Laboratory of

Diffractometry

and Spectrometry

Department of Catalysis on Metals

Institute of Physical Chemistry, Polish Academy of Sciences

General information

Equipment

Details of the measurement

Scheme of the in situ camera

Software in use

Laboratory staff

Current projects

Contact address



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General background and activity

Laboratory of X-Ray Powder Diffraction and Spectrometry has been created in 1994 in the Institute of Physical Chemistry (Warsaw,Poland) within the Department of Catalysis on Metals. It was based on the established in 1960-ties by the Department of Catalysis on Metals, X-Ray Laboratory headed by dr A.Janko and later by prof.J.Pielaszek. The laboratory undertakes projects involving widely understood phase analysis and Rietveld refinement of structural data based on laboratory and synchrotron powder diffraction patterns as well as dynamical and kinetic studies in situ in variable, controlled atmosphere and programmed temperature (from R.T.upto~600 ^oC).

The laboratory specializes also in the analysis of the state of organization of quasi-amorphous materials. Our long time experience and expertise was focused on the studies of such materials using wide angle X-Ray Powder Diffraction as well as Radial Distribution Function method (RDF). We have contributed to the method developing the most accurate to date convolutional method of normalization of the scattering pattern (Kaszkur, J.Appl.Crystall.,23 ,180-185 (1990)). Quality of the method was later confirmed by Cumbrera et al.,J.Appl.Cryst.28, 408-415 (1995) in the paper entirely devoted to our method. We have also developed many numerical techniques to study highly dispersed solids (transition metals) deposited on supports (SiO₂,Al ₂O₃). These techniques include reliable background estimation in the XRD pattern, data smoothing procedures and quantitative analysis oriented towards in situ studies. Recently we develop a series of analytic tools allowing insight into the structure and dynamics of nanocrystalline metalic particles in a chemical reaction environment. These techniques are developed and verified on the basis of molecular simulations. They may detect degree of relaxation or reconstruction of the surface of metal nanoparticles exposed to chemical reagents. We can follow in situ surface violation of the crystal symmetry, nanocrystal reshaping during the reaction or anisotropic reconstruction. This opens up new avenues of insight into the elementary chemical reactions at the atomistic level. The new techniques are developed within the research group "Dynamics of nanocrystal structure induced by surface chemistry" established in 2008. The "proof of concept" papers as well as several studies are listed as methodology papers below.

Head of the Laboratory

Zbigniew Kaszkur PhD, D. Sc. zbig@ichf.edu.pl

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equipment

-X-Ray Diffractometer D5000 (Siemens) equipped with Goebel optics (Cu Ka ) (for photo click here ),

-X-Ray Diffractometer Geigerflex (Rigaku-Denki) ( for photo click here ),

-Position Sensitive Detector CPS 120 (Inel), covering 120^oarc, with channel separation ~0.03^o (for photo click here ),

-Position Sensitive Detector type Brown 50M, covering ~10^o arc, with position resolution <80ľm, set up also in scanning mode,

-Strip detector LynxEye (Bruker), allowing for quick parallel detection on 192 solid state strips and significant speed up of the overall pattern measurement (for photo click here ),

-range of our own design chemical reactors- X-ray cameras developed for in situ X-ray studies in a controlled atmosphere in flow of selected gases, mixtures or vapors of particular pressure at selected programmed temperature ( for photo click here ).

-two Mass Spectrometers (1-200 amu, from Hiden and AMETEC) adapted to probe gases in- or outgoing from the XRD camera.

- computer controlled gas supply system with two mass flow controllers from MKS,

-Energy Dispersive X-Ray Fluorescence Spectrometer (MiniPal4 from PANanalytical) for elemental analysis of elements with Z>10 (starting from Na) (for photo click here ),

- A range of software packages for powder diffraction data reduction and analysis, purchased as well as developed in the laboratory, complementing our equipment.

Experiments can be fully programmed using bash scripts of O.S. Linux. The scripts include commands for temperature controllers, mass flow controllers, mass spectrometers vacuum pumps, diffractometers etc. - all working in a local network of the Laboratory. The scripts enable detailed programming of the experiment along a precisely designed physico-chemical scenario. This approach simplify achieving full repeatability of the experiments.

