An Explanation for the Very Large Breathing Effect of a Metal–Organic Framework during CO2 Adsorption


  • This work was supported by CNRS, EU funding via FP6-Specific Targeted Research Project “DeSANNS” (SES6-020133) and UK-EPSRC funding. The authors are indebted to the Daresbury SRS and the ESRF in Grenoble for providing beamtime and the help of their staff during and after the experiments. Supporting Information is available online from Wiley InterScience or from the author.


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The unusual adsorption behavior of CO2 in a nanoporous hybrid metal– organic solid is discussed (see figure). The results indicate that the gas adsorption–desorption step is related to a breathing phenomenon. This study also suggests that the main interactions responsible for the breathing phenomenon are strong guest–framework CO2–OH interactions as well as CO2–CO2 interactions along the tunnels present in the structure.