Structural Contraction of Zeolitic Imidazolate Frameworks: Membrane Application on Porous Metallic Hollow Fibers for Gas Separation.

Positive thermal expansion coefficients (TECs) of 52 × 10 and 35 × 10 K were experimentally calculated in the -116 to 250 °C range for the III-phases of zeolitic imidazolate frameworks (ZIF) ZIF-9(Co) and ZIF-7(Zn), respectively, by means of the unit cell dimensions and volume of the materials in the monoclinic crystal system calculated from the XRD patterns. The unit cell dimensions and volume showed a significant expansion phenomenon as the temperature increased, by as much as 5.5% for ZIF-9-III in the studied range. To exploit the advantages of such thermal behavior, a new approach to the fabrication of ZIF-9-III membranes on thin, flexible, and highly porous nickel hollow fiber (Ni HF) supports by a versatile and easy-controllable microfluidic setup is herein reported. These Ni HF supports result from the sintering of 25-μm Ni particles and display very positive mechanical properties and bending resistance. As compared to the traditional polymer-based HF membranes, the ZIF metal-supported membrane exhibited good durability and robustness throughout its operation in a wide temperature range and after heating and cooling cycles. These benefits derive from (1) the pore-plugging membrane configuration resulting from the high porosity of the support and (2) the similarity between the TECs of the ZIF and the metallic support, both positive, which enhances their mutual compatibility. An increase in the H/CO separation selectivity at low temperatures (as high as 22.2 at -10 °C, along with 102 GPU permeance of H) was achieved, in agreement with the structural variations observed in the ZIF material.