近日，天津工业大学马小华团队实现了双交联聚酰亚胺前驱体制备的亚纳米精度碳分子筛膜的高H₂回收率。相关论文于2025年7月8日发表在《德国应用化学》杂志上。

节能净化技术对于推进可持续的氢经济至关重要。碳分子筛膜（CMSM）已成为有前景的候选者；然而，实现精确的亚埃微孔控制和确保结构稳定性仍然是重大挑战。研究组介绍了一种双交联策略，通过利用脱羰3,5-二氨基苯甲酸诱导的刚性网络（A型）和硫键诱导的柔性网络（B型）来设计所得CMSM的微孔性。6F-D-S-CMS膜表现出3464Barrer的创纪录的高H2渗透率，H₂/CH₄选择性为3807，超过了Robeson上限。

在850°C下热解后，6F-D-S-CMS-850膜实现了卓越的选择性值：H₂/CH₄为6538，H₂/N₂为1634，H₂/CO₂为149，优于大多数报道的CMS膜。分子动力学模拟显示，B型网络抑制了CH₄的吸附（3.6 vs.6.2 cm³/g），并在碳化过程中显著提高了小孔体积比（VH₂/VCH₄:10.3 vs.2.1），从而消除了非选择性途径并减少了骨架间距（4.09Åvs.3.78Å），从而实现了精确的分子筛选。CMSM的这种刚性-柔性交联策略为下一代氢气生产建立了可扩展的蓝图。 

附：英文原文

Title: High H2 Recovery Properties of Carbon Molecular Sieve Membranes with Sub-nanometer Precision Derived from Dual Cross-linked Polyimide Precursors

Author: Mingwei Cai, Huahui Liang, Fuhui Liang, Meiling Tao, Luxin Sun, xiaohua ma, Shiyang Zhang, Yonggang Min

Issue&Volume: 2025-07-08

Abstract: Energy-efficient purification technologies are essential for advancing a sustainable hydrogen economy. Carbon molecular sieve membranes (CMSMs) have emerged as promising candidates; however, achieving precise sub-Angstrom micropore control and ensuring structural stability remain significant challenges. Here, we introduce a dual cross-linked strategy to engineer microporosity of the resulting CMSMs by utilizing decarbonylated 3,5-diaminobenzoic acid-induced rigid network (Type A) in conjunction with sulfur bond-induced flexible network (Type B). The 6F-D-S-CMS membrane exhibits a record-high H2 permeability of 3,464 Barrer with H2/CH4 selectivity of 3,807, surpassing the Robeson upper bound. Upon pyrolysis at 850°C, the 6F-D-S-CMS-850 membrane achieves exceptional selectivity values: H2/CH4 at 6,538, H2/N2 at 1,634 and H2/CO2 at 149—outperforming most reported CMS membranes. Molecular dynamics simulations revealed that the Type B network suppressed CH4 adsorption (3.6 vs. 6.2 cm3/g) and significantly enhanced the small pore volume ratio (VH2/VCH4: 10.3 vs. 2.1) during carbonization, thereby eliminating non-selective pathways and reducing inter-skeletal spacing (4.09 vs. 3.78 ), which enables precise molecular sieving. This rigid-flexible cross-linked strategy for CMSMs establishes a scalable blueprint for next-generation hydrogen production.

DOI: 10.1002/anie.202509756

Source: https://onlinelibrary.wiley.com/doi/10.1002/anie.202509756