Metal-containing inorganic-organic nanocomposites

1. Metal-containing inorganic-organic nanocomposites A.C. Finnefrock, G.E.S. Toombes, R. Ulrich, U. Wiesner, S.M. Gruner

2. Bio-inspired inorganic-organic hybrids Diatoms: an example of organic-directed inorganic synthesis Inspiration: use block copolymers as structure- directing agents.

3. Background • 1986: Fetters and Thomas: Bicontinuity • EM textures in diblock copolymer • bicontinuous since one block permeable to CO2 • textures correlate to the high permeability • 1986: Alward et al., student of Thomas • Kratky camera: OBDD symmetry • 1988: Dave Anderson projection • OBDD  wagon wheel • (OBDD  wagon wheel) • 1994: Gyroid paper • SAXS: Gyroid, not OBDD • MFT: Bates et al. Gyroid to be preferred • folks think that G  wagon wheel

4. Background, continued • 1995: Re-evaluation of OBDD findings • Hadjuk et al. (Gruner, Thomas, Fetters) • OBDD (Pn3m) SAXS really Gyroid (Ia3d) • 2001: Plumber’s Nightmare structure • Finnefrock et al. (Gruner, Wiesner) • New structure: Plumber’s Nightmare (Im3m) • but, not claiming PN  wagon wheel • instead, need combination of TEM and SAXS

5. Surface Area • BET: 300 m2/g • Applications in • Molecular separation • Catalysis • Dielectrics

6. Synthesis Approach

7. Synthesis concept

8. Phase mixing and segregation

9. Synthesis of inorganic-organic hybrids

10. Morphology and specificity

11. Mesophases from block copolymers

12. TEM images uncalcined calcined

13. Small angle x-ray scattering data uncalcined calcined

14. SAXS at CHESS

15. Radial X-ray Plots

16. Peak Positions

17. Peak Positions

18. Radial q2 circles

19. Domain Assignments

20. Labeled Peaks

21. Real-space bicontinuous structures gyroid (Ia3d) plumber’s nightmare (Im3m) X-ray scattering can distinguish between these structures, as they belong to distinct space groups (symmetries).

23. D G P I-WP N

25. D G P I-WP N

26. D G P I-WP N

27. D G P I-WP N

28. D G P I-WP N

29. Skeletal surface comparison

30. Skeletal surface comparison

31. Skeletal surface comparison

32. Skeletal surface comparison Plumber’s Nightmare is only known low-genus continuous structure consistent with both TEM and SAXS data

33. I vs q2, data • All data are consistent with Im3m symmetry and others • (Ia3d, Pn3m) are ruled out. • We can also explain systematic absences.

38. I vs q2, predicted

39. I vs q2, data • All data are consistent with Im3m symmetry and others • (Ia3d, Pn3m) are ruled out. • We can also explain systematic absences.

40. Anisotropy

41. Anisotropy

42. Ellipsoid rotation

43. Data rotation

44. BET: high surface area TEM: bicontinuous and “wagon wheel” SAXS: Im3m symmetry Systematic peak absences understood Plumber’s Nightmare skeletal surface Understand elliptical patterns Results

45. Rational hybrid design Based upon block copolymers 30 years of surfactant research 3-phase to 2-phase problem Demonstration of Im3m symmetry Expected Ia3d (from gyroid) Determination of Plumber’s Nightmare Conclusions

46. Cornell University Gil Toombes, Sol Gruner, Uli Wiesner Max Planck Institute for Polymer Research Ralph Ulrich, Alexander Du Chesne, Christian Honecker, Kai Schumacher, Klaus K. Unger Department of Energy National Science Foundation Cornell Center for Materials Research Cornell High Energy Synchrotron Source (CHESS) D-1 (Ernie Fontes) Acknowledgements