Synthesis of mesoporous materials based on titanium(IV)oxide and titanium nitride

Nanoparticles of titania were obtained by the controlled hydrolysis of Ti(i-OC3H7)(4) in the reverse micelles of dodecylamine derived from dodecylamine-isopropanol-water solution (water/oil microemulsion). The mesolamellar phase based on titanium nitride (TiN) was obtained by first decomposing TiN atleast partially using the 1:1 solution of acid mixture (HF and HNO3 in the ratio of 9:1) in water and then templating onto the cationic surfactant namely, cetyltrimethylammaniumbromide (abbreviated as CTAB) at 80 degrees C. The synthesis of mesolamellar phase based on TiN involves the charge matched templating approach following the counter-ion mediated pathway. The samples thus obtained were characterized by small angle x-ray diffraction using Cuk(a) radiation, scanning electron microscopy and transmission electron microscopy, which indicated some satisfactory results. (C) 1999 Acta Metallurgica Inc.

Direct synthesis of Al-SBA-15 mesoporous materials via hydrolysis-controlled approach

Aluminum-substituted mesoporous SBA-15 (Al-SBA-15) materials were directly synthesized by a hydrolysis-controlled approach in which the hydrolysis of the silicon precursor (tetraethyl orthosilicate, TEOS) is accelerated by fluoride or by using tetramethyl orthosilicate (TMOS) as silicon precursor rather than TEOS. These materials were characterized by powder X-ray diffraction (XRD), N-2 sorption isotherms, TEM, Al-27 MAS NMR, IR spectra of pyridine adsorption, and NH3-TPD. It is found that the matched hydrolysis and condensation rates of silicon and aluminum precursors are important factors to achieve highly ordered mesoporous materials. Al-27 MAS NMR spectra of Al-SBA-15 show that all aluminum species were incorporated into the silica framework for the samples prepared with the addition of fluoride. A two-step approach (sol-gel reaction at low pH followed by crystallization at high pH) was also employed for the synthesis of Al-SBA-15. Studies show that the two-step approach could efficiently avoid the leaching of aluminum from the framework of the material. The calcined Al-SBA-15 materials show highly ordered hexagonal mesostructure and have both Bronsted and Lewis acid sites with medium acidity.

Chiral synthesis on catalysts immobilized in microporous and mesoporous materials

This paper reviews the recent progress made in the asymmetric synthesis on chiral catalysts in porous materials and discusses the effects of surface and pores on enantio-selectivity (confinement effect). This paper also summarizes various approaches of immobilization of the chiral catalysts onto surfaces and into pores of solid inorganic supports such as microporous and mesoporous materials. The most important reactions surveyed for the chiral synthesis in porous materials include epoxidation. hydrogenation, hydroformylation, Aldol and Diels-Alder reactions, etc. The confinement effect originated from the surfaces and the pores turns out to be a general phenomenon. which may make the enantioselectivity increase (positive effect) or decrease (negative effect). The confinement effect becomes more pronounced particularly when the bonding between the catalyst and the surface is more rigid and the pore size is tuned to a suitable range. It is proposed that the confinement in chiral synthesis is essentially a consequence of subtle change in transition states induced by weak-interaction in pores or on surfaces. It is also anticipated that the enantioselectivity could be improved by tuning the confinement effect based on the molecular designing of the pore/surface and the immobilized catalysts according to the requirements of chiral reactions.

Design and synthesis of near-IR luminescent mesoporous materials covalently linked with tris(8-hydroxyquinolinate) lanthanide(III) complexes

By using the bifunctional ligand, 8-hydroxyquinoline-functionalized organosilane (Q-Si), the new mesoporous material Q-MCM-41 covalently bonded with 8-hydroxyquinoline was synthesized. Through the ligand exchange reaction, the new near-infrared (NIR) luminescent mesoporous LnQ(3)-MCM-41 (Ln = Er, Nd, Yb) materials were prepared by linking the lanthanide quinolinate complexes to the ordered mesoporous Q-MCM-41 material. The LnQ(3)-MCM-41 materials were characterized by powder X-ray diffraction and N-2 adsorption/desorption, and they all show the characteristic mesoporous structure of MCM-41 with highly uniform pore size distributions.