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IN-SITU REACTOR

(TO USE WITH PSD, SCHEMATIC VIEW)

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Technical details of the measurement

For analysis we usually require 50-200mg of powdered sample that can be either deposited (smeared over and/or pressed) on a surface of a rectangular piece of porous glass (~10x20 mm) for in situ studies, or pressed into sample holder in the form of a shallow ditch in the surface of glass or plastic. To avoid texture problems occurring on pressing the sample we sometimes use flat surface MYLAR envelopes spread over thin frame or Capton self-adhesive tape. The envelope can be loosely filled with the material under study which, for the materials of low absorption, provides means to use transmission geometry of X-ray Diffraction measurement. In the latter case the amount of the material available has to be increased to 1-2 g (depending on its density).

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Software in use

Among the programs routinely used in the laboratory there are packages for data and structure visualization, powder diffraction pattern synthesis (LAZY-PULVERIX, MERCURY) and Rietveld refinement (GSAS, FULLPROF) or phase analysis (Match, HighScore Plus). For handling long series of data files collected in dynamical in situ measurements we have developed software basing on the concept of the list of data (program INEL). Most of the developed routines can then be applied to survey the desired feature of all marked data patterns from the active list. Such approach enables e.g. extraction of a one-peak characteristics evolution during thermal treatment and/or a phase transition. Thermal expansion coefficient, peakwidth and intensity evolution can thus be reliably calculated and displayed. The program, written in Borland Pascal 7.0 using a user friendly platform of Turbo Vision, is currently rewritten into free pascal Lazarus platform (OS Linux). The program uses data formats as provided by Inel's Diffractinel software as well as ASCII free format.

Development of our software included theoretical simulations of small metallic clusters (graphic interface, energy relaxation, Molecular Dynamics (MD), Monte Carlo (MC), powder diffraction simulation etc.). The modeling encompasses a long range Sutton-Chen potential for metals and Embedded Atom Method. Most of the simulation tools is included into program CLUSTER written as 32 bit Delphi application (currently rewritten to 64 bit Lazarus) and handling a large number of metal atoms limited only by the size of physical memory. For typical fcc metal it enables tracking down consequences of structural details on the diffraction pattern and radial distribution function (RDF) of nanocrystals. The topics which may be addressed this way include thermal expansion and melting of nanocrystals (employing MD), surface segregation in bimetallic nanocrystals (employing MC techniques), surface contraction of metal nanocrystals, impact of surface interactions on the geometry (powder diffraction), surface reconstruction, cluster agglomeration and many other. A specific experiment-oriented approach enables averaging of RDF and diffraction pattern over long MD run as well as estimation of thermal expansion from the shifting position of a main diffraction peak.
Recently the laboratory addressing the general strategy of software investment made a move towards Linux environment and attempts to base most of experimental software on open source projects. Program CLUSTER is being developed in two versions: strictly computational in Linux (Free Pascal) command line mode, and in Linux X-windows environment based on Lazarus. Data acquisition software for INEL CPS120 position sensitive detector is being developed in network based form under Linux GPIB open source project. Also 5 temperature controllers and the environmental camera gas feeding system control have been arranged under Linux with networked, written in c programs. The development allows for easy experiment control via the extensive scripting environment.

The Laboratory has been also involved in EXAFS studies of catalysts using synchrotron radiation (LURE, Daresbury, DESY-Hasylab ) as well as in construction of a laboratory EXAFS spectrometer. The experience gathered profited in the development of EXAFS analysis and simulation program (XAS) written with Turbo Vision platform of Borland Pascal 7.0. The package includes most of a widely used data reduction and normalization routines, FourierTransform, one coordination sphere extraction and fitting, extraction of amplitudes and phases from experiment as well as the use and fitting of simulated data from the worldwide acknowledged FEFF program, with which the package is well integrated.

Older home-based software includes simulation of the stereographic projections of a defined structure along any chosen axis-the program designed to aid single crystal orientation procedure.

