The research activities
of the GRECAT group focus mainly on the following areas:
1. Catalytic Functionalization of Abundant and Cheap Low Alkanes
Preparation and physico-chemical characterization
of unsupported and supported, doped and undoped catalysts based on mixed oxides
prepared by coprecipitation and sol-gel techniques. Test of the prepared catalysts
for the oxidative dehydrogenation of n-butane and isobutane. Correlation of the
physico-chemical properties of the prepared catalysts with the catalytic activity
for oxidative dehydrogenation of n-butane and isobutane, and for degradation. Study
of the kinetics and mechanisms of the reactions.
2. Selective
Oxidation of Olefins over Mixed Oxides
Study of the physico-chemical properties of the catalytic
active pure and mixed phases of the bismuth molybdate catalysts by XRD, FTIR, Raman,
XPS, thermogravimetry, oxygen temperature programmed description, hydrogen temperature
programmed reduction, measurements of lattice oxygen diffusivity and catalysts reducibility
by hydrogen and olefins, etc. .Correlation of the results with the catalytic activity
for the oxidative dehydrogenation, isomerization and degradation of 1-butene. Test
of the prepared mixed oxide catalysts by citrate technique with the same reactions.
3. Polymerization and Technology of Polymerization
of Olefins over Metalocenic Catalysts:
Homo and copolymerization of vinyl based monomers
by transition metal catalysts. Synthesis of unsaturated polyolefins by means of
diene comonomers and chemical modification of these copolymers, for development
of novel functional polymeric materials. Development of supported metallocene systems
on inorganic mesoporous materials as catalysts for polymerization of vinyl monomers.
Analysis of the thermal and mechanical properties of the copolymer and correlation
studies with the composition and distribution of polar units along the polymeric
chain.
4. Selective Catalytic Oxidations of Methanol
and Ethanol
Investigation of the cerium role on the catalytic
behavior of silica-supported M0FeO catalysts for the methanol oxidation. Test of
mixed oxide catalysts prepared by citrate technique for the selective oxidation
of low alcohols like methanol and ethanol.
5. First Generation Biodiesel by alcoholysis
of vegetable oils
Preparation and characterization of catalyst with
basic character for methanolysis of vegetable oils (soyabean and others). Study
of activity and stability of Mg-Al LDH modified with Ce as catalysts precursors.
Study of the catalytic performances of modified (with several elements) MgO.
Emeritus Full Professor of Chemical Engineering
Agregação, IST, 1974
Ph. D. in Chemical Engineering, IST, 1972
Ph. D. Research Work at French Petroleum Institute (Rueil-Malmaison,
France), 1967–1969
Graduation in Chemical Engineering, IST, 1954
Assistant Professor of Chemical and Biological Engineering (IST)
Ph.D. in Polymer Chemistry, Université Bordeaux-I, Bordeaux,
France, 1993
M.Sc. in Chemistry of Catalytic Processes, Instituto Superior Técnico, Lisboa, 1987
Graduated in Chemical Engineering, Instituto Superior
Técnico, Lisboa, 1983
Assistant Professor of Chemical and Biological Engineering (IST)
Ph.D. in Chemical Engineering, Instituto Superior Técnico,
Lisboa, 1996
M.S. equivalent in Chemical Engineering, Instituto Superior
Técnico, Lisboa, 1991
Bachelor´s Degree in Chemical Engineering, Instituto
Superior Técnico, Lisboa, 1987
Polymerization of olefins over modified mesoporous supports: catalytic behaviour and polymer properties
Novel approaches to the resolution of common problems in olefin polymerisation
First Generation Biodiesel by soybean oil methanolysis
over Strontium and Barium modified MgO
Heterogeneous Catalysts for Biodiesel Production. Soybean
Oil Methanolysis over Modified Mg-Al Hydrotalcites (December 2007)
IST - Torre Sul building
The facilities available for Catalysis Research at GRECAT
include:
Modulated Diferential Scanning Calorimetry, M-DSC
with controlled N2 liquid cooling for measurements from -150ºC
TPD, TPR and TPO
Vitor Rosa, Sónia A. Carabineiro, Teresa Avilésa, Pedro
T. Gomes, Richard Welter, João M. Campos, M. Rosário Ribeiro “Synthesis, characterisation
and solid state structures of
alpha-diimine cobalt(II) complexes. Ethylene polymerisation tests”
Journal of Organometallic Chemistry (in press) JORGANCHEM-D-07-00758R1
Ana I. Vicente, João M. Campos, João M. Bordado, M. Rosário Ribeiro, “Maleic anhydride modified ethylene-diene copolymers: Synthesis and properties” Reactive and Functional Polymers (in press), online at www.sciencedirect.com
J. M. Campos, M. Rosário
Ribeiro, J. P. Lourenço, A. Fernandes, “Ethylene polymerization with zirconocene
supported in Al-modified MCM-41: Catalytic behaviour
and polymer properties” Journal of Molecular Catalysis A: Chemical 277, 93–101(2007)
María L. Cerrada, R.
