Pascal Van Der Voort Ghent University Center for Ordered Materials, Organometallics & Catalysis Ordered porous materials in liquid phase catalytic reactions Towards zero leaching supports
2 Multi-scale modeling and design of chemical reactions and reactors
3 Evolving from Performance analysis To Kinetics Based Design...
4 Methusalem – formal and informal • Formal: 1 PhD student (+ benchfee) ▫ Working on catalytic activity of MOFs • Informal ▫ Collaboration on acid catalysis (transesterification reactions, modelling) ▫ Use of infrastructure (GC-GC/MS, ammonia ads) ▫ Preparing joint research projects (JT @ FWO; possibly @IWT) ▫ Copromotorships in PhDs & mastertheses (starting 2010)
5 COMOC – Center for Ordered Materials, Organometallics and Catalysis • Development of ordered porous materials ▫ S ynthesis and characterization ▫ Applications in versatile fields Adsorbents Low k-materials; for heavy metals Thin films Packing materials Zero leaching catalysts in for HPLC liquid phase reactions
6 Spray drying mesoporous particles Packing materials for HPLC
7 Packing materials for HPLC S pray drying is robust Varying spray dryer Buchi B290, two-fluid GEA Niro A/S Mobil Minor, rotary nebulizer nozzle
8 Packing materials for HPLC S pray drying is robust Results - Morphology 700 eq 1400 eq 2800 eq 5600 eq 8400 eq H 2 O concentration is the main factor
9 Packing materials for HPLC HPLC evaluation Results – S tability vs Packing and evaluation Packing conditions: 30 minutes at 900 bar Measurement after 170 chromatographic runs
10 Packing materials for HPLC HPLC evaluation Results – Chromatographic performance A, B: Analysis of a mixture containing uracil (1), 1-phenyl-1-ethanone (2), 1- phenyl-1-butanone (3), 1-phenyl-1- pentanone (4), 1-phenyl-1-hexanone (5), 1-phenyl-1-heptanone (6), 1- phenyl-1-octanone (7), 1-phenyl-1- decanone (8) and 1-phenyl-1- dodecanone (9) (50 µg/mL each); C: Analysis of a mixture of uracil (1, 50 µg/mL), benzene (2, 80 µg/mL), naphthalene (3, 50 µg/mL), antracene (4, 300 µg/mL), fluoranthene (5, 50 µg/mL), benzo[k]fluoranthene (6, 300 µg/mL); D: Analysis of a mixture containing uracil (1), methyl-4- hydroxybenzoate (2), ethyl-4- hydroxybenzoate (3), propyl-4- hydroxybenzoate (4) and butyl-4- hydroxybenzoate (5) (50 µg/mL each). The flow rate was 0.2 ml/min in A and 0.3 mL/min in B,C and D.
11 Packing materials for HPLC Action points • Back pressure is not reduced to the expected level • Shift attention to ▫ CEC (Capilary Electro Chromatography) - Excellent preliminary results by coating open tubular columns with mesoporous layer; ▫ Spraydrying of hybrid materials (PMOs) ▫ Lab on a chip – Collaboration VUB – Work in Progress.
Low k-materials; Thin films Low-k materials: Low relative dielectric constant compared to S iO 2 (k<4) In microelectronics industry: Low-k materials are used as insulators of interconnect wiring in computerchips •Frederik Goethals, Benjamin Meeus, An Verberckmoes, Pascal Van Der Voort and Isabel Van Driessche, “Hydrophobic high quality ring PMOs with an extremely high stability”, Journal of Materials Chemistry, 2010, 20 (9) , 1709‐1716. •Frederik Goethals, Carl Vercaemst, Veerle Cloet, Serge Hoste, Pascal Van Der Voort and Isabel Van Driessche, “Comparative study of ethylene and ethenylene‐bridged periodic mesoporous organosilicas”, Microporous and Mesoporous Materials, 2010, 131 (1 3) , 68‐74. DOI
Low k-materials; Thin films New low-k materials: • Low-k value (current value 2.3) • Thin Films PMOs • Porous • Low polarisable • Hydrophobic •Mechanical stable
Low k-materials; Thin films Carl Vercaemst, Matthias Ide, Bart Allaert, Nele Ledoux, Francis Verpoort and Pascal Van Der Voort, “Ultra-fast hydrothermal synthesis of PMO -- What is a PMO ? diastereoselective pure ethenylene-bridged periodic mesoporous organosilica”, Chemical Communications, 2007 , 2261-2263. Calcination not possible, important step Limited commercial availability; « home made » precursors Functional groups in ENTIRE WALL
Precursors Low k-materials; Thin films
Low k-materials; Thin films Formation of porous material = surfactant removal SEM HRTEM
Low k-materials; Thin films Influence of porogen loading on porosity
Low k-materials; Thin films Precursor Porosity k 58 1.96 55 1.8
