Atomistic Mechanisms of Thermal Transformation in a Zr-Metal Organic Framework, MIL-140C

To understand the mechanisms responsible for thermal decomposition of a Zr-MOF (MIL-140C), we perform atomistic-scale molecular dynamics (MD) simulations and discuss the simulation data in comparison with the TEM images obtained for the decomposed Zr-MOF. First, we introduce the ReaxFF parameters suitable for the Zr/C/H/O chemistry and then apply them to investigate the thermal stability and morphological changes in the MIL-140C during heating. Based on the performed simulations we propose an atomic mechanism for the collapse of the MIL-140C and the molecular pathways for carbon monoxide formation, the main product of the MIL-140C thermal degradation. We also determine that the oxidation state of the ZrO clusters, evolved due to the thermal degradation, approximates the tetragonal phase of ZrO₂. Both simulations and experiments show a distribution of very small ZrO clusters embedded in the disrupted organic sheet that could contribute to the unusual high catalytic activity of the decomposed MIL-140C.