Metal-organic frameworks in heterogeneous catalysis Catalysis - - PowerPoint PPT Presentation

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Metal-organic frameworks in heterogeneous catalysis Catalysis - - PowerPoint PPT Presentation

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WIR SCHAFFEN WISSEN HEUTE FR MORGEN Dr. Marco Ranocchiari :: Syncat Group Leader - LSK :: Paul Scherrer Institut Metal-organic frameworks in heterogeneous catalysis Catalysis Lecture 2017 ETH Zurich Catalysis: Heterogeneous vs

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SLIDE 1

WIR SCHAFFEN WISSEN – HEUTE FÜR MORGEN

Metal-organic frameworks in heterogeneous catalysis

  • Dr. Marco Ranocchiari :: Syncat Group Leader - LSK :: Paul Scherrer Institut

Catalysis Lecture 2017 ETH Zurich

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SLIDE 2

Catalysis: Heterogeneous vs Homogeneous vs Enzymatic

2

Heterogeneous Enzymatic
 Homogeneous

Engineering flexibility Chemical flexibility Chemical control Selectivity

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SLIDE 3

... Some acronym

M O F

3

P C P e
 t
 a
 l r
 g
 a
 n i c r
 a
 m
 e w

  • r

k

r


u s

r
 d i n a t i

  • n

l
 y
 m e r 1) Metal 2) Organic 3) Polymer 4) Well defined structure 5) Can be porous

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SLIDE 4
  • Coordination polymers: 1950-1960.
  • Pioneer work on porous coordination polymers: 1990-1995

by Feréy and Johnson.

  • The Boost: 1999 by Yaghi (MOF-5).
  • H. Li, M. Eddaoudi, M. O'Keeffe and O. M. Yaghi, Nature,

1999, 402, 276-279.

  • Exponential growth of the 


number of publications over
 the last decade

4

History

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SLIDE 5

MOF-5

5

Organic BB

O O O O

Inorganic Unit

Zn O Zn Zn Zn

6+

Zn O O Zn O

Features

  • Self assembly synthesis (Solvothermal)
  • Surface area >3000 m2/g
  • Thermal stability: up to 300 °C
  • Stable upon guest molecules removal
  • Size of the cavity ∼12 Å

Structure

MOF-5

  • H. Li, M. Eddaoudi, M. O'Keeffe and O. M. Yaghi, Nature, 1999, 402, 276-279.
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SLIDE 6

ISORETICULARITY AND CAVITY DESIGN

Zn O Zn Zn Zn

6+

FIXED

O O O O

Linear Geometry

Organic BB Cavity Size

O O O O O O O O O O O O

15.4 Å Name IRMOF-10 IRMOF-14 IRMOF-16 13.8 Å 19.1 Å

  • M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O'Keeffe and O. M. Yaghi, Science, 2002, 295, 469-472.

6

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SLIDE 7

ISORETICULARITY AND FUNCTIONALIZATION

MOF-5 or IRMOF-1 cavity size = 11.8 Å

Organic BB Cavity Size

O O O O Zn O Zn Zn Zn

6+

FIXED Linear Geometry

9.6 Å Name IRMOF-3 IRMOF-4 5.8 Å

  • M. Eddaoudi, J. Kim, N. Rosi, D. Vodak, J. Wachter, M. O'Keeffe and O. M. Yaghi, Science, 2002, 295, 469-472.

O O O O NH2

O O O O O O 7

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SLIDE 8

MIXMOFS

  • Mixing of different organic building blocks into the MOF

8

Inorganic Unit

Zn O Zn Zn Zn

6+

Zn O O Zn O

  • H. Deng, C. J. Doonan, H. Furukawa, R. B. Ferreira, J. Towne, C. B. Knobler, B. Wang and O. M. Yaghi, Science, 2010, 327, 846-850.

Organic BB

O O O O O O O O NH2 O O O O Br

Structure

MIXMOF or MTV-MOF

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SLIDE 9

MOFs Chemical and Structural Flexibility

9

REFERENCE TOPOLOGY isoreticular chemistry pore tuning mixMOF chemistry multiple functions isoreticular chemistry introducing functional groups

Eddaoudi, M. Science 2002, 469. Deng, H. Science 2010, 846.

