9th International Symposium

of the Romanian Catalysis Society

BOOK OF ABSTRACTS

- 2010 –
 Organizing Committee of RomCat 2010

CHAIR

Vasile I. Parvulescu (RO)

INTERNATIONAL ADVISORY BOARD

Pascal Granger (FR)

Veronique Michelet (FR)
Dmitry Murzin (FI)
Ryan Richards (US)
Angelo Vaccari (IT)

INTERNAL ORGANIZING COMMITTEE

Emil Dumitriu , Technical University of Iasi - Chairman

Dragos Ciuparu , Institute of Petrol (RO)
Ligia Frunza , INCDFM (RO)
Viorica Parvulescu , Institute of Physical Chemistry (RO)
Viorel Sasca , Institute of Chemistry, Timisoara (RO)
Valer Almasan , INCDTIM, Cluj-Napoca (RO)
Ioan Sandulescu, University of Bucharest (RO)
Emilian Angelescu, University of Bucharest (RO)

SECRETARIAT

Nicolae Apostolescu (TUI)

Bogdan Cojocaru (UB)
Octavian Pavel (UB)
Adrian Ungureanu (TUI)
Brindusa Dragoi (TUI)
 23.06.2010 24.06.2010 25.06.2010 26.06.2010
Hour Activity Hour Activity Hour Activity Hour Activity
9.00 9.00 Plenary R. Richards 9.00 Plenary E.M. 9.00 Oral - A. Savin
9.30 9.30 (USA) 9.30 Eftsathiou (CY) 9.30 Oral - M. Lazar
10.00 10.00 Plenary M. Kocevar 10.00 Oral - R. Zavoianu 10.00 Project presentation
Registration
10.30 10.30 (SLO) 10.30 Oral - M. Jedrzejczyk 10.30 Oral - C. Munteanu
11.00 11.00 Coffee Break 11.00 Coffee Break 11.00 Oral - G. Blanita
11.30 11.30 Plenary M.A. Centeno 11.30 Oral - C. Teodorescu 11.30 Goodbye
12.00 12.00 (ES) 12.00 Oral - V. Sasca 12.00
12.30 12.30 Plenary P. Granger 12.30 Oral - N. Aldea 12.30
13.00 13.00 (FR) 13.00 Oral - E. Maćkiewicz 13.00
13.30 13.30 13.30 13.30
Lunch Break Lunch Break
14.00 14.00 14.00 14.00
14.30 Welcome 14.30 Oral - S.M. Coman 14.30 14.30
SCR Meeting
15.00 Plenary V. Michelet 15.00 Oral - B. Dragoi 15.00 15.00
15.30 (FR) 15.30 Oral - L. Frunza 15.30 Poster flash 15.30
16.00 Plenary A. Vaccari 16.00 Coffee Break 16.00 presentation (5 min.) 16.00
16.30 (IT) 16.30 Oral - I.C. Marcu 16.30 Coffee Break 16.30
17.00 Plenary D. Y. Murzin 17.00 Oral - A. Ungureanu 17.00 17.00
17.30 (FIN) 17.30 Oral - V. Parvulescu 17.30 Poster session 17.30
18.00 18.00 18.00 18.00
18.30 18.30 18.30 18.30
Tour of Iasi
19.00 Cocktail 19.00 19.00 Banquet 19.00
 Table of Contents
Plenary Lectures

V. Michelet Towards atom economy: recent developments in Ir-, Au- and Pt- 1
(FR) catalyzed reactions
A. Vaccari Improved syntheses of hydroatlcite-type phases, precursors of
(IT) catalysts for H2 production from natural gas
D. Y. Murzin Catalysis in biomass valorization
(FI)
R. Richards Nanotechnology, catalysis, the environment and alternative energy
(US)
M. Kočevar Microwave-Assisted Catalyzed Organic Transformations
(SLO)
M. A. Centeno CO oxidation on gold catalysts: towards microreactor technology
(ES)
P. Granger Surface reconstructions of noble metal-modified perovskites and
(FR) induced effect on the catalytic properties in DeNOx reactions
A. M. Efstathiou Green and Novel Low-Temperature (T<200 oC) Industrial NOx
(CY) Control Catalytic Technologies for Stationary Applications: H2-
SCR?

Oral communications

S. Coman Greener catalytic routes for the Vitamins synthesis 1

(RO)
B. Dragoi Effect of the support topology on the catalytic activity of CoMo-
(RO) based catalysts in HDS reaction
L. Frunza Probing the specific surface interactions of TiO2 catalysts with
(RO) cyanobiphenyl molecules
I.C. Marcu New M-Mg-Al mixed oxides (M = Mn, Fe, Co, Ni, Cu, Zn) catalysts
(RO) obtained from LDH precursors for light alkanes total oxidation
A. Ungureanu Study of hydrogen chemisorption on NiCu-containing SBA-15
(RO) mesoporous catalysts
V. Parvulescu Catalytic and electrocatalytic properties of mesoporous mixed
(RO) oxides applicable as SOFC anodes for direct oxidation of
hydrocarbons
R. Zavoianu Tert-butanethiol oxidation using Mg-Co-Al-Mo mixed oxides
(RO) catalysts obtained from hydrotalcite-like precursors
M. Jedrzejczyk Pt supported on Ga2O3, Al2O3 and Ga2O3/Al2O3 in reaction of
(PL) crotonaldehyde hydrogenation in gas phase: Effect of reduction
temperature on selectivity and activity
C. Teodorescu Structure, reactivity and magnetism of 3d and 4f metals deposited
(RO) as thin layers on atomically clean Si(001) by molecular beam
epitaxy
V. Sasca Ethanol conversion on CsxH3-xPW12O40 and catalyst microstructure
(RO) model
N. Aldea Local and electronic structure of supported gold nanoclusters
(RO) determined by X-ray absorption spectroscopy
E. Maćkiewicz Catalytic oxidation of ammonia on the hopcalite based catalysts
(POL) modified with noble metals
A. Savin The use of immobilized yeast cells in gellan-bentonite matrix for
(RO) sparkling wine processes
M.D. Lazar Hydrogen production by low temperature methane steam reforming
(RO) using Ag and Au modified alumina supported nickel catalysts
C. Munteanu Catalytic performance and structural characterization of copper
(RO) ferrite as a catalyst for propane oxidation
G. Blanita Pleading for metal-organic frameworks
(RO)

Poster presentations

N. Aldea New version of XRLINE software for crystallite size determination

(RO) of the supported platinum catalysts by single X-ray profile analysis
V. Almăşan Hydrogen production from bio diesel residues on modified
(RO) supported Ni catalysts
P. Apopei Photocatalytic oxidation of 4-chlorophenol over pure rutile and
(RO) anatase separated from Degussa P-25 TiO2 powder
O. Ardelean Supported Pt and Pd catalysts for hydrogen adsorption in MOFs
(RO)
D. Arsene Catalytic wet peroxide oxidation of para-chlorophenol over
(RO) different mixed Al2O3/Fe2O3 pillared clays (AlFe PILCs)
K. Bachari High activities of tin-mesoporous materials synthesized by a
(DZ) microwave-hydrothermal process in Friedel–Crafts alkylations
I. Bibicu Tin superficial layers studied by Mössbauer spectroscopy and X-
(RO) ray diffraction
S. B. Bukallah Activation of H2O2 by Methyltrioxorhenium(VII) Inside -
(AE) Cyclodextrin
S. B. Bukallah Synthesis and Characterization of Vanadium oxide supported on
(AE) high surface area Titanium Oxide
A. Chirieac Effect of the preparation method on the catalytic properties of
(RO) bimetallic CuNi/SBA-15 catalysts in the hydrogenation of
cinnamaldehyde
C. Cobzaru Preparation of encaged heteropolyacid catalyst by synthesizing 12-
(RO) molybdophosphoric acid in the volcanic tuff
C. Cobzaru Comparative study between natural zeolites and anion exchange
(RO) resins used as catalysts in the reaction of acetic acid with
epichlorohydrin
B. Cojocaru Zeolite-encapsulated sensitizers for the photocatalytic
(RO) decomposition of chemical warfare agent Yperite
M. Dan Methane steam reforming over Ni/Al2O3 promoted by CeO2 and
(RO) La2O3
V. Dascaleanu Characterization of RF sputtered WO3/TiO2 bilayer photocatalyst
(RO)
B. Dragoi HDS catalytic activity of CoMo supported on inorganic and
(RO) organic-inorganic SBA-15 mesoporous materials
M. Frajtak Highly Stable PdTe/SiO2 Catalyst For Glucose Oxidation
(PL)
L. Frunza Oxidation activity of Horseradish peroxidase hosted in molecular
(RO) sieves: spectroscopic investigations
C.B. Grosan Biosynthesis of 15N Labelled L-Glutamic Acid: Experimental and
(RO) Computational Studies
E. Indrea Rietveld analysis of nanocrystalline titania prepared by sol-gel
(RO) method
E. Indrea Rietveld refinement of powder X-ray diffraction of nanocrystalline
(RO) transition metals - tungsten trioxide
E. Indrea Photocatalytic activity of the TiO2 based aerogels: TiO2-SiO2
(RO) versus noble metal-TiO2 composites
I. Iordache Magnetron sputtering as a feasible technique for palladium
(RO) deposition and its applications for PEM Fuel Cell Systems
N.G. Kostova Titania-Alumina-Supported Polyoxomolybdate-Containing
(BG) Hydrodesulfurization Catalysts
N. Krawczyk Catalytic hydrogenation of nitrates and nitrites on Pd-In/TiO 2
(PL) catalysts
A. Królak Stability of Pd/Al2O3 and Pd-M/Al2O3 catalysts (M = Au, Bi, Fe, Tl)
(PL) in catalytic hydrodechlorination of 2,4-dichlorophenol
L. Lazar Nano-Au/TiO2 suspensions for the preparation of mercury-
(RO) oxidation catalysts: electro-steric stabilization, particle size and
coating efficiency
L. Lazar Mercury oxidation by metal oxide impregnated SCR-DeNOx
(RO) catalysts
A. Manole Surface wettability of photo-catalytic TiO2-xNx nano-crystalline
(RO) films
A.M. Manta Catalytic Activity of Manganese Ions in Different Coordination
(RO) Sites Investigated by Liquid Phase Ethylbenzene Oxidation
M. Mihet Low temperature hydrogen selective catalytic reduction of NO on
(RO) Pd/Al2O3
V. Parvulescu Catalytic activity of Cu (II) complexes immobilized on mesoporous
(RO) silica in oxidation of organic compounds
O.D. Pavel Mg0.75Al0.25 hydrotalcite (HT) synthesis without aging step catalyst
(RO) for cyanoethylation reaction
F. Pogacean Kinetic determination of drug concentration via enzyme-catalyzed
(RO) decomposition of Hydrogen Peroxide
A. Popa Cesium Substituted Dodecamolybdophosphoric Acid Supported On
(RO) Sba-15 Molecular Sieve: Synthesis And Characterization
P. Rosca Hydrogen From Renewable Bio-Sources
(RO)
M.C. Rosu Influence of mass proportions of TiO2 in preparation of ITO/TiO2
(RO) nanostructured films
V. Sasca About the effects of Pd-doping on the CsxH3-xPW12O40 structure,
(RO) texture and Brőnsted acidity
V. Sasca Concerning the influence of Pd-doping on CsxH3-xPW12O40 catalytic
(RO) activity in the ethanol conversion
A. Sasu MgCoCuAl hydrotalcite-like materials as catalysts for selective
(RO) hydrogenation reactions
S. Simon The advantages of Carbon Nanotubes Synthesis by Catalytic
(RO) Chemical Vapor Deposition Method Using Induction Heating
V.V. Styrov A means for insight into the nonequilibrium electronic processes
(UA) during heterogeneous chemical reactions
R.C. Suciu TiO2 thin films prepared by spin coating technique
(RO)
C. Ungureanu Study of relationship between enzymes production, growth rate and
(RO) pigmentogenesis in five mutant strains of Monascus purpureus
A. Urda Ni/SBA-15 catalysts for methane dry reforming
(RO)
M. Verziu Mesoporous Tin-Triflate Based Catalysts for Transesterification of
(RO) Sunflower Oil
D. Ciuparu Performances of acidic catalysts supported on mesoporous
(RO) materials used in glycerol etherification with isobutene
T. Juganaru Hydrogenation of monocyclic aromatic hydrocarbon on Ru-
(RO) catalysts

Author index
Plenary lectures

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 Towards atom economy: recent developments in Ir-, Au- and Pt-
catalyzed reactions

V. Michelet
Ecole Nationale Supérieure de Chimie de Paris, Laboratoire Charles Friedel, UMR 7223
11 rue P. et M. Curie, 75231 PARIS cedex 05, FRANCE
e-mail : veronique-michelet@chimie-paristech.fr

Over the past few years, significant research has been directed toward the development of
new methodologies for synthetic efficiency and atom economy processes. Among them, the
potential of transition-metal-catalyzed reactions have been steadily demonstrated, as they
give a direct and selective way toward the synthesis of highly valuable products. Several
transition metals (Pd, Ru, Rh, Ir) and very recently gold have been used to perform C-C and
C-heteroatom bond formation reactions. We have been engaged in a wide project dedicated to
the development of catalytic methodologies for the synthesis of original carbo- and
heterocycles [1]. Our interest has been focused on the cyclization of functionalized alkynes.
An unprecedented selectivity was observed for homopropargylic alcohols and diols. The use
of iridium catalyst or gold led respectively to functionalized mono- and bicyclic ketals.
Simple and commercially available gold catalysts might also function as promoters for the
reaction of other functionalized alkynes such as carboxylic acids, which gave rise to en
efficient entry to functionalized lactones [2].

In the case of functionalized enynes [3], the use of platinum and gold catalysts promoted
novel rearrangements, based on the addition of nucleophile to alkenes followed by the
cyclization of the enyne [4]. Some novel systems (based on chiral platinum and gold
complexes) have been developed for the asymmetric cycloisomerization of enynes, leading to
good and excellent enantiomeric excesses [5]. This presentation will show an overview of the
latest results. Mechanistic rationales will be presented including the discussion of catalytic
species responsible for the highest enantiomeric excesses.

