Recent developments in carbon nanotube membranes for water purification and gas separation

Carbon nanotubes (CNTs) are nanoscale cylinders of graphene with exceptional properties such as high mechanical strength, high aspect ratio and large specific surface area. To exploit these properties for membranes, macroscopic structures need to be designed with controlled porosity and pore size. This manuscript reviews recent progress on two such structures: (i) CNT Bucky-papers, a non-woven, paper like structure of randomly entangled CNTs, and (ii) isoporous CNT membranes, where the hollow CNT interior acts as a membrane pore. The construction of these two types of membranes will be discussed, characterization and permeance results compared, and some promising applications presented.

Acid–organic base swollen polymer membranes

In this work, two different polymer membrane systems based on Nafion and Teflon were investigated as proton conductors for polymer membrane fuel cells. Water-free Nafion117 membranes swollen with different non-aqueous solvents were prepared. The solvents included imidazole, imidazole–imidazolium salt solutions, room temperature molten salts and molten salt–acid solutions. Teflon films were treated with a surfactant, or a Nafion solution, to improve their surface properties, and were subsequently swollen with phosphoric acid. Conductivity measurements were carried out on both the Nafion and Teflon membranes. Conductivities in the range of 10⁻³ S cm⁻¹ at around 100°C were obtained. This is still an order of magnitude lower than the corresponding water swollen Nafion at 80°C.

Enhanced oxygen permeation through perovskite hollow fibre membranes by methane activation

Hollow fibre membranes of mixed conducting perovskite La_0.6Sr_0.4Co_0.2Fe_0.8O₃ (LSCF) were prepared via the combined phase inversion and sintering technique. The fibres were tested for air separation with a home-made reactor under the oxygen partial pressure gradient generated by the air/He streams. Some fibres were in situ activated by introducing methane in the He sweeping gas at high temperatures. The activated membranes with new morphology were created by transforming the inner densified surface layer to a porous structure. Compared to the original membranes, the activated gave appreciable higher oxygen fluxes. At 800 °C, the oxygen fluxes were increased by a factor of 10 after activation was carried out at 1000 °C for 1 h.

Proton conductive composite membranes

In this work we investigated the synthesis of composite organic and inorganic membranes for proton conduction. Particles derived from metal alkoxides (M(OR)n) sol-gel processes (Ti, Zr, W with phosphoric acid) were embedded in polymeric matrices of poly-vinyl alcohol, (3-glycidoxypropyl)-trimethoxysilane and ethylene glycol. The structure of the composite membranes was complex as several IR peaks were convoluted, indicating the assignment of several functional groups. However, the peaks assigned to OH groups reduced in intensity in the composite membranes, indicating that cross-linking of hydroxyl groups in the organic and inorganic phases of the membrane may have occurred. The particles allowed for re-arrangement of the polymer matrix, as crystallinity was reduced compared to a polymer blank membrane. The composite membrane process resulted in homogeneous dispersion of nanoparticles into the polymer film. Proton conduction of the inorganic phase was mainly dominated by titania. Binary mixtures of titania phosphate (sample name TiP) resulted in proton conduction of 7.15 × 10−2 S.cm−1, one order of magnitude higher than zirconia phosphate (ZrP). The addition of Zr and W to TiP forming ternary or quaternary phases also led to lower proton conduction as compared to TiP. Similar trends were also observed for the composite membranes, though the TiP composite membrane proton conduction reduced after several hours of testing at 50°C, which was mainly attributed to acid leaching.