1. N. Aldea 1, S. Pintea 1, V. Rednic 1, P. Marginean 1, R. Turcu 1, S. Gergely 1, M. Neumann 2, Y. Xie 3, F. Matei 4 1 National Institute for R&D of Isotopic and Molecular Technologies, Cluj - Napoca, Romania 2 University of Osnabrück, Fachberiech Physik, Osnabruck, Germany 3 Beijing Synchrotron Radiation Facilities of Beijing, National Laboratory, P. R. China 4 University of Agriculture Sciences and Veterinary Medicine, Math. Department, Cluj-Napoca, Romania LOCAL, GLOBAL AND ELECTRONIC STRUCTURE OF NANOSTRUCTURED SYSTEMS National Institute for R&D of Isotopic and Molecular Technologies, Cluj-Napoca, Romania The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania

2. Outlook The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania A.Some physical and chemical properties of nanostructured materials (supported Au and Ni catalysts, Fe 3 O 4 polypyrrole core-shell composites) B.Theoretical background of EXAFS, XRD and XPS methods C.Experimental, data analysis, results and discussion D.Conclusions

3. A. Physical and chemical properties The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Supported metal catalysts (SMC) are special materials used in complete or partial oxidation, reduction or hydrogenation reactions that change the reaction speed without changing the chemical equilibrium. Fe 3 O 4 nanocomposites based on polypyrrole and magnetites are biocompatible and offer great promise applications in biotechnology. A1. Why are we interested to determine crystalline and electronic nanostructure ? A2. Crystallite size (global structure) determination methods: Chemisorption of the hydrogen TEM Magnetic measurements method - based on Longevins theory Powder X-ray diffraction - a new package program: XRSIZE strong correlation Catalytic activity the global (XRD), local (XAS) and electronic structure (XPS)

4. A. Physical and chemical properties The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania P. Marginean and A. Olaru, Appl. Catalysis A: General 140 (1996) 59 Crystallite domain Adsorbed hydrogen atoms Grain size A3. A3. Grain size chemosorption of the hydrogen HRTEM micrograph of Au/TiO 2 Masatake Haruta, "Catalyst of gold nanoparticles deposited on metal oxides" Cattech 6 (2002) 102

5. A. Physical and chemical properties The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania A4. The activity of supported gold catalysts R. Grisel, Kees-Jan Weststrate, Andrea Gluhoi, B.E. Nieuwenhuys, "Catalysis by Gold Nanoparticles", Gold Bulletin 35/2 (2002) 45 b) CO oxidation 2CO + O 2 2CO 2 a) conversion of propene 2C 3 H 6 + 9O 2 6CO 2 + 6H 2 O Synergistic and particle size effects for reactions: c) Temperature needed for 95% CO conversion versus the average gold particle size of Au/Al 2 O 3 calcined at 300 °C (), Au/Al 2 O 3 calcined at 600 °C ( ), Au/Al 2 O 3 calcined at 900 °C ()and Au/MO x /Al 2 O 3 () catalysts. The three Au/Al 2 O 3 catalysts have been calcined at 300, 400 and 600 °C in order to change the average Au particle size

6. B. Theoretical background The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Theoretical outline of local structure of the metal particle nanosize based on EXAFS method B1. Theoretical outline of local structure of the metal particle nanosize based on EXAFS method B 1.1 The EXAFS function χ(k) is defined in terms of the atomic absorption coefficient B 1.2 The theoretical EXAFS signal is defined by the relation Total amplitude function: B 1.3 The single shell contribution may be isolated by Fourier transform technique B 1.4 The inverse Fourier transform of the radial structure function is obtained for any coordination shell with:

