Research Group n. 1
UNIVERSITA’ di Bologna
Preparation, characterization and reactivity of heterogeneous and homogeneous catalysts
Albonetti Stefania, Basile Francesco, Cavani Fabrizio*, Fornasari Giuseppe, Vaccari Angelo,
Lucarelli Carlo, Trifirò Ferruccio
Department of Industrial Chemistry “Toso Montanari”, University of Bologna, viale Risorgimento
4, I-40136 Bologna.
e-mail: [email protected]
The research activity is focused on the preparation and characterization of mixed oxide
catalysts and their use in selective oxidation, acid-base reactions, hydrogenation/dehydrogenation
and reforming reactions of industrial interest. The activity involves: i) preparation of new catalytic
systems; ii) structural and surface characterization of the materials; iii) evaluation of the catalytic
properties. The aim is: i) the understanding of the correlation among structure, surface properties
and reactivity, in order to determine the nature of the active phases involved and optimize the
composition of the systems; ii) the knowledge of the surface catalytic mechanism of selective
conversion of the interest molecules.
Many catalytic systems are investigated, such as:
(a) mixed W/V/(Nb) oxides for the gas-phase oxidehydration of glycerol into acrylic acid;
(b) spinel-type mixed Me ferrites for the cycle reforming of alcohols
(c) mixed Mg/Me oxides with basic properties for the gas-phase alkylation of activated aromatic
substrates;
(d) supported Au catalysts for the liquid-phase oxidation of cyclohexandiol into adipic acid;
(e) Metal phosphate for the direct hydrolysis of lignocellulosic materials into sugars.
(f) Metals based nanoparticles for the hydrogenation of 4-nitrophenol
(g) TiO2 based photo-catalytic coatings for self-cleaning application.
(h) Cu/Pd based catalysts supported over C and mesoporous silica for the hydrodechlorination of
CF3OCFCl-CF2Cl to CF3OCF=CF2
(i) Pt/Sn based catalysts for the partial dehydrogenation of hydrocarbons to produce H2 “onboard” of aircraft
(j) Cu/Zn/M/Al mixed oxides for the water gas shift reaction obtained form hydrotalcite-type
precursors
(k) Structurated catalysts obtained by electro-synthesis on metallic foams
(l) Nobel metal containing catalysts for steam and dry reforming of methane or biomasses
(m) Alkali-bonded ceramics with tailored hierarchical porosity
(n) Acid catalyst for functionalization of aromatic substrates in the fragrance synthesis
(o) Innovative synthesis of supports or catalysts by inverse suspension micelles.
Oxidehydration of glycerol into acrylic acid: we have developed a bifunctional catalytic system able
to transform directly glycerol into acrylic acid, via intermediate formation of acrolein. The catalyst
possesses both acid sites, necessary for the dehydration of glycerol into acrolein, and redox sites, for
the selective oxidation of acrolein into acrylic acid. The proper combination of the various elements
within the same crystalline structure allowed to achieve yield to acrylic acid as high as 50%.
Cycle reforming of ethanol: we have investigated spinel type Metal ferrites (Metal= Co, Ni, Cu),
able to oxidize methanol under anaerobic conditions into CO/CO2 and H2O. The reduced spinel is
than reoxidized back with water, with generation of H2. This in principle allows the reforming of
the alcohol with intrinsic separation of COx from H2.
Ni nanoparticles were synthesized by a microwave-assisted polyol route. The reaction was carried
out at 200°C in diethylenglycol in order to obtain stable and highly concentrated nano-sols whose
ratio was carefully optimized. Stable suspensions were produced with the future prospect of
improving the performance of the anodic layer in solid oxide fuel cells (SOFCs), in which the metal
is employed as catalyst . Preliminary tests on their catalytic and electrochemical activities were
carried out by studying the hydrogenation of 4-nitrophenol in the presence of NaBH4 as probe
reaction and by calculating the electrochemically active surface area with the cyclic voltammetry.
The photo-catalytic reactivity of nano-TiO2 coatings immobilized on cellulose substrate to get selfcleaning textiles was studied. The efficiency of different commercial nano-titania, in the photodegradation of organics, was investigated in different experimental conditions. The different
experimental set-ups let to assess interfaces where nano-TiO2 played its photo-catalytic activity and
provided information on self-cleaning mechanism.
The hydrogen-assisted dechlorination of CF3OCFClCF2Cl to produce unsaturated CF3OCF=CF2
was studied over a series of metal catalysts supported on activated carbon and MCM-41. The results
obtained indicated that the activity, stability, and selectivity of the materials were strongly
dependent on the metal and support used.
