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Many porous materials are able to absorb CO2 and other gas molecules. However, the selective, room-temperature extraction of CO2 at atmospheric pressure from industrial exhaust containing other gases such as nitrogen, methane, and water remains a major technical challenge. The research team has now developed porous, three-dimensional networks of coordination polymers. Various nickel complexes and organic molecules are used as building blocks that assemble into two-dimensional lattice-like planes, which in turn grow into stacks held together by “columns”. The special trick in this case is that the columns are not rigid, but very flexible. The corresponding cavities in the structure are thus of variable size and can adjust to the guest molecules that enter.
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Keeping limber:
Three-dimensional coordination polymers incorporating flexible
pillars (see picture, left) exhibit highly selective adsorption
of CO2 over N2, H2, and CH4
(see picture, right), thermal stability up to 300 °C, as well as
air and water stability, and allow efficient CO2
capture, storage, and sensing.
[Credit: Angewandte Chemie,
Wiley-VCH (1)] |
The symmetric molecule carbon dioxide has a permanent electrical quadrupole moment that can be described as two electrical dipoles sitting back-to-back and pointing in opposite directions. This quadrupole interacts with the three-dimensional lattice, and this effect causes the columns to open the “gates”, allowing the gas to enter the cavities. In contrast, nitrogen, hydrogen, and methane have much smaller quadrupole moments. The pores thus remain closed to them. The exclusion of nitrogen, which makes up a large proportion of air, is essential for any potential CO2 capture. In addition, the new nickel-containing materials are stable at temperatures up to 300 °C and are air- and water- stable - also an important requirement for potential industrial application. If the surrounding pressure is reduced, the stored CO2 is released. This type of material is thus suited for processes in which carbon dioxide must be cyclically stored and then released through a change in pressure.
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