METAL-ORGANIC FRAMEWORKS

Transcription

1 METAL-ORGANIC FRAMEWORKS Engle Lab Group Meeting Aug 10 th, 2017 Rei Matsuura

2 A rapidly growing field Articles on "Metal-Organic Frameworks"

3 What are Metal-Organic Frameworks? Porous Material A type of coordination polymers Known for: Extraordinarily high surface areas Tunable pore size Adjustable internal surface properties > 20,000 types Zhou, H-C.; Long, J. R.; Yaghi, O. M. Chem. Rev., 2012, 112, 673 Hupp, J. T. et al. Chem. Soc. Rev., 2009, 38, 1450 Peplow, M. Nature, 2015, 520, 148

4 What are Metal-Organic Frameworks?

5 What are Metal-Organic Frameworks? Cd, Co, Cr, Cu, In, Mn, Pd, Ti, Zn

6 INSPIRATION FOR MOFS?

7 Porous Materials Molecular sieves Microporous material (< 2nm) Can include materials made of Si, Al, O, Ti, Sn, Zn, etc Mesoporous material (2-50 nm) Mesoporous silica Macroporous material (> 50nm)

8 Zeolites Microporous aluminosilicates Found in nature, but also produced industrially Inner cavities are known to bind organic molecules Exhibit unique catalysis for organic reactions High regioselectivity, stereoselectivity, shape selectivity Primarily acid catalyzed reactions biocatalytic, electrocatalytic, photocatalytic, and oxidation reactions have also been studied Khouw, C. B.; Davis, M. E. In Selectivity in Catalysis; Davis, M. E., Suib, S. L., Eds.; ACS Symposium Series; American Chemical Society: Washington, DC 1992

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10 Synthesis Methods of MOFs Stock, N.; Biswas, S. Chem. Rev., 2012, 112, 933

11 Commercial MOFs

12 MOF database

13 DEVELOPMENT OF MOFS

14 Usage of MOFs Gas storage Gas purification/separation Sensors X-ray crystallography

15 CATALYSIS!

16 MOFs in catalysis First proposed by Hoskins and Robson (1989) We propose that if ways could be devised of linking together tetrahedral centers and appropriate molecular rods, an infinite molecule would be generated... [lattices] of this general type... may, after appropriate functionalization of the rods, provide tailor-made materials for the heterogenous catalysis of a wide range of transformations. Cu I [C(C 6 H 4 CN) 4 ]BF 4 x-c 6 H 5 NO 2 Hoskins, B. F.; Robson, R. J. Am. Chem. Soc., 1989, 111, 5962

17 First MOF catalysis {[Cd(4, 4 -bipy) 2 ](NO 3 ) 2 } Fujita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. J. Am. Chem. Soc., 1994, 116, 1151

18 First MOF catalysis (Fujita) Selective clathration Fujita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. J. Am. Chem. Soc., 1994, 116, 1151

19 First MOF catalysis (Fujita) Catalytic cyanosilylation of aldehydes MOF is necessary CHO 0.5 mmol TMSCN (2eq) Cd(II) cat. (20 mol%) DCM (1.5 ml) 40 C, 24h OTMS 77% yield CN Shape specific CHO CHO 40% yield 19% yield CHO CHO 62% yield 84% yield CHO n.r. Fujita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. J. Am. Chem. Soc., 1994, 116, 1151

20 First MOF without guests MOF-5 Zn 4 (O)(BDC) % of space is open Å between clusters Density = 0.59 g/cm 3 Stable at 300C (24h, air) Li, H.; Eddaoudi, M.; O Keeffe, M.; Yaghi, O. M. Nature, 1999, 402, 276

21 DIFFERENT MODES OF MOF CATALYSIS

22 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

23 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

24 Opportunistic catalysis {[Cd(4, 4 -bipy) 2 ](NO 3 ) 2 } CHO 0.5 mmol TMSCN (2eq) Cd(II) cat. (20 mol%) DCM (1.5 ml) 40 C, 24h OTMS 77% yield CN Fujita, M.; Kwon, Y. J.; Washizu, S.; Ogura, K. J. Am. Chem. Soc., 1994, 116, 1151

25 Opportunistic catalysis Pd-MOF [Pd(2-pymo) 2 ] n two different windows 4.8Å and 8.8Å 42% available Moisture-stable Llabrés i Xamena, F. X.; Abad, A.; Corma, A.; Garcia, H. J. Catal., 2007, 250, 294

