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Author: search.filters.author.Tachikawa, MasanoriSubject: search.filters.subject.Density functional theory

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    Unraveling H2 dissociation in CO2 hydrogenation on frustrated Lewis pair-functionalized UiO–67: DFT and nuclear quantum effects
    (2025-12-04)
    Yodsin, Nuttapon
    ;
    Udagawa, Taro
    ;
    Daengngern, Rathawat
    ;
    Jungsutthiwong, Siriporn
    ;
    Tachikawa, Masanori
    Understanding hydrogen (H<inf>2</inf>) activation is fundamental to developing efficient CO<inf>2</inf> hydrogenation catalysts. Thus, in this study, we examine H<inf>2</inf> dissociation and subsequent CO<inf>2</inf> hydrogenation on 12 UiO–67 frameworks functionalized with frustrated Lewis pairs (FLPs), employing both conventional density functional theory (DFT) and multicomponent DFT (MC_DFT) to account for nuclear quantum effects (NQEs). The results reveal that all FLP–MOFs lower the H<inf>2</inf> activation barrier through heterolytic cleavage, with NQEs further reducing the barriers—most notably in systems containing electron-donating groups (EDGs), where pronounced H–H bond elongation characterizes the transition state. Conversely, FLPs bearing strong electron-withdrawing groups stabilize the 2H adsorption state, rendering H<inf>2</inf> dissociation thermodynamically favorable but suppressing CO<inf>2</inf> hydrogenation owing to excessively strong hydrogen binding. Strong correlations are observed among H<inf>2</inf> dissociation energies, CO<inf>2</inf> hydrogenation activation barriers, and FLP acidity, enabling catalytic performance prediction. Incorporating NQEs enhances these correlations, providing a refined descriptor for rational catalyst screening. Overall, this study highlights the critical role of NQEs in hydrogen activation and demonstrates that EDG-functionalized FLP–MOFs are particularly promising candidates for promoting H<inf>2</inf> activation and CO<inf>2</inf> conversion.