First, 5732 MOFs with copper open sites were selected by the open metal detector from 13512 TOBACCO-MOFs. A hierarchical strategy was used to select out 1092 MOFs from those MOFs, and their adsorption capacity of the equimolar CO2/H2 mixture at 298 K and 10 bar was further calculated using the grand canonical Monte Carlo simulations. The combination metrics, TSN (a trade-off between SCO2/H2 and NCO2 ) was used to rank the CO2 /H 2 separation performance to identify the top-performance MOFs. Among top-100 MOFs, those MOFs with lvtb topology and organic linker L_13 are conducive to exhibiting high CO2/H 2 adsorption separation performance. The MOFs with pore limited diameter (PLD), largest cavity diameter (LCD), gravimetrical surface area (GSA), and void fraction in the range of 5-8Å, 5-10Å, 5500-6500 m 2 g-1 and 0.70-0.75, respectively, have high NCO2 . MOF-4641 exhibits the highest TSN of 53.71 mol kg -1 , N CO2 =24.18 mol kg -1 , SCO2/H2 =166.68. Then, the adsorption isotherms of various pure gases in top-4 MOFs called MOF-4641, MOF-8595, MOF-7159, and MOF-4867 at 298 K were calculated using GCMC simulations. The dispersed plug flow model was adopted to predict the breakthrough curves of the binary and quinary mixtures in the fixed bed packed with top-4 MOFs, while the effect of inlet concentration and adsorbents on the breakthrough time of CO2 (τCO2 ) was investigated. As inlet CO2 concentration decreases, τCO2 increases. τCO2 in the fixed bed packed with MOF-4641 can reach 261 for the quinary mixture inlet. Finally, the adsorption mechanism of CO2 in the top-4 MOFs was investigated by the RDF and mass center probability density distribution, etc
