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Controlling the Adsorption of Carbon Monoxide on Platinum Clusters by Dopant‐Induced Electronic Structure Modification
Author(s) -
Ferrari Piero,
Molina Luis M.,
Kaydashev Vladimir E.,
Alonso Julio A.,
Lievens Peter,
Janssens Ewald
Publication year - 2016
Publication title -
angewandte chemie
Language(s) - English
Resource type - Journals
eISSN - 1521-3757
pISSN - 0044-8249
DOI - 10.1002/ange.201604269
Subject(s) - dopant , platinum , carbon monoxide , density functional theory , chemistry , reactivity (psychology) , catalysis , adsorption , inorganic chemistry , electronic structure , doping , photochemistry , computational chemistry , materials science , organic chemistry , medicine , alternative medicine , optoelectronics , pathology
Abstract A major drawback of state‐of‐the‐art proton exchange membrane fuel cells is the CO poisoning of platinum catalysts. It is known that CO poisoning is reduced if platinum alloys are used, but the underlying mechanism therefore is still under debate. We study the influence of dopant atoms on the CO adsorption on small platinum clusters using mass spectrometry experiments and density functional calculations. A significant reduction in the reactivity for Nb‐ and Mo‐doped clusters is attributed to electron transfer from those highly coordinated dopants to the Pt atoms and the concomitant lower CO binding energies. On the other hand Sn and Ag dopants have a lower Pt coordination and have a limited effect on the CO adsorption. Analysis of the density of states demonstrates a correlation of dopant‐induced changes in the electronic structure with the enhanced tolerance to CO poisoning.