To prevent greenhouse
emissions into the atmosphere, separations
like CO2/CH4 and CO2/N2 from natural gas, biogas, and flue gasses are crucial. Polymer membranes
gained a key role in gas separations over the past decades, but these
polymers are often not organized at a molecular level, which results
in a trade-off between permeability and selectivity. In this work,
the effect of molecular order and orientation in liquid crystals (LCs)
polymer membranes for gas permeation is demonstrated. Using the self-assembly
of polymerizable LCs to prepare membranes ensures control over the
supramolecular organization and alignment of the building blocks at
a molecular level. Robust freestanding LC membranes were fabricated
that have various, distinct morphologies (isotropic, nematic cybotactic,
and smectic C) and alignment (planar and homeotropic), while using
the same chemical composition. Single gas permeation data show that
the permeability decreases with increasing molecular order while the
ideal gas selectivity of He and CO2 over N2 increases
tremendously (36-fold for He/N2 and 21-fold for CO2/N2) when going from randomly ordered to the highly
ordered smectic C morphology. The calculated diffusion coefficients
showed a 10-fold decrease when going from randomly ordered membranes
to ordered smectic C membranes. It is proposed that with increasing
molecular order, the free volume elements in the membrane become smaller,
which hinders gasses with larger kinetic diameters (Ar, N2) more than gasses with smaller kinetic diameters (He, CO2), inducing selectivity. Comparison of gas sorption and permeation
performances of planar and homeotropic aligned smectic C membranes
shows the effect of molecular orientation by a 3-fold decrease of
the diffusion coefficient of homeotropic aligned smectic C membranes
resulting in a diminished gas permeation and increased ideal gas selectivities.
These results strongly highlight the importance of molecular order
and orientation in LC polymer membranes for gas separation.