Research Group n. 4
UNIVERSITA’ DEGLI STUDI DI TORINO
Investigation of the active sites in heterogeneous catalysts
by in situ and operando spectroscopies
Caterina Barzan, Gloria Berlier, Francesca Bonino, Silvia Bordiga, Valentina Crocellà, Alessandro
Damin, Elena Groppo, Carlo Lamberti, Lorenzo Mino, Giuseppe Spoto
Department of Chemistry, University of Torino, via Pietro Giuria 5, 10125 Torino
[email protected]
The main goals of the research group are the understanding at a molecular level of the structure
and function of the active sites in heterogeneous catalysts., through the synergic combination of
highly sensitive spectroscopic techniques (IR, Raman, UV-Vis, XANES, XES), structural techniques
(XRD, EXAFS, SAXS) and microscopies (SEM and TEM), applied in controlled atmosphere and in
operando. When possible, the experimental data are used to validate theoretical models and
viceversa. Among the main systems investigated there are:
 Acid zeolites to be used in the MHT process. The attention is focused on effect of topologies,
morphologies and defects concentration in the activities, selectivity and deactivation.
 Zeolites containing heteroatoms, such as: Cu-exchanged zeolites to be used in SCR DeNOx
process; Ni-exchanged zeolites to be used in olefin oligomerization reactions; heteroatoms
substituted zeolites (Ti- and Fe-zeolites) in partial oxidation reactions with H2O2 or N2O,
respectively.
 Aluminophosphates (AlPOs) doped with transition metal ions (Co, Ti, Fe, V etc) for selective
oxidation reactions with benign oxidants or Si ions for acid catalysed reactions.
 Supported metal nano-particles (Pd, Pt) on different supports (including non-reducible metaloxides, activated carbons, cross-linked micro-porous polymers) to be used as catalysts for
hydrogenation and oxidation reactions and for purification of terephthalic acid, with attention
to the effects of support doping, loading and deactivation in industrial plants.
 Catalysts for polymerization and oligomerization of olefins of the Phillips (Cr/SiO2) and
Ziegler-Natta types (TiClx/MgClx), with particular attention to the rational design of the active
centres and modification of their ligand coordination sphere, in order to tune the catalytic
activity/selectivity and thus the properties/distribution of the polymeric (or oligomeric)
products.
 TiO2-based materials with controlled morphology and nano-structures having a different
reduced state, to be exploited for ethylene polymerization and acetylene oligomerization.
 Nanostructured materials for CO2 capture and use (CCU). Mesoporous silicates functionalized
by amines and poly-Ionic Liquids are used to co-react CO2 with simple molecules such as
alcohols or ethers, to make more valuable chemicals.
Key words: heterogeneous catalysts, in situ techniques, operando, structure of the active sites
Publications
1. Bleken, F. L.; Barbera, K.; Bonino, F.; Olsbye, U.; Lillerud, K. P.; Bordiga, S.; Beato, P.; Janssens, T. V. W.;
Svelle, S. Catalyst deactivation by coke formation in microporous and desilicated zeolite H-ZSM-5 during
the conversion of methanol to hydrocarbons, J. Catal., 307, (2013), 62-73.
2. Borfecchia, E.; Lomachenko, K. A.; Giordanino, F.; Falsig, H.; Beato, P.; Soldatov, A. V.; Bordiga, S.;
Lamberti, C. Revisiting the nature of Cu sites in the activated Cu-SSZ-13 catalyst for SCR reaction, Chem.
Sci., 6, (2015), 548-563.
3. Gallo, E.; Piovano, A.; Marini, C.; Mathon, O.; Pascarelli, S.; Glatzel, P.; Lamberti, C.; Berlier, G.
Architecture of the Ti(IV) sites in TiAlPO-5 determined using Ti K-edge X-ray absorption and x-ray emission
spectroscopies, J. Phys. Chem C 118, (2014), 11745-11751.
4. Agostini, G.; Lamberti, C.; Pellegrini, R.; Leofanti, G.; Giannici, F.; Longo, A.; Groppo, E. Effect of prereduction on the properties and the catalytic activity of Pd/carbon catalysts: A comparison with Pd/Al2O3,
ACS Catal., 4, (2014), 187-194.
5. Budnyk, A.; Damin, A.; Barzan, C.; Groppo, E.; Lamberti, C.; Bordiga, S.; Zecchina, A. Cr-doped porous
silica glass as a model material to describe Phillips catalyst properties, J. Catal., 308, (2013), 319-327.
6. Groppo, E.; Gallo, E.; Seenivasan, K.; Lomachenko, K. A.; Sommazzi, A.; Bordiga, S.; Glatzel, P.; van
Silfhout, R.; Kachatkou, A.; Bras, W.; Lamberti, C. XAS and XES Techniques Shed Light on the Dark Side of
Ziegler–Natta Catalysts: Active-Site Generation, Chemcatchem, (2015), DOI: 10.1002/cctc.201402989
7. Jain, S. M.; Biedrzycki, J. J.; Maurino, V.; Zecchina, A.; Mino, L.; Spoto, G. Acetylene oligomerization on
the surface of TiO2: A step forward in the in situ synthesis of nanostructured carbonaceous structures on
the surface of photoactive oxides, J. Mater. Chem. A, 2, (2014), 12247-12254.
SUPPLEMENTARY MATERIAL
Position of the components of the Research Groups
Name
Surname
Position *
Affiliation
Caterina
Barzan
PoD
University of Torino
Gloria
Berlier
RU
University of Torino
Francesca
Bonino
RU
University of Torino
Silvia
Bordiga
PA
University of Torino
Valentina
Crocellà
PoD
University of Torino
Alessandro
Damin
T
University of Torino
Elena
Groppo
RTD
University of Torino
Carlo
Lamberti
PA
University of Torino
Lorenzo
Mino
PoD
University of Torino
Giuseppe
Spoto
PA
University of Torino
*: PO = Full professor; PA = Associate professor; RU = University researcher; CO = contract; PoD
= Postdoctoral fellows; RC = CNR staff or other Institutions Research; T = technician, VR =
visiting researcher, S = student
Equipment
The list of the equipment can be found at:
http://www.instm.it/ricerca/cr_instm/schede_cr/superfici_ed_interfasi_nanostrutturate_material
i_ad_alto_svilup_03.aspx
and
http://www.nis.unito.it/
Technical skills
• Investigation of the active sites in heterogeneous catalysts at the molecular level by means of
complementary characterization techniques. Determination of the structural, vibrational, and
electronic properties.
• Ability in the rational modification of the active sites to change the catalytic performances.
• Manipulation of air sensitive samples in controlled atmosphere
• Monitoring of the catalytic performances by means of spectroscopic techniques applied in situ
and/or in operando.