Lin Shengjie, Liang Ye, Ke Peiren, Wang Limin, Chen Deli, Zhang Lin, He Yabing
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, College of Chemistry and Materials Science, Zhejiang Normal University, Jinhua, 321004, China.
Key Laboratory of the Ministry of Education for Advanced Catalysis Materials, Institute of Physical Chemistry, Zhejiang Normal University, Jinhua, 321004, China.
Angew Chem Int Ed Engl. 2025 Apr 11;64(16):e202500970. doi: 10.1002/anie.202500970. Epub 2025 Feb 11.
Efficient separation and purification of methane is a key step in promoting its wide application as an environmentally friendly energy carrier and an important chemical raw material. Development of single solid adsorbents simultaneously combining robust structure, high separation capacity, and easy performance recovery is highly desired but quite a challenge for realizing methane depuration. In the present study, we report an ultramicroporous hydrogen-bonded organic framework compound constructed from a tetracyano bithiophene-functionalized ligand. Similar to the acting principle of enzymes, multisite supramolecular interactions endow the material with not only extraordinary chemical stability in wide pH range including 12 M HCl and 20 M NaOH solutions but also highly selective recognition of acetylene and carbon dioxide over methane. The packing densities and adsorption selectivities toward acetylene and carbon dioxide are the highest reported for the hydrogen-bonded organic framework materials. Dynamic breakthrough experiments demonstrate its highly efficient methane purification ability from binary and even ternary mixed gases, with not only methane productivities up to 2.34 mol kg but also moderate regeneration energy. Furthermore, the title compound can be easily regenerated in almost quantitative yield via simple rato-evaporation of its dichloromethane solution once its activity is attenuated or lost.
高效分离和提纯甲烷是推动其作为环境友好型能源载体和重要化学原料广泛应用的关键步骤。开发同时兼具坚固结构、高分离能力和易于性能恢复的单一固体吸附剂是非常理想的，但对于实现甲烷净化来说却是一项颇具挑战的任务。在本研究中，我们报道了一种由四氰基联噻吩功能化配体构建的超微孔氢键有机骨架化合物。类似于酶的作用原理，多位点超分子相互作用赋予该材料不仅在包括12 M HCl和20 M NaOH溶液在内的宽pH范围内具有非凡的化学稳定性，而且对乙炔和二氧化碳具有高于甲烷的高度选择性识别能力。对于氢键有机骨架材料而言，其对乙炔和二氧化碳的堆积密度及吸附选择性是已报道中的最高值。动态突破实验证明了其从二元甚至三元混合气体中高效净化甲烷的能力，不仅甲烷产率高达2.34 mol kg，而且再生能量适中。此外，一旦其活性减弱或丧失，通过简单地对其二氯甲烷溶液进行减压蒸发，标题化合物就能以几乎定量的产率轻松再生。
