Spectroscopic Investigation of Microporous Titanosilicate ETS-10 Crystals of Controlled Morphology, Size and Defect Concentration
Zhaoxia Ji1, Juliusz Warzywoda1, Russell F. Howe2, Trevor Goodrich1, Zhuhua Cai1, Katherine Ziemer1 and Albert Sacco Jr.1, (1)Department of Chemical Engineering, Northeastern University, 360 Huntington Ave, Boston, MA 02115, (2)Chemistry Department, University of Aberdeen, AB24 3UE, Scotland, United Kingdom

The potential of quantum wires in optoelectronics, non-linear optics, chemical sensors, and photocatalysis has motivated research on growing ETS-10 crystals with controlled morphology, size and defect concentration. Titanosilicate ETS-10, a microporous zeotype material built of corner-sharing TiO6 octahedra and SiO4 tetrahedra [1], shows potential as a natural occurring alignment of monatomic ...Ti-O-Ti-O-Ti... chains or wires. These titania chains are separated from one another by an insulating silicate matrix [2], and show unique quantum confinement effects and make ETS-10 a promising candidate for quantum wire applications [3].

Hydrothermal synthesis of ETS-10 was conducted at 473 K by adjusting the Na2O/K2O ratio and water content in synthesis mixtures. Square truncated bipyramidal ETS-10 crystals with increasing basal width and decreasing aspect ratio were grown upon decreasing Na2O/K2O ratio and increasing water content. Plate-like ETS-10 crystals with dimensions up to ~80x80x22 mm were obtained. These are the largest ETS-10 reported to date. Atomic force microscopy and high resolution SEM revealed the presence of stepped island-like structures on the square facets of ETS-10 crystals. Linear dimensions of these island-like structures increased concomitantly with the increasing crystal dimensions. These results suggest that the replacement of Na ions by K ions and increasing water content in synthesis mixtures suppressed both three- and two-dimensional nucleation of ETS-10. Consistent with the microtopographic analysis results, UV-vis diffuse reflectance spectroscopic analysis showed that the band attributed to the delocalized charge transfer transitions along the ...Ti-O-Ti-O-Ti... chains had smaller FWHM for the larger ETS-10 crystals that are expected to have less crystal defects. X-ray photoelectron spectroscopic analysis showed that the area ratio of the Ti 2P3/2 peak assigned to the five coordinated Ti species to the Ti 2P3/2 peak assigned to the octahedral Ti species decreased for the larger ETS-10 crystals. Since the five coordinated Ti species were assigned to Ti appearing in the defects of ...Ti-O-Ti-O-Ti... chains or on the external crystal surfaces where these chains end [4], the lower five coordinated Ti to octahedral Ti peak area ratio indicated the lower defect concentration in the larger ETS-10 crystals. Currently, further confocal Raman spectroscopic analysis is being performed on these ETS-10 crystals with various morphologies, sizes, and defect concentrations. The spectroscopic analyses of these crystals will improve understanding of nucleation and crystal growth of ETS-10 and thus help growing ETS-10 crystals with desired properties for potential quantum wire applications.

[1] S.M. Kuznicki, US Patent 4,853,202 1989. [2] M.W Anderson, O. Terasaki, T. Ohsuna, P.J.O. Malley, A. Philippou, S.P. MacKay, A. Ferreira, J. Rocha, S. Lidin, Philosophical Magazine B 71 (1995) 813. [3] C. Lamberti, Micropor. Mesopor. Mater. 30 (1999) 155. [4] L. Lv, F.Y. Lee, J. Zhou, F. Su, X.S. Zhao, Micropor. Mesopor. Mater. 96 (2006) 270.

Extended Abstract Status: Not Uploaded

Catalysis with Mesoporous and Microporous Materials I

The Preliminary Program for 2007 Annual Meeting