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References
[1] a) A.S.K. Hashmi, Chem. Rev. 107 (2007) 3180; b) A.R. Chianese, S.L. Lee, M.R. Gagné, Angew. Chem.
Int. Ed. 46 (2007) 4042; c) A. Fürstner, P.M. Davies Angew. Chem. Int. Ed. 47 (2007) 3410
[2] a) E. Genin, S. Antoniotti, V. Michelet, J.-P. Genêt, Angew. Chem. Int. Ed. 44 (2005) 4949; b) E. Genin,
P.Y. Toullec, S. Antoniotti, C. Brancour, J.-P. Genêt, V. Michelet, J. Am. Chem. Soc. 128 (2006) 3112; c) F.
Neatu, Z. Li, R. Richards, P.Y. Toullec, J.-P. Genêt, K. Dumbuya, J.M. Gottfried, H.-P. Steinrück, V.I.
Pârvulescu, V. Michelet, Chem. Eur. J. 14 (2008) 9412
[3] a) V. Michelet, P.Y. Toullec, J.-P. Genêt, Angew. Chem. Int. Ed. 47 (2008) 4268; b) L. Zhang, J. Sun, S.A.
Kozmin, Adv. Synth. Catal. 348 (2006) 2271
[4] a) L. Charruault, V. Michelet, R. Taras, S. Gladiali, J.-P. Genêt, Chem. Commun. (2004) 850; b) V.
Michelet, L. Charruault, S. Gladiali, J.-P. Genêt, Pure & Appl. Chem. 78 (2006) 397; c) C. Nieto-Oberhuber,
M. P. Muñoz, S. Lopez, E. Jimenez-Nuñez, C. Nevado, E. Herrero-Gomez, M. Raducán, A.M. Echavarren,
Chem. Eur. J. 12 (2006) 1677; d) A.K. Buzas, F.M. Istrate, F. Gagosz, Angew. Chem. Int. Ed. 46 (2007)
1141; e) E. Genin, L. Leseurre, P. Y. Toullec, J.-P. Genêt, V. Michelet, Synlett 11 (2007) 1780; f) P.Y.
Toullec, E. Genin, L. Leseurre, J.-P. Genêt, V. Michelet, Angew. Chem. Int. Ed. 44 (2006) 7427
[5] a) P. Y. Toullec, C.-M. Chao, Q. Chen, S. Gladiali, J.-P. Genêt, V. Michelet, Adv. Synth. Catal. 350 (2008)
2401; b) C.-M. Chao, M. R. Vitale, P. Y. Toullec, J.-P. Genêt, V. Michelet, Chem. Eur. J. 15 (2009) 1319; c)
C.-M. Chao, D. Beltrami, P. Y. Toullec, V. Michelet, Chem. Commun. (2009) 6988

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Improved syntheses of hydroatlcite-type phases, precursors of catalysts for
H2 production from natural gas

Angelo Vaccari
Dipartimento di Chimica Industriale e dei Materiali, ALMA MATER STUDIORUM –
Università di Bologna, Viale Risorgimento 4, 40136 BOLOGNA (Italy)
H2 is expected to become a major source of energy in the future. The catalytic partial
oxidation (CPO) of methane or the steam methane reforming (SMR) may be currently
considered the most common and economical way to obtain H 2. However, both processes
present some relevant drawbacks, such as in the CPO the catalyst stability in the hard reaction
conditions (high temperature and GHSV values), while SMR is highly endothermic and
operate at high temperatures. Hydrotalcite-type (HT) compounds are layered materials with
chemical formula [M2+1-xM3+x(OH)2]x+ [Ab-]x/b • nH2O. Ni- and noble-metal-containing HT
compounds are useful precursors of natural gas conversion catalysts, since after calcination
and reduction, well dispersed metallic particles, highly stabilized in an oxide matrix, may be
obtained. In this talk, some innovative syntheses of HT precursors with special features, able
to solve the above reported drawbacks are presented. The role of the addition of silicates to
improve the properties and stabilize the catalysts for CPO of methane is discussed,
evidencing the role of the silicate amount and the M2+/M3+ ratio, which affect the nature of the
phases formed after calcination and the catalyst activity and stability. In the SMR the active
phase is mainly supported on oxide pellets (i.e. insulating materials), thus thermal
conductivity is low and high temperatures must be maintained outside the reactor tubes.
Furthermore, temperature gradients take place both longitudinally, from the inlet to the outlet
of the tubes, and radially across the wall, thus creeps occur and lifetime of the tubes is
reduced. Especially in small scale H2 production, the development of structured catalysts in
which the active phase is supported over a structured metallic support (foams, plates, walls)
are a promising alternative to conventional pelletized catalysts. Structurated catalysts offer
advantages such as a decrease in pressure drop and high mechanical strength; moreover, by
selecting the metallic support, an enhanced heat transfer (not available for the random
packing of catalyst pellets) may be achieved. Taking into account the high thermal
conductivity of a FeCrAlY foam, the electrochemical in situ synthesis/deposition of Ni- and
noble-metal-containing HT compounds on foam pellets is showed. The effect of the
synthesis parameters on the properties of the coating film and catalytic activity is presented,
paying special attention on the influence of the composition of the starting HT precursor.

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 Catalysis in biomass valorization

D. Y. Murzin
Åbo Akademi University, Turku, Finland

Biomass as a source of renewable energy and chemicals is attracting more and more
attention. Woody biomass utilization in particular can lead, besides a range of such biobased
products as lumber, paper and pulp, furniture, housing components and ethanol, also to
chemicals and fuels.

Chemical treatment of wood can have several targets. One option is delignification of the
biomass leading to cellulose and some residual hemicelluloses, which are further applied in
production of paper or board, or the derivatives of cellulose. Thermal (or catalytic) treatment
of biomass, e.g. thermal or catalytic pyrolysis, is a route to bio-based synthesis gas and
biofuels. Depolymerization of wood components (cellulose, hemicelluloses and lignin),
which can be done with an aid of heterogeneous catalysts, results in the formation of low-
molecular-mass components (sugars or sugar alcohols, phenols, furfural, various aromatic
and aliphatic hydrocarbons, etc.), e.g. unique building blocks for further chemical synthesis.

In addition wood biomass contains many valuable raw materials for producing fine and
specialty chemicals, such as fatty acids, terpenoids and polyphenols, i.e. stilbenes, lignans
and tannins. The catalytic derivatization methods for these chemical compounds will be
reviewed in the lecture.

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 Nanotechnology, catalysis, the environment and alternative energy

R. M. Richards
Department of Chemistry and Geochemistry, Colorado School of Mines

The interface of the fields of catalysis and nanoscale materials is one of the most exciting
areas of modern science and is at the forefront of the quest for a sustainable future. The field
of nanotechnology has generated a great deal of interest primarily because on this size scale
numerous new and potentially useful properties have been observed. These size dependent
properties include melting point, specific heat, surface reactivities, catalytic, magnetic, and
optical properties. In particular, the Richards’ group is working on new methods to control
the size, shape and composition of nanoscale materials and applying them as catalysts for
reactions integral to alternative energy technologies, pharmaceuticals, petrochemicals and
environmental cleanup. Recently, the Richards’ research group has developed techniques to
produce a number of new nanoscale materials that have demonstrated unique physical and
chemical properties. Here, an overview of the recent highlights regarding these materials and
their applications will be presented.

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 Microwave-Assisted Catalyzed Organic Transformations

M. Kočevar
Faculty of Chemistry and Chemical Technology, University of Ljubljana, Aškerčeva 5, SI-
1000 Ljubljana, Slovenia, marijan.kocevar@fkkt.uni-lj.si

Microwave (MW)-assisted reactions in chemistry - and in organic synthesis in particular - are

becoming increasingly important [1,2]. Microwaves display some singular characteristics that
influence their interaction with matter and enable their application in organic synthesis. The
reaction mixtures, in which at least one component is able to interact with the microwaves,
are rapidly heated as the radiation is applied. The gradient of the temperature increase is
steeper and of a different form than any achievable with conventional heating. Due to the
different interactions that exist between the microwaves and various materials, there is also
the possibility of differential heating. For example, the energy of the microwaves is delivered
directly to the reaction mixture, without any heating of the vessel walls (if made of quartz,
which is nearly transparent to microwaves). Furthermore, the heat is not primarily transported
by convection and other heat-transport phenomena, as is the case in conventional heating, but
instead the heat is generated in situ by the microwaves throughout the reaction mixture quite
homogeneously. Therefore, at least in principle, one could expect changed reaction profiles
(selectivity, reaction times) in comparison with conventional heating. In general, three
different types of heating mechanism are encountered when matter interacts with
microwaves: dielectric (dipolar) heating caused by dipole rotation, ionic conduction, and
resistance heating. The third mechanism is only encountered in strongly conducting
materials, such as metals, and semiconductors. When a material possessing loosely bonded
electrons is irradiated with microwaves, the electrons start to flow (an electric current)
through the material, generating heat because of the resistance of the material. This
mechanism is important when elementary metals (in the form of thin foils or films), graphite
supports or passive heating elements (made of silicon carbide, for example) are employed
during the synthesis. On the other hand, larger metal parts reflect most of the microwave
energy and so do not tend to heat up.
During last decades a number of catalytic MW-assisted reactions of different types were
developed [1,2]. In transition metal catalyzed reactions, for example, Cu(I)-catalyzed click
azide-alkyne cycloaddition toward the corresponding 1,2,3-triazole derivatives have been
widely investigated [3a]. Kappe et al. [3b] investigated the transition-metal catalyzed
Mizoroki−Heck couplings of aryl iodides and bromides with an acrylate building block to
obtain substituted butyl 3-phenyl-2-propenoates. Van der Eycken et al. successfully carried
out MW-assisted palladium-catalyzed phosphonium coupling procedure of pyrazin-2(1H)-
ones [3c], etc.
Recently, we investigated various transformations starting from 2H-pyran-2-ones and fused
pyran-2-ones under conventional and MW-assisted conditions [2j]. These reactions were
controlled by the appropriate selection of reaction conditions, such as solvents and/or
catalysts (transition metals, ionic liquids, organic or inorganic bases). For example, the pyran-
2-ones were transformed by the Diels-Alder cycloaddition reaction with cyclic alkenes into
the fused bicyclo[2.2.2]octenes, which were further used as substrates for the heterogeneous
catalytic hydrogenation [4a-e], and those containing fused anhydride rings for the ionic
liquids catalyzed conversion into the corresponding esters [4f]. Furthermore, we have shown
that ethyl vinyl ether as a dienophil in the presence of a suitable base catalyst (for example,
DABCO) can be used as a very successful synthetic equivalent of acetylene 4f,5. Here, in
the reaction with 2H-pyran-2-ones a set of disubstituted aniline derivatives was prepared.
With various amidines in ethanol (or ethanol/water mixtures) in the presence of sodium (or

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cesium) carbonate as the base 5-acyl-2H-pyran-2-ones were transformed into (E)-α,β-
didehydro-α-amino acid derivatives [6a]. The purpose for the preparation of these
dehydroamino acid derivatives was their further application as synthons in chemoselective
hydrogenation [6b].
Recently, we developed a new method for the microwave-assisted O-methylation of phenols
using tetramethylammonium chloride under heterogeneous reaction conditions with
potassium or cesium carbonate as the base and 1,2-dimethoxyethane or toluene as the solvent
[7]. Cs2CO3 has shown a higher activity comparing to K 2CO3 or to any other base used. It is
important to note that the heterogeneity of the reaction mixture did not present any obstacles
with respect to efficient microwave heating.

Acknowledgements
The Ministry of Higher Education, Science, and Technology of the Republic of Slovenia and
the Slovenian Research Agency are kindly acknowledged for financial support (P1-0230-
0103).

References

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Parvulescu, M.E. Pérez-Bernal, R.J. Ruano-Casero, V. Rives, K. Kranjc, S. Polanc, M. Kočevar, E. Genin,
J.-P. Genêt, V. Michelet, J. Mol. Catal. A: Chem. 276 (2007) 34; d) F. Neaţu, A. Kraynov, V.I. Pârvulescu,
K. Kranjc, M. Kočevar, V. Ratovelomanana-Vidal, R. Richards, Nanotechnology 19 (2008) 225702; e) F.
Neaţu, A. Kraynov, L. D'Sozua, V.I. Pârvulescu, K. Kranjc, M. Kočevar, V. Kuncser, R. Richards, Applied
Catal. A 46 (2008) 28; f) J. Hren, A. Juranovič, K. Kranjc, M. Gazvoda, F. Perdih, S. Polanc, M. Kočevar,
Unpublished results
[5] K. Kranjc, M. Kočevar, Synlett (2008) 2613
[6] a) J. Hren, F. Požgan, A. Bunič, V.I. Parvulescu, S. Polanc, M. Kočevar, Tetrahedron 65 (2009) 8216; b) V.
Cimpeanu, M. Kočevar, V.I. Parvulescu, W. Leitner, Angew. Chem. Int. Ed. 48 (2009) 1085
[7] N. Maraš, S. Polanc, M. Kočevar, Tetrahedron 64 (2008) 11618

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 CO oxidation on gold catalysts: towards microreactor technology
M. A. Centeno
Instituto de Ciencia de Materiales de Sevilla. CSIC-Universidad de Sevilla. Avda. Americo
Vespucio 49. 41092 Sevilla. Spain

Since the discovery made by Haruta in the 1980`s of the high catalytic activity towards low
temperature CO oxidation of gold nanoparticles supported on transition metal oxides, the
interest of the scientific community in gold-containing catalysts has strongly increased. The
efforts have been addressed to amplify the use of gold to other catalytic reactions, especially
oxidation ones, and to understand the structure and mechanisms associated with this so high
activity. The activity and selectivity of the gold catalysts depends on the gold particles
morphology (i.e. size and shape), the nature of the support (i.e. redox properties, state and
structure) and the contact type between the gold nanoparticles and the support. However,
many questions remain under debate, such as the nature of the active sites and species and of
the specific gold-support interaction.

On the other hand, monolithic reactors are the most widely used catalytic systems in
environmental applications because of their advantages over pellet catalysts, such as the low
pressure drop at the usual high flow rates in these reactions. If the channel size of the
monoliths ranges in the micrometer scale, a microchannel reactor is produced. The use of
microchannel catalytic reactors for chemical processes intensification is one of the most
promising technologies nowadays. The development of microchannel catalytic reactors is a
complex multidisciplinary technology which requires a deep study of the materials
constituting the miniaturised device, both catalysts and metal hosts, as well as their
preparation and interactions. In particular, the adequate deposition of the catalyst on the
microchannels surface is a key step. Due to its reduced size, microrreactors are ideal, for
instance, for portable hydrogen production devices capable to feed fuel cells. The hydrogen
produced must be cleaned-up before being introduced to the fuel cell by CO oxidation
reactions such as water gas shift (WGS) and preferential oxidation of CO (PrOx) reactions, in
which gold-based catalysts have been described as very actives ones.

Taking into account all above, this lecture will focus on the use and design of gold-based
catalytic devices for CO oxidation processes, from powders to monolithic and microchannel
reactors.

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 Surface reconstructions of noble metal-modified perovskites and induced
effect on the catalytic properties in DeNOx reactions

P. Granger
Université de Lille 1, Unité de Catalyse et de Chimie du Solide, UMR 8181, Bâtiment C3,
59650 – Villeneuve d’Ascq Cedex

Perovskite based catalysts have been widely studied for catalytic oxidation reactions [1] but
recent investigations also reported potential applications in DeNO x reactions which imply an
optimal balance between oxidation and reduction reactions in order to selectively convert
NOx into nitrogen under lean conditions. Promising results were also obtained for three-way
applications with commercial developments on sol-gel modified catalysts with Pd
incorporated inside the perovskite structure. A strong enhancement of the catalyst activity
and durability was reported in comparison with conventional supported alumina catalysts [2]
ascribed to reversible dynamic changes under typical cycling conditions protecting noble
metals to thermal sintering.
This concept has been profitably used in our lab but a different strategy was implemented
which consisted in successive impregnation and reductive/oxidative thermal treatments (see
Table 1). This approach has been successively developed for the catalytic decomposition of
N2O at high temperature with a catalytic activity correlated to Pd redispersion.

Table 1. Influence of thermal ageing on the catalytic performances of supported Pd catalysts

Catalyst Thermal treatment N2O Conversion Intrinsic rate Eapp
at 460°C (mol.h-1.Pdsurf-1) (kJ mol-1)
PdO/Al2O3 Calcination in air at 400°C 0.15 1.6 93  5
PdO/LaCoO3 Calcination in air at 400°C 0.32 19 55  3

Pd/LaCoO3 Reduction in H2 at 250°C 0.48 26 51  3

ageing in N2O/NO at 250°C
Pd/LaCoO3 Reduction in H2 at 250°C 0.74 66 42  3
ageing in N2O/NO at 500°C
Pd/LaCoO3 Reduction in H2 at 500°C 0.30 25 52  3
ageing in N2O/NOat 400°C

Similarly such activation procedure was implemented for Pt/LaFeO 3 catalyst but in that case
for the NO/H2 reaction at low temperature. Previous kinetic investigations emphasized the
fact that the metal/support interface was a key parameters supported by HR-TEM
observations which evidence the presence of microstructures corresponding to epitaxially
orientated Pt particles with the characteristic plans of the perovskite. Such a finding offers for
the first time a direct correlation between kinetic parameters and structural properties and
might explained why those catalysts exhibit a better durability than conventional noble metal
supported catalysts on alumina.

