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.