Preparation and characterization of novel layer-structured metal catalysts, applications in heterogeneous catalitic reactions  Page description

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Details of project

 
Identifier
47390
Type K
Principal investigator Mastalir, Ágnes
Title in Hungarian Új típusú, rétegszerkezetű fémkatalizátorok előállítása, jellemzése és alkalmazása heterogén katalitikus reakciókban
Title in English Preparation and characterization of novel layer-structured metal catalysts, applications in heterogeneous catalitic reactions
Panel Chemistry 1
Department or equivalent Department of Organic Chemistry (University of Szeged)
Participants Dékány, Imre
Király, Zoltán
Papp, Attila
Starting date 2004-01-01
Closing date 2008-12-31
Funding (in million HUF) 5.248
FTE (full time equivalent) 0.00
state closed project





 

Final report

 
Results in Hungarian
Új szintézismódszereket dolgoztunk ki kationos tenziddel stabilizált, szabályozott méretű Pd és Pt nanorészecskék előállítására rétegszerkezetű agyagásványokban és mezopórusos hordozókban. A minták szerkezetét röntgendiffrakcióval és elektronmikroszkópos vizsgálatokkal tanulmányoztuk, katalitikus tulajdonságaikat folyadékfázisú hidrogénezési reakciókban vizsgáltuk. Pd katalizátorokon főként sztereoszelektív átalakulásokat tanulmányoztunk, Pt katalizátorokon kemoszelektív és enantioszelektív reakciókat is végrehajtottunk. A fenti reakciókban a minták nagymértékben aktív és szelektív katalizátoroknak bizonyultak. MCM-41 alapú katalizátorokra kimutattuk, hogy a mezopórusokban elhelyezkedő fémrészecskék katalitikusan aktívak, ezért a minták alakszelektív tulajdonsággal rendelkeznek. A fenti szintézismódszerek alapján monodiszperz Pd nanorészecskéket állítottunk elő rétegszerkezetű grafit-oxid hordozóban. A jelentős rétegközti fémtartalommal rendelkező Pd/grafit-oxid minták belső alkinek hidrogénezési reakcióiban kimagasló katalitikus aktivitást és cisz-alkén sztereoszelektivitást mutattak. Hordozós Pd katalizátorok folyadékfázisú diszperzitásának meghatározására új kísérleti módszert dolgoztunk ki, amely folyadékkromatográfiás vizsgálatokon alapul. Királis kationos tenzidet immobilizáltunk montmorillonit agyagásványon, tanulmányoztuk a minta szerkezetét, duzzadóképességét és katalitikus tulajdonságait benzaldehid dietil-cinkkel végzett enantioszelektív alkilezési reakciójában.
Results in English
Novel synthesis methods, based on the application of cationic surfactants as stabilizers, have been developed for the generation of Pd and Pt nanoparticles of controlled crystallite size in layer-structured clay minerals and mesoporous materials. Structural characterization was performed by X-ray diffraction and transmission electron microscopy. The catalytic performances of the samples were tested in liquid-phase alkene and alkyne hydrogenations. For Pd nanoparticles, mostly stereoselective reactions were studied, whereas for Pt particles, chemoselective and enantioselective reactions were also investigated. Most of the samples proved to be highly active and selective catalysts. Further, Pd and Pt nanoparticles immobilized in the mesopores of MCM-41 were found to be shape selective catalysts. The above synthesis procedure was extended to the preparation of monodispersed Pd nanoparticles in graphite oxide. The Pd/graphite-oxide materials, which contained a significant amount of intercalated metal particles, exhibited outstanding catalytic activities and Z-alkene stereoselectivities for the hydrogenations of internal alkynes. A novel experimental method, liquid chromatography, has been developed for determination of the liquid-phase dispersion of supported Pd catalysts. A chiral cationic surfactant was immobilized in montmorillonite and investigated as a heterogeneous catalyst for the enantioselective alkylation of benzaldehyde with diethylzinc.
Full text http://real.mtak.hu/1769/
Decision
Yes





 

