Understanding the Impacts of Support-Polymer Interactions on the Dynamics of Poly(ethyleneimine) Confined in...

Supported amines are a promising class of CO₂ sorbents offering large uptake capacities and fast uptake rates. Among supported amines, poly(ethyleneimine) (PEI) physically impregnated in the mesopores of SBA-15 silica is widely used. Within these composite materials, the chain dynamics and morphologies of PEI strongly influence the CO₂ capture performance, yet little is known about chain and macromolecule mobility in confined pores. Here, we probe the impact of the support-PEI interactions on the dynamics and structures of PEI at the support interface and the corresponding impact on CO₂ uptake performance, which yields critical structure-property relationships. The pore walls of the support are grafted with organosilanes with different chemical end groups to differentiate interaction modes (spanning from strong attraction to repulsion) between the pore surface and PEI. Combinations of techniques, such as quasi-elastic neutron scattering (QENS), ¹H T₁-T₂ relaxation correlation solid-state NMR, and molecular dynamics (MD) simulations, are used to comprehensively assess the physical properties of confined PEI. We hypothesized that PEI would have faster dynamics when subjected to less attractive or repulsive interactions. However, we discover that complex interfacial interactions resulted in complex structure-property relationships. Indeed, both the chain conformation of the surface-grafted chains and of the PEI around the surface influenced the chain mobility and CO₂ uptake performance. By coupling knowledge of the dynamics and distributions of PEI with CO₂ sorption performance and other characteristics, we determine that the macroscopic structures of the hybrid materials dictate the first rapid CO₂ uptake, and the rate of CO₂ sorption during the subsequent gradual uptake stage is determined by PEI chain motions that promote diffusive jumps of CO₂ through PEI-packed domains.