Metal-organic frameworks in heterogeneous catalysis

Transcription

1 WIR SCHAFFE WISSE HEUTE FÜR MRGE Dr. Marco Ranocchiari :: Syncat Group Leader - LSK :: Paul Scherrer Institut Metal-organic frameworks in heterogeneous catalysis Catalysis Lecture 2017 ETH Zurich

2 Catalysis: Heterogeneous vs Homogeneous vs Enzymatic Heterogeneous Homogeneous Enzymatic Engineering flexibility Chemical flexibility Chemical control Selectivity 2

3 3... Some acronym M e t a l F r g a n i c r a m e w o r k P C P o r o u s o o r d i n a t i o n o l y m e r 1) Metal 2) rganic 3) Polymer 4) Well defined structure 5) Can be porous

4 History Coordination polymers: Pioneer work on porous coordination polymers: by Feréy and Johnson. The Boost: 1999 by Yaghi (MF-5). H. Li, M. Eddaoudi, M. 'Keeffe and. M. Yaghi, ature, 1999, 402, Exponential growth of the number of publications over the last decade 4

5 MF-5 rganic BB Inorganic Unit Structure 6+ Features Self assembly synthesis (Solvothermal) Surface area >3000 m 2 /g Thermal stability: up to 300 C Stable upon guest molecules removal Size of the cavity 12 Å MF-5 H. Li, M. Eddaoudi, M. 'Keeffe and. M. Yaghi, ature, 1999, 402,

6 ISRETICULARITY AD CAVITY DESIG Linear Geometry 6+ FIXED rganic BB ame IRMF-10 Cavity Size 15.4 Å IRMF Å IRMF Å M. Eddaoudi, J. Kim,. Rosi, D. Vodak, J. Wachter, M. 'Keeffe and. M. Yaghi, Science, 2002, 295,

7 ISRETICULARITY AD FUCTIALIZATI Linear Geometry MF-5 or IRMF-1 cavity size = 11.8 Å rganic BB ame 6+ FIXED Cavity Size IRMF Å H 2 IRMF Å M. Eddaoudi, J. Kim,. Rosi, D. Vodak, J. Wachter, M. 'Keeffe and. M. Yaghi, Science, 2002, 295,

8 MIXMFS Mixing of different organic building blocks into the MF rganic BB Inorganic Unit Structure 6+ H 2 Br MIXMF or MTV-MF H. Deng, C. J. Doonan, H. Furukawa, R. B. Ferreira, J. Towne, C. B. Knobler, B. Wang and. M. Yaghi, Science, 2010, 327,

9 MFs Chemical and Structural Flexibility isoreticular chemistry pore tuning REFERECE TPLGY mixmf chemistry multiple functions isoreticular chemistry introducing functional groups Eddaoudi, M. Science 2002, 469. Deng, H. Science 2010,

10 MFs Chemical and Structural Flexibility MIL-101 Ui-66 MF-74 [M 3 X()] 6+ M = Cr 3+, Fe 3+, 3+ X = F, Cl, H- [Zr 6 (H) 4 4 ] 12+ [M 2 (H 2 )] n 2n+ M = Co 2+,Mn 2+,i 2+,Mg 2+ Ferey, G. Science 2005, Cavka, J. JACS 2008, Rosi,. L. JACS 2005,

11 MFs as catalytic materials + [ 4 ] 6+ Yaghi. M. ature 1999, 276. MF-5 Engineering flexibility Chemical flexibility Chemical control at the atomic level Selectivity solid fine tunable well-defined structure active site resembling the pocket of an enzyme 11

12 Post-synthetic Modification Entry 1 Parent MF Functionalizing group Reactant Product Yield (%) 3 IRMF-3 89 a (R= (CH 2 ) 4 CH 3 ) 5 M M 46 a (R= HC 6 H 5 ) 6 7 DMF-1 UMCM-1 R 64 a (R= C 6 H 5 ) 77 a (R= C 6 H 5 ) 8 R 88 (R= CH 3 ) H R 9! 92 b (R= CH 3 ) 10 M M 50 (R= (CH 2 ) 3 CH 3 ) M M (R= CH=CH-CH) M M H 2 >80 a (R= CH 3 ) 2. a. (R= CH=CHCH 3 ) 4 70 a (R= C 6 H 5 ) 11 Ui b (R= (CH 2 ) 3 CH 3 ) (R= (CH 2 ) 6 CH 3 ) b (R= CH=CH-CH) M M 3 a (R = 2-H-C 6 H 4 ) IRMF-3 17 >99 b (R = 2-H-C 6 H 4 ) 18 H 67 (R = CH 3 ) M=, Zr, Gd,! 19 MIXMF-5 R H!! R >99 b (R = 2-H-C 6 H 4 ) 20 UMCM-1 87 (R= C 5 H 4 ) 13 (R = 2-H-C 6 H 4 ) 21 M M 10 (R = 2-H-C 6 H 4 ) Ui b (R = 2-H-C 6 H 4 ) M M. r. (R= C(CH 3 ) 3 ) 26 IRMF-3 R C 60 (R= (CH 2 ) 2 CH 3 ) 27! HR 51 (R= (CH 2 ) 4 CH 3 ) M M H 99(R= Si(CH 3 ) 3 ) (R= CH 2 CH 3 ) (R= CH 2 CH=CH 2 ) (R= C 6 H 5 ) (R= C 6 H 11 ) a conversion of amino containing MF b vapor-phase post-synthetic modification (VP-PSM) 12