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SLIDE 10

MOFs Chemical and Structural Flexibility

10

[Zr6(OH)4O4]12+ [M2(H2O)]n2n+

M = Co2+,Mn2+,Ni2+,Mg2+

[M3X(O)]6+

M = Cr3+, Fe3+, Al3+ X = F, Cl, OH-

MIL-101 UiO-66 MOF-74

Ferey, G. Science 2005, 2040. Cavka, J. JACS 2008, 13850. Rosi, N. L. JACS 2005, 1504.

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SLIDE 11

MOFs as catalytic materials

11

  • solid
  • fine tunable
  • well-defined structure
  • active site resembling the

pocket of an enzyme

≡ +

  • Engineering flexibility
  • Chemical flexibility
  • Chemical control at 


the atomic level

  • Selectivity

[Zn4O]6+

MOF-5

Yaghi O. M. Nature 1999, 276.

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SLIDE 12

Post-synthetic Modification

12 Entry Parent MOF Functionalizing group Reactant Product Yield (%) 1 IRMOF-3

O O M M O O M M NH2 M= Zn, Zr, Gd, Al !

!

R O O O R

!

O O M M O O M M N H R O

>80a (R= CH3) 2

  • N. a. (R= CH=CHCH3)

3 89a (R= (CH2)4CH3) 4 70a (R= C6H5) 5 46a (R= NHC6H5) 6 DMOF-1 64a (R= C6H5) 7 UMCM-1 77a (R= C6H5) 8 UiO-66 88 (R= CH3) 9 92b (R= CH3) 10 50 (R= (CH2)3CH3) 11 61b (R= (CH2)3CH3) 12 25 (R= (CH2)6CH3) 13 25 (R= CH=CH-COOH) 14 34b (R= CH=CH-COOH) 15 IRMOF-3

R H O

!

O O M M O O M M N R H

13 (R = 2-OH-C6H4) 16 3a (R = 2-OH-C6H4) 17 >99b (R = 2-OH-C6H4) 18 67 (R = CH3) 19 MIXMOF-5 >99b (R = 2-OH-C6H4) 20 UMCM-1 87 (R= C5H4N) 21 UiO-66 10 (R = 2-OH-C6H4) 22 29b (R = 2-OH-C6H4) 23 IRMOF-3

R N C O

!

O O M M O O M M N H NHR O

99(R= Si(CH3)3) 24

  • N. r. (R= C(CH3)3)

25 71 (R= CH2CH3) 26 60 (R= (CH2)2CH3) 27 51 (R= (CH2)4CH3) 28 75 (R= CH2CH=CH2) 29 53 (R= C6H5) 30 27 (R= C6H11)

a conversion of amino containing MOF b vapor-phase post-synthetic modification (VP-PSM)

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SLIDE 13

Post-synthetic Modification

13

Entry Parent MOF Functionalizing group Reactant Product Yield (%) 1 IRMOF-16

O O Zn Zn N3 N3 R O O Zn Zn R= N N N N R N N R O O

  • N. a.

2 DMOF-1

M= Zn, In O O M M O O M M N3 R O O M M O O M M N N N R

>90 (R= C6H5) 3 Zn-DPYI

O O Zn Zn O O Zn Zn R R= O

HN N3

O O Zn Zn O O Zn Zn R1 R1=O N N N R2

80 (R2= CH2C4H8N) 4 Alkyne-MOF

N N Zn Zn R1 R1= Si R2 N3 N N Zn Zn N N N R2

  • N. a.

a conversion of functional MOFs

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SLIDE 14

Post-synthetic Modification

14 Entry Parent MOF Functionalizing group Reactant Product Yield (%) 1 ZIF-90

N Zn Zn N O

NaBH4

N Zn Zn N OH

77 (R= CH2OH) 2 ZIF-90

HO NH2

N Zn Zn N N R

80 (R= (CH2)2OH) 3 SIM-1

H2N

10

22 (R= (CH2)11CH3) 4 IRMOF-9

O O Zn Zn O O Zn Zn CHO HN NO2 NO2 NH2 O O Zn Zn O O Zn Zn N R

60 (R= NHC6H4(NO2)2) 5 UiO-66

O O Zr Zr O O Zr Zr Br

CuCN/ KCN

O O Zr Zr O O Zr Zr N

95a

a conversion of MOFs

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SLIDE 15

Post-synthetic Modification

15

Entry Parent MOF Functionalizing group Reactant Product Yield (%) 1 IRMOF-3

O O Zn Zn O O Zn Zn N H O

Br2

O O Zn Zn O O Zn Zn N H O Br

  • N. a.

