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, Gutierrez, RA, Prats, H, Vines, F, Ramirez, PJ, Illas, F, Rodriguez, JA |
Revista | PHYSICAL CHEMISTRY CHEMICAL PHYSICS |
Volumen | 22 |
Número | 13 |
Páginas | 7110-7118 |
Type of Article | Article |
Abstract | 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. |
DOI | 10.1039/d0cp00228c |