Figueras Valls, MarcGutiérrez, Ramón A.Prats Garcia, HèctorViñes Solana, FrancescRamírez, Pedro J.Illas i Riera, FrancescRodríguez, José A.2020-06-162021-03-132020-03-131463-9076https://hdl.handle.net/2445/165783The 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 Brønsted-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.9 p.application/pdfeng(c) Figueras Valls, Marc et al., 2020CarbursMolibdèTeoria del funcional de densitatNanopartículesCarbidesMolybdenumDensity functionalsNanoparticlesinfo:eu-repo/semantics/article7016712020-06-16info:eu-repo/semantics/openAccess