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Heterogeneous Catalysis, Biomass and Coal



The escalating oil price draws our attention to alternative feedstocks for liquid fuels. Plants are the largest reserves of renewable carbon on Earth. To obtain desired products from them, it is necessary to understand the reactivity of their main constituents (cellulose, lignin and hemicellulose) and to invent catalysts able to handle simultaneously different chemical functionalities. This is a great challenge and it is also what our research group is aiming at.



Roberto Rinaldi

Dr. Roberto Rinaldi

Independent Group Leader (Sofja Kovalevskaja awardee, Alexander von Humboldt Foundation)
Group Leader, MPI für Kohlenforschung (Prof. Ferdi Schüth)
Post doctoral fellow, MPI für Kohlenforschung (Prof. Ferdi Schüth)
Post doctoral fellow, Brazilian Synchrotron Laboratory (LNLS), Campinas, Sao Paulo, Brazil (Dr. Daniela Zanchet)
PhD work and graduate teaching assistant, UNICAMP (Prof. Ulf Schuchardt)
BSc. Chemistry, State University of Campinas (UNICAMP) Campinas, Sao Paulo, Brazil
Born September 8th in Campinas, Sao Paulo/Brazil
Sofja Kovalevskaja Award - Alexander von Humboldt Foundation
Thieme Chemistry Journal Award
TMFB Outstanding Project Award 2010 der Shell Global Solutions
Member of the Global Young Faculty - Mercator Foundation
Award for outstanding PhD work, Evonik-Degussa and Brazilian Catalysis Society
Lavoisier medal, outstanding student of chemistry, Sao Paulo Council of Chemistry
15 invited lectures and oral presentations
Academic exchange, RWTH-Aachen (Prof. Wolfgang Hölderich)
Academic exchange, TU-Berlin (Prof. Herbert Schumann)

Ferrini, P., Rinaldi, R.*:
Inside cover: Catalytic biorefining of plant biomass to non-pyrolytic lignin bio-oil and carbohydrates through hydrogen transfer reactions.
Angewandte Chemie International Edition, Volume 53, Issue 33, 2014, page 8526
DOI: 10.1002/anie.201403747 and 10.1002/ange.201403747

Rinaldi, R.*:
Plant biomass fractionation meets catalysis.
Angewandte Chemie International Edition, Volume 53, Issue 33, 2014, pages 8559-8560DOI:10.1002/anie.201404464 and 10.1002/ange.201404464

Käldström, M., Meine, N., Farès, C., Schüth, F., Rinaldi, R.*:
Deciphering ‘water-soluble lignocellulose’ obtained by mechanocatalysis: New insights into the chemical processes leading to deep depolymerization.
Green Chemistry, 16, 2014, 3528-3538, DOI 10.1039/C4GC00004H

Käldström, M., Meine, N., Farès, C., Rinaldi, R.*, Schüth, F.*:
Fractionation of ‘water-soluble lignocellulose’ into C5/C6 sugars and sulfur-free lignins.
Green Chemistry, 16, 2014, 2454-2462. DOI: 10.1039/C4GC00168K

Schüth, F.*, Rinaldi, R.*, Meine, N., Käldström, M., Hilgert, J., Kaufman Rechulski, M. D.: Mechanocatalytic depolymerization of cellulose and raw biomass and downstream processing of the products.
Catalysis Today, Volume 234, 2014, 24-30, DOI:10.1016/j.cattod.2014.02.019

Geboers, J., Wang, X., de Carvalho, A. B., Rinaldi, R.*: Densification of biorefinery schemes by H-transfer with Raney Ni and 2-propanol: A case study of a potential avenue for valorization of alkyl levulinates to alkyl γ-hydroxypentanoates and γ-valerolactone.
Journal of Molecular Catalysis A, Volume 388-389, 2014, 106-115, DOI: 10.1016/j.molcata.2013.11.031


Wang, X., Rinaldi, R.*
A route for lignin and bio-oil conversion: Dehydroxylation of phenols into arenes by catalytic tandem reactions.
Angewandte Chemie International Edition, 52, 11499-11503, DOI: 10.1002/anie.201304776

Loerbroks, C.; Rinaldi, R.*, Thiel, W.*
The electronic nature of the 1,4-β-glycosidic bond and its chemical environment: DFT insights into cellulose chemistry.
Chemistry a European Journal, in press, DOI: 10.1002/chem.201301366

