Models Facilitating the Design of a New Metal‐Organic Framework Catalyst for the Selective Decomposition of Formic Acid into Hydrogen and Carbon Dioxide

Abstract

Abstract Here we describe a new conceptual approach for the design of a heterogeneous metal‐organic framework (MOF) catalyst based on UiO‐67 for the selective decarboxylation of formic acid, a reaction with important applications in hydrogen storage and in situ generation of H 2 . Models for the {CuH} reactive catalytic site at the organic linker are assessed. In the first model system, gas‐phase mass spectrometry experiments and DFT calculations on a fixed charge bathophen ligated copper hydride complex, [(phen*)Cu(H)] 2− , were used to demonstrate that it acts as a catalyst for the selective decomposition of formic acid into H 2 and CO 2 via a two‐step catalytic cycle. In the first step liberation of H 2 to form the carboxylate complex, [(phen*)Cu(O 2 CH)] 2− occurs, which in the second step selectively decomposes via CO 2 extrusion to regenerate the hydride complex. DFT calculations on four other model systems showed that changing the catalyst to neutral [(LCu(H)] complexes or embedding it within a MOF results in mechanisms which are essentially identical. Thus catalytic active sites located on the organic linker of a MOF appear to be close to a gas‐phase environment, thereby benefitting from the favorable characteristics of gas‐phase reactions and validating the use of gas‐phase models to design new MOF based catalysts.