In this work the study of the partial dehydrogenation of different hydrocarbons blends and
desulfurized JetA1 fuel has been performed by using Pt/sn based catalysts to produce H2 “onboard” for the feeding of the fuel-cell apparatus. The mechanism of deactivation by coke was
studied in depth combining Raman spectroscopy and Temperature-programmed oxidation (TPO)
analyses. A relatively complex reaction pathway, which is able to evidence the role of different
sites and reactions involved in PDH processes, was proposed.
Production of hydrogen and light hydrocarbons by aqueous phase reforming of polyols and sugars,
i.e.mild reaction conditions (150-250°C) for the hydrogen production from biomass derived
solution using novel catalyst produced in microemulsion.
The H2 production by steam or dry reforming of light hydrocarbons or biomasses have been
investigated developing innovative noble metal containing catalysts with best performances. To
improve the thermal conductivity, structured catalysts have been prepared by electro-synthesis on
metallic foams, deeply characterizing them. Finally, new catalysts for the water gas shift reaction at
medium temperature were prepared starting from hydrotalcite-type precursors.
The synthesis of alkali-bonded ceramics (also called geoceramics) were investigated defining the
main parameters and their effect on the final materials. Since they may be used as supports or
catalysts (after functionalization), the preparation of samples with tailored hierarchical porosity
were investigated. Ceramic foams with meso and macroporoisty have been prepared operating in
soft conditions.
Integration of the hydrogen production and the separation membrane by multistep or single catalytic
integrated reaction carried using multifunctional structured system
The possibility to develop new synthetic way for the functionalization of aromatic c substrates in
the fragrance synthesis has been investigated using different solid catalysts, evidencing the nature of
the intercations present and justifying the unusual catalytic behaviors observed.
Key words: Heterogeneous catalysis, homogeneous catalysis, green chemistry, renewable raw
materials, biofuels, geoceramics, Ex-hydrotalcite mixed oxides, structured catalysts.
Publications:
M. Dolores Soriano, P. Concepcion, J. M. Lopez Nieto, F. Cavani, S. Guidetti, C. Trevisanut,
“Tungsten-Vanadium mixed oxides for the oxidehydration of glycerol into acrylic acid”, Green
Chem, 13 (2011) 2954-2962.
Juliana Velasquez Ochoa, Cristian Trevisanut, Jean-Marc M. Millet, Guido Busca, Fabrizio Cavani,
“In Situ DRIFTS-MS Study of the Anaerobic Oxidation of Ethanol over Spinel Mixed Oxides”, J.
Phys. Chem. C 2013, 117, 23908−23918
M. Blosi, S. Albonetti, A.L. Costa, N. Sangiorgi, A. Sanson “Easily scalable synthesis of Ni
nanosols suitable for the hydrogenation of 4-nitrophenol to p-aminophenol under mild condition”
Chemical Engineering Journal 215-216 (2013) 616–625.
A.L. Costa, S. Ortelli, M. Blosi, S. Albonetti, A. Vaccari, M. Dondi “TiO2 based photocatalytic
coatings: from nanostructure to functional properties” Chemical Engineering Journal 225 (2013)
880-88.
M. Gregori, G. Fornasari, G. Marchionni, V. Tortelli, S. Millefanti, S. Albonetti “Hydrogenassisted dechlorination of CF3OCFCl-CF2Cl to CF3OCF=CF2 over different metal supported
catalysts.” Appl. Catal A 470 (2014) 123-131.
M. Gregori, P. Benito, G. Fornasari, M. Migani, S. Millefanti, F. Ospitali, S. Albonetti “Preparation
of Pd/Cu MCM-41 catalysts for hydrodechlorination: influence of the synthesis procedure.”
Macroporous Mesoporous Materials 190 (2014) 1-9.
C. Lucarelli, G. Pavarelli, C. Molinari, S. Albonetti, W. Mista, D. Di Domenico, A. Vaccari
“Catalyst deactivation in on-board H2 production by fuel dehydrogenation International Journal of
Hydrogen Energy” Int. J. Hydrogen Energy 39 (2014) 1336-1349.
A. Ballarini, F. Basile, P. Benito, I. Bersani, G. Fornasari, S. de Miguel, S.C.P. Maina, J. Vilella, A.
Vaccari, O.A. Scelza, Platinum supported on alkaline and alkaline earth metal-doped alumina as
catalysts for dry reforming and partial oxidation of methane”, Appl. Catal. A433-434 (2012) 1-11.
G. Brenna, A. Vaccari, F. Basile, G. Fornasari, R. Faure, D. Gary, “Water gas shift catalysts
operating at medium temperatures and process for its preparation”, Eur. Pat. Application
11306604.7 – 1270 (2012) to AIR LIQUIDE
C. Lucarelli, A. Giugni, GT. Moroso and A. Vaccari, “FT-IR investigation of methoxy substituted
benzenes adsorbed on solid acid catalysts”, J. Phys. Chem. C116 (2012) 21308-21317.
