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Supported metal clusters comprising of well-tailored low-nuclearity heteroatoms have great potentials in catalysis owing to the maximized exposure of active sites and metal synergy. However, atomically precise design of these architectures is still challenging for the lack of practical approaches. Herein, we report a defect-driven nanostructuring strategy through combining defect engineering of nitrogen-doped carbons and sequential metal depositions to prepare a series of Pt and Mo ensembles ranging from single atoms to sub-nanoclusters. When applied in continuous gas-phase decomposition of formic acid, the low-nuclearity ensembles with unique Pt3Mo1N3 configuration deliver CO-free hydrogen at full conversion with unexpected high activity of 0.62 molHCOOH molPt−1 s−1 and remarkable stability, significantly outperforming the previously reported catalysts. The remarkable performance is rationalized by a joint operando dual-beam Fourier transformed infrared spectroscopy and density functional theory modeling study, pointing to the Pt-Mo synergy in creating a new reaction path for consecutive HCOOH dissociations.

As one of the most widely used catalysts, palladium is unfortunately inefficient for practical applications due to its over-binding with alkyne species and excessive dissolution in an oxidative environment. Herein, an effective and universal strategy is developed to enhance the stability of the Pd catalyst by improving the bonding strength between Pd and chalcogen-functionalized ionic liquids (CIL) via p-band engineering. We show that Pd atoms dispersed in CIL with a unique Pd-CIL2-Cl2 coordination can achieve remarkable catalytic activity, stability, and recyclability for acetylene hydrochlorination. The catalyst has a high turnover frequency (2392 h− 1) and excellent stability (tos > 2000 h, Pd leaching 0.05 wt.%). For the other sublimable metals, such as Hg and Ru, CIL also demonstrates excellent anti-leaching performance. This work provides a versatile strategy for constructing strong covalent coupling between metal and ligands via p-band engineering for the design of highly durable metal catalysts.

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