|Área de investigación||Química y Ciencia y Tecnología de los Materiales|
|Título||Boosting the activity of transition metal carbides towards methane activation by nanostructuring|
|Tipo de publicación||Artículo de revista|
|Año de publicación||2020|
|Autores||Figueras, M., R. A. Gutierrez, H. Prats, F. Vines, P. J. Ramirez, F. Illas, y J. A. Rodriguez|
|Revista||PHYSICAL CHEMISTRY CHEMICAL PHYSICS|
|Type of Article||Article|
The interaction of methane with pristine surfaces of bulk MoC and Mo2C is known to be weak. In contrast, a series of X-ray photoelectron spectroscopy (XPS) experiments, combined with thermal desorption mass spectroscopy (TDS), for MoCy (y = 0.5-1.3) nanoparticles supported on Au(111)-which is completely inert towards CH4-show that these systems adsorb and dissociate CH4 at room temperature and low CH4 partial pressure. This industrially-relevant finding has been further investigated with accurate density functional theory (DFT) based calculations on a variety of MoCy supported model systems. The DFT calculations reveal that the MoCy/Au(111) systems can feature low C-H bond scission energy barriers, smaller than the CH4 adsorption energy. Our theoretical results for bulk surfaces of Mo2C and MoC show that a simple Bronsted-Evans-Polanyi (BEP) relationship holds for C-H bond scission on these systems. However, this is not the case for methane activation on the MoCy nanoparticles as a consequence of their unique electronic and chemical properties. The discovery that supported molybdenum carbide nanoparticles are able to activate methane at room temperature paves the road towards the design of a new family of active carbide catalysts for methane activation and valorisation, with important implications in climate change mitigation and carbon cycle closure.