List of publications

 
Z. Király, Á. Mastalir, G.H. Findenegg: Chain-length anomaly in the two-dimensional ordering of the cationic surfactants CnTAB at the graphite/water interface, Calorimetry and Thermal Effects in Catalysis (CTEC), Villeurbanne, Lyon, July 6-9, 2004, Book of Abstracts, P 17 (poszter)., 2004
Z. Király, Á. Mastalir, G.H. Findenegg: Adsorption at solid/solution interfaces studied by advanced calorimetric methods, Calorimetry and Thermal Effects in Catalysis (CTEC), Villeurbanne, Lyon, July 6-9, 2004, Book of Abstracts, O 19 (előadás)., 2004
Z. Király, B. Veisz, Á. Mastalir: CS2 poisoning of size-selective cubooctahedral Pd particles in styrene hydrogenation, Catal. Lett. 95, 57, 2004
B. Veisz, B. Pécz, L. Tóth, Z. Király, Á. Mastalir: Size-quantized cubooctahedral palladium particles: structural and catalytic investigations, 18th Conference of the European Colloid and Interface Society, Almeria, 19-24 September 2004, Book of Abstracts, P 7.08 (poszter)., 2004
A. Papp, Á. Mastalir, Z. Király: Synthesis and catalytic applications of Pd nanoparticles in layered double hydroxides, 2nd Szeged International Workshop on Advances in Nanoscience, Szeged, 30 September - 2 October 2004, Book of Abstracts, P 8 (poszter)., 2004
B. Veisz, Z. Király, Á. Mastalir: Structural and catalytic investigation of size-quantized cubooctahedral Pd particles, 2nd Szeged International Workshop on Advances in Nanoscience, Szeged, 30 September - 2 October 2004, Book of Abstracts, P 13 (poszter)., 2004
A. Schmidt, Á. Mastalir, R. Schomäcker: Kinetische Untersuchungen zur partiellen Hydrierung von Phenylacetylen und Geraniol im Membranreaktor im Vergleich mit anderen Katalysatorsystemen, XXXVIII. Jahrestreffen Deutscher Katalytiker, 16-18 March 2005, Weimar, Book of Abstracts, P 30., 2005
A. Papp, Á. Mastalir, P. Forgó, Á. Molnár: Preparation of novel Pd-MCM catalysts, characterization and application in organic reactions, 19th North American Catalysis Society Meeting, Philadelphia, 22-27 May 2005, Book of Abstracts, O-247 (előadás)., 2005
Á. Mastalir, Z. Király: Liquid-phase semihydrogenations of alkynes on Pd-montmorillonite catalysts with controlled Pd particle size, 19th North American Catalysis Society Meeting, Philadelphia, 22-27 May 2005, Book of Abstracts, P-202 (poszter)., 2005
Z. Király, Á. Mastalir, G. H. Findenegg: Pulsed-flow calorimetry: a versatile tool for the study of nonreversible adsorption phenomena at solid/solution interfaces, Russian International Conference on Chemical Thermodynamics, Moscow, 27 June- 2 July, 2005, Book of Abstracts, OV-19 (előadás)., 2005
Z. Király, Á. Mastalir, G.H. Findenegg: Two-dimensional ordering of the cationic surfactants CnTAB at the graphite/water interface studied by advanced calorimetric methods, Russian International Conference on Chemical Thermodynamics, Moscow, 27 June- 2 July, 2005, Book of Abstracts, PV-76 (poszter)., 2005
Á. Mastalir, Z. Király, I. Dékány: Controlled colloid synthesis of Pd nanoparticles by using a cationic surfactant stabilizer, 19th Conference of the European Colloid and Interface Society, Geilo, 18-23 September 2005, Book of Abstracts, P6.3. (poszter)., 2005
Á. Mastalir, Z. Király, I. Dékány: Generation of nanosized Pd clusters in layered double hydroxides and application in hydrogenation reactions, 19th Conference of the European Colloid and Interface Society, Geilo, 18-23 September 2005, Book of Abstracts, P6.4. (poszter)., 2005
Z. Király, Á. Mastalir, G. Findenegg: Pulsed-flow calorimetry: a versatile tool for the study of nonreversible adsorption phenomena at solid/solution interfaces, International Chemical Congress of Pacific Basin Societies (Pacifichem), Honolulu, Hawaii, 15-20 December 2005, O-904, Book of Abstracts, p. 143. (előadás)., 2005