Benavente, E. Pérez, J. Santos, J. M. Campos, M. Rosário Ribeiro, “Synthesis
and properties of ethylene-co-10-undecenoic acid copolymers prepared with different
metallocene catalysts” Macromol. Chem. Phys. 208, 841-850 (2007)
Joana Tudella, M. Rosário Ribeiro, H. Cramail and A. Deffieux “Novel organic activators for single site iron catalysts”, Macromol. Chem. Phys. 208, 815-822 (2007)
J. Arranz-Andrés, R.
Benavente, M. R. Ribeiro, E. Pérez, M. L. Cerrada, "Evolution of a metallocenic
sPP with time: Changes in crystalline content and enthalpic relaxation”, Macromol.
Chem. Phys. 207, 1564-1574 (2006)
R. Zavoianu, C. R. Dias, A. P.
V. Soares, M. F. Portela, Oxidative dehydrogenation of i-butane over nanostructured
silica – supported NiMoO4 catalysts with low content of active phase, Appl.
Catal A: Gen. 298, 40-49 (2006)
Soares A. P., Portela
M.F., Kienneman A. “Methanol Selective Oxidation
to Formaldehyde over Iron--Molybdate Catalysts”, CATALYSIS REVIEWS, 47, 125-174,
2005
S. J. Solomon, T. Custer, G. Schade, A.
P. Soares Dias, J. Burrows, “Atmospheric
methanol measurement using selective catalytic methanol to formaldehyde conversion”,
Atmos. Chem. Phys. Discuss., 5, 3533-3559, 2005
Madeira, L.M., Portela,
M.F., “Mechanistic Effects Resulting from the Cesium
– Doping of a NiM0O4
Catalyst in n-Butane Oxidative Dehydrogenation”, Applied Catalysis A:
General, 281, 179-189, 2005.
Zavoianu, R., Dias,
A.P.V.S., Pavel, O.D., Angelescu, E., Portela, M.F., “1-Octene Metathesis on
Silica Supported Zn – Doped NiM0O4 Catalysts”, Catalysis Communications, 6,
321-327, 2005.
Yuan, Jian-Chao, Silva,
L.C., Gomes, P.T., Valerga, P.,.Campos, J.M., Ribeiro, M.R., Chien, J. C. W.,
Marques, M.M. , “Living and block polymerization
of a-olefins using a Ni(II)-a-diimine catalyst containing OSiPh2 tBu groups,
Polymer 46, 2122-2132, 2005.
Madeira, L.M., Portela,
M.F., and Mazzocchia, C., “Nickel Molybdate Catalysts and Their Use in the Selective
Oxidation of Hydrocarbons”, Catalysis Reviews, 46 (1), 53 – 110, 2004.
Cerrada, M.L., Benavente,
R., Pereña, J.M., Pérez, E., Santos, J. Moniz, Ribeiro, M. Rosário, “Structural
Characterization and Mechanical Behavior of Metallocenic Copolymers of Ethylene
and 5, 7 – Dimethylocta – 1, 6 – Diene”, Macromol. Symp. 213, 315 – 325, 2004.
Dolatkhani, M., Cramail,
H., Deffieux1, A., Ribeiro, M. Rosário, Santos, Jorge M., Bordado, João M.,
“Synthesis of polyolefin based materials with improved thermo – oxidative stability”,
Macromol. Symp., 213, 347-356, 2004.
Cerrada, M.L., Benavente,
R., Pereña, J.M., Pérez, E., Santos, J. Moniz, Ribeiro, M. Rosário, “Metallocenic
Ethylene-5,7 – Dymethil – 1,6 – Octadiene Copolymers: Structural Characterization
and Mechanical Behavior”, J. Polym. Sci. Part B, Polymer Physics.42, 3797 –
3808, 2004.
Lopes, D.E.B., Marques,
M.F.V., Dias, M.L., Ribeiro, M. Rosário, Lourenço, J.P.G., “Copolymerisation
of Ethylene and Non – Conjugated Dienes with Metallocene / Methylaluminoxane
System Supported on MCM – 41 Mesoporous Material”, European Polymer Journal,
40, 2555 – 2563, 2004.
M. Dolatkhani, H. Cramail,
A. Deffieux, J. M. Santos, M. Rosario Ribeiro, J. Bordado, “Functionalisation
of polyolefins: Grafting of phenol groups on olefin/5,7-dimethylocta-1,6-diene
copolymers”, Macromol. Chem Phys. 204 1889-1897, 2003.
