Understanding Supported Nanocatalysts under Operando Conditions through Systematic Kinetic Simulations

Supported metal nanoparticles (NPs) are the most important catalysts, whose reactivity depends on exposed facets, sizes, and shapes of NPs, as well as interfaces and interactions with supports. These influential factors dynamically change during reactions, making in situ/operando experimental characterization very challenging. Meanwhile, theoretical simulations often use ideal models, leading to a material gap between theory and experiment. To comprehensively understand supported nanocatalysts, here, we propose a scheme to perform systematic kinetic simulations from single crystal surfaces to supported NPs under reaction conditions. In the example of the Pt-catalyzed water–gas shift reaction, our simulations quantitatively reproduced the experimental apparent activation energies for the Pt(111) surface and for Pt NPs on different supports, consolidated the preferred reaction mechanisms and active sites, and consistently resolved the long-standing controversy on structure-sensitivity relations from experiments. This work provides deep insights into facet coupling, catalyst reconstruction, and NP–support interactions, offering opportunities to close the materials gap and transcend the current experimental limitations.