Materials Genomics-guided Ab Initio Screening Of Mofs With Open Copper Sites For Acetylene Storage And Separation

As an important industrial raw material,acetylene is often used to produce a variety of chemical products,and also widely used in welding technology.The highly flammable and reactive nature of acetylene poses significant challenges to its safe storage and transportation.Even under anaerobic room temperature,the storage pressure of acetylene should be less than 0.2 MPa,otherwise it will cause serious explosion.Recently,metal-organic frameworks(MOFs)materials have received extensive attention from scientists in the field of safe storage and purification of acetylene,showing great application prospects.In this dissertation,with the aid of the concept of material genomics,a copper-bearing paddle structural unit containing unsaturated coordination metal sites,Cu2(COO)4,was used as a characteristic material gene,a database containing 797 Cu-MOF materials was built from the experimentally reported materials deposited in the Cambridge Crystal Strcucture Database(CSD).Such obtained database was further utilized to perform large-scale screening studies on the storage and separation of the systems related to acetylene gas.The main research contents and achievements are as follows.Firstly,using the Density Functional Theory(DFT)calculation method,a new force field that can accurately describe the interaction between acetylene and Cu-OMS was developed,which used for high-throughput computational materials screening at room temperature and atmospheric pressure.Based on the established structure-activity relationships,the ranges of the best structural features of MOFs required for this system were proposed.Through computational screening,three prospective MOFs were discovered whose acetylene storage performance is far superior to various porous materials reported so far.With respect to the separation of C2H2/CO2 system,molecular force fields suitable for describing the strong interactions between CO2 and Cu-OMS were developed on the basis of Based on the above work.From the large-scale computational materials screening,three promising MOF materials were idenfitied with performane exceeding all the materials reported currently,both in the C2H2/CO2 selectivity and C2H2 adsorption capacity.The results of the dissertation can not only save a lot of financial and material resources for the discovery and synthesis of new materials towards acetylene systems,but also provide practical theoretical guidance for the targeted design and synthesis of new high-performance materials in the future.