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

Autori
O'Hair, Richard A. J. ; Mravak, Antonija ; Krstić, Marjan ; Bonačić‐Koutecký, Vlasta

Izvornik
ChemCatChem (1867-3880) 11 (2019), 10; 2443-2448

Vrsta, podvrsta i kategorija rada
Radovi u časopisima, članak, znanstveni

Ključne riječi
MOF based catalyst, Formic Acid, Selective Decarboxylation, DFT calculations

Sažetak
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 H2. 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 H2 and CO2 via a two-step catalytic cycle. In the first step liberation of H2 to form the carboxylate complex, [(phen*)Cu(O2CH)]2- occurs, which in the second step selectively decomposes via CO2 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.

Izvorni jezik
Engleski

Znanstvena područja
Fizika, Kemija, Interdisciplinarne prirodne znanosti

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