Lei Ge,Jiaqi Li,Gaojing Du,Kai Sheng,Jingwei Hou,Binyu Zhou,Yatao Zhang,Bart Van der Bruggen,Junyong Zhu
Microporous membranes featuring 3D nanochannels present a compelling avenue for energy-efficient liquid separations, attributable to their tunable interconnected through-pore structures. However, the rational design of 3D-nanochannel membranes that simultaneously achieve high permeance and selectivity remains a challenge, arising from the scarcity of appropriate molecular building blocks and the reliance on empirical synthetic methods. Herein, an innovative 3D polyacylhydrazone (PAH) membrane with unique pore-interconnected structures is constructed on a porous hydrogel using contorted tetrahedral aldehydes (TFS) monomers via an in situ interface-confined strategy. Manipulation of side alkyl chain lengths within terephthalohydrazide (TPH) derivates enabled the enhancement of microporosity and tunable pore environment of PAH nanofilms. Molecular dynamics simulations revealed that TPH EO linkers with higher reactivity and moderate steric hindrance facilitate superior pore interconnectivity and sharpened pore size distributions. The resulting PAH membranes achieved exceptional methanol permeances of 10.1 L m −2 h −1 bar −1 and small molecular weight cut-offs of 310 Da, outperforming the state-of-the-art polyamide membranes. This further translated into an outstanding capability in the fractionation of active pharmaceutical ingredients within organic solvent systems. This work demonstrates the efficacy of rational molecular design in developing high-microporosity membranes with tailored interconnected nanochannels, underscoring the potential of 3D microporous membranes for accurate molecular separations.
Acylhydrazone linkages are attractive in designing reconfigurable and chemically recyclable polymer due to their reversible characteristics and ease of preparation. We fabricate mechanically strong, thermally stable and chemically recyclable poly(acylhydrazone)s (pDFF-IPDH) using biobased 2,5-diformylfuran (DFF) and dihydrazide compounds as monomers. The linear chains are physically cross-linked via hydrogen bonding between the acylhydrazone moieties. The pDFF-IPDH sample exhibits good mechanical properties, offering both high strength and toughness. The linear and reversible acylhydrazone backbones endow polymers with attractive temperature-dependent dynamic natures, which enables the topological network to rearrange, giving the poly(acylhydrazone)s excellent reprocessability. Moreover, the feasibility of formaldehyde-promoted depolymerization presents an effective recycling pathway, offering promising opportunities in addressing the challenge between recyclability and service performance.
危险品化学品经营许可证（带存储）