Joanna Łojewska

Molecular degradation of ancient documents revealed by 1H HR-MAS NMR spectroscopy

For centuries mankind has stored its knowledge on paper, a remarkable biomaterial made of natural cellulose fibers. However, spontaneous cellulose degradation phenomena weaken and discolorate paper over time. The detailed knowledge of products arising from cellulose degradation is essential in understanding deterioration pathways and in improving durability of cultural heritage. In this study, for the first time, products of cellulose degradation were individually detected in solid paper samples by means of an extremely powerful proton HR-MAS NMR set-up, in combination to a wise use of both ancient and, as reference, artificially aged paper samples. Carboxylic acids, in addition to more complex dicarboxylic and hydroxy-carboxylic acids, were found in all samples studied. Since these products can catalyze further degradation, their knowledge is fundamental to improve conservation strategies of historical documents. Furthermore, the identification of compounds used in ancient production techniques, also suggests for artifacts dating, authentication and provenance.

Size exclusion chromatography and viscometry in paper degradation studies. New Mark-Houwink coefficients for cellulose in cupri-ethylenediamine

The paper deals with the application of size exclusion chromatography (SEC) for the studies of paper degradation phenomena. The goal is to solve some of the technical problems connected with the calibration of multi-detector SEC system and to find the correlation between SEC and viscometric results of degree of polymerization of cellulose. The results gathered for the paper samples degraded by acidic air pollutant (NO(2)) are used as an example of SEC-MALLS application. From the correlation between intrinsic viscosities and absolute value of molecular masses obtained with SEC/MALLS (Multi Angle Laser Light Scattering) technique, Mark-Houwink coefficients for cellulose in cupri-ethylenediamine solution were determined. Thus obtained coefficients were used for the determination of viscometric degree of polymerization (molecular mass) of the aged samples. An excellent correlation was found between the chromatographic values of molecular masses obtained with SEC-UV/VIS detection and the viscometric ones utilizing the improved values of Mark-Houwink coefficients.

Spectroscopic characterization of Co3O4 catalyst doped with CeO2 and PdO for methane catalytic combustion

The study deals with the XPS, Raman and EDX characterization of a series of structured catalysts composed of cobalt oxides promoted by palladium and cerium oxides. The aim of the work was to relate the information gathered from spectroscopic analyses with the ones from kinetic tests of methane combustion to establish the basic structure-activity relationships for the catalysts studied. The most active catalyst was the cobalt oxide doped with little amount of palladium and wins a confrontation with pure palladium oxide catalyst which is commercially used in converters for methane. The analyses Raman and XPS analyses showed that this catalyst is composed of a cobalt spinel and palladium oxide. The quantitative approach to the composition of the catalysts by XPS and EDX methods revealed that the surface of palladium doped cobalt catalyst is enriched with palladium oxide which provides a great number of active centres for methane combustion indicated by kinetic parameters.

Active state of model cobalt foil catalyst studied by SEM, TPR/TPO, XPS and TG

Four states of the cobalt foil catalyst, corresponding to different redox treatment and activity, were defined: oxidised, reduced, active and deactivated. They were investigated by scanning electron microscopy (SEM), temperature-programmed reduction (TPR), temperature-programmed oxidation (TPO), X-ray photoelectron spectroscopy (XPS) and thermogravimetric (TG) methods and in the hydrogenation of ethylene used as a test reaction. Particular emphasis was laid on the study of the active state, achieved after the catalyst reduction at moderate temperatures. It was shown that the catalyst preactivated by a series of redox cycles is built of a cobalt oxide layer of a characteristic size and dispersion, which is stuck to the metallic bulk. Reduction at a moderate temperature, prolonged even to several hours, converts only a small fraction of the oxide layer into metallic Co. XPS, TPR and TPO methods distinguished various states of oxygen and cobalt on the surface of the activated or partially activated samples. The results were interpreted in terms of the mechanism of autocatalytic reduction. The deactivation was associated with the structural reconstruction of the surface, taking place either in the reaction mixture during the hydrogenation of ethylene or in hydrogen atmosphere. Formation of the inactive carbon deposit was experimentally excluded.

