Phase Transformation Behavior of a Two‐Dimensional Zeolite

Understanding the molecular‐level mechanisms of phase transformation in solids is of fundamental interest for functional materials such as zeolites. Two‐dimensional (2D) zeolites, when used as shape‐selective catalysts, can offer improved access to the catalytically active sites and a shortened diffusion length in comparison with their 3D analogues. However, few materials are known to maintain both their intralayer microporosity and structure during calcination for organic structure‐directing agent (SDA) removal. Herein we report that PST‐9, a new 2D zeolite which has been synthesized via the multiple inorganic cation approach and fulfills the requirements for true layered zeolites, can be transformed into the small‐pore zeolite EU‐12 under its crystallization conditions through the single‐layer folding process, but not through the traditional dissolution/recrystallization route. We also show that zeolite crystal growth pathway can differ according to the type of organic SDAs employed.     

An Hetero‐Epitaxially Grown Zeolite Membrane

The secondary growth methodology to form zeolite membranes has stringent requirements for homogeneous epitaxial intergrowth of the seed layer and limits the number of accessible high‐quality zeolite membranes. Despite previous reports on hetero‐epitaxial growth, high‐performance zeolite membranes have yet to be reported using this approach. Here, the successful hetero‐epitaxial growth of highly siliceous ZSM‐58 (DDR‐type zeolite) films from a SSZ‐13 (CHA‐type zeolite) seed layer is reported. The resulting membranes show excellent CO₂ perm‐selectivities, having maximum CO₂ /N₂ and CO₂ /CH₄ separation factors (SFs) as high as about 17 and 279, respectively, at 30 °C. Furthermore, the hybrid membrane maintains the CO₂ perm‐selectivity in the presence of water vapor (the third main component in both cases), that is, CO₂ /N₂ SF of about 14 and CO₂ /CH₄ SF of about 78, respectively, at 50 °C (a representative temperature of both CO₂‐containing streams).     

Organic‐Free Synthesis of a Highly Siliceous Faujasite Zeolite with Spatially Biased Q4(nAl) Si Speciation

We report the most siliceous FAU‐type zeolite, HOU‐3, prepared via a one‐step organic‐free synthesis route. Computational studies indicate that it is thermodynamically feasible to synthesize FAU with SAR=2–7, though kinetic factors seemingly impose a more restricted upper limit for HOU‐3 (SAR≈3). Our findings suggest that a slow rate of crystallization and/or low concentration of Na⁺ ions in HOU‐3 growth mixtures facilitate Si incorporation into the framework. Interestingly, Q⁴(nAl) Si speciation measured by solid‐state NMR can only be modeled with a few combinations of Al positioning at tetrahedral sites in the crystal unit cell, indicating the distribution of Si(‐O‐Si)_4−n(‐O‐Al)_n species is spatially biased as opposed to being random. Achieving higher SAR is desirable for improved zeolite (hydro)thermal stability and enhanced catalytic performance, which we demonstrate in benchmark tests that show HOU‐3 is superior to commercial zeolite Y.     

Three‐Dimensional Printing with Biomass‐Derived PEF for Carbon‐Neutral Manufacturing

Biomass‐derived poly(ethylene‐2,5‐furandicarboxylate) (PEF) has been used for fused deposition modeling (FDM) 3D printing. A complete cycle from cellulose to the printed object has been performed. The printed PEF objects created in the present study show higher chemical resistance than objects printed with commonly available materials (acrylonitrile butadiene styrene (ABS), polylactic acid (PLA), glycol‐modified poly(ethylene terephthalate) (PETG)). The studied PEF polymer has shown key advantages for 3D printing: optimal adhesion, thermoplasticity, lack of delamination and low heat shrinkage. The high thermal stability of PEF and relatively low temperature that is necessary for extrusion are optimal for recycling printed objects and minimizing waste. Several successive cycles of 3D printing and recycling were successfully shown. The suggested approach for extending additive manufacturing to carbon‐neutral materials opens a new direction in the field of sustainable development.