Layered covalent organic frameworks (2D‐COFs), composed of reversible imine linkages and accessible pores, offer versatility for chemical modifications towards the development of catalytic materials. Nitrogen‐enriched COFs are good candidates for binding Pd species. Understanding the local structure of reacting Pd sites bonded to the COF pores is key to rationalize interactions between active sites and porous surfaces. By combining advanced synchrotron characterization methods with periodic computational DFT modeling, the precise atomic structure of catalytic Pd sites attached to local defects is resolved within an archetypical imine‐linked 2D‐COF. This material was synthesized using an in situ method as a gel, under which imine hydrolysis and metalation reactions are coupled. Local defects formed in situ within imine‐linked 2D‐COF materials are highly reactive towards Pd metalation, resulting in active materials for Suzuki–Miyaura cross‐coupling reactions.

Pair distribution function, PDF, analyses are emerging as a powerful tool to characterize non-ideal metal–organic framework (MOF) materials with compromised ordering.

Encapsulating ultrasmall Cu nanoparticles inside Zr-MOFs to form core-shell architecture is very challenging but of interest for CO 2 reduction. We report for the first time the incorporation of ultrasmall Cu NCs into a series of benchmark Zr-MOFs, without Cu NCs aggregation, via a scalable room temperature fabrication approach. The Cu NCs@MOFs core-shell composites show much enhanced reactivity in comparison to the Cu NCs confined in the pore of MOFs, regardless of their very similar intrinsic properties at the atomic level. Moreover, introducing polar groups on the MOF structure can further improve both the catalytic reactivity and selectivity. Mechanistic investigation reveals that the Cu I sites located at the interface between Cu NCs and support serve as the active sites and efficiently catalyze CO 2 photoreduction. This synergetic effect may pave the way for the design of low-cost and efficient catalysts for CO 2 photoreduction into high-value chemical feedstock.

Stabilizing catalytic iron-oxo-clusters within nanoporous metal-organic frameworks (MOF) is a powerful strategy to prepare new active materials for the degradation of toxic chemicals, such as bisphenol A. Herein, we combine...

The metal-organic framework MOF-808 contains Zr6O8 nodes with a high density of vacancy sites, which can incorporate carboxylate-containing functional groups to tune chemical reactivity. Although the postsynthetic methods to modify the chemistry of the Zr6O8 nodes in MOFs are well known, tackling these alterations from a structural perspective is still a challenge. We have combined infrared spectroscopy experiments and first-principles calculations to identify the presence of node vacancies accessible for chemical modifications within the MOF-808. We demonstrate the potential of our approach to assess the decoration of MOF-808 nodes with different catechol–benzoate ligands. Furthermore, we have applied advanced synchrotron characterization tools, such as pair distribution function analyses and X-ray absorption spectroscopy, to resolve the atomic structure of single metal sites incorporated into the catechol groups postsynthetically. Finally, we demonstrate the catalytic activity of these MOF-808 materials decorated with single copper sites for 1,3-dipolar cycloadditions.