Carrasquillo-Flores, R., Käldström, M., Schüth, F., Dumesic,* J., Rinaldi, R.*
Mechanocatalytic depolymerization of dry (ligno)cellulose as an entry process for high-yield production of furfurals.
ACS Catalysis 3, 993−997, DOI: #10.1021/cs4001333

Hilgert, J., Meine, N., Rinaldi, R.,* Schüth, F.*
Mechanocatalytic depolymerization of cellulose combined with hydrogenolysis as a highly efficient pathway to sugar alcohols.
Energy & Environmental Science, 6, 92-96. DOI: 10.1039/c2ee23057g

Rinaldi, R.,* Reece, J.
Solution-based Deconstruction of (Ligno)-Cellulose.
In: Behrens, Malte and Abhaya Datye (eds.) Catalysis for the Conversion of Biomass and Its Derivatives. Max Planck Research Library for the History and Development of Knowledge, Proceedings 2. Berlin: Edition Open Access (ISBN 978-3-8442-4282-9)


Wang, X., Rinaldi, R.* :
Exploiting H-transfer reactions with Raney Ni for upgrade of phenolic and aromatic biorefinery feeds under unusual, low-severity conditions.
Energy & Environmental Science, 5, 8244-8260. DOI: 10.1039/C2EE21855K

Wang, X., Rinaldi, R.*:
Solvent effects on the hydrogenolysis of diphenyl ether with Raney Nickel and their implications for the conversion of lignin.
ChemSusChem, 5, 1455-1466. DOI: 10.1002/cssc.201200040

Meine, N., Rinaldi, R.,* Schüth, F.*:
Solvent-free catalytic depolymerization of cellulose to water-soluble oligosaccharides. ChemSusChem, 5, 1449-1454. DOI: 10.1002/cssc.201100770

Rinaldi, R.* :
Reply to “Comment on 'Instantaneous dissolution of cellulose in organic electrolyte solutions'”. Journal of Chemical and Engineering Data 57, 1341-1343. DOI: 10.1021/je3001238


Rinaldi, R.* :
Instantaneous dissolution of cellulose in organic electrolyte solutions.
Chemical Communications 47, 511-513.

Jäger, G., Girfoglio, M., Dollo, F., Rinaldi, R., Bongard, H., Commandeur, U., Fischer, R., Spiess, A. C., Büchs, J.*:
How recombinant swollenin from Kluyveromyces lactis affects cellulosic substrates and accelerates their hydrolysis.
Biotechnology for Biofuels 4, 33. DOI: 10.1186/1754-6834-4-33

Engel, P., Bonhage, B., Pernik, D., Rinaldi, R., Schmidt, P., Wulfhorst, H., Spiess, A.C.* : Population balance modelling of homogeneous and heterogeneous cellulose hydrolysis. Computer Aided Chemical Engineering 29, 1316-1320.


G. Jäger, Z. Wu, K. Garschhammer, P. Engel, T. Klement, R. Rinaldi, A. Spiess, J. Büchs; Practical screening of purified cellobiohydrolases and endoglucanases with alpha-cellulose and specification of hydrodynamics.
Biotechnology for Biofuels 3, 18, 2010

J. M. C. Bueno, A. Ferreira, D. Zanchet, R. Rinaldi, U. Schuchardt, S. Damyanova;
Effect of the CeO2 content on the surface and structural properties of CeO2-Al2O3 mixed oxides prepared by sol-gel method.
Appl. Catal. A: Gen 388, 45-56, 2010

N. Meine, F. Benedito, R. Rinaldi* ;
Thermal stability of ionic liquids assessed by potentiometric titration.
Green Chemistry 12, 1711-1714, 2010

R. Rinaldi,* P. Engel, J. Büchs, A. C. Spiess,* F. Schüth*;
An integrated catalytic approach to fermentable sugars from cellulose.
ChemSusChem 3, 1151-1153, 2010

R. Rinaldi,* N. Meine, J. vom Stein, R. Palkovits, Ferdi Schüth*;
Which controls the depolymerization of cellulose in ionic liquids: the solid acid catalyst or cellulose?
ChemSusChem 3, 266-276, 2010; Special issue MPI EnerChem

