Active Site Fluxional Restructuring as a New Paradigm in Triggering Reaction Activity for Nanocluster Catalysis

• DOI: 10.1021/acs.accounts.1c00413
• Publication Date: 2021-09-28T21:32:26Z
• Authors: Geng Sun; Philippe Sautet
• Keywords: Nanoclusters; Metastability; Reactivity

ConspectusThe rationale of the catalytic activity observed in experiments is a crucial task fundamental catalysis studies. Efficient catalyst design relies on an accurate understanding origin at atomic level. Theoretical studies have been widely developed to reach such scale activity. Current theories ascribe geometric and electronic structure active site, which geometrical effects are derived from equilibrium geometry sites characterizing static property catalyst; however catalysts, especially form nanoclusters, may present fluxional dynamic under reaction conditions, effect this behavior not yet recognized. Therefore, Account will focus fluxionality sites, driven by thermal fluctuations finite temperature.Under nanocluster catalysts can readily restructure, either being promoted another metastable isomer (named as plastic fluxionality) or presenting ample deformations around their elastic fluxionality). This summarizes our recent nanoclusters how fluxionalities play roles highly efficient pathways. Our results show that low energy isomers formed manifest high reactivity despite minor occurrence probability mixture isomers. In end, dominate total reactivity. addition, isomerization between global minimum be central step transformations order circumvent some difficult steps govern overall mechanism. fluctuation also found key role, complementary fluxionality. The creates substantial structural these deformed geometries enable activation energies activity, cannot catalyst. A dedicated search algorithm proposed for optimal pathway nanoclusters. summary, demonstrate thermal-driven provides different paradigm conditions beyond description structure. We first summarize previous then provide perspective further investigate take advantage defend picture site complete might miss critical pathways only open after thermally induced restructuring site.