Enabling Ethanol Dehydrogenation Catalysis by Postsynthetic Anion Exchange of Triazolate-Based Metal-Organic Frameworks.

Materials containing soft, polarizable elements are expanding the boundaries of catalytic properties, offering unique electronic communication and stability characteristics compared with their harder counterparts due to the enhanced covalent nature of metal-ligand interactions. However, integrating soft components like sulfur into metal-organic frameworks (MOFs) for catalytic applications remains a largely underexplored challenge. Here, we report the synthesis of a family of triazole-based MOFs and expand upon established postsynthetic anion exchange methods to incorporate sterically encumbered polarizable elements, such as alkyl thiolates.

Introducing metal-sulfur active sites in metal-organic frameworks via post-synthetic modification for hydrogenation catalysis.

Metal-sulfur active sites play a central role in catalytic processes such as hydrogenation and dehydrogenation, yet the majority of active sites in these compounds reside on the surfaces and edges of catalyst particles, limiting overall efficiency. Here we present a strategy to embed metal-sulfur active sites into metal-organic frameworks (MOFs) by converting bridging or terminal chloride ligands into hydroxide and subsequently into sulfide groups through post-synthetic modification. We apply this method to two representative MOF families: one featuring one-dimensional metal-chloride chains and another containing discrete multinuclear metal clusters.