaction schemes, they comprise bulk analyzing capability (neutron and photon activation analysis) as well as detection power in surface near regions of solids (ion beam techniques). Prominent features of NAMs are sensitivity, selectivity, multielement determination and linearity of the calibration function covering a concentration range of several orders of magnitude. Moreover, ion beam techniques allow depth profiling with nm-resolution in several cases while the ion microprobe additionally offers a lateral resolution in the micron-scale. As NAMs require expensive apparatus (nuclear reactor, accelerator in radioactive control areas) their availability is restricted to a small number of suitably equipped institutes. However, they are able to solve complex analytical tasks, take part in key comparisons and play an essential role in the certification of reference materials.     

Preparation and characterization of Pt/C catalysts for PEMFC cathode: effect of different reduction methods

Three Pt/C catalysts for PEMFC cathode were prepared by impregnation-reduction method using HCHO, NaBH₄, and N₂H₄ as reductant, respectively, and characterized by BET, CV and XRD. The effect of reduction methods on the activity of catalysts was investigated. Compared with NaBH₄ and N₂H₄, HCHO is the most suitable one among the three reductants. The catalytic activity for oxygen reduction is in the order Pt(HCHO) > Pt(NaBH₄) > Pt(N₂H₄). This revised version was published online in June 2006 with corrections to the Cover Date.     

General characterization of analytical methods: Example of mass spectrometry and chromatography-mass spectrometry

A review of the well-established and novel analytical methods in mass spectrometry and chromatography-mass spectrometry is presented. General information about the methods is given and their distribution over the fields of analysis and mass spectrometric methods is considered. The classification and validation (certification) of the methods is discussed and their necessary characteristics are specified. The identification criteria contained in the methods and isotope dilution method providing the most precise and accurate results of quantitative analysis are considered. Various characteristics of errors (uncertainty) used in analytical methods are presented.     

Synthesis and characterization of sol-gel zirconium phosphate with template surfactants by different methods

Long chain trimethylammonium salts can be successfully used as guest molecules to produce mesoporous layered materials when intercalated in sol-gel zirconium phosphate, an inorganic ion-exchanger. The obtained materials are very similar independently of the chain length and the synthesis method batch (B) or direct intercalation (DI). They show a good thermal stability, and a very high interlayer distance if compared with their precursor. By the thermal characterization it can be observed that the surfactant is lost in two or three steps depending on its position in the host. The layered structure with the expanded interlayer distance is maintained up to 300°C. From the IR spectra the different surfactant release models for (B) and (DI) are confirmed. This revised version was published online in July 2006 with corrections to the Cover Date.     

Evaluation of different instrumental and chemical parameters in analytical determinations by the use of experimental design methods

Summary The paper deals with the application of fractional experimental design, random balance method and full experimental design with two levels of variation of the input parameters for the estimation of the significance of chemical and instrumental factors in different analytical problems. The example chosen refer to the fluorimetric determination of aluminium (estimation of three chemical and two instrumental factors for optimization purposes), the ranging of environmental factors in the determination of the protective ability of polymer coatings (seven parameters are included) and the determination of several anions in aerosol samples by ion chromatography (the significance of three operational parameters for model solutions is considered). It is shown that the experimental design strategies can be used as reliable and quick tools for ranging and parameter estimation.

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Bewertung verschiedener instrumenteller und chemischer Parameter bei analytischen Bestimmungen mittels experimenteller Planung

Zusammenfassung Die Anwendung der Fraktions-Experimentalplanung, des Zufallsausgleichs und der Vollplanung auf zwei Ebenen der Eingangsparameter zur Bewertung der Wichtigkeit von instrumentellen und chemischen Parametern bei verschiedenen analytischen Aufgaben wird diskutiert. Die gezeigten Beispiele beziehen sich auf die fluorimetrische Bestimmung von Aluminium (Bewertung von drei chemischen und zwei instrumentellen Faktoren für Optimierungszwecke), die Einordnung von Umweltfaktoren bei der Bestimmung der Schutzwirkung von Polymerschichten (sieben Parameter), und die Bestimmung einiger Anionen in Aerosolproben mit der Ionen-Chromatografie (dabei wird die Wichtigkeit von drei Arbeitsparametern bei Modellösungen betrachtet). Es wird gezeigt, daß diese Planungsstrategie zur zuverlässigen und schnellen Bewertung und Einordnung von Parametern geeignet ist.