References
[1] M.A. Peňa, J.L. Fierro, Chem. Rev. 101 (2001) 1981
[2] M. Uenishi, M. Tanigushi, H. Tanaka, M. Kimura, Y. Nishihata, J. Mizuki, T. Kobayashi, Appl. Catal. B 57
(2005) 267

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 Green and Novel Low-Temperature (T<200oC) Industrial NOx Control
Catalytic Technologies for Stationary Applications: H2-SCR?
A. M. Efstathiou
Chemistry Department, Heterogeneous Catalysis Laboratory, University of Cyprus,
University Campus, CY 1678, Nicosia, CYPRUS (efstath@ucy.ac.cy)

The current industrial practice for the catalytic removal of NO x from the flue gas of
stationary polluting sources (e.g., power plants, industrial furnaces, boilers and incinerator
units) makes use of ammonia or urea as reducing agents (e.g., ammonia selective catalytic
reduction, NH3-SCR technology) mainly over V2O5/TiO2 catalysts promoted with WO3 or
MoO3, and also over some noble metal-supported catalysts operated in the 200-400oC range.
However, this technology is under re-examination due to various technical (e.g. ammonia
slip, corrosion of equipment, deposition of sulfate salts on heat exchangers) and operational
problems, such as high investment and running costs.

The development of new green industrial NO x control catalytic technologies operated in the
low-temperature range of 120-200oC and based on other than ammonia reducing agents
remains a very important target since it could reduce significantly the operational and
investment costs compared to the present NH 3-SCR technology, and can be easily retrofitted
in existing industrial plants.

Hydrogen (H2) appears to be a benign clean and green reducing agent for a potential H2-SCR
of NOx catalytic technology (see reaction network below). Thus, if a catalyst with excellent
activity and selectivity towards N2 formation (XNO and SN2>90%) and stability with time on
stream in the 120-200oC range could be found, the development of H 2-SCR would pose as an
alternative to NH3-SCR clean and green NOx control catalytic technology for many industrial
applications (stationary sources), especially those with on site hydrogen availability.

2 NO + 4 H2 + O2  N2 + 4 H2O (ΔHο= - 573.7 kJ/mol NO) (1)

2 NO + 3 H2 + O2  N2O + 3 H2O (ΔHο= - 411.9 kJ/mol NO) (2)

H2 + 1/2 O2  H2O (ΔHο= - 241.7 kJ/mol H2) (3)

The Heterogeneous Catalysis Laboratory of the University of Cyprus has developed a novel
catalytic system that consists of nano-particles of Pt and Pd deposited on a mixed metal oxide
of MgO-CeO2 that enables the use of hydrogen in the 120-200 oC range to selectively reduce
NO to N2 gas under strongly oxidizing conditions (H2-SCR). For this novel catalytic system
various patents were obtained [1-3]. A commercial exploitation of these patents by Linde
Engineering AG (Geramny) through a License Agreement is under way.

The developed novel catalytic system presents NO conversions and N 2-selectivities for the
H2-SCR larger than 90% in the 120-180oC range when a feed gas mixture containing 150-300
ppm NO, 0.6-0.8 vol%H2, 2-5 vol%O2, 20 vol%H2O and 10 vol%CO2 is used. Also, Pt
deposited on a pre-sulfated MgO-CeO2 support was found to have an excellent stability when
less than 50 ppm of SO2 are also present in the feed stream [1, 2, 4]. This catalytic system
was successfully deposited as a thin film (washcoat) on a ceramic monolith (cordierite) or
formulated in pellets of suitable size for industrial applications. The monolithic reactor was

----------------------------------------------------------------11
tested successfully under industrial flue gas conditions in a power station (Cyprus Electricity
Authority, Vasiliko).

This talk will critically review the current state of research in H 2-SCR from the catalyst
development and performance and the fundamental catalytic chemistry point of view. For the
latter, results from the use of isotopes and other transient techniques towards the elucidation
of important mechanistic aspects of the H2-SCR will be presented [5-7]. In particular, the
effect of support chemical composition, Pt metal particle size, and reaction temperature on
catalyst performance, the nature, location (metal vs. support) and surface concentration of
active and inactive NOx adsorbed reaction intermediate species, and the role of gaseous
oxygen on the reaction rate and N2-selectivity will be reviewed.

References

[1] A. M. Efstathiou, C. N. Costa, J.-L. G. Fierro, US Patent No. 7,105,137 B2 (2006)

[2] A. M. Efstathiou, C. N. Costa, J.-L. G. Fierro, EP No. 1 475 149 B1 (2008)
[3] A. M. Efstathiou, P. G. Savva, C. N. Costa, European Patent Application No. EP 08018087 (2008)
[4] C. N. Costa, P. G. Savva, J. L. G. Fierro, A. M. Efstathiou, Appl. Catal. B: Environ. 75 (2007) 147
[5] C. N. Costa, A. M. Efstathiou, J. Phys. Chem. B 108 (2004) 2620
[6] C. N. Costa, A. M. Efstathiou, J. Phys. Chem. C 111 (2007) 3010
[7] P. G. Savva, A. M. Efstathiou, J. Catal. 257 (2008) 324

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Oral communications

----------------------------------------------------------------13
 Greener catalytic routes for the Vitamins synthesis

S. Wuttke1, E. Kemnitz1, V. I. Parvulescu2, S. M. Coman2

1
Institut fur Chemie, Humboldt-Universitat zu Berlin, Brook-Taylor-Strasse 2, D-12489,
Berlin, Germany;
2
Department Of Chemical Technology and Catalysis Faculty of Chemistry, University of
Bucharest, Bdul Regina Elisabeta 4-12, 030016 Bucharest, Romania

Introduction
Increasingly, stringent environmental legislation has generated a pressing need for cleaner
methods of chemical production [1]. According to Sheldon [2] the fine chemical and the
pharmaceutical industry are the most polluting and highest waste generating industrial
segments. One reason is that many transformations from these areas are still based on
stoichiometric reactions often generating large amounts of waste. The solution is evident:
substitution of classical stoichiometric methodologies with cleaner catalytic alternatives.
In this context, the aim of this study was to design a greener approach to a set of organic
reactions as Vitamin E, Vitamins K1, K1-chromanol, and K4 synthesis.

Experimental
Catalyst preparation: The catalysts were synthesized as reported elsewhere [3, 4]. The
prepared catalysts are referred to hereafter as MgF 2-40, MgF2-57, MgF2-71, MgF2-87, and
AlF3-50 indicating the different concentrations of HF solutions used.
Catalyst characterization: XRD, MAS-NMR, TEM, thermal analysis, and elemental
analysis have been applied to study the structure, composition, and thermal behavior of the
bulk materials. XPS measurements, FTIR with probe molecules, NH 3-TPD, and the
determination of N2/Ar adsorption–desorption isotherms have been carried out to investigate
the surface properties. All characterization procedures are described elsewhere [3, 4].
Catalytic tests: Vitamin K1 and K1-chromanol were synthesized as reported elsewhere [5].
In a general procedure, 1 mmol menadiol (MDL) or menadiol acetate (MDA) was dissolved
in a mixture of propylene carbonate : heptane (50:50) as solvent in a glass vial equipped with
a magnetic stirrer. To this mixture 1 mmol of isophytol (IP) and the catalyst were added.
After this, the vial was closed, immersed in an oil bath with a temperature of 100°C, and the
charged mixture was stirred for 5-18 h. The synthesis of Vitamin E (tocopherol) was done in
a similar way, using as raw materials trimethylhydroquinone (TMHQ) and isophytol (IP) [4].
The menadiol (MDL) was also acetylated with acetic anhydride for the synthesis of Vitamin
K4, in free-solvent conditions.

Results and discussion

The modified sol-gel synthesis adopted for the preparation of the catalytic materials lead to
novel nanoscopic, partly hydroxylated inorganic fluorides with bi-acidic (Lewis/Brønsted)
properties. During the synthesis selective solvolysis of the original M–OR bond by an
aqueous HF solution (from 40 until 100 % wt. HF) results preferably in M–F, and to a minor
extent, M–OH bond formation. Thus, Lewis acid sites (partly coordinated metal) and
Brønsted sites (acidic M–OH groups) are formed. Both types of acid site can be tuned over a
wide range by applying different molar ratios of HF to H 2O during the modified sol–gel
synthesis [3].
Nitrogen adsorption-desorption isoterms show that all prepared catalysts display high specific
surface areas (180-424 m2/g) and an accessible pore system typical of mesoporous materials.
----------------------------------------------------------------14
On the other hand, it is possible to tune the Lewis/Brønsted acidic ratio onto the catalysts
surface, as a function of the HF concentration used in the preparation, as FTIR with probe
molecules technique demonstrated.
The best results obtained in these syntheses are presented in Scheme 1. As Scheme 1 shows,
whereas Vitamin K1 was obtained in higher selectivity (57.8%, comparable with the selectivity
O O obtained to the industrial level – 60%) on
OH + O
O catalysts with weaker acid sites, the
HO O formation of Vitamin K1-chromanol is
OH
favored by a stronger acidity. W ith an
OR O excess of TMHQ (TMHQ/IP = 2/1,
(R = H, COCH3)
OH
O molar ratio), in the presence of AlF3-50
+
[ ] H
3
+ Vitamin K
sample it was possible to obtain (all-
4

OH
AlF (50% HF) rac)-[]-tocopherol with > 99.9% yield
3

O S = 71.4% in only 1 h of reaction.

HO [ ] H X = 100%
3
Except MgF2 (87% HF), Vitamin K4 was
Vitamin K1-chromanol
]H
O [
3 obtained in selectivities higher than 90%
O
+
irrespective of the catalyst nature, for
tocopherol
[ ] H conversions higher than 85%.
3
AlF3 (50% HF)

S > 99% MgF2 (57% HF)

X = 100% O
S = 57.8%
Vitamin K1 X = 100%

Scheme 1. The synthesis of Vitamin E (tocopherol), K1, K1-chromanol and K4

Conclusions
The extended research of the catalytic properties of the novel nanoscopic hydroxylated
fluorides to be used for the above Vitamins synthesis demonstrated that these materials can
be successfully tuned in their acidic properties thus resulting in optimized yields of the target
product. The catalytic efficiency combined with practical advantages of the catalytic
experimental set-up make this system appealing even in the commercial stage.

Acknowledgements
This work was supported by Alexander von Humboldt Foundation.

References
[1] R. A. Sheldon, J. Mol. Catal. A: Chemical 107 (1996) 75
[2] R. A. Sheldon, H. van Bekkum, Fine Chemicals through Heterogeneous Catalysis, Wiley/VCH, (2001)
[3] S. Wuttke, S. M. Coman, G. Scholz, H. Kirmse, A. Vimont, M. Daturi, S. L. M. Schroeder, E. Kemnitz,
Chem. Eur. J. 14 (2008) 11488
[4] S. M. Coman, S. Wuttke, A. Vimont, M. Daturi, E. Kemnitz, Adv. Synth. & Catal. 350 (2008) 2517
[5] S. M. Coman, V. I. Parvulescu, S. Wuttke, E. Kemnitz, ChemCatChem, 2 (2010) 92

----------------------------------------------------------------15
 Effect of the support topology on the catalytic activity of CoMo-based
catalysts in HDS reaction

B. Dragoi1*, V. La Parola2, A. M. Venezia2, A. Ungureanu1, E. Dumitriu1

1 Faculty of Chemical Engineering and Environmental Protection, Technical University of
Iasi, Department of Organic and Biochemical Engineering, Bd. D. Mangeron, 71A, 700050,
Romania, bdragoi@ch.tuiasi.ro
2 Istituto per lo Studio dei Materiali Nanostrutturati (ISMN-CNR) via Ugo La Malfa, 153,
Palermo, I-90146

Introduction
Sulfided CoMo on silica is the most used system in hydrodesulfurization (HDS) of petroleum
fractions [1]. Other supports such as alumina, carbon, USY or mixed oxides were used as
host materials for these active phases [2]. Due to their high surface area (up to 1000 m 2.g-1),
the high concentration of the silanol groups and large pore diameter (2–50 nm), the
mesoporous silica materials were of particular interest as supports for CoMo active species.
In this context, we proposed here to study the influence of several mesoporous topologies
such as HMS, SBA-15, MCM-41 and MCF on the catalytic performance of CoMo catalysts
in hydrodesulfuration of thiophene.

Experimental
Synthesis: All mesoporous supports, SBA-15 [3], HMS [4], MCM-41 [5], and MCF [6], were
prepared according to the previously reported methods. The CoMo catalysts were obtained
by co-impregnation of the calcined supports with cobalt nitrate and ammonium
heptamolybdate. The cobalt and molybdenum oxide phases were obtained by calcination of
the impregnated solids at 400 °C for 2 h. Characterization: The supports as well as the
catalysts were characterized by the following techniques: XRD, nitrogen physisorption, DR
UV-Vis, TPR, XPS and TEM. Catalytic tests: All the catalysts were tested in the vapour
phase hydrodesulfurization of thiophene [7]. Prior to the test, 200 mg of catalyst were
sulfided in situ for 2 h in flow of 10 vol.% H2S/H2, at 50 ml.min-1 and at 400 °C. After
purging with nitrogen, the HDS of thiophene was carried out at 340 °C with 5.3 vol. %
thiophene in H2. The reaction products were analyzed by online gas chromatography.
Measurements of the rate constants at the temperatures of 355 °C, 370 °C and 395 °C were
also performed to determine the apparent activation energy for each catalyst.

Results and discussion

Physico-chemical characterization: The XRD diffractograms recorded at low 2 theta angle
for both, supports and CoMo supported catalysts, revealed specific patterns for each type of
mesoporous material. The only difference consisted in the intensity attenuation of the
corresponding peaks which indicate the fulfilling of the supports pores with CoMo species.
This information is also supported by TEM results. Accordingly, the specific surfaces areas
as well as the pore volumes of the supports (Tabel 1) decreased after the deposition of CoMo
oxides. DR-UV-Vis spectra contain characteristic bands (i) in the UV region belonging to
MoO42- (254 nm) and Mo-O-Mo bridges (305 nm), and (ii) Vis region at ≈ 580 and 670 nm
assigned to cobalt species in tetrahedral coordination and a shoulder at 520 nm assigned to
octahedral coordination of cobalt [8]. The surface composition of the catalysts was analysed
by XPS. Catalytic results: Catalytic results for the prepared catalysts in terms of reaction rate
and activation energy are reported in Figure 1.

----------------------------------------------------------------16
 1.6 60

Table 1. Textural parameters of the rHDS

1.5 Ea
supports and the catalysts. 56

rHDS, mol.g-1.s-1
. 1.4

Ea, kJ.mol-1
52
Sample SBET (m2.g-1) Vp (cm3.g-1) p(A)
1.3
HMS 1013 1.37 30 48
CoMo-HMS 533 0.83 30 1.2

SBA-15 721 1.18 65 1.1

44

CoMo-SBA-15 435 0.97 70

1.0 40
MCM-41 886 0.87 26 CoMo-
HMS
CoMo-S
BA-15
CoMo-M
CM-41 CoMo-
MCF

CoMo-MCM-
524 0.56 20 Catalysts
41 Figure 1. Thiophene HDS rate and
MCF 552 2.28 138 activation energy as a function of
CoMo-MCF 332 1.65 36 support.

It is obvious recognized that the organization of the support influences the catalytic behavior
of the final catalyst. It seems that a higher disorder in the support allows a better dispersion of
the active species and thus, more of them are able to take part at the reaction. The obtained
results led to the following order of the activity: CoMo-HMS > CoMo-SBA-15 > CoMo-
MCM-41 > CoMo-MCF. As previously reported for similar catalysts, activation energy is in
the range of 40-60 kJ.mol-1 [9].