26 Opportunistic catalysis Heterogenous Recoverable, reusable

27 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

28 Lewis acid catalysis MIL-101 Cr 3 X(H 2 O) 2 O(bdc) 3 Surface area 5900 m 2 /g Henschel, A.; Gedrich, K.; Kraehnert, R.; Kaskel, S. Chem. Commun., 2008, 4192

29 Oxidative coupling [Cu(SO 4 )(pbbm)] n {[Cu(Ac) 2 (pbbm)] CH 3 OH} n Xiao, B.; Hou, H.; Fan, Y. J. Organomet. Chem., 2007, 692, 2014

30 Oxidative coupling

31 Oxidative coupling

32 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

33 Metalloporphyrins [Cd 3 (tipp)(bpdc) 2 ] DMA 9H 2 O Stable in boiling water, DCM, MeOH, DMF H 2 tipp Jiang, W.; Yang, J.; Liu, Y-Y.; Song, S-Y.; Ma, J-F. Inorg. Chem., 2017, 56, 3036

34 Metalloporphyrins

35 Metalloporphyrins

36 Schiff base complexes Zn 2 (bpdc) 2 L 10DMF 8H 2 O Asymmetric catalyst Solvent is removable Stable at 360C Cho, S. H.; Ma, B.; Nguyen, S. T.; Hupp, J. T.; Albrecht- Schmitt, T. E. Chem. Commun., 2006, 24,

37 Schiff base complexes Cho, S. H.; Ma, B.; Nguyen, S. T.; Hupp, J. T.; Albrecht- Schmitt, T. E. Chem. Commun., 2006, 24,

38 Schiff base complexes Cho, S. H.; Ma, B.; Nguyen, S. T.; Hupp, J. T.; Albrecht- Schmitt, T. E. Chem. Commun., 2006, 24,

39 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

40 MOF-encapsulated molecular catalysts Rho-ZMOF ([In 48 (HImDC) 96 ] 48 Can trap cationic porphyrin Prevents porphyrin degradation Free-base porphyrin can then be metallated Mn, Co, Zn or Cu ions Porphyrin confirmed with UV-vis Alkordi, M. H.; Liu, Y.; Larsen, R. W.; Eubank, J. F.; Eddaoudi, M. J. Am. Chem. Soc., 2008, 130, 12639

41 MOF-encapsulated molecular catalysts

42 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

43 Catalysis by organic struts Cu(asp)bpe 0.5 Uses amino acid as struts Different form from the free amino acid Ingleson, M. J.; Barrio, J. P.; Bacsa, J.; Dickinson, C.; Park, H.; Rosseinsky, M. J. Chem. Commun., 2008, 11, 1287

44 Catalysis by organic struts Ingleson, M. J.; Barrio, J. P.; Bacsa, J.; Dickinson, C.; Park, H.; Rosseinsky, M. J. Chem. Commun., 2008, 11, 1287

45 Catalysis by cavity modifiers MIL-101 Cr(III) terephthalate Modified the interior using ethylenediamine Férey, G. et al. Angew. Chem., Int. Ed., 2008, 47, 4144

46 Catalysis by cavity modifiers Férey, G. et al. Angew. Chem., Int. Ed., 2008, 47, 4144

47 Catalysis by cavity modifiers Férey, G. et al. Angew. Chem., Int. Ed., 2008, 47, 4144

48 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

49 Catalysis by MOF-encapsulated clusters ZIF-8 Zn(MeIM) Å cavity Stable at 550C (N 2 ) Hupp, J. T.; Huo, F. et al. Nature Chem., 2012, 4, 310 Yaghi, O. M. et al. Proc. Natl Acad. Sci. 2006, 103, 10186

50 Catalysis by MOF-encapsulated clusters Examined size selectivity in CO oxidation Also compared n- hexene vs trans-2-hexene Regioselective

51 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

52 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

53 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

54 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

55 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

56 Different modes of MOF catalysis opportunistic catalysis designed catalysis homogeneous catalysts incorporated as struts MOF-encapsulated molecular catalysts catalysis by metal-free organic struts or cavity modifiers catalysis by MOF-encapsulated clusters

57 Future of MOFs? There is not yet an example of a reaction for which MOFs are so superior that a typical organic chemist would choose a MOF-based catalyst over an existing catalyst -Prof. Joseph Hupp, Northwestern, April 2015

58 Acknowledgements Prof. Keary Engle Dr. De-Wei Gao Dr. Miriam O Duill Dr. Sri Nimmagadda Dr. Jose Medina Joe Derosa John Gurak Zhen Liu Van Tran Andrew Romine Mingyu Liu Tanner Jankins Tian (May) Zeng Vincent van der Puyl Huiqi Ni Pusu Yang Forrest Graham David Hill Carrie Gabaldon