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Dedicated to Prof. Dr. Dr. h.c. Hanns Malissa on the occasion of his 65th birthday     

Synthesis and characterization of mesoporous ceria with hierarchical nanoarchitecture controlled by amino acids

In this work, we report the synthesis and characterization of mesoporous ceria with hierarchical nanoarchitectures controlled by amino acids. During the synthesis procedure, cerium oxalate precipitate was treated hydrothermally with different amino acids as crystallization modifiers, and hierarchically structured cerium oxalate precursors were obtained. Ceria can be produced after thermal decomposition of the cerium oxalate precursors. Structure and properties of the product were characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), Raman spectroscopy, N2 adsorption analysis, and X-ray photoelectron spectroscopy (XPS) methods. The results indicate that the mesoporous ceria with hierarchical nanoarchitectures are composed of nanosized ceria crystallites as building units and possess high surface area and high concentration of oxygen vacancy. Depending on different amino acids as the crystallization modifiers, the ceria exhibit different morphologies, such as dendritic aggregation of rods, dumbbells of nanorod arrays, or aggregated spheres. It is proposed that both the type of functional side groups and the length of the side groups of the amino acids influence the morphologies of the ceria. Meanwhile, the solvent and hydrothermal treatment temperatures also play important roles in the morphological control. The method reported in this work would be regarded as a general way to fabricate mesoporous metal oxides with hierarchical nanoarchitectures.     

Preparation and properties of uniform praseodymium-doped ceria colloidal particles

 A procedure to prepare submicrometre spherical particles of Pr(III), Ce(III) or Pr(III)-doped C(III) hydroxycarbonates with narrow size distribution is reported. The particles were obtained by aging aqueous solutions of Pr(III) chloride and/or Ce(III) nitrate in the presence of urea at 100 °C for 2 h. The effect of Pr and/or Ce salt concentrations in the starting solutions on the size, shape and composition of the precipitated particles is reported. The thermal behaviour of the basic carbonates up to decomposition into the metal oxides was followed by differential thermal and thermogravimetric analyses, X-ray diffraction, IR spectroscopy and transmission electron microscopy. All the systems were also characterized by their electrokinetic behaviour (determination of isoelectric point) and specific surface areas. The colour of the powders was also evaluated as a function of the Pr content and temperature and was compared with previous results on red pigments of similar composition. Received: 30 May 2001 Revised: 17 September 2001 Accepted: 20 September 2001     

合成后再处理法制备含Ti介孔分子筛Ti-KIT-1

Mesoporous molecular series Ti-KIT-1 samples were prepared by three different post-handling methods using Ti(OEt)4 as the Ti source and KIT-1 as the support .The three post-synthetic methods were impregnated method,grafting method and colloidal method.The Ti-KIT-1 samples were characterized by FT-IR,DRS,XRD,TG-DSC and physical adsorption-desorption of nitrogen.Experimental results showed that the Ti-KIT-1 samples remained the original mesoporous structure with a smaller specific BET surface area compared to the parent KIT-1 sieve.DRS and FT-IR indicate the existence of tetrahedral titanium (Ⅳ),TG-DSC and chemical analyse method proved that TiO_2 weight percentage of grafting sample is much more than impregnated and colloidal samples.The grafting method is a good post-handling method that can effectively make use of a titanium source and promise the original mesoporous structure.     

The identification of irradiated seasoned filefish (Thamnaconus modestus) by different analytical methods

Dried seasoned filefish (Thamnaconus modestus) was irradiated at 0–10 kGy and the identification of irradiation treatment was investigated by analyzing the characteristics of thermoluminescence (TL), hydrocarbon (HC), and 2-alkylacyclobutanone (2-ACB). The TL (TL₁), glow curve of the irradiated samples peaked at approximately 150 °C with high intensity, but that of the non-irradiated samples peaked at about 300 °C with little intensity, thus making it possible to discriminate between irradiated and non-irradiated samples. Moreover, TL ratio (TL₁/TL₂), through normalization steps, enhanced the reliability of the TL₁ results. Six kinds of HCs and three kinds of 2-ACBs quantitatively determined for the samples linearly increased in proportion to irradiation doses. In particular, two HCs like 1-hexadecane and 1,7-hexadecadine, and three ACBs, such as 2-dodecylcyclobutanone, 2-(5′-tetradeceyl)cyclobutanone, and 2-tetradecylcyclobutanone, were identified only in the irradiated samples as radiation-induced markers.