R. Palkovits,* K. Tajvidi, J. Procelewska, R. Rinaldi, A. Ruppert;
Hydrogenolysis of cellulose combining mineral acids and hydrogenation catalysts.
Green Chemistry 12, 972-978, 2010

Y. Liu, H. Tüysüz, C.-J. Jia, M. Schwickardi, R. Rinaldi, A.-H. Lu, W. Schmidt, F. Schüth*
From glycerol to allyl alcohol: iron oxide catalyzed dehydration and consecutive hydrogen transfer ChemComm 46, 1238-1240, 2010


R. Rinaldi,* F. Schüth*;
Acid hydrolysis of cellulose as the entry point into biorefinery schemes
ChemSusChem 2, 1096-1107, 2009

R. Rinaldi, F. Schüth*;
Design of solid catalysts for the conversion of biomass.
Energy & Environmental Science 2, 610-626, 2009

R. Rinaldi,* H. F. N. Oliveira, H. Schumann, U. Schuchardt;
Homogeneously catalyzed epoxidation of α,β-unsaturated ketones using simple aluminum salts and aqueous H2O2 –Is it possible?
Journal of Molecular Catalysis A: Chemical 307, 1-8, 2009

R. Rinaldi,* A. M. Porcari, T. C. R. Rocha, W. H. Cassinelli, R. U. Ribeiro, J. M. C. Bueno, D. Zanchet*;
Construction of heterogeneous Ni catalysts from supports and colloidal nanoparticles – A challenging puzzle.
Journal of Molecular Catalysis A: Chemical 301, 11-17, 2009


R. Rinaldi, R. Palkovits, F. Schüth*;
Depolymerisation von Cellulose unter Einsatz heterogener Säurekatalysatoren in ionischen Flüssigkeiten. (Depolymerization of cellulose using solid catalysts in ionic liquids)
Chemie Ingenieur Technik 80, 1248-1248, 2008

R. Rinaldi, R. Palkovits, F. Schüth*;
Depolymerization of cellulose using solid catalysts in ionic liquids.
Angewandte Chemie International Edition 47, 8047-8050, 2008

C. S. Araujo, D. Zanchet, R. Rinaldi, U. Schuchardt, C.E. Hori, J. L. G. Fierro, J. M. C. Bueno*;
The effects of La2O3 on the structural properties of La2O3-Al2O3 prepared by the sol–gel method and on the catalytic performance of Pt/La2O3-Al2O3 towards steam reforming and partial oxidation of methane.
Applied Catalysis B: Environmental 84, 552-562, 2008

A. Steffen, S. Teixeira, J. Sepulveda, R. Rinaldi, U. Schuchardt*;
Alumina-catalyzed Baeyer-Villiger oxidation of cyclohexanone with hydrogen peroxide.
Journal of Molecular Catalysis A: Chemical, 287, 41-44, 2008

R. Rinaldi,* P. L. O. Volpe, I. L. Torriani;
L-Tryptophan transport through a hydrophobic liquid membrane using AOT micelles: Dynamics of the process as revealed by small angle X-ray scattering.
Journal of Colloid and Interface Science, 318, 59-67, 2008


Research Topics



Analyzing the composition of materials that contain cellulose (e.g. crop residues, straw, sugarcane bagasse, leaves and wood) reveals that lignin corresponds up to 30 % of plant biomass. Therefore, the success of the cellulosic biofuels also depends on finding uses for lignin. Our activities on lignin chemistry cover the extraction of lignin by the organosolv process, characterization of lignin and development of catalysts for lignin hydrogenolysis, oxidation and depolymerization.

Figure: The use of lignin poses a challenge for catalysis.



The huge reserves of coal are estimated to last for the next 100 years. Considering that the production of biomass is seasonal, co-feeding biorefineries with coal emerges as an interesting process choice for the production of clean fuels. The similarity between the chemical structures of low ranking coals and lignin encourages us to develop integrated strategies to process coal and biomass together. Our activities on coal chemistry cover the direct coliquefaction of low ranking coals and biomass to produce liquid fuels.

Figure: Coal chemistry may fill the feedstock gap in the transition towards a renewable-based economy.



To use cellulose as material requires commonly its dissolution. From cellulosic solutions, the biopolymer is transformed into desirable products (e.g. rayon). Here, we are aiming at understanding the process of dissolution of cellulose in non-conventional solvent systems and at exploring the reactivity of cellulose in new solvent systems.


Research Reports





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