Exploring similarities in reactivity of superatom species: a combined theoretical and experimental investigation

Abstract

The replacement of group 10-based materials by superatoms has gained great attention due to studies presenting similarities in electronic character and reactive nature between pairs. The current study extends the concept to systems of larger and varied composition as the pairs PdO⁺ and ZrO₂⁺ as well as NiO⁺ and TiO₂⁺ are interacted with C₂H₄ and CO through DFT calculations and guided-ion-beam mass spectrometry. It is determined that the pairs readily oxidize C₂H₄ while oxygen transfer is limited towards CO. Interestingly, within the reaction profiles for oxidation of C₂H₄ by PdO⁺ and NiO⁺, a spin crossover is observed which greatly increases the exothermicity of the process. This investigation presents a major step in identifying replacements for expensive group 10 metals in catalytic materials.