How to Translate the [LCu2(H)]+‐Catalysed Selective Decomposition of Formic Acid into H2 and CO2 from the Gas Phase into a Zeolite.

Abstract: Translating a homogenous catalyst into a heterogeneous catalyst requires a fundamental understanding of how the catalyst “fits” into the zeolite and how the reaction is influenced. Previous studies of bimetallic catalyst design identified a potent copper homobinuclear catalyst, [(L)Cu2(H)]+ for the selective decomposition of formic acid. Here, a close interplay between theory and experiment shows how to preserve this selective reactivity within zeolites. Gas‐phase experiments and DFT calculations showed that switching from 1,1‐bis(diphenylphosphino)‐methane ligand to the 1,8‐naphthyridine ligand produced an equally potent catalyst. DFT calculations show that this new catalyst neatly fits into a zeolite which does not perturb reactivity, thus providing a unique example on how “heterogenization” of a homogenous catalyst for the selective catalysed extrusion of carbon dioxide from formic acid can be achieved, with important application in hydrogen storage and in situ generation of H2. [ABSTRACT FROM AUTHOR]