Conclusions
Hydrodesulfurion of thiophene over CoMo catalysts obtained by impregnation of cobalt and
molybdenum salts on different mesoporous silica topologies (SBA-15, MCM-41, MCF and
HMS) showed different catalytic activities depending on the support organization. Worm
hole like structures seemed to be more proper for CoMo dispersion on the surface while the
MCF with large spherical pores and windows led to the catalysts with the lower activity in
the studied series. SBA-15 and MCM-41 with ordered two-dimensional hexagonal (P6mm)
mesostructures led to catalysts which had almost similar reaction rate (48 mol.g-1.s-1); it
could be stipulated that for Co and Mo oxides as well as the sulfided CoMo the distribution
on the internal surface of the pores is somehow limited by their cylindrical shape.

References
[1] A.M. Venezia, V. La Parola, G. Deganello, D. Cauzzi, G. Leonardi, G. Predieri, Appl. Catal. A 229 (2002)
261
[2] T.I. Korányi, Z. Vít, D.G. Poduval, R. Ryoo, H.S. Kim, E.J.M. Hensen, J. Catal. 253 (2008) 119
[3] D. Zhao, J. Feng, Q. Huo, N. Melosh, G.H. Fredrickson, B.F. Chmelka, G.D. Stucky, Science 279 (1998)
548
[4] N. Marin-Astorga, G. Pecchi, T.J. Pinnavaia, G. Alvez-Manoli, P. Reyes, J. Mol. Catal. A: Chemical 247
(2006) 145
[5] J. Rathousky, M. Zukalova, A. Zukal, J. Had, Collect. Czech. Chem. Commun. 63 (1998) 1893
[6] P. Schmidt-Winkel, W.W. Lukens Jr., P. Yang, D.I. Margolese., J.S. Lettow, J.Y. Ying, G.D. Stucky,
Chem. Mater. 12 (2000) 686
[7] V. La Parola, G. Deganello, A.M. Venezia, Appl. Catal. A, 260 (2004) 237
[8] H. Jeziorowski, H.Knozinger, J. Phys. Chem. 83 (1979) 1166
[9] A.M. Venezia, F. Raimondi, V. La Parola, G. Deganello, J. Catal. 194 (2000) 393

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 Probing the specific surface interactions of TiO2 catalysts with
cyanobiphenyl molecules

F. Ungureanu, L. Frunza, S. Frunza, P. Ganea, F. Cotorobai, C. Logofatu, M. Lazarescu

National Institute of Materials Physics, Magurele, Romania

Introduction
Titanium dioxide is largely used nowadays for anti-reflection coatings, gas sensors, as a
biomaterial, in catalytic reactions acting as promoter, support for metals and metal oxides,
additive, especially as catalyst and photocatalyst [1].
In the aim to bring more information concerning the specific surface interactions taking place
onto several TiO2 catalysts used/prepared in our group we performed a complex study by
following up these interaction with model test molecules as cyanobiphenyls (4-pentyl-4’-
cyanobiphenyl or 5CB) known as very stable molecules the behavior of which in contact with
other oxide surfaces like silica or molecular sieves was familiar as well [2, 3]. In fact, starting
from high dielectric constant and the dependence of the electric conductivity on the ambient
gas composition (cited in [1]) we expected new insights be revealed by applying less used in
this field, broadband dielectric spectroscopy (BDS) along with well-known infrared
spectroscopy (IR) and thermal analysis. Comparison was made with the behavior of some
TiO2 commercial samples.

Experimental
TiO2 samples investigated and some of their characteristics are collected in Table 1.

Table 1. TiO2 samples

Catalyst Origin BET

m2/g
TiK Kronos 100
TiD INCDFM 9
TiR IP 50
TiF film

The confinement of 5CB was performed by mixing the TiO2 with the appropriate amount of
5CB in solution; the easy evaporating solvent was then removed. X-ray photoelectron
spectroscopy (XPS) was chosen to characterize the surface of the nanostructured TiO 2
materials. The studies were done with an updated spectrophotometer VG ESCA MKII, with
Al source (Kα=1486.6 eV), at a take-off angle of 55° [4], using SDP 32 and S-PROBE
software. Peak positions were assigned by referencing the C(1s) peak (adventitious carbon) to
a binding energy of 285eV and linearly shifting all other XPS peaks by an equal amount, as it
is customary.
The 5CB content of the composites was determined by thermogravimetric (TG)
measurements, since the mass of the pure oxide changes insignificantly till 1100 K (by
dehydrating), whereas the 5CB is completely oxidized and removed from the system. TG
measurements were carried out simultaneously with differential thermal analysis (DTA) ones
using a Perkin Elmer Diamond apparatus under dry air at a heating rate of 10 K/min. For a
limited temperature range at the beginning of the interval, the heating rate was 2 K/min.
Vibrational spectra were recorded at room temperature with a FTIR Spectrum BX (Perkin
Elmer) spectrometer (DTGS detector) in KBr or on self supported disks. In the first case, a
standard procedure was adopted for an easier comparison. The spectra were analyzed by
----------------------------------------------------------------18
fitting Gaussian profiles to the data using a fitting procedure based on the least square method
getting free all the parameters.

Results and discussion

0
0.00
-2 H-bonded
(B)
0.4
-0.05

Mass loss

Absorbance
-4
monomer

DTG
-0.10
-6 0.2

-8 -0.15

-10 -0.20 0.0

400 600 800 1000
2200 2220 2240 2260
Temperature /K Wavenumbers /cm -1

Figure 1 Figure 2 Figure 3

XP spectra of the pure oxide samples have shown the surface composition of the investigated
samples. A representative example is given in Fig. 1 for a TiF sample, in which the binding
energy part where titanium peaks appear. The decomposition of the peaks is shown as well.
Some TG curves for 5CB loaded oxide samples are plotted in Fig. 2. One can note that we
very low loading degree ensuring a very thin layer (approaching the monolayer thickness).
Thus the large surface-to-volume ratio of the composite samples leads to a considerable
contribution of the 5CB molecules in the surface layer to the spectra.
A representative infrared spectrum is presented in Fig. 3 for the 5CB/TiD samples in the
region due to the stretching of cyan group. The peak at 2227 cm-1 was assigned to 5CB
monomers and that at 2234 cm-1 is due to hydrogen bonded species. As expected, the peak
half-band widths of bulk-like monomer species are larger than for bulk 5CB.
The dielectric spectroscopy measurements were performed for 5CB loaded oxide samples as
well, and the results indicated faster relaxation processes than in the bulk. These relaxations
were assigned to the rotational fluctuations of 5CB molecules in the surface layer.

Conclusions

Both dielectric and infrared spectroscopy have shown the influence of the sample history on
the observed behavior. In the dielectric investigations, this might be connected to the
interaction of test molecules with the surface changed in turn by the corresponding electronic
structure. In the latter case, the influence is manifested as the contributions of monomer and
hydrogen bonded species on the intensity and position of the cyan stretching peak.

Acknowledgements

The authors thank the Romanian Ministry of Education and Research for financial support by
the Project COMAFI of the CORE Program. Sample preparation and valuable discussions
with Dr. L. Diamandescu are highly appreciated.

References

----------------------------------------------------------------19
[1] O. Carp, C. L. Huisman, A. Reller, Prog. Solid State Chemistry 32 (2004) 33
[2] S. Frunza, L. Frunza, M. Tintaru, I. Enache, T. Beica, A. Schönhals, Liq. Cryst. 31 (2004) 913
[3] L. Frunza, H. Kosslick, S. Frunza, A. Schönhals, Micropor. Mesopor. Mater. 90 (2006) 259; L. Frunza, S.
Frunza, H. Kosslick, A. Schönhals, Phys. Rev. E. 78 (2008) 051701
[4] C. C. Negrila, C. Logofatu, R. V. Ghita, C. Cotirlan, F. Ungureanu, A. S. Manea, M. F. Lazarescu, J. Crystal
Growth, 310 (2008) 1576
New M-Mg-Al mixed oxides (M = Mn, Fe, Co, Ni, Cu, Zn) catalysts
obtained from LDH precursors for light alkanes total oxidation

S. Tanasoi1, N. Tanchoux2, A. Urda1, F. Fajula2, I. Sandulescu1, D. Tichit2, I. C. Marcu1

1
Department of Chemical Technology and Catalysis, Faculty of Chemistry, University of
Bucharest, Bd. Regina Elisabeta 4-12, 030018, Bucharest, Romania
e-mail: ioancezar.marcu@g.unibuc.ro
2
Institut Charles Gerhardt, Matériaux Avancés pour la Catalyse et la Santé (MACS),UMR
5253 CNRS/ENSCM/UM2/UM1, Ecole Nationale Supérieure de Chimie, 8, rue de l’Ecole
Normale, 34296, Montpellier Cedex 5, France

Introduction
One of the most effective and economically attractive methods of the volatile organic
compounds (VOC) neutralization is the catalytic total oxidation to carbon dioxide and water
[1]. In recent years, many efforts were directed towards the design of catalytic materials
based on simple and mixed transition-metal oxides to replace supported noble metals
catalysts for this reaction. They were tested in the light alkanes oxidation due to the low
reactivity of these molecules [2, 3].
In this work, a series of transition metal-based mixed oxides were synthesized using layered
double hydroxide (LDH) precursors, characterized and tested as catalysts for short-chain
alkane’s total oxidation.

Experimental
The catalysts were prepared from LDH precursors calcined at 750°C in order to obtain the
corresponding mixed metal oxides noted MMgAlO, where M is Mn, Fe, Co, Ni, Cu, or Zn.
The transition metal content, as atomic percent with respect to the cations, was kept at 5 %.
XRD, N2 adsorption, TG-DTG and H2-TPR experiments were used to characterize the
catalysts. Catalytic tests were performed at 1 % vol. hydrocarbon in air, at a total volume
hourly space velocity (VHSV) of 20000 h-1, in the temperature range 300 – 750°C.

Results and discussion

The XRD analysis showed that the precursors exhibit the characteristic structure of LDH
materials and the final catalysts that of the Mg(Al)O mixed oxides with the periclase-like
structure. In addition, MnO2, Fe2O3 and ZnAl2O4 phases were also detected for MnMgAlO,
FeMgAlO and ZnMgAlO, respectively. The specific surface areas of the catalysts were in the
range of 134 – 172 m2/g. All the catalysts displayed type IV nitrogen adsorption/desorption
isotherms with a hysteresis loop, characteristic of mesoporous materials. The reduction
profiles of the transition metal-containing samples, presented in Fig. 1, show two sets of TPR
peaks in the temperature range of 100-350°C and 350-800°C, respectively. The peaks in the
low-temperature region can be attributed to the reduction of highly dispersed MOx phases. In
the high-temperature region, the broad TPR peak observed in all samples, except for
ZnMgAlO, can be decomposed in up to three well-defined components. They can be assigned
to the reduction of MOx species interacting more strongly with the support. The Cu-
containing sample was, by far, the most reducible.

----------------------------------------------------------------20
The light-off curves for methane total oxidation over MMgAlO catalysts are displayed in Fig.
2. We observe that CuMgAlO gave the highest activity, total conversion being achieved
below 585°C. The activity of the samples ranges as follows: CuMgAlO > CoMgAlO >
MnMgAlO > ZnMgAlO > NiMgAlO > FeMgAlO ≈ MgAlO >> Quartz. It is interesting to
note that the order of activity is consistent with the TPR-H 2 consumption in the low-
temperature range. This suggests that highly reducible cationic species were the catalytically
active species.

ZnMgAlO

100
CuMgAlO
MnMgAlO
90 FeMgAlO
CoMgAlO
80 NiMgAlO
Intensity (a. u.)

CuMgAlO
70 ZnMgAlO
Methane conversion (%)
NiMgAlO MgAlO
60 Quartz

50
CoMgAlO
40

30
FeMgAlO
20

10
MnMgAlO
0
0 100 200 300 400 500 600 700 800 900 400 500 600 700 800
o Temperature (°C)
Temperature ( C)

Figure 1. TPR profiles for the MMgAlO Figure 2. The light-off curves on MMgAlO
catalysts. catalysts: 1 % CH4 in air, VHSV = 20000 h-1.

The apparent activation energies corresponding to the transformation on the different

catalysts are similar and fall within the usual range measured for methane catalytic
combustion over supported MOx catalysts.
The CuMgAlO catalyst was also tested in the total oxidation of ethane, propane and propene.
The only product observed in all cases was carbon dioxide. As expected, a successive
increase in light-off temperature from propene to methane was observed.

Conclusions
Except for FeMgAlO, all the MMgAlO systems gave complete conversion of methane to
carbon dioxide at temperatures lower than 730°C. The CuMgAlO catalyst had the highest
activity, total conversion of methane being achieved at temperatures as low as 585°C and
decreased with ethane, propane and propene, respectively. It seems that the highly reducible
cationic species were the catalytic active species.

Acknowledgements
This research was supported by the Romanian National University Research Council
(CNCSIS) under the project “IDEI” No. 1906/2009.

----------------------------------------------------------------21
References
[1] L. D. Pfefferle, L. C. Pfefferle, Catal. Rev. Sci. Eng. 29 (1987) 219
[2] S.H. Taylor, S. R. O’Leary, Appl. Catal. B: Env. 25 (2000) 137
[3] M. Alifanti, G. Bueno, V. Parvulescu, V.I. Parvulescu, C. V. Corberán, Catal. Today. 143 (2009) 309
Study of hydrogen chemisorption on NiCu-containing SBA-15
mesoporous catalysts

A. Ungureanu*, A. Chirieac, A. Sasu, B. Drăgoi, E. Dumitriu

Technical University Gheorghe Asachi, Faculty of Chemical Engineering and Environmental
Protection, Iasi, Romania; e-mail: aungureanu@tuiasi.ro

Introduction
Bimetallic catalysts have been the subject of much research interest because of their
superiority over monometallic ones in the selective catalytic hydrogenation of α,β-
unsaturated aldehydes [1]. The nature of the metals, their relative content, particle size and
shape, type of support, catalyst preparation and pretreatment method are some examples of
factors that exert strong influence on the catalytic properties [2]. Particularly, supported
bimetallic particles of non-noble metals like as nickel and copper are potentially interesting
catalytic materials [3,4]. Because the ordered mesoporous materials such as SBA-15 may
play a key role as supports in accommodating these metallic particles due to their controllable
pore size, pore volume, and high surface area [5], we decided to study the dispersed SBA-15
supported Ni-Cu bimetallic systems. Since adsorption methods remain as the most sensitive
and selective means to quantitatively probe bimetallic surfaces, information about surface
composition in these catalysts have been obtained based on the hydrogen chemisorption
measurements. Catalytic performances were determined in the liquid phase hydrogenation of
cinnamaldehyde (CNA).
Experimental
Nix-Cuy/SBA-15 samples (x, y stand for the nominal loading of Ni and Cu respectively, wt.
%; total loading of 5 wt.%) were prepared by incipient wetness impregnation of the calcined
SBA-15 with aqueous solutions of the corresponding metal nitrates. Typically, the rezulted
solids were dried at 80 oC, air calcined at 500 oC to obtain SBA-15 supported oxides and
reduced at 350 oC for 10 h under hydrogen (flow of 1L/h) to obtain supported metallic
phases. The physico-chemical properties of NiOCuO/SBA-15 were investigated through low-
and high-angle powder XRD, nitrogen physisorption, DR UV-Vis, TPR and H2
chemisorption at room temperature. The catalytic properties were investigated in relation to
the liquid phase hydrogenation of CNA at atmospheric pressure and a reaction temperature of
150 oC.
Results and discussion
The reduced catalysts were first degassed under vacuum at the reduction temperature for 3 h.
Adsorption isotherms were measured at room temperature by allowing 30 min for
equilibration prior to recording the first data point and 5 min between each successive point.
The pressure range of the isotherms was 120–240 Torr and the extrapolation to zero pressure
was taken as a measure of the total hydrogen uptake on the metallic phase. After the first
isotherm was recorded, the samples were outgassed under 10 -4 torr for 30 min at the
adsorption temperature and a second isotherm was obtained. The difference between the
isotherms gives the irreversibly hydrogen uptake which counts for the number of metallic
sites able to strongly adsorb hydrogen.

