Computational Studies on Holey TMC₆ (TM = Mo and W) Membranes for H₂ Purification

The purification of hydrogen (H2) has been a vital step in H2 production processes such as steam−methane reforming. By first-principle calculations, we revealed the potential applications of holey TMC6 (TM = Mo and W) membranes in H2 purification. The adsorption and diffusion behaviors of five gas molecules (including H2, N2, CO, CO2, and CH4) were compared on TMC6 membranes with different phases. Though the studied gas molecules show weak physisorption on the TMC6 membranes, the smaller pore size makes the gas molecules much more difficult to permeate into h-TMC6 rather than into s-TMC6. With suitable pore sizes, the s-TMC6 structures not only show an extremely low diffusion barrier (around 0.1 eV) and acceptable permeance capability for the H2 but also exhibit considerably high selectivity for both H2/CH4 and H2/CO2 (>1015), especially under relatively low temperature (150−250 K). Moreover, classical molecular dynamics simulations on the permeation process of a H2, CO2, and CH4 mixture also validated that s-TMC6 could effectively separate H2 from the gas mixture. Hence, the s-MoC6 and s-WC6 are predicted to be qualified H2 purification membranes, especially below room temperature.