Near-infrared luminescent mesoporous materials covalently bonded with ternary lanthanide [Er(III), Nd(III), Yb(III), Sm(III), Pr(III)] complexes

New near-infrared-luminescent mesoporous materials were prepared by linking ternary lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) complexes to the ordered mesoporous MCM-41 through a functionalized 1,10-phenanthroline (phen) group 5-(N,N-bis-3-(triethoxysilyl)propyl)ureyl-1,10-phenanthroline. The resulting materials (denoted as Ln(hfth)(3)phen-M41 and Pr(tfnb)(3)phen-M41; Ln=Er, Yb, Nd, Sm; hfth = 4,4,5,5,6,6,6-heptafluoro-1-(2-thienyl)hexane-1,3-dionate; tfnb = 4,4,4-trifluoro-1-(2-naphthyl)- 1, 3-butanedionate) were characterized by powder X-ray diffraction, N-2 adsorption/desorption, and elemental analysis. Luminescence spectra of these lanthanide-complex functionalized materials were recorded, and the luminescence decay times were measured. Upon excitation at the absorption of the organic ligands, all these materials show the characteristic NIR luminescence of the corresponding lanthanide (Er3+, Nd3+, Yb3+, Sm3+, Pr3+) ions by sensitization from the organic ligands moiety. The good luminescent performances enable these NIR-luminescent mesoporous materials to have possible applications in optical amplification (operating at 1300 or 1500 nm), laser systems, or medical diagnostics.

Direct synthesis of highly ordered Fe-SBA-15 mesoporous materials under weak acidic conditions

Iron-substituted SBA-15 (Fe-SBA-15) materials have been synthesized via a simple direct hydrothermal method under weak acidic conditions. The powder X-ray diffraction (XRD), NZ sorption and transmission electron microscopy (TEM) characterizations show that the resultant materials have well-ordered hexagonal meso-structures. The diffused reflectance UV-vis and UV resonance Raman spectroscopy characterizations show that most of the iron ions exist as isolated framework species for calcined materials when the Fe/Si molar ratios are below 0.01 in the gel. The presence of iron species also has significant salt effects that can greatly improve the ordering of the mesoporous structure. Different iron species including isolated framework iron species, extraframework iron clusters and iron oxides are formed selectively by adjusting the pH values of the synthesis solutions and Fe/Si molar ratios. (c) 2005 Elsevier Inc. All rights reserved.

Heterogeneous enantioselective epoxidation catalyzed by Mn(salen) complexes grafted onto mesoporous materials by phenoxy group

Three chiral Mn(salen) complexes were immobilized into different mesoporous material via phenoxy group by a simplified method and they show high activity and enantioselectivity for asymmetric epoxidation of various substituted unfunctional olefins. The heterogeneous Mn(salen) catalysts show comparable ee values for asymmetric epoxidation of styrene and 6-cyano-2,2-dimethylchromene and much higher ee values for epoxidation of a-methylstyrene (heterogeneous 79.7% ee versus homogeneous 26.4% ee) and cis-beta-methylstyrene (heterogeneous 94.9% ee versus homogeneous 25.3% ee for cis-epoxide) than the homogeneous catalysts. These heterogeneous catalysts also remarkably alter the cis/trans ratio of epoxides for asymmetric epoxidation of cis-beta-methylstyrene (heterogeneous 21 versus homogeneous 0.38). The axial tether group does not make a big effect on ee values and the increase in ee value and change in cis/trans ratio are mainly attributed to the axial immobilization mode and the support effect of heterogeneous catalysts. The catalysts keep constant ee values for the recycle tests of eight times for asymmetric epoxidation of a-methylstyrene. And several possibilities were proposed to elucidate the difference in ee values of heterogeneous catalysts from homogeneous catalysts. (c) 2005 Elsevier B.V. All rights reserved.