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Laboratory staff:

Wojciech Juszczyk PhD Eng.

wjuszczyk@ichf.edu.pl

Zbigniew Kaszkur PhD, D.Sc.

zbig@ichf.edu.pl

Dmitry Lisovytskiy PhD  Eng.

dl@ichf.edu.pl

Boguslaw Mierzwa PhD

godan@ichf.edu.pl

Ewa Trzetrzewiǹska M.Sc

trzetrze@ichf.edu.pl

Ewa Tym

ewat@ichf.edu.pl

Current projects

The general subject of interest of the Laboratory is:

Structure of highly dispersed solids (nanocrystals) and its dynamics during physical processes and chemical reaction.

During last years the Laboratory carried research financially supported by the following grants:

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Jerzy Pielaszek, professor, PhD, D.Sc.

M.Sc., 1965- Department of Physics, University of Warsaw, Poland

Ph.D., 1972- Institute of Physical Chemistry PAS, Warsaw, Poland

D.Sc., 1996- Department of Physics, Warsaw Technical University, Poland

Professor, 2004 - Institute of Physical Chemistry PAS, Warsaw, Poland

Professional affiliations:

• Polish Crystallographic Association

• Polish Chemical Society

• 1972 - Commissariat à L´Enérgie Atomique, Fontenay-aux-Roses, France

• 1974 - University College of Wales, Aberystwyth, Walia, UK

• 1981-1983 - Nortwestern University, Evanston, USA

• 2001, 2002, 2003, 2005 - Université Henri Poincaré, Nancy, France

Research areas:

• Pielaszek J., "X-Ray Diffraction from Nanostructured Materials" chapter in: Nanocrystalline Metals and Oxides, Selected Properties and Application, Eds. P. Knauth, J. Schoonman, Kluwer Academic Publishers, 2002.

• Juszczyk W., Karpiński Z., Łomot D. and Pielaszek J., Transformation of Pd/SiO₂ into palladium silicide during reduction at 450 and 500°C. J. Catal., 220, 299-308 (2003).

• Skotak M., Karpiński Z., Juszczyk W., Pielaszek J., Kępiński L., Kazachkin D.W., Kovalchuk V.I, d’Itri J.L., „Characterization and catalytic activity of differently pretreated Pd/Al₂O₃ catalysts. The role of acid sites and palladium alumina interactions”, J.Catal., 227, 11-25(2004).

• Lisovytskiy D., Kaszkur Z., Pielaszek J., M. Marzantowicz M., J.R. Dygas J.R., “In situ impedance and X-ray diffraction study of phase transformation in lithium manganese spinel”, Solid State Ionics, 176, 2059-2064 (2005);

•  Dygas J.R., Kopec M., Krok F., Lisovytskiy D., Pielaszek J.,” Conductivity and dielectric relaxation phenomena in lithium manganese spinel”. Solid State Ionics, 176, 2153-2161 (2005);

• Laberty Robert Ch., Fontaine M.L., Mounis T., Mierzwa B., Lisovytskiy D., Pielaszek J., “X-ray diffraction studies of perovskite or derived perovskite phase formation”. Solid State Ionics, 176, 1213–1223 (2005);

• Pielaszek J., Mierzwa B., Medjahdi G.,Mareche J.F., Puricelli S., Celzard A., Furdin G. ”Molybdenum carbide catalyst formation from precursors deposited on active carbons; XRD studies”. Appl. Catal. A-Gen., 296, 232-237 (2005).
  

• Kopeć M., Lisovytskiy D., Marzantowicz M., Dygas J.R., Krok F., Kaszkur Z., Pielaszek J., „X-ray diffraction and impedance spectroscopy studies of lithium manganeze oxide spinel”, J.Power Sources, 159, 412-419 (2006).

• Fontaine M.L., Laberty-Robert C., Verelst M., Pielaszek J., Lenormand P., Ansart F., Tailhades P., “Synthesis of La₂NiO_4+ð oxides by sol-gel process: Structural and microstructural evolution from amorphous to nanocrystallized powders”, Mater.Res.Bull., 41, 1747-1753 (2006).