A. P. Soares, L. Dimitrov,
M . Oliveira, L. Hilaire, M. F. PORTELA, R. K. Grasselli, “Synergy
effects between
b
and γ phases of bismuth molybdates in the selective catalytic oxidation of 1-butene”,
Appl. Catal. A: General, 253 (2003), 191-200
A. P. Soares, M. F.
Portela, A. Kiennemann, L. Hilaire, “Mechanism of
deactivation of iron-molybdate catalysts prepared by coprecipitation and sol-gel
techniques in methanol to formaldehyde oxidation”, Chem. Eng. Sci.,
58 (2003), 1315-1322.
R. Zavoianu, A. P. Soares, A. Urda, “Influenta modificarii
cu P, Si, si Ti asupra paraselectivitatii zeolitului H-ZSM-5”, Rev. Chim. (Bucuresti),
54(5) 2003, 418-423.
Luis M. Madeira And Manuel F. Portela, "Catalytic oxidative dehydrogenation of n-butane", Catalysis Reviews, 44 (2), 247-286 (2002)
L. M. Madeira, J. M. Herrmann, J. Disdier, M. F. Portela And F. G. Freire, "New evidences of redox mechanism in n-butane oxidative dehydrogenation over undoped and Cs-doped nickel molybdates", Applied Catalysis A: General, 235, 1-10 (2002)
C. R. Dias, M. F. Portela, M. A. Bañares, M. Galán-Fereres, M. López-Granados, M. A. Peña And J. L. G. Fierro, "Selective oxidation of o-xylene over ternary V-Ti-Si catalysts", Applied Catalysis A: General, 224,141-151 (2002)
J.M. Santos, M.R. Ribeiro,
M. F. Portela, H. Cramail, A. Deffieux, A. Antiñolo, A. Otero, S. Prashar, “[(h5-C5Me4)SiMe2(NtBu)]TiCl2
as pre-catalyst for the copolymerisation of ethylene with 5,7 dimethylocta-1,6-diene
and with 3,7 dimethylocta 1,6-diene”, Makromol. Chem. Phys., 203, 139-145, 2002.
C-T Zhao, M.R. Ribeiro,
M. F. Portela, “Addition polymerisation of 5-vinyl-2-norbornene with nickel
Bis (acetyl acetonate)/Methylaluminoxane system”, J. Mol. Catal. A-Chem, 185
(1-2): 81-85, 2002.
Chun-Tian Zhao, M.R.
Ribeiro, M. F.Portela, Unique morphology of amorphous polystyrene synthetised
by Nickel Bis (acetyl acetonate)/Methylaluminoxane system, Macromol.
Chem Phys. 203, 1983-1987 (2002) .
Ana Paula V.Soares,
Manuel F. Portela,
Alain Kiennemann
and
Jean Marc M. Millet,
React. Kinet. Catal. Lett., 75, 2002, 13-20.
Chun-tian Zhao, M. R.
Ribeiro, M. Norberta Pinho, V. S. Subrahmanyam, C. Lopes Gil, A. P. de Lima,
“Structural Characteristics and Gas Permeation Properties of Polynorbornene
with retained bicyclic structure”, Polymer, 42, 2455-2462 (2001).
Chun-tian Zhao, M. R.
Ribeiro, M. F. Portela, S. Pereira, M. T. Nunes “Homo- and copolymerization
of norbornene and styrene with nickel (bis (acetylacetonate)/ methylaluminoxane
system” European Polymer Journal 37, 45-54 (2001)
J. M. Santos, M. R.
Ribeiro, M. F. Portela , J. M. Bordado, “Improved adhesion of polyethylene by
copolymerisation of ethylene with polar monomers”, Chemical Engineering Science
56, 1-6 (2001).
J. M. Santos, M. R.
Ribeiro, M. F. Portela, S.G. Pereira, T. G. Nunes, A. Deffieux, “Metallocene
catalysed Copolymerisation of ethylene and 10-Undecenoic Acid:
The effect of experimental conditions”, Macromol. Chem. Phys. 202, 2195 (2001)
A. Otero, J. Fernández-Baeza,
A. Antiñolo, F. Carrillo, J. Tejeda, E. Díez-Barra, A. Lara, L. Sanchez, I.
López, M.R. Ribeiro, J. M. Campos, “Polymerisation of ethylene by the electrophilic
heteroscorpionate-containing complexes [TiCl3(bdmpza)] and [TiCl2(bdmpza)
Maria. L. Cerrada, Rosario
Benavente, Ernesto Pérez, Jorge M. Santos, M. Rosario Ribeiro, Experimental
evidence of the glass transition in a metallocene ethylene-1-octene copolymer
and its composites with glass fiber, Polymer, (2001) 42, 7197
A.P. Vieira Soares, M. Farinha
Portela and A. Kiennemann, “Kinetics of the main and
side reactions of the methanoloxidation over iron molybdates”, Stud.