2 Zn4O(SDC)3

O O Zn Zn O O Zn Zn O O Zn Zn O O Zn Zn Br Br

  • N. a.
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SLIDE 16

Post-synthetic Modification

16

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SLIDE 17

Post-synthetic Modification

17

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SLIDE 18

Post-synthetic Modification

18

O O Al Al O O Al Al O Al H Si Fe O O O O Al Al Al O O Al Al O O Al Al O Al O O O O Al Al Al

Fe Si

65°C, 10-3 mbar, 72h MIL-53(Al)

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SLIDE 19

Post-synthetic Modification

19

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SLIDE 20

Post-synthetic Modification

20

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SLIDE 21

Post-synthetic Modification

21

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SLIDE 22
  • Gas storage
  • Gas purification
  • CATALYSIS
  • Non-linear optics
  • Material science (Magnetic and

Luminescent MOFs)

22

Application of MOFs

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SLIDE 23
  • Solvothermal self-assembly synthesis
  • High geometric regularity (single

crystals XRD)

  • No limit in pore size (so far the

maximum is 38 Å)

  • Design of the structure (?)
  • CHEMICAL VERSATILITY
  • Limited thermal and chemical stability
  • Issues on stability upon removal of the

solvent in the cages

  • Possible sensitivity to air/moisture

23

Properties of MOFs

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SLIDE 24

MOF Catalytic Properties

24

Organic linker Functional sites Post-synthetic modification Inorganic unit Coordinatively unsaturated sites Grafted molecules Semiconductor/photocatalysis Pores Encapsulation Particle deposition Ship-in-a-bottle

Ranocchiari, M. PCCP 2011, 6388. Kapteijn, F. ACS Catal. 2014, 361.

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SLIDE 25
  • Catalytic site on the framework 


(also zeolites and porous silicates and aluminosilicates)

  • Encapsulation of the active site

within the pore structure 
 (also zeolites and porous silicates and aluminosilicates)

  • Catalytic site produced by post-

synthetic modification 
 (also porous silicates and aluminosilicates)

25

Catalysis by MOFs

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SLIDE 26

Catalytic site on the framework

26

  • No change in oxidation

state

O Cu O O OH2 Cu O O O O H2O O

Cyanosylilation of carbonyl groups

LnM O MLn H M = Ga, Cr, Zn

Friedel–Crafts reactions IRMOF-3

  • Basic activity
  • Metal-porphyrin MOF

Knövenagel condensation of benzaldehyde with ethyl cyanoacetate Epoxidation of

  • lefins

N N N N COO COO OOC OOC Mn

Mn

[Pd(2-pymo)2]n

N N O-

2-pymo =

Cross-Coupling reaction

  • Change in oxidation state
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SLIDE 27

Incapsulation of the active site

27

  • Cu@MOF-5
  • Pd@MOF-5
  • [PW11TiO40]5-@MIL-101

Leaching might be an issue

Synthesis of methanol from syngas Hydrogenation

  • f cyclooctene
  • xidation of 


α-pinene

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SLIDE 28

Catalysis by post-synthetic modification

28 N N Cl Cl OH OH

CdCl2 Ti(OiPr)4

N N Cl Cl O O Ti OiPr OiPr

Alkylation of aldehydes with Et2Zn 
 (up to 93% ee)

Asymmetric Catalysis

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SLIDE 29

Zeolites, MOFs, and mesoporous aluminosilicates

29

Table 1 Comparison between the structural, physical, and chemical properties of zeolites, mesoporous silica and alumina, and MOFs Zeolites MOFs Mesoporous silicates and aluminosilicates Crystalline? Yes Yes No Homogeneous active sites? Yes Yes No Surface area

  • 600 m2 g1

Up to 10 400 m2 g1 a

  • 2000 m2 g1

Cavity size

  • rca. 1 nm

Up to 4 nma Z 2 nm Diffusivity Low Low to high High Thermal stability High Low to mediumb Medium Chemical stability High Variable High Chemical versatility Low High Medium-low

a Maximum value published at the moment of this publication. b Maximum value published at the moment of this publication: 540 1C.

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SLIDE 30

Catalysis by Porous Solids

30