Modelling across Multiple Scales to Design Biopolymer Membranes for Sustainable Gas Separations: 1-Atomistic Approach.

In this work, we assessed the CO 2 and CH 4 sorption and transport in copolymers of 3-hydroxybutyrate and 3-hydroxyvalerate (PHBV), which showed good CO 2 capture potential in our previous papers, thanks to their good solubility-selectivity, and are potential biodegradable alternatives to standard membrane-separation materials. Experimental tests were carried out on a commercial material containing 8% of 3-hydroxyvalerate (HV), while molecular modelling was used to screen the performance of the copolymers across the entire composition range by simulating structures with 0%, 8%, 60%, and 100% HV, with the aim to provide a guide for the selection of the membrane material. The polymers were simulated using molecular dynamics (MD) models and validated against experimental density, solubility parameters, and X-ray diffraction. The CO 2 /CH 4 solubility-selectivity predicted by the Widom insertion method is in good agreement with experimental data, while the diffusivity-selectivity obtained via mean square displacement is somewhat overestimated. Overall, simulations indicate promising behaviour for the homopolymer containing 100% of HV. In part 2 of this series of papers, we will investigate the same biomaterials using a macroscopic model for polymers and compare the accuracy and performance of the two approaches.