----------------------------------------------------------------22
Preliminary studies of hydrogen chemisorption on bimetallic Ni2.5-Cu2.5/SBA-15 calcined
at different temperatures (350, 400, 450, 500, 550 and 600 oC) revealed that the optimal
calcination temperature is 500 oC. At this temperature a maximum in both total and
irreversible hydrogen uptake respectively was observed. This is associated with the highest
dispersion (0.16) of metallic NiCu phases on the surface of SBA-15, whereas at higher
temperatures of 550 and 600 oC sintering takes place (dispersion of 0.07 and 0.03
respectively). These results are in good agreement with the catalytic activity in the
hydrogenation of CNA, a maximum of CNA conversion being noticed for the sample
calcined at 500 oC. However, the selectivity to cinnamyl alcohol (CNOL),
hidrocinnamaldehyde (HCNA) and hydrocinnamyl alcohol (HCNOL) does not depend on
calcination temperature.

250 250 45
A B Total

Selectivity to CNOL, mole %

40
Irreversible
Irreversible hydrogen uptake, mol/g

Ni5-Cu0 Col 1 vs Col 5 35

Conversion of CNA,
200 200 Col 1 vs Col 6
30
Hydrogen uptake, mol/g 25
(b)
150 150 20
(a)
15
10
100 Ni2.5-Cu2.5 100 5
Ni4-Cu1 0
50 -5
50
-10
Ni0-Cu5
-15
0 Ni1-Cu4
0 -20
100 120 140 160 180 200 220 240 260 Ni5-Cu0 Ni4-Cu1 Ni2.5-Cu2.5 Ni1-Cu4 Ni0-Cu5

Pressure, torr
Figure 1. (A) Irreversible H2 adsorption isotherms at room temperature for Nix-Cuy/SBA-15
samples; (B) Catalytic properties of Nix-Cuy /SBA-15 as a function of total and irreversible
H2 uptake: (a) conversion of CNA after 30 min of reaction, (b) selectivity to CNOL at a iso-
conversion of CNA of 10 mole %.

As shown in Figure 1A and B, the number of total sites as well as strong sites, i.e.which can
dissociatively adsorb hydrogen, significantly decreases with the increase in the copper
content. This drop in strongly held hydrogen with increased Cu concentration suggests that
copper surface segregation had taken place on the supported NiCu alloy particles [6], which
may be also responsible for the decrease in the catalytic activity in the hydrogenation of CNA
(curve a). However, the selectivity to unsaturated alcohol (CNOL) gradually increases as Cu
loading increases (curve b). Thus, the addition of Cu modifies the catalytic properties of
strong Ni sites as a result of both electronic and structural effects, which ultimately promotes
the C=O double bond polarization of CNA and enhance the selectivity to CNOL.
Conclusions
Hydrogen chemisorption on SBA-15 supported bimetallic NiCu catalysts was studied in
relation to the catalytic performances in the hydrogenation of cinnamaldehyde. The results
are explained in terms of diluting the active Ni metal in an essentially inactive Cu which
enriches the supported NiCu nanoparticles.
Acknowledgements
A. Sasu acknowledges the financial support of EURODOC “Doctoral Scholarships for
research performance at European level” project, financed by the European Social Found and
Romanian Government.
References
[1] P. Gallezot, D. Richard, Catal. Rev.-Sci. Eng. 40 (1998) 81

----------------------------------------------------------------23
[2] P. Mäki-Avela, J. Hájek, T. Salmi, D.Yu. Murzin, Appl. Catal. A: General 292 (2005) 1
[3] A.J. Marchi, D.A. Gordo, A.F. Trasarti, C.R. Apesguía, Appl. Catal. A: General 249 (2003) 53
[4] P. Mäki-Arvela, L.-P. Tiainen, M. Lindblad, K. Demirkan, N. Kumar, R. Sjöholm, T. Ollonqvist, J.
Väyrynen, T. Salmi, D.Yu. Murzin, Appl. Catal. A: General 241 (2003) 271
[5] D. Trong On, D. Desplantier-Giscard, C. Danumah, S., Kaliaguine, Appl. Catal. A: General 222 (2001) 299
[6] M.T. Tavares, I. Alstrup, C.A. Bernardo, J.R. Rostrup-Nielsen, J. Catal. 158 (1996) 402

Catalytic and electrocatalytic properties of mesoporous mixed oxides

applicable as SOFC anodes for direct oxidation of hydrocarbons
S. Somacescu1, N. Cioatera2, V. Parvulescu1
1
Institute of Physical Chemistry, Spl. Independentei 202, Bucharest, România
E-mail address: vpirvulescu@chimfiz.icf.ro
2
University of Craiova, Calea Bucuresti 107I, Craiova, Romania
Introduction
Development of direct-oxidation fuel cells could have important consequences for the
commercialization of fuel cells because direct oxidation of hydrocarbon fuels is not limited to
CH4. Developments of intermediate-temperature solid oxide fuel cells require optimization
of anode compositions and microstructure. Incorporation of titania or ceria was proved to
enhance the performance of conventional anode cermets, consisting of metallic Ni and yttria
stabilized zirconia (YSZ). The present study is centered on the synthesis of mesoporous Ni
and 8 mol% yttria-stabilized zirconia doped with titania or ceria and utilization of these
materials in direct oxidation of hydrocarbons in electrocatalytic membrane reactor (ECMR).
Oxidation of CH4 in electrocatalytic membrane reactor was presented compared with results
obtained, for same reaction, in catalytic fixed-bed reactor (CR).
Experimetal
x%TiO2 (CeO2) -ZrO2 – 8%Y2O3 powders with x = 5, 10, 15, 20 and 30 molar content were
synthesized by hydrothermal treatment and modified Pechini method. The metal precursors
were zirconium tetrachloride or zirconium oxychloride, yttrium (III) nitrate hexahydrate,
cerium nitrate and titanium (IV) propoxide. Surfactants (cetyltrimetylammonium bromide
(CTBA), Triton X-100 (Tr), polyoxyethilene (P) tridecylether (S) and Brij 97 (Br)) were used
as structure-directing agents. The obtained materials were characterized by X-ray diffraction,
SEM and TEM microscopy and N2 adsorption-desorption. Membrane for electrocatalytic
reactor was a sandwich of anode-electrolyte-cathode: anode - mesoporous Ni xTYSZ
composite (with 5-30 % Ni); electrolyte-YSZ; cathode-mesoporous CeO 2-PrO2 oxide. The
electrochemical reactor was constructed from YSZ disc of 25 mm diameter and 2 mm
thickness. Catalysts used in catalytic fixed bed reactor and membrane reactor were anode
materials. Catalytic properties were tested in direct oxidation of methane in membrane
reactor between 200 and 600oC. In catalytic membrane reactor fuel was methane (10% CH 4
in N2) and oxidant was air.
Results and Discussion
The XRD patterns, small-angle X-ray diffraction patterns, SEM and TEM microscopy show
formation of fluorite phase aggregates with low ordered mesoporous structure. The
electrocatalytic activity of anode materials was evidenced in similar conditions with SOFC.
In Fig. 1, performance curves are shown for membranes S1= A:YSZNi5, E: YSZ,
K:Ce0.9Pr0.1O2; S2= A:YSZNi10, E: YSZ, K: Ce0.9Pr0.1O2 ; S3= A:YSZNi20, E: YSZ, K:
Ce0.9Pr0.1O2; S4=A: YSZNi30, E: YSZ, K: Ce 0.9Pr0.1O2. The higher electrocatalytic activity
was obtained at 650 oC for the samples with 20% titania and 30% Ni content.

----------------------------------------------------------------24
 100

25 90
N5YZCT
N10YZCT
80
Ni/YZCT
20
70 T5YZCT

Conversion, %
T10YZCT
15 60

U, mV 50
10
40

5 30
650
20
0 600
S1 10
S2 500
S3 0
S4

200 300 400 500 o600 700 800

Temperature, C

Figure 1 Effects of membrane-anode composition Figure 2. Variation of methane conversion in CR

reactor on performance of ECMR for the samples obtained by hydrothermal
treatment

All the results show that the improvement of morphology, microstructure and composition of
the materials play an important role for achieving a high reactor performance. Higher activity
and selectivity was evidenced in catalytic reactor for samples obtained by hydrothermal
treatment with Ni supported by direct synthesis (Figure 2). In opposite, in electrocatalytic
membrane reactor the higher performances were obtained for anodes with Ni supported by
impregnation. All the oxide materials were catalytic active in oxidation of CH4. The lower
porosity of the samples obtained by Pechini method explain their lower activity (Figure 3).
The higher conversion was obtained at around 700oC for all the oxides.
Conclusions
All the results show that the improvement of morphology, microstructure and composition of
the materials for the SOFC components play an important role for achieving a cell
performance.

----------------------------------------------------------------25
 Tert-butanethiol oxidation using Mg-Co-Al-Mo mixed oxides catalysts
obtained from hydrotalcite-like precursors

R. Zăvoianu1, A. Cruceanu1, O. D. Pavel1, A.O. Vâlcu2, E. Bacalum2, R. Bîrjega3, E. Angelescu1

1
University of Bucharest, Faculty of Chemistry, Department of Chemical Technology and
Catalysis, 4-12 regina Elisabeta Blv., 030018, Bucharest, Romania,
rodicazavoianu@gmail.com
2
National Institute for Research and Development in Chemistry and Petrochemistry,
ICECHIM, Bucharest, Romania
3
National Institute for Lasers, Plasma and Radiation Physics, 409 Atomistilor Street, PO
BOX Mg-16, 077125, Magurele, Romania

Introduction

In the classical “sweetening” processes, the conversion of alkyl thiols to alkyl disulfides takes place in the
presence of a soluble redox catalyst and a strong base (NaOH) solution. The use of caustic solutions enhances
the costs of the environmental protection since they cannot be converted to a valuable product and have to be
neutralized before discharge. An ideal alternative to overcome this problem is the use of solid bases
incorporated into the catalyst formulation [1-3]. Therefore this work was aimed to investigate some redox
catalysts with base properties, e.g. nanostructured materials with molybdenum-oxoanions monodispersed in
MgxCo3-xAl mixed oxides matrices obtained by thermal decomposition of corresponding hydrotalcite-like
(HTL) precursors. Their catalytic activities for tert-Butanethiol (t-BuSH) oxidation were determined and
correlated with their physico-chemical properties. In the above formula x=0,1,2 is the Mg/Al atomic ratio used
in the preparation of HTL.

Experimental

HTL precursors prepared by co-precipitation at pH=10 and high supersaturation (using

aqueous solutions of Co(NO3)2x6H2O, Mg(NO3)2x6H2O, Al(NO3)3x9H2O, NaOH and
Na2MoO4x2H2O) were calcined at 460oC during 18h yielding MgxCo3-xAlMo mixed oxides
catalysts. The physico-chemical properties of both precursors and derived mixed oxides were
determined by chemical analysis, XRD, SEM-EDX, FTIR, DR-UV-VIS spectroscopy and
base sites quantification. The surface base sites of the solids were quantified using a method
similar to the one developed by Parida and Das [4] on the basis of the irreversible adsorption
of organic acids, such as acrylic acid, pKa=4.2 and phenol pKa=9.9. The amount of adsorbed
phenol is related to the number of strong surface base sites while the amount of adsorbed
acrylic acid is related to the total number of base sites. The number of weak base sites is
given by the difference between the amount of adsorbed acrylic acid and the adsorbed
phenol. The reproducibility of the method was checked experimentally, and the
measurements were repeated 2-3 times. The relative error was approximately 5%. The
catalytic tests for t-BuSH conversion were performed at ambiental temperature and pressure,
under continuous stirring. Synthetic samples of gasoline (50 mL) containing different
concentrations of t-BuSH in the range 100 - 310 ppm were submitted to oxidation under air
flow (3.6 L/h) in the presence of the above mentioned catalysts. Catalytic tests were carried
out during 6 hours, and the residual content of t-BuSH was determined hourly by titration
with 0.01 N AgNO3 alcoholic solution in the presence of dithizone.

Results and discussion

----------------------------------------------------------------26
The chemical analysis of catalysts showed that, even if the same amount of Na 2MoO4 was used for all
preparations, Mo-uptake increased with the amount of Co in the solid between 5.2wt%Mo (Mg2CoAlMo)
and 16wt.%Mo (Co3AlMo). XRD patterns presented in fig. 1 showed that all precursors have layered
structure typical for HTL’s rhomboedral symmetry (R-3m). While increasing Mo-uptake in samples, the
interlayer distances and crystallites size varied in the range 27-32nm, and 2.7-6nm, respectively. The basicity
of samples decreased while increasing Mo-content. Catalytic tests showed that the order of activity
MgCo2AlMo > Mg2CoAlMo >Co3AlMo could be linearly related to the atomic ratio Co/Mo (fig. 2).
[003]

[015]

[110]
[018]

(311)
[113]
[006]

[012]

[116]
[119]
I (u.a.)

HT Co3AlMo (*)
CHT Mg2CoAlMo

I (a.u.)
(o)
HT MgCo2AlMo CHT MgCo2AlMo

(x)
CHT Co3AlMo
HT Mg2CoAlMo

0 20 40 60 80 100
0 10 20 30 40 50 60 70 80
2 theta
2 theta

Figure 1. XRD patterns of the HTL precursors and the derived mixed oxides catalysts

90

80

70
t- BuSH Conversion (%)

60

50

40

30

20

10

0
4 5 6 7 8 9 10
Co/Mo

Figure 2. The correlation of the catalytic activity of MgxCo3-xAl Mo catalysts with the atomic
ratio Co/Mo determined by chemical analysis: ▲ MgCo2Al-Mo;  Mg2CoAl-Mo; ■Co3AlMo
Reaction conditions: 50 mL gasoline with 310ppm t-BuSH, air flow rate 3.6L/h, 6 h reaction
time, 0.5 g catalyst
Conclusions
The catalytic oxidation of thiols requires both redox and base properties of the catalyst. These
properties of mixed Mg-Co-Al-Mo oxides derived from hydrotalcites were tuned by varying
the proportion of cobalt in the solid which subsequently influenced the amount and dispersion
of molybdenum oxoanions embedded in their ultrafine structured layers.
Acknowledgements

The financial support of this work by CNMP grant 71-043/17.09.2007 is gratefully

acknowledged.
References
[1] D.-E. Jiang, B. Zhao, Y. Xie, G. Pan, G. Ran, E. Min, Appl. Catal. A: Gen. 219 (2001) 69
[2] A. Corma, V. Fornes, F. Rey, A. Cervilla, E. Llopis, A. Ribera, J.Catal. 152 (1995) 237
[3] M. J. Climent, A. Corma, S. Iborra, K. Epping, A. Velty, J.Catal.225 (2004) 316
[4] K. Parida, J. Das, J.Mol.Catal. A: Chem. 151 (2000) 185

----------------------------------------------------------------27
 Pt supported on Ga2O3, Al2O3 and Ga2O3/Al2O3 in reaction of
crotonaldehyde hydrogenation in gas phase: Effect of reduction
temperature on selectivity and activity

M. Jedrzejczyk, J. Farbotko, J. Rynkowski

Institute of General and Ecological Chemistry
Technical University of Lodz, Zeromskiego 116, 90-924 Lodz, Poland
e-mail: marcin.jedrzejczyk@p.lodz.pl

Introduction
The development of catalytic selective hydrogenations of α,β-unsaturated aldehydes to
corresponding unsaturated alcohols is important both from theoretical and practical (possible
application in industry) point of view. Unsaturated alcohols are widely used as a semi
products in synthesis of various fine chemicals especially in pharmaceutical and fragrance
branches of chemical production [1]. Platinum metals group supported on classical, inert
supports like SiO2 or Al2O3 usually demonstrate higher selectivity to saturated aldehydes than
to unsaturated alcohols due to the lack of interactions between supports and metals, which
changing electron properties of metals, often increase the selectivity of carbonyl bond
hydrogenation [2]. One of the way of improving the selectivity to desired products -
unsaturated alcohols, is an application of partially reducible oxides e.g.TiO 2 as a supports of
noble metals. One of the crucial parameter responsible for creation on the catalysts surface
species relevant for higher selectivity to unsaturated alcohols, is the temperature of the
catalysts reduction [3]. Our earlier work showed promising catalytic properties of noble metal
catalysts supported on Ga2O3 in the title reaction [4,5]. In the present work we focus our
attention on comparison of catalytic and physiochemical properties of platinum catalysts
supported on Ga2O3, Al2O3 and Ga2O3/Al2O3 systems.

