A method to control the arrangement of various metal elements in MOFs at atomic and mesoscopic scales is described.

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

Melt-quenched metal−organic framework (MOF) glasses have gained significant interest as the first new category of glass reported in 50 years. In this work, an amine-functionalized zeolitic imidazolate framework (ZIF), denoted ZIF-UC-6, was prepared and demonstrated to undergo both melting and glass formation. The presence of an amine group resulted in a lower melting temperature compared to other ZIFs, while also allowing material properties to be tuned by post-synthetic modification (PSM). As a prototypical example, the ZIF glass surface was functionalized with octyl isocyanate, changing its behavior from hydrophilic to hydrophobic. PSM therefore provides a promising strategy for tuning the surface properties of MOF glasses.

In the present contribution, we report how through the use of metal-organic frameworks (MOFs) composed of addressable combinations of up to four different metal elements it is possible to program the composition of multi-metal oxides, which are not attainable by other synthetic methodologies. Thus, due to the ability to distribute multiple metal cations at specific locations in the MOF secondary building units it is possible to code and transfer selected metal ratios to multi-metal oxides with novel, desired compositions through a simple calcination process. The demonstration of an enhancement in the electrocatalytic activity of new oxides by pre-adjusting the metal ratios is here reported for the oxygen reduction reaction, for which activity values comparable to commercial Pt/C catalysts are reached, while showing long stability and methanol tolerance.