In Situ Transformation of an Amorphous Supramolecular Coating to a Hydrogen-Bonded Organic Framework Membrane to Trigger Selective Gas Permeation.

We introduce a "solution-processing-transformation" strategy, deploying solvent vapor as scaffolds, to fabricate high-quality hydrogen-bonded organic framework (HOF) membranes. This strategy can overcome the mismatch in processing conditions and crystal growth thermodynamics faced during the facile solution processing of the membrane. The procedure includes the vapor-trigged in situ transformation of dense amorphous supramolecules to crystalline HOF-16, with HOF-11 as the transient state. The mechanism involves a vapor-activated dissolution-precipitation equilibrium shifting and hydrogen bonding-guided molecule rearrangement, elucidated through combined experimental and theoretical analysis. Upon removal of the molecular scaffolds, the resulting HOF-16 membranes showcase significant improvement in hydrogen separation performance over their amorphous counterparts and previously reported HOF membranes. The method's broad applicability is evidenced by successfully extending it to other substrates and HOF structures. This study provides a fundamental understanding of guest-induced ordered supramolecular assembly and paves the way for the advanced manufacture of high-performance HOF membranes for gas separation processes.

Solution processing of crystalline porous material based membranes for CO2 separation.

The carbon emission problem is a significant challenge in today's society, which has led to severe global climate issues. Membrane-based separation technology has gained considerable interest in CO2 separation due to its simplicity, environmental friendliness, and energy efficiency. Crystalline porous materials (CPMs), such as zeolites, metal-organic frameworks, covalent organic frameworks, hydrogen-bonded organic frameworks, and porous organic cages, hold great promise for advanced CO2 separation membranes because of their ordered and customizable pore structures. However, the preparation of defect-free and large-area crystalline porous material (CPM)-based membranes remains challenging, limiting their practical use in CO2 separation. To address this challenge, the solution-processing method, commonly employed in commercial polymer preparation, has been adapted for CPM membranes in recent years. Nanosheets, spheres, molecular cages, and even organic monomers, depending on the CPM type, are dissolved in suitable solvents and processed into continuous membranes for CO2 separation. This feature article provides an overview of the recent advancements in the solution processing of CPM membranes. It summarizes the differences among the solution-processing methods used for forming various CPM membranes, highlighting the key factors for achieving continuous membranes. The article also summarizes and discusses the CO2 separation performance of these membranes. Furthermore, it addresses the current issues and proposes future research directions in this field. Overall, this feature article aims to shed light on the development of solution-processing techniques for CPM membranes, facilitating their practical application in CO2 separation.