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  • Title: Spatio-Chemical Heterogeneity of Defect-Engineered Metal-Organic Framework Crystals Revealed by Full-Field Tomographic X-ray Absorption Spectroscopy.
    Author: Ferreira Sanchez D, Ihli J, Zhang D, Rohrbach T, Zimmermann P, Lee J, Borca CN, Böhlen N, Grolimund D, van Bokhoven JA, Ranocchiari M.
    Journal: Angew Chem Int Ed Engl; 2021 Apr 26; 60(18):10032-10039. PubMed ID: 33523530.
    Abstract:
    The introduction of structural defects in metal-organic frameworks (MOFs), often achieved through the fractional use of defective linkers, is emerging as a means to refine the properties of existing MOFs. These linkers, missing coordination fragments, create unsaturated framework nodes that may alter the properties of the MOF. A property-targeted utilization of this approach demands an understanding of the structure of the defect-engineered MOF. We demonstrate that full-field X-ray absorption near-edge structure computed tomography can help to improve our understanding. This was demonstrated by visualizing the chemical heterogeneity found in defect-engineered HKUST-1 MOF crystals. A non-uniform incorporation and zonation of the defective linker was discovered, leading to the presence of clusters of a second coordination polymer within HKUST-1. The former is suggested to be responsible, in part, for altered MOF properties; thereby, advocating for a spatio-chemically resolved characterization of MOFs.
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