About OMICS Group

1. About OMICS Group OMICS Group International is an amalgamation of Open Access publications and worldwide international science conferences and events. Established in the year 2007 with the sole aim of making the information on Sciences and technology ‘Open Access’, OMICS Group publishes 400 online open access scholarly journals in all aspects of Science, Engineering, Management and Technology journals. OMICS Group has been instrumental in taking the knowledge on Science & technology to the doorsteps of ordinary men and women. Research Scholars, Students, Libraries, Educational Institutions, Research centers and the industry are main stakeholders that benefitted greatly from this knowledge dissemination. OMICS Group also organizes 300 International conferences annually across the globe, where knowledge transfer takes place through debates, round table discussions, poster presentations, workshops, symposia and exhibitions.

2. About OMICS Group Conferences OMICS Group International is a pioneer and leading science event organizer, which publishes around 400 open access journals and conducts over 300 Medical, Clinical, Engineering, Life Sciences, Pharma scientific conferences all over the globe annually with the support of more than 1000 scientific associations and 30,000 editorial board members and 3.5 million followers to its credit. OMICS Group has organized 500 conferences, workshops and national symposiums across the major cities including San Francisco, Las Vegas, San Antonio, Omaha, Orlando, Raleigh, Santa Clara, Chicago, Philadelphia, Baltimore, United Kingdom, Valencia, Dubai, Beijing, Hyderabad, Bengaluru and Mumbai.

3. The design and synthesis of silica-based catalytic microreactors Raed Abu-Reziq Institute of Chemistry, Casali Center of Applied Chemistry and The Center for Nanoscience and Nanotechnology The Hebrew University of Jerusalem, Israel Ceramics-2015, Chicago, USA 17.8.2015

4. Catalysis shapes our world Basic and fine chemicals Food Environment Catalysis Health Energy New Materials Importance of catalysis: more than 90% of the industrial processes are catalyzed (chemicals, pharmaceutics, materials, polymers, energy, etc.)

5. Catalysis Heterogeneous Homogeneous • Supported metals • Supported organometallic complexes • Metal oxides, sulfides (PtO2, RuO2 etc.) • Organometallic complexes • Enzymes • Organocatalysts

6. Catalysis Homogeneous catalysis Heterogeneous catalysis • High activity and selectivity • Not easily recovered • Expensive • Decrease of activity and selectivity • Easily recovered • Economic How to bridge homogeneous and heterogeneous catalysis?!! Nanocatalysis?? K. D. Wiese et al, Top Organomet. Chem.,2006, 18, 1. H. W. Bohnen et al, Adv. Catal.2002, 47, 1.

7. Nanocatalysis; Quasi-homogeneous catalysis; Semi- heterogeneous catalysis Preparation of heterogeneous catalysts in the nanometer length scale Metal nanoparticles as active catalyst Metal nanoparticles as support W. J. Stark et al, Chem. Eur. J., 2010, 16, 8950.

8. Nanocatalysis Size Effects K. An and G. A. Somorjai, ChemCatChem, 2012, 14, 1512.

9. Nanocatalysis Shape Effects S.U. Son et al, Angew. Chem. Int. Ed. 2007, 46, 1152

10. Nanocatalysis: Magnetically separable systems a) V. Polshettiwar et al, Chem. Rev., 2011, 111, 3036. b) S. Shyles et al, Angew. Chem. Int. Ed., 2010, 49, 3428. c) Y. Zhu et al, ChemCatChem, 2010, 2, 365. d) V. Polshettiwar et al,Green Chem., 2010,12, 743.

11. Our current research activity Nano- and Microreactors Bridging homogeneous and heterogeneous catalysis Magnetically separable systems Supports with well-defined nanostructures

12. Nano & Microreactors Yolk-shell nanoreactors E. V. Shevchenko et al, Adv. Mater.2008, 20, 4323. Y. Yang et al, Angew. Chem. Int. Ed. 2012, 51, 9164. Carbon nanotubes as nanoreactors S. A. Miners et al, Chem. Commun., 2013, 49, 5586.

13. Ionic liquid based microreactors Ionic Liquids • Salts that are liquid at ambient temperatures. • Have stable liquid range of over 300 °C. • Very low vapour pressure at room temperature. m.p. (°C) for NaCl= 803 m.p. (°C) for BMIm[PF6]= -78 P. Wasserscheid, T. Welton in “ Ionic Liquids in Synthesis” 2002.

14. Ionic liquid based microreactors • Applications of ionic liquids: • Solvent and catalysts (synthesis, catalysis, microwave chemistry, nanochemistry, • multiphasic reactions and extractions) • Biological uses (biomass processing, drug delivery, biocides, personal care, embalming) • Engineering (coatings, lubricants, plasticisers, dispersing agents, compatibilisers) • Physical chemistry( refractive index, thermodynamics, binary and ternary systems) • Electrochemistry(metal plating, solar panels, fuel cells, electro-optics, ion propulsion) The high viscosity of ionic liquids limits its applications in industrial processes N. V. Plechkova, K. R. Seddon, Chem. Soc. Rev. 2008, 37, 123

15. BMIm-PF6@SiO2 microcapsules TEM image SEM image Size distribution E. Weiss et al, Chem. Mater., 2014, 26, 4781.

16. BMIm-PF6@SiO2 microcapsules Particulated ionic liquids: Converting ionic liquids into solid form TGA analysis indicates that the microcapsules are composed of 68% ionic liquid