A. Papp, Á. Mastalir, Á. Molnár: Heck coupling and semi-hydrogenations of alkynes over supported Pd catalysts, 5th International Conference of PhD students, Miskolc, 14-20 August 2005, Poster, Book of Abstracts, p. 381. (poszter)., 2005
Á. Mastalir, Z. Király, I. Dékány: Pd nanoparticles in hydrotalcite as highly selective catalysts for alkyne hydrogenation, International Chemical Congress of Pacific Basin Societies (Pacifichem), Honolulu, Hawaii, 15-20 December 2005, P 1457, Book of Abstracts, p. 99. (poszter)., 2005
Á. Mastalir, Á. Patzkó, B. Frank, R. Schomacker, T. Ressler, R. Schlögl:: Steam reforming of methanol over Cu/ZnO/Al2O3 modified with hydrotalcites, Catal. Commun. 8, 1684, 2007
Á. Mastalir, B. Rác, Z. Király, Á. Molnár, I. Dékány:: In situ generation of Pd nanoparticles in MCM-41, 3rd Zsigmondy Colloquium, Berlin, 6-7 April 2006, O 21, Book of Abstracts, p. 37., 2006
A. Papp, Á. Mastalir, Á. Molnár, Z. Király:: Novel synthesis methods for Pd/MCM-41 and Pd/SBA-15 catalysts, applications in Heck coupling and selective hydrogenation reactions, 3rd Zsigmondy Colloquium, Berlin, 6-7 April 2006, P 41, Book of Abstracts, p. 85., 2006
A.B. Páhi, D. Varga, Z. Király, Á. Mastalir, I. Dékány:: Characterization of a cationic chiral surfactant by conductometric titration, surface tension measurements, titration microcalorimetry and X-ray diffraction measurements, 3rd Zsigmondy Colloquium, Berlin, 6-7 April 2006, P 39, Book of Abstracts, p. 83., 2006
Á. Mastalir, Z. Király, I. Dékány:: Application of low-loaded Pd-hydrotalcites as catalysts for alkyne semihydrogenation, Fifth Tokyo Conference on Advanced Catalytic Science and Technology (TOCAT 5), Tokyo, 23-28 July 2006, P-123, Book of Abstracts, p. 174., 2006
Á. Mastalir, B. Rác, Z. Király, Á. Molnár:: Preparation and characterization of novel Pd-MCM-41 catalysts, Fifth Tokyo Conference on Advanced Catalytic Science and Technology (TOCAT 5), Tokyo, 23-28 July 2006, P-127, Book of Abstracts, p. 178., 2006
Á. Császár, Á. Mastalir, Z. Király, H. Demir, D. Üner:: Determination of metal dispersion by various instrumental techniques, 20th Conference of the European Colloid and Interface Society and 18th European Chemistry at Interfaces Conference, Budapest, 17-22 September, 2006, P-5.10., 2006
Á. Mastalir, B. Rác, Z. Király, Á. Molnár, I. Dékány:: Controlled colloid synthesis and catalytic application of palladium nanoparticles in MCM-41, 20th Conference of the European Colloid and interface Society and 18th European Chemistry at Interfaces Conference, Budapest, 17-22 September, 2006, P-5.15., 2006
Z. Király, Á. Mastalir, G.H. Findenegg:: Pulsed-flow calorimetry: a versatile tool for the study of non-reversible adsorption phenomena at solid/solution interfaces, 12th International Conference on Surface and Colloid Science, 15-20 October 2006, Beijing, O1-36, Book of Abstracts, p. 31., 2006
Á. Mastalir, Á. Császár, Z. Király:: Liquid-phase dispersion measurement of supported Pd particles by liquid chromatography and pulsed-flow adsorption microcalorimetry, 12th International Conference on Surface and Colloid Science, 15-20 October 2006, Beijing, O3-20, Book of Abstracts, p. 115., 2006
D. Varga, A.B. Páhi, Z. Király, Á. Császár, Á. Mastalir:: Thermodynamics of the micelle formation of the chiral surfactant dodecylmethylephedrinium bromide, 20th Conference of the European Colloid and interface Society and 18th European Chemistry at Interfaces Conference, Budapest, 17-22 September, 2006, P-3.25., 2006
Á. Mastalir, Z. Király, Á. Patzkó, I. Dékány:: Synthesis and catalytic application of Pd nanoparticles in graphite oxide, Carbon (közlésre beküldve), 2008
Á. Mastalir, Z. Király:: Liquid-phase dispersion measurement of supported Pd catalysts by liquid chromatography, XIII. International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC XIII), 16-20 July 2007, Berkeley, O 28, Book of Abstracts, p. 60., 2007
