Hydrocarbon separations are crucial to the chemical industry for the production of valuable feedstocks. However, their structural and chemical similarities have proven daunting challenges to incumbent separation technologies, which are energy- and capital-intensive. Approaches capable of discerning and exploiting minute differences in isomeric hydrocarbons, in particular, may provide solutions to this problem. Metal-organic frameworks (MOFs) integrating the merits of tunable pore size at sub-angstrom scale and pore chemistry in confined spaces have presented promising prospects in adsorptive separation to recognize the minor differences in gas molecules via the judicious design and functionalization. In this Review, we explore the usage of MOFs for the underexplored adsorptive separation of hydrocarbons in the liquid/vapor phase, especially for C6 and C8 isomers. The in-depth insights into the structure-property relationship and the dominant mechanisms, including host-guest interaction modes for the effective adsorption of C6 and C8 hydrocarbons, are systematically discussed. Finally, the effectiveness and scope to translate such design strategies into other systems and the perspective on future development in MOFs for separation are provided.

碳氢化合物分离对于化学工业生产有价值的原料至关重要。然而，事实证明，它们的结构和化学相似性对现有分离技术而言是艰巨的挑战，而现有分离技术是能源和资本密集型的​​。能够识别和利用异构烃中微小差异的方法尤其可以为该问题提供解决方案。金属有机框架（MOF）整合了亚埃级可调孔径的优点和密闭空间中的孔化学特性，在吸附分离中通过明智的设计和功能化识别气体分子中的细微差别提供了有希望的前景。在本综述中，我们探讨了MOF在液相/气相中碳氢化合物吸附开发中的不足的应用，特别是对于C6和C8异构体。系统地讨论了对结构-性质关系和主要机理的深入见解，包括有效吸附C6和C8烃的主体-客体相互作用模式。最后，提供了将此类设计策略转换为其他系统的有效性和范围，以及对MOF中分离的未来发展的看法。