Sb-Enabled Dimensional Reprogramming of Palladium Nanoclusters for Enhanced Catalysis

Area of Science:

• Materials Science
• Nanotechnology
• Catalysis

Background:

• Palladium sulfide (PdS4) motifs form planar structures due to strong Pd-S interactions, limiting atomic growth.
• Three-dimensional (3D) palladium frameworks are typically suppressed in these systems.

Purpose of the Study:

• To investigate the role of antimony (Sb) in modifying palladium nanocluster structure.
• To develop a novel 3D palladium-antimony (Pd-Sb) nanocluster catalyst.
• To explore its application in semihydrogenation reactions.

Main Methods:

• Synthesis of [Pd13Sb2(PPh3)2(S-Adm)10] (Pd13Sb2) nanocluster.
• Single-crystal X-ray diffraction (SCXRD) for structural analysis.
• Density functional theory (DFT) calculations for mechanistic insights.

Main Results:

• Successfully synthesized a novel 3D Pd-Sb nanocluster with atomic precision.
• SCXRD revealed a unique 3D metal kernel, distinct from previously reported thiolated Pd nanoclusters.
• The Pd13Sb2 catalyst demonstrated excellent performance in phenylacetylene semihydrogenation.
• DFT calculations confirmed synergistic Pd-Sb dual-site catalysis facilitating H2 activation and optimizing intermediate binding.

Conclusions:

• Antimony acts as a dimensional regulator, enabling the formation of stable 3D Pd-Sb nanoclusters.
• The 3D structure and synergistic Pd-Sb sites overcome intrinsic limitations of planar Pd nanoclusters.
• This approach unlocks enhanced catalytic potential for palladium nanoclusters in reactions like semihydrogenation.