Ordered porous materials in liquid phase catalytic reactions - - PowerPoint PPT Presentation

▶
ordered porous materials in liquid phase catalytic
SMART_READER_LITE
LIVE PREVIEW

Ordered porous materials in liquid phase catalytic reactions - - PowerPoint PPT Presentation

Nov 18, 2023 136 likes •700 views

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

slide-1
SLIDE 1

Ordered porous materials in liquid phase catalytic reactions

Towards zero leaching supports

Pascal Van Der Voort Ghent University Center for Ordered Materials, Organometallics & Catalysis

slide-2
SLIDE 2

2 Multi-scale modeling and design of chemical reactions and reactors

slide-3
SLIDE 3

3 Evolving from Performance analysis To Kinetics Based Design...

slide-4
SLIDE 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)

4

slide-5
SLIDE 5

COMOC – Center for Ordered Materials, Organometallics and Catalysis

  • Development of ordered porous materials

▫ S

ynthesis and characterization

▫ Applications in versatile fields

Low k-materials; Thin films Adsorbents for heavy metals Packing materials for HPLC Zero leaching catalysts in liquid phase reactions

5

slide-6
SLIDE 6

Spray drying mesoporous particles

6

Packing materials for HPLC

slide-7
SLIDE 7

S pray drying is robust

7

Varying spray dryer

Buchi B290, two-fluid nebulizer GEA Niro A/S Mobil Minor, rotary nozzle

Packing materials for HPLC

slide-8
SLIDE 8

8

Results - Morphology

700 eq 1400 eq 2800 eq 5600 eq 8400 eq

H2O concentration is the main factor

S pray drying is robust

Packing materials for HPLC

slide-9
SLIDE 9

HPLC evaluation

9

Results – S tability vs Packing and evaluation

Packing conditions: 30 minutes at 900 bar Measurement after 170 chromatographic runs

Packing materials for HPLC

slide-10
SLIDE 10

HPLC evaluation

10

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.

Packing materials for HPLC

slide-11
SLIDE 11

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.

11

Packing materials for HPLC

slide-12
SLIDE 12

In microelectronics industry: Low-k materials are used as insulators of interconnect wiring in computerchips

Low-k materials:

Low relative dielectric constant compared to S iO2 (k<4)

Low k-materials; Thin films

  • 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

  • rganosilicas”, Microporous and Mesoporous Materials, 2010,

131 (1­3), 68‐74. DOI

slide-13
SLIDE 13

New low-k materials:

  • Low-k value (current value 2.3)
  • Thin Films
  • Porous
  • Low polarisable
  • Hydrophobic
  • Mechanical stable

PMOs

Low k-materials; Thin films

slide-14
SLIDE 14

PMO -- What is a PMO ?

Limited commercial availability; « home made » precursors Calcination not possible, important step Functional groups in ENTIRE WALL

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 diastereoselective pure ethenylene-bridged periodic mesoporous organosilica”, Chemical Communications, 2007, 2261-2263.

slide-15
SLIDE 15

Precursors

Low k-materials; Thin films

slide-16
SLIDE 16

Formation of porous material = surfactant removal SEM HRTEM

Low k-materials; Thin films

slide-17
SLIDE 17

Influence of porogen loading on porosity

Low k-materials; Thin films

slide-18
SLIDE 18

Precursor Porosity k 58 1.96 55 1.8

Low k-materials; Thin films

slide-19
SLIDE 19

PMOs still have silanol groups -> high affinity to water => Removal of silanol groups: => Grafting with HMDS: 2SiOH + (CH3)3SiNHSi(CH3)3 -> 2SiOSi(CH3)3 + NH3

Glass PMOs Hydrophobized PMOs 33° 55° 85°

Low k-materials; Thin films

slide-20
SLIDE 20

20

Low k-materials; Thin films

Porosity k(RMPMO) k(EPMO) 32% 2.28 2.45 45% 1.95 2.12 Top contact: silver dots Bottom: Si sputtered with Pl/Ti

slide-21
SLIDE 21

Summary 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

Porosity (v%)

Low k-materials; Thin films

slide-22
SLIDE 22

Solid acid catalysis Mercury(II) ion adsorption

Adsorbents for heavy metals

PMOs as adsorbents and as catalysts

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

slide-23
SLIDE 23

Thiol containing PMOs ‐ Synthesis

Bromination with Br2 (g) Substitution with Cl‐Mg‐(CH2)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

slide-24
SLIDE 24

0.5 1 200 400 600

Va /cm

3(STP) g
  • 1

p / p0

Mercury(II) ion adsorption

  • Other mesoporous silica adsorbents

▫ One‐pot‐synthesis with –(CH2)3‐SH functionalities

  • Using this material as an

adsorbent results into:

▫ Complete loss of mesoporous structure => Hydrolysis of Si‐O‐Si bond

Before Hg2+ Adsorption After Hg2+ Adsorption

Adsorbents for heavy metals

slide-25
SLIDE 25

Mercury(II) ion adsorption

  • Other mesoporous silica adsorbents

▫ SBA‐15 functionalized with –(CH2)3‐SH (post‐synthesis)

