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
Dipartimento di Chimica Industriale “Toso Montanari”, 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 [1];
(b) spinel-type mixed Me ferrites for the cycle reforming of alcohols [2]
(c) mixed Mg/Me oxides with basic properties for the gas-phase alkylation of activated aromatic
substrates;
(d) supported Ru(OH)3 catalysts for the liquid-phase oxidation of cyclohexandiol into adipic acid;
(e) Zr phosphate for the direct hydrolysis of lignocellulosic materials into sugars.
(f) Au, Au-Cu supported catalyst synthesized from preformed nanoparticles for the oxidation of 5hydroxymethyl-furfural (HMF) to 2,5-furandicarboxylic acid (FDCA) [3]
(g) Au/FeOx supported catalysts prepared utilizing the bimetallic carbonyl cluster salt
[NEt4][AuFe4(CO)16] for the total oxidation of VOCs [4]
(h) Cu/Zn/M/Al mixed oxides for the water gas shift reaction obtained form hydrotalcite-type
precursors [6]
(i) Structurated catalysts obtained by electro-synthesis on metallic foams
(j) Nobel metal containing catalysts for steam and dry reforming of methane or biomasses [5]
(k) Alkali-bonded ceramics with tailored hierarchical porosity
(l) Acid catalyst for functionalization of aromatic substrates in the fragrance synthesis [7]
(m) Innovative synthesis of supports or catalysts by inverse suspension.
Oxidehydration of glycerol into acrylic acid [1]: 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 allows to achieve yield to acrylic acid as high as
40%.
Cycle reforming of methanol [2]: we have investigated spinel type Metal ferrites (Metal= Co, Ni,
Cu), able to oxidize methanol under anaerobic conditions into CO/CO 2 and H2O. The reduced
spinel is than reoxidized back with water, with generation of H 2. This in principle allows the
reforming of the alcohol with intrinsic separation of COx from H 2.
The oxidation of 5-hydroxymethyl-2-furfural [3] was studied under mild reaction conditions using
TiO2-supported Au and Au–Cu catalysts synthesized from pre-formed nanoparticles. Bimetallic
gold-copper catalysts display superior activity as compared to monometallic gold. Moreover, after
reaction, the bimetallic Au–Cu catalysts can be recovered by filtration and reused without
significant loss of activity and selectivity whereas gold materials are not stable.
A series of Au/FeOx/SBA-15 type materials were prepared by bimetallic carbonyl cluster
deposition on SBA-15 [4]. Chemical physical characterization and catalytic activity tests in the
complete combustion of methanol show that the new preparation method of Au/FeOx-supported
catalysts leads to the anchoring of the Au by modifying the surface of SBA-15 with FeOx species.
This effect results in a considerable improvement in catalyst performance as compared to the classic
preparation by deposition-precipitation of Au on SBA-15 and FeOx/SBA-15.
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 [5]. 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 [6].
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.
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 [7].
Key words: Heterogeneous catalysis, homogeneous catalysis, green chemistry, renewable raw
materials, biofuels, geoceramics, Ex-hydrotalcite mixed oxides, structured catalysts.
Publications:
1) 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.
2) V rocell , F. Cavani, G. Cerrato, S. Cocchi, M. Comito, G Magnacca, C. Morterra, “On the
Role of Morphology of oFeO4 Spinel in Methanol Anaerobic Oxidation”, J Phys hem
116 (2012) 14998−15009
3) T. Pasini, M. Piccinini, M. Blosi, R. Bonelli, S. Albonetti, N. Dimitratos, J.A. Lopez-Sanchez,
M. Sankar, Q. He, C.J. Kiely, G.J. Hutchings, F avani “Selective oxidation of 5hydroxymethyl-2-furfural using supported gold-copper nanoparticles ” Green hemistry 13 (8)
(2011) 2091-2099.
4) R Bonelli, Lucarelli, T Pasini, L F Liotta, S Zacchini, S Albonetti “Total oxidation of
volatile organic compounds on Au/FeOx catalysts supported on mesoporous SBA-15 silica”
Appl. Catal. A 400 (2011) 54–60.
5) 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 atal A433-434
(2012) 1-11.
6) 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
7) 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) 2130821317.
SUPPLEMENTARY MATERIAL
Position of the components of the Research Groups
Name
Surname
Position *
Affiliation
Ferruccio
Trifirò
P Emerito
Dip. Chimica Industriale
Angelo
Vaccari
PO
Dip. Chimica Industriale
Fabrizio
Cavani
PA
Dip. Chimica Industriale
Giuseppe
Fornasari
PA
Dip. Chimica Industriale
Stefania
Albonetti
RU
Dip. Chimica Industriale
Francesco
Basile
RU
Dip. Chimica Industriale
Carlo
Lucarelli
RU
Univ. Insubria
Patricia
Benito
PoD
Dip. Chimica Industriale
Giuseppe
Brenna
PoD
Dip. Chimica Industriale
Davide
Barbera
CO
Dip. Chimica Industriale
Federico
Folco
CO
Dip. Chimica Industriale
Gherardo
Gliozzi
PhD S
Dip. Chimica Industriale
Elena
Rozhko
PhD S
Dip. Chimica Industriale
Cristian
Trevisanut
PhD S
Dip. Chimica Industriale
Paolo
Ziosi
PhD S
Dip. Chimica Industriale
Giulia
Pavarelli
PhD S
Dip. Chimica Industriale
Alessandro
Chieregato
PhD S
Dip. Chimica Industriale
Tommaso
Tabanelli
PhD S
Dip. Chimica Industriale
Andrea
Malmusi
PhD S
Dip. Chimica Industriale
Massimiliano
Mari
PhD S
Dip. Chimica Industriale
Juliana
Velasquez Ochoa
PhD S
Dip. Chimica Industriale
Alice
Lolli
PhD S
Dip. Chimica Industriale
Manuel
Gregori
PhD S
Dip. Chimica Industriale
Diletta
Di Domenico
PhD S
Dip. Chimica Industriale
Alessandra
Giugni
PhD S
Dip. Chimica Industriale
Rodolfo
Mafessanti
PhD S
Dip. Chimica Industriale
Chiara
Molinari
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
DRIFT
Chemisorb 2750
FT-IR spectrophotometer
ASAP 2020MP physorption
TPDRO 1100
TPDRO 1100
TGA 2050
DSC-DTA
Raman spectrophotometer
UV-Vis-Nir spectrophotometer
Bruker
Micromeritics
Perkin-Elmer
Micromeritics
ThermoQuest CEinstrument
ThermoQuest CEinstrument
Thermal Analysis
Thermal Analysis
Renishaw
Perkin-Elmer
2007
2006
2004
2003
2002
2001
2001
1999
1998
1994