Experimental
Ga2O3/Al2O3 support was obtained by wet impregnation of Al2O3 (Fluka 507C, SBET=136
m2/g) with the methanolic solution of Ga(acac)3. Loading of Ga2O3 was calculated to
theoretical monolayer and amounted 26,1 wt.%.
The same method was applied for preparation of Pt(acac) 2 on 5 wt.% Pt/Al2O3,
5 wt.% Pt/Ga2O3, 5 wt.% Pt/Ga2O3/Al2O3 using methanolic solutions of Pt(acac)2 as catalysts
precursor. Additionally, the catalyst 1% Pt/Ga2O3/Al2O3 (with the same proportion of Pt to
Ga2O3 as in 5% Pt/Ga2O3/Al2O3 sample) was prepared. Catalytic tests were carried out at 298
K under atmospheric pressure. Before reaction catalysts were reduced in situ under hydrogen
flow at wide range of temperature 298-773 K (1h).

Results and discussion

Activity and selectivity to crotylalcohol of the catalysts under study are presented in Table 1.
For 5% Pt/Al2O3 catalyst the changes of reduction temperature in the range 298-673 K do not
influence the selectivity to desired product crotylalcohol significantly. Main product on 5%
Pt/Al2O3 is butanal, selectivity to crotylalcohol is below 5%. After reduction at 773 K, one
can observe an increase of the selectivity to crotylalcohol to 20%. Such results are in
agreement with the literature where in principle, Al 2O3 is considered as an inert support of
noble metals catalysts in presented reaction [2]. Indeed, Bhanage et al.[6] noted high
selectivity to unsaturated alcohol at high conversions on Pt/Al2O3 catalyst but using
supercritical carbon dioxide as a solvent. In comparison to 5% Pt/Al 2O3 much higher
selectivity shows 5% Pt/Ga2O3 catalyst. It is very efficient in the reduction of carbonyl bond,
reaching the highest selectivity of 93% after reduction at 573 K. Measurements of CO
----------------------------------------------------------------28
adsorption on 5%Pt/G2O3 reduced at the same temperature 573 K showed red shift of the
band ascribed to CO adsorbed in linear form. The shift of this signal into lower wavenumbers
indicates an increasing platinum electron density. Ruiz-Martinez et al.[7] showed similar
results for platinum catalysts supported on TiO2 reduced at 773K. They explained this effect
by the coverage of metal surface by reduced forms of the support. We suggest similar effect
for 5%Pt/Ga2O3 catalyst reduced at the temperature higher than 573 K. The reduction of the
catalyst 5%Pt/Ga2O3 at the temperatures above 573 K leads to complete deactivation.

Table 1. Selectivity to unsaturated alcohols and activity in the reactions of hydrogenations of

crotonaldehyde in gas phase (conversion < 20%)

Catalysts
5% Pt/Al2O3 5% Pt/Ga2O3 5% Pt/Ga2O3/Al2O3 1% Pt/Ga2O3/Al2O3
Reduction
Selectivit Selectivity Selectivit Selectivity
Temperatur Act.a Act.a Act.a Act.a
y [%]b [%]b y [%]b [%]b
e [K]
298 96 1 49 79 84 46 32 44
373 142 2 102 78 119 42 36 44
473 162 3 134 70 139 44 61 59
573 112 4 88 93 136 54 31 62
673 102 3 0 0 110 68 19 59
773 121 20 0 0 29 48 12 33
a
-activity express at µmol×s-1×g-1
b
-selectivity to crotylalcohol

Conclusions
Platinum catalysts supported on Ga2O3/Al2O3 are more selective in crotonaldehyde
hydrogenation to crotylalcohol than 5% Pt/Al2O3 but less selective than 5% Pt/Ga2O3.
Catalyst 5% Pt/Ga2O3/Al2O3 shows higher activity than 1% Pt/Ga2O3/Al2O3 but the selectivity
of both to crotylalcohol is similar. The characteristic feature of the catalyst
5% Pt/Ga2O3/Al2O3 its relatively high selectivity to butylalcohol (ca. 20%) much higher than
that of 5% Pt/Al2O3 for which butanal predominates in the reaction products. This can suggest
much more active sites reducing both olefinic and carbonyl bond on the surface of
5% Pt/Ga2O3/Al2O3 comparing to 5% Pt/Al2O3 catalyst.

References
[1] U. K.Singh, M. A. Vannice, Appl. Catal. A: Gen. 213 (2001) 1
[2] P. Maki-Arvela, J. Hajek, T. Salmi, D. Yu. Murzin, Appl. Catal. A: Gen. 292 (2005) 1
[3] M. English, A. Jentys, J. A. Lercher, J. Catal. 166 (1997) 25
[4] E. Gebauer-Henke, J. Grams, E. Szubiakiewicz, J. Farbotko, R.Touroude. J. Rynkowski, J. Catal.
250 (2007) 195
[5] E. Gebauer-Henke, J. Farbotko, R. Touroude, J. Rynkowski, Kin. Catal. 49 (2008) 574
[6] B. M.Bhanage, Y. Ikushima, M. Shirai, M. Arai, Catal. Lett. 62 (1999) 175
[7] J. Ruiz-Martinez, A. Sepulveda-Escribano, J. A. Anderson, F. Rodriguez-Reinoso, Phys. Chem.
Chem. Phys. 11 (2009) 917

----------------------------------------------------------------29
 Structure, reactivity and magnetism of 3d and 4f metals deposited as thin
layers on atomically clean Si(001) by molecular beam epitaxy

N.G. Gheorghe, R.M. Costescu, M.A. Husanu, G.A. Lungu, D. Macovei, C.M. Teodorescu*
National Institute of Materials Physics, Bucharest-Magurele, Atomistilor 105b, 077125
Magurele-Ilfov, Romania (teodorescu@infim.ro)

Experimental
Thin Fe and Sm layers (in the range from sub-angstrom to 20-50 Å) were grown on
atomically clean Si(001) surfaces by molecular beam epitaxy in ultravacuum (10 -10 mbar),
using the complex surface and interface analysis and investigation system that consists of a
molecular beam epitaxy (MBE) chamber connected to a scanning tunneling microscope
(STM) and to a spin- and angle-resolved photoelectron spectroscopy (SARPES) set-up. This
assembly became functional at the end of 2009 after the completion of a Capacities project,
suplimented with a purchase from a POS-CCE structural project.

Results and discussion

The in situ measurements on Fe/Si(001) and Sm/Si(001) using Auger electron spectroscopy
(AES), X-ray photoelectron spectroscopy (XPS), low energy electron diffraction (LEED) and
reflection high energy electron diffraction (RHEED) were correlated with ex situ
measurements on samples capped with a protection layer (Cu, Au). These measurements
consist of magneto-optical Kerr effect (MOKE) and X-ray absorption sepctroscopy (XAFS:
EXAFS, XANES). The latter investigations were achieved using synchtrotron radiation at
Hasylab, Hamburg, on beamline A1. All measurements were made on samples grown at
different metal layer thicknesses and for different substrate temperatures during growth. The
Auger measurements showed the strong reactivity of metals with Si, which clearly increases
with increasing substrate temperature. At low temperatures FeSi and SmSi form at the
interface, while at high temperatures FeSi2 and SmSi2 are formed, as shown by EXAFS [1].
Although the layers lose their long-range order very quickly (as observed by LEED), those
layers grown at low temperatures show ferromagnetism and uniaxial magnetic anisotropy, a
result previously reported in literature [2]. In other words, uniaxial magnetic anisotropy,
which was investigated extensively for Fe/GaAs(001) [3], seems to be a property specific to
several magnetic metal / semiconductor interfaces [4]. Another new result obtained in this
study consists of the presence of weak ferromagnetism even for layers grown at high
temperature (500 °C), therefore indicating that the semiconductors SmSi 2 and FeSi2
compound are also ferromagnetic [4].
The Sm reactivity with the semiconductor layer is lower than the Fe reactivity. Consequently,
one observes in some cases the formation of metal Sm on the surface, but this surface is
highly reactive and Sm oxidises very quickly, quicker than the Fe layers. In other words,
although Sm reactivity with the residual oxygen and water from the ultrahigh vacuum
chamber (whose base pressure is in 10-10 mbar range) is higher than that of Fe, its reactivity
with the substrate semiconductor is lower. At the same time, whereas Fe deposition at room
temperature exhibits no observable LEED pattern (even for very low Fe coverages), Sm
deposition exhibits specular spots due to formation of well-defined islands on Si(001).

Acknowledgements
This work is supported by the PN2-71-063/2007 Contract granted by the Romanian Authority
of Scientific Research.

----------------------------------------------------------------30
References:
[1] M. Marangolo, F. Gustavsson, G.M. Guichar, M. Eddrief, J. Varalda, V.H. Etgens, M. Rivoire, F. Gendron,
H. Magnan, D.H. Mosca, J.-M. George, Phys. Rev. B 70 (2004) 134404
[2] J. Diaz, S.M. Valvidares, R. Morales, J.M. Alameda, J. Magn. Magn. Mater. 242 (2002) 166
[3] G.A. Prinz, Science 250, 1092 (1990); M. Gester, C. Daboo, R.J. Hicken, S.J. Gray, A. Ercole, J.A.C. Bland,
J. Appl. Phys. 80 (1996) 347
[4] N.G. Gheorghe, M.A. Husanu, G.A. Lungu, D. Macovei, C.M. Teodorescu, Surf. Sci., in preparation.

----------------------------------------------------------------31
 Ethanol conversion on CsxH3-xPW12O40 and catalyst microstructure model

V. Sasca1, O. Verdes1, L. Avram1, A. Popa1, A. Erdőhelyi2, A. Oszko2

1
Chemistry Institute of Romanian Academy-Timisoara, Bd. M. Viteazul 24, 300223
Timisoara, Romania
e-mail: viorelsasca@yahoo.co.uk ; vsasca@acad-icht.tm.edu.ro
2
Institute of Physical Chemistry and Material Science-University of Szeged

Introduction
The heteropoly compounds-HPCs containing Keggin Unit (KU) as CsxH3-xPW12O40 (CsxH3-
xPW) type, x=0-3, offer the opportunity to control Brőnsted acidity in a large scale of values:
as number and strength of the acidic sites, therefore they are among the most extensively
studied catalysts. A high influence on the catalytic activity of HPCs with Mo or W has the
microstructure, which is a controversial one [1, 2]. The HPCs are effective catalysts in
important catalytic reactions which use the renewable raw materials as bioethanol for
obtaining of intermediary organic compounds necessary in the synthesis organic industry.

Experimental
The tungstophosphoric acid H3PW12O40•xH2O (H3PW) was synthesized according to the
methods described in [3]. The CsxH3-xPW, x=1; 2; 2.25, 2.5 and 3 were prepared by
precipitation from an aqueous solution of the parent acid adding the required stoichiometric
quantity of counter-ion salts as caesium nitrate, under stirring. The compounds were heated at
523 K, 1h and they were characterized by the TG-DTA, FT-IR, XRD, BET method for
surface area, TPD of N-Butyl amine for Bronsted acidity [4] and XPS. The catalytic activity
was measured by pulse reaction technique for ethanol conversion at 523, 573 and 623 K.

Results and discussion

All synthesized salts have a cubic structure and their specific surface area increase abruptly
from 1-7 m2/g, for the content of Cs≤2, to 50-140 m2/g, for the content of Cs>2 as can be seen
in Figure 1.
100
140
Conversion/Selectivity, %

Selectivity, %

3
95
120
Surface area, m2 /g

90
100
3 2
85 Ethanol Conversion
80 Ethylene selectivity
C4 fraction selectivity
80
60 2
Diethyl ether selectivity 1

75
40

70 0
20 1
0,0 0,5 1,0 1,5 2,0 2,5 3,0
Bronsted acidity, protons number per KU
0
0,00 1,00 2,00 3,00 0
Cs ions/UK
Figure 2.The ethanol conversion and
Figure1. CsxH3-xPW Surface area selectivity on the CsxH3-xPW catalysts
function of the Cs ions content per function of Brőnsted acidity: 0-Cs3PW,
UK 0.5-Cs2.5H0.5PW, 0.75-Cs2.25H0.75PW, 1-
Cs2H1PW, 2-Cs1H2PW12, 3-H3PW

The ethanol conversion and selectivity to: ethylene, C4 hydrocarbons fraction and diethyl
ether function of the Brőnsted acidity for 573 K is showed in Figure 2. The higher ethanol
conversion, over 97%, was observed on the CsxH3-xPW catalysts where x = 0; 2.0; 2.25 and

----------------------------------------------------------------32
2.5. The selectivity to ethylene decreases for lower Brőnsted acidity. The selectivity to
diethyl ether and C4 hydrocarbons fraction vary slightly with Brőnsted acidity decrease, but a
sharp increase can be observed for the catalyst where x = 2.5, especially for the selectivity to
C4 hydrocarbons fraction. On the basis of the textural and structural properties and the
catalytic behaviour function of Cs content/KU and also taking into consideration some
literature data [3], a model of Cs acid salts particles as cubes of Cs 3PW coated of H3PW
layers is proposed. The model explains the abrupt increase of specific surface area for content
of Cs>2 and the highest catalytic selectivity at ethanol conversion for C4 hydrocarbons
fractions on Cs2.5H0.5PW as results of the acid layers number embedding the particles of
catalysts. The model gives a monolayer of H3PW for Cs2.5H0.5PW and close values of
H3PW/Cs3PW molar ratio calculated of the chemical compositions with the same molar ratio
based on the cubic model with a core of Cs3PW, as can be seen in Table 1.

Table 1. Acid layers on neutral Cs salt and molar ratio H3PW12O40/Cs3PW of acid Cs salts
The Caesium Molar ratio H3PW/ H3PW layers number Molar ratio H3PW of
acid salts of Cs3PW of CsxH3-xPW on the Cs3PW cubic outer layers/Cs3PW of
H3PW as mixture aggregates inner aggregates
Cs2.5H0.5PW 1/5 1 1/5.1
Cs2.25H0.75PW 1/3 1,5 1/3.3
Cs2H1PW 1/2 2,3 1/2
Cs1.29H1.71PW* 4/3 5 4/3.1
Cs1H2PW 2/1 7 2/1

The model was confirmed by XPS analyses, as can be seen in Fig. 3. The linear fit of the
experimental Cs concentrations gives 0 % Cs concentration for 1.22 Cs/KU, close to 1.29
value (*-Table 1) that corresponds to 5 layers of H3PW according to the proposed cubic
model.
6
P 2p-Experim
5
P 2p-Theoret
% at. conc.

