Boting Yang

Post-Synthesis Treatment gives Highly Stable Siliceous Zeolites through the Isomorphous Substitution of Silicon for Germanium in Germanosilicates†

Germanosilicates, an important family of zeolites with increasing number of members and attractive porosities, but containing a large quantity of unstable Ge atoms in the framework, meet with great obstacles in terms of limited thermal and hydrothermal stability when it comes to practical use. A facile stabilization method thus has been developed to substitute isomorphously Ge atoms for Si atoms, giving rise to ultrastable siliceous analogues of the pristine germanosilicates.

Synthesis of Extra‐Large‐Pore Zeolite ECNU‐9 with Intersecting 14*12‐Ring Channels

Highly crystalline and (hydro)thermally stable zeolites with extra-large pores [≥14-ring (14-R)] are desirable as catalysts. A novel zeolite, ECNU-9, with an intersecting 14*12-R channel system was rationally designed and synthesized by a building block strategy, in which the interlayer expansion of a two-dimensional silicate structure was realized by combining organic amine assisted layer-stacking reorganization and subsequent silylation with a square-shaped single 4-ring (S4R) silane, 1,3,5,7-tetramethylcyclotetrasiloxane (TMCS). The PLS-3 precursor was disassembled into building blocks and then intercalated with flexible and removable organic amine pillars to offer enough interlayer spacing for accommodating TMCS molecules. The additionally introduced building blocks interconnected the neighboring layers to construct new 14-R and 12-R pores. ECNU-9 possesses a well-ordered structure with a novel topology. The corresponding Ti-ECNU-9, with tetrahedral Ti ions in the framework, showed superior catalytic performance in the selective epoxidation of bulky alkenes.

Size-Dependent Catalytic Activity of Oxo-Hydroxo Titanium Sub-Nanoislets Grafted on Organically Modified Mesoporous Silica

The reaction between titanium alkoxides, [Ti(OR)4], and surface silanol groups is widely used to generate grafted oxo-hydroxo titanium species, whose size is difficult to control. Partial capping of the surface silanols in the presence of the masking pattern of self-repelling tetramethylammonium ions allows us to isolate surface silanol islets, on which isolated titanium ions and dimeric oxo titanium species can be generated up to 2 Ti/Si mol %. Above this loading, and up to ∼8 Ti/Si mol %, higher oligomers (trimers, hexamers, octamers, and so on) are formed, reaching the size obtained at much lower loadings (<1 Ti/Si mol %) on a nonmodified silica surface. The downsizing effect produced on our organically modified surface is monitored from the blue-shift of the charge-transfer band of the Ti(IV) ions, measured by reflectance UV-visible spectroscopy. It is also mirrored by a higher catalytic activity in cyclohexene epoxidation, revealing that it is not only the isolated Ti species that are active but also the oligomers. Regarding the latter, the smaller they are, the more active they are.