• Pielaszek J., Dygas J.R. Krok F., Lisovytskiy D., Kopeć M., Marzantowicz M., „X-ray diffraction and electric measurements of phase transformation in Li-Mn spinels” Solid State Phenomena, 130, 63-68 (2007).

Total number of publications: 104.

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Zbigniew Kaszkur, associate professor, PhD, DSc.

M.Sc - Warsaw University, Faculty of Physics, in "Mathematical Methods of Physics", 1977.

Ph.D - Institute of Physical Chemistry Polish Academy of Science, in Solid State Physics, 1987,

D.Sc - Warsaw Technical University, Faculty of Physics, in Solid State Physics, 2008.

Field of research
Powder Difraction, Atomistic Simulations, Diffraction on nanocrystals, Radial Distribution Function analysis, Interpretation of surface phenomena on metal nanocrystals via diffraction.

Professional affiliations:

• Assoc.Professor in the Institute of Physical Chemistry of the Polish Academy of Sciences
• Head of Laboratory of X-ray Powder Diffractometry and Spectrometry in the Institute of Physical Chemistry of the Polish Academy of Sciences
• Head of the workgroup “Dynamics of nanocrystal structure induced by surface chemistry” (IPC PAS), see http://groups.ichf.edu.pl/kaszkur/
• Deputy Head of the Department of Catalysis on Metals in Institute of Physical Chemistry PAS,
• Lecturer in Cardinal Stefan Wyszyński University (crystallography),
• Coordnator of Working Group 2 in COST Action MP0903,
• Member of the Committee of Crystallography in Polish Academy of Sciences (term 2007-2010, 2011-2014, 2015-2018)
• Secretary of Polish Crystallographic Association for the term 2010-2012, 2013-2016.
• Secretary and Board member of Polish Synchrotron Radiation Society (2012-2014, 2015-2017).
• Former board member of the Polish Physical Society (Warsaw Branch),
• Member of IPC Scientific Council 1987-1989, 1993-1995, 2011-2013, 2013-2015, 2015-2017,
• Guest editor for Journal of Alloys and Compounds, Acta Physica Polonica A, Journal of X-Ray Spectrometry, Crystal Research and Technology.

Research areas:

Structural analysis of highly dispersed and amorphous solids,

Dynamical and in situ powder diffraction of highly dispersed metals,

Molecular simulations of metal nanoclusters and bimetallic nanosystems,

Diffraction full profile and peak shape analysis,

Radial Distribution Function analysis,

Interpretation of surface phenomena on metal nanocrystals via diffraction,

Transport phenomena in the nanoworld.

Selected methodology papers:

1. Kaszkur Z., Rzeszotarski P., Juszczyk W., Powder Diffraction in studies of nanocrystal surfaces - chemisorption on Pt. J.Appl.Cryst., 47, 2069-2077(2014)
2. Kaszkur Z., Mierzwa B., Juszczyk W.,Rzeszotarski P., Łomot D., Quick low temperature coalescence of Pt nanocrystals on silica exposed to NO- the case of reconstruction driven growth? RSC Adv ., 4(28), 14758 – 14765 (2014).
3. Rzeszotarski P., Kaszkur Z., "Surface reconstruction of Pt nanocrystals interacting with gas atmosphere. Bridging the pressure gap with in situ diffraction". Phys.Chem.Chem.Phys., 11, 5416 - 5421(2009)
4. Kaszkur Z., "Test of applicability of some powder diffraction tools to nanocrystals". Z. Krist. 23, 147-154 (2006).
5. Kaszkur Z., Mierzwa B., Pielaszek J., "Ab initio test of the Warren-Averbach analysis on model palladium nanocrystals". J. Appl. Cryst. 38, 266-273 (2005).
6. Kaszkur Z., "Direct observation of chemisorption induced changes in concentration profile in Pd-Au alloy nanosystems via in situ X-ray powder diffraction". Phys. Chem. Chem. Phys. 6, 193-199(2004).
7. Kaszkur Z., "Nanopowder diffraction analysis beyond the Bragg law applied to Palladium". J. Appl. Cryst. 33, 87-94(2000).
8. Kaszkur Z., "Powder Diffraction beyond the Bragg law: study of palladium nanocrystals". J. Appl. Cryst. 33, 1262-1270(2000).
9. Kaszkur Z.A., Mierzwa B., Segregation in model palladium-cobalt clusters, Phil. Mag. A 77, 781-800(1998).
10. Kaszkur Z., General Approach to the Radial Distribution Function Analysis of Solid Carbons,.Fuel , 69, 834-839 (1990).
11. Kaszkur Z., Convolutional Approach to the Normalisation of Intensity Scattered by Polycrystalline Substances, J.Appl.Cryst., 23 ,180-185 (1990).
    