4 Cs 3d-Exper corr

Cs 3d-Theoret
3
Linear (Cs 3d-
Theoret)
2

1 y = 1,8x + 0,0015 y = 3,2261x - 3,7883

R2 = 1 R2 = 0,9989
0
0 0,5 1 1,5 2 2,5 3
Cesium ions/KU

Figure 3. The theoretical and experimental Cs and P concentration by XPS of CsxH3-xPW12O40

Conclusions
The cubic model of CsxH3-xPW aggregates explains the structure and texture data and also
the results of catalytic activity tests in ethanol conversion.

References
[1] S. Berndt, D. Herein, F. Zemlin, E. Beckmann, G. Weinberg, J. Schütze, G. Mestl, R. Schlögl, Ber.
Bunsenges. Phys. Chem. 102 (1998) 763
[2] T. Okuhara, H. Watanabe, T. Nishimura, K. Inumaru, M. Misono, Chem. Mater. 12 (2000) 2230
[3] J. C. Bailar, Inorg. Synth. 1 (1939) 132
[4] V. Sasca, L. Avram, O. Verdes, A. Popa, Appl. Surf. Sci. (2010), doi:10.1016/j.apsusc.2009.12.131, in press

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 Local and electronic structure of supported gold nanoclusters determined
by X-ray absorption spectroscopy

N. Aldea1,V. Rednic1, P. Marginean1, F.Matei2

1
National Institute for Research and Development of Isotopic and Molecular Technologies,
Romania,
2
University of Agriculture Sciences and Veterinary Medicine, Math. Department. Cluj-
Napoca, Romania

Introduction
The gold was known as inert material, before nanoscale gold particles dispersed on metal
oxides supports were found to present a remarkable catalytic activity and have become
widely recognized for various reactions [1].We analyze gold nanoclusters as supported
catalysts by X-ray absorption spectroscopy in order to determine their local, and electronic
structure. The present study points out a strong deformation of the local structure of the metal
due to its interaction with oxide supports. Based on X-ray absorption fine structure
spectroscopy analysis we show that the entire local structure of the investigated systems is
strongly affected; the average Au-Au coordination number is smaller than in bulk materials.
Theoretical background of the X-ray absorption spectroscopy (XAS) was previously
presented [2]. The strong metal-support interaction is confirmed by the change in the shape of
the electron transition probability densities that appear in Au L III-edge. We have investigated
the local and electronic structure of systems Au foil, Au/CuO/Al 2O3, Au/ZnO/Al2O3,
Au/MnOx/Al2O3, Au/CeOx/ZrOx/Al2O3, Au/Li2O/CeOx/Al2O3, Au/Rb2O/CeOx/Al2O3 and
Au(OH)3. The fluorescence XAS measurements on LIII gold edge were carried out in 4W1B
beamline in Beijing Synchrotron Radiation Facilities operating at 30-50 mA and 2.2 GeV
with an energy resolution of 0.5-3 eV at 10 KeV at room temperature [3]. We used an energy
scanning range from 11582 to 12809 eV for measurement of the absorption coefficients.

Results and discussion

The extraction of EXAFS signal is based on the determination of the threshold energy for Au L III edge
followed by pre-edge and after-edge background removal with base line fitting using different
modeling functions and by absorption coefficients evaluation with 3 rd order bell spline functions. The
EXAFS signals were performed in the range 37.5-140 nm-1. In order to obtain the distribution of the
atomic distances we calculated the radial structure function [4]. The mean Au-Au distances of
the first and the second coordination shell for standard sample, at room temperature have
values close to R1=0.287 and R2=0.407 nm. Based on the Fourier transform of EXAFS
contribution, performed in the range 0.02-0.5 nm, we obtained the magnitude of the atomic
radial distribution for investigated samples as well as for standard Au foil. Table 1 contains
the best values of the local structure parameters of the investigated samples. The average
inter-atomic distances obtained for the first coordination shell have practically the same
values as those of the standard sample, but the coordination numbers are significantly
changed. We have considered that this diminution of the average nearest-neighbor
coordination number is due to a strong electron interaction between the active metal and
oxide supports [5].

----------------------------------------------------------------34
Table 1. The local structural parameters of the investigated samples for the first coordination shell

Sample Atomic number Shell radius [nm]

Au Foil 12 0.287
Au/CuO/Al2O3 4.61 0.287
Au/ZnO/Al2O3 5.69 0.284
Au/MnOx/Al2O3 2.90 0.284
Au/CeOx/ZrOx/Al2O3 3.44 0.287
Au/Li2O/CeOx/Al2O3 2.93 0.280
Au/Rb2O/CeOx/Al2O3 2.20 0.284

The electronic properties of supported gold catalysts are an interesting problem from XANES
perspective because it involves the following types of gold electron transitions: 2p3/2-6s, 2p3/2-
6d3/2, 2p3/2-6d5/2 and 2p3/2-continuous. Based on classical theory these electron transition
probabilities have been approximated by Cauchy, and arctan distributions [6]. The values of
these parameters confirm the specific strong electronic interaction between the metal and the
oxide supports.

References
[1] G. C. Bond, D. T. Thompson, Catal. Rev. Sci. Eng. 41 (1999) 319
[2] N. Aldea, A. Gluhoi, P. Marginean, C. Cosma, Xie Yaning, Hu Tiandou, Whongua Wu and Baozhong Dong,
Spectrochim. Acta B. Part B 57 (2002) 1453
[3] R. Grisel, K.-J. Weststrate, A. Gluhoi, B. E. Nieuwenhuys, Gold Bulletin 35 (2002) 39
[4] A. San-Miguel, Physica B 208-209 (1995) 177
[5] R. Zanella, S. Giorgio, C. H. Shin, C. R. Henry, C. Louis, J. Catal. 222 (2004) 357
[6] N. Aldea, E. Indrea, Comput Phys. Commun. 60 (1990) 155

----------------------------------------------------------------35
 Catalytic oxidation of ammonia on the hopcalite based catalysts modified
with noble metals

E. Maćkiewicz, M.I. Szynkowska, A. Węglińska, T. Paryjczak

Institute of General and Ecological Chemistry, Technical University of Lodz,
Żeromskiego 116, 90 – 924 Lodz, Poland

Introduction
Waste gas is one of the main emission pathways of many industries and production
processes. Complaints from the public due to odorous emissions from municipal activities,
e.g. composting plants, sewage treatment plants, solid waste landfills and agriculture. With
growing population, industrialization and urbanization, the odour problem has been assuming
objectionable proportion.
A huge number of compounds, organic and inorganic, have been identified in odour gases,
e.g. sulphur-containing compounds, nitrogen-containing compounds, volatile fatty acids and
phenols [1,2]. Ammonia is one of the main air contamination, which it has been attributed to
the intensive farming areas and notably to livestock manure.
A number of methods are used to remove odours from gases, based on adsorption,
absorption, biological methods, incineration and catalytic oxidation. The last technique is
very promising and it can be forced to proceed at much lower temperatures in the presence of
a catalyst [2, 3].
A number of transition and noble metal catalysts can be used in catalytic oxidation of
ammonia, such as: supported metal oxides catalysts [2-4] or zeolite catalysts modified with
transition and noble metals [2, 4, 5].
Hopcalite has been widely studied because of its high activity in CO oxidation at ambient
temperatures [6, 7]. However this type of catalysts has been also found active in VOC
oxidation.

Experimental
Commercial hopcalite (70% MnO2 and 30% CuO) supplied by Chemical Company
Inowrocław – Mątwy was tested in oxidation of ammonia without thermal treatment (denoted
as commercial hopcalite) or after calcination at 300ºC, 400ºC and 500ºC (denoted as
hopcalite 300, hopcalite 400, hopcalite 500, respectively). The catalysts modified with noble
metals were prepared by the wet impregnation method of the commercial hopcalite with
aqueous solutions of H2PtCl6 and PdCl2. Loading of metals in the obtained catalysts was 1
mass %. After 24 h samples were dried and calcined at 300ºC, 400ºC and 500ºC (catalysts
denoted as Pt(Pd)-hopcalite 300, Pt(Pd)-hopcalite 400, Pt(Pd)-hopcalite 500, respectively).
Catalytic activity measurements were carried out in a quartz flow reactor using 0,15 g of
catalyst at atmospheric pressure. In a typical NH3 oxidation experiment, a stream of NH3
(1.6%) and O2 (12%) in He (balance) was fed to the reactor. Analysis of reaction products
was performed using an on-line gas chromatograph equipped with TCD detector and
Chromosorb 103 column.
Moreover physical-chemical studies of catalysts were carried out. BET surface area
measurements of catalysts sample were determined by Sorptomatic 1900 Carlo-Erba using
the low temperature nitrogen adsorption-desorption method. X-ray diffraction patterns were
recorded by a Siemens D 5000 diffractometer using the Cu Kα radiation. The data were
collected in the range of 10-80° 2θ with the scanning step of 0.02°. The TPR (temperature-
programmed reduction) of the samples was carried out in the temperature range 30-900ºC.

----------------------------------------------------------------36
Results and discussion
Table 1 presents conversions of ammonia at different temperatures over hopcalite catalysts. It
can be concluded that the temperature of calcination influenced the catalytic performance. It
is shown that the most active catalyst was hopcalite modified with 1 wt.% platinum and
calcined at 300ºC. For this catalyst (Pt-hopcalite 300), 100% conversion was achieved at
220ºC. The lowest conversion of ammonia is observed over hopcalite calcined at 500ºC
because of high temperatures of thermal treatment induces an increase in the crystallinity and
decrease in the surface area of the samples and, as a consequence, the loss of catalyst activity.

Table 1. Conversion of commercial hopcalite, hopcalite calcined at 300ºC, 400ºC, 500ºC and
hopcalite modified with 1 wt. % Pt and Pd calcined at 300ºC

Conversion of NH3, %
T commercial hopcalite Pt-hopcalite Pd-hopcalite hopcalite hopcalite
hopcalite 300 300 300 400 500
220ºC 86 93 100 96 91 60
250ºC 100 100 100 100 100 82
280ºC 100 100 100 100 100 94
310ºC 100 100 100 100 100 100

Acknowledgements
The financial support of this work by the Polish Scientific Research Council
(grant G 006/T02/2007) is gratefully acknowledged.

References
[1] J. Kośmider, B. Mazur-Chrzanowska, B. Wyszyński, Odory, PWN Warszawa (2002)
[2] P. D. Le, P. M. Becker, A. A. Aarnink, A. W. Jongbloed, C. Van der Peet-Schwering, Agrotech. & Food
innov. B.V. (2004)
[3] G. Busca, C. Pistarino, J. Loss Prev. Proc. Ind. 16 (2003) 157
[2] M. I. Szynkowska, E. Wojciechowska, A. Węglińska, T. Paryjczak, Przemysł Chemiczny 87 (2008) 834
[3] G. Olofsson, L. R. Aallenberg, A. Andersson, Journal of Catalysis 230 (2005) 1
[4] L. Chmielarz, P. Kuśtrowski, A. Rafalska-Łasocha, R. Dziembaj, Appl. Catal. B: Environ. 58 (2005) 235
[5] R.Q. Long, R.T. Yang, J.Catal. 201 (2001) 145
[6] S. B. Kanungo, J.Catal. 58 (1979) 419
[7] S. Veprek, D.L. Cocke, S. Kehl, H. R. Oswald, J.Catal. 100 (1986) 250

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The use of immobilized yeast cells in gellan-bentonite matrix for sparkling
wine processes

A. Savin*, S. Ciubotaru, A. Chirieac

Technical University Gheorghe Asachi of Iasi, Faculty of Chemical Engineering and
Environmental Protection, 71A Bd D. Mangeron, 700050-Iasi, Romania,
e-mail: asavin@ch.tuiasi.ro

Introduction
Hybrid materials have an important role in the development of multifunctional systems such
as bioactive hybrid structures (immobilized biocatalysts, biosensors, matrices for controlled
release of drugs) [1]. In order to enhance the performances of sparkling wine production
yeast immobilized on different supports were used. Nevertheless the mechanical and physico-
chemical instability allows the release of the cells and fragments of the support in the
fermentation medium. To overcome this disadvantage, we studied: the immobilization of the
yeast cells into a new hybrid support, gellan/bentonite and the activity of immobilized cells in
the secondary fermentation of white wine.

Experimental
Materials: Gellan powder of food grade, type Kelkogel, (Kelco Biopolymers); Ca-betonies
of oenological use, fractionated in demineralized water; Oenological yeast, Saccharomyces
cerevisiae, Lalvin K1M ICV (Lallemand); 2 % CaCl 2 solution in water; white wine (Bucium
SA Iasi-Romania). Equipment: automatic analyzer Wine Scan FT - 120, which provides for
a wine sample the following characteristics: ethanol concentration, total sugars concentration,
total acidity, volatile acidity, pH, density; Sartorius ultrafiltration membrane, 0.45μ;
Aphrometer; Spectrophotometer Shimadzu UV-2450. Methods: Reactivation of yeasts was
achieved by dispersion in water at 37 0C. Bentonite was dispersed in demineralized water.
The fraction with average particle diameter less than 1 mm was withheld. Immobilization of
yeast cells on bentonite/gellan support. At the aqueous suspension of bentonite and yeast, the
warm solution of gellan in water was added. After mixing the suspension of the three
components, the beads were formed by a capillary extrusion in a CaCl 2 solution, 2%.
Secondary fermentations were carried out at 20 0C in a standard 750 ml champagne bottles,
filled with a tirage wine, having the characteristics listed in Table 1. Time evolution of the
secondary fermentation was followed by measuring the conventional characteristics used in
oenochemistry: titratable acidity, volatile acidity, ethanol concentration, total sugar, pH,
density, every 5 (five) days for a period of 27 days.

Table 1. The main characteristics of the tirage wine

Yeast Ethanol Total sugar Total acidity Volatile acidity pH Density
g/L [% vol.] [g/L ] [g/L]tartaric acid [g/L acetic acid] [g/mL]
0,244 10.42 28.1 6.27 0.2 3.12 1.00308
6

Results and discussion

Spherical particles of immobilized yeast cells in the gellan-bentonite matrix were tested for
stability in demineralized water at 20 0C for 7 days. Suspension turbidity resulting from the
partial degradation of beads in water was evaluated through transmittance at 620 nm (Table
2).

----------------------------------------------------------------38
Table 2. Influence of beads composition on the stability in water
Sample
control 1 2 3 4 5
Gellan (g) 1 0,54 0,55 0,44 0,49 0,55
Bentonite (g) 2,8 0,38 0,13 0,13 0,13 1,55
Yeast (g) 0 1 1 1 1 1
Transmittance % 98 78 79 69 77 98

Most stable beads (samples labeled with 5) were used in the secondary fermentation of wine.
Secondary fermentation of wine was performed in parallel with free yeast cells at
concentrations equal to those immobilized. Immobilized biomass was 1.3 g dry cells / 100 g
bead.
The results shown in Table 3 were obtained during the 26 days of secondary fermentation.

Table 3. Evolution of physico-chemical characteristics during secondary fermentation of

white wine
Time Free yeast Immobilized yeast
[day] P20 Ethanol Sugar pH Density P20 Ethanol Sugar pH Density
[atm.] [%vol.] [g/l ] [g/mL] [atm.] [%vol.] [g/l ] [g/mL]
7 4,92 10,79 13,2 3,09 0,99957 5,35 10,91 10,0 3,10 0,99785
12 6,55 11,10 7,9 3,07 0,99555 6,97 11,20 5,7 3,08 0,99393
17 8,38 11,30 5,9 3,08 0,99336 8,68 11,35 2,7 3,07 0,99209
22 8,68 11,35 2,8 3,08 0,99128 8,68 11,40 0 3,08 0,99113
27 8,68 11,31 0 3,07 0,99143 8,68 11,38 0 3,06 1,00494

The sparkling wine resulting from the fermentation with immobilized yeast was clear. In
bottles with immobilized yeast on bentonite/gellan support the remuage was completed in
few minutes, compared to 10 hours, time required by the free yeast cells. In wine, the both
gellan and bentonite shows fining properties [2].
Reuse of the immobilized yeast cells on gellan/bentonite support realized a pressure of 7.5 at
after 14 days, close to the pressure value obtained from first use. Consequently, the recycling
of the immobilized yeast cells on the hybrid support bentonite/gellan is possible.