Claudia Antonetti, Anna Maria Raspolli Galletti, Pasquale Accorinti, Stefano Alini, Pierpaolo
Babini, Katerina Raabova, Elena Rozhko, Aurora Caldarelli, Paolo Righi, Fabrizio Cavani,
Patricia Concepcion “Two alternative routes for 1,2-cyclohexanediol synthesis by means of green
processes: Cyclohexene dihydroxylation and catechol hydrogenation”, Applied Catalysis A:
General 466 (2013) 21-31
Elena Rozhko, Katerina Raabova, Francesco Macchia, Andrea Malmusi, Paolo Righi, Pasquale
Accorinti, Stefano Alini, Pierpaolo Babini, Giuseppina Cerrato, Maela Manzoli, Fabrizio Cavani,
“Oxidation of 1,2-Cyclohexanediol to Adipic Acid with Oxygen: A Study Into SelectivityAffecting Parameters”,ChemCatChem 5 (2013) 1998-2008.
Juliana Velasquez Ochoa, Cristian Trevisanut, Jean-Marc M. Millet, Guido Busca, Fabrizio
Cavani, “In Situ DRIFTS-MS Study of the Anaerobic Oxidation of Ethanol over Spinel Mixed
Oxides”, J. Phys. Chem. C 117 (2013) 23908−23918.
Gherardo Gliozzi, Anna Innorta, Alessia Mancini, Rossella Bortolo, Carlo Perego, Marco Ricci,
Fabrizio Cavani, “Zr/P/O catalyst for the direct acid chemo-hydrolysis of non-pretreated
microcrystalline cellulose and softwood sawdust”, Applied Catalysis B: Environmental 145
(2014) 24– 33
Alessandro Chieregato, M. Dolores Soriano, Francesco Basile, Giuseppe Liosi, Segundo Zamora,
Patricia Concepción, Fabrizio Cavani, José M. López Nieto, “One-pot glycerol oxidehydration to
acrylic acid on multifunctional catalysts: Focus on the influence of the reaction parameters in
respect to the catalytic performance”, Applied Catalysis B: Environmental 150–151 (2014) 37–46
A. Caldarelli, M. A. Bañares, C. Cortelli, S. Luciani, F. Cavani, “An investigation on surface
reactivity of Nb-doped vanadyl pyrophosphate catalysts by reactivity experiments and in situ
Raman spectroscopy”, Catal. Sci. Technol. 4 (2014) 419-427
Thomas Pasini, Alice Lolli, Stefania Albonetti, Fabrizio Cavani, Massimo Mella, “Methanol as a
clean and efficient H-transfer reactant for carbonyl reduction: Scope, limitations, and reaction
mechanism”, Journal of Catalysis 317 (2014) 206–219
SUPPLEMENTARY MATERIAL
Position of the components of the Research Groups
Name
Ferruccio
Angelo
Fabrizio
Giuseppe
Stefania
Francesco
Carlo
Patricia
Paolo
Tommaso
Andrea
Massimiliano
Juliana
Alice
Sara
Yu
Surname
Trifirò
Vaccari
Cavani
Fornasari
Albonetti
Basile
Lucarelli
Benito
Ziosi
Tabanelli
Malmusi
Mari
Velasquez Ochoa
Lolli
Andreoli
Zhang
Position *
P Emerito
PO
PO
PA
PA
PA
RU
PoD
PoD
PhD S
PhD S
PhD S
PhD S
PhD S
PhD S
PhD S
Affiliation
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Univ. Insubria
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Dip. Chimica Industriale
Olena
Vozniuk
PhD S
Dip. Chimica Industriale
Rodolfo
Mafessanti
PhD S
Dip. Chimica Industriale
Chiara
Molinari
PhD S
Dip. Chimica Industriale
Stefania
Solmi
PhD S
Dip. Chimica Industriale
Claudia
Bandinelli
PhD S
Dip. Chimica Industriale
Mattia
Melloni
PhD S
Dip. Chimica Industriale
Francesco
Puzzo
PhD S
Dip. Chimica Industriale
Lorenzo
Grazia
PhD S
Dip. Chimica Industriale
*: 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
Type
Producer
Year of acquisition
TPD/TPR/TPO
DRIFT
Chemisorb 2750
FT-IR spectrophotometer
ASAP 2020MP physorption
TPDRO 1100
TPDRO 1100
TGA 2050
DSC-DTA
Raman spectrophotometer
UV-Vis-Nir spectrophotometer
Micromeritics
Bruker
Micromeritics
Perkin-Elmer
Micromeritics
ThermoQuest CEinstrument
ThermoQuest CEinstrument
Thermal Analysis
Thermal Analysis
Renishaw
Perkin-Elmer
2015
2007
2006
2004
2003
2002
2001
2001
1999
1998
1994