Á. Mastalir, Z. Király, M. Benkő, I. Dékány:: Graphite oxide: a novel host material for transition metal nanoparticles, XIII. International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC XIII), 16-20 July 2007, Berkeley, P-109, Book of Abstracts, p. 185., 2007
Z. Király, Á. Mastalir: Immobilization of (1R,2S)-(-)-N-dodecyl-N-methylephedrinium bromide and its catalytic application in the enantioselective alkylation of benzaldehyde with diethylzinc, XIII. International Symposium on Relations between Homogeneous and Heterogeneous Catalysis (ISHHC XIII), 16-20 July 2007, Berkeley, P-110, Book of Abstracts, p. 186., 2007
Á. Mastalir, Z. Király, I. Dékány: Synthesis of monodispersed Pd nanoparticles in graphite oxide, a novel host material, 21st Conference of the European Colloid and Interface Society (ECIS), 10-14 September 2007, Geneva, P 3.B.3, Book of Abstracts, p. 329., 2007
Á. Mastalir, Z. Király: Determination of the dispersion of supported palladium particles by liquid chromatography, 9th Conference on Colloid Chemistry, 3-5 October 2007, Siófok, O2, Book of Abstracts, p. 20., 2007
Á. Mastalir, Á. Patzkó, Z. Király, B. Frank, R. Schomäcker: Modification of a supported copper catalyst with hydrotalcites, 9th Conference on Colloid Chemistry, 3-5 October 2007, Siófok, P 39, Book of Abstracts, p. 127., 2007
Á. Mastalir, Z. Király, M. Benkő, I. Dékány: Preparation of monodispersed Pd nanoparticles in graphite oxide, a novel host material, 9th Conference on Colloid Chemistry, 3-5 October 2007, Siófok, P 40, Book of Abstracts, p. 128., 2007
Á. Mastalir, Z. Király, F. Berger:: Comparative study of size-quantized Pd-montmorillonite catalysts in liquid-phase semihydrogenations of alkynes, Appl. Catal. A: Gen. 269, 161, 2004
R.T.K. Baker, N. Rodriguez, Á. Mastalir, U. Wild, R. Schlögl, A. Wootsch, Z. Paál: Platinum/graphite nanofiber catalysts of various structure: characterization and catalytic properties, J. Phys. Chem. B 108(38), 14348, 2004
A. Papp, Á. Molnár, Á. Mastalir: Catalytic investigation of Pd particles supported on MCM-41 for the selective hydrogenations of terminal and internal alkynes, Appl. Catal. A: Gen. 289, 256, 2005
Gy. Szöllősi, Á. Mastalir, Z. Király, I. Dékány: Preparation of Pt nanoparticles in the presence of a chiral modifier and catalytic applications in chemoselective and asymmetric hydrogenations, J. Mater. Chem. 15, 2464, 2005
Z. Király, G.H. Findenegg, Á. Mastalir:: Adsorption of dodecyltrimethylammonium bromide and sodium bromide on gold studied by liquid chromatography and flow adsorption microcalorimetry, Langmuir 22, 3207, 2006
Á. Mastalir, B. Rác, Z. Király, Á. Molnár:: In situ generation of Pd nanoparticles in MCM-41 and catalytic applications in liquid-phase alkyne hydrogenations, J. Mol. Catal. A:Chem. 264, 170, 2007
Z. Király, Á. Mastalir, Á. Császár, H. Demir, D. Üner, G.H. Findenegg:: Liquid chromatography as a novel method for determination of the dispersion of supported Pd particles, J. Catal. 245, 265, 2007
Á. Mastalir, B. Rác, Z. Király, G. Tasi, Á. Molnár:: Preparation of monodispersed Pt nanoparticles in MCM-41, catalytic applications, Catal. Commun. 9, 762, 2008
Á. Mastalir, Z. Király:: Catalytic investigation of (1R,2S)-(-)-N-dodecyl-N-methylephedrinium bromide immobilized on montmorillonite in the enantioselective alkylation of benzaldehyde with diethylzinc, Catal. Commun. 9, 1404, 2008
A.B. Páhi, Z. Király, D. Varga, Á. Mastalir:: Thermodynamics of micelle formation of the ephedrine-based chiral cationic surfactant DMEB in water, and the intercalation of DMEB in montmorillonite, Colloids Surfaces A (nyomdában), 2008




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