  • Using this material as an

adsorbent results into:

▫ Loss of thiol functionalities => Hydrolysis of Si‐O‐Si bond

% SH/gram

Loss of 90%

Adsorbents for heavy metals

slide-26
SLIDE 26

Mercury(II) ion adsorption

  • Structural stability: XRD and nitrogen adsorption measurement
  • Chemical stability: No loss of thiol groups

=> Stable C‐C bond

0.5 1 150 300 450

Va /cm

3(STP) g
  • 1

p / p0

SH‐(CH2)3‐PMO After Hg2+ Adsorption PMO SH‐(CH2)3‐PMO After Hg2+ Adsorption

Adsorbents for heavy metals

slide-27
SLIDE 27

Mercury(II) ion adsorption

  • Experiments show a

1:1 ratio Hg2+/SH

10 ppm 100 ppm

Adsorbents for heavy metals

slide-28
SLIDE 28

S ulfonic functionalized periodic mesoporous organosilicas

28

Zero leaching catalysts in liquid phase reactions

slide-29
SLIDE 29

S ulfonation

E-ePMO E-ePMO SO3H-E-ePMO SO3H-E-ePMO After catalysis After catalysis

Acidity 1.19 mmol H+/ g

+ 400 + 600

29

Zero leaching catalysts in liquid phase reactions S ULFONATED PMO

slide-30
SLIDE 30

Acidic (trans)esterification

Homogeneous versus heterogeneous catalyst

  • Propanol and acetic acid
  • 90°C
  • 3 hours

=> Conversion of propanol ~ 93%

30

Zero leaching catalysts in liquid phase reactions S ULFONATED PMO

slide-31
SLIDE 31

I Pore size and pore structure engineering Swelling agent N2-Physisorption

Zero leaching catalysts in liquid phase reactions ETHENE PMO

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

slide-32
SLIDE 32

II Controlling the pore channel length and pore connectivity

Zero leaching catalysts in liquid phase reactions ETHENE PMO

  • 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.

slide-33
SLIDE 33

II Controlling the pore channel length and pore connectivity

Zero leaching catalysts in liquid phase reactions ETHENE PMO

slide-34
SLIDE 34

III Controlling the morphology

Ethanol Pentanol Butanol (medium) Butanol (high) Butanol (low) Propanol

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

  • rganosilicas with controllable properties”, Journal of Materials Chemistry,

2009, 19, 8839‐8845.

slide-35
SLIDE 35

Action points

  • Leaching stability of sulfonated groups must improve;
  • Sulfonation mechanism of ethene functions not clear;
  • Other functionalities; great prospects by a recent silyl

ester method this Columbian PhD student comes to COMOC in September:

  • @ LCT: Use different porosities, plugs, ... to study

diffusion effects in a profound way (proven concept with nanoparticles VS-1 INSIDE SBA-15) & Recent interest in “nanoMOFs” New PhD project ? FWO project ?

  • Study “added value” reaction to compete with acid
  • resins. Introduce chirality, size exclusion.

35

Zero leaching catalysts in liquid phase reactions ETHENE PMO

slide-36
SLIDE 36

S upports: inorganic & organic

Periodic mesoporous

  • rganosilica

Metal organic frameworks Porous carbon (starbons) Macroporous metallic scaffolds Phenolic resins

Redox catalysts Acid catalysts

36

S BA-15 Zero leaching catalysts in liquid phase reactions

slide-37
SLIDE 37

Mesoporous titania on macroporous titanium scaffolds

Macroporous titanium S caffold Mesoporous titania layer

1) EIS A process titanium precursor 2) Calcination

37

Zero leaching catalysts in liquid phase reactions MES OPOROUS TITANIA

slide-38
SLIDE 38

38

Titanium scaffolds

3DFD PU replica Foaming technique

Zero leaching catalysts in liquid phase reactions MES OPOROUS TITANIA

slide-39
SLIDE 39

S ynthesis optimization

  • Variation of synthesis conditions (solvent, Ti-precursor,

template … )

  • e.g. template variation:

▫ CTAB : (C16H33)N(CH3)3Br ▫ P123 : EO20PO70EO20 ▫ F127 : EO97PO69EO297

Type Template S

BET

(m² /g) Pore volume (cc/g) Pore size (nm) A CTAB 185 0,26 2,41 C P123 232 0,50 3,55 D F127 168 0,35 4,05

50 100 150 200 250 300 350 0,2 0,4 0,6 0,8 1 Volume adsorbed nitrogen (cc/g) Relative pressure (p/p0) A C D

39

Zero leaching catalysts in liquid phase reactions MES OPOROUS TITANIA

slide-40
SLIDE 40

Action points

  • Catalysts do not work well in olefinic

epoxidations, basically form peroxide adducts;

  • Test catalysts in water phase total oxidation of

phenol; they could be very suited for gas phase reactions as well. (@ LCT ?)

