Nanostructured porous materials is one of the most growing field in the modern materials science. The collaboration between the Southern Federal University (SFedU, group leader A. Soldatov), and the Turin University (group leader C. Lamberti) was already active since some years, as SFedU has become a partner of the MaMaSELF European master in Materials Science [1]. In this frame, Master students were shared from both sides, a joint PhD program was running and two joint papers had been published [2,3] when the present project (No. 14.Y26.31.0001) was submitted. This fact allowed us to be immediately operative, already starting form the first days of January 2014, once we knew that project No. 14.Y26.31.0001 was granted by the Russian Federation Government.
On the scientific ground we already have the first results in all the main fields of project, which are: (i) supported metal nanoparticles; (ii) zeolites; (iii) metallorganic-frameworks (MOFs). On supported metal nanoparticles we have been active on both the simulations [4] and the experiments [5,6] including XRD, SAXS and X-ray absorption (XAS) experiments performed at synchrotron radiation (SR) sources. On zeolites, we combined SR XAS with X-ray emission spectroscopy (XES) to elucidate the linear nature of [NH3•••Cu+•••NH3] complexes formed inside Cu-SSZ-13 zeolite (a key step for the understanding the NH3?SCR catalytic cycle) [7] and we were able to determine the architecture of Ti(IV) sites in Ti aluminophosphate AlPO-5, proving that Ti mainly substitutes P in the zeolite framework [8]. Concerning MOFs, we started to perform the first experiments on the functionalization of UiO-67 material. Finally, on a side-subject of our project (always related to nano-materials) we demonstrated how SR X-ray nanobeams can be used to progressively change the oxygen doping level in Bi-2212 superconducting whisker-like single crystals, acting as an example of X-ray nanolithography [9].
In 2014 we already performed several successful experiments at SR sources: one at MAX-II (Lund, Sweden), one at SLS (Villingen, Swiss), five at the ESRF (Grenoble, France, a sixth being scheduled in July). At present, the results of such experiments are under the analysis step and we are confident that several high impact publications will come out from these data. Several proposals have been submitted in spring and, if granted will provide additional beamtime in the September 2014-January 2015 period.
On an infrastructural ground of laboratory set-up, we have just acquired and ordered the following instruments: microwave synthesis reactor, vacuum oven, elements for vacuum system and several sets of chemicals necessary for the synthesis of advanced porous nanostructured materials. We have hired the following research staff: Kirill Lomachenko, Aram Bugaev, Dr. Mikhail Soldatov, Dr. Antonina Kravtsova, Vera Butova, Irina Goncharenko, Lubov Guda. Among them Dr. Andriy Budnyk who has a deep international experience (6 years in the Turin laboratories) in porous nanostructured materials. He specializes on FTIR, UV-Vis and Raman spectroscopies that are used in combination with vacuum lines to perform experiments under in situ and operando conditions. He will be hired in Rostov since September 01, 2014.
We started to establish an important collaboration network linking the Southern Federal University with important international laboratories such as Turin University (Prof. E. Groppo, Dr. E. Borfecchia and Dr. L. Mino), ESRF synchrotron (Prof. V. P. Dmitriev, Dr. P. Glatzel, Dr. G. Agostini, Dr. E. Gallo); SLS synchrotron (Prof. J. A. van Bokhoven, Dr. G. Smolentsev).
References
[1] See http://www.mamaself.eu/ and http://www.mamaself.eu/english/master-materials-science-mamaself/partner-institutions/
[2] C. Garino, E. Gallo, N. Smolentsev, P. Glatzel, R. Gobetto, C. Lamberti, P. J. Sadler, L. Salassa, “Resonant X-ray emission spectroscopy reveals d–d ligand-field states involved in the self-assembly of a square-planar platinum complex”, Phys. Chem. Chem. Phys., 14 (2012) 15278. Cover of issue 44 of the journal.
[3] K. A. Lomachenko, E. Gallo, C. Garino, D. Gianolio, R. Gobetto, P. Glatzel, N. Smolentsev, G. Smolentsev, A. V. Soldatov, C. Lamberti and L. Salassa,“High energy resolution core-level X-ray spectroscopy for electronic and structural characterization of osmium compounds”, Phys. Chem. Chem. Phys., 15 (2013) 16152.
[4] G. Agostini, L. Bertinetti, A. Piovano, R. Pellegrini, G. Leofanti, E. Groppo, C. Lamberti, “The effect of different fcc nanoparticle distributions on particle size and surface area determination: a theoretical study”, J. Phys. Chem. C, 118 (2014) 4085.
[5] E. Groppo, G. Agostini, E. Borfecchia, L. Wei, F. Giannici, G. Portale, A. Longo, C. Lamberti, “Formation and growth of Pd nanoparticles inside a highly cross-linked polystyrene support: role of the reducing agent”, J. Phys. Chem. C, 118 (2014) 8406.
[6] A. L. Bugaev, A. A. Guda, K. A. Lomachenko, V. V. Srabionian, L. A. Bugaev, A. V. Soldatov, C. Lamberti, V. P. Dmitriev, J. A. van Bokhoven, “Temperature and pressure dependent hydrogen concentration in supported PdHx nanoparticles by Pd K-edge XANES”, J. Phys. Chem. C, 118 (2014) 10416.
[7] F. Giordanino, E. Borfecchia, K. A. Lomachenko, A. Lazzarini, G. Agostini, E. Gallo, A. V. Soldatov, P. Beato, S. Bordiga, C. Lamberti, “Interaction of NH3 with Cu-SSZ-13 catalyst: a complementary FTIR, XANES and XES study”, J. Phys. Chem. Lett., 5 (2014) 1552.
[8] E. Gallo, A. Piovano, C. Marini, O. Mathon, S. Pascarelli, P. Glatzel, C. Lamberti, G. Berlier, “The architecture of the Ti(IV) sites in Ti-AlPO-5 determined using Ti K-edge X-ray absorption and X-ray emission spectroscopies”, J. Phys. Chem. C, 118 (2014) 11745.
[9] A. Pagliero, L. Mino, E. Borfecchia, M. Truccato, A. Agostino, L. Pascale, E. Enrico, N. De Leo, C. Lamberti, M. Martinez-Criado, “Doping change in the Bi-2212 superconductor directly induced by a hard X-ray nano-beam”, Nano Lett., 14 (2014) 1583.