▎ 摘　　要

The computational simulation of porous graphene oxide (PGO) indicated that it has great potential for the preparation of gas separation membranes. However, scaling up the manufacture of multilayer, defect-free porous graphene oxide membrane with consistently sized nanopores is extremely challenging. Here, we prepared layer-by-layer COrphilic Pebax@1657 membranes that were functionalized by o-hydroxyazo-hierarchical porous organic polymers (o-POPs) and PGO. The d-spacing of pristine PGO could be finely regulated through COrphilic o-POPs to facilitate the permeability of CO,. In addition, the o-POPs exhibit "N-2-phobic, CO2-philic" properties with the phenolic hydroxyl and the azo group. The best of the POP-PGO membrane exhibits that the CO, permeability and ideal selectivity of CO2/N-2 are 232.7 Barrer and 80.7, respectively, and it has surpassed the Robeson's upper bound (2008).