On the contribution of Pair Distribution Function (PDF) to the characterization of nanocrystalline MOFs: The case of M-MOF-74*

Nanoporous Metal-Organic Frameworks (MOFs) have a great potential in so many industrial applications including heterogeneous catalysis and gas storage/capture/separation. MOF-74 is one of the most interesting MOFs in an academic context, as it contains open metal sites, possesses high versatility in metal nature, and can be prepared with so small crystal size. As a consequence, the catalytic activity of these nanocrystalline materials is superior to that given by their conventional counterparts. However, their characterization by conventional Xray diffraction (XRD) is insufficient. In this work, we present a joint study of XRD and Pair Distribution Function (PDF) -both acquired under synchrotron radiation- of a series of nanocrystalline M-MOF-74 materials (M = Mg, Co, Ni, Cu or Zn) prepared at room temperature. Whereas the XRD continues being lacking for an adequate structural characterization, PDF provides key structural information at medium and short range and, therefore, is ideal for studying such nano-domains. It was confirmed that these materials are exclusively composed by MOF74 phase and that their poor ability to diffract is due solely to their eminent nanocrystallinity, which resulted to be even more pronounced than it has been previously estimated. Beyond Scherrer-like approaches, PDF can give direct information about the range of crystal size in nanocrystalline materials. Moreover, the technique is also able to detect slight structural deviations in short-range environments, just like it is made clear in the case of CuMOF-74 compared with the rest of M-MOF-74 materials, which possesses a marked Jahn-Teller effect in the octahedral coordination of Cu.

Automated summary

In this study, a joint analysis of XRD and PDF was conducted on nanocrystalline M-MOF-74 materials, revealing the significance of PDF in studying nano-domains and providing information on crystal size range and slight structural deviations.