Low k-materials; Thin films PMOs still have silanol groups -> high affinity to water => Removal of silanol groups: => Grafting with HMDS: 2SiOH + (CH 3 ) 3 SiNHSi(CH 3 ) 3 -> 2SiOSi(CH 3 ) 3 + NH 3 33° 85° 55° Glass PMOs Hydrophobized PMOs
20 Low k-materials; Thin films Top contact: silver dots Bottom: Si sputtered with Pl/Ti Porosity k(RMPMO) k(EPMO) 32% 2.28 2.45 45% 1.95 2.12
Low k-materials; Summary Thin films Porosity (v%) Finding optimum between k value and Young Modulus is crucial: ⇒ HMDS treated PMOs have a high young modulus and low- k value Close collaboration with IMEC for further implementation
Adsorbents for heavy metals PMOs as adsorbents and as catalysts Solid acid Mercury(II) ion catalysis adsorption Els De Canck, Linsey Lapeire, Jeriffa De Clerq, Francis Verpoort and Pascal Van Der Voort, "A new Ultra Stable Mesoporous Adsorbent for the Removal of Mercury", Langmuir, 2010, 26(12), 10076-10083, DOI: 10.1021/la100204d
Adsorbents for heavy metals Thiol containing PMOs ‐ Synthesis Bromination with Br 2 (g) Substitution with Cl ‐ Mg ‐ (CH 2 ) 3 ‐ SH •Els De Canck, Linsey Lapeire, Jeriffa De Clerq, Francis Verpoort and Pascal Van Der Voort, "A new Ultra Stable Mesoporous Adsorbent for the Removal of Mercury", Langmuir, 2010, DOI: 10.1021/la100204d
Adsorbents for heavy metals Mercury(II) ion adsorption • Other mesoporous silica adsorbents ▫ One ‐ pot ‐ synthesis with –(CH 2 ) 3 ‐ SH functionalities 600 • Using this material as an adsorbent results into: Before Hg 2+ ▫ Complete loss of mesoporous Adsorption 400 -1 3 (STP) g structure V a /cm 200 After Hg 2+ => Hydrolysis of Si ‐ O ‐ Si bond Adsorption 0 0 0.5 1 p / p 0
Adsorbents for heavy metals Mercury(II) ion adsorption • Other mesoporous silica adsorbents ▫ SBA ‐ 15 functionalized with –(CH 2 ) 3 ‐ SH (post ‐ synthesis) % SH/gram • Using this material as an Loss of 90% adsorbent results into: ▫ Loss of thiol functionalities => Hydrolysis of Si ‐ O ‐ Si bond
Adsorbents for heavy metals Mercury(II) ion adsorption • Structural stability: XRD and nitrogen adsorption measurement • Chemical stability: No loss of thiol groups => Stable C ‐ C bond 450 After Hg 2+ Adsorption 300 SH ‐ (CH 2 ) 3 ‐ PMO -1 3 (STP) g SH ‐ (CH 2 ) 3 ‐ PMO V a /cm After Hg 2+ 150 Adsorption PMO 0 0 0.5 1 p / p 0
Adsorbents for heavy metals Mercury(II) ion adsorption • Experiments show a 1:1 ratio Hg 2+ /SH 100 ppm 10 ppm
28 Zero leaching catalysts in liquid phase reactions S ulfonic functionalized periodic mesoporous organosilicas
29 Zero leaching catalysts in liquid phase reactions S ULFONATED PMO S ulfonation After catalysis + 600 After catalysis SO 3 H-E-ePMO + 400 E-ePMO SO 3 H-E-ePMO E-ePMO Acidity 1.19 mmol H + / g
30 Zero leaching catalysts in liquid phase reactions S ULFONATED PMO Acidic (trans)esterification Homogeneous versus heterogeneous catalyst - Propanol and acetic acid - 90 ° C - 3 hours => Conversion of propanol ~ 93%
Zero leaching catalysts in liquid phase reactions ETHENE PMO I Pore size and pore structure engineering N 2 -Physisorption Swelling agent Carl Vercaemst, Bart Goderis, Petra E. de Jongh, Johannes D. Meeldijk, Francis Verpoort and Pascal Van Der Voort, Ethenylene-bridged periodic mesoporous organosilica foams with ultra-large mesopores, Chemical Communication, 2009, 4052-4054
Zero leaching catalysts in liquid phase reactions ETHENE PMO II Controlling the pore channel length and pore connectivity •Carl Vercaemst, Heiner Friedrich, Petra de Jongh, Alexander Neimark, Bart Goderis, Francis Verpoort, Pascal Van Der Voort, Periodic mesoporous organosilicas consisting of 3D hexagonally ordered interconnected globular pores”, Journal of Physical Chemistry C, 2009 , 113 , 5556‐5562.
Zero leaching catalysts in liquid phase reactions ETHENE PMO II Controlling the pore channel length and pore connectivity
Zero leaching catalysts in liquid phase reactions ETHENE PMO •Carl Vercaemst, Matthias Ide, Heiner Friedrich, Krijn P. de Jong, Francis Verpoort and Pascal Van Der Voort, “Isomeric periodic mesoporous organosilicas with controllable properties”, Journal of Materials Chemistry, 2009 , 19 , 8839‐8845. III Controlling the morphology Butanol (medium) Ethanol Pentanol Propanol Butanol (low) Butanol (high)
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