Strong Metal–Support Interaction for 2D Materials: Application in Noble Metal/TiB₂ Heterointerfaces and their Enhanced Catalytic Performance for Formic Acid Dehydrogenation

Abstract Strong metal–support interaction (SMSI) is a phenomenon commonly observed on heterogeneous catalysts. Here, direct evidence of SMSI between noble metal and 2D TiB₂ supports is reported. The temperature‐induced TiB₂ overlayers encapsulate the metal nanoparticles, resulting in core–shell nanostructures that are sintering‐resistant with metal loadings as high as 12.0 wt%. The TiO_x‐terminated TiB₂ surfaces are the active sites catalyzing the dehydrogenation of formic acid at room temperature. In contrast to the trade‐off between stability and activity in conventional SMSI, TiB₂‐based SMSI promotes catalytic activity and stability simultaneously. By optimizing the thickness and coverage of the overlayer, the Pt/TiB₂ catalyst displays an outstanding hydrogen productivity of 13.8 mmol g⁻¹_cat h⁻¹ in 10.0 m aqueous solution without any additive or pH adjustment, with >99.9% selectivity toward CO₂ and H₂. Theoretical studies suggest that the TiB₂ overlayers are stabilized on different transition metals through an interplay between covalent and electrostatic interactions. Furthermore, the computationally determined trends in metal–TiB₂ interactions are fully consistent with the experimental observations regarding the extent of SMSI on different transition metals. The present research introduces a new means to create thermally stable and catalytically active metal/support interfaces for scalable chemical and energy applications.