A comparison between monolithic and wire gauze structured catalytic reactors for CH4 and CO removal from biogas-fuelled engine exhaust

The application of the wire gauzes as the catalytic supports can provide a number of advantages in biogas exhaust abatement. In this paper, a model of wire gauze structured reactor for biogas exhaust removal is proposed and model based calculations are performed to compare the wire gauze catalytic reactor with the classic monolith. The modelling bases on kinetic data experimentally obtained in a small-scale tubular reactor for cobalt and palladium (as reference) oxide catalysts doped with promoters (Ce, Pd). The heat and mass transfer characteristics of the wire gauze reactor are taken from the former studies by the authors. The simulations show that for assumed reactor parameters, a combination of the promoted cobalt oxide catalyst and the wire gauze support can give high conversion of methane and carbon monoxide.

Far Field Combined AFM and Micro-Raman Imaging for Characterisation of Surface of Structured Catalysts: Example of Pd Doped CoOx Catalysts on Precalcined Kanthal Steel

A coupled AFM–Raman system was used to study the surface heterogeneity of catalytic materials at various stages of their preparation. The catalysts chosen for the analyses were cobalt oxide with and without palladium dopant deposited on surface of pre-calcined steel carriers. Steel carriers are surveyed here in terms of their application as fillers for structured reactors for the catalytic combustion of volatile organic compounds. Upon steel precalcination stage the interfaced AFM–Raman and in situ Raman analyses revealed the evolution of alumina and iron oxide phases on the surface with their final stable forms found as being α-Al2O3 and α-Fe2O3. Upon catalyst layering stage AFM–Raman mapping evidenced uniform coverage of precalcined steel carrier with cobalt spinel oxide Co3O4. For the doped catalyst except Co3O4 palladium(II) oxide grains were also found on the surface. The differences in the composition of cobalt catalysts were correlated with the differences in their catalytic activity.

Note: Light ageing with simultaneous colorimetry via fibre optics reflection spectrometry

In this article, the design and characteristics of a micro-fadeometer is presented. The technique allows for a non-(micro-) destructive evaluation of the light fastness of colorants on various materials and can be used to directly assess valuable materials, such as heritage objects, and develop safer display strategies to promote their preservation. The presented instrument has several benefits over standard light ageing methods--low operating cost, non-damaging, real time measurement of induced changes for kinetics studies, and automated high throughput screening of materials. A selection of data is presented to demonstrate the flexibility of the presented instrument and illustrate how it can be used to evaluate museum lighting and oxygen-free display of heritage objects.

AN EXPERIMENTAL STUDY OF THE PRESSURE DROP IN FLUID FLOWS THROUGH WIRE GAUZES

Catalytic wire gauzes have been used for many years for ammonia oxidation. The flow and transfer properties of stacked gauzes, however, have not been sufficiently examined in the literature. This study presents an experimental program designed to characterize the pressure drops observed across stacked woven and knitted wire gauzes. This work generated an extensive database of measurements and reveals that each gauze requires its own correlation equation. Furthermore, previously published general models were not able to describe all four cases with high accuracy. After surveying the literature, we present some modifications to the models based on our collected experimental results.

Structure Effects on Activity of Plasma Deposited Cobalt Oxide Catalysts for VOC Combustion

The aim of this study was to obtain and characterise the series of cobalt based structured catalysts prepared by non-equilibrium plasma deposition. The catalysts were obtained under oxygen-rich and oxygen-free conditions. The catalysts were characterised by using spectroscopic and microscopic methods including AFM, SEM, EDS, in situ μRaman and XPS. The catalytic activity of prepared catalysts was measured under n-nonane catalytic combustion reaction. The correlation of catalytic activity with the catalysts characterisation results showed that the active cobalt form of the catalysts in catalytic combustion is spinel structure and is not correlated with the particle size.

Model of activation of the cobalt foil as a catalyst for CO2 methanation

Abstract A model related to variation in the concentration of active centers is proposed. Previously obtained experimental results are briefly reviewed together with presentation of complementary results. The results are generalized in the assumptions of the model. Two steps of activation of the Co foil are distinguished: (1) formation of potential centers as referred to surface development during redox pretreatment, (2) transformation of potential centers into active centers via autocatalytic reduction by hydrogen contained in the methanation mixture. A good fit to the kinetic results and agreement with available experimental facts verify the validity of the model.