Surf. Sci. Catal., 133,
2001, 489-494
A. P. Vieira Soares, M. Farinha
Portela and A. Kiennemann, “Iron molybdates for selective
oxidation of methanol: Mo excess effects on the deactivation behaviour”
Catal. Comm., 2, 2001, 159-164
A. P. V. Soares, M. Farinha
Portela, A. Kiennemann, L. Hilaire and J. M. M. Millet, ”Iron
molybdate catalysts for methanol to formaldehyde oxidation: effects of Mo excess
on catalytic behaviour”, Appl. Catal. A, 206,
2001, 221-229
R. Benavente, J. M.
Pereña, E. Perez, A. Bello, M. R. Ribeiro, M. F. Portela “Dynamic Mechanical
Relaxations and microhardness indentations of styrene-ethylene copolymers obtained
with heterogeneous catalysts” European Polymer Journal, 36/5, 879-887 (2000)
A.Antiñolo, F. Carrillo-Hermosilla,
A. Corrochano, J. Fernández-Baeza, A. Lara-Sanchez,
M. R. Ribeiro, M. Lanfranchi, A. Otero, M.A. Pellinghelli, M. F. Portela,
J. V. Santos “Synthesis of Zirconium (IV) Monocyclopentadienyl-Aryloxy Complexes
and their Use in the Catalytic Ethylene Polymerization. X-Ray Structure of (hapto5-C5Me5)Zr
Ribeiro, M. Rosário,
Santos, J. Moniz, “Poliolefinas funcionais: Síntese e propriedades”, In Química
de Polímeros, Editores, de Melo, J.S., Moreno, M.J., Burrows, H.D., Gil, M.H.,
Imprensa da Universidade de Coimbra, 2004.of Sol-Gel Materials and Products”,
Kluwer Academic Publishers (London, 2005).
“Versatile route for
the synthesis of polyolefin based nanofibers, nanoblends and nanocomposites,
using mesoporous” – Projecto : PTDC/CTM/66488/2006, January 2008
(PI: M. Rosário Ribeiro)
"Separação
mecanizadade granulados de plásticos da recolha selectiva", Projecto Sociedade
Ponto Verde - SPV, April 2006-
“Modelação de Adesivos
Avançados para Reparação de Tecidos Rígidos”, Projecto POCT/SAU-BMA/55935/2004,
2006
"Reticulação de copolímeros
metalocénicos de etileno com dienos não conjugados". Convénio GRICES/CSIC, (
IST/ICTP) 2006 - 2007. (PI: M. Rosário Ribeiro)
“Separação de Plásticos
por Flutuação por Espumas” - Projecto POCI/ECM/60335/2004, Julho 2005-).
European Network of
Excellence on Nanoscale-based Membrane Technologies (NANOMEMPRO), RTD-Project
6th FP, NoE, Contract Nº NMP3-CT-2004-500623, September 2004-
"Valorização de derivados
terpénicos por copolimerização com etileno, via metalocenos” - Projecto POCTI
CTM /41408, Abril 2004 - September 2007; (PI: M. Rosário Ribeiro)
“Desenvolvimento de
Novos Materiais para Dentisteria Restauradora: Síntese, Propriedades e Estudos
in vitro por técnicas não invasivas avançadas” - Programa Sapiens, Octobre 2000
– 2004
“Transition Metal Catalyzed
Homo- and Copolymerization of Cicloalkenes and Functionalized Olefins” - COST
Program, COST Action D17 - Oligomers, Polymers and Co-polymers Via Metal Catalysis.
June 2000 – 2004 (Portuguese team PI: M. Rosário Ribeiro)
"Novas vias de valorizaçãode
derivados terpénicos" - Convénio ICCTI-CNRS, (IST/LCPO), 2003-2004 (PI: M. Rosário
Ribeiro)
Université
Louis Pasteur (Strasbourg
– France),
Laboratoire
de Chimie des Polyméres Organiques, Université Bordeaux I (France),
Instituto
Ciência y Tecnologia de Polímeros, CSIC, Madrid
Universidad
de Castilla la Mancha (Ciudad Real - Spain)
Instituto de Macromoléculas
(Rio de Janeiro - Brazil)
Instituto
de Catálisis y Petroleoquímica (Madrid–Spain),
Université
Claude Bernard (Lyon -France),
Université
Catholique de Louvain (Louvain-la-Neuve – Belgium),
Institute
of Organic Chemistry and Institute of Physical
– Chemistry (Moscow-Russia).
N. N. Semenov Institute of Chemical Physics,
Russian
University of Bremen (Gremany)
University of Munich (Germany)
University of Brunel (Uxbridge – UK)