Interchain-expanded extra-large-pore zeolites.

Stable aluminosilicate zeolites with extra-large pores that are open through rings of more than 12 tetrahedra could be used to process molecules larger than those currently manageable in zeolite materials. However, until very recently1-3, they proved elusive. In analogy to the interlayer expansion of layered zeolite precursors4,5, we report a strategy that yields thermally and hydrothermally stable silicates by expansion of a one-dimensional silicate chain with an intercalated silylating agent that separates and connects the chains. As a result, zeolites with extra-large pores delimited by 20, 16 and 16 Si tetrahedra along the three crystallographic directions are obtained. The as-made interchain-expanded zeolite contains dangling Si-CH3 groups that, by calcination, connect to each other, resulting in a true, fully connected (except possible defects) three-dimensional zeolite framework with a very low density. Additionally, it features triple four-ring units not seen before in any type of zeolite. The silicate expansion-condensation approach we report may be amenable to further extra-large-pore zeolite formation. Ti can be introduced in this zeolite, leading to a catalyst that is active in liquid-phase alkene oxidations involving bulky molecules, which shows promise in the industrially relevant clean production of propylene oxide using cumene hydroperoxide as an oxidant.

Confinement of CsPbBr3 Perovskite Nanocrystals into Extra-large-pore Zeolite for Efficient and Stable Photocatalytic Hydrogen Evolution.

Metal halide perovskites (MHPs), renowned for their outstanding optoelectronic properties, hold significant promise as photocatalysts for hydrogen evolution reaction (HER). However, the low stability and insufficient exposure of catalytically active sites of bulky MHPs seriously impair their catalytic efficiency. Herein, we utilized an extra-large-pore zeolite ZEO-1 (JZO) as a host to confine and stabilize the CsPbBr3 nanocrystals (3.4 nm) for boosting hydrogen iodide (HI) splitting. The as-prepared CsPbBr3@ZEO-1 featured sufficiently exposed active sites, superior stability in acidic media, along with intrinsic extra-large pores of ZEO-1 that were favorable for molecule/ion adsorption and diffusion. Most importantly, the unique nanoconfinement effect of ZEO-1 led to the narrowing of the band gap of CsPbBr3, allowing for more efficient light utilization. As a result, the photocatalytic HER rate of the as-prepared CsPbBr3@ZEO-1 photocatalyst was increased to 1734 µmol ⋅ h-1 ⋅ g-1 (CsPbBr3) under visible light irradiation compared with bulk CsPbBr3 (11 µmol ⋅ h-1 ⋅ g-1 (CsPbBr3)), and the long-term durability (36 h) can be achieved. Furthermore, Pt was incorporated with well-dispersed CsPbBr3 nanocrystals into ZEO-1, resulting in a significant enhancement in activity (4826 µmol ⋅ h-1 ⋅ g-1 (CsPbBr3)), surpassing most of the Pt-integrated perovskite-based photocatalysts. Density functional theory (DFT) calculations and charge-carrier dynamics investigation revealed that the dramatically boosted photocatalytic performance of Pt/CsPbBr3@ZEO-1 could be attributed to the promotion of charge separation and transfer, as well as to the substantially lowered energy barrier for HER. This work highlights the advantage of extra-large-pore zeolites as the nanoscale platform to accommodate multiple photoactive components, opening up promising prospects in the design and exploitation of novel zeolite-confined photocatalysts for energy harvesting and storage.

Constructing Intrapenetrated Hierarchical Zeolites with Highly Complete Framework via Protozeolite Seeding.

Creation of intrapenetrated mesopores with open highway from external surface into the interior of zeolite crystals are highly desirable that can significantly improve the molecular transport and active sites accessibility of microporous zeolites to afford enhanced catalytic properties. Here, different from traditional zeolite-seeded methods that generally produced isolated mesopores in zeolites, nanosized amorphous protozeolites with embryo structure of zeolites were used as seeds for the construction of single-crystalline hierarchical ZSM-5 zeolites with intrapenetrated mesopores (mesopore volume of 0.51 cm3 g-1 ) and highly complete framework. In this strategy, in contrast to the conventional synthesis, only a small amount of organic structure directing agents and a low crystallization temperature were adopted to promise the protozeolites as the dominant growth directing sites to induce crystallization. The protozeolite nanoseeds provided abundant nucleation sites for surrounding precursors to be crystallized, followed by oriented coalescence of crystallites resulting in the formation of intrapenetrated mesopores. The as-prepared hierarchical ZSM-5 zeolites exhibited ultra-long lifetime of 443.9 hours and a high propylene selectivity of 47.92 % at a WHSV of 2 h-1 in the methanol-to-propylene reaction. This work provides a facile protozeolite-seeded strategy for the synthesis of intrapenetrated hierarchical zeolites that are highly effective for catalytic applications.

Impact of a polymer modifier on directing the non-classical crystallization pathway of TS-1 zeolite: accelerating nucleation and enriching active sites.

The crystallization process directly affects the physicochemical properties and active centers of zeolites; however, controllable tuning of the zeolite crystallization process remains a challenge. Herein, we utilized a polymer (polyacrylamide, PAM) to control the precursor structure evolution of TS-1 zeolite through a two-step crystallization process, so that the crystallization path was switched from a classical to a non-classical mechanism, which greatly accelerated nucleation and enriched active Ti sites. The TS-1 crystallization process was investigated by means of various advanced characterization techniques. It was found that specific interactions between PAM and Si/Ti species promoted the assembly of colloidal precursors containing ordered structural fragments and stabilized Ti species in the precursors, leading to a 1.5-fold shortened crystallization time and enriched Ti content in TS-1 (Si/Ti = 29). The PAM-regulated TS-1 zeolite exhibited enhanced catalytic performance in oxidative reactions compared to conventional samples.