7. B. Theoretical background The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania B2. Particle size determination from X-ray diffraction method By X-ray line diffraction profile (XRLP) analysis one can obtain crystallite size, microstrain and stacking fault probability. Methods Diffraction line broadening analysis - Scherrer method; For non- overlapped lines Fourier transform or analysis using Generalized Fermi Function (GFF) for X-ray Line Profiles (XRLP) approximation N. Aldea, Andreea Gluhoi, P. Marginean, C. Cosma, Xie Yaning, Extended X-ray absorption fine structure and X-ray diffraction studies on supported nickel catalysts, Spectrochimica Acta B 55, 997 (2000). N. Aldea, Andreea Gluhoi, P. Marginean, C. Cosma, Xie Yaning, Hu Tiandou, Whongua Wu and Baozhong Dong, Investigation of supported nickel catalysts by X-ray absorbtion spectrometry and X- ray diffraction using synchrotron radiation, Spectrochimica Acta B 57, 1453 (2002). N. Aldea, B. Barz, S. Pintea, F. Matei,Theoretical approach regarding nanometrology of the metal nanoclusters used in heterogeneous catalysis by powderX-ray diffraction method, J. Optoelectron. Adv. Mat 9(10) (2007) 3293.

8. B. Theoretical background The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania B3. Theoretical outline of metal particle nanosize based on single x- ray line profile analysis Fourier transform method h(s) – experimental spectrum g(s) - instrumental function f(s) - true sample spectrum Fredholm integral equation of the first kind Ill-posed problem. Convolution equation: F s - depends on particle size and stacking faults probability F ε - depends on microstrains Two simultaneous events. F(L)=F s (L)F (L) B3.1 General aspects based on convolution equation: B3.2 General relation of the true sample function erfc(x)=1-erf(x).

9. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C1. Investigated systems. Preparation methods Supported gold catalysts were prepared by homogeneous deposition- precipitation with urea on support of MOx/Al 2 O 3 (M: Cu, Ce, Mg, Li in different combinations). The gold precursor was HAuCl 4 ·3H 2 O, Aldrich, 99.999% purity. The theoretical gold content for the catalysts was 5 wt %. The catalysts were calcined at 300 0 C before the measurements C1.1 Supported gold catalysts 0 - Au foil 1 - Au/LaO x /Al 2 O 3 2 - Au/ZnO/MgO/Al 2 O 3 3 - Au/CuO/Al 2 O 3 4 - Au/CeO x /Al 2 O 3 5 - Au/ZnO/Al 2 O 3 6 - Au/TiO 2 7 - Au/MnO x /Al 2 O 3 8 - Au/Al 2 O 3 9 - Au/CeO x / ZrO x / Al 2 O 3 10 - Au/Li 2 O/CeO x /Al 2 O 3 11 - Au/Rb 2 O/CeO x /Al 2 O 3

10. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C1.2 Supported nickel catalysts The Ni/Cr 2 O 3 and Ni/Al 2 O 3 catalysts were prepared by coprecipitation of the mixture of nickel nitrate and chromium nitrate, respectively, aluminum nitrate with a solution of sodium carbonate/hydroxide. After precipitation we obtained: NiCO 3.2Ni(OH) 2.4H 2 O, Al hydroxide and Cr hydroxide, respectively In order to eliminate the sodium ions the precipitate was thoroughly washed with double distilled water. Then the precipitate was dried at 105°C in stove and calcined in nitrogen flow at 340°C and reduced in flowing hydrogen. The thermal treatments of the catalysts have been done in hydrogen flow at different temperatures for 3 hours. Ni/Cr 2 O 3 Ni/Al 2 O 3 Ni85Cr15 at % Termal treatement at: 1 - 350 0 C 2 - 420 0 C 3 - 650 0 C 4 - 850 0 C 5 - 950 0 C Ni70Cr30 at % Termal treatement at: 6 - 350 0 C 7 - 650 0 C 8 - 750 0 C 9 - 900 0 C 10- 950 0 C Ni85Al15 at % Termal treatement at: 11 - 350 0 C 12 - 550 0 C 13 - 750 0 C 14 - 850 0 C 15 - 1050 0 C Ni70Al30 at % Termal treatement at: 16 - 950 0 C Ni60Al40 at % Termal treatement at: 17 - 1050 0 C