17. BMIm-PF6@SiO2 microcapsules Parameters affecting the microcapsules synthesis: • Type of surfactant • Surfactant concentration • Ionic liquid: TEOS ratio

18. BMIm-PF6@SiO2 microcapsules Brij 78 Triton X-100 Tween 80 Reax 88A Reax 88B 5% Bu-PVP SDS PS- sulfonated Pluronic 123

19. BMIm-PF6@SiO2 microcapsules Characterizations

20. BMIm-PF6@SiO2 microcapsules Immobilization of palladium nanoparticles

21. Pd/BMIm-PF6@SiO2 microcapsules Catalytic applications E. Weiss et al, Chem. Mater., 2014, 26, 4781.

22. BMIm-PF6@SiO2 microcapsules Stability and Recyclability SEM and TEM images of Pd/BMIm-PF6@SiO2after catalytic applications SEM image TEM image Recyclability

23. PEG@SiO2 microcapsules Oil phase: Toluene Heptane Cyclohexane Surfactants: Unpublished results

24. PEG@SiO2 microcapsules PEG@SiO2 in toluene PEG@SiO2 in heptane SEM image 10 µm SEM images 1 µm 1 µm TEM image TEM image

25. PEG@SiO2 microcapsules Characterizations

26. PEG@SiO2 microcapsules [Pt]/PEG@SiO2: Selective hydrosilylation catalyst a the catalyst was prepared in the presence of Agrimer AL22 b the catalyst was prepared in the presence of Span 80 Heterogeneous hydrosilylation: M. Chauhan et al, J. Organomet. Chem.2002, 645,1.

27. PEG@SiO2 microcapsules [Pt]/PEG@SiO2: Selective hydrosilylation catalyst Unpublished results

28. Chiral ruthenium catalyst@ magnetically separable silica microreactors TEM image SEM image A. Zoabi et al, Eur. J. Inorg. Chem., 2015, 2015

29. Chiral ruthenium catalyst@ magnetically separable silica microreactors Characterizations STEM/EDS analysis XRD pattern 29Si CP-MAS NMR

30. Chiral ruthenium catalyst@ magnetically separable silica microreactors Characterizations 13C NMR and 13C CP-MAS NMR

31. Chiral ruthenium catalyst@ magnetically separable silica microreactors

32. Chiral ruthenium catalyst@ magnetically separable silica microreactors Postulated mechanism for the transportation of the reactants to the core of catalytic microreactors

33. Chiral ruthenium catalyst@ magnetically separable silica microreactors

34. Chiral ruthenium catalyst@ magnetically separable silica microreactors Tethering the catalyst in the homogeneous zone of the microreactors is required for obtaining high reactivity and selectivity Comparison of catalytic activity of the microreactors versus sol-gel entrapped and anchored catalyst in the asymmetric transfer hydrogenation of 4-bromoacetophenone

35. Our current research activity Nano- and Microreactors Bridging homogeneous and heterogeneous catalysis Magnetically separable systems Supports with well-defined nanostructures

36. Magnetically separable systems Palladium nanoparticles supported on magnetically recoverable hybrid organic-silica nanoparticles Preparation of Pd(nano)/MNP@IL-SiO2 catalytic hybrid nanoparticles : S. Omar et al, J. Phys. Chem. C, 2014, 118, 30045

37. Pd(nano)/MNP@IL-SiO2 Characterizations 100 nm 200 nm TEM of Pd(nano)/MNP@IL-SiO2 SEM of MNP@IL-SiO2 100 nm 20 nm TEM of MNP@IL-SiO2 STEM of Pd(nano)/MNP@IL-SiO2

38. Pd(nano)/MNP@IL-SiO2 Characterizations TGA 29Si CP-MAS NMR 13C CP-MAS NMR XRD

39. Pd(nano)/MNP@IL-SiO2 Catalytic applications

40. Pd(nano)/MNP@IL-SiO2 Catalytic applications S. Omar et al, J. Phys. Chem. C, 2014, 118, 30045

41. Pd(nano)/MNP@IL-SiO2 Recycling of the catalysts SEM images of recycled catalyst after 4 cycles Suzuki reaction between bromonenzene and phenyl boronic acid Heck reaction between iodobenzene and ethyl acrylate

42. Conclusions: • Two methods for preparing new materials based on ionic liquids or PEG encapsulated in silica shells were developed • The methods enable particulating ionic liquids or PEGs and converting them in powder form. • The methods give opportunities to design ionic liquids or PEGs with new properties. • The methods enable controlling selectivity and reactivity of catalysts • Magnetically separable nanocatalysts were designed and applied successfully in different organic transformations.

43. Funding support Casali Foundation Ministry of Science and Culture of Lower Saxony Group members: Suheir Omar Esti Weiss Suzana Natour Amani Zoabi Charlie Batarseh Ahmad Zarour Sumaya Abu-Ghannam Diana Gertopski Dr. Maneesh Gupta Former group members: Dr. Gilat Nizri Dr. Saleh Abu-Lafi Dr. Bishnu Dutta Dr. Khalil Hamza Rony Schwarz Yafit Schnell Thank You!