13 Post-synthetic Modification Entry Parent MF Functionalizing group Reactant Product Yield (%) R 1 IRMF-16 3 R. a. 3 R R= M M M M 2 DMF-1 M M 3 R M M R >90 (R= C 6 H 5 ) M=, In 3 -DPYI R= R 3 H R 1 = R 1 R 2 80 (R 2 = CH 2 C 4 H 8 ) 4 kyne-mf R 1 R 2 3 R 2. a. R 1 = Si a conversion of functional MFs 13

14 Post-synthetic Modification Entry Parent MF Functionalizing group Reactant Product Yield (%) 1 ZIF-90 abh 4 H 77 (R= CH 2 H) 2 ZIF-90 H H 2 R 80 (R= (CH 2 ) 2 H) 3 SIM-1 H (R= (CH 2 ) 11 CH 3 ) 4 IRMF-9 CH H H 2 2 R 60 (R= HC 6 H 4 ( 2 ) 2 ) 2 Zr Zr Zr Zr 5 Ui-66 Br CuC/ KC 95 a Zr Zr Zr Zr a conversion of MFs 14

15 Post-synthetic Modification Entry Parent MF Functionalizing group Reactant Product Yield (%) 1 IRMF-3 H H B. a. Br (SDC) 3 Br Br. a. 15

16 Post-synthetic Modification 16

17 Post-synthetic Modification 17

18 Post-synthetic Modification Fe H Si Fe Si 65 C, 10-3 mbar, 72h MIL-53() 18

19 Post-synthetic Modification 19

20 Post-synthetic Modification 20

21 Post-synthetic Modification 21

22 22 Application of MFs Gas storage Gas purification CATALYSIS on-linear optics Material science (Magnetic and Luminescent MFs)

23 23 Properties of MFs Solvothermal self-assembly synthesis High geometric regularity (single crystals XRD) o 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

24 MF Catalytic Properties rganic linker Functional sites Post-synthetic modification Pores Encapsulation Particle deposition Ship-in-a-bottle Inorganic unit Coordinatively unsaturated sites Grafted molecules Semiconductor/photocatalysis Ranocchiari, M. PCCP 2011, Kapteijn, F. ACS Catal. 2014,

25 25 Catalysis by MFs 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 postsynthetic modification (also porous silicates and aluminosilicates)

26 Catalytic site on the framework o change in oxidation state H 2 Cu Cu H 2 H L n M ML n M = Ga, Cr, Cyanosylilation of carbonyl groups Friedel Crafts reactions Change in oxidation state [Pd(2-pymo)2]n 2-pymo = - Cross-Coupling reaction Basic activity IRMF-3 Knövenagel condensation of benzaldehyde with ethyl cyanoacetate Metal-porphyrin MF Mn C C Mn C C Epoxidation of olefins 26

27 Incapsulation of the active site [PW11Ti40] Synthesis of methanol from syngas Hydrogenation of cyclooctene Leaching might be an issue oxidation of α-pinene 27

28 Catalysis by post-synthetic modification Asymmetric Catalysis Cl H H CdCl2 Ti(iPr)4 Cl ipr Ti ipr kylation of aldehydes with Et2 (up to 93% ee) Cl Cl 28

29 Zeolites, MFs, and mesoporous aluminosilicates Table 1 Comparison between the structural, physical, and chemical properties of zeolites, mesoporous silica and alumina, and MFs Zeolites MFs Mesoporous silicates and aluminosilicates Crystalline? Yes Yes o Homogeneous active sites? Yes Yes o Surface area o600 m 2 g 1 Up to m 2 g 1 a o2000 m 2 g 1 Cavity size rca. 1 nm Up to 4 nm a Z 2 nm Diffusivity Low Low to high High Thermal stability High Low to medium b 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. 29

30 Catalysis by Porous Solids 30