11. C. Experimental, data analysis, results and discussions C1.3 Fe 3 O 4 polypyrrole core-shell composites The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania FerrofluidSample MF/Py (v/v) Polymerization time (h) Fe 3 O 4 : AL+DBS F10206 Fe 3 O 4 : AM+DBS F1220 Fe 3 O 4 : AL+DBS F14*210

12. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C2.1 XAS set up on synchrotron radiation for transmission measurements drivers Stepped motors encoder counter interface computer slit IC 0 ion chamber IC 1 t slit monochromater sample I0I0 I data acquisition SR BEAMLINE GPIB bus I=I 0 e - t Block diagram of the monochromator control and XAS data acquisition C2. XAS measurements

13. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania XAS spectroscopy L III gold edge, fluorescence technique, X-ray energy of incident flux between 11582 - 12806 eV BSRF - Beijing Synchrotron Radiation Facilities 4W1B beamlines, 30-50 mA, 2.2 GeV, room temperature, Δ E=1-2 eV at E=10 KeV 0 - Au foil 1 - Au/LaO x /Al 2 O 3 2 - Au/ZnO/MgO/Al 2 O 3 3 - Au/CuO/Al 2 O 3 4 - Au/CeO x /Al 2 O 3 5 - Au/ZnO/Al 2 O 3 6 - Au/TiO 2 7 - Au/MnO x /Al 2 O 3 8 - Au/Al 2 O 3 9 - Au/CeO x / ZrO x / Al 2 O 3 10 - Au/Li 2 O/CeO x /Al 2 O 3 11 - Au/Rb 2 O/CeO x /Al 2 O 3 Au(OH) 3 EXAFS signals C2.2.1 Supported Gold catalysts C2.2 Results and discussions

14. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania N1 = 12 atoms, R1 = 0.287 nm N2 = 6 atoms, R2 = 0.407 nm N3 = 24 atoms, R3 = 0.498 nm N4 = 12 atoms, R4 = 0.575 nm The local structural parameters of the investigated samples for the first coordination shell SampleNumber of atoms Shell radius [nm] Au Foil120.287 Au/LaO x /Al 2 O 3 2.820.282 Au/CuO/Al 2 O 3 4.610.287 Au/ZnO/Al 2 O 3 5.690.284 Au/MnO x /Al 2 O 3 2.900.284 Au/CeO x /ZrO x /Al 2 O 3 3.440.287 Au/Li 2 O/CeO x /Al 2 O 3 2.930.280 Au/Rb 2 O/CeO x /Al 2 O 3 2.200.284 Standard sample: Numerical results

15. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania N. Aldea, C. Tiusan, A. Chezan, "Full multiple scattering approximation to K-XANES of supported metal catalysts", Physica B, 208 & 209 (1995) 691. K edge for Ni, Cu, Fe; K edge for Cl (NaCl), F (NaF), K (KCl), K (KF), Ti (TiO), Ti (TiC). Z = 79, Au: Discrete transitions 6s L III 2p 3/2 6d 3/2 6d 5/2 XANES Analysis

16. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania, (E)dE = 1, FWHM = Γ, -life time XANES signals Transitions probability

17. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania

18. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Nb.SampleE 0 [eV]Γ 0 [eV] E 1 -E 0 [eV]Γ 1 [eV]E 2 -E 0 [eV]Γ 2 [eV]E 3 -E 0 [eV]Γ 3 [eV] 0Au foil11918.05.9314.5218.8426.868.1749.5021.05 1Au/LaO x /Al 2 O 3 11913.77.3916.17-28.5110.651.5416.12 2Au/ZnO/MgO/Al 2 O 3 12709.74.3014.724.13928.7014.850.7316.47 3Au/CuO/Al 2 O 3 11914.44.6316.171228.299.0751.5417.87 4Au/CeO x /Al 2 O 3 11909.27.5016.17-29.743.1652.588.03 5Au/ZnO/Al 2 O 3 11915.04.9714.918.4527.489.2750.3117.8 6Au/TiO 2 11908.64.8415.7510.4529.7414.352.8026.87 7Au/MnO x /Al 2 O 3 11913.7 - 15.75 - 28.51 - 51.96 - 8Au/Al 2 O 3 11909.76.1415.94-29.546.8451.9618.87 9Au/CeO x /ZrO x /Al 2 O 3 11909.14.9817.4012.1329.939.9953.4125.55 10Au/Li 2 O/CeO x /Al 2 O 3 11908.05.8618.018.6130.159.1653.4120.20 11Au/Rb 2 O/CeO x /Al 2 O 3 11907.67.1318.62-31.387.5153.4112.97 Transition probability parameters (L III edge) Transition probability parameters (L III edge) N. Aldea, V. Rednic, S. Pintea, P. Marginean, B. Barz, A. Gluhoi, B. E. Nieuwenhuys, M. Neuman, X. Yaning, F. Matei Local, global and electronic structure of supported gold nanoclustersdetermined by EXAFS, XRD and XPS sent for publication Superlattices and Microstructures, Ref: SM08-141, 2008 M. LAZAR, V. ALMASAN, S.PINTEA, B. BARZ, C. DUCU, V. MALINOVSCHI, X. YANING, N. ALDEA Preparation and structural characterization by XRD and XAS of the supported gold catalysts JOURNAL OF OPTOELECTRONICS AND ADVANCED MATERIALS, 10 (9), 2244 (2008)

19. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C2.2.2 Supported Ni catalysts XAS signals

20. Sample Coordination number N 1 ± Δ N 1 Shell radius R 1 ± Δ R 1 [Å] Shift energy E 0 ± Δ E 0 [eV] Ni standard122.498333.915 Ni85 Cr15 350 0 C10.32±0.112.497±0.0038334.252±0.0054 420 0 C10.18±0.092.485±0.0038334.064±0.0196 650 0 C10.85±0.042.480±0.0018334.115±0.0503 850 0 C11.19±0.0432.490±0.0018334.371±0.0046 950 0 C11.52±0.052.504±0.0018334.029±0.0075 Ni70 Cr 30 350 0 C8.89±0.0832.511±0.0038334.334±0.0211 650 0 C10.17±0.0682.497±0.0028333.986±0.0001 750 0 C10.44±0.0522.501±0.0028333.772± 0.0110 900 0 C11.07±0.0462.489±0.0018334.069±0.0033 950 0 C11.09±0.0582.499±0.0028333.983±0.0003 Ni85 Al 15 350 0 C6.237±0.0602.476±0.0048334.164±0.1456 550 0 C6.671±0.1212.541±0.0068333.973±0.1691 750 0 C8.682±0.1602.552+0.0058334.380+0.3152 850 0 C9.635±0.0822.514±0.0038334.004±0.0633 1050 0 C10.802±0.0562.492±0.0668334.272±0.0324 Ni70 Al 30 950 0 C8.241±0.0882.518 ±0.0048334.003±0.0857 Ni60 Al 40 1050 0 C9.862±0.0592.504±0.0028333.972±0.0356 C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania S. Pintea, V. Rednic, P. Marginean, X. Yaning, H. Tiandou, Z. Wu, M. Neumann and N. Aldea Crystalline and electronic structure investigated by XRD, XAS and XPS methods of Ni nanoclusters supported on Al 2 O 3 and Cr 2 O 3 sent for publication Superlattices and Microstructures, Ref: SM 08-136, 2008 The first coordination shell parameters

21. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C2.2.3. C2.2.3. Fe 3 O 4 polypyrrole core-shell composites (A) quadrupole transition 1s-3d, l=o, ±1, ±2 (B) dipole transition 3d-4d mixing Fe electrons, l=o, ±1 (C) d-p mixing Fe and O electrons (D) clusters size of metal oxide Fe 3 O 4 standard sample Threshold energy E B - maximum value of the first derivative Full multiple scattering theory applied to transition metals and AB compounds N. Aldea, C. Tiusan, A. Chezan, Physica B, 208-209 (1995),691 Fe K edge XANES

22. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Fe 3 O 4 χ signal of standard sample Fe 3 O 4 Normalized XANES & EXAFS 0 0.2 0.4 0.6 0.8 1 6800 7000 7200 7400 7600 7800 8000 8200 miux(energy) X-ray energy [eV] Fe3O4 - Normalized EXAFS & XANES, Miux-0, Miux Normalized EXAFS signal Fe3O4 XANES Fe3O4 miux Fe3O4 miux-zero Fe 3 O 4, µ 0, µ signals -2.4 -2.2 -2 -1.8 -1.6 -1.4 -1.2 -0.8 -0.6 -0.4 -0.2 6800 7000 7200 7400 7600 7800 8000 8200 miux(energy) X-ray energy [eV] "fe3o4s.dat" background Fe 3 O 4 as standard sample XAS signals

23. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania A.San-Miguel, Physica B 208 & 209,177 (1995) (LURE, ESRF) CDXAS computer package programs Radial structure function (RSF) Inverse Fourier transform of the RSF. Where are the first & second coordination shells? They are overlapped k r Modified Filon algorithm M. Abramowich and A. Stegun, Handbook Math. Func., EXAFS 51-65 (1996) What we have to do? Good bye FFT !!! EXAFS results N. Aldea, E. Indrea, Comput. Phys. Commun. 60 (1990) 155. N. Aldea, R. Zapotinschi, PC 94 Lugano, Switzerland, (1994)

24. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Fe 3+ tetrahedral structure Fe-O R 1 =1.89 Å, N 1 =4 Fe 2+ / Fe 3+ octahedral structure Fe-O R 2 =2.09 Å, N 2 =6 R = R 2 -R 1 = 0.2 Å R [H] = 0.52147 Å N. Aldea, R. Turcu, A. Nan, I. Craciunescu, O. Pana, X. Yaning, Z. Wu, D. Bica, L. Vekas, F. Matei Investigation of nanostructured Fe 3 O 4 polypyrrole core-shell composites by X-ray absorbtion spectroscopy and X-ray diffraction using synchrotron radiation accepted for publication Journal of Nanoparticle Research, DOI: 10.1007/s11051-008-9536-3 N. Aldea, S. Pintea, V. Rednic, F. Matei and X. Yaning Comparative study of EXAFS spectra for closed-shell systems sent for publication JOURNAL OF OPTOELECTRONICS AND ADVANCED MATERIALS

25. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Radial distribution function

26. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Sample The first shellThe second shell E 0 ± E 0 Shift energy (eV) N 1 ± N 1 Atoms numbers R 1 ± R 1 Shell radius (nm) N 2 ± N 2 Atoms numbers R 2 ± R 2 Shell radius (nm) Fe 3 O 4 40.18960.2097123.75±0.15 F102.46±0.030.189±0.0015.93±0.030.210±0.0017116.27±0.46 F123.11±0.0090.188±0.0015.15±0.010.209±0.0017118.35±0.43 F143.16±0.030.190±0.0015.25±0.010.209±0.0027114.10±0.51 Local structure parameters

27. C3. XRD measurements C. Experimental, data analysis, results and discussions CONTROLLE R SMC Time gen. COUNTER DISPLAY GATED CLOCK I/O REGISTER V/F COUNTER HV for LC HV for Na I SCA Ampl. RATEMETE R DRIVER FORTAB (6) DRIVER FOR MONO (1) I/V Ampl. SMC DRIVER FOR DIF (6) INTERFACE COMPUTER PDP11/53 TERMINAL PRINTER IC AL window BE window SLI DETECTO R SAMPLE SLIT MOTION TABLE 6 - CIRCLES DIFRACTOMETE R MONOCHROMATOR MIRROR SR BEAMLINE CAMAC CRATE BEPC The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C3.1 XRD setup SCHEMATIC DIFFRACTION STATION AT BSRL -2 montage, ionic chamber before sample

28. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C3.2.1 Supported Gold catalysts C3.2 Results and discussions Au Space Group 225, a=b=c= 0.40720 nm Instrumental correction: Au - foil 3540455055606570758085 Standard sample Au foil (111) (200) (311) (220) Relative Intensity (2 o ) RIGAKU setup with rotating anode λ = 0.15406 nm

29. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Data analysis and Fourier Transform for XRLP by Generalised Fermi Function (GFF) distribution 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 1.1 0 50 100 150 200 250 300 350 400 Fourier Transform of true sample L[ Å ] Sample Au/SiO2 (1.1), Line (111) Experimental General approximation Cubic App. Parabolic App. 0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 20 40 60 80 100 120 140 Fourier Transform of true sample L[Å] Sample Au/SiO2 IMP 3, Line (220) Experimental Parabolic App. General approximation Cubic App. 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8 0.9 1 0 10 20 30 40 50 60 Fourier Transform of true sample L[Å] Sample Au/Al2O3 (3.1), Line (311) Experimental Parabolic App. General approximation Cubic App. Background correction by polynomial approximation 0 500 1000 1500 2000 2500 3000 0.35 0.4 0.45 0.5 0.55 0.6 0.65 0.7 0.75 2*sin( )/ λ f(x) experimental fond gff1(x) gff2(x) gff3(x) Relative Intensity

30. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Global structural parameters of the investigates samples SampleLine General relation D eff [nm] x10 4 0123 Au/ZnO/MgO/Al 2 O 3 (111)1.62.06 Au/CuO/Al 2 O 3 (311)5.80.67 Au/CeOx/Al 2 O 3 (311)4.00.71 Au/ZnO/Al 2 O 3 (311)2.80.98 Au/TiO 2 (311)3.50.87 Au/MnOx/Al 2 O 3 (311)4.31.18 Au/Al 2 O 3 (311)6.30.68 Au/CeOx/ZrOx/Al 2 O 3 (111)2.11.96 Au/Li 2 O/CeOx/Al2O 3 (311)6.00.69 Au/Rb 2 O/CeOx/Al 2 O 3 (111)2.01.99

31. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C3.2.2 Supported Ni catalysts XRD Paterns measured on syncrotron radiation

32. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Global structural parameters of the investigates samples Sample (111)(200)(220) D Gr [Å] ×10 4 D Sch [Å]D Gr [Å] ×10 4 D Sch [Å]D Gr [Å] ×10 4 D Sch [Å] Ni85Cr15 at% 350 0 C 1050.3863114890.481789930.208993 420 0 C 1050.3863114890.481489880.235589 650 0 C3640.01585712810.03263083050.0046571 850 0 C 4060.00825713850.01045714190.0012800 950 0 C 4610.00568004090.00845714300.0011800 Ni70Cr30 at% 350 0 C 1310.27061381690.12141741320.0892148 650 0 C 2790.04913082130.06392352050.0210267 750 0 C 3620.01625712990.02583642510.0057444 900 0 C 3970.00975713610.01314443450.0018800 950 0 C 4200.00718004020.00875714330.0010800 Ni85Al15 at% 350 0 C 670.718882800.498989570.514562 550 0 C 860.681485770.593782670.397270 750 0 C 1880.11322111450.16741481520.0589174 850 0 C 2540.04853082010.08042112070.0215267 1050 0 C 3830.01085713380.01744443500.0023800 Ni70Al30 at% 950 0 C 2250.06992672020.07822111790.0367211 Ni60Al40 at%1050 0 C 3130.02204442980.02603642690.0072444

33. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C3.2.3 C3.2.3 Fe 3 O 4 polypyrrole core-shell composites Nanoparticles Fe 3 O 4 polypyrrole core-shell composites Silicon powder for instrumental correction

34. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Global structural parameters of the investigates samples Sampl e (hkl) h (nm -1 ) f (nm -1 ) D eff (nm) hkl 10 -3 D Sch (nm) F10 2200.292650.282813.80.604127.1 3110.243910.241244.90.322418.3 4000.198370.197066.10.1489110.1 5110.235920.235225.10.125528.5 4400.234540.232285.10.104118.6 F12 2200.286570.282994.10.611157.1 3110.216850.214925.50.256179.3 4000.251660.247164.60.232448.1 5110.184030.181826.40.0742111 4400.272290.227053.20.088628.8 F14 2200.153420.150797.70.1692513.3 3110.128110.122698.70.0788216.3 4000.114590.1142410.30.0479317.5 5110.154180.153877.80.0528213 4400.125750.111267.70.0228118

35. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C4. XPS measurements C4.1 Supported Ni catalysts Background correction for XPS profiles was done by Shirley-Tougaard approximation XPS profiles were approximated by Doniach-Sunjic distribution: Ni 2p core level lines O 1s core level lines Ni 2p 3/2 metal Ni 2p 3/2 oxide Ni 2p 1/2 oxide satellites Ni metal is missing Contribution from Cr 2 O 3 and Al 2 O 3

36. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania C4.2 Supported Gold catalysts Au(Au 2 O 3 )/Li 2 O/CeO 2 /Al 2 O 3 Ce 3d O 1s Survey Au 4f Evidence of Au 2 O 3 on the surface!

37. C. Experimental, data analysis, results and discussions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Au/ CeO 2 /Al 2 O 3 O 1s Survey Au 4f metallic state

38. D. Conclusions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania The investigated catalysts have crystallite average sizes between 1.6 - 6.3 nm for supported Au catalysts, 6.7 – 43.3 nm for supported Ni catalysts and 3.2 – 10.3 nm in case of Fe 3 O 4 polypyrrole core-shell composites; 1.6 nm is the smallest value of crystallite size determined by XRD method; The small coordination obtained from EXAFS can explain the strong metal- support interaction (SMSI) as well as the active sites occurrence; By analyzing the Au L III edge (XANES) we have shown the existence of the electronic transitions without determining or discriminating the percentage between Au +, Au 0 ; The different values of the FWHM, obtained for each electronic transition, are an evident prove for the SMSI. The microstrains of lattice can also be correlated with the effective crystallite size in the following ways: the value of the effective crystallite size increases when the microstrain value decreases, and reverse;

39. D. Conclusions The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Until now in literature we did not find the 1 st and 2 nd coordination shells evidenced by XAS for Fe 3 O 4 nanoparticles; The Ni oxide of the precursors is totally reduced, as we can see in XRD patterns only on the surface there is a thin layer of Ni oxide, evidenced from XPS measurements. Shapes and shift of XANES spectra and diminution of number of atoms from 1 st (25 %) and 2 nd (10%) from coordination shells of Fe atoms pointed out the existence of electronic interaction between magnetite nanoparticle and surrounding polypyrrole; The XPS method provided us additional information related to electronic structure and the possible existence of the gold oxide on the surface of the gold nanocrystallites.

40. Research Team and collaborators The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania Dr. Nicolae Aldea Dr. Petru Marginean PhD Student Bogdan Barz PhD Student Stelian Pintea PhD Student Vasile Rednic Prof. Dr. Manfred Neumann Dr. Rodica Turcu Dr. Florica Matei

41. Thank you for your attention ! The 14-th National Conference Progresses in Cryogenics and Isotopes Separation, 29-31 October 2008, Calimanesti-Caciulata, Valcea, Romania