  • Graft V-complexes on TiO2 surface, using the

silyl ester method.

  • Graft Ti-complexes on SiO2 surfaces.

40

Zero leaching catalysts in liquid phase reactions MES OPOROUS TITANIA

slide-41
SLIDE 41

Metal Organic Frameworks (MOFs)

  • Metal ions are linked by organic ligands
  • 3 dimensional network
  • Microporosity
  • High metal content
  • Rigid structure
  • Ligand coordination

influences electronic properties

41

Zero leaching catalysts in liquid phase reactions MOF

slide-42
SLIDE 42

MOFs

Metal ions Linkers Cu2+ V4+ Zn2+ Co2+ Ni2+ Ag+ Cd2+ Cr3+

42

Zero leaching catalysts in liquid phase reactions MOF

slide-43
SLIDE 43

V-MOF : synthesis

  • S

imple synthesis: VCl3/ terephthalic acid/ H2O 4 days, 200° C (autoclave) Calcination: 22h30 min, 300° C

  • Formula: VIVO{O2C-C6H4-CO2}

43

Zero leaching catalysts in liquid phase reactions MOF

slide-44
SLIDE 44

Catalytic performance (MIL-47)

Oxidans: TBHP in H2O S

  • lvent: Chloroform

Temperature: 50° C

VO(acac)2 MIL-47 VOx/ S iO2 VAPO-5

Chloroform TBHP , 50° C

44

Zero leaching catalysts in liquid phase reactions MOF

  • Karen Leus, Ilke Muylaert, Matthias

Vandichel, Guy B Marin, Michel Waroquier, Veronique Van Speybroeck and Pascal Van Der Voort, “The remarkable catalytic activity of the Saturated Metal Organic Framework V‐ MIL‐47 in the cyclohexene oxidation”, Chemical Communications, 2010,

DOI:10.1039/C0CC01506G.

slide-45
SLIDE 45

Reaction mechanism

VO(acac)2 V-MOF (MIL-47)

45

Zero leaching catalysts in liquid phase reactions MOF

slide-46
SLIDE 46

Regenerability : V-MOF

46

Zero leaching catalysts in liquid phase reactions MOF

slide-47
SLIDE 47

Action points

  • V-MOF synthesis from vanadium(III)-oxo acetic

clusters; avoid decavanadates ! (bottom up)

  • V-ZIF(zeolitic imidazolate framework) synthesis
  • Chiral, enantioselective catalysis: oxidation of

sulfides to sulfoxides.

47

N N T T

β (T-Imidazole-T) ~147 ˚

Zero leaching catalysts in liquid phase reactions MOF

slide-48
SLIDE 48

Mesoporous resins

48

P/ F resins ALD depositions

  • Ilke Muylaert, Marijke Borgers, Els Bruneel, Joseph

Schaubroeck, Francis Verpoort and Pascal Van Der Voort, “Ultra stable ordered mesoporous phenol/formaldehyde polymers as a heterogeneous support for vanadium

  • xide”, Chemical Communications, 2008, 4475‐4477
slide-49
SLIDE 49

Controlling the porosity

A B C D

49

P/ F resins ALD depositions

slide-50
SLIDE 50

Leaching behaviour

50

  • Comparison of leaching behaviour of

VOx/SiO vs VOx/Resin

  • S

tirring in water at 80° C

  • S

tirring in 2.5M H2S O4 at 80° C

  • VOx/ resins are currently

under investigation for their catalytic activity

P/ F resins ALD depositions

slide-51
SLIDE 51

S upported TiO2/ S BA-15: synthesis

51

Atomic layer deposition:

  • sequential exposure to a

volatile metal precursor and a reactive gas

  • self-limitingly
  • controlled deposition
  • uniform layers

P/ F resins ALD depositions

slide-52
SLIDE 52

Rotatable powder reactor

52

P/ F resins ALD depositions

slide-53
SLIDE 53

Actions points

  • Cheap, easy producable, highly stable bakelite

resins as catalytic support

  • But... Only low to moderate activity of supported

TiOx and VOx layers !

  • Controlled ALD of resin-V-O-Ti-O-V...
  • Alternative activation of the resins:

▫ Sulfonation – catalytic tests in progress ▫ Metal complexes ? ▫ Noble metals ? Reduction reactions.

53

slide-54
SLIDE 54

General remarks

  • Some nice materials, generally appreciated and COMOC is starting

to become known as center of expertise in synthesis of “new” porous materials (COMOC is founded in 2007)

  • Our materials also used in collaboration in

▫ Dentistry (University Hospital) ▫ Pesticides (bio-engineers – adsorption and controlled release)

  • Need to adapt processes to cost and advanced level of the materials

themselves ▫ High end reactions, selectivity, chirality ▫ Sensors, catalysts ▫ Stability can compensate for cost

54

slide-55
SLIDE 55

COMOC -- April 2010

55