Conclusions
The immobilization of yeast cells of Lalvin K1M ICV type on hybrid support
bentonite/gellan was performed.
Productivity of the immobilized yeast cells on hybrid support bentonite/gellan in the
secondary fermentation of white wine Bucium is greater than with free yeast cells.

References
[1] C. Sancez, L. Rozes, F. Ribot, C. Laberty-Robert, D. Grosso, C. Sassoye, C. Boissiere, L. Nicole, C.R.
Chimie 13 (2010) 3
[2] R. Santipanichwong, M. Suphantharika, J. Weiss, D.J. McClements, Food Res. Int. 41 (2008) 237

----------------------------------------------------------------39
Hydrogen production by low temperature methane steam reforming using
Ag and Au modified alumina supported nickel catalysts

M. D. Lazăr, M. Dan, M. Miheţ, V. Almăşan, G. Borodi

National Institute for Research and Development of Isotopic and Molecular Technology,
65-103 Donath Street, 400293 Cluj Napoca, Romania, diana@itim-cj.ro,

Introduction
Classic catalytically reformation of methane use nickel supported catalysts and require high
temperatures in order to obtain good catalytic activity. In this paper we report the preparation,
characterization and testing of two modified alumina supported nickel catalyst designed to
lower the reaction temperature. The new catalysts were prepared by adding gold, respectively
silver to nickel. They were tested for hydrogen production by methane steam reforming at
temperatures starting with 500oC.

Experimental
Supported Ni catalysts (8 wt.% Ni) modified with Ag (1 wt.%) and Au (1 wt.%) were
prepared by co-impregnation of γ-Al2O3 (St = 135 m2/g) with aqueous solutions of Ni(NO3)2 x
6H2O and AgNO3 and HAuCl4 x 3H2O, respectively. The impregnated samples were dried at
room temperature overnight, calcined under nitrogen at 400 oC for 4 h, and reduced in H2 at
400oC for 4h.
Total surface area (St), pore volume (Vp) and pore radius (rp) of the samples were obtained
from N2 adsorption–desorption isotherms, using the BET method for St, and Dollimore –
Heal method for Vp and rp. The isotherms were measured using a Sorptomatic 1990
apparatus. Metal surface area was determined from H 2 chemosorption data, usig the same
aparatus.
The XRD analyses were made using a Bruker D8 advanced diffractometer with Cu Kα1
radiation.
The TPR experiments were performed in an installation composed by: gas introduction unit,
tubular reactor and thermal conductivity detector (TCD). The gases used in these experiments
were 99.999% purity. The reduction agent was H2 and the temperature was programmed to
rise at 5°C/min up to 700°C, while the TCD signal was recorded.
The catalytic activity measurements for methane steam reforming, took place in a laboratory
device composed by feed section, reactor, and analytical unit. The gaseous components and
the water enter in the vaporizer using a liquid pump and mass flow controllers, respectively.
The reactions were carried out under atmospheric pressure using catalyst powders (1 g; 80 –
100 μm) diluted with alumina powder (1 g) of similar granulometry. The reaction
temperature was 500oC, 600oC and 700oC. Prior reaction, the catalysts samples were activated
at 400oC in H2 flow at 30 ml/min for 2h. Effluent gas compositions were analyzed by gas
chromatography, using two columns and TCD detector.

Results and discussion

The N2 adsorption – desorption isotherms of all three studied catalysts are of type IV which
corresponds to mesoporous solids. The pore size distribution is relatively uniform with a
medium diameter of 50 Å (Table 1). The total surface area and pores medium size does not
differ very much between the 3 catalysts.

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The TPR diagrams show that the reduction temperature of NiO is decreased by the addition
of Au with 50oC, and Ag with 170oC. In the case of Ni-Au/Al2O3 the TPR pattern contains a
shoulder situated on the left of main peak. The Ni-Ag/Al 2O3 TPR diagram contains a second
peak situated at higher temperatures then the main peak. These additional peaks are probably
due to reduction of mixed oxides.
The X-ray diffraction patterns contain certain peaks attributed to Ni, but no peak that can be
attributed to Au or Ag. This can be explained by the low content of gold and silver (1%). The
Ni crystallite sizes were determined from X-ray spectra using the Scherrer equation (Table 1).
The addition of gold does not change the nickel crystallite size. The silver addition conducive
to smaller nickel particles.

Table 1 Total surface area, pores radius and medium crystallite size for modified nickel
catalysts
Ni/Al2O3 Ni-Au/Al2O3 Ni-Ag/Al2O3
2
St (m /g) 108 111 105
rm (Å) 24 24 24
dm (Å) 85,6 86,9 72,7

The methane conversion is presented in Figure 1. The addition of silver drastically decreases
the catalytic properties of nickel catalysts. The addition of gold produces a catalyst with
improved capacities for hydrogen production at low temperature. This is due to better
methane conversion at 500oC and to better activity for water – gas shift reaction. The result is
a lower concentration of CO and a bigger concentration of H2 in the effluent gases.
100

90

80

70

60
500
50
600
40 700

30

20

10

0
Ni/Al2O3 Ni-Ag/Al2O3 Ni-Au/Al2O3

Figure 1. The methane conversion on modified nickel supported catalysts

Conclusions
The addition of gold (1%) to Ni/Al2O3 (8%Ni) improves the catalytic performances for
hydrogen production at low temperatures. The addition of Ag decreases the catalysts quality.

Acknowledgements
This research was supported by the Romanian ANCS Department: PN II Program under contract
21004/2007.

References
[1] F. Besenbacher, I. Chorkendorff, B. S. Clausen, B. Hammer, A. M. Molenbroek, J. K. Nørskov, I.
Stensgaard, Science 279 (1998) 1913

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[2] N.V. Parizotto, K.O. Rocha, S. Damyanova, F. B. Passos, D. Zanchet, C. M. P. Marques, J. M. C. Bueno,
Appl.Catal. A: Gen. 330 (2007) 12

Catalytic performance and structural characterization of copper ferrite as

a catalyst for propane oxidation

C. Munteanu1, M. Caldararu1, D. Gingasu1, M. Feder2, L. Diamandescu2 and N.I. Ionescu1

1
Institute of Physical Chemistry “Ilie Murgulescu” of the Romanian Academy, Splaiul
Independentei 202, 060041 Bucharest, Romania
e-mail: munteanuc@icf.ro, Phone/Fax (40-21) 312 11 47
2
National Institute of Material Physics, P.O. Box MG-7, Bucharest-Magurele 077125,
Romania

Ferrites, an important class of inorganic materials, are widely used in computer peripherals,
telecommunication equipments, as permanent magnets, for electronic and microwave
devices. Having a high thermodynamic stability, high electrical resistivity electro-catalytic
activity and resistance to corrosion, the spinel ferrites have been used also as active catalysts
in various catalytic reactions, as hydrocarbon oxidation, oxidative dehydrogenation,
decomposition of alcohols and peroxides and decarboxylation of some organic acids.
With the aim to identify new high performance catalysts for environmental purposes and the
mechanistic details of their action, in this paper we report about the synthesis and catalytic
performances of some copper ferrites in propane oxidation.
We synthesized copper ferrites by using two non-conventional methods: the first one
(CuFe2O4-ox) was prepared by co-precipitation and oxidation in aqueous solution and the
second one (CuFe2O4-c) was prepared by soft chemical method, i.e. by thermal
decomposition of poly-nuclear coordination compounds. The samples were studied by in situ
AC electrical conductivity measurements in operando conditions, in a special cell allowing
measurements on powders and by using the differential step technique (DST); that implies
repeated thermal cycling of the sample in various atmospheres (inert, oxygen, C 3H8/air
mixture) according to a specific protocol. Separate catalytic tests were performed in a
differential reactor by direct admission of the propane/air mixture. In order to detect the
changes induced by the catalytic test on the ferrite structure the samples were characterized
by X-ray diffraction (XRD) and Mössbauer spectroscopy before and after their use as
catalysts for propane oxidation.
AC electrical conductivity measurements showed that these materials behave like n-type
semiconductors (Figure 1).
In presence of propane, the electrical conductivity increased due to surface reduction, (Figure
2). After the catalytic test the XRD and Mössbauer spectroscopy results revealed the
appearance of CuFeO2 phase in both catalysts, indicating that the samples are reduced.
These catalysts are active in propane total oxidation. The sample prepared by complexation
method reached 95% conversion of propane at 400oC (Figure 3).

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 1.80E-05

-9
1.60E-05
CuFe2O4_ox-DHe3
CuFe2O4_ox-DO CuFe2O4_ox-DHe4

CuFe2O4_c-DHe3 CuFe2O4_ox-CT1
1.40E-05
CuFe2O4_c-DO CuFe2O4_c-DHe4
-11 CuFe2O4_c-CT1

1.20E-05

1.00E-05 -13
s (S/m)

ln s
8.00E-06

-15
6.00E-06

4.00E-06
-17

2.00E-06

0.00E+00 -19
0 100 200 300 400 1.3 1.8 2.3 2.8 3.3
temperature (oC) -1
1000/T (K )

Figure 1. Variation of electrical conductivity ( in inert Figure 2. Arrhenius plots of electrical
and oxygen atmospheres during heating conductivity () for CuFe2O4 in inert and
C3H8/air mixture
100 100

90 CuFe2O4-ox
90 CuFe2O4-ox
80 CuFe2O4-c
Propane conversion (%)

Propane conversion (%)

80
70

60 70

50 60

40
50
30
3 40
20 Vcat = 0.5 cm Vcat = 0.5 cm
3

10
C3H8:air = 1:10 30 o
t = 400 C
0 20
220 240 260 280 300 320 340 360 380 400 2:1.8 1:2 1:3 1:4 1:6
o
Temperature ( C) Molar ratio C3H8:O2

Figure 3. Variation of propane conversion during heating Figure 4. Variation of propane conversion at
for copper ferrite different C3H8:O2 molar ratios

In the case of the sample prepared by co-precipitation and oxidation, for a propane/oxygen
molar ratio of 1/6, a conversion higher than 95% (with selectivity to CO 2 close to 100%) was
obtained. We suggest that by appropriate composition optimization and oxygen content in
feed, copper ferrites can be used as possible depollution catalysts.
Based on the relative distribution of Fe3+/Fe2+ cations (evaluated by Mössbauer spectroscopy)
in fresh and respectively used catalysts the results are discussed in terms of the redox-type
mechanism.

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 Pleading for metal-organic frameworks

G. Blăniţă1, O. Ardelean1, D. Lupu1, G. Borodi1, M. Miheţ1, M. Vlassa2, I. Mişan1, I. Coldea1,

G. Popeneciu1
1
National Institute for Research and Development of Isotopic and Molecular Technologies,
65-103 Donath, 400293 Cluj-Napoca, Romania;
2
Babes-Bolyai University, Faculty of Chemistry and Chemical Engineering, 11 Arany Janos,
400028 Cluj-Napoca, Romania;
E-mail: gabriela.blanita@itim-cj.ro

Introduction
Metal-organic frameworks (MOFs) are zeolite analogues with high surface areas, permanent
porosity and adsorption capacity. This new class of porous materials shows high promises in
gas storage and separation applications as well as in catalysis, gas-sensing and photovoltaics
[1, 2].
In catalysis, different concepts can be followed depending on the nature and location of the
active sites. MOFs can act as catalyst suport or as catalyst, when the active sites are part of
the metal–organic framework structure. In the latter case, the active sites can be the mono- or
multinuclear transition metal centres, the organic linker or the functionalized organic linkers
[3]. Each active site is in an identical microenvironment due to the highly crystalline nature
of these materials. Either acting as suport or as catalyst, the apparent surface area, the pore
volume and the pore size of MOFs represent three important characteristics.
This work presents how the synthetic method and the reaction conditions affect the MOFs
surface area, pore volume and pore size. In this way, we synthesized Zn 4O(1,4-
benzenedicarboxylate)3, also known as MOF-5, under solvothermal conditions, at different
filling rate of reaction vessel and by microwave assisted synthesis.

Experimental
The studied materials were identified by X-ray powder diffraction (XRD) and characterized
by N2 adsorption/desorption. The XRD patterns of the dried samples were recorded on
Bruker D8 Advance powder X-ray diffraction apparatus, using Cu Kα radiation. Nitrogen
adsorption/desorption isotherms were obtained on a Sorptomatic sorptometer at liquid
nitrogen temperature. The specific surface areas of the samples were calculated by the
Brunauer-Emmett-Teller method in the p/p0 range of 0.02-0.1.
Solvothermal synthesis of MOF-5: The MOF-5 materials, named MOF-5(a), MOF-5(b) and
MOF-5(c), were synthesized by solvothermal reaction, at 100°C, for 7 h, using identical
starting mixtures, at different filling rates of reaction vessel: 0.197 (MOF-5a), 0.446 (MOF-
5b) and 0.837 (MOF-5c) [4].
Microwave assisted synthesis of MOF-5: An identical forementioned starting mixture was
loaded in reaction vessel and microwave irradiated at 85°C, for 84 secundes. After the
completion of the reaction, the product, hereafter named as μwMOF-5, was separated,
purified and activated using the same procedure as in solvothermal synthesis [4]. The authors
have applied for a patent for this method of MOFs synthesis.

Results and discussion

The MOF-5 materials identities were proved through comparison of the powder X-ray
diffraction patterns with simulated pattern for MOF-5 crystals [5]. The powder XRD pattern of
MOF-5(c) deviates significantly from the simulated pattern for MOF-5 crystal. Nitrogen
adsorption/desorption isotherms were measured by the standard volumetric method at 77K.

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The corresponding data for surface area and specific pore volume of MOF-5 materials,
synthesized by solvothermal synthesis, are shown in Table 1. The estimated surface areas and
pore specific volumes decrease in order MOF-5(a)>MOF-5(b)>MOF-5(c) with the increasing
filling rate of reaction vessel.

Table 1. SBET and pore specific volume of MOF-5 materials

Compound SBET (m2/ g) Pore specific volume(cm3/g) Filling rate of reaction vessel
MOF-5(a) 3018 1,36 0.197
MOF-5(b) 2680 1,14 0.446
MOF-5(c) 1099 0,42 0.837

In case of μwMOF-5, the estimated BET surface area and pore specific volume were 2488
m2/g and 1.53 cm3/g, respectively. In Fig. 1 are displayed the pore size distributions for MOF-
5(a) and μwMOF-5. Similar reaction mixtures under different synthetic methods lead to
different pore size distributions.

Figure 1. The MOF-5 materials pore size distribution

Conclusions
In MOFs case, the physical properties such as surface area, pore specific volume and pore
size distribution can be tailored, function of requirements, through selection of synthetic
method or reaction conditions.

Acknowledgements
The authors thank the National Authority for Scientific Research (ANCS) for granting the 22-
105/2008 PN II project.

References
[1] S. Qiu, G. Zhu, Coord. Chem. Rev. 253 (2009) 2891
[2] J. Lee, O. K. Farha, J. Roberts, K. A. Scheidt, S. T. Nguyen, J. Hupp, Chem. Soc. Rev. 38 (2009) 1450
[3] L. Ma, C. Abney, W. Lin, Chem. Soc. Rev. 38 (2009) 1248
[4] G. Blanita, D. Lupu, M. Lazar, A. R., Biris, V. Pascalau, O. Ardelean, I. Coldea, I. Misan, G. Popeneciu, M.
Vlassa, J.Phys.: Conference Serie (JPCS) 182 (2009) 012047
[5] M. Eddaudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O'Keeffe, O. M. Yaghi, Science 295 (2002) 469

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Poster presentations

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