Investigating the Effect of Morphology on Nanoparticle Catalyst Reactivity: Example of Anthraquinone Hydrogenation

Abstract Nowadays, nanomaterials are central in modern technology, finding applications in a huge variety of scientific fields, such as catalysis. Besides their chemical nature, their morphology also appears to play a key role in catalytic processes. Although this effect has been extensively observed in literature, no fundamental explanation has been provided yet. In this work, taking anthraquinone hydrogenation on Pd as a model process, we used density functional theory (DFT) computation to address the particle shape effect. Based on previously published experimental results, we compared the catalytic properties of cubic and octahedral nanoparticles, considering different facet orientations and edge defects to simulate geometry and the size influence. We were able to correlate the morphological impact on the surface activity and selectivity with electronic charges of various intensities, induced at the material topmost layer by the cubic shaped‐design, especially close to edges. Such an inequal charge distribution, differently affects the stability of the reaction intermediates according to their polarizability. Besides offering for the very first‐time theoretical insights to understand the surface geometry effect on reactivity, this work is expected to have practical implications for experimentalists in the rational design of efficient solid catalysts in many areas of the chemical industry.