12. Kaszkur Z., The Influence of the Texture on Radial Distribution Function of Solid Carbons, J.Appl.Cryst. , 22 (3),205(1989).
13. Kaszkur Z., Stachurski J., Pielaszek J., X-Ray Diffraction Study of the Palladium-Carbon System, J.Phys.Chem.Solids , 47 ,795(1986).

Selected other papers from 2009:

1. Bonarowska M., Kaszkur Z., Łomot D., Rawski M., Karpiński Z., Effect of gold on catalytic behavior of palladium catalysts in hydrodechlorination of tetrachloromethane. Applied Catalysis B, Environmental, 162, 45-56 (2015).
2. Tabakova T., Ilieva L., Ivanov I, Zanella R., Sobczak J.W., Lisowski W., Kaszkur Z., Andreeva D., Influence of the preparation method and dopants nature on the WGS activity of gold catalysts supported on doped by transition metals ceria. Applied Catalysis B: Environmental ,136 - 137, 70 - 80.(2013).
3. Prochowicz D., Justyniak I., Kornowicz A., Kaczorowski T., Kaszkur Z., Lewiński J. Construction of a Porous Homochiral Coordination Polymer with Two Types of CunIn Alternating Units Linked by Quinine: A Solvothermal and a Mechanochemical Approach. Chem.Eur.J., 18 (24), 7367-7371 (2012).
4. Iwanek, E., Krawczyk, K., Petryk, J., Sobczak, J.W., Kaszkur, Z. Direct nitrous oxide decomposition with CoOx-CeO2 catalysts. Applied Catalysis B: Environmental, 106 (3-4), 416-422 (2011).
5. Bury W., Krajewska E., Dutkiewicz M., Sokołowski K., Justyniak I., Kaszkur Z. Kurzydłowski K.J., Płociński T., Lewiński J. Tert-Butylzinc hydroxide as an efficient predesigned precursor of ZnO nanoparticles. Chemical Communications, 47 (19), 5467-5469 (2011).
6. Lewiński J., Kaczorowski T., Prochowicz D., Lipińska T., Justyniak I., Kaszkur Z., Lipkowski J., Cinchona Alkaloid-Metal Complexes: Noncovalent Porous Materials with Unique Gas Separation Properties. Angewandte Chemie, 49, 7035-7039 (2010).
7. Bonarowska M., Kępiński L., Kaszkur Z., Karpiński Z., Hydrodechlorination of tetrachloromethane on alumina- and silica-supported platinum catalysts. Applied Catalysis B: Environmental, 99, 248-256 (2010).
8. Truszkiewicz E., Raróg-Pilecka W., Schmidt-Szałowski K., Jodzis S., Wilczkowska E., Łomot D., Kaszkur Z., Karpiński Z., Kowalczyk Z., Barium - promoted Ru/carbon catalyst for ammonia synthesis. State of the system when operating. Journal of Catalysis, 265, 181-190 (2009).
Total number of ICI indexed publications: ~80.
about 60 presentations in international conferences, many expertises for pharmaceutical industry. List of all publications.




Link to Zbigniew Kaszkur home page

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Contact address

E-mail x-ray@ichf.edu.pl

Institute of Physical Chemistry PAS

Warszawa 01-224, ul. Kasprzaka 44/52

Telephone : (22)3433284 or 3433417

Fax : (22)3423450

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Last modified: 03/30/2015 16:30

by Zbigniew Kaszkur - zbig@ichf.edu.pl