A CO2-selective molecular gate of poly(amidoamine) dendrimer immobilized in a poly(ethylene glycol) network

A polymeric membrane composed of poly(amidoamine) (PAMAM) dendrimer immobilized in a poly(ethylene glycol) (PEG) network expresses excellent CO2 separation properties over smaller H2. The preferential CO2 permeation can be explained by specific interaction between CO2 and primary amine of the dendrimer, which enhances CO2 solubility into the polymeric membrane. CO2 forms carbamate with the amines or bicarbonate in the presence of water determined by inverse-gate decoupled 13C NMR. The resulting carbamate ion pair works to form a quasi-crosslinking, which would suppress H2 permeation by a CO2-selective Molecular Gate, while bicarbonate ion can be a major moving species to pass through the polymeric membrane. Attenuated total reflection (ATR) indicates the formation of carbamate. Small-angle X-ray scattering (SAXS) reveals increase in scattering intensity under CO2 atmosphere due to the formation of scattering particles, which can be a cluster of the dendrimer-CO2 crosslinks. Tensile testing of the membrane exhibits increase in both Young's modulus and elongation-to-break by CO2 treatment, suggesting that the crosslinking is reversible and rearrangeable. Differential scanning calorimetry (DSC) also shows an exothermic peak at 120°C, which is associated with dissociation of the crosslinks. [Display omitted] •A membrane of PAMAM dendrimer in a PEG network is promising in CO2 separation.•Mechanism of preferential CO2 permeation of the polymeric membrane is investigated.•CO2 takes carbamate and bicarbonate forms in the polymeric membrane.•PAMAM dendrimer is crosslinked by CO2 with the formation of carbamate.•The crosslinks suppress permeation of H2 in CO2 separation by a Molecular Gate.