Peter P. Wells

The reactions under which interstitial structures of Pd form are profoundly important and prevalent in catalysis; the formation and stability of Pd hydride structures are well understood, however, interstitial structures of the carbide and nitride are relatively under explored. This work reports a systematic study of the formation and stability of PdC x and PdN x at elevated temperatures and different atmospheres using in situ Pd L 3 edge XANES spectroscopy. These studies were further complemented by the application of 14 N MAS‐NMR experiments and computational DFT investigations. The experiments confirmed that PdC x was significantly more stable than PdN x ; 14 N MAS‐NMR provided direct confirmation on the formation of the nitride, however, the XANES studies evidenced very limited stability under the conditions employed. Moreover, the results suggest that the formation of the nitride imparts some structural changes that are not entirely reversible under the conditions used in these experiments. This work provides important insights into the stability of interstitial structures of Pd and the conditions in which they could be employed for directed catalytic processes.